CN108290376A - Gas barrier film - Google Patents
Gas barrier film Download PDFInfo
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- CN108290376A CN108290376A CN201680067287.7A CN201680067287A CN108290376A CN 108290376 A CN108290376 A CN 108290376A CN 201680067287 A CN201680067287 A CN 201680067287A CN 108290376 A CN108290376 A CN 108290376A
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- Prior art keywords
- gas
- barrier layer
- keys
- basement membrane
- thickness direction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- Chemical Vapour Deposition (AREA)
Abstract
Even if it is excellent the issue of the present invention is to provide a kind of barrier properties for gases and under high temperature and humidity resistance to bend(ing) also high gas barrier film.The gas barrier film of the present invention is characterized in that, has gas-barrier layer on basement membrane, above-mentioned gas barrier layer contains Si atoms, O atom and C atoms, the wave analysis of the C1s of X-ray photoelectron spectroscopy measurement is utilized based on 0~100% position in the thickness direction until from the surface of the side opposite with above-mentioned basement membrane to the surface of above-mentioned basement membrane side of above-mentioned gas barrier layer, indicate C-C keys and C-C, C-SiO, C-O, the C-C keys distribution curve of total ratio of each keys of C=O and C=OO has at least one maximum in the position in 75~100% thickness direction.
Description
Technical field
The present invention relates to gas barrier films, specifically, even if it is excellent and under high temperature and humidity to be related to barrier properties for gases
Resistance to bend(ing) also high gas barrier film.
Background technology
In the past, the electronics such as organic EL (Electro Luminescence) element, liquid crystal display element, solar cell were set
Standby encapsulation uses light-duty and flexible high gas barrier film.Gas barrier film is generally to be formed on the basement membrane of resin
There is gas-barrier layer, the immersion of the gas of water, oxygen in air etc. can be prevented.
For the gas barrier film used in electronic equipment, it is desirable that excellent barrier properties for gases, even and if in order to
Also it is able to maintain that excellent barrier properties for gases when for flexible base board, also requires high resistance to bend(ing).
In order to improve the resistance to bend(ing) of gas barrier film, it is known to use hexamethyldisiloxane (HMDSO) as former
Material, the method (example that the distribution of the carbon atom in the thickness direction of gas-barrier layer is adjusted in a manner of meeting certain condition
Such as, referring to patent document 1.).
In order to realize long lifetime, it is desirable to even if also having high resistance to bend(ing) under high temperature and humidity.Due in high temperature height
Wet lower basement membrane can be swollen, so the membrane stress for generating basement membrane and gas-barrier layer is poor, the adaptation of the two is easy to decline.If close
Conjunction property declines, then when the displacement transfer of the basement membrane caused by being bent is to gas-barrier layer, easy tos produce and split in gas-barrier layer
Line equivalent damage can lead to the decline of barrier properties for gases.
Existing technical literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2012-96531 bulletins
Invention content
The present invention in view of the above problems and situation and carry out, solve project be to provide barrier properties for gases it is excellent and
Even if the resistance to bend(ing) also high gas barrier film under high temperature and humidity.
The present inventor in order to solve the above problems, during research the reason of to the above problem etc., has found to contain
There is the barrier properties for gases of the gas-barrier layer of Si atoms, O atom and C atoms excellent, and if basement membrane in gas-barrier layer
The ratio of the C-C keys of side is high, even if then also can get high resistance to bend(ing) under high temperature and humidity, so as to complete the present invention.
That is, project of the present invention is solved by mode below.
1. a kind of gas barrier film, which is characterized in that it is the gas barrier film for having gas-barrier layer on basement membrane,
Wherein,
Above-mentioned gas barrier layer contains Si atoms, O atom and C atoms,
Based on the surface on the surface from the side opposite with above-mentioned basement membrane of above-mentioned gas barrier layer to above-mentioned basement membrane side
Until thickness direction 0~100% position using X-ray photoelectron spectroscopy measure C1s wave analysis, indicate
C-C key distribution curve of the C-C keys relative to total ratio of each key of C-C, C-SiO, C-O, C=O and C=OO, 75
The position in~100% thickness direction has at least one maximum.
2. according to the gas barrier film described in above-mentioned 1, which is characterized in that in above-mentioned C-C keys distribution curve, 90~
The average value of the ratio of the C-C keys of the position in 100% thickness direction is in the range of 20~90%.
3. according to the gas barrier film described in above-mentioned 1 or 2, which is characterized in that above-mentioned C-C keys distribution curve is had
One or more maximum maximum value in the range of 20~90%.
Aforesaid way through the invention, even if be capable of providing barrier properties for gases it is excellent and under high temperature and humidity resistance to bend(ing)
Also high gas barrier film.
The expression mechanism or mechanism of action of the effect of the present invention are still not clear, but are presumed as follows.
Gas-barrier layer at least containing Si atoms, O atom and C atoms is due to forming Si-O-Si, Si-C-Si etc.
High density key network, there is fine and close structure, so obtaining high barrier properties for gases.
In addition, thus it is speculated that if in the thickness direction of gas-barrier layer, the ratio of the C-C keys of basement membrane side is high, then C-C keys can
The membrane stress for mitigating the basement membrane being swollen under high temperature and humidity, can inhibit the decline of the adaptation of basement membrane and gas-barrier layer, energy
The patience of load when enough raisings are to bending.In addition, thus it is speculated that the deformation of basement membrane when C-C keys can also mitigate bending can reduce
The deformation transmitted inside to gas-barrier layer, so even can also obtain high resistance to bend(ing) under high temperature and humidity.
Description of the drawings
Fig. 1 is the sectional view of the gas barrier film for indicating present embodiment briefly constituted.
Fig. 2 is the figure for the C-C key distribution curves for indicating the gas-barrier layer in embodiment.
Fig. 3 is the figure for the C-C key distribution curves for indicating the gas-barrier layer in embodiment.
Fig. 4 is the figure for the C-C key distribution curves for indicating the gas-barrier layer in comparative example.
Fig. 5 is the front view of the manufacturing device for indicating gas barrier film briefly constituted.
Specific implementation mode
The gas barrier film of the present invention is the gas barrier film for having on basement membrane gas-barrier layer, and feature exists
In, above-mentioned gas barrier layer contains Si atoms, O atom and C atoms, based on above-mentioned gas barrier layer from above-mentioned basement membrane phase
0~100% position in the thickness direction until the surface of anti-side to the surface of above-mentioned basement membrane side utilizes x-ray photoelectron
The wave analysis for the C1s that spectroscopy measures, expression C-C keys and each key of C-C, C-SiO, C-O, C=O and C=OO conjunction
The C-C key distribution curves of the ratio of meter have at least one maximum in the position in 75~100% thickness direction.This feature
Be each technical solution invention in common technical characteristic.
As embodiments of the present invention, from the viewpoint of obtaining higher resistance to bend(ing), it is distributed in above-mentioned C-C keys
In curve, the C-C keys of the position in 90~100% thickness direction ratio average value preferably 20~90% range
It is interior.
From the same viewpoint, the maximum value of one or more maximum possessed by above-mentioned C-C keys distribution curve
It is preferred that in the range of 20~90%.
Hereinafter, the present invention and its inscape and form for carrying out the present invention are described in detail.
It should be noted that in the application, "~" is using the meaning comprising the numerical value being documented in before and after it as lower limiting value and upper limit value
Think to use.
(gas barrier film)
Fig. 1 is the sectional view of the gas barrier film F for indicating embodiments of the present invention briefly constituted.
As shown in Figure 1, it (base film) 1 and the gas barrier that is formed on basement membrane 1 that gas barrier film F, which has basement membrane,
Layer 2.
(gas-barrier layer)
Gas-barrier layer 2 has barrier properties for gases.
In the present invention, it refers to utilizing MOCON moisture-vapor transmission measurement devices Aquatran to have barrier properties for gases
(MOCON corporations), the steam permeability measured at 38 DEG C of temperature, humidity 90%RH are less than 0.1 [g/ (m2·24h)]。
From the viewpoint of obtaining higher barrier properties for gases, preferably steam permeability is less than 0.01 [g/ (m2·24h)]。
Gas-barrier layer 2 at least contains Si atoms, O atom and C atoms.
Such gas-barrier layer 2 for example can be by making the organo-silicon compound with Si-C skeletons be reacted with oxygen, shape
It is obtained at silicon oxide carbide (SiOC) film.It is nitrogenized in addition it is also possible to supply the gases such as nitrogen, ammonia in film forming, formation also contains
There is the gas-barrier layer 2 of N atoms.
As workable organo-silicon compound, the few organo-silicon compound of the numbers of the Si-C keys in preferably 1 molecule,
Such as it is 2 tetramethyl-ring tetrasiloxanes below that can enumerate the number of the Si-C keys relative to 1 Si atom in 1 molecule
(TMCTS), the annular siloxanes such as octamethylcy-clotetrasiloxane (OMCTS), methyltrimethoxysilane (MTMS), tetramethoxy-silicane
The alkoxy silanes such as alkane (TMOS).These organo-silicon compound can be used alone or two or more is applied in combination.
Wherein, resistance to bend(ing) is improved from the ratio for improving the C-C keys in gas-barrier layer 2, reduces C=C keys and C=
The ratio of OO keys and from the viewpoint of improving the transparency, the number of the Si-C keys of preferably 1 Si atom is 1 or 0.
Following structures for showing TMCTS, OMCTS and MTMS.
Gas-barrier layer 2 can utilize the physical vapour deposition (PVD)s (PVD such as vapour deposition method, sputtering method：Physical Vapor
Deposition) method, plasma chemical vapor deposition (PECVD：Plasma Enhanced Chemical Vapor
Deposition) CVD method, the atomic layer deposition (ALD such as：Atomic Layer Deposition) method etc. formed, from easy tune
From the viewpoint of the atom composition of whole gas-barrier layer 2, preferred PECVD.Wherein, plasma is generated between two opposed rollers
Body and the PECVD that the opposed roll shape of gas-barrier layer is concurrently formed on the basement membrane carried by each roller can make thickness direction
Atom composition be continuously changed, thus preferably.
For gas-barrier layer 2, as shown in Figure 1, based on gas-barrier layer 2 from the side opposite with basement membrane 1
Surface Sa to the surface Sb of 1 side of basement membrane until thickness direction 0~100% position utilize x-ray photoelectron spectroscopy
(XPS：X-ray Photoelectron Spectroscopy) wave analysis of C1s that measures of method, indicate C-C keys and C-
C, the C-C key distribution curves of total ratio of each key of C-SiO, C-O, C=O and C=OO, in 75~100% thickness side
To position have at least one maximum.
Maximum is the ratio of the C-C keys in C-C key distribution curves becomes reduced inflection point from increase, and is and this
The ratio of inflection point is compared, the point of the ratio low 5% or more of the position in the thickness direction away from 2~20nm of the inflection point.
Minimum is the ratio of the C-C keys in C-C key distribution curves becomes increased inflection point from reduction.
These maximum and minimum are known as extreme value.
In this way, high for the ratio of the C-C keys of basement membrane 1 side of position in the range of 75~100% in thickness direction
For gas-barrier layer 2, the film of the basement membrane 1 being swollen under high temperature and humidity can be mitigated and answer by being largely distributed in the C-C keys of 1 side of basement membrane
Power and bending when basement membrane deformation and to gas-barrier layer 2 transmit load.Even if under high temperature and humidity, also can be improved basement membrane 1 with
The adaptation of gas-barrier layer 2, and to bending when load patience improve, the decline of barrier properties for gases can be inhibited, because
This obtains the high gas-barrier layer 2 of resistance to bend(ing).
From the viewpoint of obtaining higher resistance to bend(ing), in above-mentioned C-C keys distribution curve, 90~100% thickness
The average value of the ratio of the C-C keys of the position in direction is preferably in the range of 20~90%.
The ratio of C-C keys is especially high near interface of the such gas-barrier layer 2 with basement membrane 1, therefore can obtain more
High resistance to bend(ing).
The maximum value of one or more maximum is preferably 20~90% possessed by above-mentioned C-C keys distribution curve
In range.
Such gas-barrier layer 2 because mitigate basement membrane 1 membrane stress and deformation C-C keys it is abundant there are due to can obtain
Higher resistance to bend(ing).
Above-mentioned C-C keys distribution curve can be drawn by combining XPS methods and noble gas ion sputtering.XPS methods refer to
The atom for constituting specimen surface is analyzed by measuring the photoelectronic kinetic energy that is released from the specimen surface for having irradiated X-ray
The gimmick of composition and chemical bonding state, also referred to as ESCA (Electron Spectroscopy for Chemical
Analysis：Electron spectroscopy for chemical analysis).
Specifically, the specimen surface exposed by XPS method analysis and utilization noble gas ion sputter etching samples
Atom forms and chemical bonding state, can hold the variation of the atom composition and chemical bonding state in the thickness direction of sample.
One example of the determination condition of combination XPS methods and noble gas ion sputtering is shown.
(determination condition)
Etch ion kind：Argon (Ar+)
Etching speed (SiO2Heat oxide film scaled value)：0.05nm/sec
Etching interval (SiO2Scaled value)：2.5nm
X-ray photoelectron spectroscopy device：Thermo Fisher Scientific corporations, type designation " VG Theta
Probe”
X-ray irradiation：Monocrystalline power spectrum AlK α
The hot spot and its size of X-ray：800 × 400 μm of ellipse.
The ratio of C-C keys in gas-barrier layer 2 is by the getable energy of combination to measuring C atoms using XPS methods
The peaks C1s in spectrum carry out wave analysis and acquire.Specifically, being extracted from the peaks C1s from the peak of C-C keys, by C-C keys
The ratio (Q2/Q1 × 100) of peak area (Q2) and the peak area (Q1) at the peaks C1s can be regarded as the ratio of the C-C keys in gas-barrier layer 2
Rate.That is, the ratio of C-C keys is equal to the number of C-C keys relative to C-C, C-SiO, C-O, C=O and the C=for forming the peaks C1s
The ratio of total (being always bonded number) of each keys of OO.The required wave analysis of calculating (separation at peak, the meter of peak area of ratio
Calculate, peak position it is specific etc.) the commercially available analysis software of PeakFIT (SYSTAT corporations) etc. can be used.
When being etched to gas-barrier layer 2 by noble gas ion sputtering with above-mentioned etching interval, its thickness is found out every time
The ratio of the C-C keys of the position in direction obtains the curve of approximation of the ratio of the position in each thickness direction as expression 0~100%
Thickness direction position C-C keys ratio C-C key distribution curves.
The position in the thickness direction about gas-barrier layer 2, as shown in Figure 1, gas-barrier layer 2 is opposite with basement membrane 1
The position of surface Sa of side be set as 0%, the position of the surface Sb of 1 side of basement membrane is set as 100%, with 0~100% ratio
To indicate.
That is, the position in the thickness direction of gas-barrier layer 2 can be by the sputter depth apart from surface Sa relative to from gas
The ratio of distance (thickness of gas-barrier layer 2) until the surface Sa to surface Sb of barrier layer 2 indicates.
The thickness of gas-barrier layer 2 can utilize transmission electron microscope (TEM：Transmission Electron
Microscope the section of gas barrier film F) is observed to determine.Specifically, the section of observation gas barrier film F, is surveyed
The fixed distance until the surface Sa to surface Sb of gas-barrier layer 2.The interface of gas-barrier layer 2 and basement membrane 1 by the two pair
It is determined than degree difference.10 different points of position on film surface carry out the measurement of the distance, and the average value of each measured value is true
It is set to the thickness of gas-barrier layer 2.
Focused ion beam (FIB as the sample for TEM and TEM to be made：Focused Ion Beam) device, make
Use following apparatus.
(TEM)
Device：JEM2000FX (Japan Electronics Corporation's system)
Accelerating potential：200kV
(FIB devices)
Device：SMI2050 (SII corporations)
Processing ion：Ga(30kV)
The thickness of sample：100~200nm
The gas-barrier layer of the gas barrier film of the embodiment of the present invention is analyzed in Fig. 2 and Fig. 3 expressions to be obtained
C-C key distribution curves.
Fig. 2 indicates to utilize the gas-barrier layer that PECVD is formed as raw material using methyltrimethoxysilane (MTMS) and oxygen
C-C key distribution curves, Fig. 3 indicate with tetramethyl-ring tetrasiloxane (TMCTS) be raw material utilize PECVD formed gas
The C-C key distribution curves of barrier layer.
C-C keys distribution obtained from the gas-barrier layer of the gas barrier film of comparative example is analyzed in Fig. 4 expressions is bent
Line.C-C keys distribution curve shown in Fig. 4 is formed using PECVD as raw material using hexamethyldisiloxane (HMDSO) and oxygen
Gas-barrier layer C-C key distribution curves.
As shown in Figures 2 and 3, the C-C keys distribution curve in embodiment 75~100% thickness direction position
There are one maximum for tool.Each maximum is positioned at the position in about 83% and about 85% thickness direction, the ratio of the C-C keys of basement membrane side
Rate is high, so the resistance to bend(ing) of gas-barrier layer is high as described above.
On the other hand, as shown in figure 4, the C-C keys distribution curve of comparative example has in the position in the thickness direction less than 75%
There are one maximum, but do not have maximum in the position in 75~100% thickness direction.Therefore point of the C-C keys of basement membrane side
Cloth is few, so the deformation of basement membrane when membrane stress and the bending of the basement membrane under high temperature and humidity can not be mitigated, it is possible to produce crackle
The damage of equal gas-barrier layers.
In addition, the position in thickness direction be 90~100% in the range of C-C keys ratio average value it is shown in Fig. 2
C-C key distribution curves in about 35%, about 69% in C-C key distribution curves shown in Fig. 3,20~90%
In range.In addition, the C-C key distribution curves in Fig. 2 and Fig. 3 have multiple maximum, maximum value is respectively 20~90%
In range.Therefore the ratio of the C-C keys near the interface with basement membrane is high, and C-C keys are abundant, so obtaining high resist bending
Property.
On the other hand, in C-C keys distribution curve shown in Fig. 4, the range of the maximum value of maximum 20~90%
It is interior, but the average value of the ratio of the C-C keys of the position in 90~100% thickness direction is less than 20%, it is relatively low, it can not expect
High resistance to bend(ing) same as embodiment.
It should be noted that in Fig. 2~Fig. 4, further it is shown that indicate the position in 0~100% thickness direction of gas-barrier layer 2
The key distribution curve of the ratio of the C-Si keys, C-O keys, C=O keys and each key of C=OO keys set.In the same manner as C-C keys, from C1s
Peak is extracted from the peak of each key, finds out ratio of the ratio of the peak area of peak area and the peaks C1s from the peak of each key as each key
Rate.
Fig. 2 and Fig. 3 are compared with Fig. 4, then embodiment compared with comparative example, the ratio of C=O keys and C=OO keys compared with
It is low.The yellowing for belonging to the C=O keys and the few gas-barrier layer of C=OO keys of chromophoric group is few, to requiring the electronics of high transparency to set
The usability of standby encapsulation etc. is high, thus preferably.
The ratio of the C-C keys in the thickness direction of gas-barrier layer 2 can be by from being used as workable organo-silicon compound
One or more organo-silicon compound are used according to the selection of the ratio of the C atoms of intramolecular, H atom and O atom in the substance of illustration
To adjust.
Not only it can also can adjust the C-C in thickness direction by adjusting membrance casting condition by the selection of raw material
The ratio of key.
For example, using PECVD, is supplied together with organo-silicon compound as the oxygen that unstrpped gas supplies and form gas
When body barrier layer 2, by adjusting the supply amount of oxygen, the ratio of the C-C keys in gas-barrier layer 2 can be adjusted.
In addition it is possible to by supplying nitrogen, argon, the non-active gas such as helium and the confession for adjusting the non-active gas in film forming
To amount, thus plasma is made to stabilize, control oxidation reaction, the deposition etc. of oxygen and organo-silicon compound, in gas
The thickness direction of barrier layer 2 is adjusted to the ratio of target C-C keys.
In addition, by making the interelectrode apart from consecutive variations of generation plasma, it also can be by the C-C in thickness direction
The ratio of key is adjusted to target rate.
When being formed a film using the PECVD of opposed roll shape, if making the distance change of the electrode built in each roller, connect with roller
The density of the plasma of the Surface Creation of tactile basement membrane 1 continuously changes, therefore the composition of gas-barrier layer 2 also can be continuous
Ground changes.
The thickness of gas-barrier layer 2 is preferably in the range of 50~500nm, preferably in the range of 50~300nm.
If thickness be 50nm or more, sufficient barrier properties for gases can be obtained, if thickness be 500nm hereinafter, if
It can obtain thin gas barrier film F.
(basement membrane)
As basement membrane 1, it can use and be shaped to membranaceous resin, glass, metal etc..Wherein, preferred resin, preferably clear
The high resin of property.If the transparency of resin is high, the transparency of basement membrane 1 is high, then can obtain the high barrier properties for gases of the transparency
Film F, suitable for electronic equipments such as organic EL elements.
The resin that basement membrane 1 uses is can be used as, such as methacrylate, polyethylene terephthalate can be enumerated
(PET), polyethylene naphthalate (PEN), makrolon (PC), polyarylate, polystyrene (PS), aromatic polyamide,
Polyether-ether-ketone, polysulfones, polyether sulfone, polyimides (PI), polyetherimide etc..Wherein, consider from cost and obtained easiness,
It is preferred that polyethylene terephthalate (PET), polyethylene naphthalate (PEN), makrolon (PC) etc..
Basement membrane 1 can be stacked film made of above-mentioned laminated resin of more than two kinds.
The basement membrane 1 of resin can be manufactured using well known conventional manufacturing method all the time.For example, can be by squeezing
Go out machine by the resin melting as material, is quickly cooled down after being squeezed out by annular die or T-shaped mould head, to which manufacture is substantial
Amorphous and non-oriented non-stretched resin base material.Furthermore it is possible to by the way that the resin for being used as material is dissolved in solvent, in nothing
Be cast (casting) on the metal-resin supporting mass at end, be dried, remove, to obtain it is substantial amorphous and it is non-oriented not
Stretched film is as basement membrane 1.
Can also by above-mentioned unstretching film film carrying (MD：Machine Direction) direction or with carrying side
To orthogonal width (TD：Transverse Direction) direction stretched, using obtained stretched film as basement membrane 1.
The thickness of basement membrane 1 is preferably in the range of 5~500 μm, in the range of more preferably 25~250 μm.
Gas barrier film F can have other layers such as anchor layer, smooth layer, anti-exudation layer as needed.As anchor
Gu layer, smooth layer, anti-exudation layer can use the layer described in Japanese Unexamined Patent Publication 2013-52561 bulletins etc..
(anchor layer)
From the viewpoint of the adaptation for improving basement membrane 1 and gas-barrier layer 2, gas barrier film F can basement membrane 1 with
Has anchor layer between gas-barrier layer 2.
Anchor layer for example can contain polyester resin, isocyanate resin, polyurethane resin, acrylic acid tree by coating
Fat, ethylene vinyl alcohol, vinyl modified resin, epoxy resin, modified styrene resin, modified organic silicone resin, metatitanic acid
The coating fluid of Arrcostab etc. is simultaneously dried and is formed.
(smooth layer)
Gas barrier film F can also have lower layer of the smooth layer as gas-barrier layer 2.It can be flat using smooth layer
Gas-barrier layer 2 is formed on smooth surface, can be prevented the generation etc. of the pin hole caused by bumps, can be obtained barrier properties for gases
High gas-barrier layer 2.
Smooth layer can for example be formed by being coated with the coating fluid containing photoresist and carrying out curing process.As
Photoresist, such as the resin group containing the acrylate compounds with free-radical reactive unsaturated compound can be enumerated
Close object；Resin combination containing acrylate compounds and mercaptan compound with mercapto；Make epoxy acrylate, gather
Urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, glyceral methacrylate etc.
Resin combination etc. made of polyfunctional acrylate monomer dissolving.
(anti-exudation layer)
From inhibiting unreacted oligomer etc. to be migrated to surface from basement membrane 1 and the bleeding that pollutes the face touched
Viewpoint considers that gas barrier film F can have anti-exudation layer.The basement membrane in the side opposite with smooth layer is arranged in anti-exudation layer
1 surface.Then substantially can be composition identical with smooth layer as long as anti-exudation layer has the function of inhibiting exudation.
(translucency of gas barrier film)
If the transparency of gas barrier film F is high, the usability of the encapsulating material as electronic equipment is high thus excellent
Choosing.
Specifically, being based on JIS K 7105：1981 light transmittances measured are preferably 80% or more, more preferably
85% or more, further preferably 90% or more.
(manufacturing device of gas barrier film)
Fig. 5 indicates that the brief composition of the manufacturing device 100 of above-mentioned gas barrier film F can be manufactured.
The manufacturing device 100 of gas barrier film carries base as shown in figure 5, in vacuum chamber 10 by multiple rollers 11~18
Film 1, base feed gas while applied voltage between mutually opposed a pair of rolls 13 and 16.As a result, in manufacturing device 100,
The plasma reaction that unstrpped gas occurs forms gas-barrier layer, manufacture gas barrier film F on basement membrane 1.
As shown in figure 5, being equipped with exhaust outlet 41 in vacuum chamber 10, vacuum pump 42 is equipped in the terminal of exhaust outlet 41.
In addition, as shown in figure 5, roller 11 unreels basement membrane 1, roller 18 hinders the gas obtained by the formation of gas-barrier layer
It is batched every property film F.
Roller 12~17 is unreeled from by roller 11 to being batched by roller 18, carries basement membrane 1.
A pair of rolls 13 and 16 is configured in a manner of mutually opposed, the gas supply to base feed gas between each roller 13 and 16
Portion 21 is adjacently arranged with roller 13 and 16.
A pair of rolls 13 and 16 is connect with power supply 22 respectively, is built-in with magnetic field generation device 23.By by gas supply part 21
Base feed gas, with power supply 22 between each roller 13 and 16 applied voltage, between each roller 13 and 16 discharge space generate
Plasma carries out the plasma reaction of unstrpped gas and is respectively formed gas resistance on the basement membrane 1 carried by roller 13 and 16
Interlayer.At this point, the magnetic field due to foring runway shape by magnetic field generation device 23 on the periphery of each roller 13 and 16, so plasma
Body is generated along the magnetic line of force in the magnetic field.Electric field because of discharge space and magnetic field generate high by electrons in film formation space
The plasma of density, therefore film forming efficiency improves.
Gas supply part 21 shown in fig. 5 is arranged on the center line of roller 13 and roller 16, but can also be inclined from the center line
Either one into roller 13 and 16.It is different from the unstrpped gas supply quantitative change of 16 supplies to roller 13 thereby, it is possible to make, shape can be made
It is different from the composition change of the atom for the film being formed on roller 16 at the film on roller 13.Similarly, in order to make film atom form not
Together, the position of gas supply part 21 can also be deviated on centerline so as to become remote at a distance from each roller 13 and 16 or become close.
If the membrance casting conditions such as the supply amount of the unstrpped gas in film forming is made to change, it is laminated when changing membrance casting condition every time
The not film of homoatomic composition continuously changes to make the atom in thickness direction form.
Specifically, if basement membrane 1 by the places A of roller 13 and the places B of roller 16, the thickness in gas-barrier layer 2
The ratio of the number of the C atoms in direction becomes increasing from reducing, and the ratio of the number of O atom becomes reducing from increasing.
In contrast, if basement membrane 1 passes through the places C1 and C2 of roller 13 and the places C3 and C4 of roller 16, gas barrier
The ratio of the C atoms in the thickness direction in layer 2 becomes reducing from increasing, and the ratio of O atom becomes increasing from reducing.
There are such from reduction to the extreme value for increasing or changing from increase to reduction, indicates the C in gas-barrier layer 2
The presence of atom and O atom is not than being uniform, the part low due to locally lying in the few compactness of C atoms, so gas hinders
Interlayer 2 becomes structure flexible, and resistance to bend(ing) improves.
Each roller 13 and 16 preferably configures as follows：Rotary shaft is parallel in the same plane, and the base respectively carried
The face of the formation gas-barrier layer of film 1 is opposite face.By such composition, in the roller 13 using carry direction upstream in basement membrane
After forming gas-barrier layer on 1, it can utilize the roller 16 in carry direction downstream that gas-barrier layer is further laminated, it can be further
Improve film forming efficiency.
From the viewpoint of improving film forming efficiency, preferably each roller 13 is identical with 16 diameter.
As the diameter of each roller 13 and 16, the viewpoints such as the space out of the optimization of discharging condition, reduction vacuum chamber 10 are examined
Consider, in the range of diameter phi is preferably 100~1000mm, in the range of more preferably 100~700mm.
If diameter phi is 100mm or more, sufficiently large discharge space can be formed, can be prevented under productivity
Drop.In addition, the electric discharge of short time can obtain sufficient thickness, the heat for being applied to basement membrane 1 when electric discharge can be inhibited, inhibited
Residual stress.If diameter phi be 1000mm hereinafter, if be able to maintain that the uniformity of discharge space, design upper practicality in device.
Unstrpped gas of the gas supply part 21 to the discharge space supply gas barrier layer formed between a pair of rolls 13 and 16.
For example, when making organo-silicon compound aoxidize and forming the gas-barrier layer containing silicon oxide carbide, gas supply part 21 supplies organic
The gases such as the gas and oxygen of silicon compound, ozone are as unstrpped gas.When nitridation, the unstrpped gases such as supply nitrogen, ammonia.
Gas supply part 21 can use carrier gas in base feed gas as needed, in order to promote the life of plasma
At plasma generation gas can also be supplied.As carrier gas, for example, can enumerate the rare gas such as helium, argon, neon, xenon, krypton and
Nitrogen etc. can enumerate hydrogen etc. as plasma generation gas.
As power supply 22, the well known power supply of plasma generation can be used, is preferably able to make each roller 13 and 16
The AC power of alternating polarity reversion, can improve film forming efficiency.
It, can be in the range of 0.1~10.0kW as the electricity that power supply 22 supplies.It, can if it is 0.1kW or more
Inhibit the generation for being referred to as the foreign matter of particle.In addition, if it is 10.0kW hereinafter, can then inhibit generate heat, can press down
It makes by the generation of the fold of the basement membrane 1 caused by temperature rise.In addition, when being AC power, the frequency of exchange is preferably 50Hz
In the range of~500kHz.
Pressure in vacuum chamber 10, i.e. vacuum degree can be adjusted according to type of unstrpped gas etc. using vacuum pump 42,
In the range of preferably 0.5~100.0Pa.
In addition, the transporting velocity (linear velocity) of basement membrane 1 can be determined according to the type of unstrpped gas, vacuum degree etc., it is excellent
It is selected as in the range of 0.25~100.00m/min, in the range of more preferably 0.5~20.0m/min.If it is within the scope of this,
The generation that the fold of basement membrane 1 can then be inhibited, can form the gas-barrier layer of adequate thickness.
Embodiment
The present invention is specifically described hereinafter, enumerating embodiment, but the present invention is not restricted to these example.It should be noted that
The expression of " part " or " % " is used in embodiment, unless otherwise specified, then it represents that " mass parts " or " quality % ".
(gas barrier film 1)
Prepare " the KB Off ィ Le system that thickness is 125nmTM" (registered trademark) G1SBF (KIMOTO corporations) be used as basement membrane.
In " the KB Off ィ Le systemTM" G1SBF is upper forms gas barrier by raw material of hexamethyldisiloxane (HMDSO) and oxygen
Layer.
Gas-barrier layer uses the manufacturing device similarly constituted with composition as shown in Figure 5, according to following membrance casting conditions
It is formed.
(membrance casting condition)
Unstrpped gas 1：HMDSO
Unstrpped gas 2：Oxygen
The supply amount of unstrpped gas 1：50sccm(Standard Cubic Centimeter per Minute)
The supply amount of unstrpped gas 2：650sccm
Vacuum degree：2Pa
Supply power from plasma generation power supply：0.8kW
The frequency of plasma generation power supply：80kHz
The transporting velocity of film：2m/min
(gas barrier film 2~7)
In the manufacture of above-mentioned gas barrier film 1, the type and raw material of unstrpped gas 1 are changed as described in Table 1
In addition to this supply amount of gas 1 and 2 manufactures each gas barrier film 2~7 in the same manner as gas barrier film 1.
(C-C keys distribution curve)
For each gas barrier film 1~7 of manufacture, the C-C keys point in the thickness direction of gas-barrier layer are found out as follows
Cloth curve.
The TEM samples of each gas barrier film 1~7 are made using following FIB devices.The sample is fixed on following
TEM observes the section of each gas barrier film 1~7, measures the surface from the side opposite with basement membrane of gas-barrier layer to base
Distance until the surface of film side.The interface of gas-barrier layer and basement membrane is confirmed by the poor contrast of the two.On film surface
10 different points of position carry out the measurement, and the average value of each measured value is confirmed as to the thickness (nm) of gas-barrier layer.
(TEM)
Device：JEM2000FX (Japan Electronics Corporation's system)
Accelerating potential：200kV
(FIB devices)
Device：SMI2050 (SII corporations)
Processing ion：Ga(30kV)
The thickness of sample：100~200nm
In addition, in each gas barrier film 1~7, by noble gas ion sputtering come etching gas barrier layer from
The surface of the side opposite with basement membrane is to the surface of basement membrane side, the energy of the bond energy of the C atoms on the surface exposed using XPS methods
Spectrum.XPS methods and the determination condition of noble gas ion sputtering are as described below.
(determination condition)
Etch ion kind：Argon (Ar+)
Etching speed (SiO2Heat oxide film scaled value)：0.05nm/sec
Etching interval (SiO2Scaled value)：2.5nm
X-ray photoelectron spectroscopy device：Thermo Fisher Scientific corporations, type designation " VG Theta
Probe”
X-ray irradiation：Monocrystalline power spectrum AlK α
The hot spot and its size of X-ray：800 × 400 μm of ellipse.
The peak that C-C keys are extracted from from the peaks C1s in the power spectrum obtained using XPS methods point, finds out the peak area of C-C keys
(Q2) with ratio of the ratio of the peak area at the peaks C1s (Q1) (Q2/Q1 × 100) as the C-C keys in gas-barrier layer 2.
The position in the thickness direction of the surface etching from the side opposite with basement membrane relative to gas-barrier layer, will find out
C-C keys ratio mapping, depth profiling figure is made.It is in the depth profiling figure, the approximation of ratio obtained from mapping is bent
Line is found out as C-C key distribution curves.In depth profiling figure, by the thickness direction on the surface of the side opposite with basement membrane
Position is expressed as 0%, and the position in the thickness direction on the surface of basement membrane side is expressed as 100%, by the depth distance (nm) etched
With the ratio of the thickness (nm) of the gas-barrier layer determined using above-mentioned TEM come indicate gas-barrier layer from opposite with basement membrane
The position in the thickness direction that the surface of side is counted.
In the depth profiling figure of each gas barrier film 1~7, layer of the C-C keys distribution curve 65~100% is found out
The position (%) in the thickness direction for the maximum that the position in thick direction has.It should be noted that any one C-C key distribution curve exists
The maximum of the position in 65~100% thickness direction is one.
In addition, finding out the thickness side of the maximum value in one or more maximum that C-C key distribution curves have respectively
To position (%) and 90~100% thickness direction position C-C keys ratio average value (%).It shows the result in
Following table 1.
(evaluation)
(barrier properties for gases)
Using MOCON moisture-vapor transmission measurement devices Aquatran (MOCON corporations), gas barrier film 1 is measured
~7 steam permeability [g/ (m at 38 DEG C of temperature, humidity 90%RH2·24h)]。
According to the steam permeability of measurement, grade evaluation is carried out to barrier properties for gases according to following evaluation criteria.Water steams
The numerical value of gas permeability is smaller, and barrier properties for gases is higher, and 3 or more grade is barrier properties for gases that can be practical.
5：Steam permeability is less than 0.005
4：Steam permeability is 0.005 less than 0.010
3：Steam permeability is 0.010 less than 0.100
2：Steam permeability is 0.100 less than 0.500
1：Steam permeability is 0.500 or more
(resistance to bend(ing))
Using MOCON moisture-vapor transmission measurement devices Aquatran (MOCON corporations), gas barrier film 1 is measured
~7 steam permeability (g/m at 38 DEG C of temperature, humidity 90%RH2·24h)。
After measurement, the bend test of each gas barrier film 1~7 is carried out.In bend test, first by each barrier properties for gases
Film 1~7 temperature 60 C, humidity 90%RH high temperature and humidity under preserve 100 hours.Each gas that will be taken out under high temperature and humidity
Barrier film 1~7 is cut into the size of 3cm × 10cm, by it wound on metal bar in such a way that gas-barrier layer becomes outside
The circumferential surface of (diameter 6mm) repeats 100 operating windings.To the bend test in the same manner as the situation before above-mentioned bend test
The steam permeability of each gas barrier film 1~7 afterwards is measured.
According to the steam permeability measured before and after bend test, the variation of steam permeability is calculated by following formula
Rate.
The change rate (%) of steam permeability
=(steam permeability after bend test)/(steam permeability before bend test)
According to the change rate of the steam permeability of calculating, grade evaluation is carried out as follows to resistance to bend(ing).The number of change rate
It is worth smaller, resistance to bend(ing) is more excellent, and 3 or more grade is resistance to bend(ing) that can be practical.
5：The change rate of steam permeability is 1.0 less than 2.0
4：The change rate of steam permeability is 2.0 less than 4.5
3：The change rate of steam permeability is 4.5 less than 7.0
2：The change rate of steam permeability is 7.0 less than 10.0
1：The change rate of steam permeability is 10.0 or more
Following table 1 shows evaluation result.
It should be noted that in following table 1, HMDSO, TMCTS and MTMS are respectively hexamethyldisiloxane, tetramethyl cyclotetrasiloxane
The abbreviation of siloxanes and methyltrimethoxysilane.
As shown in Table 1 above, it is known that C-C keys distribution curve has at least one in the position in 75~100% thickness direction
Not only barrier properties for gases is excellent for the gas barrier film 2~7 of a maximum, even if postponing barrier properties for gases in high temperature and humidity decentralization
Decline it is also few, resistance to bend(ing) is also high.
Industrial availability
The purposes that the gas barrier film of the present invention can be used for being used for a long time under high temperature and humidity.
Symbol description
F gas barrier films
1 basement membrane
2 gas-barrier layers
The surface of the gas-barrier layer of side opposite with basement membrane Sa
The surface of the gas-barrier layer of Sb basement membranes side
The manufacturing device of 100 gas barrier films
11~18 rollers
22 power supplys
Claims (3)
1. a kind of gas barrier film, which is characterized in that have gas-barrier layer on basement membrane,
The gas-barrier layer contains Si atoms, O atom and C atoms,
Based in the gas-barrier layer until from the surface of the side opposite with the basement membrane to the surface of the basement membrane side
Thickness direction 0~100% position using X-ray photoelectron spectroscopy measure C1s wave analysis, indicate C-C
C-C key distribution curve of the key relative to total ratio of each key of C-C, C-SiO, C-O, C=O and C=OO, 75~
The position in 100% thickness direction has at least one maximum.
2. gas barrier film according to claim 1, which is characterized in that in the C-C keys distribution curve, 90~
The average value of the ratio of the C-C keys of the position in 100% thickness direction is in the range of 20~90%.
3. gas barrier film according to claim 1 or 2, which is characterized in that the C-C keys distribution curve is had
One or more maximum maximum value in the range of 20~90%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-225268 | 2015-11-18 | ||
| JP2015225268 | 2015-11-18 | ||
| PCT/JP2016/079232 WO2017086035A1 (en) | 2015-11-18 | 2016-10-03 | Gas-barrier film |
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| Publication Number | Publication Date |
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| CN108290376B CN108290376B (en) | 2020-04-07 |
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| CN (1) | CN108290376B (en) |
| WO (1) | WO2017086035A1 (en) |
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| JPWO2018092657A1 (en) * | 2016-11-18 | 2019-10-17 | コニカミノルタ株式会社 | Optical film, polarizing plate protective film, polarizing plate including these, and display device including these |
| JP7261547B2 (en) * | 2017-08-25 | 2023-04-20 | 住友化学株式会社 | laminated film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201230429A (en) * | 2010-10-08 | 2012-07-16 | Sumitomo Chemical Co | Laminated film |
| CN104220249A (en) * | 2012-03-27 | 2014-12-17 | 住友化学株式会社 | Laminated film, organic electroluminescence device, photoelectric converter, and liquid crystal display |
| CN104736336A (en) * | 2012-10-19 | 2015-06-24 | 柯尼卡美能达株式会社 | Method for producing gas barrier film, gas barrier film, and electronic device |
| TW201529333A (en) * | 2013-12-26 | 2015-08-01 | Sumitomo Chemical Co | Laminate thin film, organic electroluminescent device, photoelectric conversion device, and liquid crystal display |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4402414B2 (en) * | 2003-09-30 | 2010-01-20 | 大日本印刷株式会社 | Laminate and sachet for liquid filling packaging using the same |
| US7947330B2 (en) * | 2004-10-19 | 2011-05-24 | Toray Industries, Inc. | Production method of film, and film |
| JP4905851B2 (en) * | 2006-07-24 | 2012-03-28 | 凸版印刷株式会社 | Method for producing vapor deposition film |
| JP6287858B2 (en) * | 2012-12-14 | 2018-03-07 | コニカミノルタ株式会社 | Gas barrier film, method for producing the same, and electronic device using the same |
| JP5966937B2 (en) * | 2013-01-15 | 2016-08-10 | コニカミノルタ株式会社 | Gas barrier film and method for producing gas barrier film |
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- 2016-10-03 JP JP2017551761A patent/JP6720980B2/en active Active
- 2016-10-03 CN CN201680067287.7A patent/CN108290376B/en not_active Expired - Fee Related
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201230429A (en) * | 2010-10-08 | 2012-07-16 | Sumitomo Chemical Co | Laminated film |
| CN104220249A (en) * | 2012-03-27 | 2014-12-17 | 住友化学株式会社 | Laminated film, organic electroluminescence device, photoelectric converter, and liquid crystal display |
| CN104736336A (en) * | 2012-10-19 | 2015-06-24 | 柯尼卡美能达株式会社 | Method for producing gas barrier film, gas barrier film, and electronic device |
| TW201529333A (en) * | 2013-12-26 | 2015-08-01 | Sumitomo Chemical Co | Laminate thin film, organic electroluminescent device, photoelectric conversion device, and liquid crystal display |
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| Publication number | Publication date |
|---|---|
| WO2017086035A1 (en) | 2017-05-26 |
| CN108290376B (en) | 2020-04-07 |
| JPWO2017086035A1 (en) | 2018-08-30 |
| JP6720980B2 (en) | 2020-07-08 |
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