CN110039866A - Laminated body and its manufacturing method - Google Patents

Abstract

The present invention relates to laminated body and its manufacturing methods.The issue of the present invention is to provide the technologies for preventing the scar of the roller surfaces such as deflector roll to be transferred to via supporting mass polyimide film surface.Solution of the invention is to provide following laminated bodies and its manufacturing method, the laminated body is the laminated body that supporting mass and transparent resin film are strippingly laminated, it is characterized in that, the Martens hardness for the side of aforementioned supporting mass contacted with aforementioned transparent resin film is 300N/mm²More than.

Description

Laminated body and its manufacturing method

Technical field

The present invention relates to laminated body and its manufacturing methods, more particularly to the clear polyimides high in manufacture visibility The laminated body and its manufacturing method used when mesentery.

Background technique

In recent years, along with slimming, lighting and flexibility of display of various image display devices etc., as generation For the material of the glass used in the past, it is utilized extensively based on the high molecular transparent resin film such as polyimides, polyamide.As One of the manufacturing method of such transparent resin film, casting method (solution casting method) is known.For casting method, lead to Often, it will be coated on supporting mass comprising high molecular varnish such as the polyimides that is dissolved in solvent, be filmed, will support After substrate removing, solvent is removed by dry, resin film can continuously be formed (for example, patent document 1) as a result,.

In addition, in the case where obtaining transparent polyimides mesentery, although also using premised on recycling sometimes The metal supporting mass such as SUS, but from the aspect of the qualitative control of supporting mass, cost, it is also used sometimes to be discarded as after The supporting mass of premise formed by resin film.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 10-310639 bulletin

Summary of the invention

Problems to be solved by the invention

In actual casting film forming apparatus, coating contains polyimides system high score on the supporting mass formed by resin film When the varnish of son, supporting mass is released from supporting mass volume made of winding supporting mass, after passing through it from some deflector rolls, is moved to clear Paint coating position.However, metal deflector roll is more for deflector roll, there is also have on its surface when making deflector roll The deflector roll of the scar of generation.In addition, also being led sometimes when being cleaned to film forming apparatus or during film forming apparatus work Roller surface generates scar.In the case where guide roller surface has scar, following events occur: the scar is transferred to bearing body surface Face is transferred to the polyimides mesentery formed in varnish painting process.Certainly, for for image display device etc. For polyimides mesentery, when surface has scar etc., it will become visibility deteriorate, quality decline the reason of, because This must be avoided.

Therefore, the inventor of the present application discovered that preventing the scar of guide roller surface to be transferred to polyimides via supporting mass The technology on mesentery surface.

Means for solving the problems

That is, the present invention provides laminated body, it is the laminated body that supporting mass and transparent resin film are strippingly laminated, It is characterized in that, the Martens hardness for the side of aforementioned supporting mass contacted with aforementioned transparent resin film is 300N/mm²More than.

The present invention also provides modes below:

Above-mentioned laminated body, wherein aforementioned transparent resin film is polyimides mesentery.

Above-mentioned laminated body, wherein aforementioned transparent resin film be mist degree be 1% or less, total light transmittance be 85% with Upper, yellow colour index is 4 polyimides mesenterys below.

Above-mentioned laminated body, wherein aforementioned supporting mass is resin film.

Laminated body, wherein aforementioned supporting mass is the resin film for being provided with hard conating.

Laminated body, wherein aforementioned supporting mass is PET film, cycloolefin mesentery, acrylic acid mesentery or poly- with hard conating (ethylene naphthalate) film.

Laminated body, wherein in the JIS B0601-2001 for the side of aforementioned supporting mass contacted with aforementioned transparent resin film Defined arithmetic average roughness (Ra) is 0.01 μm or less.

Laminated body, wherein in the JIS B0601-2001 for the side of aforementioned supporting mass contacted with aforementioned transparent resin film Defined maximum height (Rz) is 0.1 μm or less.

Laminated body film roll is obtained from winding above-mentioned laminated body.

The manufacturing method of laminated body comprising following step:

A) Martens hardness in the side of resin varnish to be coated with is 300N/mm²On above supporting mass, coating will be used for Resin varnish obtained from the resin combination of formation transparent resin film is mixed and is stirred with solvent；And

B) by keeping be coated with resin varnish dry to remove solvent, transparent resin film is formed on supporting mass Layer.

Fenestrated membrane substrate is obtained from carrying out solvent seasoning processing as the transparent resin film to above-mentioned laminated body.

Fenestrated membrane is (to be arranged on fenestrated membrane substrate at least one face of above-mentioned fenestrated membrane substrate comprising window hard conating Hard conating) and formed.

Optical laminate is the laminated body comprising above-mentioned fenestrated membrane, also comprising being selected from a face of aforementioned fenestrated membrane At least one layer in group be made of the polarizing layer comprising polaroid and touch sensor.

The effect of invention

In the present invention, it is found that the Martens hardness on the surface for the side of supporting mass contacted with clear polyimides mesentery is 300N/mm²When above, the scar for being present in guide roller surface can be prevented to be transferred to clear polyimides system via supporting mass surface Film.In addition, since scar can be prevented, thus the diffusing reflection of light is reduced, in the case where penetrating light with backlight etc., moreover it is possible to cut Subtract backlight electric power.

Martens hardness is hardness obtained from simply measuring the hardness of film surface, before using supporting mass, measurement The Martens hardness on one surface of supporting mass, discovery are 300N/mm when it²When above, clear polyimides system can be directly used for The manufacture of film, therefore, no matter which kind of material supporting mass comes from, as long as meeting above-mentioned condition can be used, it is believed that it is to manufacture The benchmark that scene can easily judge very much.

Detailed description of the invention

[Fig. 1] Fig. 1 is the figure for schematically showing the section of laminated body of the invention.

[Fig. 2] Fig. 2 is the schematic diagram for indicating the painting process of transparent resin film.

[Fig. 3] Fig. 3 is to indicate that the scar of roller surface is transferred to the photo of the state of transparent resin film.

Description of symbols

1 ... supporting mass

2 ... transparent resin films

3 ... protective films

10 ... supporting masses volume

11 ... deflector rolls

12 ... painting process

13 ... predry drying process

14 ... protection film rolls

15 ... three-layer coil coiling

Specific embodiment

Fig. 1 is the figure for schematically showing laminated body of the invention, and in figure, 1 indicates supporting mass, and 2 indicate transparent resin films, The protective film needed to form according to 3.Transparent resin film 2 be transparent resin film shown in Fig. 2 painting process 12 in be coated with 's.Supporting mass volume 10 shown in Fig. 2 is volume made of winding supporting mass, via deflector roll 11, is transported to painting process 12.Figure In 2,1 deflector roll is only described, but actually can be transported to painting process 12 via multiple deflector rolls.By each deflector roll, carry out Certain processing, or assign tension.In painting process 12, the varnish of transparent resin film is applied on supporting mass 1.It is being coated with After ming tree adipose membrane, dried in predry drying process 13.For predry drying process 13, in order to by transparent resin film 2 from branch Body removing is held, maintains the degree of film shape to be dried with transparent resin film 2, in fact, in obtaining image display device etc. When the transparent resin film used, needs the contraction for the width direction for inhibiting transparent resin film by transverse drawing mill etc. or need The formal drying process to be dried while stretching in the width direction, but the process is not described in Fig. 2.Through pre- On the face opposite with supporting mass 1 of dry transparent resin film 2, the protective film 3 sent out from protection film roll 14 is formed, forms three layers Winding volume 15.For the three-layer coil coiling 15, supporting mass 1 and protective film 3 are removed by other processes, so that only transparent Resin film 2, by formal drying process, manufacture sufficiently eliminates the transparent resin film of solvent.

Supporting mass

Laminated body of the invention is as shown in Figure 1, formed by supporting mass 1 and the transparent resin film being formed on supporting mass 2 's.Need to make the Martens hardness 300N/mm for the side of supporting mass 1 contacted with transparent resin film 2²More than.

Martens hardness is the value measured in the following manner: being fitted in obtained from glass for by the sample of prescribed level Product uses the small hardness tester of ultra micro (FISCHERSCOPE HM2000:Fischer in 23 DEG C, the atmosphere of 55%RH Instruments K.K. system), using Vickers indenter, load was applied with 0.5mN/5 seconds pressing speeds, is maintaining 0.5mN's It is kept for 5 seconds, is measured in the state of load.The measuring method of detailed Martens hardness is recorded in embodiment.

In the present invention, Martens hardness needs for 300N/mm²More than.Martens hardness is preferably 340N/mm²More than, more preferably For 380N/mm²More than, further preferably 400N/mm²More than.The upper limit value of Martens hardness is not particularly limited, but is having In the case where the supporting mass of hard conating, when Martens hardness is excessively high, hard conating may rupture in conveying, usually 700N/mm²With Under, preferably 650N/mm²Hereinafter, further preferably 600N/mm²Below.The horse for the side of supporting mass contacted with hyaline membrane Family name's hardness is less than 300N/mm²When, it is transferred on supporting mass, is also transferred to then in scar present on the rollers such as deflector roll On the transparent resin film of formation, scar is generated.In this specification, the scar of so-called transparent resin film refers to following situations: Xiang Cong The transparent resin film of supporting mass removing irradiates the high brightness lamp of 3000 lumens or more, confirms the presence or absence of scar, energy by visual observation Confirm that there are scars.For the film of optical applications, usually the exterior qualities such as scar are commented under fluorescent light Valence, but in the case where the viewing side of image display device, using (fenestrated membrane) especially as front panel, the requirement of exterior quality Level is high, and the scar that can not be observed under fluorescent light is also required to inhibit.If it is high brightness lamps more than 3000 lumens, then not Be only capable of under fluorescent light it is observed that scar evaluate, and the scar the presence or absence of weak to visibility also can be carried out Evaluation.

In the present invention, the unilateral side of supporting mass, the side contacted with transparent resin film Martens hardness be 300N/mm²With It is upper, it is not particularly dependent on the material of supporting mass.Supporting mass can be the made of metal bands such as stainless steel, or resin Film.In the case where resin film, in order to meet the value of above-mentioned Martens hardness, hard conating can be formed in its unilateral side.As preferred Supporting mass, can enumerate in polyethylene terephthalate (PET) film, cycloolefin mesentery (COP), acrylic acid mesentery, poly- naphthalene Naphthalate film, polypropylene screen, tri acetyl cellulose membrane unilateral side be formed with supporting mass of hard conating etc., as more excellent The supporting mass of choosing, to be formed with the supporting mass of hard conating in the unilateral side of PET film, cycloolefin mesentery, most preferred supporting mass be The unilateral side of PET film is formed with the supporting mass of hard conating.Hard conating is not particularly limited, and can be acrylic acid series, carbamate Any one of system, epoxy.

The arithmetic average roughness (Ra) on the surface (side contacted with transparent resin film) of supporting mass of the invention is preferred For defined range.Contact roughmeter can be used to be measured for arithmetic average roughness (Ra), according to JIS B0601- 2001.The arithmetic average roughness (Ra) on the surface of supporting mass is for 0.01 μm hereinafter, preferably 0.008 μm hereinafter, more preferably 0.006 μm or less.Since the shape of the side, i.e. surface that contact with transparent resin film will transfer to the surface of transparent resin film, Thus, the arithmetic average roughness (Ra) on the surface of supporting mass is smaller, is more easy to get the reflecting feel of transparent resin film, is suitable for The case where being configured at image display device.The lower limit value of the arithmetic average roughness (Ra) on the surface of supporting mass does not limit especially System, it is the smaller the better.

The preferably defined range of the maximum height (Rz) on the surface of supporting mass of the invention.Maximum height (Rz) can be used Contact roughmeter measurement, according to JIS B0601-2001.The maximum height (Rz) on the surface of supporting mass be 0.1 μm hereinafter, Preferably 0.08 μm hereinafter, more preferably 0.05 μm or less.Since the shape of the side, i.e. surface that contact with transparent resin film will It is transferred to the surface of transparent resin film, thus, when the maximum height (Rz) on the surface of supporting mass is big, the surface of transparent resin film The height of concave convex of part also becomes larger, and there is the tendency as coarse surface.Therefore, the maximum height (Rz) on the surface of supporting mass It is the smaller the better, the case where particularly suitable for being configured at image display device.The lower limit of the maximum height (Rz) on the surface of supporting mass Value is not particularly limited, the smaller the better.

Commercially available product can also be used in supporting mass for use in the present invention.It can enumerate for example by Dongli Ltd. with TUFTOP's Hard coat film that title is sold on the market, the hard coat film sold on the market with the title of KB FILM by Co., Ltd. KIMOTO, And the hard coat film etc. sold on the market by TOYO CLOTH CO., LTD. with the title of TOCLO HC FILM.Certainly, as long as Meet the condition of above-mentioned Martens hardness, be then also possible to other films, and is not necessarily hard coat film.

Transparent resin film

The transparent resin film of laminated body of the invention is constituted by comprising selected from sub- by polyimides, polyamide and polyamide acyl At least one kind of resin combination in the group of amine composition is formed.

In this specification, polyimides indicates the polymer for containing the constitutional repeating unit comprising imide, polyamide Acid imide indicates poly- containing the constitutional repeating unit comprising imide and the constitutional repeating unit comprising amide groups this two side Object is closed, polyamide indicates the polymer for containing the constitutional repeating unit comprising amide groups.Polyimides system macromolecule indicates Polymer more than any one in polyimides and polyamidoimide.

The constitutional repeating unit that there are polyimides system of the present embodiment macromolecule formula (10) to indicate.Herein, G table Show that the organic group of 4 valences, A indicate the organic group of divalent.It may include the repetition that two or more different formula (10) of G and/or A indicates Structural unit.In addition, polyimides system of the present embodiment macromolecule can be in the transparent resin film not damaged Any 1 in constitutional repeating unit indicated in the range of various physical property comprising any formula in formula (11), formula (12) and formula (13) Kind or more.

When the high molecular essential building blocks of polyimides system are the constitutional repeating unit that formula (10) indicate, from transparent resin It is preferred from the viewpoint of film strength and the transparency.In polyimides system of the present embodiment macromolecule, relative to For the high molecular whole constitutional repeating units of polyimides system, the constitutional repeating unit that formula (10) indicates is preferably 40 moles of % More than, more preferably 50 moles of % or more, further preferably 70 moles of % or more, particularly preferably 90 moles of % or more are special It Jin Yibuyouxuanwei not 98 moles of % or more.The constitutional repeating unit that formula (10) indicates can be 100 moles of %.

[chemical formula 1]

G and G¹The organic group of 4 valences is each independently represented, preferably indicates that carbon atom number is the organic group of 4~40 4 valences Group.Aforementioned organic group can be replaced by alkyl or fluorine-substituted alkyl, in this case, alkyl and fluorine-substituted alkyl Carbon atom number be preferably 1~8.As G and G¹, formula (20), formula (21), formula (22), formula (23), formula (24), formula can be enumerated (25), the carbon atom number of formula (26), formula (27), formula (28) or formula (29) indicate group and 4 valences is 6 chain type hydrocarbon below Base.* in formula indicates that chemical bond, Z indicate 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 that the carbon atom number that can be replaced by fluorine atoms is that 6~20 arlydene can enumerate sub- benzene as concrete example Base.From the aspect of the yellow chromaticity of the easy transparent resin film for inhibiting to obtain, as G and G¹, can preferably enumerate formula (20), formula (21), the group that formula (22), formula (23), formula (24), formula (25), formula (26) or formula (27) indicate.

[chemical formula 2]

G²It indicates the organic group of trivalent, preferably indicates that carbon atom number is the organic group of 4~40 trivalent.Aforementioned organic group Group can be replaced by alkyl or fluorine-substituted alkyl, and in this case, the carbon atom number of alkyl and fluorine-substituted alkyl is excellent It is selected as 1~8.As G², formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula can be enumerated (27), any 1 in the chemical bond for the group that formula (28) or formula (29) indicate is substituted for group and trivalent made of hydrogen atom Carbon atom number be 6 chain type alkyl below.The example of Z in formula is identical as the example of the Z in the record about G.

G³It indicates the organic group of divalent, preferably indicates that carbon atom number is the organic group of 4~40 divalent.Aforementioned organic group Group can be replaced by alkyl or fluorine-substituted alkyl, and in this case, the carbon atom number of alkyl and fluorine-substituted alkyl is excellent It is selected as 1~8.As G³, formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula can be enumerated (27), in the chemical bond for the group that formula (28) or formula (29) indicate non-conterminous 2 be substituted for group and carbon made of hydrogen atom Atomicity is the chain type alkyl of 6 divalents below.The example of Z in formula is identical as the example of the Z in the record about G.

A、A¹、A²And A³It indicates the organic group of divalent, preferably indicates that carbon atom number is the organic group of 4~40 divalent. Aforementioned organic group can be replaced by the alkyl that alkyl or fluorine-substituted carbon atom number are 1~8, in this case, alkyl and The carbon atom number of fluorine-substituted alkyl is preferably 1~8.As A, A¹、A²And A³, formula (30), formula (31), formula can be enumerated respectively (32), the group that formula (33), formula (34), formula (35), formula (36), formula (37) or formula (38) indicate；They are by methyl, fluorine-based, chlorine Group obtained from one or more of base or trifluoromethyl replace；And carbon atom number is 6 chain type alkyl below.

* in formula indicates chemical bond, Z¹、Z²And Z³Each independently represent singly-bound ,-O- ,-CH₂-、-CH₂-CH₂-、-CH (CH₃)-、-C(CH₃)₂-、-C(CF₃)₂-、-S-、-SO₂,-CO- or-NR².Herein, R²What expression can be substituted with halogen atoms The alkyl that carbon atom number is 1~12.Herein, R²Indicate that the carbon atom number that can be substituted with halogen atoms is 1~12 alkyl.It is excellent Select Z¹With Z²And Z²With Z³It is respectively relative to each ring and is located at meta or para position.

[chemical formula 3]

In the present invention, the resin combination for forming transparent resin film may include polyamide.Polyamides of the present embodiment Amine is the polymer based on the constitutional repeating unit that is indicated with formula (13).G in polyamide³And A³Preference and concrete example with G in polyimides system macromolecule³And A³Preference and concrete example it is identical.Foregoing polyamides may include G³And/or A³Different The constitutional repeating unit that formula (13) of more than two kinds indicates.

Polyimides system macromolecule can for example be obtained by the polycondensation of diamines and tetracarboxylic compound (tetracarboxylic dianhydride etc.) It arrives, for example, can be according to the side recorded in Japanese Unexamined Patent Publication 2006-199945 bulletin or Japanese Unexamined Patent Publication 2008-163107 bulletin Method synthesis.As the commercially available product of polyimides, Mitsubishi Gas Chemical Co., Ltd Neopulim (registered trademark), river can be enumerated Industry Co., Ltd, village KPI-MX300F etc..

As workable tetracarboxylic compound in the high molecular synthesis of polyimides system, can enumerate aromatic tetracarboxylic acid and Its acid anhydride, preferably aromatic tetracarboxylic acids' compound such as its dianhydride；And aliphatic tetrabasic carboxylic acid and its acid anhydride, preferred fat such as its dianhydride Race's tetracarboxylic compound etc..For tetracarboxylic compound, other than acid anhydride, it is also possible to tetracarboxylic acid acid chloride compound etc. four Carboxylic acid compound derivative, they can be used alone, or combines two or more and use.

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 Tetracarboxylic dianhydride can enumerate 4,4 '-oxygen, two O-phthalic acid dianhydride (4,4 '-oxydiphthalic dianhydride), 3, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-bibenzene tetracarboxylics Dianhydride, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic acid dianhydrides, bis- (the 3,4- dicarboxyls of 2,2- Phenyl) propane dianhydride, bis- (2,3- dicarboxyphenyi) propane dianhydrides of 2,2-, bis- (the 3,4- di carboxyl phenyloxy phenyl) propane of 2,2- Dianhydride, 4,4 '-(hexafluoroisopropyli,ene) two O-phthalic acid dianhydride (4,4 '-(hexafluoroisopropylidene) Diphthalic dianhydride, sometimes referred to as 6FDA), bis- (2,3- dicarboxyphenyi) the ethane dianhydrides of 1,2-, 1,1- it is bis- Bis- (3,4- dicarboxyphenyi) the ethane dianhydrides of (2,3- dicarboxyphenyi) ethane dianhydride, 1,2-, bis- (the 3,4- dicarboxyl benzene of 1,1- Base) ethane dianhydride, bis- (3,4- dicarboxyphenyi) methane dianhydrides, bis- (2,3- dicarboxyphenyi) methane dianhydrides, 4,4 '-(to benzene Two oxygroups (p-phenylenedioxy)) two O-phthalic acid dianhydrides, 4,4 '-(two oxygroups of isophthalic (m-phenylenedioxy)) Two O-phthalic acid dianhydrides.In addition, the aromatic tetracarboxylic dianhydride as monocyclic, can enumerate 1,2,4,5- benzene tetracarboxylic acids two Acid anhydride can enumerate 2,3,6,7- naphthalenetetracarbacidic acidic dianhydrides as the aromatic tetracarboxylic dianhydride of fused polycyclic.

In these, 4,4 '-oxygen, two O-phthalic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylics two can be preferably enumerated Acid anhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2,2 ', 3,3 '-bibenzene tetracarboxylics Dianhydride, 3,3 ', bis- (3,4- dicarboxyphenyi) propane dianhydrides of 4,4 '-diphenyl sulfone tetracarboxylic acid dianhydrides, 2,2-, the bis- (2,3- of 2,2- Dicarboxyphenyi) propane dianhydride, bis- (the 3,4- di carboxyl phenyloxy phenyl) propane dianhydrides of 2,2-, 4,4 '-(hexafluoroisopropyli,enes) two Bis- (2,3- dicarboxyphenyi) the ethane dianhydrides of O-phthalic acid dianhydride (6FDA), 1,2-, bis- (2,3- dicarboxyphenyi) second of 1,1- Bis- (3,4- dicarboxyphenyi) the ethane dianhydrides of alkane dianhydride, 1,2-, bis- (3,4- dicarboxyphenyi) the ethane dianhydrides of 1,1-, bis- (3,4- Dicarboxyphenyi) methane dianhydride, bis- (2,3- dicarboxyphenyi) methane dianhydrides, 4,4 '-(to two oxygroup of benzene) two phthalic acids Dianhydride and 4,4 '-(two oxygroup of isophthalic) two O-phthalic acid dianhydrides, can more preferably enumerate 4,4 '-oxygen, two O-phthalic acid dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydrides, 4,4 '-(hexafluoroisopropyli,ene) two O-phthalics Acid dianhydride (6FDA), bis- (3,4- dicarboxyphenyi) methane dianhydrides and 4,4 '-(to two oxygroup of benzene) two O-phthalic acid dianhydrides.It Can be used alone, or combine two or more and use.

As aliphatic tetracarboxylic dianhydride, the aliphatic tetracarboxylic dianhydride of ring type or non-ring type can be enumerated.So-called ring type rouge Fat race tetracarboxylic dianhydride, refers to the tetracarboxylic dianhydride with ester ring type hydrocarbon structure, as its concrete example, can enumerate 1,2,4,5- rings The cycloalkane tetracarboxylic acids such as hexane tetracarboxylic acid dianhydride, 1,2,3,4- cyclobutanetetracarboxylic dianhydride, 1,2,3,4- cyclopentane tetracarboxylic acid dianhydride Acid dianhydride, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic acid dianhydride, dicyclohexyl -3,3 ', 4,4 '-tetracarboxylic acid dianhydrides and Their position isomer.They can be used alone, or combines two or more and use.As non-ring type aliphatic tetracarboxylic acid The concrete example of acid dianhydride can enumerate 1,2,3,4- ethylene-dimalonic acid dianhydrides, 1,2,3,4- pentane tetracarboxylic acid dianhydrides etc., they can be with It is used alone, or combines two or more and use.In addition, can also be by ring type aliphatic tetracarboxylic dianhydride and non-ring type aliphatic Tetracarboxylic dianhydride combines and uses.

In tetracarboxylic compound, from the sight of the easy elasticity modulus, resistance to bend(ing) and optical characteristics for improving transparent resin film Point considers, can preferably enumerate the aromatic tetracarboxylic dianhydride of aforementioned ester ring type tetracarboxylic dianhydride or non-condensed polycycle.As more It is bis- can to enumerate 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydrides, 2,2- for preferred concrete example (3,4- dicarboxyphenyi) propane dianhydride, 4,4 '-(hexafluoroisopropyli,ene) two O-phthalic acid dianhydrides (6FDA).They can be independent It uses, or combines two or more and use.

For polyimides system of the present embodiment macromolecule, in each of the transparent resin film not damaged In the range of kind of physical property, it can be other than the acid anhydride of workable tetrabasic carboxylic acid in above-mentioned polyimides synthesis further with four Obtained from carboxylic acid, tricarboxylic acid compound, dicarboxylic acid compound, their acid anhydride and their derivatives reaction.

As tricarboxylic acid compound, aromatic tricarboxylic acids, aliphatic tricarboxylic acids and their similar chloride can be enumerated Object, acid anhydrides etc. are closed, they can also be used in combination of two or more.As its concrete example, the acid anhydride of 1,2,4- benzenetricarboxylic acids can be enumerated；2,3,6- Naphthalenetricarboxylic acid -2,3- acid anhydride；Phthalic anhydride and benzoic acid are via singly-bound ,-CH₂-、-C(CH₃)₂-、-C(CF₃)₂-、-SO₂Or The compound that phenylene is formed by connecting.

As dicarboxylic acid compound, aromatic dicarboxylic acid, aliphatic dicarboxylic acid and their similar chloride can be enumerated Object, acid anhydrides etc. are closed, they can also be used in combination of two or more.As its concrete example, terephthalic acid (TPA) can be enumerated；M-phthalic acid；Naphthalene two Formic acid；4,4 '-biphenyl dicarboxylic acids；3,3 '-biphenyl dicarboxylic acids；Carbon atom number is the dicarboxylic acid compound and 2 of 8 chain type hydrocarbon below A benzoic acid skeleton is via-CH₂-、-S-、-C(CH₃)₂-、-C(CF₃)₂-、-O-、-NR⁹,-C (=O)-,-SO₂Or phenylene The compound being formed by connecting.They can be used alone, or combines two or more and use.Herein, R⁹Expression can be by halogen The alkyl that the carbon atom number that atom replaces is 1~12.

As dicarboxylic acid compound, preferably terephthalic acid (TPA)；M-phthalic acid；4,4 '-biphenyl dicarboxylic acids；3,3 '-biphenyl Dioctyl phthalate；And 2 benzoic acid skeletons are via-CH₂,-C (=O)-,-O- ,-NR⁹-、-SO₂Or the chemical combination that phenylene is formed by connecting Object, more preferably terephthalic acid (TPA)；4,4 '-biphenyl dicarboxylic acids；And 2 benzoic acid skeletons are via-O- ,-NR⁹,-C (=O)- Or-SO₂The compound being formed by connecting.They can be used alone, or combines two or more and use.

Relative to tetracarboxylic compound, tricarboxylic acid compound and dicarboxylic acid compound it is total for tetrabasic carboxylic acid chemical combination The ratio of object is preferably 40 moles of % or more, more preferably 50 moles of % or more, further preferably 70 moles of % or more, more into One step is preferably 90 moles of % or more, particularly preferably 98 moles of % or more.

As workable diamines in the high molecular synthesis of polyimides system, aliphatic diamine, aromatic diamine can be enumerated Or their mixture.It should be noted that in present embodiment, it is so-called " aromatic diamine ", indicate that amino is bonded directly to Diamines made of aromatic rings can include aliphatic group or other substituent groups in a part of its structure.Aromatic rings can be with For monocycle, or condensed ring can enumerate phenyl ring, naphthalene nucleus, anthracene nucleus and fluorenes ring etc., but be not limited to these.In these, can preferably it lift Phenyl ring out.In addition, so-called " aliphatic diamine ", indicates that amino is bonded directly to diamines made of aliphatic group, it can be at it It include aromatic rings, other substituent groups in a part of structure.

As the concrete example of aliphatic diamine, the non-ring type aliphatic diamine such as 1,6- hexamethylene diamine and 1, the bis- (ammonia of 3- can be enumerated Ylmethyl) rings such as hexamethylene, bis- (amino methyl) hexamethylenes of 1,4-, norbornane diamines, 4,4 '-diamino-dicyclohexyl methanes Formula aliphatic diamine etc., they can be used alone, or combines two or more and use.

As the concrete example of aromatic diamine, p-phenylenediamine, m-phenylene diamine (MPD), 2,4- toluenediamine, isophthalic diformazan can be enumerated Amine, p dimethylamine, 1,5- diaminonaphthalene, 2,6- diaminonaphthalene etc. have aromatic diamine, the 4,4 '-diaminos of 1 aromatic rings Base diphenyl methane, 4,4 '-diamino-diphenyl propane, 4,4 '-diamino-diphenyl ethers, 3,4 '-diamino-diphenyl ethers, 3, 3 '-diamino-diphenyl ethers, 4,4 '-diamino diphenyl sulfones, 3,4 '-diamino diphenyl sulfones, 3,3 '-diamino-diphenyls Bis- (4- amino-benzene oxygen) benzene of sulfone, 1,4-, bis- (4- amino-benzene oxygen) benzene of 1,3-, bis- (4- (4- amino-benzene oxygen) phenyl) sulfones, Bis- [4- (4- amino-benzene oxygen) phenyl] propane of bis- (4- (3- amino-benzene oxygen) phenyl) sulfones, 2,2-, bis- [4- (the 3- amino of 2,2- Phenoxy group) phenyl] propane, 2,2 '-dimethylbenzidines, 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines (record sometimes For TFMB), 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, bis- (4- aminophenyl) fluorenes of 9,9-, the bis- (4- amino -3- methylbenzenes of 9,9- Base) fluorenes, bis- (4- amino -3- chlorphenyl) fluorenes of 9,9-, bis- (4- amino -3- fluorophenyl) fluorenes of 9,9- etc. have 2 or more aromatic rings Aromatic diamine.They can be used alone, or combines 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 (TFMB), 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, More preferably 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino-diphenyl propane, 4,4 '-diamino-diphenyl ethers, 4,4 '- Bis- (4- amino-benzene oxygen) benzene of diamino diphenyl sulfone, 1,4-, bis- (4- (4- amino-benzene oxygen) phenyl) sulfones, the bis- [4- (4- of 2,2- Amino-benzene oxygen) phenyl] propane, 2,2 '-dimethylbenzidines, 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines (TFMB), 4,4 '-bis- (4- amino-benzene oxygen) biphenyl.They can be used alone, or combines two or more and use.

Aforementioned diamines can also have fluorine system substituent group.As fluorine system substituent group, can enumerate the carbon atom numbers such as trifluoromethyl is 1 ~5 perfluoroalkyl and fluorine-based.

In above-mentioned diamines, from the viewpoint of high transparency and less colored property, it is preferable to use selected from by with biphenyl structural Aromatic diamine composition one or more of group, as concrete example, it is preferable to use selected from by 2,2 '-dimethylbenzidines, 2, 1 in the group of 2 '-bis- (trifluoromethyl) -4,4 '-benzidines (TFMB) and 4,4 '-bis- (4- amino-benzene oxygen) biphenyl compositions Kind or more.The more preferably diamines with biphenyl structural and fluorine system substituent group more preferably uses 2,2 '-bis- (three as concrete example Methyl fluoride) -4,4 '-benzidines (TFMB).

Polyimides system macromolecule is can be by diamines and tetracarboxylic compound (including chloride compounds, tetracarboxylic dianhydride Etc. tetracarboxylic compounds derivative) polycondensation and formed, comprising formula (10) indicate constitutional repeating unit condensed type high score Son.As starting material, in addition, tricarboxylic acid compound (including chloride compounds, tricarboxylic are also further used sometimes The tricarboxylic acids such as acid anhydrides compound derivatives) and dicarboxylic acid compound (derivatives such as including chloride compounds).In addition, polyamide is It is being formed by the polycondensation of diamines and dicarboxylic acid compound (derivatives such as including chloride compounds), indicated comprising formula (13) Constitutional repeating unit condensed type macromolecule.

The constitutional repeating unit that formula (10) and formula (11) indicate usually can be derivative by Diamines and tetracarboxylic compound.Formula (12) constitutional repeating unit indicated usually can be derivative by diamines and tricarboxylic acid compound.The constitutional repeating unit that formula (13) indicates It usually can be derivative by diamines and dicarboxylic acid compound.Diamines, tetracarboxylic compound, tricarboxylic acid compound and dicarboxylic acid compound Concrete example is as described above.

It, preferably can be relative to diamines 1.00mol about the molar ratio of the carboxylic acid compounds such as diamines and tetracarboxylic compound For, tetrabasic carboxylic acid be suitably to be adjusted in 0.9mol or more and the range of 1.1mol or less.In order to which high folding resistance is presented, preferably obtain Polyimides system macromolecule be high molecular weight, for diamines 1.00mol, tetrabasic carboxylic acid is more preferably 0.98mol Above and 1.02mol is hereinafter, further preferably 0.99mol or more and 1.01mol or less.

In addition, preferably amino is in obtained macromolecule from the viewpoint of the yellow chromaticity for inhibiting obtained transparent resin film Ratio shared by end is low, and for diamines 1.00mol, the carboxylic acid compounds such as tetracarboxylic compound are preferably 1.00mol More than.

Fluorine number in the molecule of adjustable diamines and carboxylic acid compound (such as tetracarboxylic compound), with polyimides system On the basis of high molecular quality, the 1 mass % of fluorine amount or more in polyimides system macromolecule that makes, 5 mass % or more, 10 mass % or more, 20 mass % or more.The tendency that there are the ratios of fluorine is higher, expense of raw materials is higher, therefore, for fluorine amount For the upper limit, preferably 40 mass % or less.During fluorine system substituent group either can reside in diamines or carboxylic acid compound, It also is present in two sides.By the inclusion of fluorine system substituent group, YI value can be especially reduced sometimes.

Polyimides system of the present embodiment macromolecule can be comprising different types of a variety of above-mentioned repetitive structures The copolymer of unit.The high molecular weight average molecular weight by weight of standard polystyren of polyimides system is usually 100,000 ~800,000.When the high molecular weight average molecular weight of polyimides system is big, bendability when film forming is improved, it is therefore preferable that be 200, 000 or more, more preferably 300,000 or more, further preferably 350,000 or more.In addition, from can be obtained appropriate concentration and From the aspect of the varnish of viscosity, the tendency improved there are film forming, preferably 750,000 hereinafter, more preferably 600,000 with Under, further preferably 500,000 or less.The polyimides system that two or more different weight average molecular weight can be applied in combination is high Molecule.Other high molecular materials can be further mixed in the range of not damaging physical property.

By making polyimides system macromolecule and polyamide comprising being inclined to so that display is following: not only shape containing fluoro substituents Elasticity modulus when film forming improves, and can reduce YI value.When the elasticity modulus of film is high, scar and fold etc. can be inhibited by existing The tendency of generation.From the viewpoint of the transparency of film, polyimides system macromolecule and polyamide preferably have containing fluoro substituents. As the concrete example containing fluoro substituents, fluorine-based and trifluoromethyl can be enumerated.

For containing for the fluorine atom in the mixture of polyimides system macromolecule and polyimides system macromolecule and polyamide For amount, respectively, with the high molecular quality of polyimides system or the quality of polyimides system high molecular quality and polyamide It is total on the basis of, preferably 1 mass % or more and 40 mass % are hereinafter, further preferably 5 mass % or more and 40 matter Measure % or less.When the content of fluorine atom is 1 mass % or more, there is YI value when can further decrease to form film, can be further Improve the tendency of the transparency.On the other hand, quiet due to generating when forming film if the content of fluorine atom is lower than 1 mass % Electricity is easy to happen irregular fracture in processing.When the content of fluorine atom is higher than 40 mass %, there are the height of polyimides Molecule quantifies the tendency become difficult.

In the present invention, for the solid state component of resin combination, constitute in the resin combination of transparent resin film Polyimides system macromolecule and/or the content of polyamide be preferably 40 mass % or more, more preferably 50 mass % or more, into One step is preferably 60 mass % or more, is even more preferably 70 mass % or more, can be 100 mass %.Polyimides system When the content of macromolecule and/or polyamide is above-mentioned lower limit value or more, the bendability of transparent resin film is good.It needs to illustrate It is so-called solid state component, refers to the total amount of the remaining ingredient after removing solvent in resin combination.

In the present invention, for forming the resin combination of transparent resin film, in addition to above-mentioned polyimides system macromolecule It, can be further containing inorganic material such as inorganic particulates and/or except polyamide.As inorganic material, silica can be enumerated The inorganic particulates such as particle, titanium particle, aluminium hydroxide, Zirconia particles, barium titanate particles, in addition, tetraethyl orthosilicate can be enumerated (TEOS) silicon compounds such as 4 grades of alkoxy silanes such as.It is excellent from the viewpoint of from the stability, the dispersibility of inorganic material of varnish It is selected as silicon dioxide granule, aluminium hydroxide, Zirconia particles, further preferably silicon dioxide granule.

The average primary particle diameter of inorganic material particles is preferably 1nm~200nm, more preferably 3nm~100nm, further Preferably 5~50nm is even more preferably 5~30nm.When the average primary particle diameter of silicon dioxide granule is 100nm or less, The tendency improved in the presence of the transparency.When the average primary particle diameter of silicon dioxide granule is 10nm or more, silicon dioxide granule coagulates Poly- power is weak, thus there is the tendency for becoming easy processing.

In the present invention, about silicon dioxide granule, it can be to disperse silicon dioxide granule in organic solvent etc. and form Silica solution, it is possible to use the silicon dioxide microparticle powder manufactured using vapor phase method, it is preferably sharp from the aspect of easy to operate The silica solution manufactured with liquid phase method.

The average primary particle diameter of silicon dioxide granule in transparent resin film can be by being based on transmission electron microscope (TEM) observation and find out.The size distribution of silicon dioxide granule before forming transparent resin film can utilize commercially available laser Diffraction-type particle size distribution meter is found out.

In the present invention, for the solid state component of resin combination, the content of the inorganic material in resin combination Preferably 0 mass % or more and 90 mass % hereinafter, more preferably 0 mass % or more and 60 mass % hereinafter, further preferably For 0 mass % or more and 40 mass % or less.The content of inorganic material (silicon materials) in resin combination is above-mentioned range When interior, exist and be easy while realizing the transparency of transparent resin film and the tendency of mechanical strength.It should be noted that so-called solid-state Ingredient refers to the total amount of the remaining ingredient after removing solvent in resin combination.

It, can be into one other than ingredient described above for constituting the resin combination of transparent resin film Step contains other compositions.As other compositions, can enumerate for example antioxidant, release agent, light stabilizer, blueing agent, fire retardant, Lubricant and levelling agent (leveling agent).

In the present invention, resin combination includes its in addition to the resin components such as polyimides system macromolecule and inorganic material When his ingredient, for the gross mass of transparent resin film, the content of other compositions is preferably 0 mass % or more and 20 matter % is measured hereinafter, more preferably 0 mass % or more and 10 mass % or less.

In the present invention, transparent resin film can for example be manufactured by following resin varnish, and the resin varnish can be by with lower section Prepared by formula: obtaining to comprising selecting and making it to react from aforementioned tetracarboxylic compound, aforementioned diamines and other aforementioned raw materials The tree of the reaction solution of arrive, polyimides system macromolecule and/or polyamide, inorganic material used as needed and other compositions In oil/fat composition, adds solvent and mixed and stirred.In aforementioned resin, instead of polyimides system macromolecule etc. Reaction solution, it is possible to use the solution of polyimides system macromolecule bought etc., the solid polyimides system macromolecule bought etc. Solution.

As the solvent that can be used for preparing resin varnish, can suitably select can be by resin components such as polyimides system macromolecules The organic solvent of dissolution or dispersion.Consider preferably there is 120 from viewpoints such as the dissolubility of resin component, coating and drying property The organic solvent of~300 DEG C of boiling point, preferably have more preferable 120~270 DEG C, it is 120~250 DEG C further preferred, especially excellent Select the organic solvent of 120~230 DEG C of boiling point.As such organic solvent, specifically, such as N can be enumerated, N- dimethyl The acid amides series solvents such as formamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone；The lactones such as gamma-butyrolacton, gamma-valerolactone Series solvent；The ketone series solvents such as cyclohexanone, cyclopentanone, methyl ethyl ketone；The acetic acid ester series solvent such as butyl acetate, pentyl acetate；Two The carbonate-based solvents such as the sulfur-bearings such as methyl sulfone, dimethyl sulfoxide, sulfolane series solvent, ethylene carbonate, the Asia carbonic acid 1,2- propyl ester Deng.Wherein, from the dissolubility to polyimides system macromolecule and polyamide it is excellent from the aspect of, be preferably selected from by N, N- diformazan Yl acetamide (boiling point: 165 DEG C), gamma-butyrolacton (boiling point: 204 DEG C), N-Methyl pyrrolidone (boiling point: 202 DEG C), acetic acid fourth Solvent in the group of ester (boiling point: 126 DEG C), cyclopentanone (boiling point: 131 DEG C) and pentyl acetate (boiling point: 149 DEG C) composition.As Solvent can be used alone, and also can be used in combination two or more.It should be noted that when using two or more solvent, preferably The type of solvent is selected in such a way that the boiling point of the highest solvent of solvent mid-boiling point used is fallen within the above-described range.

The amount of solvent is not particularly limited, and select i.e. in a manner of becoming the viscosity for the processing that can be carried out resin varnish Can, for example, for resin varnish total amount, preferably 50~95 mass %, more preferably 70~95 mass %, further Preferably 80~95 mass %.

Transparent resin film of the invention can be obtained and above-mentioned resin varnish is coated on supporting mass and carries out predrying It arrives.Transparent resin film is strippingly laminated on supporting mass.It is so-called peelable, refer to the shape that can be maintained as film, also, It can be removed in cases where no fracturing is occurring from supporting mass.Specifically, referring to through predrying to remain the molten of appropriate amount The mode of agent is dried.Herein, when residual solvent amount is excessive, the shape as film is unable to maintain that, in addition, residual solvent amount mistake When few, become excessively high with the adaptation of supporting mass, is broken in removing.Suitable residual solvent amount depends on transparent resin The resin combination of film, solvent, supporting mass type and change, need suitably to be adjusted.But in general, relative to transparent For the gross mass of resin film, the content of the solvent in transparent resin film is 0.1 mass % or more.Solvent in transparent resin film The upper limit value of content is not particularly limited, as long as that can be maintained as the range of the shape of film, in general, relative to transparent tree It is 50 mass % or less for the gross mass of adipose membrane.It should be noted that in the present invention, for the solvent in transparent resin film For content, for example, can be as be described hereinafter embodiment in record as, use hot weight-differential heat (TG-DTA) measurement device, measurement Rate of mass reduction (quality %) from 120 DEG C to 250 DEG C, to calculate.

In the present invention, supporting mass must be peelable with resin film.But closing force is excessively weak be easily peeled off in the case where, produce Raw other problems.For example, in actual film forming apparatus, in the conveying of laminated body, from deflector roll by when crooked position, branch Holding body may remove.It is therefore preferable that not occurring laminated body is wound in the columned stick of diameter 100mm with 180 degree Removing, it is more preferably not peeling-off laminated body is wound in the columned stick of diameter 80mm with 180 degree, it is further excellent Choosing is not peeling-off laminated body is wound in the columned stick of diameter 60mm with 180 degree, even if even more preferably The columned stick that laminated body is wound in diameter 40mm with 180 degree is not also peeling-off, even if especially more preferably by laminated body It is also not peeling-off with the columned stick that 180 degree is wound in diameter 20mm.

The thickness of transparent resin film is suitably determined according to the purposes etc. of transparent resin film, usually 10~500 μm, excellent It is selected as 15~200 μm, more preferably 20~130 μm.The thickness of transparent resin film within the above range when, transparent resin film it is curved Song is good.

In the present invention, the mist degree of preferably clear resin film is 1.0% hereinafter, total light transmittance is 85% or more, yellow Index (yellow chromaticity) is 3.0 or less.If meeting such condition, it can be used as the high good resin film of the transparency and utilize.Mist degree, The measuring method of total light transmittance and yellow colour index (yellow chromaticity) is recorded in embodiment in detail.Mist degree indicates resin film The degree to haze etc, certainly the smaller the better, preferably 0.7% hereinafter, more preferably 0.5% or less.Total light transmittance The transmitance of the light passed through from film, it is so-called transparent, be preferably close to 100%, preferably 85% or more, more preferably 87% with On, further preferably 89% or more.It is functional when no yellow chromaticity in addition, yellow colour index is yellow chromaticity, preferably 2.5 with Under, more preferably 2.2 or less.

The elasticity modulus of transparent resin film of the invention is 4.0~9.0GPa, more preferably 4.5~8.5GPa.The elasticity The measuring method of modulus is described in detail in embodiment.When elasticity modulus is in above range, become to be not likely to produce defect.

Protective film

Laminated body of the invention may include the protective film for being bonded to above-mentioned transparent resin film.Protective film can be bonded to The face without supporting mass of ming tree adipose membrane.It, can in the case where there is a problem of that adhesion etc. is windability when by laminated body wound into rolls In addition to that mentioned above, to be also bonded protective film on the face for being in opposite side with transparent resin film of supporting mass.It is bonded to transparent The protective film of resin film is not particularly limited for the film of temporary protection transparent resin film surface, as long as can protect transparent The strippable film of surface resin film.Such as polyethylene terephthalate, polybutylene terephthalate can be enumerated The polyester based resins film such as ester, polyethylene naphthalate；The polyolefin-based resins such as polyethylene, polypropylene screen film, acrylic acid series Resin film etc., preferably from by polyolefin-based resins film, PET series resin film and acrylic resin film It is selected in the group of composition.In the case where the two sides of laminated body is bonded protective film, the protective film in each face mutually can be identical, can also With difference.

The thickness of protective film is not particularly limited, usually 10~100 μm, preferably 10~80 μm, more preferably 10~ 50μm.In the case where the two sides of laminated body has been bonded protective film, the thickness of the protective film in each face can be identical, can also not Together.

Laminated body film roll

In the present invention, by above-mentioned laminated body (supporting mass, transparent resin film and protective film used as needed) with web-like It is wound in product obtained from core and is known as laminated body film roll.For laminated body film roll, when being carried out continuously manufacture, due to The limitation in space etc. is usually saved in the form of film roll for the time being, and laminated body film roll is also one of them.In the shape of laminated body film roll Under state, laminated body is more securely rolled tightly, and therefore, the scar on supporting mass will be easy to be transferred on transparent resin film.So And if scar is not easy to be transferred to supporting mass from deflector roll etc. using the supporting mass with defined Martens hardness of the invention, Even if being rolled tightly with laminate film roll form, it is not easy to produce scar.

As the material for the core for constituting laminated body film roll, such as polyvinyl resin, acrylic resin, polychlorostyrene second can be enumerated Olefine resin, polyester resin, epoxy resin, phenolic resin, melamine resin, silicone resin, polyurethane resin, polycarbonate resin The synthetic resin such as rouge, ABS resin；The metals such as aluminium；Fibre reinforced plastics (FRP: make to mention in plastics containing fibers such as glass fibres The high composite material of intensity) etc..It is, for example, 80~170mm that core, which becomes shapes, the diameter such as cylindric or cylindric,.Separately Outside, the diameter (diameter after winding) of film roll is not particularly limited, usually 200~800mm.

The present invention also provides the methods for manufacturing above-mentioned laminated body.The manufacturing method of above-mentioned laminated body includes the following steps:

A) Martens hardness in the side of resin varnish to be coated with is 300N/mm²On above supporting mass, coating will be used for Resin varnish obtained from the resin combination of formation transparent resin film is mixed and is stirred with solvent；And

B) by keeping be coated with resin varnish dry to remove solvent, transparent resin film is formed on supporting mass Layer.

In addition, needing to further include following step in the case where forming protective film:

C) protective film is bonded on the face for being in opposite side with supporting mass for the transparent resin film being formed on supporting mass.

For laminated body of the invention, only pass through the surface for the side of control supporting mass contacted with transparent resin film Martens hardness, it is sub- that transparent resin film caused by the scar because of the surface of deflector roll etc., especially transparent polyamides can be reduced The scar of amine system film, the yield rate in manufacture greatly improve, and can improve productivity.

Fenestrated membrane substrate

As dry (formal to transparent resin film further progress obtained from removing supporting mass from laminated body of the invention It is dry), residual solvent amount is reduced, so as to use as fenestrated membrane substrate.Formally dry process is not particularly limited, is Deformation when preventing dry, is preferably dried while being fixed width direction with transverse drawing mill etc..With transverse direction Stretching-machine implement it is formal dry in the case where, transparent resin film can be stretched, can also etc. multiplying powers handled, or Person can also make its contraction.In addition, the residual solvent amount of fenestrated membrane substrate can be according to required physical property appropriate adjustment, usually 3.0% hereinafter, preferably 1.5% hereinafter, further preferably 1.0% hereinafter, particularly preferably 0.8% or less.Residual solvent When amount is more than above-mentioned upper limit value, film surface is soft, is easy to produce scar, and therefore, in subsequent handling, the processing of film becomes difficult. So-called fenestrated membrane herein is the component for being configured in the viewing side surface of image display device, sometimes also on the surface of fenestrated membrane into one Step configuration protective film, other function layer or film.In addition, so-called fenestrated membrane substrate, refers to the basement membrane of fenestrated membrane, in general, for raising The purpose of surface hardness can be used by setting window hard conating as fenestrated membrane.According to the characteristic for using purpose, hyaline membrane, Fenestrated membrane substrate can also be used directly as fenestrated membrane.As fenestrated membrane substrate, preferably clear polyimides mesentery or transparent polyamides Amine film.

Fenestrated membrane

Fenestrated membrane be fenestrated membrane substrate at least one side include window hard conating and formed.Fenestrated membrane not as existing glass that Sample is upright and outspoken, but has characteristic flexible.Fenestrated membrane substrate and has window hard conating in at least one side of aforementioned fenestrated membrane substrate Fenestrated membrane plays following effects: protecting using it is other constituent elements of the image display device of constituent element from from outside The infringement of the variation of the temperature and humidity of impact or surrounding.In addition, aforementioned window hard conating has the surface hardness for improving transparent substrate Function.In addition, window hard conating has translucency and flexibility.

The thickness of the window hard conating of aforementioned fenestrated membrane is not particularly limited, for example, can be 5~100 μm.Aforementioned window hard conating Thickness less than 5 μm when, it is difficult to ensure sufficient surface hardness, be greater than 100 μm when, resistance to bend(ing) decline, sometimes generate because consolidate Change and shrinks and lead to the problem of crimping.

Aforementioned window hard conating can form the hard conating of the reactive explosive of cross-linked structure by the inclusion of irradiation light or thermal energy It is formed with the solidification of composition.

Aforementioned window hard conating can be by simultaneously comprising light-cured type (methyl) acrylate monomer or oligomer and photocuring The window composition for hard coat of type epoxy monomer or oligomer is solidified to form.

In window composition for hard coat, other than above-mentioned light-cured type (methyl) acrylate monomer, oligomer, root It include solvent, Photoepolymerizationinitiater initiater according to needs.In addition, in window composition for hard coat The effect of invention can not damaged It include inorganic filler, levelling agent, stabilizer, antioxidant, UV absorbent, antistatic agent, surfactant, lubrication in range The additives such as agent, anti-fouling agent.

Aforementioned window hard conating can be by being coated on at least one side of fenestrated membrane substrate simultaneously for above-mentioned window composition for hard coat It is solidified to form it.

Optical laminate

Another example of the invention is the optical laminate comprising fenestrated membrane above-mentioned, in particular in tool of the invention In the one side of the fenestrated membrane of standby window hard conating, the layer further included in the group being made of polarizer and touch sensor Optical laminate.In addition, as needed, aforementioned fenestrated membrane can between across adhesive layer have polarizer or touch sensor.

In addition, in at least one side of aforementioned fenestrated membrane or aforementioned polarizer, can have printed around frame it is coloured Light-shielding pattern, aforementioned light-shielding pattern can be single-layer or multi-layer form.In addition, in the one side of aforementioned fenestrated membrane, it can also be straight It connects or engages polarizing layer across adhesive layer.For example, aforementioned polarizing layer can continuously extend to aforementioned non-display area or Frame portion is also possible to include polyethenol series polaroid and at least one side for being bonded to aforementioned polyethenol series polaroid The common polarizer of protective film.

As another example of the invention, to be integrally formed polarizing layer and touch sensing in the one side of aforementioned fenestrated membrane There is no limit can be according to fenestrated membrane, polarizing layer, touch sensor for the configuration sequence of the structure of device, polarizing layer and touch sensor And display panel is arranged in order, it can also being arranged in order according to fenestrated membrane, touch sensor, polarizing layer and display panel.With In the case where fenestrated membrane, polarizing layer, being arranged in order of touch sensor and display panel, in the image display device from viewing side When, touch sensor is present in the downside of polarizing layer, therefore, has the advantages that the pattern of touch sensor is not easy to be observed. In this case, the front phase difference of the substrate of touch sensor is preferably ± 2.5nm or less.As such raw material, make For tensionless winkler foundation film, such as can be selected from by triacetyl cellulose, cycloolefin, cyclic olefine copolymer, polynorbornene copolymer The film of the raw material of one or more of the group of equal raw material composition.On the other hand, can also have no touch sensor substrate, And pattern is only transferred to the structure of fenestrated membrane and polarizing layer.

Aforementioned polarizing layer and touch sensor can be configured at fenestrated membrane and be shown by transparent adhesive layer or clear adhesive oxidant layer Show between panel, preferably clear adhesive phase.With the feelings of fenestrated membrane, polarizing layer, touch sensor and display panel being arranged in order Under condition, transparent adhesive layer can be between fenestrated membrane and polarizing layer, between touch sensor and display panel.With fenestrated membrane, touch biography In the case where sensor, being arranged in order of polarizing layer and display panel, transparent adhesive layer can be located at fenestrated membrane and touch sensor it Between, between touch sensor and polarizing layer, between polarizing layer and display panel.

Polarizer

The polarizer that aforementioned fenestrated membrane can be laminated in can be individual polaroid or have polaroid and be bonded to it extremely The structure of the protective film of few one side.The thickness of aforementioned polarizer is not particularly limited, such as can be 100 μm or less.If thickness Greater than 100 μm, then flexibility declines sometimes.It when in aforementioned range, such as can be 5 μm~100 μm.

Aforementioned polaroid can be by include be swollen for polyvinyl alcohol mesentery, dyed, be crosslinked, stretched, washed, The process of drying and other steps and the membranous type polaroid usually used in this field manufactured, as another example, can coating of liquid crystalline apply Cloth uses composition to be formed as polarisation coating layer.Foregoing liquid crystal coating composition is that coating layer forms composition, may include Polymerizable liquid crystal compound and dichroic dye.Aforementioned polarisation coating layer can be for example manufactured in the following manner: be applied on substrate Cloth alignment films form composition, assign orientation, form alignment films, and coating includes liquid-crystal compounds and two in aforementioned alignment films The coating layer of color dyestuff forms composition, forms liquid crystal coating layer.Such polarisation coating layer with comprising pass through bonding agent quilt The polarizer for the protective film for fitting in polyethenol series polaroid two sides is compared, and relatively thin thickness can be formed.Aforementioned polarisation coating The thickness of layer can be 0.5~10 μm, preferably 2~4 μm.

Alignment films form composition

It may include alignment agent usually used in the field, Photoepolymerizationinitiater initiater and molten that aforementioned alignment films, which form composition, Agent.It, can be without particular limitation using alignment agent usually used in the field as aforementioned alignment agent.For example, can be used Polyacrylate system macromolecule, polyamic acid, polyimides system macromolecule or the macromolecule comprising cinnamic acid ester group are as orientation Agent, in the case where being applied to light orientation, it is preferable to use the macromolecule comprising cinnamic acid ester group.

For aforementioned alignment films formed composition coating for, can enumerate for example spin-coating method, extrusion moulding, dip-coating, Flow coat, spraying, roller coating, intaglio plate coating, micro- intaglio plate coating etc., preferably by online coating method.Aforementioned alignment films are coated with to be formed Composition and as needed be dried after, carry out orientation process.About aforementioned orientation process, can use without limitation should Well known a variety of methods in field, preferably using light orientation membranization.Optical alignment film usually can be by that will include with light reaction The optical alignment film formation of the polymer or monomer and solvent of property group is coated on substrate with composition and irradiates polarised light (preferably Polarization UV light) and obtain.From the side that can arbitrarily control orientation restraint by the polarization direction of the polarised light of selection irradiation From the aspect of, further preferred optical alignment film.

The film thickness of aforementioned optical alignment film is usually 10nm~10000nm, preferably 10nm~1000nm, more preferably 500nm is hereinafter, further preferably 10nm or more.When in aforementioned range, orientation restraint can sufficiently be presented.

Polarisation coating layer forms composition

Polarisation coating layer can form composition by coating polarisation coating layer and be formed.Specifically, polarisation coating layer shape At composition be other than comprising dichroism pigment also comprising as host compound a kind or more polymerizable liquid crystal (hereinafter, Sometimes referred to as polymerizable liquid crystal (B)) composition (hereinafter, sometimes referred to as composition B).

So-called " dichroism pigment ", the absorbance for referring to the long axis direction with molecule are different from the absorbance of short-axis direction Property pigment.There is no limit for dichroism pigment, as long as the pigment having the quality that, can be dyestuff, It can be pigment.Two or more dye combinations can be used, two or more pigment combination can also be used, it can also be by dyestuff and face Material is applied in combination.

Dichroism pigment preferably has maximum absorption wavelength (λ in the range of 300~700nm_MAX).As such two Color pigment can enumerate acridine pigment, oxazines pigment, phthalocyanine dye, naphthalene pigment, azopigment and anthraquinone pigment, wherein it is preferred that Azopigment.As azopigment, monoazo pigment, bisazo pigment, trisazo- pigment, four azopigments and Stilbene can be enumerated (stilbene) azopigment, preferably bisazo pigment and trisazo- pigment.

The mesomorphic state that polymerizable liquid crystal (B) is presented is preferably smectic phase, higher partially from that can manufacture ordered orientation degree The consideration of photosphere this respect, more preferably high-order smectic phase.The polymerizable liquid crystal (B) that smectic phase is presented is known as polymerism smectic type Liquid-crystal compounds.Polymerizable liquid crystal (B) can be used alone or be applied in combination.In addition, combining two or more polymerizable liquid crystal In the case of, preferably at least a kind is polymerizable liquid crystal (B), and more preferably two or more is polymerizable liquid crystal (B).By combination, sometimes Liquid crystal liquid crystal property can be temporarily kept at liquid crystal-crystallization phase transition temperature temperature below.Polymerizable liquid crystal (B) is for example available The Recl.Trav.Chim.Pays-Bas such as Lub are recorded in 115,321-328 (1996) or Japanese Patent No. 4719156 etc. Known method manufactures.The content of dichroism pigment in composition B can suitably be adjusted according to type of dichroism pigment etc., phase For 100 mass parts of polymerizable liquid crystal (B), more than preferably 0.1 mass parts and 50 below the mass, more preferably 0.1 More than mass parts and 20 below the mass, more than further preferably 0.1 mass parts and 10 below the mass.Dichroism pigment Content within the above range when, can be polymerize in the case where not upsetting the orientation of polymerizable liquid crystal (B).Dichroism pigment When content is excessive, the orientation of polymerizable liquid crystal (B) may interfere with.

Composition B preferably comprises solvent.It is high generally, due to the viscosity of smectic crystal compound, thus wrap solvent-laden Composition is easy coating, as a result, is easy to carry out the formation of light polarizing film in most cases.As solvent, it can enumerate and be taken with above-mentioned The same solvent of the solvent for including in tropism polymer composition, can be according to the dissolution of polymerizable liquid crystal (B) and dichroism pigment Property suitably selects.For the total amount of composition B, the content of solvent is preferably 50~98 mass %.In other words, composition Solid state component in B is preferably 2~50 mass %.

Composition B preferably comprises a kind or more of levelling agent.Levelling agent has the mobility of adjustment composition B, makes to pass through painting The more flat function of coated film obtained from cloth composition B, specifically, surfactant can be enumerated.Composition B contains levelling When agent, for 100 mass parts of polymerizable liquid crystal, content be preferably 0.05 mass parts or more and 5 below the mass, more More than preferably 0.05 mass parts and 3 below the mass.When the content of levelling agent is in aforementioned range, there are following tendencies: It is easy that polymerizable liquid crystal is made to be horizontally oriented, in addition, obtained polarizing layer becomes smoother.For polymerizable liquid crystal Levelling agent content in aforementioned range when, exist and be not likely to generate uneven tendency in obtained polarizing layer.

Composition B preferably comprises a kind or more of polymerization initiator.Polymerization initiator can cause polymerizable liquid crystal (B) The compound of polymerization reaction, from can consider in initiated polymerization this respect under lower temperature conditions, preferred Photoepolymerizationinitiater initiater. Specifically, the Photoepolymerizationinitiater initiater that can generate living radical or acid by the effect of light can be enumerated, wherein preferably pass through The Photoepolymerizationinitiater initiater that the effect of light generates free radicals.As polymerization initiator, benzoin compound, benzophenone can be enumerated Close object, alkyl phenones compound, acylphosphine oxide compound, triaizine compounds, salt compounded of iodine and sulfonium salt.

When composition B contains polymerization initiator, content can be according to the type of the polymerizable liquid crystal contained in the composition And its amount is appropriate adjusts, and for 100 mass parts of polymerizable liquid crystal, preferably 0.1~30 mass parts, more preferably 0.5 ~10 mass parts, further preferably 0.5~8 mass parts.The content of polymerization initiator within the above range when, can not upset It is polymerize in the case where the orientation of polymerizable liquid crystal (B).When composition B contains Photoepolymerizationinitiater initiater, aforementioned composition can be with Further contain photosensitizer.When composition B contains Photoepolymerizationinitiater initiater and photosensitizer, can further it promote in the composition The polymerization reaction of the polymerizable liquid crystal contained.The usage amount of photosensitizer can be according to the kind of Photoepolymerizationinitiater initiater and polymerizable liquid crystal Class and its appropriate adjusting of amount, for 100 mass parts of polymerizable liquid crystal, preferably 0.1~30 mass parts, more preferably 0.5~10 mass parts, further preferably 0.5~8 mass parts.

In order to more stably carry out the polymerization reaction of polymerizable liquid crystal, composition B can contain suitable polymerization inhibitor, by This, it will it is easy to control the carry out degree of the polymerization reaction of polymerizable liquid crystal.When composition B contains polymerization inhibitor, content can root It is suitably adjusted according to the type and its amount of polymerizable liquid crystal and usage amount of photosensitizer etc., relative to 100 mass of polymerizable liquid crystal For part, preferably 0.1~30 mass parts, more preferably 0.5~10 mass parts, further preferably 0.5~8 mass parts.Resistance The content of poly- agent within the above range when, can be polymerize in the case where not upsetting the orientation of polymerizable liquid crystal.

The production method of polarisation coating layer

Polarisation coating layer can usually implement the substrate of orientation process by the way that polarisation coating layer formation composition to be coated on Above, the polymerizable liquid crystal in coated film made polymerize and is formed.It is coated with the method that aforementioned polarisation coating layer forms composition There is no limit.As orientation process, the method that above-illustrated can be enumerated.Composition is formed by coating polarisation coating layer, To coated film contained in polymerizable liquid crystal do not polymerize under conditions of solvent seasoning removed, to form dry coationg.Make For drying means, natural seasoning, aeration-drying method, heat drying and hypobaric drying method can be enumerated.Polymerizable liquid crystal is polymerization When property smectic crystal compound, preferably make the mesomorphic state for the polymerism smectic crystal compound for including in dry coationg at For nematic phase (nematic crystal state), then it is transformed into smectic phase.In order to form smectic phase via nematic phase, for example, can Using following such methods: dry coationg is heated to the polymerism smectic crystal compound phase-variable for including in dry coationg To more than the temperature of nematic mesomorphic state, next, being cooled to polymerism smectic crystal compound is presented smectic phase The temperature of mesomorphic state.Next, to the mesomorphic state for making the polymerizable liquid crystal in dry coationg become smectic phase after, protecting The method that hold makes polymerizable liquid crystal carry out photopolymerization in the state of the mesomorphic state of smectic phase is illustrated.In photopolymerization, Xiang Gan The light of dry envelope irradiation can type, the type of polymerizable liquid crystal according to the Photoepolymerizationinitiater initiater for including in aforementioned dry coationg The appropriate selection of (the especially type of photopolymerizable group possessed by polymerizable liquid crystal) and its amount, as its concrete example, can enumerate Active energy beam in the group being made of visible light, ultraviolet light and laser.In these, from being easy to control polymerization reaction It carries out this respect, may be used at photo-polymerization device widely used in the art as the consideration of photo-polymerization device this respect, preferably Ultraviolet light.By carrying out photopolymerization, in the state that polymerizable liquid crystal keeps the mesomorphic state of smectic phase, preferably high-order smectic phase It is polymerize, to form polarizing layer.

Phase difference coating layer

In an embodiment of the invention, polarizer may include phase difference coating layer.According to optical characteristics, by phase difference Coating layer is referred to as λ/2 layer, λ/4 layer, C layers positive etc..Phase difference coating layer can for example be formed in the following manner: be taken implementing To on the base material film of processing coating comprising liquid-crystal compounds coating layer formed composition and form liquid crystal coating layer, then via Liquid crystal coating layer is bonded by adhesive layer with polarizer, then by substrate film stripping；But it is not limited to this method.It, can as base material film The polymeric membrane enumerated used as protective film, can also be before forming alignment films, to forming alignment films and phase separation layer The substrate surface of side implements surface treatment.Aforementioned alignment films form composition and its coating and drying means etc. are coated with in polarisation Layer in illustrate it is same, therefore, in order to avoid repeat, omit record.The composition that composition is formed about coating layer, in addition to not wrapping Except dichroic dye, with illustrate in aforementioned polarisation coating layer it is same.In addition, aforementioned coating layer forms the painting of composition Cloth, drying and curing method etc. also with illustrate in aforementioned polarisation coating layer it is same, therefore, in order to avoid repeat, omit record.

Phase difference coating layer with a thickness of 0.5~10 μm, preferably 1~4 μm.

It, can thickness, polymerism by coating layer for phase difference coating layer in an embodiment of the invention State of orientation of liquid-crystal compounds etc. adjusts optical characteristics.Specifically, tax can be made by the thickness for adjusting phase separation layer Give the phase separation layer of phase difference in desired face.Phase difference value (length of delay, Re in face) is the value defined by formula (1) in face, Desired Re in order to obtain, preferably adjusting Δ n and film thickness (d).

Re=d × Δ n (λ) ... formula (1) (Δ n=nx-ny herein)

(in formula, phase difference value in the expression face Re, d indicates that film thickness, Δ n indicate birefringence.In view of passing through polymerism liquid The orientation of brilliant compound and in the case where the index ellipsoid that is formed, define as described below 3 directions refractive index, i.e. nx, Ny and nz.Nx indicates that phase separation layer is formed by the principal refractive index in the direction parallel with substrate plane in index ellipsoid.ny Indicate that phase separation layer is formed by the refraction in the orthogonal direction in the direction parallel with substrate plane and with nx in index ellipsoid Rate.Nz indicates that phase separation layer is formed by the refractive index in the direction vertical with substrate plane in index ellipsoid.Phase separation layer When for λ/4 layer, phase difference value Re (550) is the range of 113~163nm, the preferably range of 130~150nm in face.Phase difference When layer is λ/2 layer, Re (550) is the range of 250~300nm, the preferably range of 250~300nm.)

In addition, the phase that the phase difference of thickness direction is presented can be made according to the state of orientation of polymerizable liquid crystal compound Poor layer.The so-called phase difference that thickness direction is presented, indicates what the phase difference value Rth of thickness direction in following mathematical expressions (2) was negative Characteristic.

Rth=[(nx+ny)/2-nz] × d ... formula (2)

(in formula, nx, ny, nz and d are identical as definition above-mentioned.)

Phase difference value Re (550) is usually the range of 0~10nm, the preferably range of 0~5nm, thickness in positive C layers of face The phase difference value Rth in direction is usually the range of -10~-300nm, the preferably range of -20~-200nm.Polarisation of the invention Plate can have 2 layers or more of phase difference coating layer, when having 2 layers of phase difference coating layer, can be following situations: the 1st phase difference Coating layer is λ/4 layer for making circularly polarized light, and the 2nd phase difference coating layer is for improving the color observed when inclination It is C layers positive.Alternatively, it is also possible to being following situations: the 1st phase difference coating layer is the positive C for improving the color observed when inclination Layer, the 2nd phase difference coating layer is λ/4 layer for making circularly polarized light.

Adhesive layer

In an embodiment of the invention, polarisation coating layer and the 1st phase difference coating layer or the 1st phase difference coating layer It can be bonded via adhesive or bonding agent with the 2nd phase difference coating layer.As the bonding agent for forming adhesive layer, water can be used It is bonding agent, active energy ray-curable bonding agent or heat-curable adhesive, preferably water system bonding agent, active energy beam Curability bonding agent.As adhesive phase, aftermentioned adhesive phase can be used.

Adhesive layer

As water system bonding agent, bonding agent, the water system two-liquid type ammonia formed by polyvinyl alcohol resin aqueous solution can be enumerated Carbamate system emulsion adhesive etc..Wherein, it is preferable to use the water system bonding agent formed by polyvinyl alcohol resin aqueous solution.Make For polyvinyl alcohol resin, obtained in addition to the polyvinyl acetate to the homopolymer as vinyl acetate carries out saponification process Alcotex except, it is possible to use vinyl acetate and the copolymer for the other monomers that can be copolymerized with it are saponified Polyvinyl alcohol based copolymer obtained from processing or by their hydroxyl carry out it is partially modified obtained from modified polyvinylalcohol system Polymer etc..Water system bonding agent may include aldehyde compound (glyoxal etc.), epoxide, melamine based compound, hydroxyl first The crosslinking agents such as based compound, isocyanate compound, amine compounds, multivalent metal salt.

When using water system bonding agent, preferably after being bonded coating layer, implement for removing the water for including in water system bonding agent The drying process gone.

Above-mentioned active energy ray-curable bonding agent refer to containing by ultraviolet light, visible light, electron beam, X-ray this The irradiation of the active energy beam of sample and the bonding agent for carrying out cured curability compound, preferably ultra-violet solidified bonding Agent.

Above-mentioned curability compound can be curability compound, the free-radical polymerised curability of cationically polymerizable Compound.As the curability compound of cationically polymerizable, can enumerate such as epoxy compound (has 1 in the molecule Or the compound of 2 or more epoxy groups), oxetanes based compound is (in the molecule with 1 or 2 or more oxa- The compound of cyclobutane ring) or their combination.As free-radical polymerised curability compound, such as (first can be enumerated Base) acrylic compounds (in the molecule with the compound of 1 or 2 or more (methyl) acryloyl group oxygroup), have Other vinyl compounds or their combination of free-radical polymerised double bond.Consolidating for cationically polymerizable can be used together The property changed compound and free-radical polymerised curability compound.Active energy ray-curable bonding agent is usually also comprising being used for Cause the cationic polymerization initiators and/or radical polymerization initiator of the curing reaction of above-mentioned curability compound.

It, to improve cementability, can be to the binding face of either one for the face being bonded when being bonded coating layer Implement surface activation process.As surface activation process, can enumerating sided corona treatment, corona treatment, discharge treatment, (aura is put Electric treatment etc.), flame treatment, ozone treatment, UV ozone treatment, ionization activity Irradiation (UV treatment, electron beam treatment Deng) as dry process；It has used water, the ultrasonication of acetone equal solvent, saponification process, anchor to apply and has handled such wet type Processing.These surface activation process can be carried out individually, can also combine two or more.

The thickness of aforementioned adhesive layer can be adjusted according to its bonding force, can be 0.1 μm~10 μm, preferably 1 μm~5 μ m.In an embodiment of the invention, using the structure of the aforementioned adhesive layer of multilayer, using identical material Or different material manufactures, it can thickness having the same or different thickness.

Adhesive phase

Adhesive phase can by with (methyl) acrylic resin, rubber series resin, polyurethane series resin, polyester based resin, Resin as polysiloxane series resin, polyvingl ether system resin is that the adhesive composition of principal component is constituted.Wherein, preferably To be basic polymer with the excellent polyester based resin such as the transparency, against weather, heat resistance or (methyl) acrylic resin Adhesive composition.Adhesive composition can be active energy ray curable, thermohardening type.

The adhesive resin used in the present invention, in general, it is 300,000~4,000,000 range that weight average molecular weight, which can be used, Adhesive resin.In view of durability, especially heat resistance, it is preferable to use the bonding that weight average molecular weight is 500,000~3,000,000 Agent resin.In turn, more preferably 650,000~2,000,000.It is undesirable from the aspect of heat resistance when weight average molecular weight is less than 300,000. In addition, when weight average molecular weight is greater than 4,000,000, it is undesirable from the aspect of stickiness, bonding force decline.It should be noted that weight Average molecular weight refers to the value for measuring using GPC (gel permeation chromatography), calculating and by weight of polystyrene.

In addition, crosslinking agent can be contained in adhesive composition.As crosslinking agent, organic system crosslinking agent, multifunctional can be used Property metallo-chelate.As organic system crosslinking agent, isocyanates system crosslinking agent, peroxide system crosslinking agent, epoxy can be enumerated Crosslinking agent, imines system crosslinking agent etc..Multi-functional metallo-chelate is polyvalent metal with covalent bond or coordinate bond and organic compound Product obtained from object bonding.As polyvalent metal atom, can enumerate Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti etc..As the original in the organic compound that covalent bonding or coordinate bond bonding occurs Son can enumerate oxygen atom etc., as organic compound, can enumerate Arrcostab, alcoholic compound, carboxylic acid compound, ether compound, ketone Compound etc..

For 100 parts by weight of adhesive resin, the usage amount of crosslinking agent is preferably 0.01~20 parts by weight, into one Step is preferably 0.03~10 parts by weight.It should be noted that there are the cohesions of adhesive phase when crosslinking agent is less than 0.01 parts by weight Hypodynamic tendency may generate foaming when heated, and on the other hand, when being more than 20 parts by weight, moisture-proof is insufficient, it will holds It is easily peeling-off in reliability test etc..

As additive, preferably cooperation silane coupling agent.As silane coupling agent, 3- glycidoxypropyl group three can be enumerated Methoxy silane, 3- epoxy propoxy propyl methyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silicon Alkane etc. has the silicon compound of epoxy based structures；3- TSL 8330, N- (2- amino-ethyl) 3- aminopropyl The amino-containing silicon compounds such as trimethoxy silane, N- (2- amino-ethyl) 3- aminopropylmethyldimethoxysilane；3- chlorine Propyl trimethoxy silicane；Trimethoxy silane, 3- acryloyloxypropyltrimethoxysilane containing acetoacetyl, 3- first Base acryloxypropyl triethoxysilane etc. contains the silane coupling agent of (methyl) acrylic acid series group；3- isocyanate group third The silane coupling agent etc. containing isocyanate group such as ethyl triethoxy silicane alkane.Silane coupling agent can assign durability, especially add Inhibit the effect of removing under wet environment.For 100 parts by weight of adhesive resin, the usage amount of silane coupling agent is 1 weight Part is measured hereinafter, being 0.01~1 parts by weight, preferably 0.02~0.6 parts by weight in turn.

It, can be to viscous for example, according to the purposes used in addition, adhesive composition can contain other known additive Suitably added in mixture composite the powders such as colorant, pigment, dyestuff, surfactant, plasticizer, adhesiveness imparting agent, It is surface lubricant, levelling agent, softening agent, antioxidant, antiaging agent, light stabilizer, ultraviolet absorbing agent, polymerization inhibitor, inorganic Or organic filler, metal powder, particle shape, foil-like object etc..Furthermore it is possible to using added with reduction in controllable range The redox system of agent.

The thickness of adhesive phase is not particularly limited, for example, 1~100 μm or so, preferably 2~50 μm, more preferably 3 ~30 μm.By keeping the thickness of adhesive phase thinning, the total amount decline of the acid in adhesive phase.Acid ingredient will not as a result, The wiring of perishable substrate.In addition, adhesive phase possessed by the 2nd layer can be adjusted according to the thickness of chimeric flexible printed board It is whole.

Protective layer

In an embodiment of the invention, aforementioned polarizer can be the shape with protective layer more than at least one layer State can be located at the one side for foring the polaroid of polarizer, alternatively, can be located in the case where polaroid has phase separation layer The face opposite with polaroid of phase separation layer.

It as protective layer, is not particularly limited, as long as the transparency, mechanical strength, thermal stability, moisture barrier, each The film excellent to the same sex etc..Specifically, polyethylene terephthalate, poly- M-phthalic acid ethylene glycol can be enumerated The polyester mesentery such as ester, polybutylene terephthalate (PBT)；The celluloses mesentery such as diacetyl cellulose, triacetyl cellulose；Poly- carbon Acid esters mesentery；The acrylic acid mesenteries such as poly- (methyl) methyl acrylate, poly- (methyl) ethyl acrylate；Polystyrene, acrylonitrile-benzene The styrene mesentery such as ethylene copolymer；Cycloolefin, cyclic olefine copolymer, polynorbornene, polypropylene, polyethylene, ethylene, propylene The polyolefin mesenteries such as copolymer；Vinyl chloride mesentery；The polyamide mesentery such as nylon, aromatic polyamide；Acid imide mesentery；Sulfone system Film；Polyether-ketone mesentery；Polyphenylene sulfide mesentery；Vinyl alcohol mesentery；Vinylidene chloride mesentery；Vinyl butyral mesentery；Arylation Object mesentery；Polyformaldehyde mesentery；Carbamate mesentery；Epoxy mesentery；Silicon systems film etc..In these, it is contemplated that polarized light property is resistance to Long property particularly preferably has the cellulose mesentery on the surface being saponified using alkali etc..In addition, protective layer, which can be, has both phase The layer of optical compensation function as potential difference function.

Aforementioned protective layer, which can be, implements for mentioning the face Nian Jie with aforementioned polaroid or Such phase differences coating layer The protective layer of the easy bonding processing of high bonding force.Easy bonding processing is not particularly limited, as long as the processing of bonding force can be improved , the dry process such as prime treatment, corona treatment, sided corona treatment can be enumerated；Alkali process (saponification process) etc. is changed Processing；Low pressure UV processing etc..

Touch sensor

Touch sensor have substrate, be set lower electrode on base material, the upper electrode opposite with lower electrode, The insulating layer clamped by lower electrode and upper electrode.

Various resin films can be used in substrate, as long as the flexible resin(a) film with translucency.For example, as substrate, The above-mentioned material as transparent substrate can be used and the film enumerated.

Lower electrode is for example under vertical view with multiple small electrodes of square shape.Multiple small electrodes are arranged in rectangular.

In addition, an adjacent small electrode of diagonal along small electrode is connected to each other for multiple small electrodes, Form multiple electrodes column.Multiple electrodes are listed in end interconnection, can detect the capacitor between adjacent electrodes series.

Upper electrode is for example under vertical view with multiple small electrodes of square shape.Multiple small electrodes are under vertical view in not matching Set complementally be arranged on the position of lower electrode it is rectangular.That is, upper electrode and lower electrode are seamlessly matched under vertical view It sets.

In addition, the small electrode adjacent along another diagonal of small electrode connects each other for multiple small electrodes It connects, forms multiple electrodes column.Multiple electrodes are listed in end interconnection, can detect the capacitor between adjacent electrodes series.

Insulating layer insulate lower electrode and upper electrode.About the forming material of insulating layer, it can be used and passed as touch The material that the material of the insulating layer of sensor is usually known.

It should be noted that being the touching of so-called projection type electrostatic capacitance method to touch sensor in present embodiment The example for touching sensor is illustrated, but can also in the range of not damaging The effect of invention using film resistor mode etc. its The touch sensor of his mode.

Light-shielding pattern

Aforementioned light-shielding pattern can be used as fenestrated membrane or can be using the frame (bezel) or shell of the display device of fenestrated membrane (housing) at least part and provide.For example, sometimes through light-shielding pattern by each cloth line concealing of aforementioned display, Do not observe user.The color and/or material of light-shielding pattern are not particularly limited, can be by with black, white, gold etc. The resinous substances of multiple color is formed.For example, light-shielding pattern can be by being mixed with the acrylic acid series tree of the pigment of color for rendering The resinous substances such as rouge, ester system resin, epoxy system resin, polyurethane, polysiloxanes (silicone) are formed.Aforementioned light-shielding pattern Protection and the flexible characteristic of fenestrated membrane or display device can be considered to determine in material and thickness.In addition, they can be used alone, Or it can also be used in the form of mixture of more than two kinds.

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, is quality % and mass parts.The present invention is not restricted by the embodiments.

Production Example 1: the high molecular preparation of clear polyimides system

Prepare reactor and oil bath made of installation silicone tube, agitating device and thermometer in removable flask.To this 4,4 '-bis- (trifluoromethyl) -4 (hexafluoroisopropyli,ene) diphthalic anhydrides (6FDA) 75.52g and 2,2 '-are put into flask, 4 '-benzidines (TFMB) 54.44g.DMAC N,N' dimethyl acetamide is added while being stirred with 400rpm to it (DMAc) 519.84g is stirred continuously until that the content of flask becomes uniform solution.Next, will be held using oil bath on one side Temperature is adjusted to 20~30 DEG C of range in device, further persistently carries out stirring for 20 hours on one side, makes its reaction, generate polyamide Acid.After 30 minutes, mixing speed is changed to 100rpm.After carrying out stirring in 20 hours, temperature of reaction system is restored to room temperature, DMAc 649.8g is added, polymer concentration is adjusted to 10 weight %.And then pyridine 32.27g, acetic anhydride 41.65g are added, It carries out stirring for 10 hours at room temperature, carries out imidizate.Polyimide varnish is taken out from reaction vessel.By obtained polyamides Asia Amine varnish is added dropwise in methanol, is carried out reprecipitation, is thermally dried to obtained powder, solvent is removed, with solid state component Form obtains clear polyimides system macromolecule.GPC measurement is carried out to obtained polyimides system macromolecule, as a result, divide equally again Son amount is 360,000.

Production Example 2: the high molecular preparation of transparent polyamide imide series

In a nitrogen atmosphere, into the removable flask of 1L for having stirring blade, add TFMB50g (156.13mmol) and TFMB is dissolved in DMAc while stirring by DMAc 642.07g at room temperature.Next, adding 6FDA into flask 20.84g (46.91mmol), carries out stirring for 3 hours at room temperature.Then, by 4,4 '-oxygroups bis- (chlorobenzoyl chlorides) (OBBC, 4, 4 '-oxybis (benzoyl chloride)) 9.23g (31.27mmol) and subsequent paraphthaloyl chloride (TPC) 15.87g (78.18mmol) is added in flask, carries out stirring for 1 hour at room temperature.Next, adding 4- methyl into flask Pyridine 9.89g (106.17mmol) and acetic anhydride 14.37g (140.73mmol), carries out stirring for 30 minutes at room temperature, then, 70 DEG C are warming up to using oil bath, stirs within further progress 3 hours, obtains 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, obtain transparent poly- Amide imide system macromolecule.GPC measurement is carried out to obtained polyamidoimide system macromolecule, as a result, weight average molecular weight is 420,000。

Production Example 3: the preparation of silica solution

By the amorphous silicon for being 27nm using the BET diameter (average grain diameter measured using BET method) of sol-gel method production Colloidal sol is replaced as raw material by solvent, and the silica solution of gamma-butyrolacton (hereinafter, being sometimes also indicated as GBL) displacement is prepared.With Mesh is that 10 μm of molecular filter is filtered obtained colloidal sol, obtains GBL displacement silica solution.Obtained GBL displacement silica solution In, silicon dioxide granule is 30~32 mass %.

Embodiment 1

The clear polyimides system macromolecule as obtained from above-mentioned Production Example 1 is molten with 16.5% solid component concentration Solution obtains resin varnish in mixed solvent (it is made of 1:9 mixing gamma-butyrolacton (GBL) and DMAc).Utilize casting The resin varnish, is coated on the width of 870mm and is with a thickness of 193 μm of (5 μm of PET188 μm+hard conating), width by method The Martens hardness that 900mm, casting are film-made surface side (that is, hard conating surface side) is 410N/mm²Strip it is poly- with hard conating On ethylene glycol terephthalate (PET) film supporting mass (supporting mass A: matrix resin=PET has HC processing), it is filmed.Make Be made the resin varnish of film with 0.4m/ minutes linear speeds from length in the furnace of 12m (to its temperature carried out set so that its Periodically become 120 DEG C from 70 DEG C) pass through, solvent is removed from resin solution thus, forms transparent resin film (with a thickness of 80 μm).Then, protective film (Toray Advanced Film Co., Ltd. Toretec (registration is bonded on transparent resin film Trade mark) 7332K, the polyolefin protective film of weak bonding force), will be by protective film, transparent resin film and PET film structure with hard conating At membranaceous laminated body be wound in core and form web-like.

The disbonded test of laminated body

Obtained laminated body is wound in the columned stick of specified diameter with 180 degree, in this state, stands 1 minute, Then, confirm by visual observation whether peeling-off between supporting mass and transparent resin film.Even if a part of peeling-off, also regard It is peeling-off.

The laminated body obtained in embodiment 1 implement disbonded test, as a result, with 180 degree be wound in diameter 100mm, 80mm, It is not peeling-off in the case where each columned stick of 60mm, 40mm, 20mm.

On one side by the above laminated body debatching of wound into rolls, supporting mass A is removed on one side, it will be by transparent resin film The laminated body winding constituted with protective film.

The laminated body of transparent resin film and protective film obtained in above-described embodiment 1 removes protective film, according to lower section Formula evaluates scar.In addition, mist degree, total light transmittance, yellow colour index, residual solvent amount are also according to the side of following record Formula is measured.Show the result in table 1.

Scar evaluation

To the transparent resin film irradiation POLARION corporation HID portable searchlight PS-X1 removed from supporting mass, (light is logical Amount is 3400 lumens), confirm the presence or absence of scar by visual observation.At this point, firstly, from the direction of travel irradiation light of film, to scar The presence or absence of confirmed, next, also irradiation light in the width direction, confirms scar.In addition, to fall relative to film surface 20~70 ° or so of angular illumination light.Carry out visuognosis direction are as follows: from the face of the transparent resin film to be evaluated substantially just Top (being in 90 ° of angle with resin film surface) carries out.It should be noted that on the face opposite with supporting mass of transparent resin film In the case where being laminated with protective film, film stripping will be protected, the presence or absence of scar is confirmed.

Evaluation criteria

◎: scar is not observed

〇: scar is slightly observed

×: clearly observe scar.

The result that scar is evaluated is recorded in table 1.

Mist degree

According to JIS K7105:1981, the full-automatic direct-reading mist of Suga Test Instruments Co., Ltd. is utilized Spend the mist degree of computer (Haze Computer) HGM-2DP measurement transparent resin film.Show the result in table 1.It needs to illustrate It is that in the case where being laminated with protective film on the face opposite with supporting mass of transparent resin film, film stripping will be protected, measure mist Degree.

Total light transmittance

According to JIS K7105:1981, the full-automatic direct-reading mist of Suga Test Instruments Co., Ltd. is utilized Computer HGM-2DP is spent, the total light transmittance of transparent resin film is measured.Show the result in table 1.It should be noted that saturating In the case where being laminated with protective film on the face opposite with supporting mass of ming tree adipose membrane, film stripping will be protected, measures full light and penetrate Rate.

Yellow colour index (yellow chromaticity: YI value)

Using the UV, visible light near infrared spectrometer V-670 of Japan's light splitting corporation, the Huang of transparent resin film is measured Colour index (yellow chromaticity: YI value).Background measurement is carried out in the state of no sample, and transparent resin film is then set to sample Frame is measured the transmitance of the light relative to 300nm~800nm, finds out tristimulus values (X, Y, Z).It is calculated based on following formula YI value.It should be noted that will be protected in the case where being laminated with protective film on the face opposite with supporting mass of transparent resin film Film stripping measures yellow colour index.

Value=100 YI × (1.2769X-1.0592Z)/Y

The measuring method of residual solvent amount

Hot weight-differential heat (TG-DTA) measurement

As the measurement device of TG-DTA, Hitachi High-Tech Science Corporation TG/ is used DTA6300.The sample of about 20mg is obtained from the transparent resin film of production.By the sample with 10 DEG C/min of heating rate from room Temperature is warming up to 120 DEG C, keeps 5 minutes in 120 DEG C, then heats up (heating) to 400 DEG C, together with 10 DEG C/min of heating rate When measure sample mass change.

By TG-DTA measurement result, according to the following formula, the rate of mass reduction S (quality %) from 120 DEG C to 250 DEG C is calculated.

S (quality %)=100- (W1/W0) × 100

(in formula, W0 is the quality that sample after five minutes is kept in 120 DEG C, the quality of sample when W1 is 250 DEG C).

Using the rate of mass reduction S of calculating as the residual solvent amount S (quality %) in transparent resin film.It needs to illustrate It is that, in the case where being laminated with protective film on the face opposite with supporting mass of transparent resin film, film stripping, measurement residual will be protected Quantity of solvent.

The measurement of elasticity modulus

Drying in 20 minutes is carried out to transparent resin film in 200 DEG C, using dumbbell cutter, be cut to 10mm × The strip of 100mm, obtains sample.For the elasticity modulus of the sample, (strain) Shimadzu Seisakusho Ltd. autoplotter is used (Autograph) AG-IS measures S-S curve under conditions of distance is 500mm between collet, tensile speed is 20mm/ minutes, The elasticity modulus of optical film is calculated by its slope.Record the result in table 1.

For supporting mass, measurement below is carried out.Show the result in table 1.

The measuring method of Martens hardness

Above-mentioned supporting mass is cut out to the size of 40mm × 40mm, is 20 μm of adhesive phase via film thickness then, will with pour The opposite face paste in the side being film-made is cast together in the glass of 40mm × 40mm.Cast for the supporting mass for having fitted in glass The face of film, in 23 DEG C, the atmosphere of 55%RH, using the small hardness tester of ultra micro (FISCHERSCOPE HM2000: Fischer Instruments K.K. system), using Vickers indenter, load was applied with 0.5mN/5 seconds pressing speeds, then, It is kept for 5 seconds in the state of maintaining the load of 0.5mN, measures Martens hardness.It should be noted that the measurement of Martens hardness is directed to Supporting mass before carrying out casting film is implemented.

The measurement of arithmetic average roughness (Ra) and maximum height (Rz)

For the face for carrying out casting film of above-mentioned supporting mass, the Surfcorder of little Ban research institute corporation is used ET3000 measures arithmetic average roughness (Ra) and maximum height (Rz) according to JIS B0601-2001.Show the result in table 1. It should be noted that the measurement of arithmetic average roughness (Ra) and maximum height (Rz) is for the bearing carried out before casting film Body is implemented.

The laminated body of the protective film of embodiment 1 and transparent resin film is rolled up into debatching on one side, film stripping will be protected on one side, together When, transparent resin film is directed into drying oven, further progress is dry (formal dry).The temperature of drying oven is set as 200 DEG C, conveying speed is set as 1.0m/ minutes, 12 minutes will be set as drying time.For with saturating after kiln dried Ming tree adipose membrane is bonded protective film (Toray Advanced Film Co., Ltd. Toretec (registered trademark) in one side 7332K, the polyolefin protective film of weak bonding force), it is wound in core.Film stripping will be protected, the transparent tree after measuring formal drying The residual solvent amount of adipose membrane, result 1%.Transparent resin film obtained in formal drying also can be used as the use of fenestrated membrane substrate.

Embodiment 2

By transparent polyamide imide series macromolecule dissolution obtained in Production Example 2 in GBL, adds in Production Example 3 and obtain The GBL displacement silica solution arrived, is sufficiently mixed, and obtains the transparent polyamide imide series high score of composition recorded in table 1 as a result, Son/silicon dioxide granule mixing varnish (hereinafter, sometimes referred to as mixing varnish).At this point, with polyamidoimide system macromolecule/bis- Silicon oxide particle concentration (concentration for the gross mass of resin and silicon dioxide granule) becomes the mode of 10 mass % Preparation mixing varnish.Then, using casting method, obtained mixing varnish is coated on a thickness of 193 μm with the width of 870mm The Martens hardness that (5 μm of PET188 μm+hard conating), width 900mm, casting are film-made surface side (that is, hard conating surface side) is 406N/ mm²Strip with hard conating polyethylene terephthalate (PET) film supporting mass (supporting mass B: matrix resin= PET has HC processing) on, it is filmed.Make furnace of the mixing varnish that film has been made with 0.4m/ minutes linear speeds from length 12m Interior (having carried out setting so that it periodically becomes 120 DEG C from 70 DEG C to its temperature) passes through, thus by solvent from resin solution It removes, is formed transparent resin film (with a thickness of 50 μm).Then, protective film (Toray Advanced is bonded on transparent resin film Film Co., Ltd. Toretec (registered trademark) 7332K, the polyolefin protective film of weak bonding force), it will be by protective film, transparent Resin film and the membranaceous laminated body of the PET film composition with hard conating are wound in core and form web-like.

The laminated body obtained in embodiment 2 implement disbonded test, as a result, with 180 degree be wound in diameter 100mm, 80mm, It is not peeling-off in the case where each columned stick of 60mm, 40mm, 20mm.

On one side by the above laminated body debatching of wound into rolls, supporting mass B is removed on one side, it will be by transparent resin film The laminated body winding constituted with protective film.Using method similarly to Example 1, the transparent resin of protective film has been removed The evaluation of the scar of film, the evaluation of mist degree, total light transmittance, yellow colour index and residual solvent amount.Show the result in table 1.

The laminated body of the protective film of embodiment 2 and transparent resin film is rolled up into debatching on one side, film stripping will be protected on one side, together When, transparent resin film is directed into drying oven, further progress is dry (formal dry).The temperature of drying oven is set as 200 DEG C, conveying speed is set as 1.0m/ minutes, 12 minutes will be set as drying time.For with saturating after kiln dried Ming tree adipose membrane is bonded protective film (Toray Advanced Film Co., Ltd. Toretec (registered trademark) in one side 7332K, the polyolefin protective film of weak bonding force), it is wound in core.Film stripping will be protected, the transparent tree after measuring formal drying The residual solvent amount of adipose membrane, result 0.6%.Transparent resin film obtained in formal drying also can be used as the use of fenestrated membrane substrate.

Embodiment 3

As supporting mass, using with a thickness of 193 μm (5 μm of PET188 μm+hard conatings), width 900mm, casting film face The Martens hardness of side (that is, hard conating surface side) is 382N/mm²Strip the polyethylene terephthalate with hard conating Ester (PET) film (supporting mass C: matrix resin=PET has HC processing), in addition to this, be performed in the same manner as in Example 2 processing, obtains To the volume for the laminated body being made of protective film, transparent resin film and PET film with hard conating.

The laminated body obtained in embodiment 3 implement disbonded test, as a result, with 180 degree be wound in diameter 100mm, 80mm, It is not peeling-off in the case where each columned stick of 60mm, 40mm, 20mm.

On one side by the above laminated body debatching of wound into rolls, supporting mass C is removed on one side, it will be by transparent resin film The laminated body winding constituted with protective film.Using method similarly to Example 1, the transparent resin of protective film has been removed The evaluation of the scar of film, the evaluation of mist degree, total light transmittance, yellow colour index and residual solvent amount.Show the result in table 1.

The laminated body of the protective film of embodiment 3 and transparent resin film is rolled up into debatching on one side, film stripping will be protected on one side, together When, transparent resin film is directed into drying oven, further progress is dry (formal dry).The temperature of drying oven is set as 200 DEG C, conveying speed is set as 1.0m/ minutes, 12 minutes will be set as drying time.For with saturating after kiln dried Ming tree adipose membrane is bonded protective film (Toray Advanced Film Co., Ltd. Toretec (registered trademark) in one side 7332K, the polyolefin protective film of weak bonding force), it is wound in core.Film stripping will be protected, the transparent tree after measuring formal drying The residual solvent amount of adipose membrane, result 0.6%.Transparent resin film obtained in formal drying also can be used as the use of fenestrated membrane substrate.

Embodiment 4

The production of supporting mass D

Hard conating coating fluid is prepared with following formulas.

* a: by Miwon Specialty Chemical Co., Miramer SP1114 that Ltd. is sold on the market (Gu State ingredient 100%)

* b: the BEAMSET 575 (solid state component 100%) sold on the market by Arakawa Chemical Industries, Ltd.

* c: the Irgacure 651 sold on the market by BASF Japan Co., Ltd.

Above-mentioned formula is mixed, hard conating coating fluid is made.It, will be with a thickness of 188 μm using micro- gravure coating apparatus PET film volume (Co. Ltd. system COSMOSHINE A4100 spins in Japan) unreels, and obtained hard conating is coated on coating fluid The easy bonding process face for stating PET film, makes it dry, then with high voltage mercury lamp radiation ultraviolet light (exposure 400mJ/cm²), shape At the hard conating with a thickness of 3 μm, be wound into a roll shape, obtain having hard conating PET film volume (supporting mass D: matrix resin= PET has HC processing).The Martens hardness of casting film face (that is, hard conating face) is 330N/mm²。

The formation of transparent resin film

In addition to this supporting mass as casting film, using method similarly to Example 2, is obtained using supporting mass D To the volume for the laminated body being made of protective film, transparent resin film and PET film with hard conating.

The laminated body obtained in embodiment 4 implement disbonded test, as a result, with 180 degree be wound in diameter 100mm, 80mm, It is not peeling-off in the case where each columned stick of 60mm, 40mm, 20mm.

On one side by the above laminated body debatching of wound into rolls, supporting mass D is removed on one side, it will be by transparent resin film The laminated body winding constituted with protective film.Using method similarly to Example 1, the transparent resin of protective film has been removed The evaluation of the scar of film, the evaluation of mist degree, total light transmittance, yellow colour index and residual solvent amount.Show the result in table 1.

The laminated body of the protective film of embodiment 4 and transparent resin film is rolled up into debatching on one side, film stripping will be protected on one side, together When, transparent resin film is directed into drying oven, further progress is dry (formal dry).The temperature of drying oven is set as 200 DEG C, conveying speed is set as 1.0m/ minutes, 12 minutes will be set as drying time.For with saturating after kiln dried Ming tree adipose membrane is bonded protective film (Toray Advanced Film Co., Ltd. Toretec (registered trademark) in one side 7332K, the polyolefin protective film of weak bonding force), it is wound in core.Film stripping will be protected, the transparent tree after measuring formal drying The residual solvent amount of adipose membrane, result 0.6%.Transparent resin film obtained in formal drying also can be used as the use of fenestrated membrane substrate.

Embodiment 5

The production of supporting mass E

Into the autoclave for having agitating device, dipentaerythritol (wide honor chemical industry is packed into the ratio of following records Co. Ltd. system, OH value 1324) 87.1%, distilled water 12.8%, KOH 0.1%, 90 DEG C are warming up to, is stirred, slurry is made Expect the liquid of shape.It will be 1.078 times of ring for the charge of aforementioned dipentaerythritol next, being heated to 130 DEG C Oxidative ethane is slowly directed into autoclave, makes its reaction.With the importing of ethylene oxide, high pressure temperature in the kettle rises.At any time into Row cooling, remains 140 DEG C or less for reaction temperature.After reaction, by 140 DEG C to be subtracted below 10 millimetress of mercury Pressure removes the polymer of excessive ethylene oxide, the ethylene glycol generated as by-product.Then, it is neutralized with acetic acid, PH is adjusted to 6~7.With for the hardening resin composition 100g obtained in the manner described above for 3g (solid-state at Point) ratio add BASF Japan Co. Ltd. system Irgacure 184 as Photoepolymerizationinitiater initiater, on one side with 60 DEG C Hot bath is heated, and is melted in initiator in resin on one side, obtains hard conating coating fluid.

Using micro- gravure coating apparatus, (Dongyang spinning company COSMOSHINE will be rolled up with a thickness of 188 μm of PET film Above-mentioned hard conating is coated on the easy bonding process face of above-mentioned PET film, after making it dry, with gold by A4100) debatching with coating fluid Belong to halide lamp and irradiates ultraviolet light (exposure 400mJ/cm²), the hard conating with a thickness of 3 μm is formed, shape is wound into a roll, obtains (supporting mass E: matrix resin=PET has HC processing) is rolled up to the PET film with hard conating.Martens hardness is 310N/mm²。

The formation of transparent resin film

In addition to this supporting mass as casting film, using method similarly to Example 2, is obtained using supporting mass E To the volume for the laminated body being made of protective film, transparent resin film and PET film with hard conating.

The laminated body obtained in embodiment 5 implement disbonded test, as a result, with 180 degree be wound in diameter 100mm, 80mm, It is not peeling-off in the case where each columned stick of 60mm, 40mm, 20mm.

On one side by the above laminated body debatching of wound into rolls, supporting mass E is removed on one side, it will be by transparent resin film The laminated body winding constituted with protective film.Using method similarly to Example 1, the transparent resin of protective film has been removed The evaluation of the scar of film, the evaluation of mist degree, total light transmittance, yellow colour index and residual solvent amount.Show the result in table 1.

The laminated body of the protective film of embodiment 5 and transparent resin film is rolled up into debatching on one side, film stripping will be protected on one side, together When, transparent resin film is directed into drying oven, further progress is dry (formal dry).The temperature of drying oven is set as 200 DEG C, conveying speed is set as 1.0m/ minutes, 12 minutes will be set as drying time.For with saturating after kiln dried Ming tree adipose membrane is bonded protective film (Toray Advanced Film Co., Ltd. Toretec (registered trademark) in one side 7332K, the polyolefin protective film of weak bonding force), it is wound in core.Film stripping will be protected, the transparent tree after measuring formal drying The residual solvent amount of adipose membrane, result 0.6%.Transparent resin film obtained in formal drying also can be used as the use of fenestrated membrane substrate.

Comparative example 1

It the use of Martens hardness is 268N/mm as supporting mass²PET film (Japan spin Co. Ltd. system COSMOSHINE A4100: matrix resin=PET, no HC processing), it in addition to this, is handled similarly to Example 1, also determines physical property Value.Show the result in table 1.It should be noted that casting film face, the i.e. Martens hardness aspect of measure of supporting mass is and above-mentioned PET The opposite face of the easy sliding process face of film.

The laminated body obtained in comparative example 1 implement disbonded test, as a result, with 180 degree be wound in diameter 100mm, 80mm, It is not peeling-off in the case where each columned stick of 60mm, 40mm, 20mm.

On one side by the above laminated body debatching of wound into rolls, supporting mass is removed on one side, it will be by transparent resin film The laminated body winding constituted with protective film.Using method similarly to Example 1, the transparent resin of protective film has been removed The evaluation of the scar of film, the evaluation of mist degree, total light transmittance, yellow colour index and residual solvent amount.Show the result in table 1.

Comparative example 2

It the use of Martens hardness is 268N/mm as supporting mass²PET film (Dongyang spinning company COSMOSHINE A4100: matrix resin=PET, no HC processing), in addition to this, be performed in the same manner as in Example 2 processing, also determines physical property Value.Show the result in table 1.It should be noted that casting film face, the i.e. Martens hardness aspect of measure of supporting mass is and above-mentioned PET The opposite face of the easy sliding process face of film.

The laminated body obtained in comparative example 2 implement disbonded test, as a result, with 180 degree be wound in diameter 100mm, 80mm, It is not peeling-off in the case where each columned stick of 60mm, 40mm, 20mm.

On one side by the above laminated body debatching of wound into rolls, supporting mass is removed on one side, it will be by transparent resin film The laminated body winding constituted with protective film.Using method similarly to Example 1, the transparent resin of protective film has been removed The evaluation of the scar of film, the evaluation of mist degree, total light transmittance, yellow colour index and residual solvent amount.Show the result in table 1.

[table 1]

In above-described embodiment and comparative example, there are scars on the deflector roll of conveying supporting mass, but in embodiment, are obtaining Transparent resin film on do not confirm the presence of scar and confirmed scar on obtained transparent resin film in a comparative example Presence.It is thought that since the Martens hardness of the side of the coating transparent resin film of supporting mass is not specified value (300N/mm²) Caused by above.The photo with scar of comparative example 1 is recorded in Figure of description as Fig. 3.Positioned at two arrows Between white portion be scar, the scar be 10mm long, with identical as the periphery of deflector roll on the transparent resin film of comparative example 1 Period generate.

Industrial availability

Laminated body of the invention is the product used when manufacturing transparent resin film, is when can be reduced manufacture transparent resin film Defect product, yield rate improved, moreover it is possible to reduce manufacturing cost.

Claims (13)

1. laminated body is the laminated body that supporting mass and transparent resin film are strippingly laminated, which is characterized in that the branch The Martens hardness for holding the side of body contacted with the transparent resin film is 300N/mm²More than.

2. laminated body as described in claim 1, wherein the transparent resin film is polyimides mesentery.

3. laminated body as claimed in claim 1 or 2, wherein the transparent resin film is that mist degree is that 1% or less, full light is saturating The rate of mistake is 85% or more, yellow colour index is 4 polyimides mesenterys below.

4. laminated body according to any one of claims 1 to 3, wherein the supporting mass is resin film.

5. laminated body as described in any one of claims 1 to 4, wherein the supporting mass is the resin for being provided with hard conating Film.

6. such as laminated body according to any one of claims 1 to 5, wherein the supporting mass is poly- to benzene with hard conating Naphthalate film, cycloolefin mesentery, acrylic acid mesentery, poly (ethylene naphthalate) film, polypropylene screen, triacetyl are fine Tie up any one of plain film.

7. such as laminated body according to any one of claims 1 to 6, wherein the supporting mass connects with the transparent resin film Arithmetic average roughness (Ra) specified in the JIS B0601-2001 of the side of touching is 0.01 μm or less.

8. such as laminated body according to any one of claims 1 to 7, wherein the supporting mass connects with the transparent resin film Maximum height (Rz) specified in the JIS B0601-2001 of the side of touching is 0.1 μm or less.

9. laminated body film roll, being will be obtained from laminated body according to any one of claims 1 to 8 winding.

10. the manufacturing method of laminated body described in claim 1 comprising following step:

A) Martens hardness in the side of resin varnish to be coated with is 300N/mm²On above supporting mass, coating will be used to form Resin varnish obtained from the resin combination of transparent resin film is mixed and is stirred with solvent；And

B) by keeping be coated with resin varnish dry to remove solvent, the layer of transparent resin film is formed on supporting mass.

11. fenestrated membrane substrate is the transparent tree by will remove from laminated body according to any one of claims 1 to 8 Obtained from adipose membrane further progress solvent seasoning processing.

12. fenestrated membrane is to be formed at least one face of the fenestrated membrane substrate described in claim 11 comprising window hard conating.

13. optical laminate is the optical laminate comprising fenestrated membrane described in claim 12, in a face of the fenestrated membrane On also comprising at least one layer in the group being made of polarizer and touch sensor.