CN108521769A - Thin-film laminate - Google Patents

Abstract

The present invention provides a kind of thin-film laminate inhibiting thickness.The thin-film laminate has：PET film；TAC film is set on the faces 1PET of PET film；And adhesive layer, it is set on the faces 2PET of PET film.When the thickness of TAC film is set as TA, and the thickness of PET film is set as TB, thin-film laminate meets 1~condition of the following conditions 4：20 μm≤TA+TB≤100 μm ... condition 1；10 μm≤TA≤60 μ ... conditions 2；10 μm≤TB≤80 μm ... condition 3；0.1≤TB/TA≤3.0 ... condition 4.

Description

Thin-film laminate

Technical field

The present invention relates to a kind of thin-film laminates.

Background technology

As the fenestrated membrane for being pasted onto glass pane etc., it is known to the anti-film that disperses, thermal isolation film, ultraviolet cutoff film and antifog Film etc..About such fenestrated membrane, it is provided with the adhesive layer comprising adhesive on a pellicular front of transparent thin polymer film, is led to The adhesive function that adhesive layer is crossed relative to the pasted objects object such as glass is stuck.

Above-mentioned antifog film prevents the fog generated by moisture condensation to be additionally operable to be pasted onto bathroom etc. for example, other than glass pane Mirror and freeze on the glass etc. of showcase.As antifog film, there is the fiber for implementing the saponification process as hydrophilicity-imparting treatment Plain acylate film, but cellulose acylate film is swollen because of water.Usually it is by the method for attaching of this kind of film as a result, It can stretch when being pasted after being soaked with water, therefore occasionally result in localized delamination.

Thus, for example proposing a kind of antifog film in Japanese Unexamined Patent Publication 2000-043203 bulletins, which has reality Cellulose acylate (cellulose fatty acid ester) film, polyethylene terephthalate thin film and the bonding of antifog processing are applied Agent, and the thickness of polyethylene terephthalate thin film is in 120 μm or more and 300 μm or less of range.Poly terephthalic acid Second diester is used as an example of non-swelling property resin film, and in the antifog film, the thickness of polyethylene terephthalate thin film is set It is 120 μm or more, thus inhibits the peeling from the glass through stickup.

Invention content

The invention technical task to be solved

However, in antifog film recorded in Japanese Unexamined Patent Publication 2000-043203 bulletins, due to poly terephthalic acid second two The thickness of ester film is larger, therefore the weight as antifog film becomes larger.Also, such as it is pasted on the window of building and the mirror in bathroom Deng the area like that such as situation it is bigger, then weight is bigger, therefore application property is deteriorated.As the example that application property is deteriorated, can enumerate From the contraposition relative to glass or mirror to during stickup, antifog film is heavier, it is therefore necessary to increase the work of pressing antifog film The number of personnel.Also, in the case where antifog film to be pasted on window, antifog film is cut into more than glass in advance, and is glued After being affixed on glass, extra edge part is cut off along the inner edge of the window frame equipped with glass by cutter etc..So excision When, the thickness of the more big then antifog film of thickness of polyethylene terephthalate thin film is bigger, rapid and accurate to be difficult to sometimes Really cut off.This example is also the poor an example of operability.

Therefore the object of the present invention is to provide a kind of thin-film laminates inhibiting thickness.

Means for solving technical task

To achieve the goals above, thin-film laminate of the invention has polyester film, cellulose acylate film and glues Close layer.Cellulose acylate film is set on a pellicular front of polyester film.Adhesive layer is set to the another thin of polyester film On film surface.In thin-film laminate, when the thickness of cellulose acylate film is set as TA, and the thickness of polyester film is set as TB When, meet following all conditions, i.e. condition 1, condition 2, condition 3 and condition 4.

20 μm≤TA+TB≤100 μm ... condition 1

10 μm≤TA≤60 μm ... condition 2

10 μm≤TB≤80 μm ... condition 3

0.1≤TB/TA≤3.0 ... condition 4

It is up to 7.0 × 10 preferably with respect to the expansion rate of humidity variation^-4.Preferably with respect to the bonding force of pasted objects object At least 10N/25mm.

The polyester for forming polyester film is preferably polyethylene terephthalate.Form the fiber of cellulose acylate film Plain acylate is preferably Triafol T.

Cellulose acylate film has on the pellicular front of the side opposite with polyester film side and includes the fibre through saponification The contact angle after pure water after 15 seconds is added dropwise as 20 ° hereinafter, when will in the saponification layer of the plain acylate of dimension on the surface of saponification layer The acyl group amount on the surface of saponification layer is set as X, and the acyl group amount of the pellicular front of the polyester film side of cellulose acylate film is set For Y when, the acyl group ratio found out with X/Y is preferably 0.7 or less.

Preferred cellulose acylate film is set to via adhesive linkage on a pellicular front of polyester film.It is preferred that adhesive linkage by Acrylic adhesive is formed.About acrylic adhesive, in the air that preferable temperature is 25 DEG C and relative humidity is 85% Equilibrium moisture content in 0.1% or more and 1.0% or less range.

Invention effect

The thickness of the thin-film laminate of the present invention is suppressed.

Description of the drawings

Fig. 1 is the schematic cross-section for implementing the thin-film laminate of the present invention.

Specific implementation mode

Thin-film laminate 10 shown in Fig. 1 is fenestrated membrane, the i.e. antifog film for the fog for preventing from being generated by moisture condensation, in addition to can Other than being pasted onto on glass pane, additionally it is possible to the mirror of glass or bathroom or the dresser that washes one's face for being pasted onto freezing showcase On son etc..In addition, the thin-film laminate 10 of the example has following function：Anticracking work(when being impacted to applications such as glass or mirrors It can and prevent function of dispersing；Such as inhibit the heat insulating function of the rising of summer indoor temperature caused by sunshine；And for example inhibit the winter Season is to outdoor exothermic heat insulating function.As shown in Figure 1, thin-film laminate 10 be following film, i.e., by partition board 11, adhesive layer 12, Polyethylene terephthalate (hereinafter referred to as PET) film 13, adhesive linkage 14, triacetyl cellulose (Triafol T, with Be known as TAC down) film 15 and protection materials 16 be overlapped with the sequence made of multilayered structure film.In the example, film layer Stack 10 is strip, and is set as being wound into a roll the state of tubular as will be described hereinafter, but can be as mesh The sheet of target form and dimension.

About thin-film laminate 10, removal partition board 11 and protection materials 16 when pasting, and as comprising adhesive layer 12, The film portion of PET film 13, adhesive linkage 14 and TAC film 15 is pasted on the state on glass or mirror.About partition board 11, use The adhesive layer 12 of thin-film laminate 10 before preventing use and the object other than pasted objects object (hereinafter referred to as adherend) Matter is stuck when contacting, and is stripped before stickup, and be removed from thin-film laminate 10.By the partition board 11, such as prevent The mutual thin-film laminate 10 pasted and/or be set as sheet of thin-film laminate 10 being overlapped in the case where being wound into a roll tubular Stickup to the substance in addition to adherend.About the raw material of partition board 11, be not particularly limited, preferably polyethylene, polypropylene, Any of PET has used PET in present embodiment.

About protection materials 16, for protecting the thin-film laminate 10 before use, glued during use, i.e. being pasted on In the state of object during use, a pellicular front (hereinafter referred to as 1TAC of the TAC film 15 exposed as outer surface is protected Face) 15a, keeping and/or transmission against thin-film laminate 10, pollution and/or damage when pasting.The film layer of the example Stack 10 is pasted on adherend as follows：Adherend, and commonly referred to as squeegee are contacted when pasting (squeegee) welded part of plate (Plate shape), makes it in the state of being pressed from 16 side of protection materials It is moved.The faces the 1TAC 15a of TAC film 15 is also protected the protection of material 16, by rubber when also can be from so pasting Damage caused by the contact of rubber-surfaced roll axis.Protection materials 16 are stripped after gluing, and are removed from thin-film laminate 10.It closes It in the raw material of protection materials 16, is not particularly limited, preferably any of polyethylene, polypropylene, PET, present embodiment In used polyethylene.Protection materials 16 are suitable according to the scratch resistance of the faces the 1TAC 15a of TAC film 15 and/or soil resistance etc. Locality setting.Therefore, thin-film laminate 10 does not have protection materials 16 sometimes.

Adhesive layer 12 undertakes the adhesive function relative to adherend.About the adhesive layer 12 of present embodiment, soaked with water After bonded, but water can not also be applied, even if without showing certain bonding force if water adhesive layer 12.Water can be applied Both it is added on any one of the surface of adhesive layer 12 and adherend, be more preferably applied to.More preferable water includes surfactant (for example, commercially available neutral detergent).In addition, in the present specification, so-called " bonding " is one kind of bonding, refer to be pasted on by After viscous object, even across certain time, the variation of adherence force (bonding force) is also smaller, can be removed as needed.It is excellent Adhesive layer 12 is selected to be formed by any one of acrylic adhesive, silicone-based adhesive, elastomeric adhesive, present embodiment In used acrylic adhesive.In addition, the thickness of adhesive layer 12, is not particularly limited, 25 μm are set as in present embodiment.

TAC film 15 prevents the fog generated by moisture condensation for inhibiting rainbow shape uneven.Rainbow shape is uneven to be The light interference phenomena caused by the refraction on each pellicular front of the reflection of the light on pellicular front and incident light when irradiation light, and by It is considered the irregular colour of the multiple color as rainbow.TAC film 15 be set to PET film 13 a pellicular front (hereinafter, The referred to as faces 1PET) on 13a, in the example, it is arranged via adhesive linkage 14.TAC film 15, which becomes, has base 21 and saponification The double-layer structure of layer 22, and configured in such a way that base 21 is as 13 side of PET film.As previously mentioned, protection materials 16 are because viscous Stripping after patch and be removed, therefore saponification layer 22 becomes the outer surface exposed in thin-film laminate 10 during use.

TAC film 15 is an example of the cellulose acylate film formed by cellulose acylate, and by as cellulose The TAC of acylate is formed.More specifically, base 21 is formed by TAC, and saponification layer 22 is formed by the TAC being saponified.Cellulose acyl Compound film is not limited to the double-layer structure as the example, can be the single layer structure of only base 21, or also may be used To be 3 layers or more of multilayered structure.For example, in present embodiment, saponification layer 22 is only arranged on a base face of base 21, but It is that it's not limited to that, can also be set on another base face.Also, in order to improve the difficulty with the peeling of adhesive linkage 14, The processing such as Corona discharge Treatment can be carried out to another base face for the base 21 for being provided with saponification layer 22.In no TAC film In the case of 15, confirm that rainbow shape is uneven, but since the outside of the PET film 13 in thin-film laminate 10 is provided with TAC film 15, therefore it is uneven to can inhibit rainbow shape, and TAC film 15 has saponification layer 22, therefore can prevent from being produced by moisture condensation Raw fog.

Base 21 is the main film body of TAC film 15, and for inhibiting rainbow shape uneven.Base 21 is also as support soap Change the supporter of layer 22 and functions.Base 21 does not contain the cellulose acylate (being TAC in the example) being saponified.

Hereinafter, the detailed content of the cellulose acylate to that can use illustrates.About cellulose acylate, especially It is preferred that under the degree of substitution (hereinafter referred to as acyl substitution) of the ratio of the hydroxy esterification of cellulose, i.e. acyl group is met with carboxylic acid State all formulas, i.e. formula (1)~formula (3).In addition, in (1)~(3), A and B are acyl substitution, and the acyl group in A is acetyl group, The carbon atom number of acyl group in B is 3~22.

2.4≤A+B≤3.0……(1)

0≤A≤3.0……(2)

0≤B≤2.9……(3)

Cellulose is constituted, and the glucose unit for being bonded with β-Isosorbide-5-Nitrae has hydroxyl at 2,3 and 6.Cellulose acylated Object is that part or all of hydroxyl of this cellulose is esterified, and the hydrogen of hydroxyl by carbon number for 2 or more acyl group replaces and At polymer.In addition, if the esterification of 1 hydroxyl in glucose unit is set as 100%, degree of substitution 1, therefore for In the case of cellulose acylate, if 2,3 and 6 hydroxyls are respectively by 100% esterification, degree of substitution becomes 3.

Here, in glucose unit, 2 acyl substitutions are set as DS2, are set as 3 acyl substitutions DS3,6 acyl substitutions are set as DS6 and by total acyl substitution that " DS2+DS3+DS6 " is found out be preferably 2.00~ 3.00, it is 2.86 in present embodiment.

Acyl group can be only a kind, or two or more.It is preferred that in the case that acyl group be it is of more than two kinds, one of them For acetyl group.When the hydrogen of 2,3 and 6 hydroxyls is set as DSA by the summation for the degree of substitution that acetyl group replaces, and by 2, When the summation of the degree of substitution replaced by acyl group in addition to acetyl group on 3 and 6 is set as DSB, the value of " DSA+DSB " is excellent It is selected as 2.2~2.86, especially preferably 2.40~2.80.DSB is preferably 1.50 or more, and especially preferably 1.7 or more.Also, About DSB, preferably its 28% or more be 6 hydroxyls substitution, but more preferable 30% or more, it is further preferred 31% or more, outstanding Its preferably 32% or more be 6 hydroxyls substitution.Also, the value of 6 " DSA+DSB " of cellulose acylate is preferably 0.75 More than, more preferably 0.80 or more, especially preferably 0.85 or more.

The acyl group for being 2 or more as carbon number, can be aliphatic group, can also be aryl, be not particularly limited.Such as Have alkyl carbonyl ester, alkene carbonyl ester or aromatic carbonyl ester, the aromatic series alkyl carbonyl ester etc. of cellulose, they can be respectively provided with into The substituted group of one step.Propiono, bytyry, valeryl, caproyl, caprylyl, capryl, dodecanoyl can be enumerated Base, tridecane acyl group, tetradecane acyl group, hexadecane acyl group, octadecanoyl, isobutyryl, tertiary bytyry, cyclohexane carbo, Oleoyl, benzoyl, naphthyl carbonyl, cinnamoyl etc..Wherein, more preferably propiono, bytyry, dodecane acyl group, ten Eight alkanoyls, tertiary bytyry, oleoyl, benzoyl, naphthyl carbonyl, cinnamoyl etc., especially preferably propiono, butyryl Base.

Can also include that plasticizer, ultra-violet absorber, degradation inhibitor etc. are various other than TAC in base 21 Additive.

About base 21, the quality of the cellulose acylate relative to base 21, the matter of plasticizer of the molecular weight less than 500 Amount is preferred to be inhibited to be at most 4% or less 4%, i.e..The quality of the cellulose acylate in base 21 is set as MA that is, working as, and will When the quality of the plasticizer of molecular weight in base 21 less than 500 is set as MB, in base 21, the matter that is found out by (MB/MA) × 100 Amount ratio (unit；It is preferably %) 4% or less.The mass ratio be 4% hereinafter, thus with more than 4% the case where compared with, inhibit On plasticizer to the faces 1TAC 15a of the molecular weight less than 500, and further reliably performance prevents from being produced by moisture condensation for a long time The performance (hereinafter referred to as long-term anti-fog properties) of raw fog.About the base 21, pass through soap as will be described hereinafter Change handles the remainder not being saponified, therefore is set as the group with the aftermentioned TAC material identicals of the material as TAC film 15 At.Plasticizer of the molecular weight less than 500 becomes interferes the reduction of aftermentioned acyl group ratio, in the faces 1TAC 15a in saponification process The reason that contact angle after upper 15 second becomes larger etc..But the mass ratio found out by (MB/MA) × 100 in TAC film 15 (unit；%) be suppressed to it is smaller, and for 4% hereinafter, thus with more than 4% the case where compared with, the acyl group caused by saponification process In the reduction of ratio and the reduction of contact angle after 15 seconds at least any one become more reliable.In addition, the contact after 15 seconds Angle is the contact angle being added dropwise after pure water after 15 seconds.Contact angle can be found out by sessile drop method.In addition, above-mentioned molecular weight is Elemental analysis, liquid chromatography, gas chromatographic analysis, NMR (nuclear magnetic resonance, nuclear-magnetism can be passed through Resonance), IR (Infrared Spectroscopy, infra-red sepectrometry) etc. commonly uses the molecular weight of chemical substance to determine that method is come true Fixed molecular weight in present embodiment, is compared with standard substance by gas chromatographic analysis and found out.It is small as molecular weight In 500 plasticizer, triphenyl phosphate (TPP), biphenyldiphenyl phosphate (BDP) etc. can be enumerated.

The repetitive unit with the ester linkage comprising dicarboxylic acids and glycol, preferably comprises molecular weight and exists in base 21 Ester oligomer in 500 or more and 10000 or less range is used as plasticizer, and the base 21 of present embodiment also includes it. About the molecular weight, since ester oligomer has the distribution of the molecular weight different less than 500 plasticizer from aforementioned molecular weight, because This can by be based on GPC (Gel Permeation Chromatography, gel permeation chromatography) weight average molecular weight and Number-average molecular weight is measured fixed, the number-average molecular weight measuring method of osmometry based on functional end-group, is based on viscosimetric analysis viscous Any one of average molecular weight etc. is spent to find out.It is by being divided equally based on the number that functional end-group measures in present embodiment Son amount measuring method is found out.Increasing is used as by using ester oligomer of the molecular weight in 500 or more and 10000 or less range Agent is moulded, thin-film laminate 10 is reliably improved and the so-called operability such as is easy to paste, is easy to re-paste when pasting adherend. Also, be used as plasticizer using above-mentioned ester oligomer, thus with use molecular weight less than 500 common plasticizers monomer feelings Condition is compared, the precipitation that can be further reliably suppressed on the 15a of the faces 1TAC, and the contact angle on the 15a of the faces 1TAC after 15 seconds It is easy to reduce and further reliably performance is long-term anti-fog properties.The the molecular weight of ester oligomer the big then long-term anti-fog properties the better, And molecular weight is smaller then the better with the compatibility of cellulose acylate, therefore the molecular weight of ester oligomer is more preferably in molecular weight In 700 or more and 5000 or less range, further preferably in 900 or more and 3000 or less range.

Above-mentioned dicarboxylic acids is more preferably aliphatic dicarboxylic acid of the carbon number in 2 or more and 10 or less range.It is above-mentioned Glycol is more preferably aliphatic diol of the carbon number in 2 or more and 10 or less range.The reason is that by using aliphatic Dicarboxylic acids and aliphatic diol can assign flexibility to thin-film laminate 10, and be difficult to generate obstruction after aftermentioned 15 seconds The decomposition product of the reduction of contact angle.As aliphatic carboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, the last of the ten Heavenly stems two can be enumerated Acid, azelaic acid, cyclohexane dicarboxylic carboxylic acid, maleic acid, fumaric acid etc..As aliphatic diol, ethylene glycol, 1,2- the third two can be enumerated Alcohol, 1,3- propylene glycol, 1,2- butanediols, 1,3 butylene glycol, 2- methyl-1,3-propanediols, 1,4- butanediols, 1,5- pentanediols, 2,2- dimethyl -1,3- propylene glycol (neopentyl glycol), 1,4- hexylene glycols, 1,4- cyclohexanediols, 1,4 cyclohexane dimethanol etc..This In embodiment, having used the ester oligomer based on adipic acid and ethylene glycol as ester, (number based on terminal hydroxyl sizing technique is equal 1000) molecular weight is about.

Then, about antifog film recorded in Japanese Unexamined Patent Publication 2000-043203 bulletins, for often generating moisture condensation Window or bathroom mirror etc. in the case of, become white opacity sometimes.The reason is that under high humidity and the more environment of water When antifog film exposes, the adhesive linkage between cellulose acylate film and PET film becomes white opacity, it is known that in cellulose acyl Compound film include a large amount of water in the case of can obviously change.Window or the visibility variation of mirror, gonorrhoea portion are generated because of gonorrhoea The problem of point becoming uneven and degraded appearance.Therefore, in thin-film laminate 10, in order to inhibit above-mentioned gonorrhoea, preferably base 21 include that moisture content is suppressed to lower additive.Moisture content is suppressed to lower additive as base 21, can be lifted Go out triphenyl phosphate (TPP), biphenyldiphenyl phosphate (BDP), molecular weight in 500 or more and 10000 or less range And in terminal hydroxyl and acidic group at least any one by the ester oligomer of the sealings such as monocarboxylic acid or single methanol, include O-phthalic The aromatic binary carboxylic acids such as acid, terephthalic acid (TPA), M-phthalic acid are used as the ester oligomer etc. of dicarboxylic acids.These are added Agent is contained in after adjusting additive amount in base 21, thus the moisture content of base 21 is suppressed to it is relatively low, as a result, can press down The gonorrhoea of made membrane laminated body 10.At this time it is aftermentioned initial anti-fog properties and aforementioned it is anti-fog properties for a long time can be by adjusting saponification process Condition etc. assign.

Saponification layer 22 undertakes initial anti-fog properties and long-term anti-fog properties function.The initial anti-fog properties property to prevent moment from condensing Energy.Saponification layer 22 forms 1TAC face 15a.As previously mentioned, saponification layer 22 includes in the cellulose acylate being saponified, the example Including the TAC being saponified.

When the acyl group amount of the faces 1TAC 15a is set as X, and by another pellicular front of TAC film 15 (hereinafter referred to as The faces 2TAC) the acyl group amount of 15b is when being set as Y, and the acyl group ratio found out by X/Y is 0.7 hereinafter, in present embodiment, such as is set as 0.3.Refer to：Acyl group ratio is smaller, and relative to the faces 2TAC 15b, the acyl group of the faces 1TAC 15a is then fewer, in cellulose acylated In the saponification process of object film, more acyl groups are saponified, and become hydrophilic radical.

Acyl group ratio has relationship with initially anti-fog properties.Specifically, acyl group ratio is smaller, it is initial anti-fog properties the better.Example Such as, the longitudinal axis is being set as initial anti-fog properties, and horizontal axis is being set as in the chart of acyl group ratio, it is initial anti-fog properties between acyl group Relationship is in substantially straight line.Acyl group ratio be 0.7 hereinafter, i.e. in 0 or more and 0.7 or less range, thus with the feelings more than 0.7 Condition is compared, and is showed excellent initial anti-fog properties.Acyl group ratio is more preferably in 0.01 or more and 0.6 or less range, further It is preferred that in 0.05 or more and 0.5 or less range.

About acyl group amount X and acyl group amount Y, as passing through fourier transform infrared spectroscopy (FT-IR, Fourier Transform Infrared Spectroscopy, hereinafter referred to as FT-IR) total reflection measure (ATR, decaying total reflection： Attenuated Total Reflection) spectral intensity of acyl group that finds out of method (hereinafter referred to as ATR methods) and find out.Specifically For, by the spectral intensity of the common signal of cellulose-based polymer, to the spectrum of the signal of the acyl group of cellulose acylate Intensity is corrected (standardization).In present embodiment, it is used as cellulose acylate using TAC, therefore acyl group is acetyl group, The signal of acetyl group is 1210cm^-1.It is preferred that the common signal of cellulose-based polymer is set as 1030cm^-1.Also, find out into Row corrects and the spectral intensity of the signal of the acyl group of the cellulose acylate of acquisition is used as acyl group amount X, acyl group amount Y.In this way, acyl Base unit weight X and acyl group amount Y is the index substituted by the quantity of acyl group.

ATR methods about FT-IR, it is well known that it is the method for making light invade measurement sample, and finding out spectral intensity, The spectral intensity obtained is not the intensity on the proper surface for measuring sample.ATR methods used as common FT-IR In a method, diamond prism (Diamond prism), and will measure angle be set as 45 degree and when implementing, from measuring sample The depth of invasion of light on surface be about 2~3 μm.The saponification layer 22 of present embodiment as will be described hereinafter very It is thin, therefore the depth of invasion of light is deeper than 2 μm, the reliability as the acyl group amount found out for saponification layer 22 is more reduced.Therefore, It is preferred that the spectral intensity for finding out the range for being 2 μm from the faces 1TAC 15a depth is used as acyl group amount X, in present embodiment, also will The depth of invasion of light is set as 2 μm, and will be set as acyl group from the spectral intensity that the faces 1TAC 15a depth is 2 μm of ranges below Measure X.

Similarly, the spectral intensity for preferably finding out the range for being 2 μm from the faces 2TAC 15b depth is used as acyl group amount Y, this In embodiment also so.In the case where being also equipped with saponification layer on the 15b of the faces 2TAC, in the thickness direction of base 21 Acyl group amount is begged out, it is excellent from the viewpoint of the reliability from the viewpoint of simplicity and as the acyl group amount found out for base 21 Choosing is used as acyl group amount Y using the acyl group amount.The feelings of acyl group amount Y in being difficult to find out the faces 2TAC 15b by the above method Under condition, film can be formed by the solution, and ask by IR by the way that base 21 to be dissolved in dichloromethane and/or chloroform etc. The other methods such as the acyl group amount gone out in the pellicular front of the film are found out.

Contact angle after 15 seconds has relationship with anti-fog properties for a long time.Specifically, if contact angle is less than 20 degree, display is long-term Anti-fog properties particularly good tendency.More specifically, long-term anti-fog properties contact angle after 15 second becomes rapid at 20 degree or less Optimization has and shows good long-term anti-fog properties tendency at 20 degree or less.Contact angle after 15 seconds is to indicate enough parents Water composition is present in the characteristic on the 15a of the faces 1TAC, it is believed that in such hydrophilic composition feelings more on the 15a of the faces 1TAC Under condition, since the water droplet to condense on the 15a of the faces 1TAC is able to maintain that the state for being sufficiently humidified so as to and extending, to long-term antifog Property is effective.Contact angle behind 15 seconds of the faces 1TAC 15a is set as 20 ° hereinafter, in present embodiment, for example, 13 °.After 15 seconds Contact angle with it is long-term it is anti-fog properties have a relationship, but in order to by the contact angle after 15 seconds be set as 20 ° hereinafter, with above-mentioned acyl group ratio at The acyl group amount X of the faces 1TAC 15a is controlled for 0.7 mode below.Contact angle after 15 seconds is preferably below at 5 ° or more and 20 ° In range, more preferably in 8 ° or more and 20 ° or less of range, further preferably in 10 ° or more and 18 ° or less of range. Additionally, it is contemplated that time after pure water is added dropwise and find out contact angle, and it is contact angle after i.e. 15 seconds after 15 seconds to be set as the time, Thus it can get long-term anti-fog properties excellent TAC film 15.Contact angle after 15 seconds is the compatibility indicated with the water of pellicular front Characteristic.In measurement relative to the contact angle of water, as the time after dropwise addition pure water passs, generates pure water and penetrate into soap Change the inside for being formed as membranaceous hydrophilic parts (hereinafter referred to as hydrophilic film) on the surface of layer 22 with very thin thickness, or The phenomenon of person's thin film composition exudation etc. inside the hydrophilic film, however, it was found that be measured by 15 seconds after the drop wise addition, it can It measures and the long-term anti-fog properties corresponding hydrophily of pellicular front.

About the contact angle after 15 seconds, preferably the thin-film laminate 10 after humidity regulation (humidity adjustment) is surveyed Fixed, the treatment conditions of preferably humidity regulation are set as temperature in 23 DEG C or more and 28 DEG C or less of range, and relative humidity exists Under atmosphere in 55% or more and 65% or less range, more preferably the time of humidity regulation is set as 1 hour or more.This implementation In mode, humidity regulation 1 hour under the atmosphere that temperature is 25 DEG C and relative humidity is 60%.It is handled about the humidity regulation, Whole to thin-film laminate 10 humidity regulation can be carried out, as long as but being at least then enough to the progress humidity regulation of saponification layer 22. In addition, in this specification, relative humidity is also recorded with the unit of " %RH " sometimes, but identical as above-mentioned " % " meaning.

Also, in the range of the thickness of saponification layer 22 is set as regulation, further can reliably it have both initial anti- Mist and long-term anti-fog properties.Specifically, as follows.There are correlation between acyl group ratio and the thickness of thickness saponification layer 22, Acyl group ratio is smaller, then the thickness of saponification layer 22 is bigger.As previously mentioned, acyl group ratio is smaller, then it is initial anti-fog properties the better, because The thickness of this saponification layer 22 is the bigger the better.

Also, as the thickness of saponification layer 22 becomes larger from 0 (zero), the contact angle after 15 seconds successively decreases, if but saponification layer 22 Thickness become greatly to a certain degree more than, then be incremented by.Think that the incremental reason is：If in order to increase the thickness of saponification layer 22 Degree, reinforces the condition of aftermentioned saponification, then the aforementioned hydrophilic film that the contact angle after 15 seconds reduces reduces or the thickness of saponification layer 22 It spends greatly, thus, it is possible to keep the holding area of water excessive, water penetrates into the inside of 1TAC face 15a.As previously mentioned, long-term antifog Property is showed by the contact angle after 15 seconds for 20 ° or less, thus preferably by the incremental zone of the contact angle after 15 seconds with 20 ° Corresponding thickness is as upper limit value, the thickness of setting saponification layer 22.It not only can further reliably ensure as a result, initial antifog Property, it can also further reliably ensure long-term anti-fog properties.

According to the above, in order to which further reliably performance is initial anti-fog properties and long-term anti-fog properties, the thickness of saponification layer 22 is excellent It is selected in 1 μm or more and 6 μm or less of range, in present embodiment, is located in the range of 2 μm or more and 5 μm.That is, saponification layer 22 thickness is 1 μm or more, thus with less than 1 μm the case where compared with, it is initial it is anti-fog properties become relatively reliable, be 6 μm hereinafter, by It is long-term anti-fog properties to become relatively reliable compared with this is with more than 6 μm the case where.

In addition, in present embodiment, the thickness of saponification layer 22 is found out by the following method.It will be adopted from thin-film laminate 10 The sample of sample was impregnated in through 24 hours in dichloromethane.Undissolved sample in the dipping is dried, the examination to being dried The thickness of sample carries out 3 measurement.By the average thickness as saponification layer 22 of 3 measured values.

Adhesive linkage 14 is for being bonded TAC film 15 and PET film 13.It is preferred that adhesive linkage 14 is by vinyl acetate resin, epoxy The formation of any one of resin, vinyl chloride resin, acrylic adhesive, silicone-based adhesive, elastomeric adhesive, this implementation In mode, acrylic adhesive has been used.From durability in the environment of the intensity and high temperature and humidity of adhesive linkage 14 and thin From the viewpoint of the transparency and cost of film laminated body 10, preferred acrylic adhesive.About acrylic adhesive, temperature The equilibrium moisture content in air for being 85% for 25 DEG C and relative humidity is particularly preferably in 0.1% or more and 1.0% model below In enclosing.So-called equilibrium moisture content, it is well known that refer to the water content in the air of certain temperature and humidity in material at it The moisture content in the state of balance is realized in atmosphere.In present embodiment, equilibrium moisture content is found out by the following method.That is, The sample (being used to form above-mentioned each resin of adhesive linkage 14 and/or each adhesive) of measure object is coated on measurement base material On (for example, by base material of the PET film-forms formed), and with formed adhesive linkage 14 the case where be dried under the same conditions And/or heating, film is consequently formed.In the environment of 25 DEG C, relative humidity 80% through 24 it is more than the time to being formed by film After carrying out humidity regulation, karl Fischer (Karl Fischer) moisture teller (AQ-2200, HIRANUMA SANGYO is used Co., Ltd. manufactures) it is measured, by the quality of the moisture in film divided by it is formed by the quality of film, is thus found out flat Weigh moisture content.In addition, the thickness of adhesive linkage 14 is not particularly limited, in present embodiment, it is set as 10 μm.In this specification, institute It calls " bonding ", refer to the object to be pasted (is each other TAC film 15 in present embodiment simply including aforementioned " bonding " With PET film 13) it is pasted with the state being integrally formed.

In adhesive linkage 14 use acrylic adhesive in the case of, preferably by thin-film laminate 10 be used as it is antifog Under the hot and humid environment of film, it can inhibit to make adhesive linkage 14 containing gonorrhoea caused by moisture by moisture penetration TAC film 15 The acrylic adhesive declined with bonding force.As its method, it is preferred for the acrylate copolymer of acrylic adhesive Polymeric composition in, including the monomer containing hydroxyl of certain ratio is used as hydrophilic composition to improve the parent of polymer itself It is aqueous and/or addition crosslinking agent come improve hydrophily and make its crosslinking etc..Also, in present embodiment, in adhesive linkage 14 There is PET film 13 on the face of the side opposite with TAC film 15, therefore can further be reliably suppressed the white of adhesive linkage 14 It is turbid.As the acrylate copolymer used in this acrylic adhesive, can enumerate comprising carbon number be 1~18 (methyl) Acrylate and it is used as the vinyl monomer of hydrophilic composition or the copolymer etc. of (methyl) acrylic acid derivative with hydroxyl.Make For (methyl) acrylate of carbon number 1~18, such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (first can be enumerated Base) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) Sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) third The own ester of olefin(e) acid, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) propylene The different monooctyl ester of acid, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) acrylic acid are different Last of the ten Heavenly stems ester, (methyl) acrylic acid hendecane ester, (methyl) lauryl ester, (methyl) acrylic acid tridecane ester, (methyl) third Olefin(e) acid tetradecane ester, (methyl) acrylic acid pentadecane ester, (methyl) acrylic acid hexadecane ester etc..As the ethylene list with hydroxyl Body, (methyl) acrylic acid derivative can enumerate (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 3- hydroxypropyl acrylates, (methyl) The hydroxyls such as (methyl) hydroxyalkyl acrylate, vinyl alcohol, the allyl alcohols such as acrylic acid 4- hydroxy butyl esters, the own ester of (methyl) acrylic acid 6- hydroxyls The monomer etc. of (hydroxyl).100 mass parts of (methyl) acrylate for being 1~18 relative to carbon number, in these acrylate copolymers The ratio of hydrophilic composition be preferably 5~50 mass parts, more preferably 10~30 mass parts.Hydrophilic composition with hydroxyl Amount be that thus can further be reliably suppressed the gonorrhoea of the thin-film laminate 10 under high humidity environment more than certain.Also, from viscous From the viewpoint of resultant force and cohesiveness etc., 100 mass parts of (methyl) acrylate for being 1~18 relative to carbon number have hydroxyl Hydrophilic composition be preferably 50 below mass part.In addition, in these acrylate copolymers, additionally it is possible to make other vinyl monomers And/or the monomer copolymerization containing polar group.In addition, in this specification, it includes "~" to use the range of the numerical value of "~" label Front and back numerical value.

Also, it by coordinating crosslinking agent to acrylate copolymer and being crosslinked, can further be reliably suppressed thin with TAC The bonding force and the gonorrhoea under high temperature and humidity of film 15 and PET film 13.As this crosslinking agent, the friendship of isocyanates system can be enumerated Join agent, epoxy crosslinking agent, metal chelate crosslinMng agent, aziridine crosslinker etc., especially preferably have in the molecule 2 with On isocyanate group isocyanates system crosslinking agent.As the example of isocyanate compound system crosslinking agent, toluene can be enumerated Diisocyanate (being labeled as TDI sometimes), chlorine phenylene vulcabond, hexamethylene diisocyanate, tetramethylene two are different Cyanate, isophorone diisocyanate, methyl diphenylene diisocyanate etc., particularly preferred hexamethylene diisocyanate. Relative to 100 mass parts of acrylate copolymer, crosslinking agent is preferably 0.5~20 mass parts, more preferably 1~15 mass parts, especially It is preferably 2~10 mass parts.Also, in the range for not damaging the desired performances such as the transparency corresponding with intended applications Interior, adhesive linkage 14 can include various additives.As this additive, rosin derivative resin, polyterpene resin, oil can be enumerated The tackifier of dissolubility phenolic resin etc., plasticizer, filler, antioxidant, surfactant, colorant, silane coupling agent, nothing Machine system cures cocatalyst and ultra-violet absorber etc..

PET film 13 is used to inhibit the water suction of TAC film 15 when pasting and during use.Aforementioned adhesion layer 12 is arranged In on another pellicular front (the hereinafter referred to as faces 2PET) 13b of the PET film 13.In addition, the water suction refers to absorbing the water of liquid With both the water (i.e. vapor) for absorbing gas.PET film 13 is an example of the polyester film formed by polyester, by as poly- The PET of ester is formed.Polyester is not limited to PET.As polyester, preferably PET, polyethylene naphthalate are (hereinafter referred to as PEN), polybutylene terephthalate (referred to as " PBT ") etc., more preferably PET, PEN, especially preferably PET.Do not having In the case of PET film 13, TAC film 15 is when pasting and absorbs water during use, thus causes to expand.But film is laminated Body 10 has PET film 13, therefore inhibits the water suction of TAC film 15, thus inhibits expansion.In addition, in present embodiment, it is not right Any one of the faces 1PET 13a and the faces 2PET 13b implement special processing.But in order to improve the stripping with adhesive linkage 14 Degree of meeting with misfortune can carry out the faces 1PET 13a the processing such as Corona discharge Treatment and/or in order to improve and the peeling of adhesive layer 12 hardly possible Degree can carry out the processing such as Corona discharge Treatment to the faces 2PET 13b.

Here, the thickness of TAC film 15 is set as TA (unit be μm), the thickness of PET film 13 is set as TB, and (unit is μm), by for use film portion, include adhesive layer 12, PET film 13, adhesive linkage 14 and TAC film 15 in the example The thickness of film portion be set as TT (unit be μm).About thin-film laminate 10, for example, the sum of thickness TA and thickness TB (with Under, referred to as thickness summation) i.e. TA+TB is 56 μm, thickness TA is 40 μm, and thickness TB is 16 μm, by thickness TB divided by thickness TA At ratio (hereinafter referred to as thickness ratio) TB/TA be set as 0.4.

But so-called thickness summation TA+TB, thickness TA, thickness TB, thickness ratio TB/TA, be not limited to it is above-mentioned, thin Under conditions of the thickness summation TA+TB of film laminated body 10 is in 20 μm or more and 100 μm or less of range, thickness TA 10 μm with In upper and 60 μm or less of range, thickness TB is in 10 μm or more and 80 μm or less of range, and thickness ratio TB/TA is 0.1 or more And in 3.0 or less range.That is, as long as thin-film laminate 10 meets following all conditions, i.e., condition 1, condition 2, Condition 3 and condition 4.

20 μm≤TA+TB≤100 μm ... condition 1

10 μm≤TA≤60 μm ... condition 2

10 μm≤TB≤80 μm ... condition 3

0.1≤TB/TA≤3.0 ... condition 4

About thin-film laminate 10, due to meeting condition 1, thickness can be suppressed to smaller.It as a result, also can rapidly simultaneously And accurately carry out the excision of the extra edge part by the progress such as cutter in the case of being pasted on window.Also, it pastes When, even if it is smaller if the weight weight of increase protection materials 16, therefore the number of staff can be suppressed to less.In this way, The operability of thin-film laminate 10 is excellent.Thickness summation TA+TB more preferably in 30 μm or more and 100 μm or less of range, into One step is preferably in 50 μm or more and 80 μm or less of range.That is, condition 1 is more preferably 30 μm≤TA+TB≤100 μm, into one Step is preferably 50 μm≤TA+TB≤80 μm.

Since thickness TA is 10 μm or more, the rainbow shape for being reliably suppressed thin-film laminate 10 is uneven, due to thickness Even if degree TA be 60 μm hereinafter, therefore in the case where TAC film 15 absorbs water if can limit its water absorption.Thickness TA is more preferable In 20 μm or more and 60 μm or less of range, further preferably in 25 μm or more and 50 μm or less of range.That is, condition 2 More preferably 20 μm≤TA≤60 μm, further preferably 25 μm≤TA≤50 μm.In addition, in the current technology, manufacture is thick It is higher and actually more difficult less than the difficulty of 10 μm of TAC film 15 to spend TA, therefore the lower limit of thickness TA is 10 μm.From suppression From the viewpoint of the gonorrhoea of made membrane laminated body 10, thickness TA is smaller within the above range, the more preferred.The reason is that can incite somebody to action TAC film 15, especially base 21 water absorption be suppressed to it is relatively low.

Since thickness TB is 80 μm hereinafter, therefore the thickness of thin-film laminate 10 will not be excessive, since thickness TB is 10 μm More than, therefore even if in the case of using water when pasting, PET film 13 is fully functioned as waterproof layer, can be pressed down Make the water suction to TAC film 15.The expansion of thin-film laminate 10 can be suppressed to as a result, smaller.Thickness TB is more preferably at 10 μm Above and in 60 μm or less of range, further preferably in 15 μm or more and 50 μm or less of range.That is, condition 3 is more preferable For 10 μm≤TB≤60 μm, further preferably 15 μm≤TB≤50 μm.In addition, about the PET for using thickness TB to be less than 10 μm Film 13 manufactures thin-film laminate 10, technical from the viewpoint of ensuring stable transporting in aftermentioned manufacturing method Difficulty is higher, actually more difficult in current technology, therefore the lower limit of thickness TB is 10 μm.

It, can be by thin by TAC film 15 of the stylus contact before being bonded each other and PET about thickness TA and thickness TB The each of film 13 and directly measure the method for thickness, be measured using the equipment by non-contacting laser determination thickness Either method in method is found out.In present embodiment, about each other be bonded before TAC film 15 and PET film 13 it is every One uses commercially available thickness measurement equipment (elcometer：Film Thickness Tester, ANRITSU CORPORATION is manufactured, model：KG-601B and/or F20 film thickness measuring systems, Filmetrics Japan, Inc.) etc. and into Row measures.But the assay method of thickness TA and thickness TB are not only defined in said determination equipment.As by thin-film laminate 10 methods for finding out the thickness TA of TAC film 15 and the thickness TB of PET film 13, such as there are as below methods, that is, utilizes glass cutter Deng cut-out thin-film laminate 10, by optical microphotograph sem observation by cutting off exposed section, measured in observing image thick Spend the method for TA and thickness TB etc..

Since thickness ratio TB/TA is in 0.1 or more and 3.0 or less range, though thickness TB be 80 μm hereinafter, TAC film 15 can also obtain the balance for the power of TAC film 15 and PET film 13 to be deformed in the case of absorbing water.As a result, closing In thin-film laminate 10, curling is can inhibit, may also suppress and float from the part of adherend.The part floats for following phenomenon, i.e., In the various films such as fenestrated membrane, air enters between the adhesive layer 12 and adherend of the periphery of the film, and is generated with tunnel-like The phenomenon that chamber portion.Thickness ratio TB/TA is more preferable in 0.2 or more and 3.0 or less range, further preferably 0.2 with In upper and 2.5 or less range.That is, more preferably 0.2≤TB/TA≤3.0 of condition 4, further preferably 0.2≤TB/TA≤ 2.5。

About thin-film laminate 10 in addition to the partition board 11 and protection materials 16, for use film portion, i.e. should The film portion being made of adhesive layer 12, PET film 13, adhesive linkage 14 and TAC film 15 in example becomes preferably with respect to humidity The expansion rate of change is up to 7.0 × 10^-4, be 7.0 × 10^-4Hereinafter, being 6.3 × 10 in present embodiment^-4.With relative to wet The expansion rate of degree variation is more than 7.0 × 10^-4The case where compare, the expansion rate changed relative to humidity be 7.0 × 10^-4Below In the case of, it is difficult to further reliably generate the curling of thin-film laminate 10 and/or being partially stripped from adherend.More preferably Expansion rate relative to humidity variation is up to 6.5 × 10^-4, be 6.5 × 10^-4Hereinafter, further preferably it is up to 6.0 × 10^-4, be 6.0 × 10^-4Below.

The expansion rate changed relative to humidity can be found out by the following method.First, 3mm is cut out from thin-film laminate 10 The rectangle sample of × 20mm.It is right after the sample is exposed in the atmosphere that temperature is 25 DEG C and relative humidity is 50%RH The size L0 (unit mm) of long side direction is measured.Later, it is 25 DEG C about the condition of atmosphere is changed to rapidly temperature And relative humidity is 80%RH, and from the sample for changing the time point for beginning to pass through 2 minutes, to the size L1 (units of long side direction For mm) it is measured.The expansion rate that the value found out according to the formula of (L1-L0)/L0 is set as changing relative to humidity.It can pass through Adjust in thickness TA, thickness TB and thickness ratio TB/TA at least any one adjust the expansion rate changed relative to humidity.

About thin-film laminate 10 in addition to the partition board 11 and protection materials 16, for use film portion, i.e. should The film portion being made of adhesive layer 12, PET film 13, adhesive linkage 14 and TAC film 15 in example, preferably bonding force are at least 10N/25mm, it is 10N/25mm or more, more preferably 15N/25mm or more, further preferably 20N/25mm or more, this reality Apply in mode is 26N/25mm.Bonding force is 10N/25mm or more, thus with less than 10N/25mm the case where compared with, can be further Thin-film laminate 10 is reliably prevented to peel off from adherend during use.Bonding force be 15N/25mm or more, thus with less than The case where 15N/25mm, is compared, it is difficult to generate curling when stickup and/or the localized delamination from adherend.Bonding force is 20N/ 25mm or more, with less than 20N/25mm the case where compared with, it is difficult to further reliably generate thin-film laminate 10 curling and/or From being partially stripped for adherend.

Bonding force can be found out according to Japanese Industrial Standards JIS Z0237.Specifically, as follows.First, from film layer Stack 10 cuts out the rectangle sample that width is 25mm, length is 150mm." 25mm " of denominator in the unit of above-mentioned bonding force with The width of the sample corresponds to.It will be pasted on glass plate from the range of the length of the Yi Duan Vela 100mm on the long side direction of the sample On.In addition, applying the water for including micro surfactant to both the adhesive layer 12 of the stickup range and glass plate, and carry out It pastes.By by the sample for the state being so pasted on glass plate in the environment that temperature is 25 DEG C and relative humidity is 50%RH It is lower to place 3 days or more to be dried.After drying, to sample along the direction that long side direction extends with speed be 300mm/ minutes Speed tensile sample long side direction on the sides Ling mono- Duan Vela, and power when being peeled off from glass plate to sample is measured, and The power is set as bonding force.Can by adjust the raw material of adhesive layer 12, adhesive layer thickness and thickness ratio TB/TA in Lack any one to adjust bonding force.

About thin-film laminate 10, strip is manufactured in present embodiment, therefore cuts into the sheet of desired size And for using.

Thin-film laminate 10 can manufacture as follows：Make partition board 11, PET film 13, TAC film 15 respectively in advance And protection materials 16, and they are laminated.Hereinafter, about manufacturing method, illustrate, but as an example of the manufacturing method, and It is not limited to this.

TAC film 15 be by the thin-film material of the single layer structure to being formed by the TAC for being used as cellulose acylate (with Under, referred to as TAC materials) it carries out saponification and is made.About TAC materials, in the example, by comprising TAC polymer solution (with Under, referred to as dope) curtain coating in forming casting films on supporter, casting films are removed from supporter and being dried, is thus made Strip.Alkaline solution of the coating as saponification liquor in a material face of the TAC materials of strip, to coated TAC materials into Row heating, is used in combination water to be cleaned, thus to obtain TAC film 15.Contain isopropanol in saponification liquor.With based on being impregnated in saponification Saponification process in liquid is compared, and according to the saponification process of the coating based on saponification liquor, thickness smaller, and acyl group ratio is further Clearly become 0.7 or less.Therefore, even if clearly being showed if thickness TA is small as condition 2 anti-fog properties.Saponification layer 22 is Saponification is carried out to TAC by the saponification process based on coating and heating, and is formed as the region of stratiform.Base 21 is TAC materials In be not saponified non-saponified portions, the remainder i.e. in addition to saponification layer 22.Therefore, before aforementioned acyl group amount Y and saponification TAC materials thickness direction on arbitrary 2 μm of range acyl group amount it is equal.

Contact angle after capable of being adjusted 15 seconds by increasing or decreasing isopropanol amount in saponification liquor and/or alkalinity amount, The thickness of acyl group ratio and saponification layer 22.It can be according to the formula adjustment base 21 of the above-mentioned dope for making TAC materials The type and amount of plasticizer.

The PET film 13 of the strip made of well-known extrusion by melting is conveyed along long side direction, and to conveying In the faces the 1PET 13a of PET film 13 be coated with the coating fluid (hereinafter referred to as bonding coating fluid) to form adhesive linkage 14, it Afterwards, which is dried.For example, use dried gas (such as air) be fed into internal chamber be used as it is dry Dry device, and it is made to pass through in the chamber interior, thus carry out the drying process.About the gas dried, such as can add Heat is 40 DEG C etc..The adhesive linkage 14 formed relative to the drying process through film, it is thin that an edge long side direction conveys above-mentioned TAC Film 15 makes its coincidence on one side.By TAC film 15 and the guiding of PET film 13 for being formed with adhesive linkage 14 to shape opposite each other Between a pair roller of state configuration, and overlapped by the pressing of the circumferential surface based on a pair roller.In present embodiment, After the coincidence, the laminated member that will be provided with PET film 13, adhesive linkage 14 and TAC film 15 is wound into a roll tubular, but can To be not necessarily to wind, and it is the process overlapped with partition board 11 for next process.In addition, being used in molten in bonding coating fluid Agent preferably comprises at least one of ethyl acetate, toluene, ethyl alcohol, water etc., in present embodiment, is used as using ethyl acetate The ingredient of solvent.

The partition board 11 of strip is conveyed along long side direction, and a surface of the partition board 11 in conveying is coated with to form adhesive layer 12 Coating fluid (hereinafter referred to as bonding coating fluid) film is dried later.For example, by using the gas dried Body (such as air) is fed into internal chamber and is used as drying device, and it is dry to carry out this so that it is passed through in the chamber interior Dry processing.The gas of drying used herein can also also be heated in the same manner as aforementioned dried gas.Relative to The adhesive layer 12 formed through the drying process of film, an edge long side direction conveying have PET film 13, adhesive linkage 14 and The laminated member of TAC film 15 makes its coincidence on one side.In the state that the faces 2PET 13b is in contact with adhesive layer 12, by TAC The laminated member of film 15, the laminated member of adhesive linkage 14 and PET film 13 and adhesive layer 12 and partition board 11, guiding to Between a pair roller of state configuration opposite each other, and overlapped by the pressing of the circumferential surface based on a pair roller. After the coincidence, the laminated member volume of partition board 11, adhesive layer 12, PET film 13, adhesive linkage 14 and TAC film 15 will be provided with It is coiled into scroll-like and is set as rolling up.It is preferably comprised in ethyl acetate, toluene etc. with the solvent in coating fluid in addition, being used in bonding At least one, in present embodiment, is used as the ingredient of solvent using ethyl acetate.

By the volume obtained in the above described manner for aging (aging) process.Aging process is steadily to show adhesive layer 12 Bonding force process, and will for example roll up quiet be put under the atmosphere that temperature is 25 DEG C and relative humidity is 50%RH.From through aging The volume of process draws laminated member.Together by the protection materials 16 with the strip separately transmitted, the laminated member that will be drawn Thus guiding can get thin-film laminate 10 between a pair roller, making it be overlapped with protection materials 16.Can with protected material After 16 coincidence of material etc., there is the excision process that each side is cut off in a manner of as defined width.The film layer obtained Stack 10 can be wound into a roll tubular, can also cut into defined size, shape.It will be obtained with strip in present embodiment Thin-film laminate 10 is wound into a roll tubular.

Embodiment

[embodiment 1]~[embodiment 4]

By solution film-forming method, 2 kinds of different TAC materials of thickness are made by dope.By that will include following match The composition of square A devotes in closed container, and keeps the temperature at 40 DEG C on one side under normal pressure, is stirred on one side and makes it It is completely dissolved, dope is thus made.The raw material of TAC is short flannel.The acyl substitution of TAC is 2.86, and viscosity average polymerization degree It is 320.Particle is R972 (NIPPON AEROSIL CO., LTD. manufacture).About the particle, by being mixed in advance by TAC Disperseed in solution made of being dissolved in the mixture i.e. solvent of dichloromethane and methanol.Also, the dispersion liquid is thrown Enter in above-mentioned closed container, and is made the composition of following formulas.It is quiet put after, use filter paper (No.63, Toyo Roshi Kaisha, Ltd. are manufactured) it is filtered in the state that the liquid is remained 30 DEG C, after implementing deaeration operation, obtain dense Liquid.

＜ is formulated A ＞

As plasticizer, the ester oligomer based on adipic acid and ethylene glycol as ester has been used.Point of the ester oligomer Son amount is about 1000 in terms of the number-average molecular weight based on terminal hydroxyl sizing technique.

The dope that temperature is adjusted to 30 DEG C of formula A is cast on supporter.Supporter is the annular of stainless steel making Band.Relative to casting films, 100 DEG C of warm air is and then blown after being formed, is thus dried, and after formation after 120 seconds, Casting films are removed from supporter with the stripping tension of 150N/m, TAC materials are formed as into strip.Support on stripping position The temperature of body is set as 10 DEG C.The amount of residual solvent of casting films when stripping is 100 mass %.

On one side by being configured at multiple volumes of transport path in the state that the tension on long side direction is set as 100N/m The removed TAC materials of conveying, on one side dry it.By be set as 80 DEG C the 1st dry section convey 5 minutes it Afterwards, and then in the 2nd dry section for being set as 120 DEG C it conveys 10 minutes, is dried.After drying, TAC materials are wound into It is scroll-like, TAC material volumes thereby is achieved.The width of TAC materials is 1.5m, and the spooling length in TAC material volumes is 2000m.The amount of residual solvent of TAC materials when winding is 0.3%.

By carrying out saponification to the TAC materials obtained, TAC film 15 has been manufactured.Specifically, making by the following method TAC film 15 is made.TAC materials are rolled out and conveyed from TAC material volumes, by the apparatus for coating for being set to transport path Saponification liquor is coated on a surface of TAC materials.The formula of saponification liquor is as follows.In addition, in following formulas, % is quality percentage Than.

The TAC materials for being coated with saponification liquor are guided to the heating room being arranged on transport path, are conveyed on one side, one While being heated.Later, which is transmitted in the sink for accommodating water and is cleaned with water.By by TAC The temperature on the surface of material is maintained at about 55 DEG C about 1 minute, has carried out saponification.The acyl of the TAC film 15 of the strip so obtained Base ratio is 0.7, and the contact angle after 15 seconds is 20 °.Each computation of contact angle and acyl group ratio after 15 seconds is for example aforementioned. Thickness TA is the average value of the value gone out with width direction 0.5mm measuring spaces using contact thickness gauge, and is shown in Table 1.

By preceding method, keep obtained TAC film 15 Chong Die with partition board 11, PET film 13, protection materials 16, makes 4 kinds of thin-film laminates 10 are made, and as 1~embodiment of embodiment 4.In addition, used PET film 13 be thickness TB not With 2 kinds, the thickness TB in each embodiment is shown in Table 1.About each thin-film laminate 10, thickness ratio TB/TA etc. is shown in table 1 In.By using commercially available acrylic adhesive (Soken Chemical＆Engineering Co., Ltd. manufacture SK1478), adhesive linkage 14 is formd.

About the thin-film laminate 10 obtained, evaluation method and benchmark are stated below, it is uneven to rainbow shape, edge part Excision easiness, the peeling caused by crimping and part, which float, to be evaluated.

(1) rainbow shape is uneven

Thin-film laminate 10 is pasted on glass plate.It is irradiated from glass plate side using fluorescent lamp in the state of stickup Light is evaluated by visually being observed, and with following benchmark.

It is qualified；Irregular colour is not confirmed.

It is unqualified；Confirm irregular colour.

(2) the excision easiness of edge part

The glass plate being embedded into window frame has been used to be used as adherend.The thin-film laminate more than the glass plate is prepared 10.Glass plate is fully wet with the water dissolved with micro surfactant and has removed the thin-film laminate 10 of partition board 11 Adhesive layer 12 is aligned in a manner of exceeding from the periphery of glass plate thin-film laminate 10 relative to glass plate.Later, Using cutter, the extra edge part of thin-film laminate 10 has been cut off along the inner edge of window frame.About the easiness of excision, with Following benchmark is evaluated.In addition, so-called following " once resecting operations ", refers to by making to be inserted into plural layers 10 Cutter moves operation that is primary and cutting off along prescribed direction.A and B is qualification, and C and D are unqualified.

A；It can successfully be cut off by once resecting operation

B；Although feeling resistance to cutter, can be cut off by once resecting operation

C；Unless consumingly pushing down cutter, otherwise can not be cut off by once resecting operation

D；It can not be cut off by once resecting operation, repeatedly excision operation is needed when excision

(3) it is peeled off caused by crimping

Use the water dissolved with micro surfactant fully wet as adherend glass plate and removed partition board The adhesive layer 12 of 11 thin-film laminate 10, and thin-film laminate 10 is pasted on glass plate using squeegee, and with such as Lower benchmark is evaluated.In addition, the surfactant for being dissolved in water is neutral detergent.A and B is qualification, and C and D is not It is qualified.

A；It does not crimp, is unquestionably stuck.

B：Although the part on four sides slightly crimps, the part crimped passes through the sticking operation based on squeegee And it pastes

C；The part curling on four sides, about the part crimped, unless the sticking operation based on squeegee repeatedly, no It can not then paste.

D；The part curling on four sides, about the part crimped, even if the sticking operation based on squeegee repeatedly It can peel off.

(4) part floats

Use the water dissolved with micro surfactant fully wet as adherend glass plate and removed partition board The adhesive layer 12 of 11 thin-film laminate 10, and thin-film laminate 10 is pasted on glass plate using squeegee.Paste it Afterwards, protection materials 16 are removed, and is evaluated with following benchmark.A and B is qualification, and C and D is unqualified.

A；Do not float in an arbitrary point.

B：Although have occurred it is minimum float, as time go on, float and disappear.

C；A part for periphery occur it is small float, although not expanding to pasted central portion, about floating Otherwise part can not paste unless pushing down thin-film laminate.

D；Float in a part for periphery, and this floats as tunnel-shaped cavity portion and expands to thin-film laminate Central portion.

[table 1]

[comparative example 1]~[comparative example 6]

6 kinds of thin-film laminates with the layer structure different from the various embodiments described above are manufactured, and as comparative example 1~compare Example 6.About each thin-film laminate, it is shown in Table 1.In addition, the case where being not provided with TAC film 15 and to be not provided with PET thin It is being respectively "-" described in " thickness of TAC film " column and " thickness of PET film " column in table 1 in the case of film 13, and It is also recorded as "-" in " thickness ratio " column.

For the thin-film laminate obtained, respectively with method identical with embodiment and benchmark, uneven to rainbow shape, The excision easiness of edge part, the peeling caused by crimping and part, which float, to be evaluated.These results are shown in Table 1.

[embodiment 5]~[embodiment 8]

Composition comprising following formula B is put into closed container, and by identical as 1~embodiment of embodiment 4 Method dope has been made.Used TAC and particle respectively with the TAC and particle phase used in 1~embodiment of embodiment 4 Together.TAC materials have been made in dope by being formulated B.

＜ is formulated B ＞

As plasticizer, the ester oligomer based on phthalic acid and ethylene glycol for as ester is used, and to end Terminal hydroxy group carries out the plasticizer of acetic acid sealing.About the molecular weight of the ester oligomer, with carry out before end seal based on end The number-average molecular weight meter of terminal hydroxy group sizing technique is about 750.

2 kinds of bonding coating fluids for being used to form adhesive linkage 14 are made.Using one of which as bonding coating fluid A, and Using another one as bonding coating fluid B.Bonding is manufactured by the following method with coating fluid A.To have cooling tube, nitrogen is led In the reaction vessel for entering pipe, thermometer and agitating device, added together with ethyl acetate 100 mass parts Isooctyl acrylate monomer, 2,2 '-azodiisobutyronitriles of the acrylic acid of 10 mass parts, the acrylic acid 2- hydroxyl ethyl esters of 0.085 mass parts and 0.4 mass parts, from And it is prepared for solution.Then, it is stirred while being blown into nitrogen into the solution, it is made to react at 60 DEG C 4 hours, by This obtains the solution for the acrylic acid series polymeric compounds for being 1,750,000 containing weight average molecular weight.In turn, it obtains to containing the acrylic acid In the solution of based polymer add ethyl acetate and solid component concentration is adjusted to 30% acrylic polymer solution.On Stating weight average molecular weight is found out by GPC (gel permeation chromatography) method.

Relative to 100 mass parts of solid constituent of above-mentioned acrylic polymer solution, coordinate the tool of 2.0 parts by weight successively Have the compound of isocyanate group make crosslinking agent as main component (Nippon Polyurethane Industry Co., Ltd. manufacture, trade name " CORONATE (registered trademark) L "), γ-glycidoxypropyl group trimethoxies of 2.0 parts by weight Silane (Shin-Etsu Chemical Co., Ltd.s manufacture, trade name " KMB-403 ") is used as silane coupling agent, to It is prepared for bonding coating fluid A.After the bonding is equably coated on coating fluid A on the faces the 2PET 13b of PET film 13 It is dried, thus forms the adhesive linkage 14 comprising acrylic adhesive.For adhesive linkage 14 is formed by, measure in temperature Moisture content in the air that degree is 25 DEG C and relative humidity is 80%RH after 24 hours progress humidity regulations is used as balance Moisture content, as a result 0.1%.

Bonding is manufactured by the following method with coating fluid B.To having cooling tube, nitrogen ingress pipe, thermometer and stirring In the reaction vessel of device, the n-butyl acrylate of 100 mass parts, the acrylic acid 2- of 20 mass parts are added together with ethyl acetate The 2 of hydroxyl ethyl ester, 0.4 mass parts, 2 '-azodiisobutyronitriles, are thus prepared for solution.Then, nitrogen is blown into the solution on one side Gas is stirred on one side, it is made to react at 60 DEG C 4 hours, and the acrylic acid series for being 800,000 containing weight average molecular weight thereby is achieved The solution of polymer a1.The third of the tert-butyl acrylate comprising 100 parts by weight and 10 mass parts is obtained by identical method The polymer a2 that olefin(e) acid 2- hydroxyl ethyl esters and weight average molecular weight are 10,000.Bonding coating fluid B is obtained as follows：So that third Olefin(e) acid based polymer a1 becomes 100 mass parts, above-mentioned polymer a2 is made to be mixed as the mode of 20 mass parts, and then adds The hexamethylene diisocyanate of 10 mass parts is used as crosslinking agent, addition toluene, ethyl acetate and by solid component concentration tune Whole is 30%.It is dried after the bonding is equably coated on coating fluid B on the faces the 2PET 13b of PET film 13, by This forms the adhesive linkage 14 comprising acrylic adhesive.For adhesive linkage 14 is formed by, measure temperature be 25 DEG C and It is used as equilibrium moisture content through having carried out within 24 hours the moisture content after humidity regulation in the air that relative humidity is 80%RH, As a result it is 0.3%.

When forming adhesive linkage 14, using above-mentioned bonding coating fluid A or bonding coating fluid B, and use by formula A or The TAC materials that the dope of B obtains are formulated, thin-film laminate are manufactured by method identical with 1~embodiment of embodiment 4, and make For 5~embodiment of embodiment 8.In " type of TAC materials " column of table 2, it is recorded as using the dope of formula A A is recorded as B using the dope of formula B.In " adhesive linkage " column of table 2, bonding coating fluid A shapes are being used It is recorded as A in the case of at adhesive linkage 14, B is recorded as in the case where forming adhesive linkage 14 with coating fluid B using bonding.

About the thin-film laminate 10 obtained by 5~embodiment of embodiment 8, with side identical with 1~embodiment of embodiment 4 Method and benchmark, implement uneven rainbow shape, excision easiness of edge part, peeled off caused by crimping, part floats and in vain Turbid evaluation.Evaluation result is shown in table in 2.About gonorrhoea, in the following manner and benchmark is evaluated.

(5) gonorrhoea

Thin-film laminate 10 is pasted on glass plate.In the state of stickup, 45 DEG C of hot water is being kept the temperature at On the liquid level of bath it is quiet put 8 hours after, be fetched into the indoor environment that temperature is 25 DEG C and relative humidity is 60%RH, meat be used in combination Eye observation gonorrhoea, is thus evaluated with following benchmark.It is so-called following " pure ", refer to do not confirm white opacity and thoroughly It is bright.In addition, compared with the case where being observed from the front, from oblique, it appears that white opacity, therefore following In the C and D of benchmark, the case where being only observed from the front as evaluation criteria, not from oblique carry out.

A；From positive and oblique, look like in any case pure.

B；Look like in the case where being observed from the front it is pure, but seem if from oblique white it is muddy It is turbid.

C；When viewed from the front, it appears that white opacity.

D；When viewed from the front, it appears that consumingly white opacity.

[table 2]

[comparative example 7]~[comparative example 8]

The thin-film laminate with the layer structure different from 5~embodiment of embodiment 8 is manufactured, and as comparative example 7 and ratio Compared with example 8.About these thin-film laminates, it is shown in Table 2.

For the thin-film laminate obtained, with method identical with 5~embodiment of embodiment 8 and benchmark, to rainbow shape Uneven, edge part excision easiness, the peeling caused by crimping, part floats and gonorrhoea is evaluated.These results It is shown in Table 2.

Claims (9)

1. a kind of thin-film laminate, has：

Polyester film,

The cellulose acylate film being set on a pellicular front of the polyester film, and

The adhesive layer being set on another pellicular front of the polyester film；

When the thickness of the cellulose acylate film is set as TA, and the thickness of the polyester film is set as TB, meet All condition 1, condition 2, condition 3 and condition 4 below,

20 μm≤TA+TB≤100 μm condition 1

10 μm≤TA≤60 μm condition 2

10 μm≤TB≤80 μm condition 3

The conditions of 0.1≤TB/TA≤3.0 4.

2. thin-film laminate according to claim 1, wherein the expansion rate relative to humidity variation is up to 7.0 × 10^-4。

3. thin-film laminate according to claim 1 or 2, wherein the bonding force relative to pasted objects object is at least 10N/25mm。

4. thin-film laminate described in any one of claim 1 to 3, wherein the polyester for forming the polyester film is Polyethylene terephthalate.

5. thin-film laminate according to any one of claims 1 to 4, wherein form the cellulose acylate film Cellulose acylate be Triafol T.

6. thin-film laminate according to any one of claims 1 to 5, wherein

The cellulose acylate film has on the pellicular front of the side opposite with the polyester film side comprising through saponification Cellulose acylate saponification layer,

Be added dropwise on the surface of the saponification layer contact angle after 15 seconds after pure water be 20 ° hereinafter,

When the acyl group amount on the surface of the saponification layer is set as X, and by the polyester film of the cellulose acylate film When the acyl group amount of the pellicular front of side is set as Y, the acyl group ratio found out with X/Y is 0.7 or less.

7. according to thin-film laminate according to any one of claims 1 to 6, wherein the cellulose acylate film via Adhesive linkage is set on a pellicular front of the polyester film.

8. thin-film laminate according to claim 7, wherein the adhesive linkage is formed by acrylic adhesive.

9. thin-film laminate according to claim 8, wherein the acrylic adhesive is for 25 DEG C and opposite in temperature Equilibrium moisture content in the air that humidity is 85% is in 0.1% or more and 1.0% or less range.