CN105934335B

CN105934335B - Multilayer film and its manufacturing method

Info

Publication number: CN105934335B
Application number: CN201580005876.8A
Authority: CN
Inventors: 村田直纪
Original assignee: Nippon Zeon Co Ltd
Current assignee: Zeon Corp
Priority date: 2014-03-26
Filing date: 2015-03-24
Publication date: 2019-01-08
Anticipated expiration: 2035-03-24
Also published as: TWI661939B; CN110229366B; KR102382953B1; KR20160138381A; JPWO2015147013A1; CN105934335A; CN110229366A; JP6565901B2; TW201540510A; WO2015147013A1

Abstract

The purpose of the present invention is to provide a kind of multilayer films, its resin layer containing particle for having base material film and being set on the base material film, wherein, the resin layer with the face of the base material film opposite side have multiple protrusions, by the protrusion of (a) height 5nm in the protrusion in every 1mm²On quantity be set as N_AA/mm², (b) height 10nm protrusion in every 1mm²On quantity be set as N_BA/mm², (c) height 15nm protrusion in every 1mm²On quantity be set as N_CA/mm², (d) height 20nm protrusion in every 1mm²On quantity be set as N_DA/mm², (e) height 25nm protrusion in every 1mm²On quantity be set as N_EA/mm², (f) height 30nm protrusion in every 1mm²On quantity be set as N_FA/mm²When, with G=N_A/N_FThe value G of expression is 3.5≤G≤7, and N_B≥N_C≥N_D≥N_E≥N_F。

Description

Multilayer film and its manufacturing method

Technical field

The present invention relates to multilayer film and its manufacturing methods.

Background technique

It is known in the state of the art to have the multilayer film (referring to patent document 1 with 2) for having multiple layers.Such multilayer film can Realization is combined with multiple functions obtained from characteristic possessed by each layer, because due to be applied to extensive use.For example, being used for In the optical film of the various image display devices such as liquid crystal display device, organic EL display device, plasma scope, also sometimes It will use multilayer film.

From the viewpoint of improving manufacture efficiency, multilayer film as described above is manufactured into the form of the film of strip more.This Outside, the multilayer film of such strip is generally taken up into film roll, and is saved and is carried with the state of the film roll.

Further, it is also known that have technology as such as patent document 3.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2000-79664 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2010-264643 bulletin

Patent document 3: Japanese Unexamined Patent Publication 8-73623 bulletin

Summary of the invention

Problems to be solved by the invention

Strip multilayer film is being batched in the film roll that manufactures, can generate be referred to as " salient point ", width in some cases The defect of the convex of 1mm~3mm or so.The defect of convex if as described above is transferred to multilayer film, then is being transferred Part, multilayer film can deform, and there is a possibility that optical characteristics for damaging the part.

In addition, leading to because the defect is not to generate before batching multilayer film but generate after film roll manufacture Cross carried out on the production line of multilayer film check be difficult to detect.

And, if it is desired to detect drawbacks described above after film roll manufacture, then need to send out multilayer film successively from film roll and into Row checks, therefore needs to take time and effort to batch the multilayer film sent out successively again.Therefore, it is difficult to keeping film roll shape The film roll of not drawbacks described above is filtered out in the case where state.

In view of such background, it is desirable that develop the multilayer for being able to suppress drawbacks described above generation in the case where film roll is made Film.

In addition, generally requiring internal haze small in the optical film as such as phase difference film etc..It is such to internal mist Spending small requirement is also same in the case where the optical film is multilayer film.Therefore, for film roll is being made as described above In the case where be able to suppress convex defect generation multilayer film, be also required to reduce its internal haze.

The present invention in view of the above problems and complete, and it is an object of the present invention to provide: can press down in the case where batching and film roll is made It makes the generation of above-mentioned convex defect and the multilayer film and its manufacturing method of internal haze can be reduced.

Solution to the problem

The present inventor has made intensive studies in order to solve the above problem, as a result, it has been found that: having base material film and comprising particle Resin layer multilayer film in, there is different prominent of height with given regularity in resin layer and the face of base material film opposite side The multilayer film risen is able to suppress the generation of convex defect, and can reduce multilayer film when film roll is made in the multilayer film Internal haze.So as to complete the present invention.

That is, the present invention is as follows.

[1] a kind of multilayer film, the resin layer containing particle for having base material film and being set on the base material film；Institute It is stating resin layer that there are multiple protrusions with base material film opposite side face, by the protrusion of (a) height 5nm in the protrusion In every 1mm²On quantity be set as N_AA/mm², (b) height 10nm protrusion in every 1mm²On quantity be set as N_BA/mm²、(c) The protrusion of height 15nm is in every 1mm²On quantity be set as N_CA/mm², (d) height 20nm protrusion in every 1mm²On quantity set For N_DA/mm², (e) height 25nm protrusion in every 1mm²On quantity be set as N_EA/mm², (f) height 30nm protrusion every 1mm²On quantity be set as N_FA/mm²When, with G=N_A/N_FThe value G of expression is 3.5≤G≤7, also, N_B≥N_C≥N_D≥N_E≥ N_F。

[2] multilayer film according to [1], wherein the resin layer includes polymer, and the polymer includes poly- ammonia Ester.

[3] multilayer film according to [1] or [2], wherein the particle includes the different a variety of particles of average grain diameter.

[4] multilayer film according to [3], wherein the particle includes the particle with the average grain diameter less than 150nm (S) particle (L) of the average grain diameter and with 150nm or more.

[5] multilayer film according to [1], wherein the resin layer includes polymer, and the particle includes to have to be less than The particle (S) of the average grain diameter of 150nm and the particle (L) of the average grain diameter with 150nm or more, the institute in the resin layer The amount of particle (S) is stated relative to 100 parts by weight of polymer, is 2 parts by weight or more and 24 parts by weight or less.

[6] multilayer film according to [1], wherein the resin layer includes polymer, and the particle includes to have to be less than The particle (S) of the average grain diameter of 150nm and the particle (L) of the average grain diameter with 150nm or more, the institute in the resin layer The amount of particle (L) is stated relative to 100 parts by weight of polymer, is 5 parts by weight or more and 20 parts by weight or less.

[7] multilayer film according to any one of [1]~[6], wherein the particle is silica.

[8] multilayer film according to any one of [1]~[7], wherein the resin layer with a thickness of 10nm or more and 100nm or less.

[9] multilayer film according to any one of [1]~[8], wherein the multilayer film is phase difference film.

[10] multilayer film according to any one of [1]~[8], wherein the multilayer film is polaroid protective film.

[11] a kind of manufacturing method of multilayer film is the manufacturing method of multilayer film described in any one of [1]~[10], Wherein, which includes:

The different a variety of particles of polymer and average grain diameter are obtained by mixing to the process of the resin of flow-like；

The resin of flow-like is coated on base material film and the process of the film that forms the resin；And

The film for making to be formed in the resin on base material film solidifies and/or the dry process for obtaining resin layer.

[12] manufacturing method of the multilayer film according to [11], wherein the particle includes with flat less than 150nm The equal particle (S) of partial size and the particle (L) of the average grain diameter with 150nm or more.

The effect of invention

Multilayer film of the invention is able to suppress the generation of convex defect in the case where batching and film roll is made, and can Reduce internal haze.

The manufacturing method of multilayer film according to the present invention can be manufactured and is able to suppress in the case where batching and film roll is made The generation of convex defect and the multilayer film that internal haze can be reduced.

Detailed description of the invention

[Fig. 1] Fig. 1 be cross-sectional view, it is schematically shown that one embodiment of the present invention relates to multilayer film one Example.

[Fig. 2] Fig. 2 is main view, it is schematically shown that in traditional film roll, generates wrinkle because of the cementation of film An example of situation.

[Fig. 3] Fig. 3 is for satisfaction 3.5≤G≤7 and N_B≥N_C≥N_D≥N_E≥N_FCondition multilayer film an example, Using the height of protrusion as horizontal axis, using number of projection as the distribution map of the longitudinal axis.

Symbol description

100 multilayer films

110 base material films

The face with resin layer opposite side of 111 base material films

120 resin layers

The face with base material film opposite side of 121 resin layers

122 protrusions

200 film rolls

210 wrinkles

220 winding off spindles

230 recess

Specific embodiment

Hereinafter, in conjunction with embodiment and example object, the present invention is described in detail, but the present invention is not limited to following Shown in embodiment and example object etc., can appoint in the range of not departing from claims of the present invention and its equivalency range The change of meaning ground is to implement.

In the following description, " (methyl) acrylic acid " includes both acrylic acid and methacrylic acid.In addition, " (methyl) Acrylate " includes both acrylate and methacrylate.

In the following description, " (co) polymer " includes both polymer and copolymer.

In addition, in the following description, the average grain diameter of particle then uses as long as no being particularly limited to and passes through laser diffraction Method measurement particle diameter distribution, the cumulative volume of calculating reaches 50% partial size from small particle side in the particle diameter distribution measured.

In the following description, the delay in direction is then Re=(nx-ny) × d as long as no being particularly limited in the face of film Represented value.In addition, the delay Rth of the thickness direction of film is value represented by Rth={ (nx+ny)/2-nz } × d.Here, Nx indicates the refractive index in the direction (face in direction) vertical with the thickness direction of film, providing the direction of largest refractive index.ny It indicates in the face of film in direction, the refractive index in the direction vertical with the direction of nx.Nz indicates the folding of the thickness direction of film Penetrate rate.The film thickness of d expression film.As long as no being particularly limited to, the measurement wavelength of the delay is 550nm.The delay can be used Commercially available measuring difference of phases device (for example, prince measures machines corporation system, " KOBRA-21ADH ") or Senarmont (Sai Na Cover) method measures.

In addition, " polarizing film " not only includes upright and outspoken component, it further include that there is flexibility as the film of such as resin Component.

[general introduction of 1. multilayer films]

Fig. 1 be schematically show one embodiment of the present invention relates to multilayer film 100 an example cross-sectional view.

As shown in Figure 1, one embodiment of the present invention relates to multilayer film 100 have: base material film 110 and setting In the resin layer 120 comprising particle on the base material film 110.In addition, the resin layer 120 with 110 opposite side of base material film Face 121 has multiple protrusions 122.In Fig. 1, symbol " T " indicates that the thickness of resin layer 120, symbol " H " indicate protrusion 122 Highly.As shown in Figure 1, the thickness T of resin layer 120 indicates the thickness in the region without protrusion 122 of resin layer 120.

In the multilayer film 100, the protrusion 122 positioned at the face of resin layer 120 121 meets: 3.5≤G≤7 and N_B≥N_C ≥N_D≥N_E≥N_F。

Here, described value G is with G=N_A/N_FThe value of expression.

In addition, N_A、N_B、N_C、N_D、N_EAnd N_FIndicate quantity below.

(a)N_A(unit: a/mm²) indicate the protrusion 122 with the face 121 of 110 opposite side of base material film for being located at resin layer 120 In, the protrusion of height 5nm is in every 1mm²On quantity.

(b)N_B(unit: a/mm²) indicate the protrusion 122 with the face 121 of 110 opposite side of base material film for being located at resin layer 120 In, the protrusion of height 10nm is in every 1mm²On quantity.

(c)N_C(unit: a/mm²) indicate the protrusion 122 with the face 121 of 110 opposite side of base material film for being located at resin layer 120 In, the protrusion of height 15nm is in every 1mm²On quantity.

(d)N_D(unit: a/mm²) indicate the protrusion 122 with the face 121 of 110 opposite side of base material film for being located at resin layer 120 In, the protrusion of height 20nm is in every 1mm²On quantity.

(e)N_E(unit: a/mm²) indicate the protrusion 122 with the face 121 of 110 opposite side of base material film for being located at resin layer 120 In, the protrusion of height 25nm is in every 1mm²On quantity.

(f)N_F(unit: a/mm²) indicate the protrusion 122 with the face 121 of 110 opposite side of base material film for being located at resin layer 120 In, the protrusion of height 30nm is in every 1mm²On quantity.

Here, in the value of the rising height, if it is considered that effective digital, then height 5nm indicate 4.5nm or more and 5.4nm following.In addition, similarly, if it is considered that effective digital, then height 10nm indicate 9.5nm or more and 10.4nm hereinafter, Height 15nm indicates 14.5nm or more and 15.4nm hereinafter, height 20nm indicates 19.5nm or more and 20.4nm hereinafter, height 25nm indicates 24.5nm or more and 25.4nm hereinafter, height 30nm indicates 29.5nm or more and 30.4nm or less.

By the way that with such composition, multilayer film 100 is able to suppress convex defect in the case where batching and film roll is made Generation, and internal haze can be reduced.

(1) inhibition about the generation of convex defect:

Multilayer film of the invention is able to suppress the reasons why generation of convex defect and non-determined, but people grinds according to the present invention Study carefully, can be presumed as follows.It should be noted that the present invention is not limited by supposition described below.

In the case where batching conventional film to manufacture film roll, cementation locally occurs sometimes for the film that wound is got up. In the part that cementation has occurred in this wise, the displacement of film is restricted.Therefore, when take-up, the tension for being applied to film can not divide It is dissipated to film entirety, unbalanced stress can be generated in film.And such unbalanced stress sometimes results in film roll and generates wrinkle.

Fig. 2 is shown schematically in traditional film roll 200, and the situation of wrinkle 210 is produced because of the cementation of film The main view of an example.As shown in Fig. 2, in the case where film roll being taken at winding off spindle 220 and manufacture film roll 200, the wrinkle 210 It is usually formed as polygon.Specifically, the recess 230 of polygon (usually diamond shape) can be in film roll 200 in most cases Are upwardly formed in axial direction and week it is multiple, and recess 230 the side for being equivalent to polygon position formed wrinkle 210.

Such wrinkle 210 can't make film generate substantially warpage when it just takes place.But if film roll is added To save, then because the self weight of film, the sinking degree (depth) of the recess 230 of above-mentioned polygon can be gradually increased.Then, if The sinking degree of the recess 230 increases, then is producing the part of wrinkle 210, the degree of the warpage of film increases.It is believed that If beyond elastic limit substantially warpage occurs for film, in the part of the warpage, film can be plastically deformed, and generation is referred to as The defect of the convex of " salient point ".

In contrast, as shown in Figure 1, being provided in satisfaction in resin layer 120 and the face 121 of base material film 110 opposite side State the multilayer film 100 of multiple protrusions 122 of condition, the excellent in sliding property in face 121.It may be speculated that due to resin layer 120 with The face 121 of 110 opposite side of base material film usually becomes the most surface of multilayer film 100, therefore by keeping the sliding property in the face 121 excellent It is different, in the case where batching multilayer film 100, it is able to suppress the cementation for the multilayer film 100 that wound is got up.Therefore, it is able to suppress The generation of wrinkle in film roll, so it is able to suppress the generation for being attributed to the convex defect of the wrinkle.

(2) about internal haze:

The method of sliding property as the face for improving film as described above, such as it is contemplated that protrusion is set on the face to increase The roughness in the big face.But in the case where rising height height, due to light such as the reflection and the refractions that are provided with the face of the protrusion Effect, will lead to Surface haze and is substantially increased, it is difficult to obtain optical film.For this purpose, present inventors studied set on the face of film Set the low protrusion for the degree for being able to maintain small Surface haze.

In addition, the resin layer is formed as the resin layer comprising particle.In general, in the resin layer comprising particle, Because of the amount of particle and the difference of size, the internal haze of resin layer can be substantially increased in some cases.Therefore, from suitable for optics From the viewpoint of film, preferably resin layer is designed, makes it possible to reduce internal haze.In general, in order to avoid internal haze Rising, preferred particle is small.In addition, the rising of internal haze caused by being mixed into of big particle and the hair of optical defect in order to prevent Life is, it is preferable to use particle of the same size.

Thus, the present inventor has attempted that small comprising size and the consistent particle of partial size resin layer is arranged on base material film, To the low protrusion of the setting height on the face of film.But the sliding property in the face with protrusion of the film obtained in this way is small, it is difficult to Inhibit the generation of convex defect in film roll.

Thus, the present inventor's prediction: if increasing the size of particle, increasing rising height, it is provided with the face of the protrusion Sliding property can improve.Then, the present inventor increases rising height, increases particle size, has carried out similar to the above Research.However, sliding property is also not fully enhanced even if increasing rising height, it is difficult to inhibit the generation of convex defect in film roll.

In addition, increasing protrusion quantity is considered being possible to improve the sliding property in the face with protrusion.But it is prominent in order to increase Quantity is played, needs to increase the quantity of particle.And if number of particles is excessive, due to the reflection and refraction of the inside of resin layer, It may cause internal haze increase.

In contrast, in multilayer film 100 shown in Fig. 1, in the face 121 with 110 opposite side of base material film of resin layer 120 It is provided with satisfaction 3.5≤G≤7 and N_B≥N_C≥N_D≥N_E≥N_FCondition protrusion 122.The condition (3.5≤G≤7 and N_B≥N_C≥N_D≥N_E≥N_F) be related to not will lead to the low protrusion 122 of the degree of Surface haze increase, indicate the height of the protrusion 122 The distribution of degree is wide and high protrusion quantity is less than low protrusion quantity.For meeting an example of the multilayer film 100 of the condition, Fig. 3 is shown Using the height of protrusion 122 as horizontal axis, using the quantity of protrusion 122 as the distribution map of the longitudinal axis.The condition indicates, with protrusion 122 height is horizontal axis, using the quantity of protrusion 122 as in distribution map as Fig. 3 of the longitudinal axis, the width at peak is wide and gentle, and And the vertex at peak is located at desired small range.Face 121 in this wise comprising the protrusion 122 with different height, has significantly high Sliding property.Traditionally it is not regarded as the low protrusion of the degree for being able to suppress Surface haze, it can be by adjusting its protrusion It is distributed to adjust the sliding property in the face with the protrusion.From the point of view of such traditional understanding, it may be said that by adjusting as described above Whole rising height is distributed to improve the sliding property in the face with the protrusion, this is unexpected effect.

Meet above-mentioned condition (3.5≤G≤7 and N in addition, having_B≥N_C≥N_D≥N_E≥N_F) protrusion resin layer, can Suitably the small particle of size and big particle combinations are used with passing through, to be manufactured using a small amount of particle.Due to energy The amount of particle is enough reduced, therefore can be avoided the increase of the internal haze as caused by the resin layer.

Therefore, even if multilayer film of the invention can also press down in the case where the particle as contained by resin layer forms protrusion It is film-made the generation of convex defect in volume, without causing internal haze to increase.Conventionally, never damage optical film is due It is smaller the more preferred using the size of particle in optical film from the viewpoint of characteristic, in addition, the partial size the consistent the more preferred.From in this way Traditional understanding from the point of view of, it may be said that be arranged by as described above using the small particle of size and big particle combinations interior The resin layer that portion's mist degree is small and surface slipperiness is excellent, this is unexpected effect.

[2. base material film]

As base material film, usually using the film of resin.As the resin for constituting base material film, can be used containing arbitrary poly- Close the resin of object.Wherein, as the resin for constituting base material film, preferred thermoplastic resin, particularly preferred ester ring type olefin resin.Rouge Ring type olefin resin is the resin comprising ester ring type olefin polymer, the transparency, agent of low hygroscopicity, dimensional stability and Lightness Equal excellents, are suitable for optical film.

In addition, base material film can be film only containing 1 layer of single layer structure, it is also possible to the more of the layer for having 2 layers or more The film of layer structure.In base material film situation with multi-layer structure, 1 layer or more in the layer that preferred substrates film has is by ester ring type Olefin resin is formed.

Ester ring type olefin polymer is the polymer in the structural unit of polymer with ester ring type structure, be can be used Polymer and side chain of the main chain with ester ring type structure have any polymer in the polymer of ester ring type structure.In addition, rouge Ring type olefin polymer can be used alone, two or more can also be applied in combination with arbitrary ratio.Wherein, from mechanical strong The polymer that the consideration of the viewpoints such as degree, heat resistance, preferably main chain contain ester ring type structure.

As ester ring type structure, for example: saturation ester ring type hydrocarbon (cycloalkane) structure, unsaturated ester ring type hydrocarbon (cycloolefin, cycloalkyne) structure etc..Wherein, consider from viewpoints such as mechanical strength, heat resistances, preferably cycloalkanes hydrocarbon structure and cycloolefin Structure, wherein particularly preferred cycloalkanes hydrocarbon structure.

With regard to constitute ester ring type structure carbon atom number for, the carbon atom number of each ester ring type structure be preferably 4 with Above, more preferably 5 or more, preferably 30 or less, more preferably 20 or less, particularly preferably 15 ranges below. Can make as a result, base material film mechanical strength, heat resistance and mouldability obtain high balance, therefore it is preferred that.

The ratio of the structural unit with ester ring type structure in ester ring type olefin polymer can be according to using purpose appropriate Selection, preferably 55 weight % or more, further preferably 70 weight % or more, particularly preferably 90 weight % or more.If The ratio of the structural unit with ester ring type structure in ester ring type olefin polymer in the range, then from the transparent of base material film It is preferred from the viewpoint of property and heat resistance.

As ester ring type olefin polymer, for example: the cyclic olefin polymerization of norbornene polymer, monocycle Object, cyclic conjugated diene polymer, alicyclic vinyl ring type hydrocarbon polymer and their hydride etc..Wherein, norbornene polymerization Object due to the transparency and good forming ability and it is preferred that.

As norbornene polymer, for example: with norbornene structure monomer ring-opening polymerization polymer or The ring-opening copolymer or their hydride of monomer and any monomer with norbornene structure；With norbornene structure Monomer addition polymer or monomer with norbornene structure and any monomer addition copolymer or their hydrogen Compound etc..Wherein, consider from the viewpoints such as the transparency, mouldability, heat resistance, agent of low hygroscopicity, dimensional stability, Lightness, especially It is preferred that the hydride of the ring-opening polymerization polymer of the monomer with norbornene structure and the monomer with norbornene structure are opened The hydride of ring copolymer.

As the monomer with norbornene structure, for example: bicyclic [2.2.1] hept-2-ene" (trivial name: drop Bornylene), tricyclic [4.3.0.1^2,5] decyl- 3,7- diene (trivial name: dicyclopentadiene), 7,8- benzo tricyclic [4.3.0.1^2,5] Decyl- 3- alkene (trivial name: nadic fluorenes), Fourth Ring [4.4.0.1^2,5.1^7,10] 12 carbon -3- alkene (trivial names: Fourth Ring Dodecylene) and the derivative (for example, with the derivative of substituent group on ring) of these compounds etc..Here, as substitution Base, for example: alkyl, alkylidene, polar group etc..In addition, these substituent groups are identical or different, multiple can be bonded Cyclization.In addition, can be used alone with the monomer of norbornene structure, can also be applied in combination with arbitrary ratio 2 kinds with On.

As the type of polar group, for example: hetero atom has heteroatomic atomic group etc..As miscellaneous original Son, for example: oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, halogen atom etc..As the specific example of polar group, It can enumerate: carboxyl, carbonyloxy group carbonyl, epoxy group, hydroxyl, oxygroup, ester group, silanol group, silicyl, amino, itrile group, sulphur Acidic group etc..

As any monomer that ring opening copolymer can occur with the monomer with norbornene structure, for example: ring The list cyclic olefin such as hexene, cycloheptene, cyclo-octene and its derivative；The cyclic conjugated dienes such as cyclohexadiene, cycloheptadiene and Its derivative etc..Any monomer that ring opening copolymer can occurs with the monomer with norbornene structure can be used alone, Two or more can be applied in combination with arbitrary ratio.

The ring-opening polymerization polymer of monomer with norbornene structure and and can be total with the monomer with norbornene structure The ring-opening copolymer of poly- any monomer, such as can be by carrying out monomer in the presence of well known ring-opening polymerization catalyst Polymerization is copolymerized to manufacture.

As any monomer that addition copolymerization can occur with the monomer with norbornene structure, for example: second The alpha-olefins of carbon atom numbers 2~20 such as alkene, propylene, 1- butylene and their derivative；The rings such as cyclobutane, cyclopentene, cyclohexene Alkene and their derivative；1,4- hexadiene, 4- methyl-1,4- hexadiene, 5- methyl-1, the non-conjugated dienes such as 4- hexadiene Deng.Wherein, preferred alpha-olefin, more preferable ethylene.In addition, appointing for addition copolymerization can occur with the monomer with norbornene structure Meaning monomer can be used alone, two or more can also be applied in combination with arbitrary ratio.

The addition polymer of monomer with norbornene structure and and can be total with the monomer with norbornene structure The addition copolymer of poly- any monomer, such as can be by carrying out monomer in the presence of well known addition polymerization catalysts Polymerization is copolymerized to manufacture.

As the cyclic olefin polymer of monocycle, for example: cyclohexene, cycloheptene, cyclo-octene etc. have monocycle Cyclic olefin monomers addition polymer.

As cyclic conjugated diene polymer, for example: make 1,3-butadiene, isoprene, chlorobutadiene etc. The addition polymer of conjugate diene monomer carries out polymer obtained from cyclization；Cyclopentadiene, cyclohexadiene etc. are cyclic annular altogether 1,2- the or 1,4- addition polymer of conjugated diene monomer；And their hydride etc..

As alicyclic vinyl ring type hydrocarbon polymer, for example: the ethylene such as vinylcyclohexene, vinyl cyclohexane The polymer and its hydride of base ester ring type hydrocarbon monomer；It will be by the vinyl aromatic hydrocarbons class list such as styrene, α-methylstyrene Hydride made of aromatic moieties contained in the polymer that body is polymerized are hydrogenated；Alicyclic vinyl ring type hydrocarbon monomer or The random copolymer that vinyl aromatic hydrocarbon monomer and any monomer that can be copolymerized with these vinyl aromatic hydrocarbon monomers are formed Or the hydride etc. of the aromatic ring of the copolymers such as block copolymer.As above-mentioned block copolymer, for example: diblock is total Polymers, triblock copolymer or segmented copolymer more than it and gradient block copolymers etc..

The weight average molecular weight (Mw) for constituting polymer contained in the resin of base material film is usually 10,000 or more, preferably 15,000 or more, more preferably 20,000 or more, usually 100,000 hereinafter, preferably 80, and 000 hereinafter, more preferably 50, 000 or less.Here, the weight average molecular weight is that hexamethylene is used to gather as solvent, by what gel permeation chromatography measured Isoprene or the weight average molecular weight of polystyrene conversion.It should be noted that in the case where sample does not dissolve in hexamethylene, Solvent of the toluene as gel permeation chromatography can be used.When weight average molecular weight is in such range, the machinery of multilayer film Intensity and molding processibility can obtain high balance, therefore it is preferred that.

Constitute the molecular weight distribution (weight average molecular weight (Mw)/number-average molecular weight of polymer contained in the resin of base material film It (Mn)) is usually 1.2 or more, preferably 1.5 or more, further preferably 1.8 or more, usually 3.5 hereinafter, preferably 3.0 Hereinafter, further preferably 2.7 or less.By making molecular weight distribution more than the lower limit value of above range, polymerization can be improved The productivity of object inhibits cost.In addition, by below the upper limit, it is possible to reduce low molecular weight compositions, therefore pine can be extended It relaxes the time.Therefore, the stability of base material film can be improved in relaxation when can inhibit to be exposed to high temperature.

The absolute value for constituting the photoelastic coefficient C of polymer contained in the resin of base material film is preferably 10 × 10^-12Pa^-1 Hereinafter, more preferably 7 × 10^-12Pa^-1Hereinafter, particularly preferably 4 × 10^-12Pa^-1Below.Δ n, stress are being set as by birefringent When being set as σ, photoelastic coefficient C is to be worth shown in " C=Δ n/ σ ".By making the photoelastic coefficient of polymer be in above range, It can reduce the deviation of the delay Re in direction in the face of base material film.

The saturated water absorption for constituting polymer contained in the resin of base material film is preferably 0.03 weight % hereinafter, further Preferably 0.02 weight % is hereinafter, particularly preferably 0.01 weight % or less.It, can be with if saturated water absorption is above range Reduce the ongoing change of the delay of the delay and thickness direction in direction in the face of base material film.It is additionally possible to suppress having the present invention Multilayer film polarizing film and image display device deterioration, the display stable for extended periods of time of display and good can be made.

Saturated water absorption be with test film is impregnated in the water of certain temperature after a certain period of time increased quality relative to The value that the percentage of the quality of test film indicates before impregnating.In general, in 23 DEG C of water immersion test piece 24 hours and surveyed It is fixed.The saturated water absorption of polymer for example can be adjusted to above range by reducing the amount of the polar group in polymer. Therefore, it from the viewpoint of further decreasing saturated water absorption, constitutes polymer contained in the resin of base material film and does not preferably have Polarized group.

As long as the effect of the present invention is not significantly impaired, then constituting can also contain other than polymer in the resin of base material film There is any ingredient.It as the example of any ingredient, can enumerate: the colorants such as pigment, dyestuff；Plasticizer；Fluorescent whitening agent； Dispersing agent；Heat stabilizer；Light stabilizer；Ultraviolet absorbing agent；Antistatic agent；Antioxidant；Lubricant；Surfactant etc. adds Add agent.These ingredients can be used alone, two or more can also be applied in combination with arbitrary ratio.

It should be noted that in the case where using ester ring type olefin resin as the resin for constituting base material film, the alicyclic ring Formula olefin resin does not preferably include particle substantially.Here, described substantially refer to not comprising particle, even if resin is made to contain grain Son, also only allowing the ascensional range to the mist degree of base material film for the state for being entirely free of particle is 0.05% below The amount of range.There is the insufficient tendency of compatibility with numerous organic fillers and inorganic particulate in ester ring type olefin polymer.Therefore, When being stretched the ester ring type olefin resin containing particle, it is easy to produce gap.But by reducing grain as described above The amount of son, the generation in gap when being able to suppress stretching, to prevent mist degree from increasing.

The amount for constituting polymer and additive contained in the resin of base material film can in multilayer film of the invention It shows arbitrarily to set in the range of desired optical characteristics.For example, constituting the ratio one of the polymer in the resin of base material film As be 50%~100% or 70%~100%.Especially use ester ring type olefin resin as constitute base material film resin In the case where, the ratio of polymer contained in ester ring type olefin resin is usual 80%~100%, preferably 90%~100%.

As described above, base material film can be only have one layer single layer structure film, or have 2 layers or more of layer Multilayered structure film.By making the film of base material film multilayered structure, multilayer film of the invention can be used as has various spies The optical film of property.

In the case that base material film has 2 layers or more of layer, can have a kind of 2 layers or more of layer, can also have difference Two or more layers.It is formed in addition, can also be equipped in base material film by the resin in addition to above-mentioned ester ring type olefin resin Layer.As the layer formed by the resin in addition to ester ring type olefin resin, for example: have antisitic defect, antireflection, The layer of the functions such as antistatic, anti-dazzle, antifouling.

The average thickness of base material film is preferably 5 μm or more, and more preferably 20 μm or more, preferably 500 μm are hereinafter, more preferably It is 300 μm or less.

In addition, the thickness change of base material film is preferably ± the 3% of above-mentioned average thickness on length direction and width direction Within.By making thickness change above range, the deviation of the optical characteristics such as the delay of base material film can reduce.

The amount of volatile component contained by base material film be preferably 0.1 weight % hereinafter, more preferably 0.05 weight % with Under, further preferably 0.02 weight % or less.By making the amount above range of volatile component, dimensionally stable can be improved Property, reduce base material film face in direction delay and thickness direction delay ongoing change.Further, since can inhibit to have Therefore the deterioration of the polarizing film or image display device of multilayer film of the invention etc. can be such that the display of display keeps for a long time It is stable and good.Here, volatile component refers to the substance below of molecular weight 200.As volatile component, for example, Residual monomer and solvent etc..Total amount of the amount of volatile component as the substance below of molecular weight 200, can be by utilizing gas Phase chromatography is analyzed to quantify.

For base material film manufacturing method there is no limit.Base material film can be by leading to the resin for being used to form the base material film It crosses the arbitrary film method of forming and is formed and obtained.As the film method of forming, for example: casting moulding, extrusion molding Method, film blowing etc..Wherein, residual volatile amount can be effectively reduced without using the extrusion by melting of solvent, from ground Ball border, the viewpoint of operating environment and manufacture efficiency it is excellent from the viewpoint of be preferred.As extrusion by melting, Ke Yiju The inflation method etc. of mold is used out, wherein from the viewpoint of the excellent, it is preferable to use side of T-shaped mould from productivity, thickness and precision Method.

In addition, in the case that base material film has 2 layers or more of layer, for base material film manufacturing method there is no limit.For example, The film layer manufactured respectively can be bonded using bonding agent as needed and manufacture base material film.Bonding agent can according to formed to The type of the resin of the film layer of fitting and select substance appropriate.It as the example of bonding agent, can enumerate: acrylic acid bonding Agent, carbamate bonding agent, polyester adhesive, polyvinyl alcohol bonding agent, Polyofefine adhesive agent, improved polyalkene bonding agent, Polyvinylalkylethers bonding agent, rubber adhesive, ethane-acetic acid ethyenyl ester bonding agent, Chlorovinyl-acetate vinyl bonding (styrene-isoprene-phenylethene block is total by agent, SEBS (styrene-ethylene-butylene-styrene copolymer) bonding agent, SIS Polymers) ethylene adhesives, ethylene-(methyl) methyl acrylate copolymer, ethylene-such as bonding agent, ethylene-styrene copolymer Acrylate adhesives such as (methyl) ethyl acrylate copolymer etc..Bonding agent can be used alone, can also be arbitrarily to compare Two or more is applied in combination in rate.The average thickness of the adhesive layer formed by bonding agent is preferably 0.1 μm or more, more preferably 0.5 μm or more, preferably 10 μm hereinafter, more preferably 5 μm or less.

In the case where the base material film for manufacturing the layer for having 2 layers or more without using bonding agent, such as coextrusion T can be used The co-extrusion modlings methods such as pattern method, coextrusion inflation method, coextruded layer platen press；Molded method of the film layers such as dry lamination method etc..

Alternatively, it is also possible to use for example in solution of the surface of a certain film layer coating containing the resin for constituting other film layers Coat forming method etc. manufactures the base material film of the layer for having 2 layers or more.

Wherein, do not make from the viewpoint of manufacture efficiency and in base material film from the viewpoint of the volatile components such as residual solvent, it is excellent Select co-extrusion modling method.In co-extrusion modling method, it is particularly preferably coextruded T-shaped mould method.Further, it is coextruded in T-shaped mould method, it can By enumerate charging block mode and more menifolds in a manner of, from the viewpoint of the deviation that can reduce each thickness degree, further preferably it is more Menifold mode.

Base material film can be the unstretching film that stretch processing is not carried out, and be also possible to implement the stretched film of stretch processing. In addition, the film layer for implementing stretch processing in advance can be made to be bonded and be drawn in the case that base material film has 2 layers or more of layer Film is stretched, stretched film can also be obtained to stretch processing is implemented by the obtained stretching cephacoria of multilayered structure such as being coextruded.

Drawing process is not particularly limited, such as can be using any means in uniaxial stretching method, biaxial stretching process.If The example of drawing process is enumerated, then as the example of uniaxial stretching method, can be enumerated: utilizing the peripheral speed of the roller of film conveying The method that is uniaxially stretched along its length of difference；The method being uniaxially stretched in the width direction using tentering stretching-machine Deng.In addition, the example as biaxial stretching process, can enumerate: widen the interval of fixture for fixing and along its length While stretching, biaxial stretching process while stretching in the width direction through the opening angle of guide rail；Utilize film After the difference of peripheral speed between the roller of conveying is stretched along its length, two end is clamped with fixture and uses tentering The gradually biaxial stretching process etc. that stretching-machine is stretched in the width direction.It further, can also be using for example using can be to width Degree direction or length direction apply left and right friction speed conveying capacity drawing force or pick up power tentering stretching-machine, along with film Width direction both not parallel or out of plumb direction continuously carries out the oblique extension method of oblique extension.

As the device for stretching, for example: it is longitudinal be uniaxially stretched machine, tentering stretching-machine, foam tensile machine, Roller stretching machine etc..For draft temperature, when the glass transition temperature for constituting the resin of film to be tensioned is set as Tg, draw Temperature preferably (Tg-30 DEG C) or more is stretched, more than more preferable (Tg-10 DEG C), preferably (Tg+60 DEG C) is hereinafter, more preferably (Tg+50 DEG C) Below.Stretching ratio can suitably be selected according to the optical characteristics of the base material film used.Specific stretching ratio is usually 1.05 Times or more, preferably 1.1 times or more, usually 10.0 times hereinafter, preferably 2.0 times or less.

[3. resin layer]

Resin layer is the layer being set on base material film, has protrusion with the face of base material film opposite side.The protrusion with G= N_A/N_FThe value G of expression is usually 3.5 or more, preferably 3.6 or more, preferably 4.0 or more, more preferable 4.5 or more, usual 7.0 or less, It is preferred that 6.4 or less, more preferable 6.0 or less, more preferable 5.5 or less.Value G, which is greater than 0, to be indicated in resin layer 120 such as shown in FIG. 1 The not set region without low protrusion in face 121.In addition, if value G is the upper limit value of above range or less, then it represents that such as The face 121 of the resin layer 120 shown in FIG. 1 not set excessively regional area with low protrusion and not set high protrusion are few Region.Thus, value G is combined in the upper limit value of above range hereinafter, indicating that low protrusion is balanced with high protrusion well.This Outside, value G is indicated more than the lower limit value of above range since protrusion quantity is suitable, can inhibit protrusion quantity not It will lead to the degree of internal haze increase.It therefore, can be in the case where batching and be film-made volume by making value G in above range Inhibit the generation of convex defect, and internal haze can be reduced.

In addition, be located at resin layer meets N with the protrusion in the face of base material film opposite side_B≥N_C≥N_D≥N_E≥N_F.This is indicated Highly low protrusion quantity is more than the high protrusion quantity of height.By meeting such as such condition, resin layer can be improved The face with protrusion sliding property, furthermore it is possible to reduce the internal haze of resin layer.

The height and quantity of protrusion as described above can be for example, by adjusting the size of particle contained by resin layer, making Solvent evaporates when molding resins layer mode, the sequence of process etc. for being used to form resin layer are controlled.In this specification " solvent " includes not only so-called solvent, further includes decentralized medium.

Resin layer includes particle.In resin layer, particle have formed in the face of resin layer and base material film opposite side it is prominent The function of rising.In addition, resin layer generally comprises polymer.Hereinafter, the polymer is suitably also referred to as " cohesive polymers ".It is setting In rouge layer, cohesive polymers have the function of keeping particle Nian Jie with base material film not from resin layer disengaging and by resin layer Function.Resin layer in this wise comprising particle and cohesive polymers can usually be manufactured by following manufacturing methods, the system The method of making includes following processes: particle and cohesive polymers are obtained by mixing to the process of the resin of flow-like；By the flow-like Resin be coated on base material film and the process that forms the film of resin；And solidify the film for the resin being formed on base material film And/or the dry process for obtaining resin layer.Hereinafter, also the resin for the flow-like for being used for the formation of resin layer is referred to as " coating resin ".Hereinafter, being illustrated for the manufacturing method.

As cohesive polymers, suitable polymer can be used according to the purposes of multilayer film and arbitrarily.Wherein, from From the viewpoint of can be stable against convex defect in the case that film roll is made in multilayer film, cohesive polymers preferably comprise poly- Urethane.

As polyurethane, the ingredient and (ii) made containing average 2 or more activation hydrogen in (i) 1 molecule can be used for example Polyurethane obtained from polyisocyanate component reaction.

In addition, can be used for example as polyurethane by expanding the prepolymer for containing isocyanate group with chain extender Chain simultaneously adds water to form dispersion and the polyurethane that manufactures.The above-mentioned prepolymer containing isocyanate group can be by making above-mentioned (i) ingredient And above-mentioned (ii) ingredient occurs under the conditions of isocyanate group is excessive urethane reaction and is manufactured.The carbamate Changing reaction can carry out to reaction torpescence and in the organic solvent big with the compatibility of water.Furthermore, it is possible to containing isocyanic acid The prepolymer is neutralized before the chain extension of the prepolymer of ester group.It, can be with as the chain extension method of the prepolymer containing isocyanate group It enumerates: the method for reacting prepolymer and chain extender containing isocyanate group in the presence of a catalyst as needed.This When, as chain extender, water, water-soluble polyamines, glycols etc. can be used.

As above-mentioned (i) ingredient, preferably there is the ingredient of the activation hydrogen of hydroxyl, for example, it is preferable to have in 1 molecule average The compound of 2 or more hydroxyls.As the specific example of (i) ingredient, following (1) polyol compounds can be enumerated, (2) gather Ethoxylated polyhydric alcohol, (3) polyester polyol, (4) polyester ether polylol and (5) polycarbonate polyol.

(1) polyol compound:

As polyol compound, for example: ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2- fourth Glycol, 1,3 butylene glycol, 2,3- butanediol, 1,4- butanediol, 1,5- pentanediol, neopentyl glycol, 1,6-HD, 2,5- oneself two Alcohol, dipropylene glycol, 2,2,4- trimethyl -1,3- pentanediol, Tricyclodecane Dimethanol, 1,4 cyclohexane dimethanol, 2,2- diformazan Base propylene glycol, 1,4- butanediol, 1,6-HD, 1,8- ethohexadiol, glycerine, trimethylolpropane etc..

(2) polyether polyol:

It as polyether polyol, can enumerate: the alkylen oxide adducts of above-mentioned (1) polyol compound；Oxyalkylene and ring The open loop (co) polymer of shape ether (such as tetrahydrofuran etc.)；Polyethylene glycol, polypropylene glycol, ethylene glycol and 1,2-propylene glycol copolymer, 1, 4- butanediol copolymer；The glycols such as ethylene glycol, polytetramethylene glycol, polyhexamethylene glycol, poly- eight methylene glycol； Deng.It as the specific example of polyether polyol, can enumerate: poly- (oxygen propylidene ether) polyalcohol, poly- (oxygen ethylidene-propylidene Ether) polyalcohol etc..

(3) polyester polyol:

As polyester polyol, for example, polybasic carboxylic acid or its acid anhydrides and above-mentioned (1) polyol compound is made to exist Substance obtained from polycondensation etc. is carried out under the conditions of hydroxyl is excessive.Here, as polybasic carboxylic acid, for example: adipic acid, The binary carboxylic such as succinic acid, decanedioic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA) Acid；The tricarboxylic acids such as trimellitic acid.As the specific example of polyester polyol, can enumerate: ethylene glycol-adipic acid condensation product, Butanediol-adipic acid condensation product, hexamethylene glycol-adipic acid condensation product, ethylene glycol and 1,2-propylene glycol-adipic acid condensation product or with Glycol is that initiator makes lactone carry out polylactone diol obtained from ring-opening polymerisation etc..

(4) polyester ether polylol:

As polyester ether polylol, for example: it will be containing the polyalcohol of ether or the polyalcohol and other glycol Mixture with as illustrated in above-mentioned (3) polybasic carboxylic acid or its acid anhydrides mix and make itself and substance made of reactions of alkylene oxide etc.. Here, as the above-mentioned polyalcohol containing ether, for example, above-mentioned (2) polyether polyol and diethylene glycol etc..As The specific example of polyester ether polylol can enumerate polytetramethylene glycol-adipic acid condensation product etc..

(5) polycarbonate polyol:

As polycarbonate polyol, for example: general formula HO-R- (O-C (O)-O-R)_x- OH compound represented Deng.Wherein, the R in above-mentioned formula indicates the saturated fatty acid polyhydric alcohol residue of carbon atom number 1~12.In addition, the x table in above-mentioned formula Show the quantity of the structural unit of molecule, usually 5~50 integer.These compounds can be obtained by following methods: make to satisfy With the pure and mild substitution carbonic ester of aliphatic polybasic (for example, diethyl carbonate, diphenyl carbonate etc.) under the conditions of hydroxyl is excessive into The ester-interchange method of row reaction；React above-mentioned representative examples of saturated aliphatic polyalcohol and phosgene or as needed then further With the method for representative examples of saturated aliphatic polyol reaction etc..

Above-mentioned (i) ingredient can be used alone, two or more can also be applied in combination with arbitrary ratio.

As (ii) ingredient (that is, polyisocyanate component) reacted with above-mentioned (i) ingredient, for example, 1 molecule In the compound containing average 2 or more isocyanate group.The compound can be aliphatic compound, be also possible to ester ring type Compound can also be aromatic compound.

As aliphatic polyisocyanate compound, the preferably aliphatic diisocyanate of carbon atom number 1~12, such as can To enumerate: hexamethylene diisocyanate, 2,2,4- trimethylhexane diisocyanate, hexane diisocyanate (HDI) etc..

As ester ring type polyisocyanate compound, preferably the ester ring type diisocyanate of carbon atom number 4~18, such as can To enumerate: 1,4- cyclohexane diisocyanate, methylcyclohexylidene diisocyanate, isophorone diisocyanate (IPDI), Dicyclohexyl methyl hydride diisocyanate (HMDI) etc..

As aromatic polyisocyanate, for example: toluene di-isocyanate(TDI) (TDI), 4,4 '-diphenyl methanes Diisocyanate, benzene dimethylene diisocyanate etc..

Above-mentioned (ii) ingredient can be used alone, two or more can also be applied in combination with arbitrary ratio.

Above-mentioned (i) ingredient and (ii) ingredient can arbitrarily be selected according to the purposes of multilayer film using those of suitable.Wherein, As (i) ingredient, it is preferable to use having those of the key of not facile hydrolysis, specific preferably (2) polyether polyol and (5) poly- carbonic acid Ester polyol, wherein particularly preferably (2) polyether polyol.

In addition, sour structure can also be contained in the molecular structure of these polyurethane.Even if the polyurethane containing sour structure is not Amount using surfactant or surfactant is few, can also be dispersed in water, and therefore, can expect the water resistance of resin layer Improvement.The polyurethane is known as self-emulsifying type, it means that even if there be no surfactant, only just by molecular ion It can make the particle of polyurethane stable dispersion in water.In addition, the polyurethane containing sour structure due to do not need surfactant or As long as a small amount of surfactant, therefore, excellent in adhesion with base material film, and can keep high transparency.

As sour structure, for example: carboxyl (- COOH), sulfo group (- SO₃The acidic groups etc. such as H).In addition, in polyurethane In, sour structure can reside in side chain, can also exist on end.Sour structure can be used a kind, can also be with arbitrary ratio group It closes and uses two or more.

As the amount of sour structure, in terms of the acid value for being coated with resin, preferably 20mgKOH/g or more, more preferably 25mgKOH/g or more, preferably 250mgKOH/g are hereinafter, more preferably 150mgKOH/g or less.By making acid value in above-mentioned model More than the lower limit value enclosed, the water dispersible of polyurethane can be made good.In addition, can be made by making acid value below the upper limit The water resistance of resin layer is good.

As the method for importing sour structure to polyurethane, for example: it is above-mentioned by being replaced with dimethylolalkanoic acids (2) some or all of (i) ingredient recorded into (4), thus more to polyether polyol, polyester polyol, polyether ester in advance The method of the importing carboxyl such as first alcohol.As dimethylolalkanoic acids used herein above, for example: dihydroxymethyl acetic acid, Dihydromethyl propionic acid, dimethylolpropionic acid etc..Dimethylolalkanoic acids can be used alone, and can also be combined with arbitrary ratio Use two or more.

Some or all of sour structure contained by polyurethane can also be neutralized by non-volatile alkali.By making sour structure It is neutralized, even if multilayer film has the thermal history being once exposed under high temperature, the characteristic as optical material can also be kept, or can It is Nian Jie with strong bonding force with other components.In addition, even if neutralizing acid structure, even if can also not use surfactant or table The particle of polyurethane is dispersed in water in the case that the amount of face activating agent is few.

In sour structure contained by polyurethane, the ratio for the sour structure being neutralized preferably 20% or more, particularly preferred 50% More than.It is neutralized by making 20% or more in sour structure, it, can also even if multilayer film has the thermal history being once exposed under high temperature To keep the characteristic as optical material, or can be Nian Jie with strong bonding force with other components.

In order to react with crosslinking agent, preferably polyurethane contains polar group.As polar group, can enumerate: Carboxyl, carbonyloxy group carbonyl, epoxy group, hydroxyl, oxygroup, ester group, silanol group, silicyl, amino, itrile group, sulfo group etc..Its In, preferably methylol, hydroxyl, carboxyl and amino, more preferable hydroxyl and carboxyl, particularly preferred carboxyl.Polar group in polyurethane The amount of group is preferably 0.0001 equivalent/1kg or more, more preferable 0.001 equivalent/1kg or more, preferably 1 equivalent/1kg or less.

As polyurethane, also can be used those of commercially available as waterborne polyurethane resin.Waterborne polyurethane resin is The combination that composition containing polyurethane and water, usually polyurethane and the arbitrary ingredient contained as needed are dispersed in water Object.As waterborne polyurethane resin, for example: " ADEKA BONTIGHTER " series of ADEKA company manufacture, three wells " OLESTER " series, " VONDIC " series of DIC company manufacture, " HYDRAN (WLS201, WLS202 of chemical company's manufacture Deng) " series, " IMPRANIL " series of Bayer company manufacture, " POIZ " series, the Sanyo's chemical conversion industry of KAO. Corp. SA's manufacture " SANPLEN " series, " SUPERFLEX " series, the Nanben Chemical Company system of the manufacture of the first industrial pharmaceutical company of company's manufacture " NEOREZ " series, " Sancure " series of Lubrizol company manufacture for making etc..In addition, polyurethane can be used alone 1 Kind, two or more can also be applied in combination with arbitrary ratio.

In addition, preferably 50 DEG C or more, more preferable 55 DEG C of the glass transition temperature of cohesive polymers or more, particularly preferred 60 DEG C or more, preferably 150 DEG C or less, more preferable 125 DEG C or less, particularly preferred 100 DEG C or less.By the glass for making cohesive polymers Change transition temperature more than the lower limit value of above range, can prevent from polluting furnace downstream after coming out in manufacturing process from drying oven The conveying roller of side.In addition, by for upper limit value hereinafter, the curling of multilayer film can be prevented.

In the coating resin of flow-like, the state of cohesive polymers is arbitrary, and can be dispersed in particle shape, can also be with It is dissolved in other ingredients such as solvent.For example, in the case where using polyurethane as cohesive polymers, polyurethane is in mostly Particle shape dispersion.At this point, from the viewpoint of the optical characteristics of multilayer film, the average grain diameter of the particle of polyurethane is preferably 0.01 μm~0.4 μm.

As particle, can be used inorganic particulate formed by inorganic material, the organic filler formed by organic material, with And the Arbitrary Particles in compound particle of the combination comprising inorganic material and organic material.And from the easy formation for carrying out resin layer , it is preferable to use the particle of water dispersible from the point of view of viewpoint.As the material of inorganic particulate, it can be cited for example that: silica, oxidation The inorganic oxides such as titanium, aluminium oxide, zirconium oxide；Calcium carbonate, talcum, clay, calcined kaolin, baked calcium silicate, silicic acid hydrate Calcium, alumina silicate, magnesium silicate, calcium phosphate etc..In addition, the material as organic filler, it can be cited for example that: organic siliconresin, fluorine Resin, acrylic resin etc..They can be used alone, two or more can also be applied in combination with arbitrary ratio.

In the material of these exemplary particles, preferred silica.The ability that silicon dioxide granule inhibits wrinkle to generate And the transparency is excellent, is not likely to produce internal haze, does not colour, therefore the influence to the optical characteristics of multilayer film is small.In addition, two Dispersibility and dispersion stabilization of the silica in coating resin are good.In silicon dioxide granule, particularly preferred amorphous state colloid Silicon dioxide granule.

As silicon dioxide granule as described above, commercially available product can be used.As the example of commercially available product, can enumerate The EPOSTAR MX-050W (average grain diameter 80nm) of Japanese catalyst company manufacture, SEAHOSTER KE-W10 (average grain diameter 110nm), EPOSTAR MX-100W (average grain diameter 150nm~200nm)；The SNOWTEX MP- of Nissan Chemical company manufacture 2040 (average grain diameter 150nm~200nm) etc..

In addition, can be used can meet above-mentioned item in the face formation with base material film opposite side of resin layer as particle The particle of the protrusion of part.In general, the rising height can be adjusted according to the size of particle.At this point, the diameter of particle will not It is directly becoming the height of protrusion, but usually relevant between the diameter of particle and the height of protrusion, therefore by adjusting particle Diameter distribution, the protrusion as described above with wide distribution can be formed on the face of resin layer.

In general, can be formed and be met on the face of resin layer by using the different a variety of particle combinations of average grain diameter State the protrusion of condition.Therefore, the particle of resin layer usually combines a variety of particles different comprising average grain diameter.If will average grain The different a variety of particle combinations of diameter can then make the whole particle diameter distribution of particle contained in resin layer broaden, therefore, can be with The distribution of the height of the protrusion formed in the face of the resin layer comprising the particle is set to broaden.Therefore, in this manufacturing method, inciting somebody to action Particle and cohesive polymers are obtained by mixing in the process of coating resin, preferably by the different a variety of particles of average grain diameter and bonding Polymer is mixed.

In addition, preferably at least a kind of particle is averaged in the case where the different a variety of particles of average grain diameter are applied in combination Partial size is greater than the thickness of resin layer.In this way, by using the particle of the average grain diameter with the thickness greater than resin layer, Neng Gouyou The protrusion that with the face formation of base material film opposite side meets above-mentioned condition of the effect ground in resin layer.In addition, in a variety of particles at least A kind of average grain diameter of particle can be less than the thickness of resin layer.

Wherein, preferably by the particle (S) with the average grain diameter less than 150nm and with the average grain diameter of 150nm or more Particle (L) be applied in combination.Therefore, the particle of resin layer is preferably combined comprising the particle with the average grain diameter less than 150nm (S) with 150nm or more average grain diameter particle (L).

The average grain diameter of particle (S) is usually 20nm or more, preferably 30nm or more, more preferable 40nm or more, and usually small In 150nm, preferably 140nm or less, more preferable 130nm or less.By making the average grain diameter of particle (S) in the lower limit of above range More than value, protrusion can be stably formed in the face of resin layer.In addition, by the way that below the upper limit, the face of resin layer can be made The distribution of rising height broaden.

In addition, mode height of the average grain diameter of particle (S) relative to the protrusion in the face for being formed in resin layer, preferably 2 Times or more, more preferable 3 times or more, particularly preferred 4 times or more, preferably 15 times or less, more preferable 14 times or less, particularly preferred 13 Times or less.Here, the mode height of protrusion refers to: in rising height 5nm, 10nm, 15nm, 20nm, 25nm and 30nm, having should The height of the most protrusion of the protrusion of height.It, can by making the average grain diameter of particle (S) more than the lower limit value of above range Protrusion is stably formed in the face of resin layer.In addition, by the way that below the upper limit, the rising height in the face of resin layer can be made Distribution broadens.

In addition, the thickness relative to resin layer, preferably 3 times or more, more preferable 4 times of the average grain diameter of particle (S) or more, spy Not preferably 5 times or more, preferably 10 times or less, more preferable 8 times or less, particularly preferred 7 times or less.By making being averaged for particle (S) Partial size can be stably formed protrusion in the face of resin layer more than the lower limit value of above range.In addition, by upper limit value with Under, the distribution of the rising height in the face of resin layer can be made to broaden.

Relative to 100 parts by weight of cohesive polymers, the amount of particle (S) be usually 2 parts by weight or more, preferably 3 parts by weight with More than upper, more preferable 5 parts by weight, usually below 24 parts by weight, below preferably 20 parts by weight, below more preferable 18 parts by weight. By making the amount of particle (S) in above range, it can be readily formed in the face of resin layer and meet the protrusion of above-mentioned condition.

The average grain diameter of particle (L) is usually 150nm or more, preferably 160nm or more, more preferable 170nm or more, usually 250nm or less, preferably 230nm or less, more preferable 200nm or less.By making the average grain diameter of particle (L) under above range More than limit value, the distribution of the rising height in the face of resin layer can be made to broaden.In addition, by for upper limit value hereinafter, can reduce The internal haze of resin layer.

In addition, the mode height of the protrusion relative to the face for being formed in resin layer, the average grain diameter of particle (L) is preferably 15 Times or more, more preferable 16 times or more, particularly preferred 17 times or more, preferably 25 times or less, more preferable 23 times or less, particularly preferred 20 Times or less.By making the average grain diameter of particle (L) more than the lower limit value of above range, the protrusion in the face of resin layer can be made high The distribution of degree broadens.In addition, by the way that below the upper limit, the internal haze of resin layer can be reduced.

In addition, the thickness relative to resin layer, the average grain diameter of particle (L) preferably 2 times or more, more preferable 3 times or more, Particularly preferred 4 times or more, preferably 10 times or less, more preferable 8 times or less, particularly preferred 7 times or less.By making the flat of particle (L) Equal partial size can make the distribution of the rising height in the face of resin layer broaden more than the lower limit value of above range.In addition, by Upper limit value is hereinafter, can reduce the internal haze of resin layer.

In addition, the preferred 70nm or more of difference, the more preferable 100nm of the average grain diameter of the average grain diameter and particle (L) of particle (S) Above, particularly preferred 120nm or more, preferably 200nm or less, more preferable 180nm or less, particularly preferred 160nm or less.By making The difference of the average grain diameter of the average grain diameter and particle (L) of particle (S) can be readily formed in above range in the face of resin layer Meet the protrusion of above-mentioned condition.

Relative to 100 parts by weight of cohesive polymers, the amount of particle (L) be usually 5 parts by weight or more, preferably 6 parts by weight with More than upper, more preferable 7 parts by weight, usually below 20 parts by weight, below preferably 18 parts by weight, below more preferable 15 parts by weight. By making the amount of particle (L) in above range, it can be readily formed in the face of resin layer and meet the protrusion of above-mentioned condition.

Relative to 100 parts by weight of cohesive polymers, the difference of the amount of the amount and particle (S) of particle (L) is preferably 0.5 parts by weight Above, more than more preferable 1 parts by weight, more than particularly preferred 2 parts by weight, below preferably 25 parts by weight, more preferable 20 parts by weight Below, particularly preferably below 15 parts by weight.By making the difference of the amount of particle (L) and the amount of particle (S) in above range, Neng Gou The face of resin layer is readily formed the protrusion for meeting above-mentioned condition.

In general, particle contained by resin layer is whole in the case where particle (S) and particle (L) is applied in combination as described above It will appear the peak for corresponding respectively to particle (S) and particle (L) in the particle diameter distribution of body.But even in this case, it is formed Simple spike is also usually shown in the distribution of the rising height in the face of resin layer.In this wise, point of the distribution of partial size and rising height Cloth not simply corresponds to.But if a variety of particle combinations that average grain diameter is different in this wise, these particles are whole Particle diameter distribution broadens, along with this, the distribution for being formed in the rising height in the face of resin layer also broadens.Therefore, using such Correlation between the distribution of the average grain diameter of particle and the distribution of rising height can obtain the protrusion for meeting above-mentioned condition.

In addition, can also include crosslinking agent in coating resin other than particle and cohesive polymers.Crosslinking agent by with Reaction-ity group reaction possessed by cohesive polymers and bonding, so as to be crosslinked cohesive polymers.Thus, for example by Will coating resin be coated on base material film after be crosslinked cohesive polymers, can be improved cementability between resin layer and base material film, And the mechanical strength and humidity resistance of resin layer.For example, in the case where using polyurethane as cohesive polymers, in general, Crosslinking agent can be reacted with the carboxyl and its anhydride group contained as above-mentioned sour structure and in (i) ingredient and (ii) ingredient Polar group as remaining hydroxyl etc. is reacted and forms cross-linked structure due to unreacted afterwards.

As crosslinking agent, 1 intramolecular can be used for example can react with 2 or more with possessed by cohesive polymers Property group reaction and the compound of the functional group of bonding.Wherein, as crosslinking agent, preferably having can be with carboxyl or its anhydride group The compound of the functional group of reaction.

As the specific example of crosslinking agent, can enumerate: epoxide, carbodiimide compound,Isoxazoline compound, Isocyanate compound etc..In addition, crosslinking agent can be used alone, two or more can also be applied in combination with arbitrary ratio.

As epoxide, the multi-functional epoxy compound that 1 intramolecular has 2 or more epoxy groups can be used.Its In, as epoxide, preferably there is dissolubility to water or be dispersed in the epoxide emulsified in water.If ring Oxygen compound has dissolubility or emulsifiable to water, then in the case where being coated with resin is water-base resin, can make the aqueous tree The coating of rouge is good, to be easy to carry out the manufacture of resin layer.Here, water-base resin refers to be dissolved or dispersed in water etc. The state of aqueous solvent contains the resin of the flow-like of the solid components such as polymer.

As the example of above-mentioned epoxide, can enumerate: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1 mole of the glycols such as propylene glycol, dipropylene glycol, 1,4- butanediol, 1,6-HD, neopentyl glycol and 2 moles of epoxychloropropane The di-epoxy compounds as obtained from etherificate；The polyalcohols such as glycerol, polyglycereol, trimethylolpropane, pentaerythrite, sorbierite 1 mole and 2 moles of epoxychloropropane of class above by polyepoxy compound obtained from etherificate；Phthalic acid, terephthaldehyde 2 moles of di-epoxy compounds as obtained from esterification of 1 mole of the dicarboxylic acids such as acid, ethanedioic acid, adipic acid and epoxychloropropane Deng.

As the more specific example of epoxide, can enumerate: Isosorbide-5-Nitrae-bis- (2 ', 3 '-glycidoxy) butane, 1, 3,5- triglycidyl group isocyanuric acid ester, 1,3- diglycidyl -5- (γ-acetoxyl group-β-oxygen propyl group) isocyanuric acid Ester, sorbierite poly epihydric alcohol ethers, polyglycerol poly epihydric alcohol ethers, pentaerythrite poly epihydric alcohol ethers, dipropyl three Alcohol polyglycidyl ether, 1,3,5- triglycidyl group (2- ethoxy) isocyanuric acid ester, glycerine poly epihydric alcohol ethers and Trimethylolpropane poly epihydric alcohol ethers etc..

In addition, the example of the commercially available product as epoxide, can enumerate: the manufacture of Nagase ChemteX company " Denacol (Denacol EX-521, EX-614B etc.) " series etc..

Epoxide can be used alone, two or more can also be applied in combination with arbitrary ratio.

Relative to 100 parts by weight of cohesive polymers, the amount of epoxide is usually 5 parts by weight or more, preferably 7 weight Part or more, it is more than more preferably 10 parts by weight, usually 50 parts by weight hereinafter, preferably 40 parts by weight hereinafter, more preferably 30 Below parts by weight.By making the amount of epoxide more than the lower limit value of above range, epoxide and cohesive polymers Reaction sufficiently carry out, therefore, the mechanical strength of resin layer can be properly increased.In addition, by that below the upper limit, can subtract The residual of few unreacted epoxide, can properly increase the mechanical strength of resin layer.

In addition, relative to the polar group with cohesive polymers at the amount of the epoxide of equivalent, epoxide Measuring benchmark meter by weight is preferably 0.2 times or more, more preferably 0.4 times or more, particularly preferably 0.6 times or more, preferably 1.4 Again hereinafter, more preferably 1.2 times hereinafter, particularly preferably 1.0 times or less.Here, with the polar groups of cohesive polymers at working as The amount of the epoxide of amount refers to, can be with the neither too much nor too little ring that reacts of ground of the total amount of the polar group of cohesive polymers The theoretical amount of oxygen compound.The polar group of cohesive polymers can react with the epoxy group of epoxide.Therefore, pass through Within the above range by the amount control of epoxide, the reaction of polar group and epoxide can be made to carry out to appropriate Degree, to effectively improve the mechanical strength of resin layer.

As carbodiimide compound, 1 intramolecular can be used that there is the compound of 2 or more carbodiimides.The carbon two The organic isocyanates such as organic single-isocyanate, organic diisocyanate, organic triisocyanate can be used to make for group with imine moiety It is manufactured for raw material.As the example of these organic isocyanates, can enumerate: aromatic isocyanate, aliphatic are different Cyanate and their mixture.Therefore, as organic group possessed by organic isocyanate, aromatic series and rouge can be used Any one of fat race, alternatively, it is also possible to which aromatic organic group and aliphatic organic group is applied in combination.Wherein, from From the viewpoint of reactivity, particularly preferably with the organic isocyanate of aliphatic organic group.In general, carbodiimide chemical combination Object can be synthesized by the condensation reaction of organic diisocyanate.

It as the specific example of organic isocyanate, can enumerate: 4,4 '-methyl diphenylene diisocyanates, 4,4- bis- Pheiiyldimetliyl methane diisocyanate, 1,4- phenylene vulcabond, 2,4 toluene diisocyanate, 2,6- toluene two are different Cyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, benzene dimethylene diisocyanate, 2,2,4- trimethyl Hexamethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanates, 1,3- phenylene vulcabond etc. organic two is different Cyanate；Isophorone diisocyanate, phenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate Equal organic single-isocyanates.

The example of commercially available product as carbodiimide compound can be enumerated: can be used as commercially available product and obtain Nisshinbo Chemical company manufacture " Carbodilite (Carbodilite V-02, V-02-L2, SV-02, V-04, E-02 etc.) " series.

Carbodiimide compound can be used alone, two or more can also be applied in combination with arbitrary ratio.

Relative to 100 parts by weight of cohesive polymers, the amount of carbodiimide compound is usually 1 parts by weight or more, preferably 3 More than parts by weight, usually 40 parts by weight are hereinafter, below preferably 30 parts by weight.By making the amount of carbodiimide compound upper The lower limit value of range or more is stated, the reaction of carbodiimide compound and cohesive polymers sufficiently carries out, and therefore, can properly increase The mechanical strength of resin layer.In addition, by making the amount of carbodiimide compound below the upper limit, it is possible to reduce unreacted carbon The residual of diimine compounds can properly increase the mechanical strength of resin layer.

AsIsoxazoline compound, can be used has shown in following formula (I)sThe polymer of oxazoline base.Following formula (I)s In, R¹、R²、R³And R⁴It is identical or different, it indicates in hydrogen atom, halogen atom, alkyl, aralkyl, phenyl and substituted-phenyl Any group.

[chemical formula 1]

It shouldIsoxazoline compound can be for example, by making containing addition polymerizationOxazoline is used as must and contain as needed There is the monomer component of arbitrary unsaturated monomer to carry out polymerisation in solution in an aqueous medium by well known polymerization to manufacture. As addition polymerizationOxazoline, for example, following formula (II) compounds represented.In following formula (II)s, R¹、R²、R³ And R⁴It is identical as the definition in formula (I).In addition, R⁵Indicate the organic group with the non-annularity of addition polymerization unsaturated bond.

[chemical formula 2]

As addition polymerizationThe specific example of oxazoline can be enumerated: 2- vinyl -2-Oxazoline, 2- vinyl- 4- methyl -2-Oxazoline, 2- vinyl -5- methyl -2-Oxazoline, 2- isopropenyl -2-Oxazoline, 2- isopropenyl -4- first Base -2-Oxazoline, 2- isopropenyl -5- ethyl -2-Oxazoline etc..In addition, they can be used alone, it can also be to appoint Ratio combine of anticipating uses two or more.Wherein, 2- isopropenyl -2-Oxazoline is industrially also easy to obtain, therefore it is preferred that.

The addition polymerizationThe amount of oxazoline relative toWhole monomer component used in the manufacture of isoxazoline compound 100 parts by weight, more than preferably 3 parts by weight.To include as a result,When the coating resin solidification of isoxazoline compound, it can make Solidification sufficiently carries out, and obtains the resin layer of durability and excellent water resistance.

As can be used forThe arbitrary unsaturated monomer of the manufacture of isoxazoline compound, can be used can be with addition polymerizationOxazoline copolymerization and not withThe arbitrary monomer that oxazoline base reacts.Such arbitrary unsaturated monomer can be from above-mentioned Arbitrarily selection uses in monomer.

AsThe example of the commercially available product of isoxazoline compound can enumerate Japanese catalyst company manufacture in water-soluble type EPOCROS WS-500 and WS-700.In addition, Japanese catalyst company manufacture can be enumerated for example in emulsion-type EPOCROS K-2010, K-2020 and K-2030.Wherein, preferably with high reactivity with cohesive polymers contained by coating resin Water-soluble type.

In addition,Isoxazoline compound can be used alone, two or more can also be applied in combination with arbitrary ratio.

AsThe amount of isoxazoline compound, can be set so that polar group possessed by cohesive polymers withAzoles Possessed by quinoline compoundOxazoline base molar ratio (molal quantity of polar group/The molal quantity of oxazoline base) in given model In enclosing.Specifically, can be set so that above-mentioned molar ratio is 100/20~100/100.By making above-mentioned molar ratio upper The lower limit value of range or more is stated, can prevent unreacted polar group from remaining.In addition, by making above-mentioned molar ratio in upper limit value Hereinafter, can prevent remainingThe generation of oxazoline base, to prevent hydrophilic radical from becoming excessive.

In addition, in the case where there is cohesive polymers carboxyl and the carboxyl to be neutralized, cohesive polymers withAzoles In the reaction of quinoline compound,Oxazoline base is not susceptible to react with carboxylate.It therefore, can be by adjusting for the non-of neutralization The type of volatile base and non-volatile degree and control its reactivity.

As isocyanate compound, the compound containing 2 or more isocyanate group in 1 molecule can be used.These are different Cyanate esters can be aliphatic compound, is also possible to ester ring type compound, can also be aromatic compound.As The specific example of isocyanate compound can be enumerated and illustrate the identical example of (ii) ingredient with the raw material as polyurethane Son.

In above-mentioned crosslinking agent, preferably epoxide and carbodiimide compound, particularly preferred epoxide.If made It uses epoxide as crosslinking agent, then the cementability between resin layer and base material film can especially be significantly increased.In addition, such as Fruit uses carbodiimide compound as crosslinking agent, then can improve the working life (pot life) of coating resin.

In addition, coating resin is other than comprising particle and cohesive polymers, it can also include non-volatile alkali.As non- Volatile base, can enumerate will be coated under treatment conditions when making it dry after resin is coated on base material film is essentially non-wave The alkali of hair property.As the treatment conditions, the processing for example placed in 80 DEG C 1 hour can be enumerated.Here, being essentially Non-volatile to typically refer to, the reduction amount of non-volatile alkali is 80% or less.Such non-volatile alkali, which can be used as, neutralizes poly- ammonia The neutralizer of sour structure contained by the cohesive polymers such as ester and function.

As non-volatile alkali, inorganic base can be used, organic base also can be used.Wherein, preferably 100 DEG C of boiling point or more Organic base, the amine compounds of 100 DEG C of more preferable boiling point or more, the amine compounds of 200 DEG C of particularly preferred boiling point or more.In addition, Organic base can be low molecular compound, be also possible to polymer.

If enumerating the example of non-volatile alkali, it is used as inorganic base, for example, sodium hydroxide and potassium hydroxide. In addition, as organic base, for example: 2-amino-2-methyl-1-propanol (AMP), triethanolamine, triisopropanolamine (TIPA), monoethanolamine, diethanol amine, three [(2- hydroxyl) -1- propyl] amine, 2- amino-2-methyl -1,3- propylene glycol (AMPD), 2- amino -2- methylol -1,3- propane potassium hydroxide, zinc ammonium complex, cuprammonium complex, silver-colored ammonium complex compound, γ - Aminopropyltriethoxywerene werene, gamma-amino propyl trimethoxy silicane, N- β (amino-ethyl)-gamma-amino propyl trimethoxy Base silane, N- β (amino-ethyl)-gamma-amino oxypropyl trimethyl dimethoxysilane, N- phenyl-gamma-amino propyl trimethoxy Silane, N, bis- (trimethyl silyl) ureas of N-, 3- ureido-propyl trimethoxy silane, (the 2- methoxyl group-of 3- aminopropyl-three Ethoxy-ethoxy) silane, N- methyl -3- aminopropyl trimethoxy carboxylic acid dihydrazide, ethylene acid hydrazide, malonic acid two Hydrazides, succinic acid hydrazide ii, adipic dihydrazide, sebacic dihydrazide, dodecane acid dihydrazide, isophthalic dihydrazide, Terephthaldehyde's acid dihydrazide, quinoline, picoline, pyridine, morpholine, piperazine, cyclohexylamine, hexamethylene diamine, N, N- dimethyl Formamide, ethylenediamine, diethylenetriamines, tetren, five ethylidene, five amine, monoethanolamine, diethanol amine, isopropanol Amine, N, N- diethyl carbinol amine, N, N- dimethylethanolamine, amino ethyl ethanolamine, N- methyl-N-N- diethanol amine, 1,2- Propane diamine, 1,6- hexamethylene diamine, piperazine, 2- methyl piperazine, 2,5- lupetazin, isophorone diamine, 4,4 '-two rings Hexyl methane diamines, 3,3 '-dimethyl-dicyclohexylmethane diamine, 1,2- cyclohexane diamine, 1,4- cyclohexane diamine, amino Ehtylethanolamine, aminopropyl ethanol amine, Aminohexyl ethanol amine, amino ethyl propanol amine, aminopropyl Propanolamine, amino oneself Base Propanolamine, diethylenetriamines, three imidazoles of dipropylene, 1- (2- amino-ethyl) -2-methylimidazole, 1- (2- amino second Base) -2- ethyl imidazol(e), 2- aminooimidazole sulfate, 2- (2- amino-ethyl)-benzimidazole, pyrazoles, 5- amino-pyrazol, 1- first Base -5- amino-pyrazol, 1- isopropyl -5- amino-pyrazol, 1- benzyl -5- amino-pyrazol, 1,3- dimethyl -5- amino-pyrazol, 1- Isopropyl -3- methyl -5- amino-pyrazol, 1- benzyl -3- methyl -5- amino-pyrazol, the chloro- 5- amino-pyrazol of 1- methyl -4-, 1- first Base -4- cyano -5- amino-pyrazol, the chloro- 5- amino-pyrazol of 1- isopropyl -4-, the chloro- 5- amino-pyrazol of 3- methyl -4-, 1- benzyl - The chloro- 5- amino-pyrazol of 4-, amino resins are (for example, the chloro- melamine resin of 1,3- dimethyl -4-, Lauxite, guanamine resin Deng) etc..In addition, they can be used alone, two or more can also be applied in combination with arbitrary ratio.

Relative to 100 parts by weight of cohesive polymers, the amount of non-volatile alkali is usually 0.5 parts by weight or more, preferably 1 weight Measure part more than, it is more than more preferably 2 parts by weight, usually 30 parts by weight hereinafter, preferably 20 parts by weight hereinafter, more preferably 10 Below parts by weight.By making the amount of non-volatile alkali more than the lower limit value of above range, available sufficient bonding force.Separately Outside, below the upper limit by the amount that makes non-volatile alkali, the decoloration of the polarizing film of polyvinyl alcohol can be prevented.

In addition, coating resin is other than comprising particle and cohesive polymers, it can also include wetting agent.By using Wetting agent, the coating that can make will to be coated with when resin is coated on base material film are good.

As wetting agent, can be used such as acetylenic surfactant, fluorine class surfactant.It is living as acetylenic surface Property agent, can be used for example: Air Products and Chemicals corporation Surfynol series, Dynol series etc..Separately Outside, as fluorine class surfactant, can be used for example: DIC corporation MEGAFAC series, Neos corporation Ftergent system Column, AGC corporation SURFLON series etc..As wetting agent, it is preferable to use acetylenic surface from the viewpoint of repeating coating Activating agent.

In addition, these wetting agents can be used alone, two or more can also be applied in combination with arbitrary ratio.

Relative to solid content contained by coating resin, the use level of wetting agent is usually 0.01 weight % or more, excellent Be selected as 0.05 weight % or more, more preferably 0.1 weight % or more, usually 5 weight % hereinafter, preferably 4 weight % hereinafter, More preferably 3 weight % or less.By making the amount of wetting agent more than the lower limit value of above range, available sufficient coating Property.In addition, repetition coating can be made be more good by the way that below the upper limit, the exudation of wetting agent can be inhibited.

Coating resin usually contains solvent.As solvent, water or water-soluble solvent are used.As water-soluble solvent, For example: methanol, ethyl alcohol, isopropanol, acetone, tetrahydrofuran, N-Methyl pyrrolidone, dimethyl sulfoxide, ethylene glycol list Methyl ether, ethylene glycol monobutyl ether etc..Wherein, as solvent, it is preferable to use water.It, can also be in addition, solvent can be used alone Two or more is applied in combination with arbitrary ratio.

The amount of solvent can be set so that the viscosity of coating resin reaches the range suitable for coating.In general, the amount of solvent It is set so that the solid component concentration of coating resin is fallen in the desired range.It is above-mentioned desired to range preferably from 0.5 weight % More than, more preferably 1 weight % or more, preferably 15 weight % are hereinafter, more preferably 10 weight % or less.Thus, it is possible to make Operability and the coating for being coated with resin are good.

Being coated in resin can also include curing accelerator with above-mentioned crosslinking agent in combination.For example, using epoxide In the case where as crosslinking agent, as curing accelerator, preferred tertiary amine class compound (have 2,2,6 with tertiary amine on the position 4-, Except the compound of 6- tetramethyl-piperidyl), boron trifluoride complex etc..In addition, curing accelerator can be used alone, Two or more can also be applied in combination with arbitrary ratio.

The amount of curing accelerator is relative to 100 parts by weight of cohesive polymers, usually more than 0.001 parts by weight, preferably More than 0.01 parts by weight, more than more preferable 0.03 parts by weight, usually below 30 parts by weight, below preferably 10 parts by weight, more excellent Select 5 parts by weight or less.

Being coated in resin can also include auxiliary curing agent with above-mentioned crosslinking agent in combination.Concrete example as auxiliary curing agent Son can be enumerated: the oximes such as quininie dioxime, benzoquinones dioxime, p-Nitrosophenol-nitrous base class auxiliary curing agent；N, N- metaphenylene are double The maleimides auxiliary curing agent such as maleimide；Diallyl phthalate, triallylcyanurate, triallyl The allylics auxiliary curing agent such as isocyanuric acid ester；Ethylene glycol dimethacrylate, trimethylol-propane trimethacrylate Equal methyl acrylic esters auxiliary curing agent；The vinyl-based solidification such as vinyltoluene, vinyl xylene, ethyl vinyl benzene, divinylbenzene helps Agent；Deng.In addition, auxiliary curing agent can be used alone, two or more can also be applied in combination with arbitrary ratio.

The amount of auxiliary curing agent is relative to 100 parts by weight of crosslinking agent, usually more than 1 parts by weight, more than preferably 10 parts by weight, Usually below 100 parts by weight, below preferably 50 parts by weight.

As long as the effect of the present invention is not significantly impaired, coating resin can also contain such as heat-resisting stabilizing agent, weather-stable Agent, levelling agent, surfactant, antioxidant, antistatic agent, slip agents, antiblocking agent, antifoggant, lubricant, dyestuff, face Material, natural oil, synthetic oil, wax etc..In addition, these substances can be used alone, 2 can also be applied in combination with arbitrary ratio Kind or more.

It is the crosslinking agent that by particle and cohesive polymers and optionally uses, non-in the process for obtaining coating resin Volatile base, wetting agent, solvent and any ingredient mixing, obtain the coating resin of flow-like.Gained coating resin is preferably able to Equably it is coated on the surface of base material film.From the viewpoint of having excellent coating in this wise, the viscosity for being coated with resin is excellent Select 15mPas or less, particularly preferred 10mPas or less.Here, the viscosity is using tuning-fork-type vibrating type viscometer 25 The value measured under conditions of DEG C.The viscosity can be for example adjusted according to partial size of the ratio of solvent and particle etc..

After obtaining coating resin, which is coated on base material film and form the work for being coated with the film of resin Sequence.At this point, coating resin is not set up directly on the surface of base material film usually via other layers such as the layer of bonding agent.In addition, applying Cloth resin can only be coated on the one side of base material film, can also be coated on two sides.Wherein, from the manufacturing cost for inhibiting multilayer film From the point of view of viewpoint, resin only preferably is coated in the coated on one side of base material film.

In the case where coating coating resin on base material film, arbitrary rubbing method can be used.As specific rubbing method, For example: bar rubbing method, infusion process, spray-on process, spin-coating method, rolling method, gravure coating process, air knife coating method, curtain Flow rubbing method, slip rubbing method, extrusion coating methods etc..

It is formed on base material film after the film of coating resin, carries out the film solidification for making the coating resin and/or drying and obtain To the process of resin layer.In general, coating resin contains solvent, therefore, the process for obtaining resin layer includes making solvent seasoning and removing It goes.Drying means is arbitrary, for example, can by being dried under reduced pressure, the arbitrary methods such as heat drying carry out.Wherein, from making to apply Cross-linking reaction etc. is swift in response from the viewpoint of progress in cloth resin, preferably makes to be coated with resin solidification and do by heat drying It is dry.In the case where being thermally dried, it will usually the cross-linking reaction of cohesive polymers occur.

Made in the case where being coated with resin solidification and drying by heating, heating temperature can make solvent seasoning and make to be coated with It is suitably set in the range of component of polymer solidification in resin.It should be noted that using stretched film as base material film and In the case that the undesirable delay for showing the base material film changes, heating temperature is preferably set to not produce in base material film The temperature of raw Orientational relaxation.Specifically, when the glass transition temperature for forming the material of base material film is set as Tg, preferably More than (Tg-30 DEG C), more preferably more than (Tg-10 DEG C), preferably (Tg+60 DEG C) hereinafter, more preferably (Tg+50 DEG C) with Under.

In addition, above-mentioned manufacturing method is other than including above-mentioned operation, it can also include any process.For example, the system The method of making can be formed on base material film before the film of coating resin, implement the work of modification including the surface to base material film Sequence.Thus, it is possible to improve the cementability of base material film and resin layer.As the surface modification treatment to base material film, such as can lift Energy-ray treatment with irradiation and drug processing etc. out.As energy-ray treatment with irradiation, for example: at corona discharge Reason, corona treatment, electron beam treatment with irradiation, ultraviolet treatment with irradiation etc. consider from viewpoint for the treatment of effeciency etc., preferably electric Corona processing and corona treatment, particularly preferred Corona discharge Treatment.In addition, as drug processing, for example: Saponification process.In addition, the oxygen such as base material film is impregnated in potassium bichromate solution, the concentrated sulfuric acid can be enumerated as drug processing In agent aqueous solution, then the method washed with water.

In addition, above-mentioned manufacturing method may include implementing the work of hydrophilized surface processing to the face with protrusion of resin layer Sequence.The face with protrusion of resin layer usually becomes binding face when being bonded multilayer film with other components.Therefore, by into one Step improves the hydrophily in the face with protrusion of resin layer, can significantly improve the cementability of multilayer film Yu other components.

As hydrophilized surface processing, for example: Corona discharge Treatment, corona treatment, saponification process, purple Outside line treatment with irradiation etc..Wherein, consider from viewpoint for the treatment of effeciency etc., preferably Corona discharge Treatment and corona treatment, more It is preferred that Corona discharge Treatment.In addition, preferred atmosphere presses corona treatment as corona treatment.

By the above-mentioned manufacture method, resin layer can be formed on base material film.As shown in Figure 1, the resin layer obtained in this way 120 with the face 121 of 110 opposite side of base material film have protrusion 122, thus sliding property is good.Therefore, resin layer can be reduced 120 rub with quiet between the face 111 of 120 opposite side of resin layer of the face 121 of 110 opposite side of base material film and base material film 110 Wipe coefficient.The confficient of static friction is preferably 0.3~0.5.It, can as a result, in the case where multilayer film 100 is coiled into web-like Effectively inhibit the generation of convex defect.

In addition, the resin layer does not include a large amount of particle that will lead to the degree of internal haze increase of the resin layer.One As for, every 1 weight of the small particle of partial size is small.Therefore, even if the amount with weight basis is few, the number of the particle can also With more.Therefore, the big particle combinations of the small particle of partial size and partial size are used in this way, is formed with the face in resin layer The degree that a large amount of protrusions of the degree of sliding property can be improved is compared, and the amount of particle can be reduced.Therefore, resin layer can be reduced Internal haze.

The thickness of resin layer is usually 10nm or more, preferably 15nm or more, more preferable 20nm or more, usually 100nm with Under, preferably 80nm or less, more preferable 70nm or less.It, can by making the thickness of resin layer more than the lower limit value of above range Improve the mechanical strength of resin layer.In addition, can be stably formed in the face of resin layer desired prominent by below the upper limit It rises, it is thus possible to effectively improve the sliding property in the face of resin layer.In addition, being led to by the thickness for reducing resin layer as described above Often resin layer can be made to be not easy to impact optical characteristics possessed by base material film.It is therefore not necessary in order to adjust multilayer film Optical characteristics and the composition for changing resin layer, so can easily be done the adjustment of the optical characteristics of multilayer film.

In addition, the mode height of the protrusion relative to the face for being formed in resin layer, the thickness of resin layer be preferably 1 times with Upper, more preferable 2 times or more, particularly preferred 3 times or more, preferably 10 times or less, more preferable 7 times or less, particularly preferred 5 times or less. By making the thickness of resin layer more than the lower limit value of above range, haze value can reduce.In addition, by upper limit value with Under, the sufficient lubricity that will not generate surface defect can be assigned to film surface.

The refringence at the interface of base material film and resin layer is preferably 0.05 or less.If the refringence is in above range It is interior, then it is able to suppress the loss that light penetrates the multilayer film time.

[physical property of 4. multilayer films]

Multilayer film of the invention has above-mentioned resin layer, thus the sliding property in the face of resin layer side is high.Therefore, it is coiling into Web-like and after film roll is made, be able to suppress the generation of convex defect.

In addition, multilayer film of the invention has the small resin layer of internal haze as described above, it is thus possible to reduce in it Portion's mist degree.Specifically, the internal haze of multilayer film preferably 5% or less, more preferable 3% or less, particularly preferred 1% or less.Here, The internal haze of multilayer film can be measured using following methods.

Prepare the quartz cell of height 55mm, width 36mm, optical path length 10mm.The filling silicon oil in the quartz cell.By multilayer Film is put into the silicone oil, obtains measurement sample.Using the measurement sample prepared in this way, the inside of haze meter measurement multilayer film is utilized Mist degree.

In addition, the total light transmittance of preferably multilayer film is high from the viewpoint of playing consistently the function as optical film.Tool Body, the total light transmittance with 1mm thickness conversion is preferably 80% or more, more preferable 90% or more.Here, total light transmittance can be with base In JIS K0115, use spectrophotometer (Japanese light splitting company manufactures, UV, visible light near infrared spectrometer " V-570 ") To measure.

Multilayer film can be the phase difference film that direction or thickness direction in face have delay.As the model specifically postponed It encloses, can be set according to the purposes of multilayer film.If enumerating specific range, the delay Re in direction can be in usual face 10nm~500nm, thickness direction delay Rth can suitably be selected in -500nm~500nm range.

In addition, in the face of multilayer film the deviation of the delay Re in direction be usually within 10nm, within preferably 5nm, more preferably Within 2nm.By making the deviation for postponing Re in direction in face in above range, multilayer film is being used as liquid crystal display device phase In the case where potential difference film, display quality can be made good.Here, the deviation of the delay Re in direction refers in face: in the width along film In face at 0 ° of angle of light of the measurement of degree direction when the delay Re in direction, the maxima and minima of the delay Re in direction in the face Difference.Here, refer to the incident ray state orthogonal with the surface of film for 0 ° of angle of light.

The amount of the residual volatile ingredient of multilayer film is preferably 0.1 weight % or less, more preferable 0.05 weight % or less, more It is preferred that 0.02 weight % or less.By making the amount of volatile component in above range, dimensional stability is improved, and can reduce multilayer The ongoing change of the delay Rth of the delay Re and thickness direction in direction in the face of film.

The size of the width direction of multilayer film can be such as 1000mm~3000mm.In addition, for the length of multilayer film There is no limit for the size in direction, but the film of preferably strip.Here, the film of " strip " refers to the width relative to film, has extremely Few 5 times or more of length preferably the length with 10 times or more than it, in particular to is taken care of with that can coil into web-like Or carry the film of the length of degree.

[manufacturing methods of 5. multilayer films]

Multilayer film of the invention can be by including preparing the process of base material film and manufacturing resin on the base material film of preparation The manufacturing method of the process of layer manufactures.Here, as described above, the process for manufacturing resin layer on base material film includes obtaining fluid The coating resin is coated on base material film and forms the process of the film of coating resin and make by the process of the coating resin of shape The film for the coating resin being formed on base material film solidifies and/or the dry process for obtaining resin layer.Therefore, multilayer film can lead to The manufacturing method for example including following processes is crossed to manufacture: preparing the process of base material film；By the different a variety of particles of average grain diameter And the process that cohesive polymers are obtained by mixing the coating resin of flow-like；Coating resin is coated on base material film and forms painting The process of the film of cloth resin；And make to be formed in the film solidification of coating resin on base material film and/or drying obtains resin layer Process.

In addition, in the case where multilayer film has the random layer in addition to base material film and resin layer, it can be in multilayer film The process that any point-in-time in manufacturing method is configured arbitrary layer.It should be noted that resin layer with base material film phase The face tossed about usually becomes the most surface of multilayer film and exposes.Therefore, in general, arbitrary layer is arranged in base material film and resin layer The face of opposite side.

Further, it is also possible to which any point-in-time in the manufacturing method of multilayer film is carried out to base material film, resin layer and multilayer The process that film is stretched.

Furthermore, it is possible to carry out the process that multilayer film is coiled into web-like.

[purposes of 6. multilayer films]

Multilayer film of the invention is used usually as optical film.The example of optical film as the purposes for becoming multilayer film, Protective film, phase difference film, optical compensation films etc. can be enumerated.Wherein, multilayer film of the invention be preferably used as phase difference film or Polaroid protective film is particularly preferably used as polaroid protective film.

Polarizing film is generally configured with the polarizer and polaroid protective film.Therefore, multilayer film of the invention is protected as polarizing film In the case where cuticula, multilayer film of the invention is usually fitted in into the polarizer.At this point, usually in the face of the resin layer side of multilayer film Multilayer film and the polarizer are bonded.

When multilayer film to be bonded with the polarizer, directly multilayer film and the polarizer can not be pasted via adhesive layer It closes, can also be bonded via adhesive layer.Furthermore, it is possible to it only is bonded multilayer film in the one side of the polarizer, it can also be on two sides Fitting.Only in the case where the one side of the polarizer is bonded multilayer film, it is high the transparency can also to be bonded in the another side of the polarizer Other films.

The polarizer can be for example, by carrying out after making polyvinyl alcohol film absorption iodine or dichroic dye in boric acid bath It is uniaxially stretched to manufacture.Alternatively, it is also possible to for example, by making polyvinyl alcohol film absorption iodine or dichroic dye and being stretched, into And a part of the polyvinyl alcohol units in strand is modified as polyvinylene unit and is manufactured.In addition, as the polarizer, Can be used for example: the grid polarizer, the multilayer polarizer, cholesteryl liquid crystal polarizer etc., which have, is separated into reflected light for polarised light With the polarizer of the function of transmitted light.Wherein, the polarizer of polyvinyl alcohol is preferably comprised.The degree of polarization of the polarizer is preferably 98% More than, more preferably 99% or more.The average thickness of the polarizer is preferably 5 μm~80 μm.

As for optically transparent bonding agent to can be used by the bonding agent of the polarizer and multilayer film bonding.As The bonding agent, for example: aqueous adhesive, solvent type adhesive, bi-component curing type bonding agent, light-cured type bonding Agent, pressure-sensitive bonding agents etc..Wherein, preferred aqueous adhesive, the aqueous adhesive of particularly preferred polyvinyl alcohol.In addition, viscous Connecing agent can be used alone, two or more can also be applied in combination with arbitrary ratio.

As light-cured type bonding agent, can be used for example containing carbamate (methyl) acrylate, (methyl) third The esters of acrylic acid bonding agent of olefin(e) acid hydroxy alkyl ester and acrylamide derivative.

Carbamate (methyl) acrylate can be for example, by after making polyisocyanates and polyol reaction, into one Step makes the allyl ether compound reaction of (methyl) acyclic compound and hydroxyl as needed of hydroxyl, thus conduct Oligomer containing free-radical polymerised unsaturated group and obtain.In addition, carbamate (methyl) acrylate can also be with After (methyl) acyclic compound and polyol reaction for example, by making hydroxyl, further reacts and obtain with polyisocyanates It arrives.

As carbamate (methyl) acrylate, due to being easy to make adhesive strength, flexibility, photo-curable and viscosity Equal acquirements balance, therefore having the number-average molecular weight of 2~3 double bonds and every 1 double bond it is preferable to use each molecule is 500 ~3000 carbamate (methyl) acrylate.

The amount of carbamate (methyl) acrylate in light-cured type bonding agent is usually 30 weights of weight %~50 Measure %.By making the amount of carbamate (methyl) acrylate more than the lower limit value of above range, bonding agent can be prevented Layer becomes fragile.In addition, by the way that below the upper limit, the viscosity of bonding agent can be reduced, furthermore it is possible to improve adhesive strength.

As (methyl) acrylic acid hydroxy alkyl ester, for example: (methyl) hydroxy-ethyl acrylate, (methyl) acrylic acid Hydroxypropyl acrylate, (methyl) hy-droxybutyl.Wherein, particularly preferred hydroxyethyl methacrylate.

The amount of (methyl) acrylic acid hydroxy alkyl ester in light-cured type bonding agent is usually 13 weight of weight %~40 %.It is logical Crossing makes the amount of (methyl) acrylic acid hydroxy alkyl ester more than the lower limit value of above range, and the hydrophilic of bonding agent entirety can be improved Property, therefore, the adhesive strength relative to polyvinyl alcohol polarizing coating especially can be improved.In addition, by below the upper limit, It can prevent adhesive layer from becoming fragile, furthermore it is possible to improve the photo-curable of bonding agent.

As acrylamide derivative, it can be cited for example that: N,N-DMAA, N, N- diethyl acryloyl Amine, N, N- dimethylaminoethylacrylamide, N, N- dimethylaminopropylacryl amide, n-isopropyl acrylamide, N, N- dimethylaminopropylacryl amide, N- hydroxyethyl acrylamide.Wherein, particularly preferred N, N- acrylamide, N- N-isopropylacrylamide, N, N- dimethylaminopropylacryl amide, N- hydroxyethyl acrylamide.

The amount of acrylamide derivative in light-cured type bonding agent is usually 0~30 weight %, and preferably 1 weight %~ The range of 30 weight %.

Light-cured type bonding agent in addition to the above ingredients, further preferably (methyl) propylene containing 30 weight of weight %~40 % Sour isobornyl thiocyanoacetate.By containing (methyl) isobornyl acrylate, adhesive layer can be assigned with heat resistance.Furthermore, it is possible to right Viscosity for improveing coating performance is adjusted, without will lead to adhesive property reduction.

Light-cured type bonding agent preferably comprises Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater, for example: 1- hydroxyl Butylcyclohexyl phenyl ketone, 2,2- dimethoxy -2- phenyl acetophenone, xanthone, Fluorenone, benzaldehyde, fluorenes, anthraquinone, triphenylamine, Carbazole, 3- methyl acetophenone, 4- chlorobenzophenone, 4,4 '-dimethoxy-benzophenones, 4,4 '-diaminobenzophenones, rice Chi Ketone, benzoin propyl ether, benzoin ethyl ether, benzoin dimethylether, 1- (4- isopropyl phenyl) -2- hydroxy-2-methyl propane - 1- ketone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, thioxanthones, diethyl thioxanthone, 2-isopropylthioxanthone, 2- diuril Ton ketone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholino propane-1- ketone, 2,4,6- trimethyl benzoyl diphenyl base oxygen Change phosphine etc..In addition, the amount of the Photoepolymerizationinitiater initiater in Photocurable adhesive agent is usually 2 weight of weight %~10 %.

The viscosity of bonding agent usually 20mPa or more, preferably 30mPa or more at 23 DEG C, more preferably 50mPa with On, usually 5000mPa hereinafter, preferably 3000mPa hereinafter, more preferably 1500mPa or less.

The average thickness of adhesive layer is preferably 0.05 μm or more, and more preferably 0.1 μm or more, preferably 5 μm hereinafter, more Preferably 1 μm or less.

For the method that is bonded multilayer film with the polarizer there is no limit.Such as preferred following methods: the one of the polarizer Face is bonded the polarizer and multilayer film as needed and after coating adhesive, using roller laminator, and is done as needed The irradiation of the light such as dry or ultraviolet light.

Embodiment

Hereinafter, the present invention is specifically described in conjunction with the embodiments.But the present invention is not limited to implementations as shown below Example.

In the following description, " % ", " ppm " of expression amount and " part " are then weight basis unless otherwise specified. In addition, operation below is unless otherwise specified, then carried out in room temperature, normal pressure atmosphere.

[evaluation method]

[height of protrusion and the measuring method of quantity]

Using fine shape measurement device (small slope studies made " ET4000M "), with cutoff value (cutoff) 0.8mm, survey Determine the height and number of protrusion present on the face with base material film opposite side for the resin layer that range 1mm × 1mm determines multilayer film Amount.The measurement is carried out in the central portion of the width direction of multilayer film.

[measuring method of internal haze]

The quartz cell of height 55mm, width 36mm, optical path length 10mm are prepared.Filling silicon oil (the Toray in the quartz cell Dow Corning company manufactures " SH710 ").Multilayer film is put into the silicone oil, measurement sample has been prepared.Prepared using such Measurement sample, the internal haze of multilayer film is determined using haze meter (Japanese electricity Se industrial group manufacture " NDH-2000 ").

[measuring method of peel strength]

(manufacturing method of bonding agent)

Pure water 66.5g is measured in 100g glass container.The pure water is heated up to 80 DEG C, is stirred using stirrer. It is slowly added to polyvinyl alcohol (Japan's synthesis chemistry system " GOHSEFIMER Z200 ") 3.5g into the pure water, is allowed to be completely dissolved, 5% poly-vinyl alcohol solution is obtained.Then, restore the poly-vinyl alcohol solution to room temperature.Add into the poly-vinyl alcohol solution Add relative to the polyvinyl alcohol in poly-vinyl alcohol solution be 1% glyoxal as crosslinking agent, be sufficiently stirred, be bonded Agent.

(manufacturing method of the polarizer)

80 μm of thickness of polyvinyl alcohol film is dyed in 0.3% iodine aqueous solution.It then, will be poly- after dyeing Vinyl alcohol film is stretched to 5 times in the boric acid comprising 4% and the aqueous solution of 2% potassium iodide, 4 minutes dry in 50 DEG C, obtains The polarizer.

(manufacture of polarizing film)

Above-mentioned bonding agent is coated with using rod coaters on the face of the resin layer side of multilayer film.It is loaded on the adhesive layer The polarizer is squeezed with roller laminator, and multilayer film is bonded with the polarizer.It has obtained successively having the polarizer as a result, glue Connect the polarizing film of oxidant layer, resin layer and base material film.

(measurement of peel strength)

The polarizing film of manufacture is cut into width 10mm, has obtained test film.Using adhesive, (Dong electrician company is manufactured " No.5601 ") face of the multilayer film side of the test film is fitted on the face of glass plate.Then, accurate universal testing machine is utilized The upper jaw of (company of Shimadzu Seisakusho Ltd. manufacture " Autograph AGS-5kNG ") clamps the polarizer of test film, with 20mm/ The speed of min is pulled towards the vertical direction in the face relative to glass plate.Since the polarizer is pulled, in resin layer and base It is removed at the interface of material film.At this point, determining the size of the power of the drawing polarizer.By the length direction measurement in test film The measured value of the stable 50mm range of size of power find out average value, using the average value as peel strength.

[evaluation method of volume appearance]

For the appearance of film roll made of batching multilayer film 3000m, evaluated by estimating and touching identification.

The case where recess that polygon will be not present in the circumferential surface of film roll, is evaluated as " good ", will exist in the circumferential surface of film roll The case where recess of polygon, is evaluated as " bad ".

[evaluation method of the surface state of multilayer film]

Sample is cut from multilayer film.Prepare 2 linear polarization pieces, is cut with the clamping of these linear polarization pieces from multilayer film Sample.At this point, 2 linear polarization pieces is made to be orthogonal Nicolle (Cross Nicol), the polarizing transmission observed from thickness direction Axis is mutually perpendicular to.The laminated body for successively having linear polarization piece, sample and linear polarization piece has been obtained as a result,.

The above-mentioned laminated body from thickness direction.Using light leakage part as optical defect, the quantity of optical defect is counted.This In, light leakage part refers to the part for being able to observe that the light for having penetrated laminated body.In addition, the area of sample used in measurement is 100m².The quantity of light leakage part is fewer, indicates that more there is no wrinkle and folding line, its surface state are the better in multilayer film.

[embodiment 1]

(manufacture of water-base resin)

Polyester polyol (Kawasaki is added in the reactor equipped with thermometer, blender, nitrogen ingress pipe and condenser pipe Chemical conversion industry company manufactures " MAXIMOL FSK-2000 "；Hydroxyl value 56mgKOH/g) 840 parts, 119 parts of toluene di-isocyanate(TDI), with And 200 parts of methyl ethyl ketone, in while importing nitrogen 75 DEG C react 1 hour.

After reaction, 60 DEG C are cooled to, 35.6 parts of dihydromethyl propionic acid is added, is reacted in 75 DEG C.As a result, The polyurethane solutions containing sour structure are arrived.The content of the isocyanate group (- NCO base) of polyurethane contained in the solution is 0.5%.

Then, which is cooled to 40 DEG C.In polyurethane solutions after the cooling period be added 1,500 parts of water, with And 120 parts of the isopthalic dihydrazide (224 DEG C of boiling point or more) (being 7 parts relative to 100 parts of polyurethane) as non-volatile alkali, lead to It crosses and is carried out high-speed stirred with homogenizer and emulsified.First and second are distilled off from the liquid after the emulsification under heating decompression Ketone, the aqueous dispersion for the polyurethane being neutralized.The solid component concentration of the aqueous dispersion is 40%.

Then, the amount taken so that contained polyurethane amount is 100 parts is only divided from the aqueous dispersion of the polyurethane.It is taken dividing Cooperate glycerine polyglycidyl ether (the Nagase ChemteX public affairs as epoxide in the aqueous dispersion of polyurethane out Department's manufacture " Denacol EX-313 "；Epoxide equivalent 141g/eq) 40 parts, the silicon dioxide granule of average grain diameter 40nm it is (electrified Learn industrial group's manufacture " UFP-80 ") 24 parts, silicon dioxide granule (the Nissan Chemical Industries system of average grain diameter 200nm " SNOWTEX MP-2040 ") 20 parts, as the 4,7- dihydroxy -2,4,7,9- tetramethyl -5- last of the ten Heavenly stems of nonionic surface active agent Ethylene oxide adduct (Xin chemical industrial company manufactures " Surfynol 465 "), the Yi Jishui of alkynes, it is not solid to have obtained conduct The liquid aqueous resin of the solid component concentration 5% of the polyurethane resin of change state.Here, nonionic surface active agent adds Dosage is the amount for being 100ppm relative to gained water-base resin.

(manufacture of multilayer film)

By ester ring type olefin resin, (Nippon Zeon Co., Ltd. manufactures " ZEONOR "；135 DEG C of glass transition temperature) pellet It is 2 hours dry in 70 DEG C using the hot-air drier of ventilating air.Then, (has diameter using with resin melting kneading machine The screw rod of 65mm) T-shaped mould hair style film melting extrusion molding machine, with 270 DEG C of molten resin temperature, the width of T-die The condition of molding of 500mm has manufactured the base material film of 100 μm of thickness, length 1000m.The base material film is by ester ring type olefin resin shape At base material film.

Implement discharge treatment using corona treatment plant in the one side of the base material film.Discharge treatment is implemented in base material film Surface use sized roller applicator be coated with above-mentioned liquid aqueous resin, make dry thickness be 50nm, form the film of water-base resin. Then, it is heated 60 seconds in 100 DEG C of temperature, makes the film solidification and drying of water-base resin, resin layer is formd on base material film.By This, has obtained the multilayer film for having base material film and resin layer.Using film thickness gauge, (big tomb electronics Zhu Shihui company manufactures " FE- 300 ") thickness of the resin layer of gained multilayer film, result 50nm are determined.

For gained multilayer film, evaluated using the above method.

[embodiment 2,3 and comparative example 1~4]

When manufacturing water-base resin, by amount, the average grain diameter as the glycerine polyglycidyl ether of epoxide The amount of the silicon dioxide granule of the amount and average grain diameter 200nm of the silicon dioxide granule of 40nm is changed to respectively such as 1 institute of table Show.

In addition to the above item, the manufacture and evaluation of multilayer film have been carried out as in Example 1.

[result]

Embodiment and the result of comparative example are as shown in the table.In the following table, the meaning of abbreviation is as follows.

The amount of big particle: the amount of the silicon dioxide granule of average grain diameter 200nm.

The amount of small particles: the amount of the silicon dioxide granule of average grain diameter 40nm.

Epoxy amount: the amount of glycerine polyglycidyl ether.

[table 1]

[results of 1. Examples and Comparative Examples of table]

[investigation]

It may validate that in the multilayer film that combination has base material film and resin layer, lead to by the result of Examples and Comparative Examples Crossing makes to meet 3.5≤G≤7 and N in the protrusion of resin layer formed with the face of base material film opposite side_B≥N_C≥N_D≥N_E≥N_F, In the case where batching and film roll being made, it is able to suppress the generation of convex defect, and internal haze can be reduced.

Claims

1. a kind of multilayer film, has:

Base material film and

The resin layer containing particle being set on the base material film,

Wherein,

The resin layer has multiple protrusions with the face of the base material film opposite side,

By the protrusion of (a) height 5nm in the protrusion in every 1mm²On quantity be set as N_AA/mm², (b) height 10nm Protrusion is in every 1mm²On quantity be set as N_BA/mm², (c) height 15nm protrusion in every 1mm²On quantity be set as N_CA/mm²、 (d) protrusion of height 20nm is in every 1mm²On quantity be set as N_DA/mm², (e) height 25nm protrusion in every 1mm²On number Amount is set as N_EA/mm², (f) height 30nm protrusion in every 1mm²On quantity be set as N_FA/mm²When,

With G=N_A/N_FThe value G of expression is 3.5≤G≤7,

Also, N_B≥N_C≥N_D≥N_E≥N_F,

The particle includes: the grain of the particle S with the average grain diameter less than 150nm and the average grain diameter with 150nm or more Sub- L,

The resin layer with a thickness of 10nm or more and 100nm hereinafter,

The resin layer includes polymer,

The amount of the particle S in the resin layer is 2 parts by weight or more and 24 weight relative to 100 parts by weight of polymer Part hereinafter,

The amount of the particle L in the resin layer is 5 parts by weight or more and 20 weight relative to 100 parts by weight of polymer Part hereinafter,

The difference of the average grain diameter of the particle S and the average grain diameter of the particle L be 120nm or more and 160nm hereinafter,

The difference of the amount of the particle L and the amount of the particle S is 0.5 parts by weight or more relative to 100 parts by weight of the polymer And 25 below parts by weight.

2. multilayer film according to claim 1, wherein the polymer includes polyurethane.

3. multilayer film according to claim 1, wherein thickness of the average grain diameter of the particle L relative to the resin layer Degree is 2 times or more.

4. multilayer film described in any one of claim 1 to 3, wherein the particle is silica.

5. multilayer film according to claim 4, wherein the multilayer film is phase difference film.

6. multilayer film according to claim 4, wherein the multilayer film is polaroid protective film.

7. a kind of manufacturing method of multilayer film is the manufacturing method of multilayer film according to any one of claims 1 to 6,

Wherein, which includes: