CN110199210A

CN110199210A - The manufacturing method of optical film and optical film

Info

Publication number: CN110199210A
Application number: CN201880007358.3A
Authority: CN
Inventors: 宫本皓史; 杉山纮子; 池内淳一
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2017-01-20
Filing date: 2018-01-15
Publication date: 2019-09-03
Anticipated expiration: 2038-01-15
Also published as: WO2018135433A1; TWI758399B; CN110199210B; TW201840651A

Abstract

The issue of the present invention is to provide the optical films comprising polyamide-imide resin, especially can be used as the optical film comprising polyamide-imide resin that the front panel of flexible display etc. suitably uses, can improving under the heating condition of lower temperature surface hardness.The present invention provides optical film, and it includes polyamide-imide resins within the temperature range of 300~370 DEG C with the peak value based on the DMA tan δ measured, and have 3 YI values below.

Description

The manufacturing method of optical film and optical film

Technical field

The present invention relates to the manufacturing methods of the optical film comprising polyamide-imide resin and optical film.

Background technique

Now, the image display devices such as liquid crystal display device, organic EL display device are applied not only to television set, and Also it is widely applied in the various uses of mobile phone, smartwatch etc.Along with the extension of such purposes, seeking Image display device (flexible display) with flexible characteristic.Image display device is shown by liquid crystal display element or organic EL The member of formation such as the display elements such as element and polarizer, phase plate and front panel are constituted.In order to reach flexible display, Need above-mentioned whole member of formation that there is flexibility.

Before this, as front panel, glass has been used.For glass, transparency is high, different according to the type of glass, energy High rigidity is presented, it is but then, very upright and outspoken, it is easily broken, thus be difficult to come as plate material before flexible display It utilizes.

Therefore, as the material for replacing glass, the application of high molecular material is studied.It is formed by high molecular material Front panel be easy present flexible characteristic, thus it can be expected that be used for various uses.As the resin with flexibility, can enumerate each Kind resin, polyamide-imide resin is one of them.From the viewpoint of the transparency, heat resistance, polyamide-imide resin Have been used for various uses.

For example, describing copolymerization has the viscous with specific logarithm of the compound containing polyoxyalkylenes in patent document 1 The copolyamide imide resin of degree and elongation at break.In patent document 2, describe by specific monomer (a), (b1) and (b2) polyamide-imide resin obtained from polymerizeing.In patent document 3, describe using have anhydride group 3 yuan of carboxylic acids at Point and isocyanates or diamines manufacture the polyamide-imide resin with defined number-average molecular weight.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 9-328550 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2008-285660 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2009-286826 bulletin

Summary of the invention

Problems to be solved by the invention

In the past, in the case where using the film comprising polyamide-imide resin as front panel, for improving, surface is hard The purpose of spending has carried out the process heated under the high temperature conditions to film.However, there are following such problems: due to The heating carried out under hot conditions causes film that xanthochromia occurs, or goes back other than comprising polyamide-imide resin in film In the case where additive (such as ultraviolet absorbing agent etc.), additive is decomposed, and damages the quality of film as a result,.

Therefore, the purpose of the present invention is to provide the front panels that especially can be used as flexible display etc. suitably to use , the optical film comprising polyamide-imide resin that surface hardness can be improved under the heating condition of lower temperature.

Means for solving the problems

Present inventor in order to solve the above problems, for the various characteristics of polyamide-imide resin, is conceived to Heating temperature and surface hardness have made intensive studies.As a result, it has been found that if using the polyamidoimide for meeting specific condition Resin can then improve surface hardness, so as to complete the present invention under the heating condition of lower temperature.

That is, the present invention includes preferred embodiment below.

[1] optical film, it includes polyamides in the range of 300~370 DEG C with the peak value based on the DMA tan δ measured Amine imide resin, and there are 3 YI values below.

[2] optical film as described in aforementioned [1], wherein according to ASTM D 3363 under the illumination conditions of 4000 luxs It is measured, the optical film has the pencil hardness of 3B or more.

[3] optical film as described in any one of aforementioned [1] or [2] also includes the additive with light absorption function.

[4] optical film as described in any one of aforementioned [1]~[3], wherein the additive with light absorption function is selected from The group being made of ultraviolet absorbing agent and blueing agent.

[5] optical film as described in any one of aforementioned [1]~[4], wherein polyamide-imide resin includes that fluorine is former Son.

[6] optical film as described in any one of aforementioned [1]~[5], wherein polyamide-imide resin at least has formula (1) structural unit indicated.

[chemical formula 1]

[in formula (1), R¹~R⁸Each independently represent hydrogen atom, the alkyl that carbon atom number is 1~6 or carbon atom number are 6 ~12 aryl, R¹~R⁸In include hydrogen atom can be substituted with halogen atoms each independently,

A each independently represents-O- ,-S- ,-CO- or-NR⁹, R⁹Indicate the carbon atom number that can be substituted with halogen atoms For 1~12 alkyl,

The integer that m is 1~4,

* chemical bond is indicated]

[7] optical film as described in any one of aforementioned [1]~[6], wherein polyamide-imide resin, which at least has, to be come From the structural unit of dicarboxylic acids.

[8] optical film as described in any one of aforementioned [1]~[7], wherein polyamide-imide resin, which at least has, to be come From the diamines containing fluorine atom and/or the structural unit of the tetracarboxylic dianhydride containing fluorine atom.

[9] optical film as described in any one of aforementioned [1]~[8], with 30 μm or more of thickness.

[10] manufacturing method of optical film includes at least following processes:

(1) resin composition of polyamide-imide resin and solvent will be included at least in the process of supporting mass；With And

The process that (2-1) removes the film of the resin combination after 240 DEG C of temperature below are dry from supporting mass, or Person,

Process that (2-2) removes the film of the resin combination after 240 DEG C of temperature below are dry from supporting mass and In the process that 240 DEG C of temperature below heat the film of removing.

[11] manufacturing method as described in aforementioned [10], wherein resin combination also includes adding with light absorption function Add agent.

[12] manufacturing method as described in aforementioned [10] or [11], wherein solvent includes dimethyl acetamide.

The effect of invention

For optical film of the invention, surface hardness can be improved under the heating condition of lower temperature.Therefore, this hair Bright optical film has both sufficient surface hardness and high transparency and low yellow chromaticity.

Specific embodiment

Hereinafter, detailed description of embodiments of the present invention.It should be noted that the scope of the present invention is not by herein The limitation of the embodiment of explanation can make various changes without departing from the gist of the present invention.

Optical film of the invention includes gathering with the peak value based on the DMA tan δ measured in the range of 300~370 DEG C Amide imide resin.Hereinafter, also there is the temperature of the peak value based on the DMA tan δ measured to be known as polyamide-imide resin " tan δ peak temperature ".

It should be noted that the tan δ peak temperature of resin is also known as the temperature of the glass transition temperature of resin.On Stating range is range more lower than the tan δ peak temperature that previous polyamide-imide resin usually has.Included in above-mentioned regulation Range temperature with tan δ peak value polyamide-imide resin optical film of the invention can lower temperature plus Reach sufficiently high surface hardness under heat condition.It is thought that because, the heating condition of the free volume of resin in lower temperature Lower reduction.It should be noted that above-mentioned mechanism does not generate any restrictions to the present invention.For optical film of the invention, by The Huang of film caused by it can reach sufficiently high surface hardness under the heating condition of lower temperature, thus can inhibit because of heating Become, the according to circumstances decomposition of the low additive of heat resistances such as additive with light absorption function for including, film can be improved Quality.When the tan δ peak temperature for the polyamide-imide resin for including in optical film of the invention is lower than 300 DEG C, the elasticity of resin Modulus decline, accordingly, there exist the tendencies for becoming to be not easy to present high surface hardness.In addition, above-mentioned tan δ peak temperature is higher than 370 DEG C When, for high surface hardness is presented, the heat treatment under high temperature is necessary, sometimes the optical characteristics decline of resin.This The tan δ peak temperature for the polyamide-imide resin for including in the optical film of invention is preferably 305~365 DEG C, more preferably.? In a certain embodiment, the tan δ peak temperature for the polyamide-imide resin for including in optical film of the invention is preferably 305~ 365 DEG C, more preferably 320~365 DEG C, further preferably 340~365 DEG C.

As the method that the tan δ peak temperature of polyamide-imide resin is adjusted to above range, it is not particularly limited, For example, can enumerate: the method for adjusting the amount for the structural unit that the aftermentioned formula (1) for including in polyamide-imide resin indicates； The method for adjusting the acid imide rate in polyamide-imide resin；Etc..It should be noted that increasing aftermentioned formula (1) table The amount of the structural unit shown or when improving the acid imide rate of polyamide-imide resin, there are the tendency of tan δ decline, because This, is adjusted them in a manner of becoming desired value.

The measurement of tan δ peak temperature is measured using DMA and is carried out.Specifically, DMA analyzer (TA can be used Instrument corporation DMA Q800), it is evaluated according to the embodiment of this specification.

The YI value of optical film of the invention is 3 or less.When YI value is greater than 3, the yellow chromaticity of optical film becomes excessively high, therefore, It cannot get sufficient visibility.The YI value of optical film of the invention is preferably 3.0 hereinafter, more preferably 2.5 hereinafter, into one Step preferably 2.0 or less.When YI value is the above-mentioned upper limit or less, the visibility of optical film can be further improved.It needs Bright, the lower limit of YI value is not particularly limited, in general, being 0 or more.Yellow chromaticity (the yellow colour index of YI value expression film (Yellow Index): YI value), the spectrophotometer (purple of Japan's light splitting (strain) system can be used according to JIS K 7373:2006 Outer visible near-infrared spectrophotometer V-670) it is measured.Specifically, by carrying out the saturating of the light relative to 300~800nm The tristimulus values (X, Y, Z) crossing rate measurement and finding out, is calculated based on following formula.

[mathematical expression 1]

YI=100 × (1.2769X-1.0592Z)/Y

For the pencil hardness (surface hardness) of optical film of the invention, pressed under the illumination conditions of 4000 luxs It is measured according to ASTM D 3363, preferably 3B or more, more preferably 2B or more, further preferably B or more, particularly preferably For HB or more, very preferably H or more, most preferably 2H or more.The pencil hardness of optical film of the invention is above-mentioned lower limit When above, it is easy to inhibit image display device surface in the case where front panel (fenestrated membrane) use as image display device Damage, in addition, be easy to prevent the contraction of optical film and expansion, thus preferably.The upper limit of the pencil hardness of optical film of the invention It is not particularly limited.Pencil hardness can be measured according to JIS K5600-5-4:1999.Specifically, being 100g, scanning in load Speed is to be measured under conditions of 60mm/ minutes, is evaluated in the case where light quantity is the illumination conditions of 4000 luxs.It needs It is bright, it is as a result different sometimes according to the difference of the illumination conditions used in the case where the evaluation for carrying out pencil hardness.Specifically For, with evaluated in the case where light quantity is the illumination conditions of 4000 luxs and compared with the pencil hardness that measures, for lower Light quantity illumination conditions under evaluated for the pencil hardness that measures, since light quantity is lower, thus become to be not easy to observe Scar on to film, as a result, a possibility that obtaining than practical higher result is high.Therefore, by the pencil hardness in this specification It is set as the value obtained from being evaluated under light quantity is the illumination conditions of 4000 luxs.

For the thickness of optical film of the invention, from the viewpoint of also resulting in influence to film thickness from pencil hardness, Preferably 20 μm or more, more preferably 30 μm or more, further preferably 40 μm or more.For the thickness of optical film of the invention For, from the viewpoint of resistance to bend(ing), preferably 300 μm hereinafter, more preferably 200 μm hereinafter, further preferably 100 μm Below.The digital display dial gauge (digimatic indicator) of contact can be used to measure for above-mentioned thickness.

The total light transmittance (Tt) of optical film of the invention according to JIS K 7105:1981 measurement preferably 70% with On, more preferably 80% or more, further preferably 85% or more, particularly preferably 90% or more.Total light transmittance is upper When more than the lower limit stated, it is easy to improve visibility when optical film of the invention to be assembled to image display device.It needs Illustrate, the upper limit of the total light transmittance of optical film of the invention is usually 100% or less.Total light transmittance can be according to JIS K 7105:1981, it is calculated using the full-automatic direct-reading mist degree of such as Suga Test Instruments Co., Ltd. Machine (haze computer) HGM-2DP measurement.

For the elasticity modulus of optical film of the invention, from the viewpoint of the flexibility of film, preferably 5.9GPa Hereinafter, more preferably 5.5GPa hereinafter, further preferably 5.2GPa hereinafter, particularly preferably 5.0GPa hereinafter, be most preferably 4.5GPa following.If elasticity modulus be the above-mentioned upper limit hereinafter, if flexible display bending when, be easy inhibit due to optical film The damage of other caused components.It should be noted that the lower limit of the elasticity modulus of optical film of the invention is not particularly limited, Usually 2.0GPa or more.For example, (strain) Shimadzu Seisakusho Ltd. autoplotter (AUTOGRAPH) AG-IS can be used, for The test film of 10mm wide under conditions of distance is 500mm between collet, tensile speed is 20mm/min, measures S-S curve, by Its slope measures elasticity modulus.

For the reciprocal bending times of optical film of the invention, from the viewpoint of the resistance to bend(ing) of film, in R= 1mm, 135 °, load 0.75kgf, speed be 175cpm under conditions of until measurement to film fracture, preferably 10,000 time with On, more preferably 20,000 time or more, further preferably 30,000 time or more, particularly preferably 40 are 000 time or more, optimal It is selected as 50,000 times or more.When the reciprocal bending times of optical film of the invention are above-mentioned lower limit or more, it is easy to inhibit inciting somebody to action The fold that optical film can generate when being bent.It should be noted that the upper limit of the reciprocal bending times of optical film is not particularly limited, In general, if can be carried out 1,000,000 time or less Zuo You bending, then it is practical enough.Reciprocal bending times for example can be used (strain) Toyo Seiki makes made MIT folding fatigue tester (model 0530), will be from a thickness of 50 μm, the light that width is 10mm The test film that film is cut out is learned to find out as measurement sample.

The weight average molecular weight (Mw) for the polyamide-imide resin for including in optical film of the invention be preferably 5,000 with On, more preferably 10,000 or more, further preferably 50,000 or more, particularly preferably 70,000 or more, especially preferably 100,000 or more, preferably 800,000 hereinafter, more preferably 600, and 000 hereinafter, further preferably 500, and 000 hereinafter, special It You Xuanwei 450,000 or less.When the weight average molecular weight (Mw) of polyamide-imide resin is above-mentioned lower limit or more, it is easy to mention The resistance to bend(ing) of high optical film of the invention.The weight average molecular weight (Mw) of polyamide-imide resin is the above-mentioned upper limit or less When, the dissolubility of polyamide-imide resin in a solvent improves, the polyamide that can will be used when making optical film of the invention The viscosity of acid imide varnish is suppressed to low-level, therefore, it will optical film of the invention easy to manufacture.In addition, the drawing of optical film It stretches and becomes easy, therefore, processability is good.Weight average molecular weight (Mw) for example can by carry out GPC measurement, according to standard polyphenyl second Alkene converts and finds out, specifically, finding out using the method recorded in embodiment.

The acid imide rate for the polyamide-imide resin for including in optical film of the invention is preferably 90% or more, more excellent It is selected as 95% or more.When acid imide rate is above-mentioned lower limit or more, it is easy that high surface hardness is presented.Polyamide-imide resin The upper limit of acid imide rate be not particularly limited, be 100% or less.Acid imide rate indicates sub- relative to polyamide acyl It is for 2 times of value of the molal quantity of the structural unit from tetracarboxylic dianhydride in polyimide resin, in polyamide-imide resin Imide bond molal quantity ratio, in this specification, measured using two-dimentional NMR.

The detailed determination condition of two-dimentional NMR is as shown in the Examples.

The structure list that preferably at least there is the polyamide-imide resin for including in optical film of the invention formula (1) to indicate Member.

[chemical formula 2]

The integer that m is 1~4,

* chemical bond is indicated.]

When the structural unit that there is polyamide-imide resin formula (1) to indicate, the main chain of polyamide-imide resin will Include the structure being indicated by-the A- in above-mentioned formula, high bendability can be assigned when film is made.By making polyamidoimide tree Rouge moderately has the structure that can assign high bendability, can moderately reduce the tan δ peak temperature of polyamide-imide resin, knot Fruit can improve the surface hardness of the film comprising the polyamide-imide resin under the heating condition of lower temperature.

About the symbol in formula (1), it is described below.

A each independently represents-O- ,-S- ,-CO- or-NR⁹, herein, R⁹Indicate that the carbon that can be substituted with halogen atoms is former The alkyl that subnumber is 1~12.From the viewpoint of the flexibility of optical film of the invention, A preferably each independently represents-O- Or-S-, more preferable expression-O-.

R¹~R⁸Each independently represent hydrogen atom, the alkyl that carbon atom number is 1~6 or the virtue that carbon atom number is 6~12 Base.From the viewpoint of the flexibility and surface hardness of optical film of the invention, R¹~R⁸It is preferred each independently to indicate hydrogen atom Or the alkyl that carbon atom number is 1~6, more preferably indicate that hydrogen atom or carbon atom number for 1~3 alkyl, further preferably indicate Hydrogen atom.Herein, R¹~R⁸In include hydrogen atom can be substituted with halogen atoms each independently.

M be 1~4 range integer, from raw material it is acquired from the viewpoint of, the integer of preferably 1~3 range, More preferably 1 or 2, further preferably 1.When m is in above range, raw material it is acquired good, in addition, being easy to improve this hair The flexibility of bright optical film.

In a preferred embodiment of the present invention, formula (1) is the structural unit that formula (1 ') indicates.In this case, originally For the optical film of invention while playing high surface hardness, elasticity modulus is low, is easy have high flexibility.

[chemical formula 3]

The structural unit that there is the polyamide-imide resin for including in optical film of the invention formula (1) or formula (1 ') to indicate A preferred embodiment in, the amount of the structural unit based on the entire infrastructure unit for including in polyamide-imide resin and Speech be preferably 3 moles of % or more, more preferably 5 moles of % or more, further preferably 10 moles of % or more, particularly preferably 20 Mole % or more.When the amount for the structural unit that formula (1) or formula (1 ') indicate is above-mentioned lower limit or more, it is easy to get at 370 DEG C The polyamide-imide resin of peak value within the scope of following temperature with tan δ.

In addition, the amount for the structural unit that formula (1) or formula (1 ') indicate is based on the whole for including in polyamide-imide resin For structural unit be preferably 45 moles of % hereinafter, more preferably 40 moles of % hereinafter, further preferably 30 moles of % or less. When the amount for the structural unit that formula (1) or formula (1 ') indicate is the above-mentioned upper limit or less, it is easy to get the temperature model at 300 DEG C or more The polyamide-imide resin of peak value in enclosing with tan δ.

The polyamide-imide resin for including in optical film of the invention for example can using dicarboxylic acids, diamines and tetrabasic carboxylic acid as Primary raw material manufactures, and preferably at least has the structural unit from them.Herein, the structure list that formula (1) or formula (1 ') indicate Member is preferably the structural unit from dicarboxylic acids.

For the polyamide-imide resin for including in optical film of the invention, from pencil hardness, elasticity modulus Viewpoint considers preferably at least there is the structural unit from dicarboxylic acids.Structural unit from dicarboxylic acids preferably comes from dicarboxyl The structural unit of acyl dichloro.

As dicarboxylic acids, the compound of formula (2) expression can be enumerated.Polyamide-imide resin can have a kind from two The structural unit of carboxylic acid can also have two or more structural unit from dicarboxylic acids.

[chemical formula 4]

[in formula (2), Z indicates the organic group of divalent, B¹And B²OH or halogen atom are each independently represented, preferably chlorine is former Son.]

The polyamide-imide resin for including in optical film of the invention has the structure of the dicarboxylic acids indicated from formula (2) In one preferred embodiment of unit, the amount of the structural unit is based on the entire infrastructure list for including in polyamide-imide resin It is preferably 5 moles of % or more, more preferably 15 moles of % or more, further preferably 20 moles of % or more for member.From formula (2) it when the amount of the structural unit of the dicarboxylic acids indicated is above-mentioned lower limit or more, is easy that high surface hardness is presented.In addition, coming from The amount of the structural unit for the dicarboxylic acids that formula (2) indicates is based on excellent for the entire infrastructure unit for including in polyamide-imide resin 45 moles of % are selected as hereinafter, more preferably 40 moles of % are hereinafter, further preferably 30 moles of % or less.It is indicated from formula (2) Dicarboxylic acids structural unit amount be the above-mentioned upper limit below when, being easy to get has within the scope of 370 DEG C or less of temperature The polyamide-imide resin of the peak value of tan δ.

Z in formula (2) indicates the organic group of divalent, and preferably the hydrogen atom in expression organic group can be by alkyl or warp The organic group that fluorine-substituted alkyl replaces.As the organic group of divalent, the group that formula (2a) and formula (2b) indicate can be enumerated； The group that the hydrogen atom in group that formula (2a) and formula (2b) indicate is replaced by methyl, fluorine-based, chloro or trifluoromethyl；And carbon Atomicity is the chain type alkyl of 6 divalents below.

[chemical formula 5]

[in formula (2a) and formula (2b),

* chemical bond is indicated,

U¹Indicate singly-bound ,-O- ,-CH₂-、-CH₂-CH₂-、-CH(CH₃)-、-C(CH₃)₂-、-C(CF₃)₂-、-Ar-、- SO₂-、-CO-、-O-Ar-O-、-Ar-O-Ar-、-Ar-CH₂-Ar-、-Ar-C(CH₃)₂- Ar- or-Ar-SO₂-Ar-.Ar indicates hydrogen The arlydene that the carbon atom number that atom can be replaced by fluorine atoms is 6~20 can enumerate phenylene as concrete example.]

As formula (2) indicate dicarboxylic acids, specifically, can enumerate aromatic dicarboxylic acid, aliphatic dicarboxylic acid and they Similar chloride compounds, acid anhydrides etc., can also be used in combination of two or more.As concrete example, terephthalic acid (TPA) can be enumerated；Isophthalic two Formic acid；Naphthalenedicarboxylic acid；4,4 '-biphenyl dicarboxylic acids；3,3 '-biphenyl dicarboxylic acids；Carbon atom number is the dicarboxylic acids of 8 chain type hydrocarbon below Compound and 2 benzoic acid are by singly-bound ,-CH₂-、-C(CH₃)₂-、-C(CF₃)₂-、-SO₂Or the compound that phenylene is formed by connecting And their chloride compounds.The dicarboxylic acids that above-mentioned formula (2) indicates more preferably includes the double benzoic acid of 4,4 '-oxygen and/or its acyl Chlorine compound.Specifically, it is preferable that 4 '-oxygen are bis- (chlorobenzoyl chloride) comprising 4, further preferred 4,4 '-oxygen bis- (chlorobenzoyl chlorides) with Paraphthaloyl chloride is used in combination.

Polyamide-imide resin has in a preferred embodiment of the present invention of the structural unit from dicarboxylic acids, From the viewpoint of the easy surface hardness for improving optical film of the invention, elasticity modulus and flexibility, polyamidoimide tree The structural unit for the dicarboxylic acids that preferably at least there is rouge the Z in formula (2) to be indicated by formula (1).Polyamide-imide resin tool When having two or more structural unit from dicarboxylic acids, examined from the viewpoint of the surface hardness of optical film, elasticity modulus and flexibility Consider, generally speaking based on the structural unit from dicarboxylic acids for including in polyamide-imide resin, Z in formula (2) by The amount of the structural unit for the dicarboxylic acids that formula (1) indicates is preferably 5 moles of % or more, more preferably 7 moles of % or more, further excellent It is selected as 9 moles of % or more, particularly preferably 11 moles of % or more.The knot for the dicarboxylic acids that Z in formula (2) is indicated by formula (1) The upper limit of the amount of structure unit is not particularly limited, based on the structural unit from dicarboxylic acids for including in polyamide-imide resin It generally speaking is 100 moles of % or less.The ratio of the structural unit for the dicarboxylic acids that Z in formula (2) is indicated by formula (1) Such as it can be used¹H-NMR calculates to measure or can also be compared by the charging of raw material.

From the viewpoint of dissolubility from transparent, agent of low hygroscopicity and in a solvent, include in optical film of the invention Polyamide-imide resin preferably at least has the structural unit from diamines.

As diamines, the compound of formula (3) expression can be enumerated.

[chemical formula 6]

H₂N-X-NH₂ (3)

[in formula (3), X indicates the organic group of divalent.]

Polyamide-imide resin can have a kind of structural unit from diamines, can also have two or more from diamines Structural unit.

The polyamide-imide resin for including in optical film of the invention has the structure list of the diamines indicated from formula (3) In one preferred embodiment of member, the amount of the structural unit is based on the entire infrastructure unit for including in polyamide-imide resin For preferably 47.5 moles of % or more, more preferably 49.0 moles of % or more, further preferably 49.5 moles of % or more.Come When the amount of the structural unit of the diamines indicated from formula (3) is above-mentioned lower limit or more, it is easy to get the polyamide acyl of high molecular weight Imide resin is easy that high surface hardness is presented.In addition, the amount of the structural unit of the diamines from formula (3) expression is based on polyamide For the entire infrastructure unit for including in imide resin be preferably 50.5 moles of % hereinafter, more preferably 50.0 moles of % with Under, further preferably 49.99 moles of % or less.The amount of the structural unit of the diamines indicated from formula (3) is the above-mentioned upper limit When following, it is easy that high transparency and low yellow chromaticity is presented.

X in formula (3) indicates the organic group of divalent, and preferably the hydrogen atom in expression organic group can be by alkyl or warp The organic group that fluorine-substituted alkyl replaces.As the organic group of divalent, formula (3a), formula (3b), formula (3c), formula can be enumerated The group that (3d), formula (3e), formula (3f), formula (3g), formula (3h) and formula (3i) indicate；The hydrogen atom in group that these formulas indicate The group replaced by methyl, fluorine-based, chloro or trifluoromethyl；And carbon atom number is the chain type alkyl of 6 divalents below.

[chemical formula 7]

[in formula (3a), formula (3b), formula (3c), formula (3d), formula (3e), formula (3f), formula (3g), formula (3h) and formula (3i),

* chemical bond is indicated,

V¹~V³Each independently represent singly-bound ,-O- ,-S- ,-CH₂-、-CH₂-CH₂-、-CH(CH₃)-、-C(CH₃)₂-、-C (CF₃)₂-、-SO₂Or-CO-.]

As an example, V¹And V³For singly-bound ,-O- or-S-, also, V²For-CH₂-、-C(CH₃)₂-、-C(CF₃)₂Or- SO₂-。V¹And V²Bonding position and V relative to each ring²And V³Bonding position relative to each ring is respectively preferably with respect to each ring For meta or para position, more preferably align.

What formula (3a), formula (3b), formula (3c), formula (3d), formula (3e), formula (3f), formula (3g), formula (3h) and formula (3i) indicated In group, from the viewpoint of the surface hardness and flexibility of optical film of the invention, preferred formula (3d), formula (3e), formula (3f), The group that formula (3g) or formula (3h) indicate, the group that more preferable formula (3e), formula (3f) or formula (3g) indicate.In addition, from the present invention Optical film surface hardness and flexibility from the viewpoint of, V¹~V³Each independently be preferably singly-bound ,-O- or-S-, it is more excellent It is selected as singly-bound or-O-.

As the diamines that formula (3) indicate, specifically, aliphatic diamine, aromatic diamine and their mixing can be enumerated Object.It should be noted that in present embodiment, it is so-called " aromatic diamine ", indicate that amino is bonded directly to the diamines of aromatic rings, It may include aliphatic group or other substituent groups in a part of its structure.The aromatic rings can may be condensed ring for monocycle, Phenyl ring, naphthalene nucleus, anthracene nucleus and fluorenes ring etc. can be enumerated, but is not limited to these.In these, preferably phenyl ring.In addition, so-called " aliphatic Diamines " indicates that amino is bonded directly to the diamines of aliphatic group, may include in a part of its structure aromatic rings, other Substituent group.

As aliphatic diamine, the non-ring type aliphatic diamine and 1 such as hexamethylene diamine, the bis- (ammonia of 3- can be enumerated Ylmethyl) hexamethylene, bis- (amino methyl) hexamethylenes of 1,4-, norbornane diamines and 4,4 '-diamino-dicyclohexyl methanes etc. Ring type aliphatic diamine etc..They can be used alone or can also combine two or more and use.

As aromatic diamine, such as p-phenylenediamine, m-phenylene diamine (MPD), 2,4- toluenediamine, m-xylene diamine, right can be enumerated Benzene dimethylamine, 1,5- diaminonaphthalene and 2,6- diaminonaphthalene etc. have the aromatic diamine of 1 aromatic rings；4,4 '-diamino two Phenylmethane, 4,4 '-diamino-diphenyl propane, 4,4 '-diamino-diphenyl ethers, 3,4 '-diamino-diphenyl ethers, 3,3 '- Diamino-diphenyl ether, 4,4 '-diamino diphenyl sulfones, 3,4 '-diamino diphenyl sulfones, 3,3 '-diamino diphenyl sulfones, 1, Bis- (4- amino-benzene oxygen) benzene of 4-, bis- (4- amino-benzene oxygen) benzene of 1,3-, 4,4 '-diamino diphenyl sulfones, bis- (4- (4- amino Phenoxy group) phenyl) sulfone, bis- (4- (3- amino-benzene oxygen) phenyl) sulfones, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane, 2, Bis- [4- (3- amino-benzene oxygen) phenyl] propane of 2-, 2,2 '-dimethylbenzidines, 2,2 '-bis- (trifluoromethyl) benzidine are (sometimes Be recorded as TFMB), 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, bis- (4- aminophenyl) fluorenes of 9,9-, the bis- (4- amino -3- first of 9,9- Base phenyl) fluorenes, bis- (4- amino -3- chlorphenyl) fluorenes of 9,9- and bis- (4- amino -3- fluorophenyl) fluorenes of 9,9- etc. have 2 or more The aromatic diamine of aromatic rings.They can be used alone or can also combine two or more and use.

As aromatic diamine, preferably 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino-diphenyl propane, 4, 4 '-diamino-diphenyl ethers, 3,3 '-diamino-diphenyl ethers, 4,4 '-diamino diphenyl sulfones, 3,3 '-diamino-diphenyls Bis- (4- amino-benzene oxygen) benzene of sulfone, 1,4-, bis- (4- (4- amino-benzene oxygen) phenyl) sulfones, bis- (4- (3- amino-benzene oxygen) phenyl) Bis- [4- (4- amino-benzene oxygen) phenyl] propane of sulfone, 2,2-, 2,2- bis- [4- (3- amino-benzene oxygen) phenyl] propane, 2,2 '-two Methyl biphenyl amine, 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, more preferably For 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino-diphenyl propane, 4,4 '-diamino-diphenyl ethers, 4,4 '-diamino Bis- (4- amino-benzene oxygen) benzene of diphenyl sulfone, 1,4-, bis- (4- (4- amino-benzene oxygen) phenyl) sulfones, bis- [4- (the 4- aminobenzenes of 2,2- Oxygroup) phenyl] propane, 2,2 '-dimethylbenzidines, 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines, 4,4 '-bis- (4- Amino-benzene oxygen) biphenyl.They can be used alone or can also combine two or more and use.

In above-mentioned diamine compound, from the surface hardness of optical film of the invention, flexibility, resistance to bend(ing), the transparency and From the viewpoint of yellow chromaticity, it is preferable to use selected from one or more of the group being made of the aromatic diamine with biphenyl structural, more It is preferable to use selected from by 2,2 '-dimethylbenzidines, 2,2 '-bis- (trifluoromethyl) benzidine, 4,4 '-bis- (4- amino-benzene oxygens) Biphenyl and 4, one or more of the group of 4 '-diamino-diphenyl ethers composition, still more preferably uses 2,2 '-bis- (fluoroforms Base) benzidine.

Polyamide-imide resin has in a preferred embodiment of the present invention of the structural unit from diamines, from It is easy from the viewpoint of the surface hardness and the transparency that improve optical film of the invention, polyamide-imide resin preferably at least has The structural unit for the diamines for thering is the X in formula (3) to be indicated by formula (3e ').

[chemical formula 8]

[in formula (3e '), R¹⁰~R¹⁷Each independently represent the alkyl or carbon atom number of hydrogen atom, carbon atom number for 1~6 For 6~12 aryl, R¹⁰~R¹⁷In include hydrogen atom can be substituted with halogen atoms each independently,

* chemical bond is indicated.]

In formula (3e '), R¹⁰~R¹⁷Each independently represent the alkyl or carbon atom number of hydrogen atom, carbon atom number for 1~6 For 6~12 aryl, preferably expression hydrogen atom or carbon atom number is 1~6 alkyl, more preferably indicates hydrogen atom or carbon atom number For 1~3 alkyl, herein, R¹⁰~R¹⁷In include hydrogen atom can be substituted with halogen atoms each independently.From the present invention The surface hardness of optical film, from the viewpoint of flexibility and the transparency, R¹⁰~R¹⁷It is each independently more preferably that hydrogen is former Son, methyl, fluorine-based, chloro or trifluoromethyl, particularly preferably hydrogen atom or trifluoromethyl.

In said one preferred embodiment, polyamide-imide resin preferably at least has the X in formula (3) by formula The structural unit for the diamines that (3e ") is indicated.

[chemical formula 9]

[in formula (3e "), * indicates chemical bond]

In this case, optical film of the invention has high transparency, meanwhile, polyamide-imide resin, which has, contains fluorine The skeleton of element, polyamide-imide resin dissolubility in a solvent improves as a result, when can be by optical film of the invention is made The viscosity of the polyamidoimide varnish used is suppressed to low-level, therefore, it will optical film of the invention easy to manufacture.

When polyamide-imide resin has two or more structural unit from diamines, from the transparency for improving optical film And from the viewpoint of the easiness of manufacture, the structure for the diamines that the X in formula (3) is indicated by formula (3e '), preferred formula (3e ") Generally speaking the amount of unit is preferably 30 moles of % in polyamide-imide resin based on the structural unit from diamines for including More than, more preferably 50 moles of % or more, further preferably 70 moles of % or more.X in formula (3) is by formula (3e '), excellent The upper limit of amount of the structural unit for the diamines for selecting formula (3e ") to indicate is not particularly limited, based on wrapping in polyamide-imide resin Generally speaking the structural unit from diamines contained is 100 moles of % or less.X in formula (3) is by formula (3e ') or formula The ratio of the structural unit for the diamines that (3e ") is indicated for example can be used¹H-NMR counts to measure or can also be compared by the charging of raw material It calculates.

From the viewpoint of dissolubility from transparent, moisture-absorption characteristics and in a solvent, include in optical film of the invention Polyamide-imide resin preferably at least has the structural unit from tetracarboxylic dianhydride.

As tetracarboxylic dianhydride, the compound of formula (4) expression can be enumerated.Polyamide-imide resin can have a kind to come from The structural unit of tetracarboxylic dianhydride can also have two or more structural unit from tetracarboxylic dianhydride.

[chemical formula 10]

[in formula (4), Y indicates the organic group of 4 valences]

The polyamide-imide resin for including in optical film of the invention has the tetracarboxylic dianhydride indicated from formula (4) In one preferred embodiment of structural unit, the amount of the structural unit is based on the whole knot for including in polyamide-imide resin It is preferably 5 moles of % or more, more preferably 10 moles of % or more, further preferably 20 moles of % or more for structure unit.Come When the amount of the structural unit of the tetracarboxylic dianhydride indicated from formula (4) is above-mentioned lower limit or more, the knot from dicarboxylic acids can be inhibited The ratio of structure unit is easy to get the polyamide-imide resin of the peak value within the scope of 370 DEG C or less of temperature with tan δ. In addition, the amount of the structural unit of the tetracarboxylic dianhydride from formula (4) expression is based on the whole for including in polyamide-imide resin For structural unit be preferably 45 moles of % hereinafter, more preferably 40 moles of % hereinafter, further preferably 30 moles of % or less. When the amount of the structural unit of the tetracarboxylic dianhydride indicated from formula (4) is the above-mentioned upper limit or less, it can increase from dicarboxylic acids The ratio of structural unit is easy that high surface hardness is presented.

Y in formula (4) indicates the organic group of 4 valences, and preferably the hydrogen atom in expression organic group can be by alkyl or warp The organic group that fluorine-substituted alkyl replaces.As the organic group of 4 valences, formula (4a), formula (4b), formula (4c), formula can be enumerated The group that (4d), formula (4e), formula (4f), formula (4g), formula (4h), formula (4i) and formula (4j) indicate；In the group that these formulas indicate The group that is replaced by methyl, fluorine-based, chloro or trifluoromethyl of hydrogen atom；And carbon atom number is the chain type hydrocarbon of 64 valences below Base.

[chemical formula 11]

[formula (4a), formula (4b), formula (4c), formula (4d), formula (4e), formula (4f), formula (4g), formula (4h), formula (4i) and formula In (4j),

* chemical bond is indicated,

W¹Indicate singly-bound ,-O- ,-CH₂-、-CH₂-CH₂-、-CH(CH₃)-、-C(CH₃)₂-、-C(CF₃)₂-、-Ar-、- SO₂-、-CO-、-O-Ar-O-、-Ar-O-Ar-、-Ar-CH₂-Ar-、-Ar-C(CH₃)₂- Ar- or-Ar-SO₂-Ar-.Ar indicates hydrogen The arlydene that the carbon atom number that atom can be replaced by fluorine atoms is 6~20 can enumerate phenylene as concrete example.]

Formula (4a), formula (4b), formula (4c), formula (4d), formula (4e), formula (4f), formula (4g), formula (4h), formula (4i) and formula In the group that (4j) is indicated, from the viewpoint of the surface hardness and flexibility of optical film of the invention, preferred formula (4g), formula The group that (4i) or formula (4j) indicate, the group that more preferable formula (4g) indicates.In addition, from the surface hardness of optical film of the invention And from the viewpoint of flexibility, W¹Preferably singly-bound ,-O- ,-CH₂-、-CH₂-CH₂-、-CH(CH₃)-、-C(CH₃)₂Or-C (CF₃)₂, more preferably singly-bound ,-O- ,-CH₂-、-CH(CH₃)-、-C(CH₃)₂Or-C (CF₃)₂, further preferably singly-bound ,- O-、-C(CH₃)₂Or-C (CF₃)₂, especially preferably-O- or-C (CF₃)₂-。

As the tetracarboxylic dianhydride that formula (4) indicate, aromatic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride etc. can be enumerated. 1 kind of tetracarboxylic dianhydride can be used, can also be used in combination of two or more.

As the concrete example of aromatic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, the list of non-condensed polycycle can be enumerated The aromatic tetracarboxylic dianhydride of ring type and the aromatic tetracarboxylic dianhydride of fused polycyclic.Aromatic series as non-condensed polycycle The concrete example of tetracarboxylic dianhydride can enumerate 4,4 '-oxygen, two O-phthalic acid dianhydride (sometimes referred to as OPDA), 3,3 ', 4,4 '-two Benzophenone tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2,2 ', Bis- (3,4- dicarboxyphenyi) propane two of 3,3 '-bibenzene tetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic acid dianhydrides, 2,2- Bis- (2,3- dicarboxyphenyi) propane dianhydrides of acid anhydride, 2,2-, 2,2- bis- (3,4- di carboxyl phenyloxy phenyl) propane dianhydrides, 4,4 '- Bis- (2,3- dicarboxyphenyi) the ethane dianhydrides of (hexafluoroisopropyli,ene) two O-phthalic acid dianhydride (sometimes referred to as 6FDA), 1,2-, Bis- (2,3- dicarboxyphenyi) the ethane dianhydrides of 1,1-, bis- (3,4- dicarboxyphenyi) the ethane dianhydrides of 1,2-, bis- (the 3,4- dicarboxyls of 1,1- Base phenyl) ethane dianhydride, bis- (3,4- dicarboxyphenyi) methane dianhydrides, bis- (2,3- dicarboxyphenyi) methane dianhydrides, 4,4 '- (to two oxygroup of benzene) two O-phthalic acid dianhydrides and 4,4 '-(two oxygroup of isophthalic) two O-phthalic acid dianhydrides.In addition, respectively, As the aromatic tetracarboxylic dianhydride of monocyclic, 1,2,4,5- pyromellitic dianhydride, the fragrance as fused polycyclic can be enumerated Race tetracarboxylic dianhydride can enumerate 1,2,4,5- pyromellitic dianhydride, as the aromatic tetracarboxylic dianhydride of fused polycyclic, can lift 2,3,6,7- naphthalenetetracarbacidic acidic dianhydride out.They can be used alone or can also combine two or more and use.

In these, preferably 4,4 '-oxygen, two O-phthalic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydrides, 3, Bis- (3,4- dicarboxyphenyi) propane dianhydrides of 3 ', 4,4 '-diphenyl sulfone tetracarboxylic acid dianhydrides, 2,2-, bis- (the 2,3- dicarboxyl benzene of 2,2- Base) propane dianhydride, bis- (the 3,4- di carboxyl phenyloxy phenyl) propane dianhydrides of 2,2-, 4,4 '-(hexafluoroisopropyli,ene) two O-phthalics Bis- (2,3- dicarboxyphenyi) the ethane dianhydrides of acid dianhydride, 1,2-, bis- (2,3- dicarboxyphenyi) the ethane dianhydrides of 1,1-, 1,2- are bis- Bis- (3,4- dicarboxyphenyi) the ethane dianhydrides of (3,4- dicarboxyphenyi) ethane dianhydride, 1,1-, bis- (3,4- dicarboxyphenyi) first Alkane dianhydride, bis- (2,3- dicarboxyphenyi) methane dianhydrides, 4,4 '-(to two oxygroup of benzene) two O-phthalic acid dianhydrides and 4,4 '-( Two oxygroup of benzene) two O-phthalic acid dianhydrides, more preferable 4,4 '-oxygen, two O-phthalic acid dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylics Dianhydride and 4,4 '-(hexafluoroisopropyli,ene) two O-phthalic acid dianhydrides.

As aliphatic tetracarboxylic dianhydride, the aliphatic tetracarboxylic dianhydride of ring type or non-ring type can be enumerated.As ring type rouge Fat race tetracarboxylic dianhydride, can enumerate the tetracarboxylic dianhydride with ester ring type hydrocarbon structure, as its concrete example, can enumerate 1,2,4,5- The cycloalkane four such as cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4- cyclobutanetetracarboxylic dianhydride, 1,2,3,4- cyclopentane tetracarboxylic acid dianhydride Carboxylic acid dianhydride, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic acid dianhydride, dicyclohexyl -3,3 ' -4,4 '-tetracarboxylic acid dianhydride And their position isomer.They can be used alone or can also combine two or more and use.As non-ring type aliphatic The concrete example of tetracarboxylic dianhydride can enumerate 1,2,3,4- ethylene-dimalonic acid dianhydrides and 1,2,3,4- pentane tetracarboxylic acid dianhydrides etc., it Can be used alone or two or more can also be combined and used.In addition, can be by ring type aliphatic tetracarboxylic dianhydride and non-ring type Aliphatic tetracarboxylic dianhydride is applied in combination.

In above-mentioned tetracarboxylic dianhydride, from easy surface hardness, flexibility, resistance to bend(ing), the transparency, the appearance for improving optical film From the viewpoint of easily reducing yellow chromaticity, preferably 4,4 '-oxygen, two O-phthalic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylics two Acid anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic acids Bis- (3,4- dicarboxyphenyi) propane dianhydrides of dianhydride, 2,2-, 4,4 '-(hexafluoroisopropyli,ene) two O-phthalic acid dianhydrides and it Mixture, more preferable 4,4 '-oxygen, two O-phthalic acid dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides and 4,4 '-(hexafluoros Isopropylidene) two O-phthalic acid dianhydrides and their mixture, further preferred 4,4 '-(hexafluoroisopropyli,ene) two adjacent benzene two Formic acid dianhydride.

Polyamide-imide resin has an of the invention preferred implementation side for the structural unit from tetracarboxylic dianhydride In formula, the knot for the tetracarboxylic dianhydride that preferably at least there is polyamide-imide resin the Y in formula (4) to be indicated by formula (4g ') Structure unit.

[chemical formula 12]

[in formula (4g '), R¹⁸~R²⁵Each independently represent the alkyl or carbon atom number of hydrogen atom, carbon atom number for 1~6 For 6~12 aryl, R¹⁸~R²⁵In include hydrogen atom can be substituted with halogen atoms each independently,

* chemical bond is indicated]

In this case, optical film of the invention has high transparency, meanwhile, the height with polyamide-imide resin is curved Song skeleton, the dissolubility of polyamide-imide resin in a solvent improves as a result, can will make when making optical film of the invention The viscosity of polyamidoimide varnish is suppressed to low-level, therefore, it will optical film of the invention easy to manufacture.

In formula (4g '), R¹⁸~R²⁵Each independently represent the alkyl or carbon atom number of hydrogen atom, carbon atom number for 1~6 For 6~12 aryl, preferably expression hydrogen atom or carbon atom number is 1~6 alkyl, more preferably indicates hydrogen atom or carbon atom number For 1~3 alkyl, herein, R¹⁸~R²⁵In include hydrogen atom can be substituted with halogen atoms each independently.From the present invention Optical film surface hardness and flexibility from the viewpoint of, R¹⁸~R²⁵It is each independently more preferably hydrogen atom, first Base, fluorine-based, chloro or trifluoromethyl, particularly preferably hydrogen atom or trifluoromethyl.

In an above-mentioned preferred embodiment, polyamide-imide resin preferably at least have the Y in formula (4) by The structural unit for the tetracarboxylic dianhydride that formula (4g ") indicates.

[chemical formula 13]

[in formula (4g "), * indicates chemical bond]

When polyamide-imide resin has two or more structural unit from tetracarboxylic dianhydride, from improving optical film From the viewpoint of the transparency and the easiness of manufacture, the Y in formula (4) is by formula (4g '), the tetracarboxylic acid of preferred formula (4g ") expression The amount of the structural unit of acid dianhydride is whole based on the structural unit from tetracarboxylic dianhydride for including in polyamide-imide resin For preferably 50 moles of % or more, more preferably 60 moles of % or more, further preferably 70 moles of % or more.From formula (4) upper limit of the amount of the structural unit for the tetracarboxylic dianhydride that the Y in is indicated by formula (4g '), preferred formula (4g ") does not limit especially System, based on the structural unit from tetracarboxylic dianhydride for including in polyamide-imide resin be generally speaking 100 moles of % with It is lower.The ratio of the structural unit for the diamines that X in formula (4) is indicated by formula (4g ') or formula (4g ") for example can be used¹H-NMR calculates to measure or can also be compared by the charging of raw material.

The polyamide-imide resin for including in optical film of the invention can also have the structural unit from tricarboxylic acids. As tricarboxylic acids, chloride compounds, the acid anhydrides of aromatic tricarboxylic acids, aliphatic tricarboxylic acids and the analog as them can be enumerated Deng.1 kind of tricarboxylic acids can be used, can also be used in combination of two or more.

As concrete example, the acid anhydride of 1,2,4- benzenetricarboxylic acids can be enumerated；2,3,6- naphthalenetricarboxylic acid -2,3- acid anhydride；Phthalic acid Acid anhydride and benzoic acid are by singly-bound ,-O- ,-CH₂-、-C(CH₃)₂-、-C(CF₃)₂-、-SO₂Or the compound that phenylene is formed by connecting.

In a preferred embodiment of the present invention, include in optical film of the invention in the range of 300~370 DEG C The polyamide-imide resin of peak value with the tan δ measured based on DMA are as follows: (omega-dicarboxylic acids such as acyl chlorides are seemingly as dicarboxylic acids Object), diamines and tetrabasic carboxylic acid (tetracarboxylic acids such as acyl chlorides, tetracarboxylic dianhydride acid-like substance), according to circumstances further with tricarboxylic acids (acyl chlorides The tricarboxylic acids compound such as compound, tricarboxylic acid anhydride analog) polycondensation product condensed type macromolecule.In which, polyamide The structural unit that the structural unit and formula (6) that there are imide resin formula (5) to indicate indicate.

[chemical formula 14]

[in formula (5) and formula (6), X, Y and Z are the same meaning as the above]

X, Y and Z in formula (5) and formula (6) respectively with the X in formula (3), the Y in formula (4) and the Z meaning phase in formula (2) Together, the preferred record hereinbefore described about X, Y and Z in formula (2)~formula (4), is applied equally to formula (5) and formula (6) X, Y and Z in.The structural unit that formula (5) indicates is usually the structural unit from diamines and tetrabasic carboxylic acid, what formula (6) indicated Structural unit is usually the structural unit from diamines and dicarboxylic acids.

In a preferred embodiment of the present invention, include in optical film of the invention in the range of 300~370 DEG C The polyamide-imide resin of peak value with the tan δ measured based on DMA can also have formula (7) indicate structural unit and/ Or the structural unit that formula (8) indicates.

[chemical formula 15]

[in formula (7), X¹Indicate the organic group of divalent, Y¹Indicate the organic group of 4 valences,

In formula (8), X²Indicate the organic group of divalent, Y²Indicate the organic group of trivalent]

In formula (7), Y¹It is each independently the organic group of 4 valences, the preferably hydrogen atom in organic group can be by hydrocarbon The organic group that base or fluorine-substituted alkyl replace.As Y¹, formula (4a), formula (4b), formula (4c), formula (4d), formula can be enumerated The carbon atom number of group and 4 valences that (4e), formula (4f), formula (4g), formula (4h), formula (4i) and formula (4j) indicate is 6 below Chain type alkyl.Polyamide-imide resin can have the structural unit of a kind of formula (7) expression, can also have Y¹And/or X¹Mutually The structural unit that two or more different formulas (7) indicates.

In formula (8), Y²It is each independently the organic group of trivalent, the preferably hydrogen atom in organic group can be by hydrocarbon The organic group that base or fluorine-substituted alkyl replace.As Y², formula (4a), formula (4b), formula (4c), formula (4d), formula can be enumerated Any of the chemical bond of group that (4e), formula (4f), formula (4g), formula (4h), formula (4i) or formula (4j) indicate is substituted for hydrogen The carbon atom number of group and trivalent obtained from atom is 6 chain type alkyl below.Polyamide-imide resin can have a kind of formula (8) structural unit indicated, can also have Y²And/or X²The structural unit that two or more mutually different formula (8) indicates.

In formula (7) and formula (8), X¹And X²It is each independently the organic group of divalent, the hydrogen preferably in organic group is former The organic group that son can be replaced by alkyl or fluorine-substituted alkyl.As X¹And X², formula (3a), formula (3b), formula can be enumerated The group that (3c), formula (3d), formula (3e), formula (3f), formula (3g), formula (3h) and formula (3i) indicate；In the group that these formulas indicate The group that is replaced by methyl, fluorine-based, chloro or trifluoromethyl of hydrogen atom；And carbon atom number is 6 chain type alkyl below.

In a preferred embodiment of the present invention, the polyamide-imide resin for including in optical film of the invention is by formula (5) and the structural unit that indicates of formula (6) and structural unit that according to circumstances existing formula (7) and/or formula (8) indicate are formed. In which, from the viewpoint of the easy flexibility and surface hardness for improving optical film, include in polyamide-imide resin The structural unit that indicates of formula (5) and the amount of structural unit that indicates of formula (6) be based on formula (5) and formula (6) and according to circumstances deposit Formula (7) and/or formula (8) indicate structural unit summation for preferably 80% or more, more preferably 90% or more, into One step is preferably 95% or more.It should be noted that the formula (5) and formula (6) that include in above-mentioned polyamide-imide resin indicate The upper limit of amount of structural unit be based on formula (5) or formula (6) or structure list that according to circumstances existing formula (7) or formula (8) indicate It is usually 100% or less for the summation of member.It should be noted that aforementioned proportion for example can be used¹H-NMR measuring or It can be by the charging of raw material than calculating.

The polyamide-imide resin for including in optical film of the invention preferably comprises halogen atom, more preferably former comprising fluorine Son.As the concrete example containing fluoro substituents, fluorine-based and trifluoromethyl can be enumerated.By making polyamide-imide resin include halogen Atom, to be easily reduced the yellow chromaticity (YI value) of optical film of the invention, and be easy while realizing higher flexibility and Resistance to bend(ing).From the viewpoint of the reduction of the yellow chromaticity of optical film of the invention, the reduction and resistance to bend(ing) of water absorption rate, halogen Plain atom is preferably fluorine atom.Consider from above-mentioned viewpoint, polyamide-imide resin, which preferably at least has to come from, contains fluorine atom Diamines and/or the tetracarboxylic dianhydride containing fluorine atom structural unit.

The viewpoint inhibited from the deformation of the reduction (transparent raising) of yellow chromaticity, the reduction of water absorption rate and optical film is examined Consider, the content of the halogen atom in polyamide-imide resin is based on the polyamidoimide tree for including in optical film of the invention It is preferably 1~40 mass %, more preferably 3~35 mass %, further preferably 5~32 mass % for the quality of rouge.

The manufacturing method for the polyamide-imide resin for including in optical film of the invention is illustrated below.Polyamide Imide resin can be for example manufactured in the following manner: dicarboxylic acids, diamines and tetrabasic carboxylic acid described herein above is primary raw material, root According to situation by their further polycondensations together with tricarboxylic acids described above.

The reaction temperature of above-mentioned polycondensation reaction is not particularly limited, and for example, 50~350 DEG C.Reaction time is also without special Limitation, for example, 30 minutes~10 hours or so.As needed, it can be reacted under conditions of inert atmosphere or decompression. In addition, reaction preferably carries out in a solvent, as solvent, for example, can enumerate used in the preparation of polyamidoimide varnish Aftermentioned solvent.

In above-mentioned polycondensation reaction, imidization catalyst can be used.As imidization catalyst, such as 3 third can be enumerated The aliphatic amines such as base amine, dibutyl propyl amine, Dibutylethylamine；N-ethylpiperidine, N- propylpiperdine, N- butyl pyrrolidine, N- butyl piperidine and N- propyl hexahydro azepine(azepine) the ester ring types amine (monocyclic) such as；Azabicyclo [2.2.1] heptane, The ester ring types amine such as azabicyclo [3.2.1] octane, azabicyclo [2.2.2] octane and azabicyclo [3.2.2] nonane are (polycyclic Formula)；And pyridine, 2- picoline, 3- picoline, 4- picoline, 2- ethylpyridine, 3-ethylpyridine, 4- ethyl pyrrole Pyridine, 2,4- lutidines, 2,4,6- trimethylpyridine, 3,4- cyclopenta pyridine, 5,6,7,8- tetrahydroisoquinoline and isoquinoline The aromatic amines such as quinoline.

For optical film of the invention, examined from the visibility of optical film and the viewpoint of quality for improving of the invention Consider, also comprising the additive with light absorption function preferably other than above-mentioned polyamide-imide resin.It is inhaled as with light The additive for receiving function, can enumerate such as ultraviolet absorbing agent, blueing agent.Additive with light absorption function is selected from by purple When the group of ultraviolet absorbers and blueing agent composition, it is easy to improve the visibility and quality of optical film of the invention, thus it is excellent Choosing.Optical film of the invention can contain 2 with light absorption function containing a kind of additive with light absorption function Kind or more additive.Herein, ultraviolet absorbing agent and blueing are being added into the previous film comprising polyamide-imide resin In the case that agent etc. has the additive of light absorption function, there are following such problems for these additives: since heat resistance is low, Thus it is to decompose in the process for heating the film comprising polyamide-imide resin under hot conditions, makes film Quality variation.It is therefore desirable, for example, carrying out adding these additions in the layer different from the layer comprising polyamide-imide resin Agent makes it reply such as be bonded with PA membrane.According to the polyamide comprising the peak value within the specified temperature range with tan δ The optical film of the invention of imide resin can reach sufficiently high surface hardness under the heating condition of lower temperature, therefore, Even if to include in the identical layer of the layer of polyamide-imide resin addition there is the case where additive of light absorption function Under, it can also inhibit the decomposition etc. of these additives, the decline of film quality can be inhibited.

As ultraviolet absorbing agent, the substance that can be used from the field of resin material usually as ultraviolet absorbing agent In suitably selection use.Ultraviolet absorbing agent may include the compound for absorbing the light of 400nm wavelength below.It is inhaled as ultraviolet light Agent is received, can be enumerated for example selected from by benzophenone based compound, salicylate based compound, benzotriazole based compound and three At least one kind of compound in the group of piperazine based compound composition.When optical film of the invention contains ultraviolet absorbing agent, it can inhibit poly- Therefore the deterioration of amide imide resin can improve the visibility of optical film.It should be noted that in this specification, institute It calls " based compound ", refers to the derivative for being accompanied with the compound of " based compound ".For example, so-called " benzophenone series chemical combination Object " refers to the compound with the benzophenone as precursor skeleton and the substituent group for being bonded to benzophenone.

When optical film contains ultraviolet absorbing agent, the additive amount of ultraviolet absorbing agent can be according to the ultraviolet absorbing agent used Type suitably select, as substantially standard, for the gross mass based on optical film, preferably 1 mass % or more, more preferably 2 mass % or more, further preferably 3 mass % or more, preferably 10 mass % hereinafter, more preferably 8 mass % hereinafter, into One step is preferably 6 mass % or less.Preferred additive amount is different according to the difference of the ultraviolet absorbing agent used, with 400nm Light transmittance when adjusting additive amount as 20~60% or so mode, be easy to improve the light resistance of optical film of the invention, and And it is easy to get the high optical film of the transparency, thus preferably.

As blueing agent, suitably selection makes in the substance that can be used from the field of resin material usually as blueing agent With.Blueing agent is for example orange light to yellow equiwavelength region absorbed in visible light region to adjust the additive of form and aspect (dyestuff, pigment), can enumerate such as ultramarine, Prussian blue, inorganic system cobalt blue dyestuff, pigment, such as phthalocyanine system blueing agent, Dyestuff, pigment of the organic systems such as fused polycyclic system blueing agent etc..Blueing agent is not particularly limited, from heat resistance, light resistance, dissolution From the viewpoint of property, preferred fused polycyclic system blueing agent, more preferable anthraquinone system blueing agent.From the viewpoint of heat resistance, blueing Agent preferably has the thermal decomposition temperature of 200 DEG C or more, preferably 240 DEG C or more.As fused polycyclic system blueing agent, can enumerate for example Anthraquinone system blueing agent, indigo system's blueing agent, phthalocyanine system blueing agent.

When optical film contains blueing agent, the additive amount of blueing agent can suitably be selected according to the type of the blueing agent used, be made For substantially standard, for the gross mass based on optical film, preferably 0.01 mass % or more, more preferably 0.02 mass % with On, further preferably 0.03 mass % or more, preferably 1.0 mass % are hereinafter, more preferably 0.5 mass % is hereinafter, into one Step is preferably 0.2 mass % or less.

For optical film of the invention, other than polyamide-imide resin, it can further contain inorganic grain The inorganic material such as son.As inorganic material, such as TiO 2 particles, aluminium oxide particles, zirconium dioxide particle, dioxy can be enumerated Silicon compounds such as the tetraalkoxysilanes such as the inorganic particulates such as SiClx particle and tetraethyl orthosilicate etc..It is clear from polyamidoimide From the viewpoint of the stability of paint, inorganic material is preferably inorganic particulate, particularly preferably silicon dioxide granule.Inorganic particulate that This can pass through the molecular linkage with siloxanes key (that is,-SiOSi-).

From the viewpoint of the agglutination of the transparency of optical film, mechanical properties and inhibition inorganic particulate, inorganic particulate is put down Equal primary particle size is preferably 10~100nm, more preferably 20~80nm.In the present invention, average primary particle diameter can be by using thoroughly The average value of emitting determination of electron microscopy 10 unidirectional partial sizes determines.

Optical film of the invention may include inorganic material.Total matter of the content of inorganic material in optical film based on optical film It is preferably 0~90 mass %, more preferably 0.01~60 mass %, further preferably 5~40 mass % for amount.Inorganic material The content of material within the above range when, exist be easy and meanwhile realize the transparency of optical film and the tendency of mechanical properties.

Optical film of the invention can contain other additives.As other additives, such as antioxidant can be enumerated, taken off Mould agent, stabilizer, fire retardant, pH adjusting agent, silica dispersions, lubricant, thickener and levelling agent etc..Other additives Quality of the content based on optical film of the invention for preferably 0 mass % or more and 20 mass % hereinafter, more preferably 0.01 mass % or more and 10 mass % or less.

(layer structure)

The layer structure of optical film of the invention is not particularly limited, and can be single layer, or 2 layers or more of multilayer. When optical film of the invention also contains the additives such as the additive with light absorption function, from the filming of image display device, From the viewpoint of economy, the additive and polyamide-imide resin are contained preferably in 1 layer.In this case, this hair Bright optical film, which is more preferably the single layer containing the additive and polyamide-imide resin or at least has, contains the additive With the laminated body of the layer of polyamide-imide resin.From the viewpoint of impact resistance characteristic, optical film of the invention preferably has At least contain 2 layers or more of multilayered structure of the layer comprising polyamide-imide resin.Optical film of the invention, which also contains, to be had It can be that at least there is the layer containing the additive and polyamide-imide resin when the additives such as the additive of light absorption function Laminated body or at least with the layer comprising the additive and the layer comprising polyamide-imide resin laminated body.

Optical film of the invention can be that the polyamide acyl for the functional layer that 1 layer or more is further laminated on above-mentioned layer is sub- Amine layer stack.As functional layer, the tool such as hard conating, UV-absorbing layer, adhesive layer, adjustable refractive index layer, priming coat can be enumerated There is the layer of various functions.Optical film of the invention can have one or more layers functional layer.In addition, an one functional layer can have it is a variety of Function.For example, above-mentioned functional layer can be formed on the film comprising polyamide-imide resin, the optical film of multilayered structure is obtained.

Optical film of the invention can for example be manufactured by including at least the manufacturing method of following processes.

Process that (2-2) removes the film of the resin combination after 240 DEG C of temperature below are dry from supporting mass and In the process that 240 DEG C of temperature below heat the film of removing

The present invention also provides the manufacturing methods of above-mentioned optical film.

In order to include at least resin combination (this of polyamide-imide resin and solvent used in manufacturing process (1) In specification, also referred to as " polyamidoimide varnish "), by dicarboxylic acids described above, diamines, tetrabasic carboxylic acid and as needed Other compositions (tertiary amine, dehydrating agent for playing a role as imidization catalyst etc.) mixing, make its reaction, so that manufacture is poly- Amide imide resin mixed liquor.As tertiary amine, aromatic amine above-mentioned, aliphatic amine etc. can be enumerated.As dehydrating agent, can lift Acetic anhydride, propionic andydride, isobutyric anhydride, pivalic acid acid anhydride, butyric anhydride, isovaleric anhydride etc. out.By in the polyamide-imide resin Solvent and above-mentioned additive as needed are added in mixed liquor and is stirred, so that manufacture includes at least polyamidoimide The resin combination of resin and solvent.Poor solvent can be added into above-mentioned polyamidoimide mixed liquor, utilize reprecipitation Polyamide-imide resin is precipitated in method, is dried, and is taken out with precipitated form, and the polyamide-imide resin of taking-up is sunk Starch is dissolved in solvent, to obtain polyamidoimide mixed liquor.In addition, polyamide-imide resin can also be replaced to mix The solid polyamide-imide resin of the solution of the polyamide-imide resin of purchase, purchase is dissolved in solvent by liquid, system It is used at solution.

Workable solvent is not particularly limited in the manufacture of polyamidoimide varnish, as long as can be by polyamidoimide Resin dissolution.As the solvent, the amide system such as n,N-dimethylacetamide, n,N-Dimethylformamide can be enumerated Solvent；Ester series solvent in gamma-butyrolacton, gamma-valerolactone etc.；The sulfur-bearings series solvent such as dimethyl sulfone, dimethyl sulfoxide, sulfolane； The carbonate-based solvents such as ethylene carbonate, the Asia carbonic acid 1,2- propyl ester；And their combination (mixed solvent).It is excellent in these solvents Acid amides series solvent or interior ester series solvent are selected, more preferably includes the solvent of dimethyl acetamide.In addition, in polyamidoimide varnish It may include water, alcohol series solvent, ketone series solvent, non-annularity ester series solvent, ether series solvent etc..

Next, for example by known roll-to-roll, batch mode, in branch such as resin base material, SUS band or glass baseplates Polyamide coating acid imide varnish on body is held, the film of polyamidoimide varnish can be formed as a result,.Example as supporting mass Son can enumerate PET film, pen film, polyimide film and polyamidoimide film etc..Wherein, it is examined from the viewpoint of excellent heat resistance Consider, preferably PET film, pen film, polyimide film and other polyamidoimide films.From the adaptation with optical film of the invention And from the viewpoint of cost, more preferable PET film.

Next, in process (2-1) or process (2-2), in 240 DEG C of temperature below, by polyamidoimide varnish Dried coating film, removed after dry from supporting mass.The drying of film can preferably be carried out in 50~240 DEG C of temperature.As needed, The drying of film can be carried out under conditions of inert atmosphere or decompression.By the way that film is removed from supporting mass after the drying, energy Obtain optical film of the invention.It should be noted that for the manufacturing method of the present invention, as recorded that in process (2-2) Sample, for example, in order to further increase the surface hardness of optical film of the invention (for example, pencil hardness), can further comprise in The process that 240 DEG C of temperature below heat the optical film of removing.

It can also carry out implementing at the surface of surface treatment at least one surface of the optical film manufactured in the manner described above Science and engineering sequence.As surface treatment, such as UV ozone treatment, corona treatment and Corona discharge Treatment can be enumerated.

In the process carried out after process (2-1) or process (2-2) in the case where heat tracing, temperature is preferably 280 DEG C hereinafter, more preferably 240 DEG C or less.

Optical film of the invention includes that of the invention one of the additives such as the additive with light absorption function is preferred real It applies in mode, it is described in the case that optical film of the invention contains polyamide-imide resin and the additive within the same layer Layer can be added by using this is further added in the above-mentioned resin combination for including at least polyamide-imide resin and solvent Add polyamidoimide varnish obtained from agent, manufactures in same manner described above.Containing with light absorption in 1 layer , it is preferable to use extremely in a preferred embodiment of the present invention of the additives such as the additive of function and polyamide-imide resin Additive with 200 DEG C or more, preferably 240 DEG C or more of thermal decomposition temperature less.

Optical film of the invention can be also equipped with functional layer.As functional layer, can enumerate hard conating, UV-absorbing layer, Adhesive layer, adjustable refractive index layer, priming coat etc. have the layer of various functions.Optical film of the invention can have one or more layers function Ergosphere.In addition, an one functional layer can have multiple functions.

Hard conating is preferably arranged at the viewing side surface of optical film.Hard conating can be single layer structure, or more Layer structure.Hard conating include hard coat resin, as hard coat resin, can enumerate for example acrylic resin, epoxy system resin, Polyurethane series resin, benzyl chloride system resin, vinyl resin or the ultraviolet lights such as organic silicon-type resin or their hybrid resin Curing type, electronic beam solidified or thermohardening type resin.Especially, from the mechanical properties such as surface hardness and industrial sight Point considers that hard conating preferably comprises acrylic resin.It should be noted that in a preferred embodiment of the present invention, this The optical film of invention has high surface hardness, therefore, even if not having hard conating, it may have in image display device etc. Sufficient surface hardness for use.It therefore, also can be further in the case that optical film of the invention further has hard conating Improve the surface hardness of optical film.

UV-absorbing layer is the layer absorb with ultraviolet light, such as the transparent tree by being selected from ultraviolet hardening Main material in the transparent resin of rouge, electronic beam solidified transparent resin and thermohardening type and disperse in the main material ultraviolet Light absorbers are constituted.By setting UV-absorbing layer as functional layer, yellow caused by capable of easily suppressing because of light irradiation The variation of degree.

Adhesive layer is to have the function of the layer of adhesiveness, has the function that optical film of the invention is adhered to other components Energy.As the forming material of adhesive layer, commonly known material can be used.For example, compositions of thermosetting resin or light can be used Hardening resin composition.

Adhesive layer can be made of the resin combination comprising the ingredient with polymerizable functional group.In this case, by light After film is sealed at other components, further make the resin combination polymerization for constituting adhesive layer, is able to achieve as a result, firm viscous It connects.The adhesive strength of optical film and adhesive layer of the invention can be 0.1N/cm or more or 0.5N/cm or more.

Adhesive layer may include compositions of thermosetting resin or Photocurable resin composition as material.In this case, By supplying energy afterwards, resin combination producing high-molecular can be made its solidification.

Adhesive layer can be by being referred to as the logical of pressure sensitive bonding agent (Pressure Sensitive Adhesive, PSA) It crosses pressing and is bonded to the layer that the bonding agent of object is constituted.Pressure sensitive bonding agent can be as " at normal temperature with viscous Conjunction property is to be adhered to the substance of glued material by light pressure " adhesive of (JIS K6800), it is also possible to as " will be special Determine ingredient to be contained in protection envelope (micro-capsule), be able to maintain before being destroyed envelope by means appropriate (pressure, heat etc.) The capsule-type bonding agent of the bonding agent of stability " (JIS K6800).

Form and aspect regulating course is the layer with form and aspect regulatory function, is that optical film of the invention can be adjusted to target form and aspect Layer.Form and aspect regulating course is, for example, the layer containing resin and colorant.As the colorant, can enumerate for example titanium oxide, zinc oxide, The inorganic pigments such as iron oxide red, titanium oxide base firing pigment, ultramarine, cobalt aluminate and carbon black；Azo compound, quinacridone Based compound, anthraquinone based compound, based compound, isoindolinone based compound, phthalocyanine based compound, quinophthalone system chemical combination The organic pigments such as object, intellectual circle's (threne) based compound and diketopyrrolo-pyrrole based compound；Barium sulfate and calcium carbonate etc. Extender pigment；And the dyestuffs such as basic dye, acid dyes and mordant dye.

Adjustable refractive index layer is the layer with adjustable refractive index function, be with in optical film of the invention comprising poly- The different refractive index of the layer of amide imide resin, the layer that defined refractive index can be assigned to optical film of the invention.Refractive index Regulating course for example can be containing the resin suitably selected and according to circumstances further containing the resin layer of pigment, be also possible to gold The film of category.

As the pigment for adjusting refractive index, such as silica, aluminium oxide, antimony oxide, tin oxide, titanium oxide, oxygen can be enumerated Change zirconium and tantalum oxide.The average primary particle diameter of pigment can be 0.1 μm or less.By 0.1 μ of average primary particle diameter for making pigment M hereinafter, can prevent through adjustable refractive index layer light diffusing reflection, the decline of transparency can be prevented.

As workable metal in adjustable refractive index layer, can enumerate for example titanium oxide, tantalum oxide, zirconium oxide, zinc oxide, The metal oxides such as tin oxide, silica, indium oxide, titanium oxynitrides, titanium nitride, silicon oxynitride, silicon nitride or metal nitride.

Optical film of the invention as the front panel of image display device, especially flexible display front panel (that is, window Film) it is useful.Optical film of the invention can be used as the sight that front panel is configured at image display device, especially flexible display See side surface.The front panel has the function of protecting the image-displaying member in flexible display.

As image display device, television set, smart phone, mobile phone, auto navigation, tablet PC, portable can be enumerated Wearable devices such as game machine, Electronic Paper, indicator, notice board, clock and watch and smartwatch etc..As flexible display, can lift Provide above-mentioned such image display device of flexible characteristic.

Embodiment

Hereinafter, illustrating the present invention in further detail by embodiment.For " % " and " part " in example, as long as not having There is special record, refers to quality % and mass parts.Firstly, being illustrated to evaluation method.

The measurement > of < weight average molecular weight (Mw)

The weight average molecular weight (Mw) of polyamide-imide resin is measured using gel permeation chromatography (GPC), by according to mark Quasi- polystyrene converts and finds out.Specific determination condition is as described below.

(1) pre-treating method

Adding DMF eluent into polyamide-imide resin in such a way that concentration becomes 2mg/mL, (10mM lithium bromide is molten Liquid), it is heated while carrying out stirring in 30 minutes in 80 DEG C, after cooling, 0.45 μm of membrane filter is carried out, by what is obtained Solution is as measurement solution.

(2) determination condition

Column: SuperAWM-H × 2+SuperAW2500 × 1 TSKgel (I.D. × 150mm × 3 piece 6.0mm) (are Tosoh Corporation system)

Eluent: DMF (lithium bromide added with 10mM)

Flow: 1.0mL/min.

Detector: RI detector

Column temperature: 40 DEG C

Sample volume: 100 μ L

Molecular weight standard: standard polystyren

The measurement > of < tan δ and tan δ peak temperature

Using TA Instrument corporation DMA Q800, following such samples and under the conditions of be measured, obtain Tan δ curve as the ratio between the value of loss modulus and storage modulus.It is sub- that polyamide acyl is calculated by the most vertex at the peak of tan δ curve The tan δ peak temperature of polyimide resin.

Sample: length 5-15mm, width 5mm

Experiment model: DMA multifrequency strains (Multi-Frequency-Strain)

Experiment model detailed conditions:

(1) it fixture: stretches: film (Clamp:Tension:Film)

(2) amplitude (Amplitude): 5 μm

(3) frequency (Frequncy): 10Hz (no change in whole temperature ranges)

(4) pretightning force (Preload Force): 0.01N

(5) force follow-up (Force Track): 125N

Temperature condition: (1) temperature elevating range: room temperature~400 DEG C, (2) heating rate: 5 DEG C/min

It is main to collect data: (1) storage modulus (Storage modulus, E '), (2) loss modulus (Loss Modulus, E "), (3) tan δ (E "/E ')

The measurement > of < acid imide rate

The acid imide rate of polyimide resin and polyamide-imide resin used in Examples and Comparative Examples utilizes NMR is measured, and is calculated using the signal for coming from the proton in partial structurtes (A)~(E) shown in formula (XXX).Measurement The method that condition and the result by obtaining calculate acid imide rate is as described below.

[chemical formula 16]

(pre-treating method)

Sample is dissolved in deuterated dimethyl sulfoxide (DMSO-d6), 2 mass % solution are made, using acquired solution as survey Determine sample.

(determination condition)

Measurement device: Bruker corporation 600MHzNMR device AVANCE600

Specimen temperature: 303K

Measuring method:¹H-NMR, HSQC

(calculation method of the acid imide rate of polyimide resin)

Using the solution comprising polyimide resin as obtained from measurement sample¹In H-NMR wave spectrum, formula will be come from (XXX) integrated value of the signal of the proton (A) in is denoted as Int_A, the integrated value of the signal from proton (B) is denoted as Int_B.By Their value finds out acid imide rate (%) using formula (NMR-1).

[mathematical expression 2]

Acid imide rate (%)=100 × (1-Int_B/Int_A) (NMR-1)

(calculation method of the acid imide rate of polyamide-imide resin)

Using the solution comprising polyimide resin as in hsqc spectrum figure obtained from measurement sample, formula (XXX) will be come from In the integrated value of signal of proton (C) be denoted as Int_C, by being averaged for the integrated value from proton (D) and the signal of proton (E) Value is denoted as Int_DE.β value is found out by their value, using formula (NMR-2).

[mathematical expression 3]

β=Int_DE/Int_C (NMR-2)

Next, finding out β value using formula (NMR-2), also, ask using formula (NMR-1) for a variety of polyimide resins Acid imide rate (%) out obtains correlation (NMR-3) by the result.

[mathematical expression 4]

Acid imide rate (%)=- 115.9 × β+100 (NMR-3)

Moreover, using the solution comprising polyamide-imide resin as obtained from measurement sample in hsqc spectrum figure, according to Mode similar to the above finds out β value using formula (NMR-2).The β value is substituted into above-mentioned correlation (NMR-3), as a result, To the acid imide rate (%) of polyamide-imide resin.

The measurement > of < total light transmittance (Tt)

The total light transmittance Tt of sample according to JIS K7105:1981, using Suga Test Instruments Co., Ltd. the full-automatic direct-reading haze computer HGM-2DP measurement made.

The measurement > of < yellow chromaticity (YI value)

The yellow chromaticity (Yellow Index:YI value) of sample is made according to JIS K 7373:2006, using Japan's light splitting (strain) UV, visible light near infrared spectrometer V-670 measurement.Background determination is carried out in the state of no sample, then, by sample It is set to specimen holder, the transmitance of the light relative to 300~800nm is measured, finds out tristimulus values (X, Y, Z).YI value It is calculated based on following formula.

[mathematical expression 5]

YI=100 × (1.2769X-1.0592Z)/Y

The measurement > of < surface hardness

The pencil hardness of sample surfaces is measured according to JIS K5600-5-4:1999 as the surface hardness of sample.Negative Lotus is 100g, scanning speed is measured under conditions of being 60mm/ minutes, light quantity be 4000 luxs illumination conditions under into Row, evaluates the presence or absence of scar, determines pencil hardness.

The measurement > of < elasticity modulus

The elasticity modulus of sample uses (strain) Shimadzu Seisakusho Ltd. autoplotter AG-IS to measure.

The sample of 10mm wide will be already cut into as test film, between collet distance be 500mm, tensile speed 20mm/ S-S curve is measured under conditions of min, and elasticity modulus is calculated by its slope.

The measurement > of < resistance to bend(ing)

As the resistance to bend(ing) of sample, (strain) Toyo Seiki is used to make made MIT folding fatigue tester (model 0530) reciprocal bending times are measured.Using be already cut into a thickness of 50 μm, width be 10mm sample as test film, in R= 1mm, 135 °, load 0.75kgf, speed be 175cpm under conditions of measurement until film be broken until reciprocal bending times.

[Production Example 1: the preparation of polyamide-imide resin (1)]

In a nitrogen atmosphere, into the removable flask of 1L for having stirring blade, 2,2 '-bis- (trifluoromethyl) biphenyl are added Amine (TFMB) 52g (162.38mmol) and n,N-dimethylacetamide (DMAc) 734.10g is incited somebody to action while stirring at room temperature TFMB is dissolved in DMAc.Next, adding 4,4 '-(hexafluoroisopropyli,ene) two O-phthalic acid dianhydrides (6FDA) into flask 28.90g (65.05mmol), carries out stirring for 3 hours at room temperature.Then, by 4,4 '-oxygen bis- (chlorobenzoyl chlorides) (OBBC) 28.80g (97.57mmol) is added in flask, carries out stirring for 1 hour at room temperature.

Next, pyridine 7.49g (94.65mmol) and acetic anhydride 26.56g (260.20mmol) are added into flask, It carries out stirring for 30 minutes at room temperature, then, is warming up to 70 DEG C using oil bath, stirs within further progress 3 hours, obtain reaction solution.

Obtained reaction solution is cooled to room temperature, with threadiness investment into a large amount of methanol, the sediment of precipitation is taken out, After impregnating 6 hours in methyl alcohol, washed with methanol.Next, being dried under reduced pressure in 100 DEG C to sediment, polyamide is obtained Imide resin (1).According to said determination method, weight average molecular weight (Mw), the peak tan δ of polyamide-imide resin (1) are measured Temperature and acid imide rate, as a result, Mw 200,000, tan δ peak temperature are 345 DEG C, and acid imide rate is 96%.

[embodiment 1: the film of polyamidoimide film (1)]

To in polyamide-imide resin obtained in Production Example 1 (1), added in such a way that concentration becomes 15 mass % DMAc makes polyamidoimide varnish (1).It will be obtained in such a way that the film thickness of self-supported membrane becomes 55 μm using applicator Polyamidoimide varnish (1) be coated on the even surface of polyester base material (Japan spinning, trade name " A4100 "), in 50 DEG C Drying in 30 minutes is carried out, next in 140 DEG C of progress drying in 15 minutes, then, obtained film is removed from polyester base material, is obtained To self-supported membrane.

Self-supported membrane is fixed on metal frame, further under atmosphere, in 230 DEG C of progress drying in 30 minutes, is had The polyamidoimide film (1) of 50 μm of thickness.

[embodiment 2: the film of polyamidoimide film (2)]

To in polyamide-imide resin obtained in Production Example 1 (1), added in such a way that concentration becomes 15 mass % DMAc, further mixed phase are the ultraviolet absorbing agent of 4 mass parts for (1) 100 mass parts of polyamide-imide resin (Sumika Chemtex Company, Limited system, product name " Sumisorb340 ") makes polyamidoimide varnish (2).Instead of polyamidoimide varnish (1), using polyamidoimide varnish (2), in addition to this, similarly to Example 1 Operation obtains the polyamidoimide film (2) of the thickness with 50 μm.

[embodiment 3: the film of polyamidoimide film (3)]

To in polyamide-imide resin obtained in Production Example 1 (1), added in such a way that concentration becomes 15 mass % DMAc, further mixed phase are the blueing agent of 0.05 mass parts for (1) 100 mass parts of polyamide-imide resin (CHEMI PLAST corporation, product name " VIOLET B ") makes polyamidoimide varnish (3).Instead of polyamidoimide Varnish (1) is in addition to this operated similarly with example 1 using polyamidoimide varnish (3), obtains the thickness with 50 μm The polyamidoimide film (3) of degree.

[Production Example 2: the preparation of polyamide-imide resin (2)]

In a nitrogen atmosphere, into the removable flask of 1L for having stirring blade, add TFMB52g (162.38mmol) and TFMB is dissolved in DMAc while stirring by DMAc705.94g at room temperature.Next, being added into flask 6FDA25.28g (56.92mmol), carries out stirring for 3 hours at room temperature.Then, OBBC21.60g is added into flask (73.18mmol), paraphthaloyl chloride (TPC) 6.60g (32.52mmol) is then added, carries out stirring for 1 hour at room temperature. Next, add pyridine 8.11g (102.53mmol) and acetic anhydride 23.24g (227.67mmol) into flask, at room temperature into It stirs within row 30 minutes, then, is warming up to 70 DEG C using oil bath, stirs within further progress 3 hours, obtain reaction solution.

Obtained reaction solution is cooled to room temperature, with threadiness investment into a large amount of methanol, the sediment of precipitation is taken out, It is impregnated 6 hours with methanol, then, is washed with methanol.Next, being dried under reduced pressure in 100 DEG C to sediment, polyamide is obtained Imide resin (2).According to said determination method, weight average molecular weight (Mw), the peak tan δ of polyamide-imide resin (2) are measured Temperature and acid imide rate, as a result, Mw 180,000, tan δ peak temperature are 340 DEG C, and acid imide rate is 99%.

[embodiment 4: the film of polyamidoimide film (4)]

To in polyamide-imide resin obtained in Production Example 2 (2), added in such a way that concentration becomes 15 mass % DMAc makes polyamidoimide varnish (4).Instead of polyamidoimide varnish (1), using polyamidoimide varnish (4), In addition to this, it operates similarly with example 1, obtains the polyamidoimide film (4) of the thickness with 50 μm.

[embodiment 5: the film of polyamidoimide film (5)]

To in polyamide-imide resin obtained in Production Example 2 (2), added in such a way that concentration becomes 15 mass % DMAc, further mixed phase are the ultraviolet absorbing agent of 4 mass parts for (2) 100 mass parts of polyamide-imide resin (Sumika Chemtex Company, Limited system, product name " Sumisorb340 ") makes polyamidoimide varnish (5).Instead of polyamidoimide varnish (1), using polyamidoimide varnish (5), in addition to this, similarly to Example 1 Operation obtains the polyamidoimide film (5) of the thickness with 50 μm.

[embodiment 6: the film of polyamidoimide film (6)]

To in polyamide-imide resin obtained in Production Example 2 (2), added in such a way that concentration becomes 15 mass % DMAc, further mixed phase are the blueing agent of 0.05 mass parts for (2) 100 mass parts of polyamide-imide resin (CHEMI PLAST corporation, product name " VIOLET B ") makes polyamidoimide varnish (6).Instead of polyamidoimide Varnish (1) is in addition to this operated similarly with example 1 using polyamidoimide varnish (6), obtains the thickness with 50 μm The polyamidoimide film (6) of degree.

[Production Example 3: the preparation of polyamide-imide resin (3)]

In a nitrogen atmosphere, into the removable flask of 1L for having stirring blade, add TFMB52g (162.38mmol) and TFMB is dissolved in DMAc while stirring by DMAc698.10g at room temperature.Next, being added into flask 6FDA25.28g (56.92mmol), carries out stirring for 3 hours at room temperature.Then, BPDOC20.43g is added into flask (73.18mmol), paraphthaloyl chloride (TPC) 6.60g (32.52mmol) is then added, carries out stirring for 1 hour at room temperature. Next, add pyridine 8.11g (102.53mmol) and acetic anhydride 23.24g (227.67mmol) into flask, at room temperature into It stirs within row 30 minutes, then, is warming up to 70 DEG C using oil bath, stirs within further progress 3 hours, obtain reaction solution.

Obtained reaction solution is cooled to room temperature, with threadiness investment into a large amount of methanol, the sediment of precipitation is taken out, It is impregnated 6 hours with methanol, then, is washed with methanol.Next, being dried under reduced pressure in 100 DEG C to sediment, polyamide is obtained Imide resin (3).According to said determination method, weight average molecular weight (Mw), the peak tan δ of polyamide-imide resin (3) are measured Temperature and acid imide rate, as a result, Mw 200,000, tan δ peak temperature are 380 DEG C, and acid imide rate is 99%.

[comparative example 1: the film of polyamidoimide film (7)]

To in polyamide-imide resin obtained in Production Example 3 (3), added in such a way that concentration becomes 15 mass % DMAc makes polyamidoimide varnish (7).Polyamidoimide varnish is used instead of polyamidoimide varnish (1) (7), instead of carrying out dry operation in 30 minutes under atmosphere, in 230 DEG C to the self-supported membrane for having been attached to metal frame, and big It in addition to this operates similarly with example 1, is had under gas, in 300 DEG C to self-supported membrane progress drying in 30 minutes The polyamidoimide film (7) of 50 μm of thickness.

[comparative example 2: the film of polyamidoimide film (8)]

Instead of polyamidoimide varnish (1), using polyamidoimide varnish (7) obtained in comparative example 1, except this it Outside, it operates similarly with example 1, obtains the polyamidoimide film (8) of the thickness with 50 μm.

[Production Example 4: the preparation of polyamide-imide resin (4)]

In a nitrogen atmosphere, into the removable flask of 1L for having stirring blade, add TFMB52g (162.38mmol) and TFMB is dissolved in DMAc while stirring by DMAc655.58g at room temperature.Next, being added into flask 6FDA23.84g (53.67mmol), carries out stirring for 3 hours at room temperature.Then, paraphthaloyl chloride is added into flask (TPC) 22.12g (108.96mmol), carries out stirring for 1 hour at room temperature.Next, adding pyridine 8.36g into flask (105.69mmol) and acetic anhydride 21.91g (214.66mmol), carries out stirring for 30 minutes at room temperature, then, uses oil bath liter Temperature stirs to 70 DEG C, obtains reaction solution for further progress 3 hours.

Obtained reaction solution is cooled to room temperature, with threadiness investment into a large amount of methanol, the sediment of precipitation is taken out, It is impregnated 6 hours with methanol, then, is washed with methanol.Next, being dried under reduced pressure in 100 DEG C to sediment, polyamide is obtained Imide resin (4).According to said determination method, weight average molecular weight (Mw), the peak tan δ of polyamide-imide resin (4) are measured Temperature and acid imide rate, as a result, Mw 200,000, tan δ peak temperature are 379 DEG C, and acid imide rate is 96%.

[comparative example 3: the film of polyamidoimide film (9)]

To in polyamide-imide resin obtained in Production Example 4 (4), added in such a way that concentration becomes 15 mass % DMAc makes polyamidoimide varnish (8).Polyamidoimide varnish is used instead of polyamidoimide varnish (1) (8), instead of carrying out dry operation in 30 minutes under atmosphere, in 230 DEG C to the self-supported membrane for having been attached to metal frame, and big It in addition to this operates similarly with example 1, is had under gas, in 300 DEG C to self-supported membrane progress drying in 30 minutes The polyamidoimide film (9) of 50 μm of thickness.

[comparative example 4: the film of polyamidoimide film (10)]

Instead of polyamidoimide varnish (1), using polyamidoimide varnish (8) obtained in comparative example 3, except this it Outside, it operates similarly with example 1, obtains the polyamidoimide film (10) of the thickness with 50 μm.

[comparative example 5: the film of polyamidoimide film (11)]

Instead of carrying out dry operation in 30 minutes under atmosphere, in 230 DEG C to the self-supported membrane for having been attached to metal frame, It in addition to this operates similarly with example 1, is had under atmosphere, in 300 DEG C to self-supported membrane progress drying in 30 minutes There is the polyamidoimide film (11) of 50 μm of thickness.

[comparative example 6: the film of polyamidoimide film (12)]

Instead of carrying out dry operation in 30 minutes under atmosphere, in 230 DEG C to the self-supported membrane for having been attached to metal frame, It in addition to this operates, is had similarly to Example 2 under atmosphere, in 300 DEG C to self-supported membrane progress drying in 30 minutes There is the polyamidoimide film (12) of 50 μm of thickness.

[comparative example 7: the film of polyamidoimide film (13)]

Instead of carrying out dry operation in 30 minutes under atmosphere, in 230 DEG C to the self-supported membrane for having been attached to metal frame, It in addition to this operates, is had similarly to Example 4 under atmosphere, in 300 DEG C to self-supported membrane progress drying in 30 minutes There is the polyamidoimide film (13) of 50 μm of thickness.

[comparative example 8: the film of polyamidoimide film (14)]

Instead of carrying out dry operation in 30 minutes under atmosphere, in 230 DEG C to the self-supported membrane for having been attached to metal frame, It in addition to this operates, is had similarly to Example 5 under atmosphere, in 300 DEG C to self-supported membrane progress drying in 30 minutes There is the polyamidoimide film (14) of 50 μm of thickness.

[Production Example 5: the preparation of polyimide resin (5)]

In a nitrogen atmosphere, into the removable flask of 1L for having stirring blade, add TFMB52g (162.38mmol) and TFMB is dissolved in DMAc while stirring by DMAc831.46g at room temperature.Next, being added into flask 6FDA72.24g (16.262mmol), carries out stirring for 5 hours at room temperature.Next, adding pyridine 9.65g into flask (121.97mmol) and acetic anhydride 66.41g (650.49mmol), carries out stirring for 30 minutes at room temperature, then, uses oil bath liter Temperature stirs to 70 DEG C, obtains reaction solution for further progress 3 hours.

Obtained reaction solution is cooled to room temperature, with threadiness investment into a large amount of methanol, the sediment of precipitation is taken out, It is impregnated 6 hours with methanol, then, is washed with methanol.Next, being dried under reduced pressure in 100 DEG C to sediment, polyamides Asia is obtained Polyimide resin (5).According to said determination method, weight average molecular weight (Mw), tan δ peak temperature and the acyl of polyimide resin (5) are measured Amination rate, as a result, Mw 220,000, tan δ peak temperature are 350 DEG C, and acid imide rate is 99%.

[comparative example 9: the film of polyimide film (15)]

Into obtained polyimide resin (5), DMAc is added in such a way that concentration becomes 15 mass %, production polyamides is sub- Amine varnish (9).Instead of polyamidoimide varnish (1), using polyimide varnish (9), in addition to this, similarly to Example 1 Ground operation, obtains the polyimide film (15) of the thickness with 50 μm.

[Production Example 6: the preparation of polyamide-imide resin (6)]

In a nitrogen atmosphere, it into the removable flask of 1L for having stirring blade, adds TFMB14.67g (45.8mmol) And DMAc233.3g, TFMB is dissolved in DMAc while stirring at room temperature.Next, adding 4,4 '-into flask Oxygen two O-phthalic acid dianhydride (OPDA) 4.283g (13.8mmol), carries out stirring for 16.5 hours at room temperature.Then, to flask Middle addition OBBC1.359g (4.61mmol) and TPC5.609g (27.6mmol), carry out stirring for 1 hour at room temperature.Next, Acetic anhydride 4.937g (48.35mmol) and 4- picoline 1.501g (16.12mmol) are added into flask, are carried out at room temperature It stirs within 30 minutes, then, is warming up to 70 DEG C using oil bath, stirs within further progress 3 hours, obtain reaction solution.

Obtained reaction solution is cooled to room temperature, then, methanol 360g and ion exchange water 170g is added, obtains polyamide Imido precipitating.It is impregnated 12 hours in methyl alcohol, is recycled by filtering, is washed with methanol.Next, in 100 DEG C sediment is dried under reduced pressure, obtains polyamide-imide resin (6).According to said determination method, polyamide acyl is measured Weight average molecular weight (Mw), tan δ peak temperature and the acid imide rate of imide resin (6), as a result, the peak Mw 259,000, tan δ temperature Degree is 362 DEG C.

[embodiment 7: the film of polyamidoimide film (16)]

To in polyamide-imide resin obtained in Production Example 6 (6), added in such a way that concentration becomes 12 mass % GBL makes polyamidoimide varnish (16).Polyamidoimide varnish is used instead of polyamidoimide varnish (1) (16), self-supported membrane is fixed on metal frame, is in addition to this grasped similarly to Example 1 in 200 DEG C of progress drying in 30 minutes Make, obtains the polyamidoimide film (16) of the thickness with 50 μm.

For polyamidoimide film (1)~(14) and (16) and polyamides obtained in the above embodiments and comparative example Imines film (15) measures total light transmittance (Tt), yellow chromaticity (YI value), pencil hardness, springform according to said determination method Amount and resistance to bend(ing) (reciprocal bending times).The obtained results are shown in tables 1.In addition, the polyamide acyl for including in these films is sub- The number of polyimide resin or polyimide resin is also depicted in table 1.

[table 1]

Claims

1. optical film, it includes polyamide acyls in the range of 300~370 DEG C with the peak value based on the DMA tan δ measured Imide resin, and there are 3 YI values below.

2. optical film as described in claim 1, wherein under the illumination conditions of 4000 luxs according to ASTM D 3363 into Row measurement, the optical film have the pencil hardness of 3B or more.

3. optical film as claimed in claim 1 or 2 also includes the additive with light absorption function.

4. optical film according to any one of claims 1 to 3, wherein the additive with light absorption function is selected from by purple The group of ultraviolet absorbers and blueing agent composition.

5. optical film as described in any one of claims 1 to 4, wherein polyamide-imide resin includes fluorine atom.

6. such as optical film according to any one of claims 1 to 5, wherein polyamide-imide resin at least has formula (1) table The structural unit shown,

[chemical formula 1]

In formula (1), R¹~R⁸Each independently represent hydrogen atom, the alkyl that carbon atom number is 1~6 or carbon atom number are 6~12 Aryl, R¹~R⁸In include hydrogen atom can be substituted with halogen atoms each independently,

A each independently represents-O- ,-S- ,-CO- or-NR⁹, R⁹Indicate the carbon atom number that can be substituted with halogen atoms be 1~ 12 alkyl,

The integer that m is 1~4,

* chemical bond is indicated.

7. such as optical film according to any one of claims 1 to 6, wherein polyamide-imide resin at least has from two The structural unit of carboxylic acid.

8. such as optical film according to any one of claims 1 to 7, wherein polyamide-imide resin, which at least has to come from, to be contained There are the diamines of fluorine atom and/or the structural unit of the tetracarboxylic dianhydride containing fluorine atom.

9. such as optical film according to any one of claims 1 to 8, with 20 μm or more of thickness.

10. the manufacturing method of optical film includes at least following processes:

(1) resin composition of polyamide-imide resin and solvent will be included at least in the process of supporting mass；And

11. manufacturing method as claimed in claim 10, wherein resin combination also includes the addition with light absorption function Agent.

12. manufacturing method as described in claim 10 or 11, wherein solvent includes dimethyl acetamide.