CN105934335A - Multilayered film and method for manufacturing same - Google Patents

Abstract

The invention aims to provide a multilayered film provided with a base film and a resin layer containing particles provided on the base film, wherein the resin layer has a plurality of projections on the surface on the opposite side of the base film such that the value G expressed by G=NA/NF fulfills the relation 3.5</=G</=7, and NB>/=NC>/=ND>/=NE>/=NF, where (a) the number of 5-nm-high projections per square millimeter is defined as NA/mm2, (b) the number of 10-nm-high projections per square millimeter is defined as NB/mm2, (c) the number of 15-nm-high projections per square millimeter is defined as NC/mm2, (d) the number of 20-nm-high projections per square millimeter is defined as ND/mm2, (e) the number of 25-nm-high projections per square millimeter is defined as NE/mm2, and (f) the number of 30-nm-high projections per square millimeter is defined as NF/mm2.

Description

Multilayer film and manufacture method thereof

Technical field

The present invention relates to multilayer film and manufacture method thereof.

Background technology

Known in the state of the art have the multilayer film (with reference to patent documentation 1 and 2) possessing multiple layers.Such Multilayer film is capable of being combined with the characteristic that each layer is had and the several functions obtained, because being employed In extensive use.Such as, for liquid crystal indicator, organic EL display, plasma display Show in the blooming of the various image display devices such as device, use multilayer film the most sometimes.

From the viewpoint of improving manufacture efficiency, multilayer film as above is manufactured into the film of strip more Form.Additionally, the multilayer film of such strip is typically taken up into film roll, and with the state quilt of this film roll Preserve and carrying.

Further, it is also known that have the such as such technology of patent documentation 3.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2000-79664 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2010-264643 publication

Patent documentation 3: Japanese Unexamined Patent Publication 8-73623 publication

Summary of the invention

The problem that invention is to be solved

In film roll strip multilayer film batched and manufacture, can produce in some cases and be referred to as " salient point " , the defect of the convex of width about 1mm～3mm.The defect of convex is transferred if as described above To multilayer film, then in the part being transferred, multilayer film can deform, and there is the optics damaging this part The probability of characteristic.

Additionally, because this defect is not to produce before being batched by multilayer film but produces after film roll manufactures , so being difficult to detect by carrying out checking on the production line of multilayer film.

And, if it is desired to after film roll manufactures, detect drawbacks described above, then need to send successively from film roll many Tunic and check, therefore to the multilayer film sent successively is batched again and needs to take time and effort. The film roll of drawbacks described above is not had therefore, it is difficult to filter out in the case of keeping film roll state.

In view of such background, it is desirable to develop and drawbacks described above can be suppressed in the case of making film roll to send out Raw multilayer film.

Additionally, in such bloomings such as such as phase retardation film, typically require that internal haze is little.So The requirement little to internal haze be also same in the case of this blooming is multilayer film.Therefore, right In the multilayer film of the generation that can suppress convex defect as described above in the case of making film roll, also want Ask and can reduce its internal haze.

The present invention completes in view of the above problems, it is therefore intended that provide: make the situation of film roll batching The generation of above-mentioned convex defect can be suppressed down and multilayer film and the manufacturer thereof of internal haze can be reduced Method.

The method of solution problem

The present inventor for solve the problems referred to above conduct in-depth research, found that: possess base material film and In the multilayer film of the resin bed comprising particle, resin bed with the face of base material film opposition side with given rule Rule property has the multilayer film of the most different projections, when this multilayer film is made film roll, it is possible to suppress convex The generation of shape defect, and the internal haze of multilayer film can be reduced.Thus complete the present invention.

That is, the present invention is as follows.

[1] a kind of multilayer film, it possess base material film and be arranged on described base material film containing particle Resin bed；The mask with described base material film opposition side of described resin bed has multiple projection, by described prominent The projection of the highly 5nm of (a) in Qiing is at every 1mm²On quantity be set to N_AIndividual/mm², (b) highly 10nm Projection at every 1mm²On quantity be set to N_BIndividual/mm², (c) highly 15nm projection at every 1mm² On quantity be set to N_CIndividual/mm², (d) highly 20nm projection at every 1mm²On quantity be set to N_D Individual/mm², (e) highly 25nm projection at every 1mm²On quantity be set to N_EIndividual/mm², (f) highly The projection of 30nm is at every 1mm²On quantity be set to N_FIndividual/mm²Time, with G=N_A/N_FValue G represented It is 3.5≤G≤7, and, N_B≥N_C≥N_D≥N_E≥N_F。

[2] according to the multilayer film described in [1], wherein, described resin bed comprises polymer, described polymer Comprise polyurethane.

[3] according to the multilayer film described in [1] or [2], wherein, it is different many that described particle comprises mean diameter Plant particle.

[4] according to multilayer film described in [3], wherein, described particle comprises have less than 150nm average The particle (S) of particle diameter and there is the particle (L) of mean diameter of more than 150nm.

[5] according to the multilayer film described in [1], wherein, described resin bed comprises polymer, described particle bag Containing there is the particle (S) of the mean diameter less than 150nm and there is the mean diameter of more than 150nm Particle (L), the amount of the described particle (S) in described resin bed relative to described polymer 100 weight portion, It is below more than 2 weight portions and 24 weight portions.

[6] according to the multilayer film described in [1], wherein, described resin bed comprises polymer, described particle bag Containing there is the particle (S) of the mean diameter less than 150nm and there is the mean diameter of more than 150nm Particle (L), the amount of the described particle (L) in described resin bed relative to described polymer 100 weight portion, It is below more than 5 weight portions and 20 weight portions.

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

[8] according to the multilayer film according to any one of [1]～[7], wherein, the thickness of described resin bed is More than 10nm and below 100nm.

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

[10] according to the multilayer film according to any one of [1]～[8], wherein, described multilayer film is that polaroid is protected Cuticula.

[11] manufacture method of a kind of multilayer film, it is the system of the multilayer film according to any one of [1]～[10] Making method, wherein, this manufacture method includes:

Multiple mix particles different to polymer and mean diameter is obtained the work of the resin of flow-like Sequence；

Operation by the described resin-coated film forming described resin on base material film of flow-like；And

Make the film solidification of the described resin being formed on base material film and/or be dried and obtain the work of resin bed Sequence.

[12] according to the manufacture method of multilayer film described in [11], wherein, described particle comprises to have and is less than The particle (S) of the mean diameter of 150nm and there is the particle (L) of mean diameter of more than 150nm.

The effect of invention

The multilayer film of the present invention can suppress the generation of convex defect in the case of batching and making film roll, And internal haze can be reduced.

The manufacture method of the multilayer film according to the present invention, it is possible to manufacture batch and in the case of making film roll The generation of convex defect can be suppressed and the multilayer film of internal haze can be reduced.

Accompanying drawing explanation

[Fig. 1] Fig. 1 is sectional view, it is schematically shown that an embodiment of the invention relates to many One example of tunic.

[Fig. 2] Fig. 2 is front view, it is schematically shown that in traditional film roll, because of the cementation of film Produce an example of the situation of wrinkle.

[Fig. 3] Fig. 3 is for satisfied 3.5≤G≤7 and N_B≥N_C≥N_D≥N_E≥N_FCondition One example of multilayer film, the scattergram with the height of projection as transverse axis, with number of projection as the longitudinal axis.

Symbol description

100 multilayer films

110 base material films

The face with resin bed opposition side of 111 base material films

120 resin beds

The face with base material film opposition side of 121 resin beds

122 projections

200 film roll

210 wrinkles

220 winding off spindles

230 depressions

Detailed description of the invention

Hereinafter, in conjunction with embodiment and example thing, the present invention is described in detail, but the present invention does not limit Due to embodiment shown below and example thing etc., can without departing from claims of the present invention and In the range of its equivalency range, at random change is implemented.

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

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

It addition, in the following description, the mean diameter of particle as long as no being particularly limited to, then uses logical Cross laser diffractometry measure particle diameter distribution, in the particle diameter distribution measured from small particle side calculating tired Long-pending volume reaches the particle diameter of 50%.

In the following description, in the face of film, the delay in direction is as long as no being particularly limited to, then be Value represented by Re=(nx-ny) × d.Additionally, the delay Rth of the thickness direction of film is Value represented by Rth={ (nx+ny)/2-nz} × d.Here, nx represents vertical at the thickness direction with film In direction (direction in face), provide the refractive index in the direction of largest refractive index.Ny represents described at film The refractive index in direction vertical with the direction of nx in interior direction.Nz represents the refraction of the thickness direction of film Rate.D represents the thickness of film.As long as no being particularly limited to, the mensuration wavelength of described delay is 550nm. Described delay can use commercially available measuring difference of phases device (such as, prince measures machines corporation system, " KOBRA-21ADH ") or Senarmont (Sai Nameng) method measure.

It addition, " polaroid " not only includes upright and outspoken component, also include such as resinous film There is the component of flexibility.

[1. multilayer film general introduction]

Fig. 1 is the example schematically showing the multilayer film 100 that an embodiment of the invention relates to Sectional view.

As it is shown in figure 1, the multilayer film 100 that an embodiment of the invention relates to possesses: base material film 110 and the resin bed 120 comprising particle that is arranged on this base material film 110.Additionally, described tree Lipid layer 120 has multiple projection 122 with the face 121 of base material film 110 opposition side.In FIG, symbol Number " T " represents the thickness of resin bed 120, and symbol " H " represents the height of projection 122.Such as Fig. 1 Shown in, the thickness T of resin bed 120 represents the thickness in the region not having projection 122 of resin bed 120.

In this multilayer film 100, the projection 122 in the face 121 being positioned at resin bed 120 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 represented.

Additionally, N_A、N_B、N_C、N_D、N_EAnd N_FRepresent following quantity.

(a)N_A(unit: individual/mm²) represent be positioned at resin bed 120 with base material film 110 opposition side face In the projection 122 of 121, the projection of highly 5nm is at every 1mm²On quantity.

(b)N_B(unit: individual/mm²) represent be positioned at resin bed 120 with base material film 110 opposition side face In the projection 122 of 121, the projection of highly 10nm is at every 1mm²On quantity.

(c)N_C(unit: individual/mm²) represent be positioned at resin bed 120 with base material film 110 opposition side face In the projection 122 of 121, the projection of highly 15nm is at every 1mm²On quantity.

(d)N_D(unit: individual/mm²) represent be positioned at resin bed 120 with base material film 110 opposition side face In the projection 122 of 121, the projection of highly 20nm is at every 1mm²On quantity.

(e)N_E(unit: individual/mm²) represent be positioned at resin bed 120 with base material film 110 opposition side face In the projection 122 of 121, the projection of highly 25nm is at every 1mm²On quantity.

(f)N_F(unit: individual/mm²) represent be positioned at resin bed 120 with base material film 110 opposition side face In the projection 122 of 121, the projection of highly 30nm is at every 1mm²On quantity.

Here, in the value of described rising height, if it is considered that significant digits, then height 5nm represents More than 4.5nm and below 5.4nm.Additionally, similarly, if it is considered that significant digits, then height 10nm Represent more than 9.5nm and below 10.4nm, highly 15nm represent more than 14.5nm and 15.4nm with Under, highly 20nm represents more than 19.5nm and below 20.4nm, highly 25nm represent 24.5nm with Upper and below 25.4nm, highly 30nm represent more than 29.5nm and below 30.4nm.

By having such composition, multilayer film 100 is in the case of batching and making film roll, it is possible to press down The generation of convex defect processed, and internal haze can be reduced.

(1) about the suppression of generation of convex defect:

The multilayer film of the present invention can suppress reason the non-determined of the generation of convex defect, but according to this The research of a person of good sense, can be presumed as follows.It should be noted that the present invention is not by the supposition of following description Limit.

In the case of conventional film being batched and manufacturing film roll, the film that wound is got up is sent out the most locally Raw cementation.There occurs that the part of cementation, the displacement of film are restricted in this wise.Therefore, when take-up, The tension force being applied to film cannot be dispersed to film entirety, can produce unbalanced stress in film.And such stress Inequality sometimes results in film roll and produces wrinkle.

Fig. 2 is to be shown schematically in traditional film roll 200, creates wrinkle because of the cementation of film The front view of one example of the situation of 210.As in figure 2 it is shown, manufacture film roll is taken at winding off spindle 220 In the case of film roll 200, described wrinkle 210 is usually formed as polygon.Specifically, most cases Depression 230 meeting of lower polygon (usually rhombus) in the axial of film roll 200 and is upwardly formed multiple in week, And form wrinkle 210 in the position being equivalent to polygonal limit of depression 230.

Such wrinkle 210, when it just starts to occur, can't make film produce significantly warpage.But, If film roll being preserved, then because the deadweight of film, the sinking degree of above-mentioned polygonal depression 230 is (deep Degree) can be gradually increased.Then, if the sinking degree of this depression 230 increases, then wrinkle is being created The part of 210, the degree of the warpage of film increases.If it is believed that film occurs beyond elastic limit Significantly warpage, then in the part of this warpage, film can occur plastic deformation, produces and is referred to as " salient point " The defect of convex.

On the other hand, as it is shown in figure 1, in the face 121 with base material film 110 opposition side of resin bed 120 It is provided with the multilayer film 100 of the multiple projections 122 meeting above-mentioned condition, the excellent in sliding property in its face 121. It may be speculated that owing to the face 121 with base material film 110 opposition side of resin bed 120 usually becomes multilayer film The most surface of 100, therefore by making the excellent in sliding property in this face 121, batched by multilayer film 100 In the case of, it is possible to the cementation of the multilayer film 100 that suppression wound is got up.Therefore, it is possible to suppression film roll is wrinkled The generation of stricture of vagina, so the generation of the convex defect owing to this wrinkle can be suppressed.

(2) about internal haze:

As the method for sliding in the face of film increased as mentioned above, such as it is contemplated that arrange on this face Projection increases the roughness in this face.But, in the case of rising height height, dash forward owing to being provided with this The optical effects such as the reflection in the face risen and refraction, can cause Surface haze to be substantially increased, it is difficult to obtain optics Film.To this end, present inventors studied setting on the face of film can keep the degree of little Surface haze Low projection.

Additionally, described resin bed is formed as comprising the resin bed of particle.It is said that in general, comprising particle In resin bed, because of amount and the difference of size of particle, the internal haze of resin bed can be significantly in some cases Rise.Therefore, from the viewpoint of being applicable to blooming, preferably resin bed designed, made it possible to Enough reduce internal haze.Generally, in order to avoid the rising of internal haze, preferred particle is little.Additionally, be Prevent the rising being mixed into the internal haze caused and the generation of optical defect of big particle, be preferably used big Little consistent particle.

Thus, the present inventor has attempted setting on base material film and has comprised the particle that size is little and particle diameter is consistent Resin bed, thus the projection that rational height is low on the face of film.But, having of the film so obtained is prominent The sliding in the face risen is little, it is difficult to the generation of convex defect in suppression film roll.

Thus, the present inventor predicts: if increasing the size of particle, increasing rising height, then be provided with The sliding in the face of this projection can improve.Then, the present inventor increases rising height, increases particle Size, has carried out research similar to the above.But, even if increasing rising height, sliding does not fills yet Divide and improve, it is difficult to the generation of convex defect in suppression film roll.

Additionally, increase projection quantity to be considered likely to improve the sliding of bossed of tool.But, In order to increase projection quantity, need to increase the quantity of particle.And if number of particles is too much, then due to tree The reflection of the inside of lipid layer and refraction, may cause internal haze to increase.

On the other hand, in the multilayer film 100 shown in Fig. 1, resin bed 120 with base material film 110 The face 121 of opposition side is provided with satisfied 3.5≤G≤7 and N_B≥N_C≥N_D≥N_E≥N_FCondition Projection 122.This condition (3.5≤G≤7 and N_B≥N_C≥N_D≥N_E≥N_F) relate to being not result in table The low projection 122 of the degree that face mist degree increases, represents that the distribution width of the height of this projection 122 and height are prominent Play quantity less than low projection quantity.For meeting an example of the multilayer film 100 of this condition, Fig. 3 shows Scattergram with the height of projection 122 as transverse axis, with the quantity of projection 122 as the longitudinal axis.Described condition table Show, at as the Fig. 3 with the height of projection 122 as transverse axis, with the quantity of projection 122 as the longitudinal axis point In Butut, the width width at peak and mild, and also the summit at peak is positioned at desired little scope.Comprise in this wise There is the face 121 of the projection 122 of differing heights, there is significantly high sliding.It is not regarded as traditionally For the low projection of the degree of Surface haze can be suppressed, tool can be adjusted by adjusting the distribution of its projection There is the sliding in the face of this projection.From the point of view of such traditional understanding, it may be said that as described above The distribution adjusting rising height improves the sliding in the face with this projection, and this is unexpected effect Really.

Above-mentioned condition (3.5≤G≤7 and N is met additionally, have_B≥N_C≥N_D≥N_E≥N_F) prominent The resin bed risen, can pass through suitably to be used with big particle combinations by particle little for size, thus sharp Manufacture with a small amount of particle.Owing to the amount of particle can be reduced, therefore, it is possible to avoid being drawn by this resin bed The increase of the internal haze risen.

Therefore, even if the multilayer film of the present invention is in the case of being formed projection by the particle contained by resin bed, It also is able to suppress the generation of convex defect in film roll, without causing internal haze to increase.Conventionally, Never from the viewpoint of the infringement due characteristic of blooming, the size using particle in blooming is the least more excellent Choosing, additionally, particle diameter is the most consistent more preferred.From the point of view of such traditional understanding, it may be said that by as above Particle little for size and big particle combinations are made for arranging internal haze is little and slides in surface describedly Property excellent resin bed, this is unexpected effect.

[2. base material film]

As base material film, generally use resinous film.As the resin of composition base material film, can use and contain There is the resin of arbitrary polymer.Wherein, as constitute base material film resin, preferred thermoplastic resin, Particularly preferably ester ring type olefin resin.Ester ring type olefin resin is the tree comprising ester ring type olefin polymer Fat, its transparency, agent of low hygroscopicity, dimensional stability and the excellent such as Lightness, it is adaptable to blooming.

It addition, base material film can be the film of the single layer structure containing only 1 layer, it is also possible to be possess 2 layers with On the film of multiple structure of layer.In the case of base material film has multiple structure, preferred substrates film is possessed Layer in more than 1 layer formed by ester ring type olefin resin.

Ester ring type olefin polymer is the polymer in the construction unit of polymer with ester ring type structure, Main chain can be used to have the polymer of ester ring type structure and side chain has in the polymer of ester ring type structure Any polymer.It addition, ester ring type olefin polymer can be used alone a kind, it is also possible to arbitrarily Ratio combine uses two or more.Wherein, consider from the viewpoint such as mechanical strength, thermostability, preferably main chain Polymer containing ester ring type structure.

As ester ring type structure, such as, can enumerate: saturated fat ring type hydrocarbon (cycloalkane) structure, unsaturation Ester ring type hydrocarbon (cycloolefin, cycloalkyne) structure etc..Wherein, consider from the viewpoint such as mechanical strength, thermostability, Preferably cycloalkane structure and cycloolefin structure, wherein particularly preferred cycloalkane structure.

For constituting the carbon number of ester ring type structure, the carbon number of each ester ring type structure is preferred It is more than 4, more preferably more than 5, preferably less than 30, more preferably less than 20, The scope of particularly preferably less than 15.Thus, the mechanical strength of base material film, thermostability and one-tenth can be made Type acquirement high balance, therefore preferably.

The ratio of the construction unit with ester ring type structure in ester ring type olefin polymer can be according to use Purpose suitably selects, more than preferably 55 weight %, more preferably more than 70 weight %, especially It is preferably more than 90 weight %.If the structure with ester ring type structure in ester ring type olefin polymer The ratio of unit within the range, is then preferred from the viewpoint of the transparency and thermostability of base material film 's.

As ester ring type olefin polymer, such as, can enumerate: norbornene polymer, monocycle ring-type Olefin polymer, cyclic conjugated diene polymer, alicyclic vinyl ring type hydrocarbon polymer and their hydrogenation Thing etc..Wherein, norbornene polymer is preferred due to the transparency and good forming ability.

As norbornene polymer, such as, can enumerate: there is the open loop of the monomer of norborene structure Polymer or there is the monomer of norborene structure and the ring-opening copolymer of any monomer or their hydrogen Compound；There is the addition polymer of the monomer of norborene structure or there is the monomer of norborene structure Addition copolymer or their hydride etc. with any monomer.Wherein, from the transparency, mouldability, Thermostability, agent of low hygroscopicity, dimensional stability, the viewpoint such as Lightness consider particularly preferably have norborneol The hydride of the ring-opening polymerization polymer of the monomer of alkene structure and there is the open loop of monomer of norborene structure The hydride of copolymer.

As having the monomer of norborene structure, such as, can enumerate: dicyclo [2.2.1] hept-2-ene" is (usual Name: norborene), three ring [4.3.0.1^2,5] decyl-3,7-diene (trivial name: dicyclopentadiene), 7,8-benzo Three ring [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 The derivant of carbon-3-alkene (trivial name: tetracyclododecane) and these compounds (such as, ring has takes The derivant of Dai Ji) etc..Here, alternatively base, such as, can enumerate: alkyl, alkylidene, pole Property group etc..It addition, these substituent groups are identical or different, can multiple bonding cyclization.It addition, have The monomer of norborene structure can be used alone a kind, it is also possible to arbitrary ratio be applied in combination 2 kinds with On.

As the kind of polar group, such as, can enumerate: hetero atom or there is heteroatomic atomic group etc.. As hetero atom, such as, can enumerate: oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, halogen atom etc.. As the object lesson of polar group, can enumerate: carboxyl, carbonyloxy group carbonyl, epoxy radicals, hydroxyl, Epoxide, ester group, silanol group, silicyl, amino, itrile group, sulfonic group etc..

As can be the most permissible with any monomer of the monomer generation ring opening copolymer with norborene structure Enumerate: single cyclic olefin such as cyclohexene, cycloheptene, cyclo-octene and derivant thereof；Cyclohexadiene, ring Cyclic conjugated diene and the derivants etc. thereof such as heptadiene.Can open with the monomer with norborene structure Any monomer of ring copolymerization can be used alone a kind, it is also possible to is applied in combination two or more with arbitrary ratio.

Have the monomer of norborene structure ring-opening polymerization polymer and and can with there is norborene structure The ring-opening copolymer of any monomer of monomer copolymerization, such as can gather in known open loop by making monomer Close and carry out in the presence of catalyst being polymerized or copolymerization manufactures.

As can be the most permissible with any monomer of the monomer generation addition copolymerization with norborene structure Enumerate: the alpha-olefin of the carbon numbers 2～20 such as ethylene, propylene, 1-butylene and their derivant；Ring Cycloolefin and their derivants such as butylene, cyclopentenes, cyclohexene；1,4-hexadiene, 4-methyl isophthalic acid, 4- Hexadiene, 5-methyl isophthalic acid, the non-conjugated diene etc. such as 4-hexadiene.Wherein, preferably alpha-olefin, more preferably second Alkene.It addition, can be independent with any monomer of the monomer generation addition copolymerization with norborene structure Use a kind, it is also possible to be applied in combination two or more with arbitrary ratio.

Have the monomer of norborene structure addition polymer and and can with there is norborene structure The addition copolymer of any monomer of monomer copolymerization, such as can gather in known addition by making monomer Close and carry out in the presence of catalyst being polymerized or copolymerization manufactures.

As the cyclic olefin polymer of monocycle, such as, can enumerate: cyclohexene, cycloheptene, cyclo-octene Addition polymer etc. the cyclic olefin monomers with monocycle.

As cyclic conjugated diene polymer, such as, can enumerate: make 1,3-butadiene, isoprene, The polymer that the addition polymer of chlorobutadiene equiconjugate diene monomers carries out cyclization and obtains；Ring penta 1,2-or the 1,4-addition polymer of the cyclic conjugated diene monomer such as diene, cyclohexadiene；And their hydrogen Compound etc..

As alicyclic vinyl ring type hydrocarbon polymer, such as, can enumerate: VCH, ethylene basic ring The polymer of the alicyclic vinyl ring type hydrocarbon monomers such as hexane and hydride thereof；Will be by styrene, Alpha-Methyl benzene second Aromatic moieties contained in the polymer that the vinyl aromatic hydrocarbon monomer such as alkene are polymerized hydrogenates Hydride；Alicyclic vinyl ring type hydrocarbon monomer or vinyl aromatic hydrocarbon monomer and can be with these second The copolymerization such as the random copolymer of any monomer formation of alkenyl aroma race hydrocarbon monomer copolymerization or block copolymer The hydride etc. of the aromatic ring of thing.As above-mentioned block copolymer, such as, can enumerate: diblock copolymer, Triblock copolymer or its above segmented copolymer and gradient block copolymers etc..

Constitute the weight average molecular weight (Mw) of polymer contained in the resin of base material film usually 10,000 with On, preferably 15, more than 000, more preferably 20, more than 000, usually 100, less than 000, excellent Elect 80 as, less than 000, more preferably 50, less than 000.Here, described weight average molecular weight is to use Cyclohexane give is solvent, the polyisoprene measured by gel permeation chromatography or polystyrene conversion Weight average molecular weight.It should be noted that in the case of sample is insoluble in hexamethylene, it is possible to use first Benzene is as the solvent of gel permeation chromatography.When weight average molecular weight is in such scope, the machine of multilayer film Tool intensity and molding processibility can obtain high balance, therefore preferably.

Constitute molecular weight distribution (weight average molecular weight (the Mw)/number of polymer contained in the resin of base material film Average molecular weight (Mn)) usually more than 1.2, preferably more than 1.5, more preferably more than 1.8, Usually less than 3.5, preferably less than 3.0, more preferably less than 2.7.By making molecular weight It is distributed in more than the lower limit of above-mentioned scope, the productivity of polymer, suppression cost can be improved.It addition, By below higher limit, it is possible to reduce low molecular weight compositions, therefore slack time can be extended.Therefore, Relaxing when can suppress to be exposed to high temperature, can improve the stability of base material film.

The absolute value of the photoelastic coefficient C constituting polymer contained in the resin of base material film is preferably 10×10^-12Pa^-1Hereinafter, more preferably 7 × 10^-12Pa^-1Hereinafter, particularly preferably 4 × 10^-12Pa^-1Below. Birefringence is set to Δ n, stress is when being set to σ, and photoelastic coefficient C is the value shown in " C=Δ n/ σ ". By making the photoelastic coefficient of polymer be in above-mentioned scope, prolonging of direction in the face of base material film can be reduced The deviation of Re late.

Constitute the saturated water absorption of polymer contained in the resin of base material film be preferably 0.03 weight % with Under, more preferably below 0.02 weight %, below particularly preferably 0.01 weight %.If it is saturated Water absorption rate is above-mentioned scope, then can reduce delay and the delay of thickness direction in direction in the face of base material film Rheological parameters' change with time.It is additionally possible to suppress possess polaroid and the image display device of the multilayer film of the present invention Deterioration, the display stable for extended periods of time of display and good can be made.

Saturated water absorption is the matter to increase after test film impregnates in the water of uniform temperature certain time Measure the value represented relative to the percentage rate of the quality of test film before dipping.Generally, soak in the water of 23 DEG C Stain test film 24 hours and be measured.The saturated water absorption of polymer such as can be polymerized by minimizing The amount of the polar group in thing regulates to above-mentioned scope.Therefore, from reducing saturated water absorption further Viewpoint considers, constitutes polymer contained in the resin of base material film and does not the most have polar group.

As long as significantly damaging the effect of the present invention, then constitute in the resin of base material film in addition to polymer Any composition can also be contained.As the example of this any composition, can enumerate: pigment, dyestuff are waited Toner；Plasticizer；Fluorescent whitening agent；Dispersant；Heat stabilizer；Light stabilizer；UV absorbent； Antistatic agent；Antioxidant；Lubricant；The additives such as surfactant.These compositions can individually make With a kind, it is also possible to be applied in combination two or more with arbitrary ratio.

It should be noted that using the ester ring type olefin resin situation as the resin constituting base material film Under, this ester ring type olefin resin does not the most comprise particle.Grain is not the most comprised here, described Son refers to, even if making resin contain particle, the most only allows to for the state being entirely free of particle The ascensional range of the mist degree of base material film is the amount of the scope of less than 0.05%.Ester ring type olefin polymer exists The tendency not enough with the affinity of numerous organic fillers and inorganic particulate.Therefore, by the fat containing particle When ring type olefin resin stretches, easily produce space.But, by reducing particle as described above Amount, it is possible to the generation in space during suppression stretching, thus prevent mist degree from increasing.

The amount constituting polymer contained in the resin of base material film and additive can be many in the present invention Tunic can show and arbitrarily set in the range of desired optical characteristics.Such as, the tree of base material film is constituted The ratio of the polymer in fat is generally 50%～100% or 70%～100%.Particularly using alicyclic ring In the case of the formula olefin resin resin as composition base material film, polymerization contained in ester ring type olefin resin The ratio of thing is usual 80%～100%, preferably 90%～100%.

As it has been described above, base material film can be the film of the single layer structure only possessing a layer, it is also possible to for possessing 2 The film of the multiple structure of the layer that layer is above.By the film making base material film be multiple structure, can be by the present invention Multilayer film be used as to have the blooming of various characteristic.

In the case of base material film possesses the layer of more than 2 layers, can possess a kind of layer of more than 2 layers, it is possible to To possess different two or more layers.It addition, base material film can also be provided with by except above-mentioned ester ring type The layer of the resin formation beyond olefin resin.As by the resin formation beyond grease removal ring type olefin resin Layer, such as, can enumerate: has antisitic defect, antireflection, antistatic, the layer of the function such as anti-dazzle, antifouling.

The average thickness of base material film is preferably more than 5 μm, and more than more preferably 20 μm, preferably 500 μm Hereinafter, below more preferably 300 μm.

Additionally, the thickness change of base material film is preferably above-mentioned average thickness on length direction and width ± 3% within.By making thickness be changed to above-mentioned scope, the optics such as delay that can reduce base material film is special The deviation of property.

The amount of the volatile ingredient contained by base material film is preferably below 0.1 weight %, and more preferably 0.05 Below weight %, more preferably below 0.02 weight %.It is above-mentioned by the amount making volatile ingredient Scope, can improve the delay in direction and prolonging of thickness direction in the face of dimensional stability, reduction base material film Slow rheological parameters' change with time.Additionally, due to the polaroid possessing the multilayer film of the present invention or image can be suppressed to show The deterioration of showing device etc., therefore, it can the display stable for extended periods of time making display with good.Here, Volatile ingredient refers to the material of molecular weight less than 200.As volatile ingredient, such as, can enumerate residual Stay monomer and solvent etc..The amount of volatile ingredient, can as the total amount of the material of molecular weight less than 200 With by utilizing gas chromatogram to be analyzed to quantitatively.

Manufacture method for base material film does not limit.Base material film can be by being used for forming this base material film Resin be shaped by the arbitrary film method of forming and obtain.As the film method of forming, such as, can enumerate: Casting moulding, extrusion moulding, film blowing etc..Wherein, the extrusion by melting of solvent is not used Residual volatile amount can be efficiently reduced, from earth environment, the viewpoint of operating environment and manufacture effect It is preferred from the viewpoint of rate excellence.As extrusion by melting, the inflation method using mould can be enumerated Deng, wherein, from the viewpoint of productivity, thickness and precision excellence, the method that T-shaped mould is preferably used.

Additionally, in the case of base material film possesses the layer of more than 2 layers, the manufacture method for base material film does not has Limit.For example, it is possible to use bonding agent to carry out fitting as required on the film layer manufactured respectively and manufacture base Material film.Bonding agent can select suitable material according to the kind of resin forming film layer to be fit.Make For the example of bonding agent, can enumerate: acrylic adhesive, carbamate bonding agent, polyester-bonded Agent, 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 agent, SEBS (styrene-ethylene-butylene-styrene copolymer) bonding agent, SIS (styrene-isoprene-benzene second Alkene block copolymer) ethylene adhesive such as bonding agent, ethylene-styrene copolymer, ethylene-(methyl) propylene The acid acrylate adhesive etc. such as methyl terpolymer, ethylene-(methyl) ethyl acrylate copolymer.Bonding agent Can be used alone a kind, it is also possible to be applied in combination two or more with arbitrary ratio.Formed by bonding agent The average thickness of bond layer is preferably more than 0.1 μm, and more than more preferably 0.5 μm, preferably 10 μm Hereinafter, below more preferably 5 μm.

In the case of not using bonding agent to manufacture the base material film of the layer possessing more than 2 layers, it is possible to use example The co-extrusion modling methods such as modulus method as T-shaped in coextrusion, coextrusion inflation method, coextruded layer platen press；Dry type layer The film methods laminated into type etc. such as platen press.

Alternatively, it is also possible to use the resin such as containing other film layer of composition in the coating of the surface of a certain film layer The coat forming method etc. of solution manufacture the base material film of the layer possessing more than 2 layers.

Wherein, from manufacturing the viewpoint of efficiency and not making the viewpoint of the volatile ingredients such as residual solvent base material film Consider, preferably co-extrusion modling method.In co-extrusion modling method, the T-shaped modulus method of particularly preferred coextrusion.Enter One step, in the T-shaped modulus method of coextrusion, can be to enumerate feed block mode and many menifolds mode, from reducing From the viewpoint of the deviation of each layer thickness, further preferred many menifolds mode.

Base material film can be the unstretching film that stretch processing is not carried out, it is also possible to implement stretch processing Stretched film.It addition, in the case of base material film possesses the layer of more than 2 layers, can make to implement stretching in advance The film laminating processed closes and obtains stretched film, it is also possible to drawing of the multiple structure obtained by coextrusion etc. Stretch cephacoria to implement stretch processing and obtain stretched film.

Drawing process without particular limitation of, such as can use in uniaxial stretching method, biaxial stretching process is any Method.If enumerating the example of drawing process, then as the example of uniaxial stretching method, can enumerate: profit The method carrying out uniaxial tension along its length by the difference of the peripheral speed of the roller of film conveying；Use tentering Stretching-machine carries out the method etc. of uniaxial tension in the width direction.It addition, as the example of biaxial stretching process, Can enumerate: while widening and stretching along its length for the interval of fixing fixture, logical Biaxial stretching process while crossing the opening angle of guide rail and stretching in the width direction；Film conveying is utilized to use Roller between the difference of peripheral speed stretch along its length after, with two end of holder and make The progressively biaxial stretching process etc. stretched is carried out in the width direction with tentering stretching-machine.Further, it is also possible to adopt With such as using carrying capacity or the stretching that width or length direction can be applied left and right friction speed Power or access the tentering stretching-machine, along the most not parallel also off plumb direction with the width of film even of power Carry out the oblique extension method of oblique extension continuously.

As the device for stretching, such as, can enumerate: longitudinal uniaxial tension machine, tentering stretching-machine, Foam tensile machine, roller stretching-machine etc..For draft temperature, at the resin by constituting film to be tensioned When glass transition temperature is set to Tg, more than draft temperature preferably (Tg-30 DEG C), more preferably (Tg-10 DEG C) Above, preferably (Tg+60 DEG C) below, more preferably (Tg+50 DEG C) below.Stretching ratio can be according to use The optical characteristics of base material film and suitably select.Concrete stretching ratio is usually more than 1.05 times, preferably It is more than 1.1 times, usually less than 10.0 times, preferably less than 2.0 times.

[3. resin bed]

Resin bed is disposed on the layer on base material film, has projection at the mask with base material film opposition side.This is dashed forward Rise with G=N_A/N_FValue G represented is usually more than 3.5, preferably more than 3.6, preferably more than 4.0, More preferably more than 4.5, usual less than 7.0, preferably less than 6.4, more preferably less than 6.0, more preferably 5.5 below.Value G is not provided with not in the face 121 of all resin beds 120 as shown in Figure 1 more than 0 expression There is the region of low projection.If additionally, below the higher limit that value G is above-mentioned scope, then it represents that all The face 121 of resin bed 120 as shown in Figure 1 be not provided with excessively having low projection regional area, with And it is not provided with the region that high projection is few.Thus, G is below the higher limit of above-mentioned scope for value, represents low Projection is balanced with high projection and combines well.Additionally, value G is more than the lower limit of above-mentioned scope, Represent owing to projection quantity is suitable, therefore, it is possible to the suppression of projection quantity is being not result in that internal haze increases Degree.Therefore, by making value G in above-mentioned scope, it is possible to batch and masking volume in the case of press down The generation of convex defect processed, and internal haze can be reduced.

Additionally, the projection with the face of base material film opposition side being positioned at resin bed meets N_B≥N_C≥N_D≥N_E ≥N_F.This represents that the lowest projection quantity is more than the projection quantity that height is high.By meet such as this The condition of sample, it is possible to increase the sliding of bossed of the tool of resin bed, furthermore it is possible to reduce resin The internal haze of layer.

The height of projection as above and quantity can be by such as adjusting the particle contained by resin bed Size, the mode of solvent evaporation when manufacturing resin bed, come for forming the order etc. of the operation of resin bed It is controlled by." solvent " in this specification not only includes so-called solvent, also includes disperse medium.

Resin bed comprises particle.In resin bed, particle have at resin bed with base material film opposition side Face forms the function of projection.Additionally, resin bed generally comprises polymer.Hereinafter, also suitably by this polymerization Thing is referred to as " cohesive polymers ".In resin bed, cohesive polymers has holding particle not from resin bed Depart from function and by function bonding with base material film for resin bed.Comprise particle and bonding in this wise The resin bed of polymer generally can be manufactured by following manufacture method, and described manufacture method includes following work Sequence: particle and cohesive polymers are obtained by mixing the operation of the resin of flow-like；By the tree of this flow-like Fat coats the operation of the film forming resin on base material film；And, make the resin being formed on base material film Film solidification and/or be dried and obtain the operation of resin bed.Hereinafter, also the formation of resin bed will be used for The described resin of flow-like is referred to as " coating resin ".Hereinafter, illustrate for this manufacture method.

As cohesive polymers, can at random use suitable polymer according to the purposes of multilayer film. Wherein, can come stable against the viewpoint of convex defect from the case of multilayer film is made film roll Seeing, cohesive polymers preferably comprises polyurethane.

As polyurethane, such as, can use in (i) 1 molecule containing average more than 2 one-tenth activating hydrogen Divide the polyurethane reacted and obtain with (ii) polyisocyanate component.

Additionally, as polyurethane, it is possible to use such as by by the prepolymer chain extension containing NCO Agent carries out chain extension the polyurethane forming dispersion and manufacture that adds water.The above-mentioned pre-polymerization containing NCO Thing can occur amino by making above-mentioned (i) composition and above-mentioned (ii) composition under conditions of NCO excess Formic acid esterification reacts and manufactures.The reaction of this urethane can be to reaction torpescence and the parent with water The organic solvent big with property is carried out.Furthermore, it is possible to before the chain extension of the prepolymer containing NCO This prepolymer is neutralized.As the chain extension method of the prepolymer containing NCO, can enumerate: make to contain The method that the prepolymer of NCO and chain extender carry out reacting the most in the presence of a catalyst. Now, as chain extender, it is possible to use water, water-soluble polyamines, glycols etc..

As above-mentioned (i) composition, preferably there is the composition of the activation hydrogen of hydroxyl, for example, it is preferable to 1 molecule In there is the compound of average more than 2 hydroxyls.As the object lesson of (i) composition, can enumerate following (1) polyol compound, (2) polyether polyol, (3) PEPA, (4) polyester ether polylol and (5) polycarbonate polyol.

(1) polyol compound:

As polyol compound, such as, can enumerate: ethylene glycol, propylene glycol, diethylene glycol, three second Glycol, 1,2-butanediol, 1,3 butylene glycol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, new penta Glycol, 1,6-HD, 2,5-HD, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, three rings Decane dimethanol, 1,4 cyclohexane dimethanol, pentaglycol 2,1,4-butanediol, 1,6-oneself two Alcohol, 1,8-ethohexadiol, glycerol, trimethylolpropane etc..

(2) polyether polyol:

As polyether polyol, can enumerate: the alkylen oxide adducts of above-mentioned (1) polyol compound；Oxygen Change alkene and the open loop (co) polymer of cyclic ether (such as oxolane etc.)；Polyethylene Glycol, polypropylene glycol, Ethylene glycol and 1,2-propylene glycol copolymer, 1,4-butanediol copolymer；Ethylene glycol, polytetramethylene glycol, poly-six The glycolss such as methylene glycol, poly-eight methylene glycols；Deng.As the object lesson of polyether polyol, Can enumerate: poly-(oxygen propylidene ether) polyhydric alcohol, poly-(oxygen ethylidene-propylidene ether) polyhydric alcohol etc..

(3) PEPA:

As PEPA, such as, can enumerate and make polybasic carboxylic acid or its anhydride and above-mentioned (1) polynary alcoholization The material etc. that compound carries out polycondensation under conditions of hydroxyl excess and obtains.Here, as polybasic carboxylic acid, Such as can enumerate: adipic acid, succinic acid, decanedioic acid, 1,3-propanedicarboxylic acid, maleic acid, fumaric acid, adjacent benzene The dicarboxylic acids such as dioctyl phthalate, M-phthalic acid, p-phthalic acid；The tricarboxylic acids such as trimellitic acid.As The object lesson of PEPA, can enumerate: ethylene glycol-adipic acid condensation substance, butanediol-adipic acid Condensation substance, hexamethylene glycol-adipic acid condensation substance, ethylene glycol and 1,2-propylene glycol-adipic acid condensation substance or with Glycol is that initiator makes lactone carry out the polylactone diol etc. that ring-opening polymerisation obtains.

(4) polyester ether polylol:

As polyester ether polylol, such as, can enumerate: by the polyhydric alcohol containing ether or this polyhydric alcohol and The mixture of other glycol mixes and makes itself and oxygen with the polybasic carboxylic acid as illustrated in above-mentioned (3) are middle or its anhydride Change the material etc. of alkene reaction.Here, as the above-mentioned polyhydric alcohol containing ether, such as, can enumerate State (2) polyether polyol and diethylene glycol etc..As the object lesson of polyester ether polylol, can enumerate Polytetramethylene glycol-adipic acid condensation substance etc..

(5) polycarbonate polyol:

As polycarbonate polyol, such as, can enumerate: formula HO-R-(O-C (O)-O-R)_x-OH institute The compound etc. shown.Wherein, the R in above-mentioned formula represents that the satisfied fatty acid of carbon number 1～12 is polynary Alcohol residue.It addition, the x in above-mentioned formula represents the quantity of the construction unit of molecule, usually 5～50 Integer.These compounds can be obtained by following method: makes representative examples of saturated aliphatic polyhydric alcohol and replaces carbonic acid The ester that ester (such as, diethyl carbonate, diphenyl carbonate etc.) carries out reacting under conditions of hydroxyl excess is handed over Change method；Above-mentioned representative examples of saturated aliphatic polyhydric alcohol and phosgene is made to carry out reacting or as required further Method etc. with representative examples of saturated aliphatic polyol reaction.

Above-mentioned (i) composition can be used alone a kind, it is also possible to is applied in combination two or more with arbitrary ratio.

As (ii) composition (that is, polyisocyanate component) reacted with above-mentioned (i) composition, such as, can enumerate 1 molecule contains the compound of average more than 2 NCOs.This compound can be aliphatic Compound, it is also possible to be ester ring type compound, it is also possible to be aromatic compound.

Aliphatic two Carbimide. as aliphatic polyisocyanate compound, preferably carbon number 1～12 Ester, such as, can enumerate: hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, Hexane diisocyanate (HDI) etc..

Ester ring type two Carbimide. as ester ring type polyisocyanate compound, preferably carbon number 4～18 Ester, such as, can enumerate: Isosorbide-5-Nitrae-cyclohexane diisocyanate, methylcyclohexylidene diisocyanate, different Isophorone diisocyanate (IPDI), dicyclohexyl methyl hydride diisocyanate (HMDI) etc..

As aromatic polyisocyanate, such as, can enumerate: toluene di-isocyanate(TDI) (TDI), 4,4 '- Methyl diphenylene diisocyanate, XDI etc..

Above-mentioned (ii) composition can be used alone a kind, it is also possible to is applied in combination two or more with arbitrary ratio.

Above-mentioned (i) composition and (ii) composition arbitrarily can select to use suitable those according to the purposes of multilayer film. Wherein, as (i) composition, those with the not key of facile hydrolysis being preferably used, concrete preferably (2) polyethers is many Unit's alcohol and (5) polycarbonate polyol, wherein particularly preferred (2) polyether polyol.

It addition, can also be containing acid structure in the molecular structure of these polyurethane.Poly-ammonia containing acid structure Even if the amount that ester does not use surfactant or surfactant is few, it is also possible to be dispersed in water, therefore, The improvement of the resistance to water of resin bed can be expected.This polyurethane is referred to as self-emulsifying type, it means that even if There is not surfactant, only the particle of polyurethane just can be made to stablize in water by molecular ion and divide Dissipate.As long as it addition, the polyurethane containing acid structure is owing to need not surfactant or a small amount of surface activity Agent, therefore, excellent in adhesion with base material film, and high transparent can be kept.

As acid structure, such as, can enumerate: carboxyl (-COOH), sulfo group (-SO₃The acidic group etc. such as H).Separately Outward, in polyurethane, acid structure may reside in side chain, it is also possible to is present in end.Acid structure is permissible Use a kind, it is also possible to be applied in combination two or more with arbitrary ratio.

As the amount of acid structure, in terms of the acid number of coating resin, preferably more than 20mgKOH/g, more It is preferably more than 25mgKOH/g, preferably below 250mgKOH/g, more preferably 150mgKOH/g Below.By making acid number more than the lower limit of above-mentioned scope, the water dispersible that can make polyurethane is good. It addition, by making acid number below higher limit, the resistance to water that can make resin bed is good.

As the method importing acid structure to polyurethane, such as, can enumerate: by by dimethylolalkanoic acids Replace above-mentioned (2) part or all of to (i) composition described in (4), thus in advance to polyether polyol, PEPA, polyester ether polylol etc. import the method for carboxyl.As dihydroxymethyl used herein above Alkanoic acid, such as, can enumerate: dihydroxymethyl acetic acid, dihydromethyl propionic acid, dimethylolpropionic acid etc..Two Methylol alkanoic acid can be used alone a kind, it is also possible to is applied in combination two or more with arbitrary ratio.

Partly or entirely can also being neutralized by non-volatile alkali of sour structure contained by polyurethane.Pass through Acid structure is made to be neutralized, even if multilayer film has the thermal history being once exposed under high temperature, it is also possible to keep making For the characteristic of optical material, or can be bonding with strong bonding force with other component.Even if it addition, neutralizing acid knot Structure, it is also possible to even if making polyurethane in the case of the amount not using surfactant or surfactant is few Particle be dispersed in water.

In sour structure contained by polyurethane, the ratio preferably more than 20% of the sour structure being neutralized, especially Preferably more than 50%.By making in acid structure more than 20% to be neutralized, once exposed even if multilayer film has Thermal history under high temperature, it is also possible to keep the characteristic as optical material, or can be with other component with by force Bonding force is bonding.

In order to enable to react with cross-linking agent, optimization polyurethane contains polar group.As polar group, Can enumerate: carboxyl, carbonyloxy group carbonyl, epoxy radicals, hydroxyl, epoxide, ester group, silanol group, first Silylation, amino, itrile group, sulfo group etc..Wherein, preferably methylol, hydroxyl, carboxyl and amino, more Preferably hydroxyl and carboxyl, particularly preferred carboxyl.The amount of the polar group in polyurethane is preferably 0.0001 Equivalent/more than 1kg, more preferably 0.001 equivalent/more than 1kg, preferably 1 equivalent/below 1kg.

As polyurethane, it is possible to use commercially available those as waterborne polyurethane resin.The poly-ammonia of aqueous Ester resin is the compositions containing polyurethane and water, it is common that polyurethane and contain as required arbitrary The compositions that composition is dispersed in water.As waterborne polyurethane resin, such as, can enumerate: ADEKA " OLESTER " that " the ADEKA BONTIGHTER " that company manufactures is serial, Mitsui Chemicals, Inc. manufactures Series, " VONDIC " series of DIC company manufacture, " HYDRAN (WLS201, WLS202 etc.) " Serial, the manufacture of Bayer company " IMPRANIL " is serial, KAO. Corp. SA's manufacture " POIZ " is serial, " SANPLEN " series, the first industrial pharmaceutical company that chemical conversion industrial group of Sanyo manufactures manufacture " NEOREZ " that " SUPERFLEX " series, nanmu this chemical conversion company manufacture is serial, Lubrizol company system " Sancure " series etc. made.It addition, polyurethane can be used alone a kind, it is also possible to arbitrary ratio It is applied in combination two or more.

Additionally, the glass transition temperature of cohesive polymers preferably more than 50 DEG C, more preferably more than 55 DEG C, Particularly preferred more than 60 DEG C, preferably less than 150 DEG C, more preferably less than 125 DEG C, particularly preferred 100 DEG C Below.By making the glass transition temperature of cohesive polymers more than the lower limit of above-mentioned scope, it is possible to Prevent the conveying roller from drying oven out after stain stove downstream in manufacturing process.Additionally, by for upper Below limit value, it is possible to prevent the curling of multilayer film.

In the coating resin of flow-like, the state of cohesive polymers is arbitrary, can divide in particle shape Dissipate, it is also possible to be dissolved in other compositions such as solvent.Such as, using polyurethane as cohesive polymers In the case of, polyurethane is scattered in particle shape mostly.Now, from the sight of the optical characteristics of multilayer film Point considers, the mean diameter of the particle of polyurethane is preferably 0.01 μm～0.4 μm.

As particle, it is possible to use the inorganic particulate that formed by inorganic material, by having that organic material is formed Machine particle and combination comprise inorganic material and the Arbitrary Particles in the compound particle of organic material.And from From the viewpoint of easily carrying out the formation of resin bed, the particle of water dispersible is preferably used.As inorganic grain The material of son, can enumerate such as: the inorganic oxides such as silicon dioxide, titanium oxide, aluminium oxide, zirconium oxide Thing；Calcium carbonate, Talcum, clay, calcined kaolin, baked calcium silicate, afwillite, aluminium silicate, Magnesium silicate, calcium phosphate etc..It addition, as the material of organic filler, can enumerate such as: organosilicon tree Fat, fluororesin, acrylic resin etc..They can be used alone a kind, it is also possible to arbitrary ratio group Close and use two or more.

In the material of the particle of these examples, preferably silicon dioxide.Silicon dioxide granule suppression wrinkle produces Raw ability and the transparency are excellent, are not likely to produce internal haze, not coloring, the therefore light to multilayer film The impact learning characteristic is little.It addition, silicon dioxide dispersibility in coating resin and dispersion stabilization are good. In silicon dioxide granule, particularly preferred amorphous state colloidal silica particles.

As silicon dioxide granule as above, it is possible to use commercially available product.As the example of commercially available product, Can list Japan catalyst company manufacture EPOSTAR MX-050W (mean diameter 80nm), SEAHOSTER KE-W10 (mean diameter 110nm), EPOSTAR MX-100W (mean diameter 150nm～200nm)；SNOWTEX MP-2040 (the mean diameter that Nissan Chemical company manufactures 150nm～200nm) etc..

Additionally, as particle, it is possible to use can be formed full in the face with base material film opposition side of resin bed The particle of the projection of the above-mentioned condition of foot.Generally, described rising height can adjust according to the size of particle. Now, the diameter of particle will not be directly becoming the height of projection, but the height of the diameter of particle and projection it Between be typically relevant, therefore by adjusting the distribution of the diameter of particle, it is possible to shape on the face of resin bed Become the projection as described above with wide distribution.

Generally, by multiple particle combinations different for mean diameter is used, meeting shape on the face of resin bed Become to meet the projection of above-mentioned condition.Therefore, the particle of resin bed generally combines that to comprise mean diameter different Multiple particle.If by multiple particle combinations different for mean diameter, then can make in resin bed contained The overall particle diameter distribution of particle broadens, and therefore, it can make to be formed in the face of the resin bed comprising this particle The distribution of height of projection broaden.Therefore, in this manufacture method, by particle and cohesive polymers It is obtained by mixing in the operation of coating resin, preferably multiple particles different for mean diameter is polymerized with bonding Thing mixes.

Additionally, in the case of being applied in combination the multiple particle that mean diameter is different, preferably at least a kind of grain The mean diameter of son is more than the thickness of resin bed.So, by use, there is the thickness more than resin bed The particle of mean diameter, it is possible to effectively the face with base material film opposition side at resin bed formed meet above-mentioned The projection of condition.Additionally, the mean diameter of at least one particle in multiple particle can be less than resin bed Thickness.

Wherein, preferably will there is the particle (S) of the mean diameter less than 150nm and there is more than 150nm The particle (L) of mean diameter be applied in combination.Therefore, the particle preferred compositions of resin bed comprise have little Particle (L) in particle (S) and the mean diameter with more than 150nm of the mean diameter of 150nm.

The mean diameter of particle (S) is usually more than 20nm, preferred more than 30nm, more preferably 40nm Above, and typically smaller than 150nm, preferred below 140nm, more preferably below 130nm.By making The mean diameter of particle (S) is more than the lower limit of above-mentioned scope, it is possible to stablize landform in the face of resin bed Become projection.Additionally, by below higher limit, it is possible to make the distribution of the rising height in the face of resin bed become Wide.

Additionally, the mean diameter of particle (S) is relative to the mode height of the projection in the face being formed at resin bed, It is preferably more than 2 times, more preferably more than 3 times, particularly preferred more than 4 times, preferably less than 15 times, More preferably less than 14 times, particularly preferred less than 13 times.Here, the mode height of projection refers to: projection Highly in 5nm, 10nm, 15nm, 20nm, 25nm and 30nm, the projection with this height is most The height of projection.By making the mean diameter of particle (S) more than the lower limit of above-mentioned scope, it is possible to It is stably formed projection in the face of resin bed.Additionally, by below higher limit, it is possible to make resin bed The distribution of the rising height in face broadens.

It addition, relative to the thickness of resin bed, the mean diameter of particle (S) preferably more than 3 times, more excellent Select more than 4 times, particularly preferred more than 5 times, preferably less than 10 times, more preferably less than 8 times, especially Preferably less than 7 times.By making the mean diameter of particle (S) more than the lower limit of above-mentioned scope, it is possible to It is stably formed projection in the face of resin bed.Additionally, by below higher limit, it is possible to make resin bed The distribution of the rising height in face broadens.

Relative to cohesive polymers 100 weight portion, the amount of particle (S) is usually more than 2 weight portions, preferably More than 3 weight portions, more than more preferably 5 weight portions, usually below 24 weight portions, preferably 20 weight Below part, below more preferably 18 weight portions.By making the amount of particle (S) in above-mentioned scope, it is possible in tree The face of lipid layer is readily formed the projection meeting above-mentioned condition.

The mean diameter of particle (L) is usually more than 150nm, preferred more than 160nm, more preferably 170nm Above, usually below 250nm, preferred below 230nm, more preferably below 200nm.By making The mean diameter of particle (L) is more than the lower limit of above-mentioned scope, it is possible to the projection making the face of resin bed is high The distribution of degree broadens.Additionally, by below for higher limit, it is possible to reduce the internal haze of resin bed.

Additionally, the mode height of the projection relative to the face being formed at resin bed, the average particle of particle (L) Footpath preferably more than 15 times, more preferably more than 16 times, particularly preferred more than 17 times, preferably 25 times with Under, more preferably less than 23 times, particularly preferred less than 20 times.Existed by the mean diameter making particle (L) More than the lower limit of above-mentioned scope, it is possible to make the distribution of the rising height in the face of resin bed broaden.Additionally, By below higher limit, it is possible to reduce the internal haze of resin bed.

It addition, relative to the thickness of resin bed, the mean diameter of particle (L) preferably more than 2 times, more Preferably more than 3 times, particularly preferred more than 4 times, preferably less than 10 times, more preferably less than 8 times, special The most preferably less than 7 times.By make the mean diameter of particle (L) more than the lower limit of above-mentioned scope, energy The distribution enough making the rising height in the face of resin bed broadens.Additionally, by below higher limit, it is possible to subtract The internal haze of little resin bed.

Additionally, preferred more than the 70nm of difference of the mean diameter of the mean diameter of particle (S) and particle (L), More preferably more than 100nm, particularly preferred more than 120nm, preferably below 200nm, more preferably 180nm Below, particularly preferred below 160nm.The average particle of mean diameter Yu particle (L) by making particle (S) The difference in footpath is in above-mentioned scope, it is possible to be readily formed the projection meeting above-mentioned condition in the face of resin bed.

Relative to cohesive polymers 100 weight portion, the amount of particle (L) is usually more than 5 weight portions, excellent Select more than more than 6 weight portions, more preferably 7 weight portions, usually below 20 weight portions, preferably 18 weights Below amount part, below more preferably 15 weight portions.By making the amount of particle (L) in above-mentioned scope, it is possible to The face of resin bed is readily formed the projection meeting above-mentioned condition.

Relative to cohesive polymers 100 weight portion, the amount of particle (L) is preferably with the difference of the amount of particle (S) More than 0.5 weight portion, more than more preferably 1 weight portion, more than particularly preferred 2 weight portions, preferably 25 Below weight portion, below more preferably 20 weight portions, below particularly preferred 15 weight portions.By making particle (L) difference of the amount of amount and particle (S) is in above-mentioned scope, it is possible to be readily formed satisfied in the face of resin bed The projection of above-mentioned condition.

Generally, in the case of being applied in combination particle (S) and particle (L) as described above, contained by resin bed The overall particle diameter distribution of particle in there will be and correspond respectively to particle (S) and the peak of particle (L).But, Even if the distribution in this case, being formed at the rising height in the face of resin bed the most generally shows single Peak.In this wise, the distribution of particle diameter and the distribution of rising height are the most corresponding.But, if this Multiple particle combinations different for mean diameter, then the particle diameter distribution that these particles are overall are broadened by sample ground, with This accompanies, and the distribution of the rising height being formed at the face of resin bed also broadens.Therefore, such grain is utilized Dependency between distribution and the distribution of rising height of the mean diameter of son, it is possible to be met above-mentioned bar The projection of part.

Additionally, in coating resin in addition to particle and cohesive polymers, it is also possible to comprise cross-linking agent.Hand over Connection agent is bonding by the reaction-ity group reaction that had with cohesive polymers, thus bonding can be made to be polymerized Thing cross-links.It is thus possible, for instance by making cohesive polymers cross-link after coating resin is coated base material film, The cementability between resin bed and base material film and the mechanical strength of resin bed and wet-heat resisting can be improved Property.Such as, in the case of using polyurethane as cohesive polymers, generally, cross-linking agent can be with work For above-mentioned acid structure the carboxyl that contains and anhydride group thereof and after (i) composition and (ii) composition react because of not Such polar groups such as the hydroxyl reacted and remain carry out reacting and forming cross-linked structure.

As cross-linking agent, 1 intramolecular such as can be used to have more than 2 can be with cohesive polymers institute The reaction-ity group reaction that has and the compound of the functional group of bonding.Wherein, as cross-linking agent, preferably There is the compound of the functional group can reacted with carboxyl or its anhydride group.

As the object lesson of cross-linking agent, can enumerate: epoxide, carbodiimide compound, Isoxazoline compound, isocyanate compound etc..It addition, cross-linking agent can be used alone a kind, it is also possible to It is applied in combination two or more with arbitrary ratio.

As epoxide, it is possible to use 1 intramolecular has the multi-functional epoxy of more than 2 epoxy radicals Compound.Wherein, as epoxide, preferably water is had dissolubility or is dispersed among in water occurring The epoxide of emulsifying.If epoxide has dissolubility or emulsifiable to water, then in coating tree In the case of fat is water-base resin, the coating that can make this water-base resin is good, thus easily carries out The manufacture of resin bed.Here, the state that water-base resin refers to be dissolved or dispersed in the aqueous solvents such as water contains There is the resin of the flow-like of the solid constituents such as polymer.

As the example of above-mentioned epoxide, can enumerate: ethylene glycol, diethylene glycol, triethylene glycol, The glycolss such as Polyethylene Glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-HD, neopentyl glycol 1 mole of di-epoxy compounds obtained by etherificate with epoxychloropropane 2 moles；Glycerol, polyglycereol, The polyalcohols 1 mole such as trimethylolpropane, tetramethylolmethane, sorbitol and epoxychloropropane 2 moles with On the polyepoxy compound that obtained by etherificate；Phthalic acid, p-phthalic acid, ethanedioic acid, oneself The di-epoxy compounds that the dicarboxylic acids such as diacid 1 mole and epoxychloropropane 2 moles are obtained by esterification Deng.

As the more specifically 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, sorbitol poly epihydric alcohol ethers, polyglycerol poly epihydric alcohol ethers, Tetramethylolmethane poly epihydric alcohol ethers, two glycerol polyglycidyl ethers, 1,3,5-triglycidyl group (2- Ethoxy) isocyanuric acid ester, glycerol poly epihydric alcohol ethers and trimethylolpropane polyglycidyl ether Class etc..

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

Epoxide can be used alone a kind, it is also possible to is applied in combination two or more with arbitrary ratio.

Relative to cohesive polymers 100 weight portion, the amount of epoxide is usually more than 5 weight portions, It is preferably more than 7 weight portions, more than more preferably 10 weight portions, usually below 50 weight portions, excellent Elect below 40 weight portions as, below more preferably 30 weight portions.By making the amount of epoxide upper The reaction stating more than the lower limit of scope, epoxide and cohesive polymers is fully carried out, therefore, and can To properly increase the mechanical strength of resin bed.It addition, by below higher limit, it is possible to reduce unreacted The residual of epoxide, the mechanical strength of resin bed can be properly increased.

It addition, relative to the amount of the epoxide becoming equivalent with the polar group of cohesive polymers, epoxy The amount of compound benchmark meter by weight is preferably more than 0.2 times, more preferably more than 0.4 times, the most excellent Elect more than 0.6 times as, preferably less than 1.4 times, more preferably less than 1.2 times, particularly preferably 1.0 Below Bei.Here, become the amount of the epoxide of equivalent to refer to the polar group of cohesive polymers, can Reason with the epoxide that react neither too much nor too little with the total amount of the polar group of cohesive polymers Stoichiometric.The polar group of cohesive polymers can react with the epoxy radicals of epoxide.Therefore, logical Cross and the amount of epoxide is controlled within the above range, the anti-of polar group and epoxide can be made Should carry out to suitable degree, thus be effectively improved the mechanical strength of resin bed.

As carbodiimide compound, 1 intramolecular can be used to have the chemical combination of more than 2 carbodiimides Thing.This carbodiimide compound can use organic single-isocyanate, organic diisocyanate, organic three different The organic isocyanates such as cyanate manufacture as raw material.Example as these organic isocyanates Son, can enumerate: aromatic isocyanate, aliphatic isocyanates and their mixture.Therefore, The organic group being had as organic isocyanate, it is possible to use arbitrary in aromatic series and aliphatic Kind, alternatively, it is also possible to be applied in combination aromatic organic group and aliphatic organic group.Wherein, From the viewpoint of reactivity, particularly preferably there is the organic isocyanate of aliphatic organic group.Logical Often, carbodiimide compound can be synthesized by the condensation reaction of organic diisocyanate.

As the object lesson of organic isocyanate, can enumerate: 4,4 '-methyl diphenylene diisocyanate, 4,4-diphenyldimethyhnethane diisocyanate, 1,4-phenylene vulcabond, 2,4-toluene diisocyanate Acid esters, 2,6-toluene di-isocyanate(TDI), hexamethylene diisocyanate, cyclohexane diisocyanate, benzene Dimethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 4,4 '-dicyclohexyl first The organic diisocyanates such as alkane diisocyanate, 1,3-phenylene vulcabond；Isophorone Carbimide. Ester, phenyl isocyanate, cyclohexyl isocyanate, isocyanic acid butyl ester, naphthyl isocyanate etc. are organic Monoisocyanates.

As the example of the commercially available product of carbodiimide compound, can enumerate: can obtain as commercially available product The Nisshinbo Chemical company taken manufacture " Carbodilite (Carbodilite V-02, V-02-L2, SV-02, V-04, E-02 etc.) " series.

Carbodiimide compound can be used alone a kind, it is also possible to arbitrary ratio be applied in combination 2 kinds with On.

Relative to cohesive polymers 100 weight portion, the amount of carbodiimide compound be usually 1 weight portion with On, more than preferably 3 weight portions, usually below 40 weight portions, below preferably 30 weight portions. By making the amount of carbodiimide compound more than the lower limit of above-mentioned scope, carbodiimide compound is with viscous The reaction of knot polymer is fully carried out, and therefore, it can properly increase the mechanical strength of resin bed.It addition, By making the amount of carbodiimide compound below higher limit, it is possible to reduce unreacted carbodiimide chemical combination The residual of thing, can properly increase the mechanical strength of resin bed.

AsIsoxazoline compound, can use having shown in following formula (I)The polymer of oxazoline base.Under State in formula (I), R¹、R²、R³And R⁴Identical or different, represent selected from hydrogen atom, halogen atom, alkane Any group in base, aralkyl, phenyl and substituted-phenyl.

[chemical formula 1]

ShouldIsoxazoline compound can be by such as making containing addition polymerizationOxazoline is as necessary and basis Need the monomer component containing arbitrary unsaturated monomer by known polymerization in an aqueous medium Carry out polymerisation in solution and manufacture.As addition polymerizationOxazoline, such as, can enumerate following formula (II) institute The compound shown.In following formula (II), R¹、R²、R³And R⁴Identical with the definition in formula (I).It addition, R⁵Represent the acyclic organic group with addition polymerization unsaturated bond.

[chemical formula 2]

As addition polymerizationThe object lesson of oxazoline, can enumerate: 2-vinyl-2-Oxazoline, 2- Vinyl-4-methyl-2-Oxazoline, 2-vinyl-5-methyl-2-Oxazoline, 2-isopropenyl-2-Oxazoline, 2-isopropenyl-4-methyl-2-Oxazoline, 2-isopropenyl-5-ethyl-2-Oxazoline etc..It addition, they can To be used alone a kind, it is also possible to be applied in combination two or more with arbitrary ratio.Wherein, 2-isopropenyl -2-Oxazoline the most easily obtains, therefore preferably.

Described addition polymerizationThe amount of oxazoline relative toUse in the manufacture of isoxazoline compound is whole Monomer component 100 weight portion, more than preferably 3 weight portions.Thus, will compriseIsoxazoline compound Coating resin solidification time, it is possible to make solidification fully carry out, it is thus achieved that durability and the resin of excellent water resistance Layer.

As can be used forThe arbitrary unsaturated monomer of the manufacture of isoxazoline compound, can use can with add Become polymerismOxazoline copolymerization and not withThe arbitrary monomer that oxazoline base reacts.Such arbitrarily Unsaturated monomer can from above-mentioned monomer at random select use.

AsThe example of the commercially available product of isoxazoline compound, in water solublity type, can enumerate Japan's catalyst EPOCROS WS-500 and WS-700 that company manufactures.It addition, such as in emulsion-type, Ke Yiju Go out EPOCROS K-2010, K-2020 and K-2030 that catalyst company of Japan manufactures.Wherein, preferably The water solublity type high with the reactivity of the cohesive polymers contained by coating resin.

It addition,Isoxazoline compound can be used alone a kind, it is also possible to is applied in combination 2 with arbitrary ratio More than Zhong.

AsThe amount of isoxazoline compound, can be set so that the polar group that cohesive polymers is had WithIsoxazoline compound is hadThe mol ratio of oxazoline base (molal quantity of polar group/Oxazoline base Molal quantity) in given range.Specifically, can be set so that above-mentioned mol ratio is 100/20～100/100.By making above-mentioned mol ratio more than the lower limit of above-mentioned scope, it is possible to prevent not The polar group residual of reaction.It addition, by making above-mentioned mol ratio below higher limit, be possible to prevent to remain RemainingThe generation of oxazoline base, thus prevent hydrophilic group from becoming excess.

Additionally, in the case of cohesive polymers has carboxyl and this carboxyl has been neutralized, poly-in bonding Compound withIn the reaction of isoxazoline compound,Oxazoline base and carboxylate are not susceptible to reaction.Therefore, may be used To control its reaction by adjusting the kind of non-volatile alkali for neutralizing and nonvolatile degree Property.

As isocyanate compound, the chemical combination containing more than 2 NCOs in 1 molecule can be used Thing.These isocyanate compounds can be aliphatic compound, it is also possible to is ester ring type compound, also It can be aromatic compound.As the object lesson of isocyanate compound, can enumerate poly-with conduct The raw material of urethane and illustrate the example that (ii) composition is identical.

In above-mentioned cross-linking agent, preferably epoxide and carbodiimide compound, particularly preferred epoxy compound Thing.If using epoxide as cross-linking agent, then resin bed and base material can be significantly increased especially Cementability between film.If it addition, use carbodiimide compound as cross-linking agent, then can improve The working life (pot life) of coating resin.

Additionally, coating resin is in addition to comprising particle and cohesive polymers, it is also possible to comprise non-volatile Alkali.As non-volatile alkali, can enumerate when making it dry after coating resin is coated base material film Nonvolatile alkali it is essentially under treatment conditions.As described treatment conditions, can list such as The process of 1 hour is placed in 80 DEG C.Here, be essentially non-volatile typically referring to, non-volatile The decrement of alkali is less than 80%.Such non-volatile alkali can be as neutralizing the cohesive polymers such as polyurethane The nertralizer of contained sour structure and function.

As non-volatile alkali, it is possible to use inorganic base, it is possible to use organic base.Wherein, preferably boil The amines of the some organic base of more than 100 DEG C, more preferably boiling point more than 100 DEG C, particularly preferred boiling point The amines of more than 200 DEG C.It addition, organic base can be low molecular compound, it is also possible to be polymerization Thing.

If enumerating the example of non-volatile alkali, then as inorganic base, such as can enumerate sodium hydroxide and Potassium hydroxide.It addition, as organic base, such as can enumerate: 2-amino-2-methyl-1-propanol (AMP), Triethanolamine, triisopropanolamine (TIPA), monoethanolamine, diethanolamine, three [(2-hydroxyl)-1-propyl group] 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 ammonium complex compound, γ aminopropyltriethoxy silane, gamma-amino Propyl trimethoxy silicane, N-β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β (amino second Base)-gamma-amino oxypropyl trimethyl dimethoxysilane, N-phenyl-gamma-amino propyl trimethoxy silicane, N, N- Double (trimethyl silyl) urea, 3-ureido-propyl trimethoxy silane, 3-aminopropyl-three (2-methoxyl group -ethoxy-ethoxy) silane, N-methyl-3-aminopropyl trimethoxy carboxylic acid dihydrazide, ethanedioic acid two Hydrazides, acid dihydrazide, succinic acid hydrazide ii, adipic dihydrazide, sebacic dihydrazide, 12 Alkane acid dihydrazide, isophthalic dihydrazide, terephthaldehyde's acid dihydrazide, quinoline, picoline, pyrrole Pyridine, morpholine, piperazine, cyclohexylamine, hexamethylene diamine, N,N-dimethylformamide, ethylenediamine, two Ethylenetriamine, tetren, five ethylidene five amine, monoethanolamine, diethanolamine, isopropanol Amine, N, N-diethyl carbinol amine, N, N-dimethylethanolamine, amino ethyl ethanolamine, N-methyl-N-N- Diethanolamine, 1,2-propane diamine, 1,6-hexamethylene diamine, piperazine, 2-methyl piperazine, 2,5-dimethyl Piperazine, isophorone diamine, 4,4 '-dicyclohexyl methyl hydride diamidogen, 3,3 '-dimethyl-dicyclohexyl methyl hydride two Amine, 1,2-cyclohexane diamine, 1,4-cyclohexane diamine, amino ethyl ethanolamine, aminopropyl ethanolamine, Aminohexyl ethanolamine, amino ethyl propanol amine, aminopropyl Propanolamine, Aminohexyl Propanolamine, two Ethylenetriamine, dipropylene three imidazoles, 1-(2-amino-ethyl)-2-methylimidazole, 1-(2-amino-ethyl)-2- Ethyl imidazol(e), 2-aminooimidazole sulfate, 2-(2-amino-ethyl)-benzimidazole, pyrazoles, 5-amino pyrrole Azoles, 1-methyl-5-amino-pyrazol, 1-isopropyl-5-amino-pyrazol, 1-benzyl-5-amino-pyrazol, 1,3-bis- Methyl-5-amino-pyrazol, 1-isopropyl-3-methyl-5-amino-pyrazol, 1-benzyl-3-methyl-5-amino-pyrazol, 1-methyl-4-chloro-5-amino-pyrazol, 1-methyl-4-cyano group-5-amino-pyrazol, 1-isopropyl-4-chloro-5-amino Pyrazoles, 3-methyl-4-chloro-5-amino-pyrazol, 1-benzyl-4-chloro-5-amino-pyrazol, amino resins are (such as, The chloro-melmac of 1,3-dimethyl-4-, Lauxite, guanamine resin etc.) etc..It addition, they can To be used alone a kind, it is also possible to be applied in combination two or more with arbitrary ratio.

Relative to cohesive polymers 100 weight portion, the amount of non-volatile alkali is usually more than 0.5 weight portion, It is preferably more than 1 weight portion, more than more preferably 2 weight portions, usually below 30 weight portions, excellent Elect below 20 weight portions as, below more preferably 10 weight portions.By making the amount of non-volatile alkali upper State more than the lower limit of scope, sufficient bonding force can be obtained.It addition, by making non-volatile alkali Amount, below higher limit, is possible to prevent the decolouring of the polaroid of polyvinyl alcohol.

Additionally, coating resin is in addition to comprising particle and cohesive polymers, it is also possible to comprise wetting agent. By using wetting agent, it is possible to coating when making to coat coating resin base material film is good.

As wetting agent, it is possible to use such as acetylenic surfactant, fluorine class surfactant etc..As Acetylenic surfactant, such as, can use: Air Products and Chemicals company Surfynol Series, Dynol series etc..It addition, as fluorine class surfactant, such as can use: DIC is public Take charge of MEGAFAC processed series, Neos company Ftergent series, AGC company SURFLON Series etc..As wetting agent, from the viewpoint of repeating coating, acetylenic surfactant is preferably used.

It addition, these wetting agent can be used alone a kind, it is also possible to be applied in combination 2 kinds with arbitrary ratio Above.

Relative to the solid constituent amount contained by coating resin, the use level of wetting agent is usually 0.01 weight % Above, more than preferably 0.05 weight %, more than more preferably 0.1 weight %, usually 5 weight % Hereinafter, below preferably 4 weight %, below more preferably 3 weight %.Existed by the amount making wetting agent More than the lower limit of above-mentioned scope, sufficient coating can be obtained.It addition, pass through below higher limit, Oozing out of wetting agent can be suppressed, repetition coating can be made the best.

Coating resin usually contains solvent.As solvent, use water or water miscible solvent.As water-soluble The solvent of property, such as, can enumerate: methanol, ethanol, isopropanol, acetone, oxolane, N-methyl Ketopyrrolidine, dimethyl sulfoxide, glycol monoethyl ether, ethylene glycol monobutyl ether etc..Wherein, as solvent, Water is preferably used.It addition, solvent can be used alone a kind, it is also possible to be applied in combination 2 with arbitrary ratio More than Zhong.

The amount of solvent can be set so that the viscosity of coating resin reaches to be suitable to the scope of coating.Generally, The amount of solvent is set so that the solid component concentration of coating resin falls in desired scope.Above-mentioned desired Range preferably from more than 0.5 weight %, more than more preferably 1 weight %, below preferably 15 weight %, Below more preferably 10 weight %.Thus, it is possible to make the operability of coating resin and coating good.

In coating resin can also with above-mentioned crosslinker combination comprise curing accelerator.Such as, ring is used In the case of oxygen compound is as cross-linking agent, as curing accelerator, preferred tertiary amine compounds is (on 4-position Except there is the compound with 2,2,6,6-tetramethyl-piperidyl of tertiary amine), boron trifluoride complex etc.. It addition, curing accelerator can be used alone a kind, it is also possible to be applied in combination two or more with arbitrary ratio.

The amount of curing accelerator relative to cohesive polymers 100 weight portion, usually 0.001 weight portion with More than upper, preferably 0.01 weight portion, more than more preferably 0.03 weight portion, usually below 30 weight portions, Below preferably 10 weight portions, below more preferably 5 weight portions.

In coating resin can also with above-mentioned crosslinker combination comprise auxiliary curing agent.As auxiliary curing agent Object lesson, can enumerate: the oxime-nitrous base class such as quininie dioxime, benzoquinone dioxime, p-Nitrosophenol are solid Change auxiliary agent；The maleimide auxiliary curing agents such as N, N-meta-phenylene bismaleimide；Phthalic acid The allylic auxiliary curing agents such as diallyl, triallylcyanurate, Triallyl isocyanurate； The methyl acrylic ester such as ethylene glycol dimethacrylate, trimethylol-propane trimethacrylate is solid Change auxiliary agent；The vinyl-based auxiliary curing agents such as vinyltoluene, vinyl xylene, ethyl vinyl benzene, divinylbenzene；Deng. It addition, auxiliary curing agent can be used alone a kind, it is also possible to be applied in combination two or more with arbitrary ratio.

The amount of auxiliary curing agent is relative to cross-linking agent 100 weight portion, usually more than 1 weight portion, preferably More than 10 weight portions, usually below 100 weight portions, below preferably 50 weight portions.

As long as significantly damaging the effect of the present invention, coating resin can also contain such as heat-resisting stabilizing agent, Weathering stabilizers, levelling agent, surfactant, antioxidant, antistatic agent, slip agents, tissue adhesion Agent, antifoggant, lubricant, dyestuff, pigment, natural oil, artificial oil, wax etc..It addition, these things Matter can be used alone a kind, it is also possible to is applied in combination two or more with arbitrary ratio.

In the operation obtaining coating resin, by particle and cohesive polymers and optionally use Cross-linking agent, non-volatile alkali, wetting agent, solvent and arbitrarily composition mixing, obtain the coating tree of flow-like Fat.Gained coating resin is preferably able to be coated on equably the surface of base material film.From having excellence in this wise Coating from the viewpoint of, preferred below the 15mPa s of viscosity of coating resin, particularly preferred 10mPa s Below.Here, described viscosity utilizes tuning-fork-type vibrating type viscometer to measure under conditions of 25 DEG C Value.This viscosity such as can be adjusted according to the particle diameter etc. of the ratio of solvent and particle.

After obtaining coating resin, carry out coating this coating resin on base material film, forming coating resin The operation of film.Now, coating resin is generally set directly at not via other layer such as layer of bonding agent The surface of base material film.Additionally, coating resin can only be coated on the one side of base material film, it is also possible to be coated on Two sides.Wherein, from the viewpoint of the manufacturing cost of suppression multilayer film, the most only in the one side of base material film Coating coating resin.

In the case of base material film is coated with coating resin, arbitrary rubbing method can be used.As specifically Rubbing method, such as can enumerate: bar rubbing method, infusion process, nebulization, spin-coating method, rolling method, Gravure coating process, air knife coating method, curtain stream rubbing method, slip rubbing method, extrusion coating methods etc..

After base material film is formed the film of coating resin, carry out making this coating resin film solidification and/or It is dried and obtains the operation of resin bed.Generally, coating resin contains solvent, therefore, obtains resin bed Operation includes making solvent seasoning remove.Drying means is arbitrary, such as can pass through drying under reduced pressure, The arbitrary method such as heat drying is carried out.Wherein, from make cross-linking reaction etc. coating resin be swift in response into From the viewpoint of row, preferably make coating resin solidify by heat drying and be dried.It is thermally dried In the case of, it will usually there is the cross-linking reaction of cohesive polymers.

In the case of being made coating resin solidify by heating and be dried, heating-up temperature can make solvent seasoning And make suitably to set in the range of the component of polymer solidification in coating resin.It should be noted that make Situation about changing as base material film and the delay that undesirably makes this base material film be shown by stretched film Under, heating-up temperature is preferably set in base material film not produce the temperature of Orientational relaxation.Specifically, when inciting somebody to action When the glass transition temperature of the material forming base material film is set to Tg, it is preferably more than (Tg-30 DEG C), more It is preferably more than (Tg-10 DEG C), is preferably (Tg+60 DEG C) below, be more preferably (Tg+50 DEG C) below.

Additionally, above-mentioned manufacture method is in addition to including above-mentioned operation, it is also possible to include any operation.Example As, before described manufacture method can form the film of coating resin on base material film, including to base material film The operation of modification is implemented on surface.Thus, it is possible to improve the cementability of base material film and resin bed.As Surface modification treatment to base material film, such as, can enumerate energy-ray treatment with irradiation and medicine process etc.. As energy-ray treatment with irradiation, such as, can enumerate: Corona discharge Treatment, Cement Composite Treated by Plasma, electricity Son bundle treatment with irradiation, ultraviolet treatment with irradiation etc., consider from the viewpoint for the treatment of effeciency etc., preferably corona is put Electric treatment and Cement Composite Treated by Plasma, particularly preferred Corona discharge Treatment.It addition, process as medicine, example As enumerated: saponification processes.Additionally, process as medicine, can enumerate and such as base material film be impregnated In the aqueous oxidizing agent solution such as potassium bichromate solution, concentrated sulphuric acid, then the method carrying out washing with water.

Additionally, above-mentioned manufacture method can include that bossed of the tool to resin bed implements hydrophilized surface The operation processed.The bossed face that has of resin bed usually becomes when being fitted with other component by multilayer film Binding face.Therefore, by improving the hydrophilic of bossed of the tool of resin bed further, it is possible to notable Improve the cementability of multilayer film and other component.

As hydrophilized surface process, such as can enumerate: Corona discharge Treatment, Cement Composite Treated by Plasma, Saponification process, ultraviolet treatment with irradiation etc..Wherein, consider from the viewpoint for the treatment of effeciency etc., preferably corona Discharge process and Cement Composite Treated by Plasma, more preferably Corona discharge Treatment.It addition, as Cement Composite Treated by Plasma, Preferred atmosphere pressure Cement Composite Treated by Plasma.

By above-mentioned manufacture method, resin bed can be formed on base material film.As it is shown in figure 1, such To the face 121 with base material film 110 opposition side of resin bed 120 there is projection 122, thus sliding Well.Therefore, it is possible to reduce the face 121 with base material film 110 opposition side and the base material of resin bed 120 Film 110 and confficient of static friction between the face 111 of resin bed 120 opposition side.Described confficient of static friction It is preferably 0.3～0.5.Thus, in the case of multilayer film 100 is coiled into web-like, it is possible to effectively press down The generation of convex defect processed.

Additionally, this resin bed does not comprise the substantial amounts of of degree that the internal haze of this resin bed can be caused to increase Particle.It is said that in general, the weight of little every 1 of the particle of particle diameter is little.Therefore, even if with weight basis Amount few, the number of this particle can also be more.Therefore, by this wise by particle little for particle diameter and grain The particle combinations use that footpath is big, dashes forward with forming a large amount of of degree that can improve sliding in the face of resin bed The degree risen is compared, it is possible to reduce the amount of particle.Therefore, it is possible to reduce the internal haze of resin bed.

The thickness of resin bed is usually more than 10nm, preferred more than 15nm, more preferably more than 20nm, Usually below 100nm, preferred below 80nm, more preferably below 70nm.By making resin bed Thickness is more than the lower limit of above-mentioned scope, it is possible to increase the mechanical strength of resin bed.Additionally, pass through Below higher limit, it is possible to be stably formed desired projection in the face of resin bed, it is thus possible to be effectively improved The sliding in the face of resin bed.Additionally, reduce the thickness of resin bed as described above, usually The optical characteristics making resin bed be difficult to be had base material film impacts.It is therefore not necessary to it is many in order to adjust The optical characteristics of tunic and change the composition of resin bed, it is possible to the optics easily carrying out multilayer film is special The adjustment of property.

Additionally, the mode height of the projection relative to the face being formed at resin bed, the thickness of resin bed is preferred It is more than 1 times, more preferably more than 2 times, particularly preferred more than 3 times, preferably less than 10 times, more excellent Select less than 7 times, particularly preferred less than 5 times.By making the thickness lower limit in above-mentioned scope of resin bed Above, it is possible to reduce haze value.Additionally, by below higher limit, it is possible to giving film surface will not Produce the sufficient lubricity of surface defect.

Base material film is preferably less than 0.05 with the refractivity at the interface of resin bed.If this refractivity exists In above-mentioned scope, then can suppress the loss in light transmission multilayer film time.

[the 4. physical property of multilayer film]

The multilayer film of the present invention possesses above-mentioned resin bed, thus the sliding in the face of resin bed side is high.Therefore, Coil into web-like and after making film roll, it is possible to the generation of suppression convex defect.

Additionally, the multilayer film of the present invention possesses the resin bed that internal haze is little as described above, it is thus possible to Reduce its internal haze.Specifically, the internal haze of multilayer film preferably less than 5%, more preferably less than 3%, Particularly preferred less than 1%.Here, the internal haze of multilayer film can use following method to measure.

Prepare height 55mm, width 36mm, the quartz cell of optical path length 10mm.In this quartz cell Filling silicon oil.Multilayer film is put in this silicone oil, obtain measuring sample.Use the mensuration examination of so preparation Sample, utilizes haze meter to measure the internal haze of multilayer film.

Additionally, from the viewpoint of playing consistently as the function of blooming, preferably multilayer film is total saturating Light rate is high.Specifically, it is preferably more than 80%, more preferably 90% with the total light transmittance of 1mm thickness conversion Above.Here, total light transmittance can be based on JIS K0115, use spectrophotometer (Japanese light splitting company Manufacture, UV, visible light near infrared spectrometer " V-570 ") measure.

Multilayer film can be the phase retardation film that direction or thickness direction have delay in face.As concrete The scope postponed, can set according to the purposes of multilayer film.If enumerating concrete scope, then usual face The delay Re in interior direction can be at the delay Rth of 10nm～500nm, thickness direction The scope of-500nm～500nm suitably selects.

Additionally, within the face of multilayer film, the deviation of the delay Re in direction is usually 10nm, preferred 5nm Within, within more preferably 2nm.By make in face the deviation of the delay Re in direction in above-mentioned scope, In the case of multilayer film is used as liquid crystal indicator phase retardation film, it is possible to make display quality good.This In, in face, the deviation of the delay Re in direction refers to: when measuring angle of light 0 ° along the width of film Face in the delay Re in direction time, the difference of the maxima and minima of the delay Re in direction in this face.This In, angle of light 0 ° refers to the state of incident ray and the surface normal of film.

The amount of the residual volatile composition of multilayer film is preferably below 0.1 weight %, more preferably 0.05 weight % Below, below more preferably 0.02 weight %.By making the amount of volatile ingredient in above-mentioned scope, size is steady Qualitative raising, it is possible to the delay Re and the delay Rth of thickness direction in direction in the face of reduction multilayer film Rheological parameters' change with time.

The size of the width of multilayer film can be such as 1000mm～3000mm.Additionally, for many The size of the length direction of tunic does not limit, but the film of preferably strip.Here, the film of " strip " Refer to the width relative to film, there is the length of more than at least 5 times, preferably have 10 times or its more than Length, specifically refer to have and can coil into web-like and carry out taking care of or carrying the film of the length of degree.

[the 5. manufacture method of multilayer film]

The multilayer film of the present invention can be by including the operation preparing base material film and on the base material film prepared The manufacture method of the operation manufacturing resin bed manufactures.Here, as it has been described above, manufacture tree on base material film The operation of lipid layer includes obtaining the operation of the coating resin of flow-like, this coating resin being coated base material film Above form the operation of the film of coating resin and make the film solidification of the coating resin being formed on base material film And/or be dried and obtain the operation of resin bed.Therefore, multilayer film can be by such as including following operation Manufacture method manufacture: prepare base material film operation；By multiple particles different for mean diameter and bonding Polymer mixed and obtain the operation of the coating resin of flow-like；Coating resin is coated on base material film Form the operation of the film of coating resin；And, the film solidification of the coating resin making to be formed on base material film and / or be dried and obtain the operation of resin bed.

Additionally, in the case of the random layer that multilayer film possesses in addition to base material film and resin bed, Ke Yi Random time point in the manufacture method of multilayer film is configured the operation of arbitrary layer.Need explanation It is that the face with base material film opposition side of resin bed usually becomes the most surface of multilayer film and exposes.Therefore, Generally, arbitrary layer is arranged on base material film with resin bed opposition side face.

Further, it is also possible to the random time point in the manufacture method of multilayer film is carried out base material film, resin Layer and multilayer film carry out the operation stretched.

Furthermore, it is possible to carry out multilayer film to be coiled into the operation of web-like.

[the 6. purposes of multilayer film]

The multilayer film of the present invention uses usually used as blooming.Blooming as the purposes becoming multilayer film Example, protecting film, phase retardation film, optical compensation films etc. can be listed.Wherein, the present invention is many Tunic is preferably used as phase retardation film or polaroid protective film, is particularly preferably used as polaroid protective film.

Polaroid is generally configured with the polarizer and polaroid protective film.Therefore, the multilayer film of the present invention is used as In the case of polaroid protective film, generally the multilayer film of the present invention is fitted in the polarizer.Now, generally In the face of the resin bed side of multilayer film, multilayer film and the polarizer are fitted.

When multilayer film and the polarizer are fitted, can not via bond layer directly by multilayer film with rise Device laminating partially, it is also possible to fit via bond layer.Furthermore, it is possible to only the one side at the polarizer is fitted Multilayer film, it is also possible to fit on two sides.Only in the case of the one side laminating multilayer film of the polarizer, it is possible to With other the film that the another side laminating transparency at the polarizer is high.

The polarizer can be by such as after making polyvinyl alcohol film absorption iodine or dichroic dye, at boric acid Bath carries out uniaxial tension manufacture.Alternatively, it is also possible to by such as making polyvinyl alcohol film adsorb iodine or two Color dyestuff also stretches, and then a part for the polyvinyl alcohol units in strand is modified as poly-Asia Vinyl units and manufacture.Additionally, as the polarizer, such as can use: the grid polarizer, multilamellar The polarizer, the cholesteryl liquid crystal polarizer etc. have the function that polarized light is separated into reflection light and transmission light The polarizer.Wherein, the polarizer of polyvinyl alcohol is preferably comprised.The degree of polarization of the polarizer be preferably 98% with On, more preferably more than 99%.The average thickness of the polarizer is preferably 5 μm～80 μm.

As for by bonding agent bonding to the polarizer and multilayer film, it is possible to use optically transparent is bonding Agent.As this bonding agent, such as, can enumerate: aqueous adhesive, solvent type adhesive, bi-component are solid Change type bonding agent, light-cured type bonding agent, pressure-sensitive bonding agent etc..Wherein, preferably aqueous adhesive, The particularly preferably aqueous adhesive of polyvinyl alcohol.It addition, bonding agent can be used alone a kind, it is possible to To be applied in combination two or more with arbitrary ratio.

As light-cured type bonding agent, such as can use containing carbamate (methyl) acrylate, The esters of acrylic acid bonding agent of (methyl) acrylic acid hydroxy alkyl ester and acrylamide derivative.

Carbamate (methyl) acrylate can be by such as making polyisocyanates and polyol reaction After, make (methyl) acyclic compound of hydroxyl and the allyl ether of hydroxyl as required further Compound reacts, thus obtains as the oligomer containing free-radical polymerised unsaturated group.It addition, Carbamate (methyl) acrylate can also be by such as making (methyl) acyclic compound of hydroxyl After polyol reaction, react with polyisocyanates further and obtain.

As carbamate (methyl) acrylate, owing to easily making adhesive strength, flexibility, light solid The property changed and viscosity etc. obtain balance, every a part is therefore preferably used and has 2～3 double bonds and every 1 The number-average molecular weight of individual double bond is carbamate (methyl) acrylate of 500～3000.

The amount of carbamate (methyl) acrylate in light-cured type bonding agent is usually 30 weights Amount %～50 weight %.By making the amount lower limit in above-mentioned scope of carbamate (methyl) acrylate Above, it is possible to prevent bond layer to become fragile.It addition, by below higher limit, bonding agent can be reduced Viscosity, furthermore it is possible to improve adhesive strength.

As (methyl) acrylic acid hydroxy alkyl ester, such as, can enumerate: (methyl) 2-(Acryloyloxy)ethanol, (first Base) Hydroxypropyl acrylate, (methyl) hy-droxybutyl.Wherein, particularly preferred hydroxyethyl methylacrylate.

The amount of (methyl) acrylic acid hydroxy alkyl ester in light-cured type bonding agent is usually 13 weight %～40 weights Amount %.By make the amount of (methyl) acrylic acid hydroxy alkyl ester more than the lower limit of above-mentioned scope, Ke Yiti The hydrophilic that high bonding agent is overall, therefore, particularly can improve relative to polyvinyl alcohol polarizing coating Adhesive strength.It addition, by below higher limit, be possible to prevent bond layer to become fragile, furthermore it is possible to Improve the photo-curable of bonding agent.

As acrylamide derivative, can enumerate such as: N,N-DMAA, N, N-diethyl Base acrylamide, N, N-dimethylaminoethylacrylamide, N, N-dimethylaminopropylacryl amide, NIPA, N, N-dimethylaminopropylacryl amide, N-hydroxyethyl acrylamide.Its In, particularly preferred N, N-acrylamide, NIPA, N, N-dimethylamino Propylacrylamide, N-hydroxyethyl acrylamide.

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

Light-cured type bonding agent in addition to the above ingredients, further preferably contains 30 weight %～the (first of 40 weight % Base) isobornyl acrylate.By containing (methyl) isobornyl acrylate, can give bond layer with Thermostability.Furthermore, it is possible to the viscosity for improveing coating performance is adjusted, bonding without causing Performance reduces.

Light-cured type bonding agent preferably comprises Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater, the most permissible Enumerate: 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-2-phenyl acetophenone, ton ketone, Fluorenone, Benzaldehyde, fluorenes, anthraquinone, triphenylamine, carbazole, 3-methyl acetophenone, 4-chlorobenzophenone, 4,4 '- Dimethoxy-benzophenone, 4,4 '-diaminobenzophenone, Michler's keton, benzoin propyl ether, benzoin Ethylether, benzoin dimethylether, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 2-hydroxyl -2-methyl isophthalic acid-phenyl-propane-1-ketone, thiaxanthone, diethyl thioxanthone, ITX, 2-diuril Ton ketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2,4,6-trimethylbenzoyl Diphenyl phosphine oxide etc..It addition, the amount of the Photoepolymerizationinitiater initiater in Photocurable adhesive agent is usually 2 weights Amount %～10 weight %.

The viscosity of bonding agent is usually more than 20mPa when 23 DEG C, and preferably more than 30mPa is more excellent Elect more than 50mPa as, usually below 5000mPa, preferably below 3000mPa, more preferably Below 1500mPa.

The average thickness of bond layer is preferably more than 0.05 μm, more than more preferably 0.1 μm, preferably It is below 5 μm, below more preferably 1 μm.

Method for making multilayer film and the polarizer fit does not limits.The most preferred following method: rising Partially after the one side coating adhesive as desired of device, roller laminator is used to make the polarizer and multilayer film patch Close, and be dried as required or the irradiation of the light such as ultraviolet.

Embodiment

Hereinafter, the present invention is specifically described in conjunction with the embodiments.But the present invention is not limited to following institute The embodiment shown.

In the following description, " % ", " ppm " and " part " of expression amount is as long as no saying especially Bright, then it is weight basis.It addition, following operation is unless otherwise specified, then at room temperature, normal pressure Air is carried out.

[evaluation methodology]

[height of projection and the assay method of quantity]

Use fine shape determinator (little slope studies made " ET4000M "), with cutoff value (cutoff) 0.8mm, measurement range 1mm × 1mm determines the resin bed of multilayer film with base material film opposition side face Present on the height of projection and quantity.This mensuration is carried out at the central part of the width of multilayer film.

[assay method of internal haze]

Height 55mm, width 36mm, the quartz cell of optical path length 10mm are prepared.At this quartz cell Interior filling silicon oil (Toray Dow Corning company's manufacture " SH710 ").Multilayer film is put into this silicone oil In, prepare mensuration sample.Use the mensuration sample of so preparation, utilize haze meter (Japan's electricity color work Industry company manufactures " NDH-2000 ") determine the internal haze of multilayer film.

[assay method of peel strength]

(manufacture method of bonding agent)

Pure water 66.5g is measured in 100g glass container.This pure water is heated up to 80 DEG C, utilizes stirring Son is stirred.Polyvinyl alcohol (Japan synthesis chemistry system " GOHSEFIMER it is slowly added in this pure water Z200 ") 3.5g, it is allowed to be completely dissolved, has obtained the poly-vinyl alcohol solution of 5%.Then, this poly-second is made Enolate solution recovers to room temperature.Add in this poly-vinyl alcohol solution relative to gathering in poly-vinyl alcohol solution Vinyl alcohol be the Biformyl of 1% as cross-linking agent, be sufficiently stirred for, obtained bonding agent.

(manufacture method of the polarizer)

The polyvinyl alcohol film of thickness 80 μm is dyeed in the iodine aqueous solution of 0.3%.Then, will Polyvinyl alcohol film after dyeing is stretched to 5 in the aqueous solution comprising the boric acid of 4% and the potassium iodide of 2% Times, it is dried 4 minutes in 50 DEG C, has obtained the polarizer.

(manufacture of polaroid)

The face of the resin bed side of multilayer film use rod coaters be coated with above-mentioned bonding agent.At this bonding agent Load the polarizer on Ceng, extrude with roller laminator, multilayer film is fitted with the polarizer.Thus, Obtain the polaroid possessing the polarizer, bond layer, resin bed and base material film successively.

(mensuration of peel strength)

The polaroid of manufacture is cut into width 10mm, obtains test film.Utilize binding agent (day east electricity Work company manufactures " No.5601 ") face of the multilayer film side of this test film is fitted on the face of glass plate. Then, accurate universal testing machine (company of Shimadzu Seisakusho Ltd. manufactures " Autograph AGS-5kNG ") is utilized Upper jaw clamp the polarizer of test film, with the speed of 20mm/min towards relative to glass plate Vertical direction, face carries out tractive.Owing to the polarizer is pulled, occur at the interface of resin bed with base material film Peel off.Now, the size of the power of the tractive polarizer is determined.Measured by the length direction at test film The measured value of the stable 50mm scope of the size of power obtain meansigma methods, this meansigma methods is strong as peeling off Degree.

[evaluation methodology of volume outward appearance]

The outward appearance of the film roll for being batched by multilayer film 3000m, is differentiated by range estimation and touch Evaluated.

Side face in film roll is not existed the situation of polygonal depression be evaluated as " well ", will be in film roll Side face there is the situation of polygonal depression and be evaluated as " bad ".

[evaluation methodology of the surface state of multilayer film]

Sample is cut from multilayer film.Prepare 2 linear polarization sheets, clamp from many with these linear polarization sheets The sample that tunic cuts.Now, make 2 linear polarization sheets be orthogonal Nicolle (Cross Nicol), from The polarizing transmission axle that thickness direction is observed is mutually perpendicular to.Thus, obtained possessing successively linear polarization sheet, Sample and the laminated body of linear polarization sheet.

Above-mentioned laminated body is observed from thickness direction.Using light leak part as optical defect, count optical defect Quantity.Here, light leak part refers to observe the part of the light having passed through laminated body.Additionally, The area of the sample used in mensuration is 100m².The quantity of light leak part is the fewest, represents in multilayer film and gets over There is not wrinkle and folding line, its surface state the best.

[embodiment 1]

(manufacture of water-base resin)

Polyester is added many in the reactor equipped with thermometer, blender, nitrogen ingress pipe and condensing tube Unit's alcohol (Kawasaki chemical conversion industrial group's manufacture " MAXIMOL FSK-2000 "；Hydroxyl value 56mgKOH/g) 840 Part, toluene di-isocyanate(TDI) 119 parts and butanone 200 parts, import nitrogen in 75 DEG C React 1 hour.

After reaction terminates, it is cooled to 60 DEG C, adds dihydromethyl propionic acid 35.6 parts, carry out in 75 DEG C Reaction.Thus, the polyurethane solutions containing acid structure has been obtained.Polyurethane contained in this solution different The content of cyanic acid ester group (-NCO base) is 0.5%.

Then, this polyurethane solutions is cooled to 40 DEG C.Polyurethane solutions after the cooling period adds water 1,500 parts and as non-volatile alkali isopthalic dihydrazide (boiling point more than 224 DEG C) 120 parts (relatively It is 7 parts in polyurethane 100 parts), carry out emulsifying by carrying out high-speed stirred with homogenizer.Adding From the liquid after this emulsifying, butanone is distilled off under heat decompression, has obtained the water of the polyurethane being neutralized Dispersion.The solid component concentration of this aqueous dispersion is 40%.

Then, only point take so that contained polyurethane amount is 100 parts from the aqueous dispersion of this polyurethane Amount.Coordinate the glycerol bunching water as epoxide sweet in point aqueous dispersion of the polyurethane taken out Oil ether (Nagase ChemteX company's manufacture " Denacol EX-313 "；Epoxide equivalent 141g/eq) 40 Part, the silicon dioxide granule (Denki Kagaku Kogyo kabushiki manufactures " UFP-80 ") 24 of mean diameter 40nm Part, the silicon dioxide granule (Nissan Chemical Industries system " SNOWTEX of mean diameter 200nm MP-2040 ") 20 parts, 4,7-dihydroxy-2,4,7,9-tetramethyl-5-as nonionic surfactant The ethylene oxide adduct (Xin chemical industrial company manufactures " Surfynol 465 ") of decine, Yi Jishui, Obtain the liquid aqueous resin of the solid component concentration 5% of the polyurethane resin as its uncured state. Here, the addition of nonionic surfactant is to be the amount of 100ppm relative to gained water-base resin.

(manufacture of multilayer film)

By ester ring type olefin resin, (Nippon Zeon Co., Ltd. manufactures " ZEONOR "；Glass transition temperature 135 DEG C) pellet use ventilating air hot-air drier in 70 DEG C be dried 2 hours.Then, apparatus is made The film having the T-shaped die head formula of resin melting mixing roll (possessing the screw rod of diameter 65mm) melt extrudes molding Machine, has manufactured thickness with the condition of molding of molten resin temperature 270 DEG C, the width 500mm of T-shaped die head 100 μm, the base material film of length 1000m.This base material film is the base material film formed by ester ring type olefin resin.

One side at this base material film uses corona treatment plant to implement discharge process.Implementing at base material film The surface of discharge process uses the above-mentioned liquid aqueous resin of sized roller applicator coating, makes the dry thickness to be 50nm, defines the film of water-base resin.Then, heat 60 seconds in temperature 100 DEG C, make water-base resin Film solidification and be dried, base material film defines resin bed.Thus, obtained possessing base material film and tree The multilayer film of lipid layer.Film thickness gauge (big electronics Zhu Shihui company's manufacture " FE-300 ") is utilized to determine institute Obtaining the thickness of the resin bed of multilayer film, result is 50nm.

For gained multilayer film, said method is used to be evaluated.

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

When manufacturing water-base resin, using the amount of the glycerol polyglycidyl ether as epoxide, put down The amount of the silicon dioxide granule of all particle diameter 40nm and the silicon dioxide granule of mean diameter 200nm Amount is changed to as shown in table 1 respectively.

Beyond upper item, carry out manufacture and the evaluation of multilayer film as in Example 1.

[result]

The result of embodiment and comparative example is as shown in the table.In the following table, the implication of abbreviation is as follows.

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

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

Epoxy amount: the amount of glycerol polyglycidyl ether.

[table 1]

[table 1. embodiment and the result of comparative example]

[investigation]

The multilamellar possessing base material film and resin bed in combination is may validate that by the result of embodiment and comparative example In film, by make the projection formed with the face of base material film opposition side of resin bed meet 3.5≤G≤7, And N_B≥N_C≥N_D≥N_E≥N_F, batch and in the case of making film roll, it is possible to suppression convex defect Generation, and internal haze can be reduced.

Claims (12)

1. a multilayer film, it possesses:

Base material film and

The resin bed containing particle being arranged on described base material film,

Wherein,

Described resin bed has multiple projection at the mask with described base material film opposition side,

By the projection of the highly 5nm of (a) in described projection at every 1mm²On quantity be set to N_AIndividual /mm², (b) highly 10nm projection at every 1mm²On quantity be set to N_BIndividual/mm², (c) highly 15nm Projection at every 1mm²On quantity be set to N_CIndividual/mm², (d) highly 20nm projection at every 1mm² On quantity be set to N_DIndividual/mm², (e) highly 25nm projection at every 1mm²On quantity be set to N_E Individual/mm², (f) highly 30nm projection at every 1mm²On quantity be set to N_FIndividual/mm²Time,

With G=N_A/N_FValue G represented is 3.5≤G≤7,

Further, N_B≥N_C≥N_D≥N_E≥N_F。

Multilayer film the most according to claim 1, wherein, described resin bed comprises polymer, institute State polymer and comprise polyurethane.

Multilayer film the most according to claim 1 and 2, wherein, described particle comprises mean diameter Different multiple particles.

Multilayer film the most according to claim 3, wherein, described particle comprises: have less than 150nm The particle (S) of mean diameter and there is the particle (L) of mean diameter of more than 150nm.

Multilayer film the most according to claim 1, wherein,

Described resin bed comprises polymer,

Described particle comprises: has the particle (S) of the mean diameter less than 150nm and has 150nm The particle (L) of above mean diameter,

The amount of the described particle (S) in described resin bed is 2 weights relative to described polymer 100 weight portion More than amount part and below 24 weight portions.

Multilayer film the most according to claim 1, wherein,

Described resin bed comprises polymer,

Described particle comprises: has the particle (S) of the mean diameter less than 150nm and has 150nm The particle (L) of above mean diameter,

The amount of the described particle (L) in described resin bed is 5 weights relative to described polymer 100 weight portion More than amount part and below 20 weight portions.

7. according to the multilayer film according to any one of claim 1～6, wherein, described particle is dioxy SiClx.

8. according to the multilayer film according to any one of claim 1～7, wherein, the thickness of described resin bed Degree is more than 10nm and below 100nm.

9. according to the multilayer film according to any one of claim 1～8, wherein, described multilayer film is phase Potential difference film.

10. according to the multilayer film according to any one of claim 1～8, wherein, described multilayer film is inclined Shake sheet protecting film.

The manufacture method of 11. 1 kinds of multilayer films, it is the multilamellar according to any one of claim 1～10 The manufacture method of film,

Wherein, this manufacture method includes:

Multiple mix particles different to polymer and mean diameter is obtained the work of the resin of flow-like Sequence；

Operation by the described resin-coated film forming described resin on base material film of flow-like；And

Make the film solidification of the described resin being formed on base material film and/or be dried and obtain the work of resin bed Sequence.

The manufacture method of 12. multilayer films according to claim 11, wherein, described particle comprises: The particle (S) with the mean diameter less than 150nm and the grain of the mean diameter with more than 150nm Son (L).