CN105934339B

CN105934339B - Stack membrane

Info

Publication number: CN105934339B
Application number: CN201580005374.5A
Authority: CN
Inventors: 三羽规文; 大桥纯平; 石田康之; 高田育
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2014-01-31
Filing date: 2015-01-19
Publication date: 2018-01-23
Anticipated expiration: 2035-01-19
Also published as: WO2015115227A1; CN105934339A; JPWO2015115227A1; KR102314335B1; JP6481607B2; KR20160118211A; TW201545869A; TWI643743B

Abstract

The present invention relates to a kind of stack membrane, is the stack membrane for having superficial layer at least side of support base material, it is characterised in that meet following condition 1 and condition 2.Condition 1：Logarithmic decrement at 25 DEG C of superficial layer measured by rigid body pendulum test method(s), described is more than 0.1.Condition 2：The resin contained in above-mentioned superficial layer includes following (1)~(4).(1) polycaprolactone segment (2) amino-formate bond (3) polysiloxanes segment and/or PolydimethylsiloxaneChain Chain section (4) tricyclodecyl segment.The present invention provides a kind of mouldability not only realized simultaneously required by moulding material and the marresistance brought by self-repairability but also meets the stack membrane of closely sealed durability, soil resistance.

Description

Stack membrane

Technical field

The present invention relates to the mouldability and marresistance but also closely sealed durability not only realized simultaneously required by moulding material With soil resistance also excellent stack membrane.

Background technology

For the moulding material of decorated molded grade, in order to which the article after the damage and/or shaping when preventing shaping makes Damage during, cementation zone can be set.However, because cementation zone chases after the elongation deficiency from shaping, because And ruptured in shaping, either film fracture or cementation zone are peeled off in extreme situations, therefore, commonly used Following means：Cementation zone is formed after shaping；Or after being molded under semi-cured state, penetrated using heating, activity Line irradiation etc. makes it be fully cured etc..However, because the article after shaping is processed to 3-dimensional shape, therefore, in post-processing Set cementation zone be it is extremely difficult, in the case of being molded in addition under semi-cured state, according to condition of molding not Together, the pollution of mould is occasionally resulted in.From the above considerations, expect to chase after marresistance material from shaping, can by itself Elasticity recover scope deformation " self-repair material " of slight damage self-repairing is attracted attention, it is proposed that patent document 1 and 2。

On the other hand, using these formed bodys such as smart mobile phone housing, tablet PC housings as surfacing in use, requiring Durability when long-term use of.Especially, the moisture being present in air is molded to moulding material internal penetration, especially invasion and attack The surface of material, therefore the surface that moulding material be present is destroyed or the problem of stripping of superficial layer etc occurs.As for So the problem of and to cementation zone assign durability technology, it is proposed that the material of patent document 3.In addition, as formation The technology to the dhering strength of base material and the layer of durability is realized simultaneously, it is proposed that the material of patent document 4.

In addition, the one side as soil resistance, the common sheet material formed by soft resin and twill (jeans) And/or when dress material or natural leather containing dyestuff, synthetic leather contact, above-mentioned dyestuff be present and shifted to the surface of the sheet material The problem of, the method as the patience (hereinafter, being referred to as the metastatic of resistance to dyestuff) for assigning tolerance above mentioned problem, it is proposed that The material of patent document 5.

Prior art literature

Patent document

Patent document 1:International Publication No. 2011/136042

Patent document 2:No. 3926461 publications of Japanese Patent No.

Patent document 3:Japanese Unexamined Patent Publication 2013-166889 publications

Patent document 4:Japanese Unexamined Patent Publication 2012-233079 publications

Patent document 5:Japanese Unexamined Patent Publication 2008-62408 publications

The content of the invention

Invent problem to be solved

On the technology of the above-mentioned patent document 1 for proposing self-repair material, patent document 2, through present invention People have found after confirming, although mouldability and self-repairability are identified, closely sealed durability and/or soil resistance apply material than hard Decline to a great extent.

In addition, the technology on above-mentioned patent document 3, finds after present inventors confirm, although closely sealed The effect of durability is identified to a certain extent, but does not show mouldability, self-repairability.In addition, by its with it is above-mentioned special The technical combinations of sharp document 1 and 2 are impossible, can not realize self-repairability simultaneously.

In addition, the technology on above-mentioned patent document 4, is effective in terms of closely sealed durability, but be not shown as Type, self-repairability, in addition, being impossible by the technical combinations of itself and above-mentioned patent document 1~3.

In addition, the method described in above-mentioned patent document 5 is effective in terms of the metastatic of resistance to dyestuff, but do not show Mouldability, self-repairability, it is in addition impossible by the technical combinations of itself and above-mentioned patent document 1~4, it is known that can not be simultaneously Realize self-repairability.

Therefore, problem to be solved by this invention is to provide a kind of stack membrane, and the stack membrane is not only implemented as simultaneously Mouldability required by section bar material and the marresistance brought by self-repairability, and meet closely sealed durability, soil resistance.

Means for solving the problems

In order to solve above-mentioned problem, further investigation has been repeated in present inventors, as a result completes following Invention.That is, the present invention is as described below.

A kind of stack membranes of the ＞ of ＜ 1, it is the stack membrane for having superficial layer at least side of support base material, and its feature exists In meeting following condition 1 and condition 2.

Condition 1：Logarithmic decrement at 25 DEG C of superficial layer measured by rigid body pendulum test method(s), above-mentioned is more than 0.1.

Condition 2：The resin contained in above-mentioned superficial layer includes following (1)~(4).

(1) polycaprolactone segment

(2) amino-formate bond

(3) polysiloxanes segment and/or PolydimethylsiloxaneChain Chain section

(4) tricyclodecyl segment

Stack membrane described in the above-mentioned ＞ of ＜ 1 of the ＞ of ＜ 2, it is characterised in that above-mentioned stack membrane meets following condition 3.

Condition 3：Closely sealed index by stretching-boiling superficial layer that closely sealed test method(s) measures, above-mentioned is more than 3.

Stack membrane described in the ＞ of the ＜ 3 above-mentioned ＞ of ＜ 1 or the ＞ of ＜ 2, it is characterised in that above-mentioned stack membrane meets following condition 4。

Condition 4：Stored energy modulus at 100 DEG C of superficial layer measured by rigid body pendulum test method(s), above-mentioned is higher than 25 DEG C when Stored energy modulus.

Stack membrane any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 3 of the ＞ of ＜ 4, it is characterised in that above-mentioned stack membrane meet with Under 5~condition of condition 7.

Condition 5：Storage modulus at 25 DEG C of superficial layer measured by dynamic viscoelastic method, above-mentioned is more than 10MPa Below 1,000MPa.

Condition 6：When storage modulus at 100 DEG C of superficial layer measured by dynamic viscoelastic method, above-mentioned is higher than 25 DEG C Storage modulus.

Condition 7：Loss angle tangent at 25 DEG C of superficial layer measured by dynamic viscoelastic method, above-mentioned for 0.15 with On.

Stack membrane any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 4 of the ＞ of ＜ 5, it is characterised in that above-mentioned stack membrane meet with Under condition 8.

Condition 8：Ultimate elongation rate at 23 DEG C of superficial layer measured by tension test method, above-mentioned is more than 20%.

Stack membrane any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 5 of the ＞ of ＜ 6, it is characterised in that in above-mentioned stack membrane, shape Support base material into superficial layer meets following condition 9.

Condition 9：The swelling capacity index for supporting base material is more than 0.01.

Stack membrane any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 6 of the ＞ of ＜ 7, it is characterised in that above-mentioned stack membrane meet with Under condition 10.

Condition 10：The resin contained in above-mentioned superficial layer includes following (5).

(5) fluorochemical segment

Stack membrane any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 7 of the ＞ of ＜ 8, it is characterised in that above-mentioned stack membrane meet with Under condition 11.

Condition 11：The resin contained in above-mentioned superficial layer includes following (6).

(6) makrolon segment

The effect of invention

According to the present invention, can obtain meeting mouldability, self-repairability, closely sealed durability, the stack membrane of soil resistance.

Brief description of the drawings

Fig. 1 is one using the logarithmic decrement data obtained by rigid body pendulum test method(s).

Fig. 2 is one using the Storage Moduli data obtained by dynamic viscoelastic method.

Fig. 3 is one using the loss modulus data obtained by dynamic viscoelastic method.

Fig. 4 is one using the loss angle tangent data obtained by dynamic viscoelastic method.

Embodiment

Before embodiments of the present invention are illustrated, with the viewpoint of the present inventor, to problem of the prior art, that is, it is molded Property, self-repairability, closely sealed durability and realizing while soil resistance investigated.

First, patent document 1 and the self-repairability material of the prior art described in patent document 2 can not be realized close simultaneously Close durability the reason for be, in the prior art in order that soft film coating and reduce the density of the cross-linked structure in film, so as to Obtain self-repairability, mouldability.However, as side effect effect, the amount that the moisture in air permeates to film increases, long-term Film is destroyed under use condition or film is peeled off from base material etc., and closely sealed durability is insufficient.

In addition, for the technology of patent document 3~5, due to improving the crosslink density of material surface, prevent in air The infiltration of moisture or the infiltration of dyestuff, so the excellent closely sealed durability of display and/or the metastatic of resistance to dyestuff, but the opposing party Face, mouldability and/or self-repairability are not shown.In addition, even if by the material of patent document 3 and/or 4 and patent document 1 and/or 2 combination of materials, also due to self-repairability and mouldability and closely sealed durability and/or soil resistance are shifting (trade Off relation), thus above-mentioned characteristic can not be realized simultaneously.In addition, in the technology of patent document 4, the intensity difference of material, thus Marresistance required by moulding material is insufficient.

Therefore, mouldability of the present inventors required by moulding material and the anti-scratch brought by self-repairability On the basis of wound property is studied, as the mechanical characteristic of superficial layer, it is conceived to viscoelastic property and shows elastic property Loss modulus, the loss angle tangent obtained from loss modulus divided by storage modulus of the property of storage modulus and display viscosity. In addition, also it is conceived to the logarithmic decrement with loss angle tangent equivalent meanings.

When superficial layer bears the load from outside, its mechanical response depends on above-mentioned viscoelastic property.For damage Consume for the strong material of the low material of angle tangent, i.e. elastic property, due to most of load will be stored in the form of mechanical energy, Thus load it is big and when exceeding storable scope, cause material to be destroyed.In this case, damage is produced on superficial layer Deng marresistance is insufficient.On the other hand, for the high material of loss angle tangent, i.e. for the material that the property of viscosity is strong, with Dissipation energy is that the effect that form of thermal energy discharges load is big, and the mechanical energy of storage is relatively small.Therefore, even if load is big, It is likely to be less than storable scope, material is not easy to be destroyed.As a result, can suppress to produce damage etc. on superficial layer, it is resistance to It is scratch resistance excellent.

In addition, by making storage modulus in certain scope, so as to which the effect of above-mentioned loss angle tangent further carries Height, therefore, if make above-mentioned superficial layer storage modulus and loss angle tangent in a specific range, the shaping of above-mentioned superficial layer Property and self-repairability improve, be preferable.

Specifically, the logarithmic decrement for the superficial layer for preferably making to measure by rigid body pendulum test method(s) is in specific scope It is interior, and/or make the storage modulus of superficial layer that is measured by dynamic viscoelastic method and loss angle tangent in a specific range.

In addition, the self-repairability of the superficial layer for stack membrane, it is conceived to the temperature-independent of the viscoelastic sexual behaviour of superficial layer The reasons why property is to be based on following discoveries：The selfreparing material of storage modulus when storage modulus during for high temperature is higher than certain temperature For material, along with the rising of the storage modulus of superficial layer caused by heating, self-repairability improves.

Present inventors are analyzed above-mentioned phenomenon, are as a result found, adjoint when superficial layer produces scratch Its displacement and caused residual stress has dependency relation with storage modulus.That is, distinguished that the storage modulus of superficial layer rises When, the elastic force inside superficial layer turns into the power of the caused residual stress release along with scratch, as a result, repaiies scratch It is multiple.

Contemplate in the case of utilizing above-mentioned property under actual use situation, because the stack membrane of the present invention can be used suitably In the moulding material of smart mobile phone etc., therefore, release from surface of shell in the various electronic equipments such as smart mobile phone and internally produce Heat and when causing the surface temperature to rise, the temperature of self-repair material also correspondingly rises, and scratch caused by room temperature is repaired, Therefore, it can expect that self-repairability improves.

Specifically, Stored energy modulus at 100 DEG C of the superficial layer preferably measured by rigid body pendulum test method(s) is higher than Stored energy modulus at 25 DEG C.Additionally, it is preferred that measured by dynamic viscoelastic method, 100 DEG C of superficial layer when energy storage mould Amount is higher than storage modulus at 25 DEG C.

In addition, present inventors are conceived to and are immersed in superficial layer when analyzing closely sealed durability Moisture in air.It was found that especially under the conditions of long-term use, the moisture of immersion reaches superficial layer-support substrate interface, breaks Bad interface, superficial layer is thus caused to be peeled off from support base material.Think especially for for self-repair material, due to reducing surface The crosslink density of layer, thus it is immersed in the washiness of superficial layer.

The method for preventing superficial layer-support substrate interface from destroying is studied, but is improved in superficial layer The density of cross-linked structure, improved although result is closely sealed durability, as described above, mouldability, selfreparing can not be realized simultaneously Property.

Pair therefore, realize that mouldability and self-repairability and the method for closely sealed durability are studied simultaneously, as a result send out Existing, it is effective that hydrophobic chain segment is imported in the resin contained in superficial layer.

When the resin contained in superficial layer includes hydrophobic chain segment, the moisture immersed in the air of superficial layer is reduced.In addition, When being conceived to the moisture of immersion, due to since the layer surface of surface during reaching superficial layer-support substrate interface, meeting Hydrophobic segment is contacted repeatedly, and therefore, the amount of moisture for reaching interface is further reduced.Therefore, can suppress to lead because of the moisture of immersion The destruction of the superficial layer of cause-support substrate interface, as a result, closely sealed durability can be improved.

In addition, the effect above has been repeated checking, as a result find, be especially introduced into from the hydrophobic of alicyclic structure Property segment is effective.Because alicyclic structure has stereochemical structure, so than the segment from chain structure, motility phase To relatively low.Therefore, when shaping and/or when causing superficial layer to deform due to the load from outside, table can also be suppressed There is density inequality in the distribution of the hydrophobic chain segment in surface layer, therefore can prevent the reduction of closely sealed durability.Need to illustrate , the effect above will not make the cross-linked structure density of superficial layer change, thus be not easy to cause into due to alicyclic structure Type, self-repairability reduce.

Specifically, the resin contained in preferably above-mentioned superficial layer includes tricyclodecyl segment.

In addition, when present inventors are analyzed dyestuff metastatic, it is conceived to the transfer process of dyestuff.Thus It was found that the dyestuff metastatic shifted on dyestuff to superficial layer, is separately by process and the process of dyestuff set that dyestuff immerses Important.

First, the process immersed on dyestuff, in the immersion of dyestuff, water turns into medium, therefore, by preventing water to table Surface layer immerses, and can suppress the immersion of dyestuff.By suppressing the immersion of dyestuff, the chance that dyestuff set described later occurs can be reduced, As a result, the metastatic of resistance to dyestuff can be improved.As such method, the resin contained into above-mentioned superficial layer imports hydrophobic chain Section, the hydrophobic chain segment especially from alicyclic structure are effective.

Specifically, for the immersion of dyestuff, the resin contained in preferably above-mentioned superficial layer includes tricyclodecyl segment.

Next, the process on dyestuff set, if the resin and the compatibility of dyestuff that contain in superficial layer are high, dyestuff The probability of set improves.Therefore, the resin and the compatibility of dyestuff contained by reducing in superficial layer, can suppress consolidating for dyestuff , as a result, the metastatic of resistance to dyestuff can be improved.As such method, in the resin contained into above-mentioned superficial layer import with The segment that the compatibility of dyestuff is low is effective.

Specifically, the resin contained in preferably above-mentioned superficial layer includes tricyclodecyl segment, polycaprolactone segment, poly- carbon Acid esters segment.

In addition, load and/or long-term use of condition when present inventors are conceived to shaping it is inferior superficial layer- Support load caused by the interface of base material.It was found that in shaping, in the interface of superficial layer-support base material generation Mechanical loading, i.e. Stress and/or deformation, local closely sealed destruction occurs at superficial layer-support substrate interface sometimes, this is to reduce mouldability Reason.In addition, it is found that under the conditions of long-term use, the moisture in air immerses superficial layer, destroys the boundary of superficial layer-support base material Face, thus superficial layer is peeled off from support base material, this is the reason for reducing closely sealed durability.Therefore, to prevent above-mentioned superficial layer- Support that the method for the closely sealed destruction of substrate interface is studied, as a result find, selection is certain with the compatibility with solvent The support base material on surface more than degree is effective.

If supporting, the compatibility of substrate surface and solvent is high, when forming superficial layer on supporting base material, superficial layer into Sub-dip is extremely supported on base material thoroughly, can improve the closing force of superficial layer-support substrate interface.This is for suppressing superficial layer-support base The local closely sealed destruction at material interface and/or suppress superficial layer and peel off from base material to be effective, therefore, mouldability, close can be improved Close durability.Specifically, the swelling capacity index for preferably making support base material is specific scope.

Hereinafter, embodiments of the present invention are specifically illustrated.

In order to solve above-mentioned problem, that is, meet mouldability, self-repairability, closely sealed durability and soil resistance, of the invention is folded Tunic is the stack membrane for having superficial layer at least side of support base material, preferably meets following 1~condition of condition 3.

(1) polycaprolactone segment

(2) amino-formate bond

(3) polysiloxanes segment and/or PolydimethylsiloxaneChain Chain section

(4) tricyclodecyl segment

It should be noted that for rigid body pendulum test method(s), it is described below.

So-called resin herein, refer to the material for including high-molecular compound.

From the viewpoint of mouldability and self-repairability, for the stack membrane of the present invention, pass through rigid body pendulum test method(s) Logarithmic decrement at 25 DEG C of superficial layer measure, above-mentioned is preferably more than 0.1, and more preferably more than 0.2, particularly preferably More than 0.4.Response when logarithmic decrement represents to bear Mechanical loading, by making logarithmic decrement be specific value, it can carry High-mouldability and self-repairability.

When logarithmic decrement is big, the effect that the above-mentioned load from outside discharges is improved with form of thermal energy, therefore, into Type and self-repairability improve, and are preferable.Logarithmic decrement is bigger, and the effect above is bigger, but because self-repair material has Cross-linked network, thus the limit be present, it is believed that higher limit is 1.0 or so.On the other hand, when logarithmic decrement is less than 0.1, superficial layer Destroyed by the load from outside, mouldability and self-repairability reduce sometimes.

In order that measured by rigid body pendulum test method(s), 25 DEG C of above-mentioned superficial layer when logarithmic decrement be more than 0.1, Above-mentioned condition 2 can be met by the resin for making to contain in above-mentioned superficial layer to realize.

Above-mentioned (1) polycaprolactone segment refers to the segment that chemical formula 1 represents, (2) amino-formate bond refers to the table of chemical formula 2 The key shown, (3) polysiloxanes segment refer to the segment that chemical formula 3 represents, PolydimethylsiloxaneChain Chain section refers to that chemical formula 4 represents Segment, (4) tricyclodecyl segment refer to chemical formula 5 represent segment.Their detailed content is described below.

(n is 1~35 integer.)

(R₁、R₂For any of alkyl of OH or carbon number 1~8, in formula, have OH and each at least one of alkyl with On, n is 100~300 integer.)

(m is 10~300 integer.)

(n is 1~50 integer.)

When the resin contained in above-mentioned superficial layer has (1) polycaprolactone segment, the superficial layer that can improve to obtain is reviewed one's lessons by oneself Renaturation, it is preferable.

When the resin contained in above-mentioned superficial layer has (2) amino-formate bond, the superficial layer that can not only improve to obtain Obdurability, and self-repairability can be improved, it is preferable.

, can when the resin contained in above-mentioned superficial layer has (3) polysiloxanes segment and/or PolydimethylsiloxaneChain Chain section Heat resistance, against weather and/or the marresistance brought by the lubricity of superficial layer of obtained superficial layer are improved, is preferred 's.

When the resin contained in above-mentioned superficial layer includes (4) tricyclodecyl segment, the obtained shaping of superficial layer can be improved Property, the obdurability of closely sealed durability, the metastatic of resistance to dyestuff, film, are preferable.

In addition, from the viewpoint of closely sealed durability, preferably above-mentioned stack membrane meets following condition 3.

It should be noted that for stretching-boiling closely sealed test method(s), illustrate below.

From the viewpoint of closely sealed durability, by stretching-boiling the closely sealed of superficial layer that closely sealed test method(s) measures, above-mentioned Index is preferably more than 3, more preferably more than 4, particularly preferably 5.The adaptation of closely sealed exponential representation superficial layer and support layer, The size of closely sealed index represents the size of adaptation and closely sealed durability.

When closely sealed index is big, especially under the conditions of long-term use, it can also suppress superficial layer from supporting base material to peel off, Closely sealed durability improves, thus preferably.On the other hand, when closely sealed index is less than 3, especially under the conditions of long-term use, sometimes From supporting base material to peel off, closely sealed durability reduces superficial layer sometimes.

In order that the closely sealed index of the above-mentioned superficial layer measured by stretching-boiling closely sealed test method(s) is more than 3, can pass through The resin for making to contain in above-mentioned superficial layer meets above-mentioned condition 2 and realized.

And then from the viewpoint of self-repairability and mouldability, preferably above-mentioned stack membrane meets following condition 4.

It should be noted that for rigid body pendulum test method(s), illustrate below.

From the viewpoint of self-repairability and mouldability, superficial layer preferably measured by rigid body pendulum test method(s), above-mentioned Stored energy modulus at 100 DEG C is higher than Stored energy modulus at 25 DEG C.Material when Stored energy modulus represents to apply load Which kind of degree can be returned to, Stored energy modulus, which rises, represents that self-repairability improves.

During Stored energy modulus when Stored energy modulus at 100 DEG C of above-mentioned superficial layer is higher than 25 DEG C, by above-mentioned Effect, self-repairability improve.

In order that Stored energy modulus when Stored energy modulus at 100 DEG C of above-mentioned superficial layer is higher than 25 DEG C, can lead to The resin that crossing makes to contain in superficial layer meets condition 2 and realized.

And then from the viewpoint of self-repairability and mouldability, preferably above-mentioned stack membrane meets following 5~condition of condition 7。

It should be noted that for dynamic viscoelastic method, illustrate below.

From the viewpoint of self-repairability and mouldability, 25 DEG C of superficial layer measured by dynamic viscoelastic method, above-mentioned When storage modulus be preferably 1, below 000MPa of more than 10MPa, more preferably more than 10MPa below 800MPa, particularly preferably For more than 150MPa below 500MPa.Elastic response when storage modulus represents to bear Mechanical loading, by making energy storage mould Measure as specific value, mouldability and self-repairability can be improved.

Storage modulus as low as to a certain degree when, improve the effect of above-mentioned loss angle tangent, made with form of thermal energy from outer The effect of the load release in portion improves, and therefore, mouldability and self-repairability improve, and are preferable.Storage modulus is smaller, the effect Fruit is bigger, but it is too small when, cause the obdurability of superficial layer to reduce, it is therefore contemplated that lower limit is 10MPa or so.On the other hand, store up When energy modulus is more than 1,000MPa, superficial layer is destroyed by the load from outside, and mouldability and self-repairability reduce sometimes.

In order that storage modulus at 25 DEG C of the above-mentioned superficial layer measured by dynamic viscoelastic method is more than 10MPa 1, Below 000MPa, above-mentioned condition 2 can be met by the resin for making to contain in above-mentioned superficial layer to realize.

From the viewpoint of self-repairability, at 100 DEG C of superficial layer preferably measured by dynamic viscoelastic method, above-mentioned Storage modulus is higher than storage modulus at 25 DEG C.Material can return to which kind of degree, energy storage when storage modulus represents to apply load Modulus, which rises, represents that self-repairability improves.

During storage modulus when storage modulus at 100 DEG C of above-mentioned superficial layer is higher than 25 DEG C, by above-mentioned effect, from Prosthetic improves.In order that storage modulus when storage modulus at 100 DEG C of above-mentioned superficial layer is higher than 25 DEG C, can be by making on The resin contained in superficial layer is stated to meet above-mentioned condition 2 and realize.

From the viewpoint of mouldability and self-repairability, for the stack membrane of the present invention, pass through dynamic viscoelastic method Loss angle tangent at 25 DEG C of superficial layer measure, above-mentioned is preferably more than 0.15, and more preferably more than 0.20, particularly preferably For more than 0.30.Response when loss angle tangent represents to bear Mechanical loading, can by making loss angle tangent be specific value Improve mouldability and self-repairability.

When loss angle tangent is big, the effect that the above-mentioned load from outside discharges is improved with form of thermal energy, therefore, into Type and self-repairability improve, and are preferable.Loss angle tangent is bigger, and the effect is bigger, but is handed over because self-repair material has Networking network, thus the limit be present, it is believed that higher limit is 1.00 or so.On the other hand, when loss angle tangent is less than 0.15, superficial layer Destroyed by the load from outside, mouldability and self-repairability reduce sometimes.

In order that loss angle tangent at 25 DEG C of the above-mentioned superficial layer measured by dynamic viscoelastic method is more than 0.15, Above-mentioned condition 2 can be met by the resin for making to contain in above-mentioned superficial layer to realize.

In addition, from the viewpoint of mouldability, preferably above-mentioned stack membrane meets following condition 8.

It should be noted that for tension test method, illustrate below.

From the viewpoint of mouldability, ultimate elongation at 23 DEG C of superficial layer measured by tension test method, above-mentioned Rate is preferably more than 20%, more preferably more than 30%, more preferably more than 40%.When ultimate elongation rate represents to be molded Following, the size of ultimate elongation rate represent the height of mouldability.

When ultimate elongation rate at 25 DEG C is big, it may be such that above-mentioned stack membrane chases after the shape from the article being formed, therefore, into Type improves.Ultimate elongation rate at 23 DEG C is the bigger the better, but superficial layer is with supporting base material to exist in the flexibility in shaping Difference, it is taken as that higher limit is 500% or so.On the other hand, 25 DEG C when ultimate elongation rate be less than 20% when, shaping plus In man-hour, cracked in superficial layer, cause to be molded bad, thus mouldability reduces sometimes.

In order that ultimate elongation rate at 25 DEG C is more than 20%, can be met by the resin for making to contain in above-mentioned superficial layer Above-mentioned condition 2 and realize.

And then from the viewpoint of mouldability and closely sealed durability, preferably above-mentioned stack membrane meets following condition 9.

It should be noted that the assay method on swelling capacity index, is described below.

The swelling capacity index of above-mentioned support base material is preferably more than 0.01, and more preferably more than 0.05, more preferably More than 0.10.Swelling capacity exponential representation and the compatibility of solvent and coating composition, the size of swelling capacity index represent to support base The height of the adaptation of material and superficial layer, i.e. represent the height of mouldability and/or closely sealed durability.

Support base material swelling capacity index it is big when, superficial layer with support base material adaptation improve, thus mouldability and/or Closely sealed durability improves.Swelling capacity index is the bigger the better, but it is excessive when, when forming superficial layer, cause support base material be destroyed, It is thus regarded that higher limit is 10 or so.On the other hand, when swelling capacity index is less than 0.01, during deformation in shaping, because making for a long time When being deteriorated year in year out caused by, with supporting the interface of base material to be destroyed, mouldability and/or closely sealed durability drop superficial layer sometimes It is low.

In order that the swelling capacity index for supporting base material is more than 0.01, can be by selecting the branch with specific surface physical property Hold base material and realize.

And then from the viewpoint of soil resistance, preferably above-mentioned stack membrane meets following condition 10.

Condition 10：The resin contained in superficial layer includes following (5).

(5) fluorochemical segment

So-called resin herein, refers to the material for including high-molecular compound, and its scope is included from polymer to oligomer Scope.

Fluorochemical segment described in above-mentioned (5), which refers to include, to be selected from containing fluoroalkyl, fluorine-containing epoxide alkyl, fluorine-containing alkene The segment of at least one of base, fluorine-containing alkane diyl and fluorine-containing epoxide alkane diyl, further preferred above-mentioned fluorochemical Segment is fluorochemical polyether segment.Above-mentioned so-called fluorochemical polyether segment, it is by containing fluoroalkyl, epoxide fluoroalkyl, epoxide fluothane hydrocarbon two The segment of the formation such as base, for the structure representated by chemical formula (6), chemical formula (7).

CF_n1H_(3-n1)-(CF_n2H_(2-n2))_kO-(CF_n3H_(2-n3))_mO- chemical formulas 6

-(CF_n4H_(2-n4))_pO-(CF_n5H_(2-n5))_sO- chemical formulas 7

(herein, n1 is 1~3 integer, and n2~n5 is 1 or 2 integer, and k, m, p, s are more than 0 integer, and p+s For more than 1.It is preferred that n1 is the integer that more than 2, n2~n5 is 1 or 2, more preferably n1 is that 3, n2 and n4 is that 2, n3 and n5 is 1 or 2 Integer.)

The details of above-mentioned fluorochemical polyether segment illustrates below, by including the resin of composition superficial layer Above-mentioned fluorochemical polyether segment, it may be such that the molecule for existing to high-density in most surface and showing low surface energy.

There is preferable scope in the chain length of above-mentioned fluorochemical polyether segment, preferably carbon number is less than more than 4 12, more preferably For less than more than 4 10, particularly preferably less than more than 68.When carbon number is less than 3, surface energy does not reduce fully, thus Sometimes grease proofness reduces, and when carbon number is more than 13, dissolubility in a solvent reduces, thus the quality of superficial layer drops sometimes It is low.

When the resin contained in above-mentioned superficial layer includes (5) fluorochemical segment, the superficial layer that can improve to obtain it is close Durability, the metastatic of resistance to dyestuff are closed, thus preferably.

And then from the viewpoint of self-repairability and mouldability, preferably above-mentioned stack membrane meets following condition 11.

Condition 11：The resin contained in superficial layer includes following (6).

(6) makrolon segment

Above-mentioned (6) makrolon segment refers to the segment that chemical formula 8 represents.Their details is described below.

(n is 2~16 integer.R₃Refer to the alkylidene or cycloalkylidene of carbon number 1~8.)

When the resin contained in above-mentioned superficial layer has (6) makrolon segment, the superficial layer that can improve to obtain is reviewed one's lessons by oneself Renaturation and mouldability, it is preferable.

Hereinafter, embodiments of the present invention are described in detail.

[stack membrane and superficial layer]

The stack membrane of the present invention has the superficial layer for showing specific characteristic, as long as plane (film, sheet material, plate) is i.e. Can.Herein, the superficial layer of the so-called specific characteristic of display, refers to the superficial layer for meeting above-mentioned condition 1 and condition 2.

Above-mentioned superficial layer is except mouldability, self-repairability, closely sealed durability, soil resistance with the problem as the present invention Outside, can also have glossiness, anti-finger printing, design, antireflection, antistatic, electric conductivity, heat ray reflection, near infrared ray Absorption, easily electromagnetic wave shielding, other functions such as bonding.

The thickness of above-mentioned superficial layer is not particularly limited, preferably less than more than 5 μm 200 μm, more preferably more than 10 μm Less than 100 μm, its thickness can be selected according to other above-mentioned functions.

[support base material]

The resin for forming support base material used in the stack membrane of the present invention can be thermoplastic resin, thermosetting resin Any one, can be equal poly resin or copolymerization or blend of more than two kinds.It is further preferred that due to thermoplastic resin Good forming ability, thus the resin for forming support base material is preferably thermoplastic resin.

As the example of thermoplastic resin, the polyolefin such as polyethylene, polypropylene, polystyrene, polymethylpentene can be used The polyamides such as resin, alicyclic polyolelfin resin, nylon 6, nylon66 fiber, aromatic polyamide resin, polyester resin, poly- carbonic acid Ester resin, polyarylate resin, polyacetal resin, polyphenylene sulfide, TFE, trifluoro-ethylene resin, trifluoro chloroethene The fluorine resins such as olefine resin, tetrafluoraoethylene-hexafluoropropylene copolymer, vinylidene fluoride resin, acrylic resin, metering system Acid resin, polyacetal resin, polyglycolic acid resin, polylactic resin etc..Thermoplastic resin is preferably to have sufficient draftability With the resin of following.From intensity, heat resistance, the transparency from the viewpoint of, thermoplastic resin especially be more preferably polyester resin, Polycarbonate resin, acrylic resin or methacrylic resin.

Polyester resin in the present invention is the high molecular general name using ester bond as the main bonding chain of main chain, can by acid into Point and its ester and diol component polycondensation and obtain.As concrete example, polyethylene terephthalate can be enumerated, be poly- to benzene two Formic acid propylene glycol ester, poly- 2,6- (ethylene naphthalate)s, polybutylene terephthalate (PBT) etc..Alternatively, it is also possible to being at it In copolymerization as copolymer obtained from sour composition, the other dicarboxylic acids and its ester of diol component, diol component.They In, consider from the transparency, dimensional stability, heat resistance etc., particularly preferred polyethylene terephthalate, poly- 2,6- naphthalenes Naphthalate.

In addition, various additives can be added in base material is supported, for example, antioxidant, antistatic agent, Nucleating Agent, inorganic Particle, organic filler, subtract thick dose, heat stabilizer, lubricant, infrared absorbent, ultra-violet absorber, for adjusting refractive index Dopant etc..It can be any of individual layer composition, lamination composition to support base material.

Also various surface treatments can be implemented to the surface for supporting base material before above-mentioned superficial layer is formed.At surface The example of reason, chemicals processing, mechanical treatment, Corona discharge Treatment, flame treatment, ultraviolet treatment with irradiation, height can be enumerated Frequency processing, glow discharge process, reactive plasma treatment, laser treatment, nitration mixture processing and ozone Oxidation Treatment.In these, It is preferred that glow discharge process, ultraviolet treatment with irradiation, Corona discharge Treatment and flame treatment, further preferred glow discharge process And UV treatment.

In addition, for the support base material used in the stack membrane of the present invention, as described above, it is preferred to be referred to using swelling capacity The support base material (hereinafter referred to as supporting base material A) that number is more than 0.01.During using supporting base material A, as described above, superficial layer and branch The adaptation for holding base material improves, be as a result, mouldability therefore, closely sealed durability improve, thus preferably.

As the support base material A used in the present invention, can be suitably exemplified by " U スモシャイ Application " (registration mark) A4300, A4100 (Co., Ltd. is spun by Japan), " パ Application ライト " (registration mark) PC-2151 (Teijin Chemicals, Ltd.) etc. Product.

[coating composition]

The manufacture method of the stack membrane of the present invention is not particularly limited, and stack membrane of the invention can be by above-mentioned support Process, the process being dried as needed and/or the process solidified of at least side applied coating composition of base material And obtain.The coating composition is preferably comprised comprising above-mentioned (1) polycaprolactone segment, (2) amino-formate bond, (3) poly- silicon Oxygen alkane segment and/or PolydimethylsiloxaneChain Chain section, the resin of (4) tricyclodecyl segment can be formed in coating process The material (hereinafter referred to as precursor) of resin is stated, by the way that the coating composition is used for into manufacture method described later, can be made Obtaining the resin contained in superficial layer has above-mentioned segment and key.

In addition, aforementioned coating composition further preferably includes the resin or precursor of (5) fluorochemical segment.In addition, The resin or precursor for replacing including (5) fluorochemical segment containing the resin comprising (6) makrolon segment or precursor, Resin containing the resin comprising (5) fluorochemical segment or precursor and comprising (6) makrolon segment or precursor this two Person.

In addition, in coating composition, solvent described later and/or other compositions can be included.

[polycaprolactone segment]

In the stack membrane of the present invention, the resin contained in superficial layer preferably comprises (1) polycaprolactone segment.It is so-called poly- herein Caprolactone segment, refer to the segment that above-mentioned chemical formula 1 represents.The resin contained in superficial layer includes (1) polycaprolactone segment When, the self-repairability and mouldability of superficial layer can be improved, thus preferably.

Contain resin or precursor comprising polycaprolactone segment by using in the coating composition for forming superficial layer, so as to The resin contained in superficial layer can have polycaprolactone segment.

Resin comprising polycaprolactone segment preferably has hydroxyl (hydroxy group) more than at least one.Hydroxyl is excellent Bit selecting is in the end of the resin comprising polycaprolactone segment.

As the resin for including polycaprolactone segment, the polycaprolactone of the hydroxyl particularly preferably with 2~3 functions.As The polycaprolactone of hydroxyl with 2~3 functions, specifically, polycaprolactone glycol, the chemical formula of the expression of chemical formula 9 can be enumerated Polycaprolactone modified (methyl) Hydroxyethyl Acrylate that 10 polycaprolactonetriols represented or chemical formula 11 represent.Herein, change The polycaprolactonetriol that the polycaprolactone glycol and chemical formula 10 that formula 9 represents represent is commonly known as polycaprolactone polyol.

The polycaprolactone glycol that chemical formula 9 represents is as follows.

Herein, m+n be 4~35 integer, R₄For C₂H₄、C₂H₄OC₂H₄、C(CH₃)₃Or (CH₂)₂Any of.

In addition, the polycaprolactonetriol that chemical formula 10 represents is as follows.

Herein, l+m+n be 3~30 integer, R₅For CH₂CHCH₂、CH₃C(CH₂)₃Or CH₃CH₂C(CH₂)₃In any Kind.

In addition, Polycaprolactone modified (methyl) Hydroxyethyl Acrylate is as follows.

Herein, n be 1~25 integer, R₆For H or CH₃Any of.It should be noted that R₆For H or CH₃In appoint When a kind of, they are referred to alternatively as active energy beam polymerism caprolactone.It should be noted that (methyl) acrylate represents first Base acrylate or acrylate.

So-called active energy beam polymerism herein, refer to utilize ultraviolet (UV lines), electron beam (EB lines) isoreactivity energy Amount ray and the property that is crosslinked, the compound for the functional group such as have (methyl) acrylate-based have the quality that.Make For the example of other active energy beam polymerism caprolactones, Polycaprolactone modified (methyl) dihydroxypropyl third can be enumerated Ester, Polycaprolactone modified (methyl) hydroxy butyl acrylate etc..

In addition, in the present invention, the resin comprising polycaprolactone segment can also contain in addition to containing polycaprolactone segment (or copolymerization has) other segments and/or monomer.For example, (or copolymerization has) can be contained containing tricyclodecyl segment described later, poly- two Methylsiloxane segment and/or polysiloxanes segment, makrolon segment, the compound of isocyanate compound.

In addition, in the present invention, in the resin containing polycaprolactone segment, polycaprolactone segment weight average molecular weight is preferred For 500~2,500, preferred weight average molecular weight is 1,000~1,500.The weight average molecular weight of polycaprolactone segment be 500~ When 2,500, the effect of self-repairability is further presented, in addition, marresistance further improves, thus preferably.

Either in the case where being copolymerized polycaprolactone segment, or in the case where separately adding polycaprolactone segment, From the aspect of self-repairability, design, mouldability, in whole solid state components of the coating composition for forming superficial layer In 100 mass %, the content of polycaprolactone segment is preferably 5~50 mass %.

[amino-formate bond]

In the stack membrane of the present invention, the resin contained in superficial layer preferably comprises (2) amino-formate bond.So-called ammonia herein Carbamate key, refer to the segment that above-mentioned chemical formula 2 represents.The resin contained in superficial layer includes (2) amino-formate bond When, the obdurability of superficial layer can be not only improved, and self-repairability can be improved, it is preferable.

Commercially available urethane-modified resin is included by using in the coating composition for forming superficial layer, so as to surface The resin contained in layer can have amino-formate bond.In addition, precursor also can be used as by being coated with to contain when forming superficial layer The compound containing NCO and the compound containing hydroxyl coating composition, so as to producing ammonia in painting process Carbamate key so that contain amino-formate bond in superficial layer.

In the present invention, preferably make NCO and hydroxyl reaction and generate amino-formate bond, thus, contain in superficial layer Some resins have amino-formate bond.Amino-formate bond is generated by making NCO with hydroxyl reaction, not only may be used The obdurability of superficial layer is improved, and self-repairability can be improved.

In addition, in the above-mentioned resin comprising polycaprolactone segment and/or resin and/or bag comprising tricyclodecyl segment The resin of the segment containing makrolon, the resin described later comprising polysiloxanes segment and/or include PolydimethylsiloxaneChain Chain section Resin etc. when there is hydroxyl, can also be made by heat etc. these resins and be used as precursor the compound containing NCO it Between generate amino-formate bond.Using the compound containing NCO and with hydroxyl comprising polysiloxanes segment Resin and/or during with resin formation superficial layer of the hydroxyl comprising PolydimethylsiloxaneChain Chain section, can improve the strong of superficial layer Toughness and elastic recovery (self-repairability) and the sliding on surface, thus preferably.

In the present invention, the compound containing NCO refers to, the resin containing NCO and/or containing different The monomer and/or oligomer of cyanic acid ester group.On the compound containing NCO, for example, di-2-ethylhexylphosphine oxide -4- rings can be enumerated Hexyl isocyanates, the trimethylolpropane adduct of toluene di-isocyanate(TDI), the trihydroxy methyl third of hexamethylene diisocyanate Alkane adduct, the trimethylolpropane adduct of IPDI, toluene di-isocyanate(TDI) isocyanuric acid ester body, Polyisocyanates such as the isocyanuric acid ester body of hexamethylene diisocyanate, the biuret body of hexa-methylene isocyanates and above-mentioned End-blocking thing of isocyanates etc..

It is aliphatic different compared with alicyclic, aromatic isocyanates in the above-mentioned compound containing NCO The self-repairability of cyanate is high, is preferable.Compound containing NCO is more preferably hexamethylene diisocyanate.Separately Outside, from the aspect of heat resistance, the compound containing NCO particularly preferably has the isocyanates of isocyanurate ring, The most preferably isocyanuric acid ester body of hexamethylene diisocyanate.Isocyanates with isocyanurate ring forms and has selfreparing concurrently The superficial layer of property and heat-resistant quality.

[polysiloxanes segment and/or PolydimethylsiloxaneChain Chain section]

In the stack membrane of the present invention, the resin contained in superficial layer preferably comprises (3) polysiloxanes segment and/or poly- diformazan Radical siloxane segment.Polysiloxanes segment refers to the segment that above-mentioned chemical formula 3 represents herein, and PolydimethylsiloxaneChain Chain section is Refer to the segment that above-mentioned chemical formula 4 represents.The resin contained in superficial layer includes (3) polysiloxanes segment and/or poly dimethyl During siloxanes segment, PolydimethylsiloxaneChain Chain section is coordinated in the most surface side in superficial layer, so as to due to the lubrication of superficial layer Property improve with the effect of release load, suppress to produce the scratch that can not repair in superficial layer, thus superficial layer can be improved Self-repairability, it is preferable.

Contain by using in the coating composition for forming superficial layer comprising polysiloxanes segment and/or polydimethylsiloxanes The resin or precursor of alkane segment, so as to which the resin contained in superficial layer can have polysiloxanes segment and/or polydimethylsiloxanes Alkane segment.

In addition, resin or precursor comprising polysiloxanes segment and/or PolydimethylsiloxaneChain Chain section preferably comprise reaction Property position.The reactive moieties refer to, using external energies such as heat or light with the position of other compositions reaction.As so Reactive moieties, from the viewpoint of reactivity, can enumerate alkoxysilyl and alkoxysilyl is hydrolyzed and Obtained silanol group, carboxyl, hydroxyl, epoxy radicals, vinyl, pi-allyl, acryloyl group, methylacryloyl etc..Wherein, from From the viewpoint of reactivity, operability, preferred vinyl, pi-allyl, alkoxysilyl, silicyl ether or silanol Base, epoxy radicals, acryloyl group, methylacryloyl.

Hereinafter, the detailed content of polysiloxanes segment and PolydimethylsiloxaneChain Chain section is illustrated in order.

[polysiloxanes segment]

In the present invention, polysiloxanes segment refers to the segment that above-mentioned chemical formula 3 represents.

In the present invention, can by the partial hydrolystate of the silane compound containing hydrolyzable silyl group, organic silicon sol or In the organic silicon sol addition with composition obtained from the hydrolysable silanes compound of free radical polyalcohol be used as with The compound of polysiloxanes segment uses.

On the compound with polysiloxanes segment, tetraalkoxysilane, methyl trialkoxysilane, diformazan can be enumerated Base dialkoxy silicane, γ-glycidoxypropyl group trialkoxy silane, γ-glycidoxypropyl group alkyl dialkoxy silicon Alkane, γ-methacryloxypropyl trialkoxy silane, γ-methacryloxypropyl alkyl-dialkoxysilanes etc. The complete or partial hydrolysate of silane compound with hydrolyzable silyl group and/or obtained from being distributed in organic solvent Organic silicon sol, the material obtained from the hydrolysising silane compound of addition hydrolyzable silyl group on the surface of organic silicon sol Deng.

In addition, in the present invention, the resin comprising polysiloxanes segment can also contain in addition to polysiloxanes segment (copolymerization has) other segments etc..For example, can contain (copolymerization has) has polycaprolactone segment, tricyclodecyl segment, makrolon The monomer component of segment, PolydimethylsiloxaneChain Chain section.

In the present invention, as the resin for including polysiloxanes segment, preferably copolymerization, which has, has and NCO reaction Monomer of hydroxyl etc..Copolymerization has the monomer with the hydroxyl with NCO reaction in the resin containing polysiloxanes segment Deng when, the obdurability of superficial layer improves.

Resin comprising polysiloxanes segment for copolymer with hydroxyl when, using comprising containing poly- silicon with hydroxyl , can be efficient when the resin (copolymer) of oxygen alkane segment and the coating composition of the compound containing NCO form superficial layer Ground forms the superficial layer with polysiloxanes segment and amino-formate bond.

[PolydimethylsiloxaneChain Chain section]

In the present invention, PolydimethylsiloxaneChain Chain section refers to the segment that above-mentioned chemical formula 4 represents.

In the present invention, as the compound with PolydimethylsiloxaneChain Chain section, dimethyl silicone polymer is preferably used in Copolymerization has the copolymer of vinyl monomer in segment.

Can be block copolymerization when compound with PolydimethylsiloxaneChain Chain section is the copolymer with vinyl monomer Any of thing, graft copolymer, random copolymer.Compound with PolydimethylsiloxaneChain Chain section be and vinyl list During the copolymer of body, dimethyl silicone polymer based copolymer is referred to as.

It is poly- in order to synthesize as the compound (dimethyl silicone polymer based copolymer) with PolydimethylsiloxaneChain Chain section Dimethyl siloxane based block copolymer, made using living polymerization, polymeric initiator method, macromolecular chain transfer method etc. When making, but considering productivity ratio, preferably using polymeric initiator method, macromolecular chain transfer method.

When using polymeric initiator method, there is the compound (dimethyl silicone polymer of PolydimethylsiloxaneChain Chain section Based copolymer) can be by using the polymeric azo system radical polymerization initiator of the expression of chemical formula 12 and other vinyl lists Body is copolymerized and obtained.

(m is 10~300 integer, and n is 1~50 integer.)

In addition, it can also carry out 2 following stage polymerizations：Make peroxide monomer and poly- two with unsaturated group at low temperature Methylsiloxane is copolymerized, and the prepolymer that peroxide group is imported with side chain is synthesized, by the prepolymer and vinyl monomer Copolymerization.

When using macromolecular chain transfer method, there is the compound (dimethyl silicone polymer of PolydimethylsiloxaneChain Chain section Based copolymer) it can obtain in the following manner：Such as the addition HS-CH in the silicone oil shown in chemical formula 13₂COOH、HS- CH₂CH₂COOH etc. and form the compound with SH bases, then using the chain tra nsfer of SH bases by the silicone compounds and second Alkenyl monomer is copolymerized.

(m is 10~300 integer.)

It is poly- in order to synthesize as the compound (dimethyl silicone polymer based copolymer) with PolydimethylsiloxaneChain Chain section Dimethyl silica methane series graft copolymer, can be for example, by making the compound shown in the chemical formula 14 i.e. first of dimethyl silicone polymer Base acrylate etc. is copolymerized and is readily derived with vinyl monomer.

(m is 10~300 integer.)

As the vinyl monomer used in the copolymer formed with the compound with PolydimethylsiloxaneChain Chain section, example Such as, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethyl hexyl acrylate, acrylic acid ring can be enumerated Own ester, acrylic acid tetrahydro furfuryl ester, methyl methacrylate, EMA, n-BMA, metering system Sour isobutyl ester, 2-Ethylhexyl Methacrylate, stearyl methacrylate, lauryl methacrylate, ethylene methacrylic Base ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, acetic acid second Alkene ester, vinyl chloride, vinylidene chloride, PVF, vinylidene fluoride, glycidyl acrylate, methyl propenoic acid glycidyl Ester, allyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, acryloyl Amine, Methacrylamide, N hydroxymethyl acrylamide, N, N- DMAAs, methacrylic N, N-dimethylamino Ethyl ester, methacrylic acid N, N- diethylamino ethyl ester, DAAM, acrylic acid 2- hydroxy methacrylates, methacrylic acid 2- hydroxy methacrylates, acrylic acid 2- hydroxy propyl esters, methacrylic acid 2- hydroxy propyl esters, allyl alcohol etc..

In addition, dimethyl silicone polymer based copolymer is preferably in the aromatic hydrocarbon series solvents such as toluene, dimethylbenzene, Methylethyl Alcohol series solvents such as the ester series solvents such as the ketone series solvents such as ketone, methyl iso-butyl ketone (MIBK), ethyl acetate, butyl acetate, ethanol, isopropanol etc. Single solvent or in the mixed solvent utilize solution polymerization process manufacture.In addition, as needed, preferably and with benzoyl peroxide, The polymerization initiators such as azobisisobutylonitrile base nitrile.Polymerisation is preferable over 50~150 DEG C and carried out 3~12 hours.

For the amount of the PolydimethylsiloxaneChain Chain section in the dimethyl silicone polymer based copolymer in the present invention, from From the aspect of the lubricity of superficial layer, stain resistance, in the mass % of whole compositions 100 of dimethyl silicone polymer based copolymer In, preferably 1~30 mass %.In addition, the weight average molecular weight of PolydimethylsiloxaneChain Chain section is preferably 1,000~30,000.

Either in the case where being copolymerized PolydimethylsiloxaneChain Chain section, or separately adding PolydimethylsiloxaneChain Chain In the case of section, from the aspect of self-repairability, stain resistance, against weather, heat resistance, in the coating for forming superficial layer In the mass % of whole compositions 100 of composition, dimethyl siloxane segment is preferably 1~20 mass %.Coating composition it is complete The mass % of portion's composition 100 does not include the solvent for being not involved in reaction.Include the monomer component for participating in reaction.

In the present invention, the resin for containing PolydimethylsiloxaneChain Chain section is being used as the coating group for forming superficial layer During compound, in addition to PolydimethylsiloxaneChain Chain section, it can also contain (copolymerization has) other segments etc..For example, (copolymerization can be contained Have) polycaprolactone segment, tricyclodecyl segment, makrolon segment and/or polysiloxanes segment.

For being formed in the coating composition of superficial layer, polycaprolactone segment and PolydimethylsiloxaneChain Chain section can be used Copolymer, polycaprolactone segment and polysiloxanes segment copolymer, polycaprolactone segment and PolydimethylsiloxaneChain Chain section and Copolymer of polysiloxanes segment etc..The superficial layer obtained using such coating composition can have polycaprolactone segment and gather Dimethyl siloxane segment and/or polysiloxanes segment.

For with polycaprolactone segment, polysiloxanes segment and PolydimethylsiloxaneChain Chain section be used for form superficial layer Coating composition in dimethyl silicone polymer based copolymer, polycaprolactone and polysiloxanes reaction for, can be poly- two When methylsiloxane based copolymer synthesizes, it is properly added polycaprolactone segment and polysiloxanes segment and is copolymerized.

[tricyclodecyl segment]

In the stack membrane of the present invention, the resin contained in superficial layer preferably comprises (4) tricyclodecyl segment.Herein so-called three Cyclodecyl segment, refer to the segment that above-mentioned chemical formula 5 represents.The resin contained in superficial layer includes (4) tricyclodecyl segment When, the soil resistance of superficial layer and closely sealed durability can be improved, is preferable.

Contain resin or precursor comprising tricyclodecyl segment by using in the coating composition for forming superficial layer, so as to The resin contained in superficial layer can have tricyclodecyl segment.

On the structure of tricyclodecyl segment, shown in chemical formula 5 described above, but it is preferable in above-mentioned coating composition Resin or precursor comprising tricyclodecyl segment are the compound that chemical formula 15 represents.

R₇Represent alkane diyl, the base of alkane three, epoxide alkane diyl, the base of epoxide alkane three and the ester knot derived from them It is any number of in structure, carbamate structures, ether structure, triazine structure, D₁Represent reactive moieties.

Above-mentioned reactive moieties refer to, using external energies such as heat or light with the position of other compositions reaction.It is used as this The reactive moieties of sample, from the viewpoint of reactivity, alkoxysilyl can be enumerated and alkoxysilyl is hydrolyzed Obtained from silanol group, carboxyl, hydroxyl, epoxy radicals, vinyl, pi-allyl, acryloyl group, methylacryloyl etc..Wherein, From the viewpoint of reactivity, operability, preferred vinyl, pi-allyl, alkoxysilyl, silicyl ether or silane Alcohol radical, epoxy radicals, acryloyl group (methylacryloyl).

More preferably R₇To be any number of in alkane diyl, carbamate structures or ester structure, D₁For acryloyl group (methyl Acryloyl group) or hydroxyl.

As the preferable resin or precursor for including tricyclodecyl segment in above-mentioned coating composition, as above-mentioned change D in formula 15₁For acryloyl group (methylacryloyl), i.e. (methyl) acrylate with tricyclodecyl segment is commercially available The example of material, IRR214-K (ダイセ Le オ Le ネ Network ス Co., Ltd.), SR833S (サートマー can be enumerated), FA- 513AS, FA-513M (Hitachi Chemical Co., Ltd.), A-DCP, DCP (KCC of Xin Zhong villages), ライトア Network リレート DCP-A (Kyoeisha Chemical Co., Ltd.) etc..

[fluorochemical segment]

In the stack membrane of the present invention, the resin contained in superficial layer preferably comprises (5) fluorochemical segment.In superficial layer When the resin contained includes (5) fluorochemical segment, the soil resistance and anti-finger printing of superficial layer can be improved, is preferable.

Contain resin or precursor comprising fluorochemical segment by using in the coating composition for forming superficial layer, from And the resin contained in superficial layer can have fluorochemical segment.

Fluorochemical segment, which refers to include, to be selected from containing fluoroalkyl, fluorine-containing epoxide alkyl, fluorine-containing alkenyl, fluorine-containing alkane two The segment of at least one of base and fluorine-containing epoxide alkane diyl.

Herein, it is containing fluoroalkyl, fluorine-containing epoxide alkyl, fluorine-containing alkenyl, fluorine-containing alkane diyl, fluorine-containing epoxide alkane diyl Refer to, part or all of alkyl, epoxide alkyl, alkenyl, alkane diyl, hydrogen possessed by epoxide alkane diyl are substituted by fluorine Obtained from substituent, be the substituent being mainly made up of fluorine atom and carbon atom, can have branch in the structure, also can shape Into multiple structures with these positions are formed by connecting dimer, trimer, oligomer, polymer architecture.

In addition, as above-mentioned fluorochemical segment, preferably fluorochemical polyether segment, the fluorochemical polyether segment be by containing The position of the formation such as fluoroalkyl, epoxide fluoroalkyl, epoxide fluothane hydrocarbon diyl, more preferably chemical formula (6), chemical formula (7) institute's generation The fluorochemical polyether segment of table, this has explained above.

In order that the resin contained in above-mentioned superficial layer includes fluorochemical segment, preferably make above-mentioned coating composition Contain following fluorochemical.Above-mentioned fluorochemical is the compound that chemical formula 16 represents.

R^f1-R₈-D¹... chemical formula 16

R herein^f1Represent fluorochemical segment, R₈Represent alkane diyl, the base of alkane three and by their derivative ester knots Structure, carbamate structures, ether structure, triazine structure, D¹Represent reactive moieties.

Above-mentioned reactive moieties refer to, using external energies such as heat or light with the position of other compositions reaction.It is used as this The reactive moieties of sample, from the viewpoint of reactivity, alkoxysilyl can be enumerated and alkoxysilyl is hydrolyzed Obtained from silanol group, carboxyl, hydroxyl, epoxy radicals, vinyl, pi-allyl, acryloyl group, methylacryloyl etc..Wherein, From the viewpoint of reactivity, operability, preferred vinyl, pi-allyl, alkoxysilyl, silicyl ether or silicon Silane alcohol base, epoxy radicals, acryloyl group (methylacryloyl).

As one of fluorochemical, compound shown below can be enumerated.3,3- trifluoro propyl trimethoxies can be enumerated Base silane, 3,3,3- trifluoro propyls triethoxysilane, the isopropoxy silane of 3,3,3- trifluoro propyls three, 3,3,3- trifluoro propyls Trichlorosilane, 3,3,3- trifluoro propyl triisocyanates silane, 2- perfluoro capryls trimethoxy silane, 2- perfluorooctylethyl groups three Ethoxysilane, the isopropoxy silane of 2- perfluorooctylethyl groups three, 2- perfluorooctylethyl groups trichlorosilane, 2- perfluoro capryl isocyanides Acid esters silane, acrylic acid 2,2,2- trifluoro ethyl esters, the fluorine propyl ester of acrylic acid 2,2,3,3,3- five, acrylic acid 2- perfluoro butyls ethyl ester, Acrylic acid 3- perfluoro butyl -2- hydroxy propyl esters, acrylic acid 2- perfluoro hexyls ethyl ester, acrylic acid 3- perfluoro hexyl -2- hydroxy propyl esters, Acrylic acid 2- perfluorooctylethyls, acrylic acid 3- perfluoro capryl -2- hydroxy propyl esters, acrylic acid 2- perfluoro decyls ethyl ester, acrylic acid 2- perfluor -3- methyl butyls ethyl ester, acrylic acid 3- perfluor -3- methoxybutyl -2- hydroxy propyl esters, acrylic acid 2- perfluor -5- first Base hexyl ethyl ester, acrylic acid 3- perfluor -5- methylhexyl -2- hydroxy propyl esters, acrylic acid 2- perfluor -7- Methyl Octyl -2- hydroxyls Propyl ester, acrylic acid tetrafluoro propyl ester, acrylic acid octafluoro pentyl ester, dodecafluorhe-ptylacrylate, the hexafluoro nonyl ester of acrylic acid ten, acrylic acid six Fluorine butyl ester, methacrylic acid 2,2,2- trifluoro ethyl esters, the fluorine propyl ester of methacrylic acid 2,2,3,3,3- five, methacrylic acid 2- perfluors Butyl ethyl ester, methacrylic acid 3- perfluoro butyl -2- hydroxy propyl esters, methacrylic acid 2- perfluorooctylethyls, methacrylic acid 3- perfluoro capryl -2- hydroxy propyl esters, methacrylic acid 2- perfluoro decyls ethyl ester, methacrylic acid 2- perfluor -3- methyl butyl second Ester, methacrylic acid 3- perfluor -3- methyl butyl -2- hydroxy propyl esters, methacrylic acid 2- perfluor -5- methylhexyls ethyl ester, first Base acrylic acid 3- perfluor -5- methylhexyl -2- hydroxy propyl esters, methacrylic acid 2- perfluor -7- Methyl Octyls ethyl ester, metering system Sour 3- perfluors -6- methyloctyls, tetrafluoropropyl propyl ester, methacrylic acid octafluoro pentyl ester, methacrylic acid octafluoro pentyl ester, Dodecafluoroheptyl methacrylate, the hexafluoro nonyl ester of methacrylic acid ten, methacrylic acid 1- trifluoromethyls trifluoro ethyl ester, methyl-prop Olefin(e) acid hexafluoro butyl ester, the fluorine nonenyl of triacryl-ten seven-pentaerythrite etc..

It should be noted that every 1 molecule fluorochemical can have multiple fluorochemical polyether positions.

As the example of the commercially available product of above-mentioned fluorochemical, RS-75 (Dainippon Ink Chemicals), オプツー Le can be enumerated DAC-HP (ダイキ Application Industrial Co., Ltd), C10GACRY, C8HGOL (Yushi Seihin Co., Ltd.) etc., these productions can be utilized Product.

[makrolon segment]

In the stack membrane of the present invention, the resin contained in superficial layer preferably comprises (6) makrolon segment.It is so-called poly- herein Carbonic ester segment, refer to the segment that above-mentioned chemical formula 8 represents.The resin contained in superficial layer includes (6) makrolon segment When, the obdurability and self-repairability of superficial layer can be improved, is preferable.

Contain resin or precursor comprising makrolon segment by using in the coating composition for forming superficial layer, so as to The resin contained in superficial layer can have makrolon segment.

Resin containing makrolon segment preferably has hydroxyl (hydroxy group) more than at least one.Hydroxyl is excellent Bit selecting is in the end of the resin containing makrolon segment.

PCDL as the resin containing makrolon segment, the particularly preferably hydroxyl with 2 functions.Specifically For, for the PCDL of chemical formula (17) expression.

(R₉To be any number of in the alkyl of carbon number 1~8, n is more than 1 integer.)

For PCDL, the repeat number of carbonate unit can be some, but the repetition of carbonate unit When number is excessive, the intensity decreases of the solidfied material of carbamate (methyl) acrylate, thus repeat number n is preferably less than 10. It should be noted that PCDL can be the different PCDL of more than two kinds of repeat number of carbonate unit Mixture.

The number-average molecular weight of PCDL is preferably 500~10,000, more preferably 1, and 000~5,000.Number is divided equally When son amount is less than 500, be difficult to obtain suitable flexibility sometimes, in addition, when number-average molecular weight is more than 10,000, heat resistance and/ Or solvent resistance reduces sometimes, thus the number-average molecular weight of above-mentioned degree is suitable.

In addition, as the PCDL used in the present invention, UH-CARB, UD-CARB, UC- can be suitably exemplified by CARB (Ube Industries, Ltd), PLACCEL CD-PL, PLACCEL CD-H (ダイセ Le chemical industry Co., Ltd.), Serial (the Asahi Chemical Industry's ケミカ Le ズ strain formula meetings of Network ラレ Port リオー Le C series (Network ラレ Co., Ltd.), デュラノー Le Society) etc. product.These PCDLs can be used alone, or can also combine two or more and use.

In addition, in the present invention, resin or precursor containing makrolon segment are in addition to containing makrolon segment, also (or copolymerization has) other segments and/or monomer can be contained.For example, contain above-mentioned polycaprolactone chain containing (or copolymerization has) Section, tricyclodecyl segment, PolydimethylsiloxaneChain Chain section and/or polysiloxanes segment, the compound of isocyanate compound.

In the present invention, preferably make the hydroxyl reaction of the above-mentioned compound containing NCO and PCDL, Carbamate (methyl) acrylate is made and is used for coating composition, thus, can make superficial layer that there is (6) polycarbonate chain Section and (2) amino-formate bond, as a result, can not only improve the obdurability of superficial layer, and self-repairability can be improved, be preferred 's.

[solvent]

Aforementioned coating composition can contain solvent.It is more excellent as the species number of solvent, preferably less than more than a kind 20 kinds Elect less than more than a kind 10 kinds, more preferably less than more than a kind 6 kinds, particularly preferably less than more than a kind 4 kinds as.

So-called herein " solvent ", refer to whole amount in drying process after coating substantially can be evaporated, Yu Chang Temperature, the material that normal pressure is liquid.

The species of so-called solvent herein, determined according to the molecular structure for forming solvent.Although that is, will be identical element group Into and functional group the species material (constitutional isomer) identical but different marriage relation with number although and on not being State constitutional isomer but configured in any case in 3-dimensional space can not be completely overlapped material (stereoisomer) be used as species Different solvent processing.For example, 2- propyl alcohol and normal propyl alcohol are handled as different solvents.

In addition, in the case of containing solvent, the solvent of following characteristic is preferably shown.

Condition 1 is by minimum molten of the relative evaporation speed (ASTM D3539-87 (2004)) on the basis of n-butyl acetate When agent is as solvent B, solvent B relative evaporation speed is less than 0.4.

Herein, the relative evaporation speed on the basis of n-butyl acetate of solvent refers to, according to ASTM D3539-87 (2004) evaporation rate measured.Specifically, it is as required for so that n-butyl acetate evaporates 90 mass % under dry air Time on the basis of evaporation rate the value that defines of relative value.

When the relative evaporation speed of above-mentioned solvent is more than 0.4, above-mentioned polysiloxanes segment and/or dimethyl silicone polymer Time required for the orientation of the most surface of segment and from fluorochemical segment to superficial layer shortens, thus, occur sometimes The self-repairability of the stack membrane arrived and the reduction of soil resistance.In addition, for above-mentioned solvent B relative evaporation speed lower limit and Speech, as long as the solvent that can be evaporated in drying process and be removed from film, in common painting process, is More than 0.005.

As solvent B, including isobutyl ketone (relative evaporation speed：0.2), isophorone (relative evaporation speed： 0.026), ethylene glycol monobutyl ether (relative evaporation speed：0.004th), DAA (relative evaporation speed：0.15), oleyl alcohol (relative evaporation speed：0.003), ethylene glycol monomethyl ether acetate (relative evaporation speed：0.2), Nonylphenoxy ethanol (phase To evaporation rate：0.25), propylene glycol monoethyl (relative evaporation speed：0.1), cyclohexanone (relative evaporation speed：0.32) Deng.

[other compositions in coating composition]

In addition, aforementioned coating composition preferably comprises polymerization initiator and/or curing agent and/or catalyst.Polymerization triggers Agent and catalyst are used for the solidification for promoting superficial layer.As polymerization initiator, preferably it can trigger or promote to wrap in coating composition The composition contained is polymerize, is condensed or the material of cross-linking reaction by anion, cation, Raolical polymerizable etc..

Many kinds of substance can be used in polymerization initiator, curing agent and catalyst.In addition, polymerization initiator, curing agent and catalysis Agent can be used individually, can also use a variety of polymerization initiators, curing agent and catalyst simultaneously.In addition, can be by acidic catalyst Agent, thermal polymerization are used in combination.As the example of acidic catalyst, aqueous hydrochloric acid solution, formic acid, acetic acid etc. can be enumerated.As heat The example of polymerization initiator, peroxide, azo-compound can be enumerated.In addition, the example as Photoepolymerizationinitiater initiater, can be enumerated Alkyl phenones based compound, containing chalcogenide compound, acylphosphine oxide based compound, amine compound etc..In addition, as promotion ammonia Carbamate key formation reaction crosslinking catalyst example, can enumerate dibutyl tin dilaurate, dibutyl diethyl oneself Sour tin etc..

In addition, aforementioned coating composition can also include melamine crosslinkers, the 3- first such as alkoxy melamine methylol Other crosslinking agents such as the amine system crosslinking agents such as the acid anhydrides such as base-hexahydrophthalic anhydride system crosslinking agent, diethyl amino propyl amine.

As Photoepolymerizationinitiater initiater, from the aspect of curability, preferred alkyl phenones based compound.As alkyl phenones system The concrete example of compound, can enumerate 1- hydroxy-cyclohexyl-phenyls -one, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, 2- methyl isophthalic acids-(4- methylsulfanylphenyls) -2- morpholinoes (morpholino) propane -1- ketone, 2- benzyl -2- dimethylaminos - 1- (4- phenyl) -1- butanone, 2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- (4- phenyl) -1- butanone, 2- benzyls Base -2- dimethylaminos -1- (4- morphlinophenyls) -1- butanone, 2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] - 1- [4- (4- morpholinyls) phenyl] -1- butanone, 1- cyclohexyl-phenyls ketone, 2- methyl isophthalic acids-phenyl-propane -1- ketone, 1- [4- (2- second Epoxide)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone, the double ethene of double (2- phenyl -2- Oxoacetic Acids) oxygen and will be above-mentioned Product etc. obtained from material molecular weight.

In addition, can be added into the coating composition for forming superficial layer levelling agent, ultra-violet absorber, lubricant, Antistatic agent etc., as long as in the range of the effect of the present invention is not hindered.Thus, superficial layer can contain levelling agent, ultraviolet Light absorbers, lubricant, antistatic agent etc..As the example of levelling agent, acrylic copolymer or siloxane-based, fluorine system can be enumerated Levelling agent.As the concrete example of ultra-violet absorber, benzophenone series, enumerate BTA system, oxanilide can be enumerated (Oxanilide) ultra-violet absorber of system, triazine system and amine system of being obstructed.As the example of antistatic agent, lithium salts, sodium can be enumerated The metal salts such as salt, sylvite, rubidium salt, cesium salt, magnesium salts, calcium salt.

[manufacture method of stack membrane]

For the superficial layer that the surface of the stack membrane in the present invention is formed, preferably using following manufacture methods：Will be upper The coating composition stated coating-drying-solidification on above-mentioned support base material, is consequently formed.Hereinafter, the process that will be coated Painting process is designated as, the process being dried is designated as drying process, the process that will be cured is designated as curing process.

In painting process, the method for applied coating composition is not particularly limited, preferably by dip coating, roller coat Method, Meyer rod coating method, gravure coating process and/or die coating method (No. 2681294 specifications of U.S. Patent No.) etc. are by Coating material composition Thing, which is coated on, to be supported base material and forms superficial layer.And then in above-mentioned coating method, more preferably gravure coating process or die coating method conduct Coating method.

After painting process, using drying process, it will have been coated with supporting the liquid film drying on base material.From fully from obtaining Stack membrane in remove solvent from the viewpoint of, with the heating of liquid film preferably in drying process.

On the drying means in drying process, heat transfer can be enumerated and dry (being close to high hot object), convection heat transfer' heat-transfer by convection (heat Wind), radiant heat transfer (infrared ray), other (microwave, sensing heatings) etc..Wherein, in manufacture method of the invention, even if due to It is also required to critically make rate of drying uniform in width, thus has preferably used the mode of convection heat transfer' heat-transfer by convection or radiant heat transfer.

Drying process in drying process be generally divided into (A) constant-rate method of drying during, (B) lapse rate dry during, for the former For, because diffusion of the solvent molecule on liquid film surface into air turns into dry rate-limiting step, thus rate of drying is herein Section is constant, and rate of drying is depending on, by evaporation solvent partial pressure, wind speed, temperature, film surface temperature is by hot blast in air The value determined by evaporation solvent partial pressure in temperature and air, is constant.For the latter, because solvent is in liquid film Diffuse into as rate-limiting step, thus rate of drying does not show steady state value in this section and lasting reduction, depending on solvent is in liquid film In diffusion coefficient, film surface temperature rise.So-called rate of drying herein, unit interval, the solvent evaporation amount of unit area are represented, Dimension is by gm^-2·s^-1Represent.

Preferable scope, preferably 0.1gm be present in above-mentioned rate of drying^-2·s^-1Above 10gm^-2·s^-1Hereinafter, more Preferably 0.1gm^-2·s^-1Above 5gm^-2·s^-1Below.By making the rate of drying in constant-rate method of drying section be above range, Can prevent because rate of drying it is uneven caused by it is uneven.As long as it can obtain 0.1gm^-2·s^-1Above 10gm^-2·s^-1With Under scope rate of drying, specific wind speed, temperature is not specially limited.

In the manufacture method of the stack membrane of the present invention, during lapse rate is dried, with the evaporation of residual solvent, polysiloxanes Segment and/or PolydimethylsiloxaneChain Chain section and fluorochemical segment are orientated.In this process, it is necessary to for being orientated Time, thus lapse rate dry during the film surface temperature rate of climb preferable scope, preferably less than 5 DEG C/sec be present, it is more excellent Elect less than 1 DEG C/sec as.

In addition, curing operation (curing process) can be carried out further, the curing operation (curing process) is by irradiating heat Or energy-ray and carry out.

In addition, when being solidified using active energy beam, from the aspect of versatility, preferably EB lines and/or UV Line.In addition, when being solidified using ultraviolet, from can anti-block hindered side face consider that preferably oxygen concentration is as low as possible, more excellent (nitrogen purging) is solidified under nitrogen atmosphere for choosing.When oxygen concentration is high, the solidification of most surface is hindered sometimes, the solidification on surface Become insufficient, self-repairability and closely sealed durability become insufficient.In addition, as the ultraviolet used when irradiating ultraviolet The species of lamp, for example, discharge lamp mode, flash lamp mode, laser mode, electrodeless lamp mode etc. can be enumerated.Using as putting When the high-pressure sodium lamp of electric light mode carries out ultraviolet curing, preferably turn into 100~3,000mW/cm in the illumination of ultraviolet², it is excellent Elect 200~2,000mW/cm as², more preferably 300~1,500mW/cm²Under conditions of carry out ultraviolet irradiation, preferably exist The accumulated light of ultraviolet turns into 100~3,000mJ/cm², preferably 200~2,000mJ/cm², more preferably 300~1, 500mJ/cm²Under conditions of carry out ultraviolet irradiation.Herein, the illumination of ultraviolet refers to that the irradiation suffered by unit area is strong Degree, according to lamp power output, luminescent spectrum efficiency, the diameter of emitting bulb, the design of speculum and shone thing and light source Distance difference and change.However, illumination does not change because of the difference of transporting velocity.In addition, so-called ultraviolet tires out Product light quantity, is the irradiation energy that unit area is subject to, and is the total amount for the photon for reaching its surface.Accumulated light under light source with leading to The irradiation speed crossed is inversely proportional, directly proportional to irradiation number and lamp number.

[purposes example]

The stack membrane of the present invention plays the advantages of mouldability, self-repairability, so closely sealed durability and soil resistance, can be suitable Ground is used for by being molded with type into the purposes of various formed bodys, especially requiring high marresistance, want to cause damage not The purposes being readily apparent from.

As an example, the plastic molded articles such as glasses sunglasses, cosmetic container, food containers, intelligent hand can be suitably used for The housing of machine, touch panel, keyboard, household appliances, building, instrument board, the auto navigation such as remote control of TV air conditioner Each surface of the decorative products in vehicles such as instrument touch panel, inside rear-view mirror and various printed articles etc..

Embodiment

Next, the present invention is illustrated based on embodiment, but the present invention is not limited to these embodiments.

[carbamate (methyl) acrylate A]

(carbamate (methyl) acrylate A1 synthesis)

By isocyanurate-modified type (the Mitsui Chemicals strain of 50 mass parts toluene, 50 mass parts hexamethylene diisocyanates Formula commercial firm system " タケネート " (registration mark) D-170N), the Polycaprolactone modified Hydroxyethyl Acrylate of 76 mass parts (ダイセ Le chemical industry Co. Ltd. system " プラ Network セ Le " (registration mark) FA5), 0.02 mass parts dibutyl tin laurate and 0.02 mass parts Hydroquinone monomethylether mixes, and is kept for 5 hours in 70 DEG C.Then, 79 mass parts toluene are added, obtain solid state component The mass % of concentration 50 carbamate (methyl) acrylate A1 toluene solution.

(carbamate (methyl) acrylate A2 synthesis)

By 50 mass parts toluene, 67 mass parts H6XDI ヌレート (Mitsui Chemicals, Inc D-127N, NCO contents 13.5 mass %), the Polycaprolactone modified Hydroxyethyl Acrylate of 76 mass parts (ダイセ Le chemical industry Co. Ltd. systems " プラ Network セ Le " (registration mark) FA5), 0.02 mass parts dibutyl tin laurate and 0.02 mass parts Hydroquinone monomethylether mix Close, kept for 5 hours in 70 DEG C.Then, 79 mass parts toluene are added, obtain the mass % of solid component concentration 50 carbamate (methyl) acrylate A2 toluene solution.

(carbamate (methyl) acrylate A3 synthesis)

By 50 mass parts toluene, biuret modified type (the Asahi Chemical Industry ケミカ Le ズ of 50 mass parts hexamethylene diisocyanates Co. Ltd. system " デュラネート " (registration mark) 24A-90CX, nonvolatile component：90 mass %, isocyanate content： 21.2 mass %), the Polycaprolactone modified Hydroxyethyl Acrylate of 92 mass parts (ダイセ Le chemical industry Co. Ltd. systems " プラ Network セ Le " (registration mark) FA2D), 0.02 mass parts dibutyl tin laurate and 0.02 mass parts Hydroquinone monomethylether mix Close, kept for 5 hours in 70 DEG C.Then, 82 mass parts toluene are added, obtain the mass % of solid component concentration 50 carbamate (methyl) acrylate A3 toluene solution.

[carbamate (methyl) acrylate B]

(carbamate (methyl) acrylate B1 synthesis)

By 100 mass parts toluene, (the consonance fermentation キリ Application strain formula meetings of 50 mass parts 2,6- diisocyanate bases methyl caproates Society LDI) and 119 mass parts PCDLs (ダイセ Le chemical industry Co. Ltd. system " プラ Network セ Le " (registrar Mark) CD-210HL) mixing, 40 DEG C are warming up to, is kept for 8 hours.Then, 28 mass parts acrylic acid 2- hydroxy methacrylate (common prosperities are added KCC of society ライトエステ Le HOA), 5 mass parts dipentaerythritol acrylates (East Asia synthesize strain formula meeting Society M-400), 0.02 mass parts Hydroquinone monomethylether, in 70 DEG C keep 30 minutes, then added for the 0.02 mass parts dibutyl moon Cinnamic acid tin, kept for 6 hours in 80 DEG C.Then, 97 mass parts toluene are finally added, obtain the mass % of solid component concentration 50 ammonia Carbamate (methyl) acrylate B1 toluene solution.

(carbamate (methyl) acrylate B2 synthesis)

By 100 mass parts toluene, (the consonance fermentation キリ Application strain formula meetings of 50 mass parts 2,6- diisocyanate bases methyl caproates Society LDI) and (ダイセ Le chemical industry Co. Ltd. system " プラ Network セ the Le " (registration of 150 mass parts PCDLs Trade mark) CD-220) mixing, 40 DEG C are warming up to, is kept for 8 hours.Then, 28 mass parts acrylic acid 2- hydroxy methacrylate (common prosperities are added KCC of society ライトエステ Le HOA), 5 mass parts dipentaerythritol acrylates (East Asia synthesize strain formula meeting Society M-400), 0.02 mass parts Hydroquinone monomethylether, in 70 DEG C keep 30 minutes, then added for the 0.02 mass parts dibutyl moon Cinnamic acid tin, kept for 6 hours in 80 DEG C.Then, 97 mass parts toluene are finally added, obtain the mass % of solid component concentration 50 ammonia Carbamate (methyl) acrylate B2 toluene solution.

[carbamate (methyl) acrylate C]

(carbamate (methyl) acrylate C1 synthesis)

Load the isocyanurate-modified body (Mitsui Chemicals, Inc system " タ of 50 mass parts hexamethylene diisocyanates ケネート " (registration mark) D-170N, isocyanate group content：20.9 mass %), 53 mass parts polyethyleneglycol acrylic acid Ester (Japan Oil Co's system " Block レンマー " (registration mark) AE-150, hydroxyl value：264 (mgKOH/g)), 0.02 mass parts two Butyl tin laurate and 0.02 mass parts Hydroquinone monomethylether.Then, kept for 5 hours, reacted in 70 DEG C.Reaction terminates Afterwards, 102 mass parts methyl ethyl ketones (hereinafter referred to as MEK) are added into reaction solution, obtain the mass %'s of solid component concentration 50 Carbamate (methyl) acrylate C1.

[silicone compounds]

(silicone compounds 1)

As silicone compounds 1, silicone diacrylate compound (EBECRYL350 ダイセ Le サイ are used The mass % of テッ Network Co. Ltd. systems solid component concentration 100).

(silicone compounds 2)

As silicone compounds 2, the acrylate compounds of siloxanes six (EBECRYL1360 ダイセ Le サ is used The mass % of イテッ Network Co. Ltd. systems solid component concentration 100).

(synthesis of polysiloxanes (a))

Load 106 mass into the flask of the 500ml capacity with agitator, thermometer, condenser and nitrogen ingress pipe Part ethanol, 320 mass parts tetraethoxysilanes, 21 mass parts deionized waters and the mass % hydrochloric acid of 1 mass parts 1, in 85 DEG C of holdings 2 hours, then heat up while reclaim ethanol, kept for 3 hours in 180 DEG C.Then cooled down, obtain sticky poly- silica Alkane (a).

(dimethyl silicone polymer based block copolymer (a))

Using the device same with the synthesis of polysiloxanes (a), load 50 mass parts toluene and 50 mass parts methyl tert-butyls Base ketone, 20 mass parts dimethyl silicone polymer system high molecular polymerization initiators (and pure medicine Co. Ltd. system of light, VPS-0501), 30 Mass parts methyl methacrylate, 26 mass parts butyl methacrylates, 23 mass parts 2-hydroxyethyl methacrylates, 1 matter Part methacrylic acid and 0.5 mass parts 1- thioglycerols are measured, is reacted 8 hours in 80 DEG C, obtains dimethyl silicone polymer system block Copolymer (a).The ratio of block copolymer (a) in obtained solution is 50 mass % in the mass % of solution 100.

[dimethyl silicone polymer system's graft copolymer (b)]

Using the device used in the synthesis of polysiloxanes (a), load 50 mass parts toluene, 50 mass parts Sucrose Acetates Ester, it is warming up to 110 DEG C.In addition, by 20 mass parts methyl methacrylates, 20 mass parts butyl methacrylates, 32 mass parts Caprolactone methacrylate (ダイセ Le chemical industry (strain) makes " プラ Network セ Le " (registration mark) FM-5), 23 mass parts 2-hydroxyethyl methacrylate, 10 mass parts polysiloxanes (a), the 20 acrylic acid modified poly dimethyls of mass parts list terminal methyl group Siloxanes (East Asia synthetic chemical industry (strain) is made, X-22-174DX) and 1 mass parts methacrylic acid, 2 mass parts 1,1- azos Bis cyclohexane -1- formonitrile HCNs mix.Through 2 hours to above-mentioned toluene, butyl acetate mixed liquor in the mix monomer is added dropwise.So Afterwards, reacted 8 hours in 110 DEG C, obtain the mass % of solid component concentration 50 grafting of the dimethyl silicone polymer system with hydroxyl Copolymer (b).The ratio of graft copolymer (b) in obtained solution is 50 mass % in the mass % of solution 100.

[tricyclodecyl compound]

(tricyclodecyl compound 1)

As tricyclodecyl compound 1, acrylate compounds (the IRR214-K ダイ comprising tricyclodecyl segment are used セ Le オ Le ネ Network ス Co. Ltd. systems, the mass % of solid component concentration 100).

(tricyclodecyl compound 2)

As tricyclodecyl compound 2, acrylate compounds (the FA-513AS Hitachis comprising tricyclodecyl segment are used It is melted into Co. Ltd. system, the mass % of solid component concentration 100).

(tricyclodecyl compound 3)

As tricyclodecyl compound 3, acrylate compounds (the SR833S サート comprising tricyclodecyl segment are used マー Co. Ltd. systems, the mass % of solid component concentration 100).

[fluorochemical]

(fluorochemical 1)

As fluorochemical 1, acrylate compounds (" メガ Off ァッ Network " (note comprising fluorochemical polyether segment is used Volume trade mark) RS-75, Dainippon Ink Chemicals's system, the mass % of solid component concentration 40, solvent (toluene and methyl ethyl ketone) 60 matter Measure %).

(fluorochemical 2)

As fluorochemical 2, silicone compounds (KY-108, SHIN-ETSU HANTOTAI's chemistry work comprising fluorochemical polyether segment are used Industry Co. Ltd. system, the mass % of solid component concentration 20, solvent (methanol and isopropanol) 80 mass %).

[optical free radical polymerization initiator]

(optical free radical polymerization initiator 1)

As optical free radical polymerization initiator 1, " (the BASF ジャパ Application of イ Le ガキュア " (registration mark) 184 is used Co. Ltd. system, the mass % of solid component concentration 100).

[coating composition A modulation]

(coating composition A1)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A1.

(coating composition A2)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A2.

(coating composition A3)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A3.

(coating composition A4)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A4.

(coating composition A5)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A5.

(coating composition A6)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A6.

(coating composition A7)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A7.

(coating composition A8)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A8.

(coating composition A9)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A9.

(coating composition A10)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A10.

(coating composition A11)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A11.

(coating composition A12)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A12.

(coating composition A13)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A13.

(coating composition A14)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition A14.

[coating composition B modulation]

(coating composition B1)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 40 painting Feed composition B1.

(coating composition B2)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 40 painting Feed composition B2.

The mass parts of dimethyl silicone polymer system's graft copolymer (b) solution 100

(the mass % of solid component concentration 50)

The mass parts of hexamethylene diisocyanate 12

(" バーノッ Network " (registration mark) DN-950, Dainippon Ink Chemicals's system).

[coating composition C modulation]

(coating composition C1)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition C1.

Carbamate (methyl) acrylate A1 solution (the mass % of solid component concentration 50) 100 mass parts

The mass parts of optical free radical polymerization initiator 1 1.5.

(coating composition C2)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition C2.

The mass parts of silicone compounds 13

The mass parts of optical free radical polymerization initiator 1 1.5.

(coating composition C3)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition C3.

Carbamate (methyl) acrylate C1 solution (the mass % of solid component concentration 50) 100 mass parts

The mass parts of optical free radical polymerization initiator 1 1.5.

(coating composition C4)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition C4.

Carbamate (methyl) acrylate A1 solution (the mass % of solid component concentration 50)

50 mass parts

Carbamate (methyl) acrylate C1 solution (the mass % of solid component concentration 50)

50 mass parts

The mass parts of optical free radical polymerization initiator 1 1.5.

(coating composition C5)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition C5.

[coating composition D modulation]

(coating composition D1)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 40 painting Feed composition D1.

Carbamate (methyl) acrylate B1 solution (the mass % of solid component concentration 50)

100 mass parts

The mass parts of silicone compounds 11

The mass parts of optical free radical polymerization initiator 1 1.5.

(coating composition D2)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 40 painting Feed composition D2.

Carbamate (methyl) acrylate B2 solution (the mass % of solid component concentration 50)

100 mass parts

The mass parts of silicone compounds 11

The mass parts of optical free radical polymerization initiator 1 1.5.

(coating composition D3)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition D3.

(coating composition D4)

Following material is mixed, is diluted using methyl ethyl ketone, obtains the mass % of solid component concentration 30 painting Feed composition D4.

[support base material]

(supporting base material A1)

As base material A1 is supported, using " U スモシャイ Application " (registration mark) A4300, (strain is spun by 125 μm of thickness, Japan Formula commercial firm system).

(supporting base material A2)

As base material A2 is supported, " パ Application ライト " (registration mark) PC-2151 (125 μm of thickness, Supreme Being people's chemical conversion strain are used Formula commercial firm system).

(supporting base material B1)

As base material 1 is supported, " Le ミラー " (registration mark) U48 (125 μm of thickness, eastern レ Co. Ltd. systems) is used.

[evaluation for supporting base material]

On supporting base material, implement performance evaluation as shown below, the obtained results are shown in table 1.As long as no special Illustrate, for measure, for each sample, change position and carry out 3 measure, use its average value.

(the swelling capacity index for supporting base material)

The swelling capacity index for supporting base material is calculated by following method.First, measure supports the haze value h of base material₁.Connect Get off, be coated with methyl ethyl ketone on base material is supported using bar coater (#10), placed 1 minute in 40 DEG C of temperature, make methyl second Base ketone is dried.Then, the dried haze value h for supporting base material is determined₂(%).Using this 2 values, swelling capacity is calculated by following formula Index.

Swelling capacity index：H=| h₂-h₁|

It should be noted that for mist degree measure, based on JIS K 7136 (2000), the electric color industry strain of Japan is used Formula commercial firm haze meter, it is positioned in the way of light is passed through from the side for being coated with methyl ethyl ketone of support base material on device And it is measured.

The evaluation result of obtained support base material is summarized in table 1.

[table 1]

Table 1

[manufacture method of stack membrane]

(making 1 of stack membrane)

Using the continuous apparatus for coating based on slit coater (slot die coater), with dried superficial layer The mode that thickness turns into the thickness specified adjusts the flow discharged from slit, by aforementioned coating composition A (A1~A14), applies Feed composition C (C1~C5), coating composition D (D1~D4), which are applied to, to be supported on base material.From be applied to dry, solidification during to The condition that liquid film blows dry wind is as described below.

(drying process)

Air-supply humiture：Temperature：80 DEG C, relative humidity：Less than 1%

Wind speed：It is coated with surface side：5m/ seconds, the opposite side of coated face：The 5m/ seconds

Wind direction：It is coated with surface side：It is parallel with the face of base material, the opposite side of coated face：It is vertical with the face of base material

Holdup time：2 minutes

(curing process)

Irradiate power output：400W/cm²

Accumulated light：120mJ/cm²

Oxygen concentration：0.1 volume %.

(making 2 of stack membrane)

Using the continuous apparatus for coating based on slit coater, the thickness specified is turned into the thickness of dried superficial layer Mode adjust the flow discharged from slit, by aforementioned coating composition B (B1~B2) be applied to support base material on.From coating It is as described below to the condition for blowing dry wind during drying, solidification to liquid film.

(drying process)

Air-supply humiture：Temperature：80 DEG C, relative humidity：Less than 1%

Holdup time：1 minute

(curing process)

Air-supply humiture：Temperature：160 DEG C, relative humidity：Less than 1%

Wind speed：It is coated with surface side：10m/ seconds, the opposite side of coated face：The 10m/ seconds

Wind direction：It is coated with surface side：It is vertical with the face of base material, the opposite side of coated face：It is vertical with the face of base material

Holdup time：2 minutes

It should be noted that above-mentioned wind speed, humiture, which have used, utilizes hot wire anemometer (Japanese カノマッ Network ス strain formulas Commercial firm アネモマスター wind speed air volume meter MODEL6034) value that measures.

Using the method for the above be made embodiment 1~16, comparative example 1~11 stack membrane.With each embodiment, comparative example pair The thickness of the method for making for the above-mentioned stack membrane answered and respective each layer is recorded in table 2,3 described later.

[evaluation of stack membrane]

For the stack membrane of making, implement performance evaluation as shown below, the obtained results are shown in table 2,3.As long as not yet There is special instruction, for measure, in each embodiment comparative example, for 1 sample, change position and carry out 3 measure, Use its average value.

(logarithmic decrement, the Stored energy modulus (rigid body pendulum test method(s)) of superficial layer)

Free vibration attenuation method (being referred to as rigid body pendulum test method(s)) based on rigid body pendulum, utilize Co., Ltd.'s エーア Application De ディ company system rigid body pendulum-type physical property test machine RPT-3000, determine the logarithmic decrement and Stored energy modulus of superficial layer.It is right It it is in advance 15 DEG C by temperature adjustment, after setting sample and pendulum, while being warming up to 10 DEG C/min of speed for testing machine 150 DEG C of one side are measured.It is each to carry out 5 measure, evaluated with its average value.It should be noted that use following pendulum.

Use edge：Pole type cylinder edge (Co., Ltd. エーア Application De ディ company system RBP-040), knife-like edge (Co., Ltd. エーア Application De ディ company system RBE-160)

Pendulum mass/rotary inertia：15g/640gcm (Co., Ltd. エーア Application De ディ company system FRB-100)

It should be noted that Stored energy modulus when being 25 DEG C by measurement temperature is designated as G_r’₂₅, it is 100 by measurement temperature DEG C when Stored energy modulus be designated as G_r’₁₀₀.The size being respectively worth, by G_r’₂₅＜ G_r’₁₀₀The situation of establishment is designated as Y, will not be into Vertical situation is designated as N.

(the closely sealed index (stretching-boil closely sealed test method(s)) of superficial layer)

On the evaluation of the closely sealed index of superficial layer, according to mode as follows, by stretch processing, boil processing, 3 stages of closely sealed experiment are carried out.It should be noted that above-mentioned a series of flow is referred to as stretching-boiling closely sealed test method(s).

(stretch processing)

By stack membrane be cut into 20mm it is wide × 200mm length, with grips in a manner of being stretched along long side direction, utilize Instron types cupping machine (Instron company system ultraprecises Material Testing Machine MODEL5848), with the drawing of 100mm/ minutes Speed is stretched to be stretched.Measure atmosphere now is 23 DEG C.Progress stretch processing is 20% up to deflection, gathers test film.

It should be noted that making distance between incipient extension chuck be 50mm, distance between tensioning chuck is designated as a (mm), become Shape amount x (%) is calculated using following formula.

Deflection：X=((a-50)/50) × 100.

(boiling processing)

Next, for the test film for carrying out stretch processing, test film is impregnated into the boiling water formed by boiling pure water 6 hours in (100 DEG C).Then, take out test film and be dried.

(closely sealed experiment)

And then the superficial layer of the test film after processing is boiled is carved into 100 1mm²Ten stroke lattice (crosscut).Remove Operated outside following parts, the step of according to 7 of JIS K5600-5-6 (1999).

Experimental condition and experiment number：Experimental condition is 23 DEG C, relative humidity 65%.In addition, experiment number is 1.

The maintenance of breadboard：Curing condition is 23 DEG C of temperature, relative humidity 65%, and curing time is 1 hour.

Draw lattice number：It is 11 to draw lattice number.

Draw the interval of lattice：Draw lattice at intervals of 1mm.

Stack membrane based on manual step being carved into and removing：Do not carry out trying using the brush of brush.In addition, JIS In K5600-5-6 (1999) 7.2.6 items only using the 2nd section regulation (" as shown in figure 3, by adhesive tape centrally along with a prescription Shape is drawn the parallel direction of lattice and is placed on grid, with the minimum length more than 20mm in position of the part away from contact grid, uses finger Smooth adhesive tape "), do not apply miscellaneous stipulations.It should be noted that as adhesive tape, using adhesive tape, (ニチバ Application (strain) is made " セロテープ " (registration mark) CT405AP).

In addition, the fitting of adhesive tape is carried out in the following manner：Utilize hand push roller ((strain) オーディオテ Network ニカ systems HP515), with back and forth pressing 3 times of 19.6N/m load, the roller translational speed of 5cm/ seconds.Next, edge and surface layer surface side To into 90 degree of direction, adhesive tape is torn for the speed of 10cm/ seconds with second speed, the residual of the grid by being arranged at superficial layer Number carries out 5 Phase Evaluations.

Closely sealed index 5：The residual number of superficial layer is 100.

Closely sealed index 4：The residual number of superficial layer is more than 90 and less than 100.

Closely sealed index 3：The residual number of superficial layer is more than 80 and less than 90.

Closely sealed index 2：The residual number of superficial layer is more than 50 and less than 80.

Closely sealed index 1：The residual number of superficial layer is less than 50.

(metastatic of resistance to dyestuff)

On the superficial layer of the stack membrane for the size for being cut into 9cm × 6cm, the fitting 6cm × 6cm twill soaked with water Cloth (contains dyestuff), is clamped with 6cm × 6cm glass plate.It is coated with polyethylene film so that moisture does not evaporate, on a glass 3kg counterweight is placed, is encased in 70 DEG C of baking oven and places.Taken out after 24 hours, stack membrane is placed in and pollution described later It is on the blank sheet of paper of equal extent with the white portion of gray level (gray scale), utilizes pollution gray level (JIS L0805 (2005)), with 1~5 grade of (1 grade of grade：Pollute for pollution gray level No. 1 or so or more serious (dirt residual is serious), 2 Level：Pollute for pollution gray level No. 2 or so (dirt residual is more), 3 grades：Pollute for No. 3 or so (dirts of pollution gray level Slightly remain), 4 grades：It is pollution with gray level No. 4 or so (dirt hardly remains) to pollute, 5 grades：Pollute for pollution gray scale Level No. 5 or so (dirt does not remain)) decision table facing surface pollution level.It should be noted that according to JIS L0805 (2005) record, between at different levels, between for example, 1 grade and 2 grades in the case of, labeled as " 1-2 ".

(the ultimate elongation rate of superficial layer)

By stack membrane be cut into 10mm it is wide × 200mm length, clamped in the longitudinal direction with chuck, utilize Instron types stretching Testing machine (Instron company system ultraprecises Material Testing Machine MODEL5848), is drawn with the draw speed of 100mm/ minutes Stretch.Measurement temperature is 23 DEG C.When being stretched, the sample in observation stretching, stop if visually (cracking) is ruptured to generation (being adjusted deflection during to stop as 5 integer).For the sample then determined, gather successively during than stopping Deflection reduces the sample of the deflection of 5% unit, it is final carry out to visually less than the deflection ruptured untill.

It should be noted that making distance between incipient extension chuck be 50mm, distance between tensioning chuck is designated as a (mm), profit Deflection x (%) is calculated with following formula.

Deflection：X=((a-50)/50) × 100.

The film sections of the broken portion of gathered sample are cut out, with the thickness of the superficial layer of observation in transmission electron As more than 30mm multiplying power observation superficial layer on microscopical observation picture, more than the 50% of the average thickness of superficial layer is sent out The situation of raw rupture is considered as in the presence of rupture (destruction that superficial layer be present), is being considered as, in the presence of in the sample of rupture, to have most The deformation value of the sample of low deflection is as ultimate elongation rate.Then, carry out same measure to amount to 3 times, these are ruptured Ultimate elongation rate of the average value of elongation as superficial layer.

(stripping of superficial layer)

As the pre-treatment of dynamic viscoelastic method, using following method, superficial layer is only peeled off from stack membrane, experiment is made Sample.

First, stack membrane is dipped in ethanol, placed 10 minutes under conditions of 25 DEG C.Then, by the surface of stack membrane Layer gathers sample from supporting base material to peel off.

(storage modulus, the loss angle tangent (dynamic viscoelastic method) of superficial layer)

Stretching vibration-non-resonance method (being referred to as dynamic viscoelastic method) based on JIS K7244 (1998), utilizes セイ The Measurement of Dynamic Viscoelasticity device " DMS6100 " of コーイ Application ス Star Le メ Application Star Co. Ltd. systems obtains the energy storage mould of superficial layer Amount and loss modulus.

Mode determination：Stretching

Distance between chuck：20mm

The width of test film：10mm

Frequency：1Hz

Strain amplitude：10μm

Power amplitude initial value：400mN

Measurement temperature：- 150 DEG C~250 DEG C

Programming rate：5 DEG C/min

It should be noted that storage modulus when being 25 DEG C by measurement temperature is designated as G '₂₅, by measurement temperature be 100 DEG C when Storage modulus be designated as G '₁₀₀.The size being respectively worth, by G '₂₅＜ G '₁₀₀The situation of establishment is designated as Y, and invalid situation is remembered For N.

In addition, loss modulus when being 25 DEG C by measurement temperature is designated as G "₂₅, obtained using following formula and represent that measurement temperature is 25 DEG C when loss angle tangent tan δ₂₅。

tanδ₂₅=G "₂₅/G’₂₅。

(self-repairability of superficial layer)

Place 12 hours in 20 DEG C of temperature, then under identical environment, brass brush (TRUSCO systems) is applied following Load, surface layer surface is scraped in the horizontal direction 5 times, then, the damage after placing 5 minutes is visually confirmed according to following benchmark Recovery state, it is qualified that more than 4 points are considered as.

10 points：Not residual impairment when load is 9.8N (1kg weight)

7 points：Residual impairment when load is 9.8N (1kg weight), but for 6.9N (700g weights) when not residual impairment

4 points：Residual impairment when load is 6.9N (700g weight), but for 4.9N (500g weights) when not residual impairment

1 point：Residual impairment when load is 4.9N (500g weight).

(mouldability of superficial layer)

For the mouldability of superficial layer, sentenced according to ultimate elongation rate of the following benchmark based on above-mentioned superficial layer It is fixed.

10 points：The ultimate elongation rate of superficial layer is more than 40%.

7 points：The ultimate elongation rate of superficial layer is more than 30% and less than 40%.

4 points：The ultimate elongation rate of superficial layer is more than 20% and less than 30%.

1 point：The ultimate elongation rate of superficial layer is less than 20%.

(the closely sealed durability of superficial layer)

For the closely sealed durability of superficial layer, carried out according to closely sealed index of the following benchmark based on above-mentioned superficial layer Judge.

10 points：The closely sealed index of superficial layer is 5.

9 points：The closely sealed index of superficial layer is 4.

7 points：The closely sealed index of superficial layer is 3.

4 points：The closely sealed index of superficial layer is 2.

1 point：The closely sealed index of superficial layer is 1.

(soil resistance of superficial layer)

For the soil resistance of superficial layer, carried out according to resistance to dyestuff metastatic of the following benchmark based on above-mentioned superficial layer Judge.

10 points：The metastatic of resistance to dyestuff of superficial layer is 5 grades.

7 points：The metastatic of resistance to dyestuff of superficial layer is more than 4 grades and less than 5 grade.

4 points：The metastatic of resistance to dyestuff of superficial layer is more than 3 grades and less than 4 grade.

1 point：The metastatic of resistance to dyestuff of superficial layer is less than 3 grades.

The evaluation result of the stack membrane finally given is summarized in table 3.[table 2]

Table 2

[table 3]

Description of reference numerals

1 temperature (DEG C)

2 logarithmic decrements

The temperature dependency figure of 3 logarithmic decrements

4 temperature (DEG C)

5 storage modulus (MPa)

The temperature dependency figure of 6 storage modulus

7 temperature (DEG C)

8 loss modulus (MPa)

The temperature dependency figure of 9 loss modulus

10 temperature (DEG C)

11 loss angle tangents

The temperature dependency figure of 12 loss angle tangents

The utilizability of industry

The stack membrane of the present invention plays the advantages of mouldability, self-repairability, such soil resistance and closely sealed durability, can close It is used for plastic molded article, the housing of smart mobile phone, touch panel, the keys such as glasses sunglasses, cosmetic container, food containers suitablely Household appliances, building, instrument board, automobile navigation instrument touch panel, the inside rear-view mirror such as remote control of disk, TV air conditioner Etc. each surface of decorative products in vehicles and various printed articles etc..

Claims

1. a kind of stack membrane, it is to support at least side of base material to have the stack membrane of superficial layer, it is characterised in that meet with Under condition 1 and condition 2,

Condition 1：Logarithmic decrement at 25 DEG C of superficial layer measured by rigid body pendulum test method(s), described is more than 0.1,

Condition 2：The resin contained in the superficial layer includes following (1)~(4),

(1) polycaprolactone segment,

(2) amino-formate bond,

(3) polysiloxanes segment and/or PolydimethylsiloxaneChain Chain section,

(4) tricyclodecyl segment.

2. stack membrane according to claim 1, it is characterised in that the stack membrane meets following condition 3,

Condition 3：Closely sealed index by stretching-boiling superficial layer that closely sealed test method(s) measures, described is more than 3.

3. stack membrane according to claim 1 or 2, it is characterised in that the stack membrane meets following condition 4,

Condition 4：When Stored energy modulus at 100 DEG C of superficial layer measured by rigid body pendulum test method(s), described is higher than 25 DEG C Stored energy modulus.

4. stack membrane according to claim 1 or 2, it is characterised in that the stack membrane meets following 5~condition of condition 7,

Condition 5：Storage modulus at 25 DEG C of superficial layer measured by dynamic viscoelastic method, described is more than 10MPa 1, Below 000MPa,

Condition 6：Storage modulus at 100 DEG C of superficial layer measured by dynamic viscoelastic method, described is higher than storage at 25 DEG C Energy modulus,

Condition 7：Loss angle tangent at 25 DEG C of superficial layer measured by dynamic viscoelastic method, described is more than 0.15.

5. stack membrane according to claim 1 or 2, it is characterised in that the stack membrane meets following condition 8,

Condition 8：Ultimate elongation rate at 23 DEG C of superficial layer measured by tension test method, described is more than 20%.

6. stack membrane according to claim 1 or 2, it is characterised in that in the stack membrane, form the support base of superficial layer Material meets following condition 9,

7. stack membrane according to claim 1 or 2, it is characterised in that the stack membrane meets following condition 10,

Condition 10：The resin contained in the superficial layer includes following (5),

(5) fluorochemical segment.

8. stack membrane according to claim 1 or 2, it is characterised in that the stack membrane meets following condition 11,

Condition 11：The resin contained in the superficial layer includes following (6),

(6) makrolon segment.