CN101163817A - Vapor deposition film by plasma CVD method - Google Patents
Vapor deposition film by plasma CVD method Download PDFInfo
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- CN101163817A CN101163817A CNA2006800134442A CN200680013444A CN101163817A CN 101163817 A CN101163817 A CN 101163817A CN A2006800134442 A CNA2006800134442 A CN A2006800134442A CN 200680013444 A CN200680013444 A CN 200680013444A CN 101163817 A CN101163817 A CN 101163817A
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- 238000007740 vapor deposition Methods 0.000 title 1
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Abstract
A vapor deposited film is formed on a base material surface by a plasma CVD method wherein an organic metal compound and an oxidizing gas are used as a reactive gas. The vapor deposited film has three sections of a base material side adhesive layer having 5% or more carbon, a barrier intermediate layer having less than 5% carbon, and a surface protection film having 5% or more carbon, by element concentration with respect to the total amount of three elements of a metal element (M), oxygen (O) and carbon (C) derived from the organic metal compound. The vapor deposited film has excellent adhesiveness to the base material, and has excellent resistance to water, especially to alkaline aqueous solutions, as well.
Description
Technical field
The present invention relates to the vapor-deposited film that forms at the matrix surface of Plastic Bottle etc. by plasma CVD method.
Background technology
In the past, in order to improve the characteristic of various matrixes, carried out of the operation of using plasma CVD method at its surface formation vapor-deposited film.For example, in the wrapping material field,, knownly form vapor-deposited film by plasma CVD method and improve gas barrier property for plastic basis materials such as containers.
For example, the manufacture method of known a kind of plastic containers, it is characterized in that, at gas by using silicoorganic compound and oxygen or having oxidation capacity, and utilize plasma CVD method when the outside surface of plastic containers or internal surface form vapor-deposited film (blocking layer), the concentration of silicoorganic compound changes, and described vapor-deposited film contains Si oxide and comprises the compound (with reference to patent documentation 1) that is selected from least a element in carbon, hydrogen, silicon and the oxygen.
In addition, also known a kind of choke film is characterized in that, the gas barrier layer (vapor-deposited film) that have base material, forms at the one or both sides of this base material and be formed on water resisting property film (anti-water layer) (with reference to patent documentation 2) on this gas barrier layer.
Patent documentation 1: the spy opens the 2000-255579 communique
Patent documentation 2: the spy opens the 2003-53873 communique
; for example adopt the vapor-deposited film of the method formation of patent documentation 1; though blocking effect excellence to all gases such as oxygen; but the weather resistance to moisture is low; the shortcoming that has silicon stripping in the such alkaline aqueous solution of mineral water; particularly, require to improve the tack of film to matrix in the wrapping material field.In addition, the choke film of patent documentation 2 record therefore can improve the tolerance to moisture to a certain extent, but its improvement degree is insufficient owing to form anti-water layer on the surface as the gas barrier layer of vapor-deposited film, when forming anti-water layer, can not fully suppress the stripping of silicon in alkaline aqueous solution.
Though the vapor-deposited film that with the Si oxide is the metal oxide of representative shows high gas barrier property, there is the shortcoming flexibility, to the low shortcoming of tack of the matrix, the particularly plastic substrate that form this vapor-deposited film.Therefore, when forming this vapor-deposited film on plastic containers etc., this container waits when being out of shape because of expanding, and this vapor-deposited film can not be followed distortion of vessel, the problem that the result has gas barrier property significantly to reduce.
For fear of the problems referred to above, the applicant has proposed to form vapor-deposited film by following method: at first, when using organometallic compound to form the vapor-deposited film of metal oxide as the plasma CVD method of unstripped gas, the conditioned reaction condition, form the high organic property layer of carbon concentration that is imbued with organic property in the matrix surface side in advance, on this organic property layer, form the high metal oxide layer that is imbued with inorganic nature of metal concentration (with reference to patent documentation 3) continuously then.In the vapor-deposited film that forms like this, because organic property layer is formed on the downside of the high metal oxide layer of gas barrier property, promptly therefore the matrix surface side not only has excellent gas barrier property, and matrixes such as plastics are shown high tack, and flexibility is also excellent in addition.
Patent documentation 3: the spy opens 2005-89859
, in the vapor-deposited film shown in the patent documentation 3, still there is the problem that needs improvement.Promptly, vapor-deposited film at the inorganic, metal oxide layer that the matrix surface side forms the high organic property layer of carbon concentration, the formation gas barrier property is high on so organic property layer with laminate structure, the low shortcoming of thermotolerance is arranged, therefore, if form this vapor-deposited film, particularly at high temperature during the filling container content, perhaps when preserving container than higher temperature (50～60 ℃) on the surface of plastic containers, the stripping in content liquid of metal in the vapor-deposited film, thus the problem that thickness reduces produced.
Summary of the invention
Therefore, the objective of the invention is to, provide not only good the tack of matrix, and to moisture, particularly to the also excellent vapor-deposited film that utilizes plasma CVD method to obtain of the tolerance of alkali aqueous solution.
Another object of the present invention is, provides thermotolerance the also excellent vapor-deposited film that utilizes plasma CVD method to obtain.
According to the present invention, a kind of vapor-deposited film is provided, it is formed on matrix surface by using organometallic compound and oxidizing gas as the plasma CVD method of reactant gases, wherein,
With metallic element (M), oxygen (O) and 3 kinds of elements of carbon (C) of deriving from above-mentioned organometallic compound is benchmark, and it be the above matrix side tack coat of 5 element %, carbon concentration less than the block middle layer of 5 element % and carbon concentration is sealer more than the 5 element % that above-mentioned vapor-deposited film is divided into carbon concentration;
The carbon of above-mentioned sealer (C) concentration ratio oxygen (O) concentration and metallic element (M) concentration height, and surface at this sealer, the element of expression metallic element (M) oxidisability is below 1.3 than (O/M), and more than the little 1.0eV of mean value of the bound energy of metallic element (M) than the metallic element bound energy in the above-mentioned block middle layer;
In above-mentioned block middle layer, the element of expression metallic element (M) oxidisability is higher and be below 2.4 than (O/M) average specific 1.8.
According to the present invention, also provide a kind of Plastic Bottle that has formed above-mentioned vapor-deposited film at internal surface.
In the present invention, the element of the oxidisability of each concentration of element in the surface protection laminar surface, expression metallic element (M) is meant by the measured value of X ray photoelectricity spectroscopy apparatus under the surperficial 0.3nm degree of depth of distance than the bound energy of (O/M) and metallic element (M).Not adopting lip-deep measured value is for fear of the influence of staiing etc.
In vapor-deposited film of the present invention, preferred:
(1) have organic inorganic compounding zone in above-mentioned matrix side tack coat, in the compound zone of this organic-inorganic, element satisfies following formula than (C/M) and element than (O/M):
0.2＜C/M＜1.8
1.5≤O/M，
And the bound energy of metallic element (M) is in the scope than the low 0.1eV～0.7eV of mean value of the metallic element (M) in the above-mentioned block middle layer;
(2) remove above-mentioned sealer, the element in the zone that exists on the compound zone of above-mentioned organic-inorganic satisfies following formula than (C/M):
C/M≤0.2；
(3) bound energy of the metallic element (M) in the compound zone of above-mentioned organic-inorganic increases gradually from the above-mentioned organic-inorganic of matrix side direction zone, and the difference of the maximum value of the bound energy of metallic element (M) and minimum value is more than the 0.1eV.
The vapor-deposited film that using plasma CVD method of the present invention obtains forms as reactant gases by using organometallic compound and oxidizing gas; in this vapor-deposited film; matrix side tack coat (below, abbreviate tack coat as), block middle layer and sealer have been formed from matrix lateral surface side.
Tack coat is that the contact carbon concentration is the above zones of 5 element %, owing to be the high zone that is imbued with organic property of carbon concentration, therefore vapor-deposited film of the present invention shows high tack to matrix.
The carbon concentration that is formed on the block middle layer on the tack coat is low to less than 5 element %, become zone based on the oxide compound of metallic element (M), the zone that promptly is imbued with inorganic nature, the element of expression metallic element (M) oxidisability are higher and be below 2.4 than (O/M) average specific 1.8.Therefore, this block middle layer shows high gas barrier property.
In addition; on the surface that is formed on the sealer on the block middle layer (promptly; part apart from the outside surface degree of depth 0.3nm of vapor-deposited film); satisfy following condition: carbon (C) concentration ratio oxygen (O) concentration and metallic element (M) concentration height; the element of expression metallic element (M) oxidisability is below 1.3 than (O/M), and more than the little 1.0eV of mean value of the bound energy of metallic element (M) than the metallic element bound energy in the block middle layer.That is, compare with the block middle layer, sealer is the high zone of organic property.Therefore, as described later shown in the embodiment, vapor-deposited film of the present invention shows excellent tolerance to alkaline aqueous solution, for example metallic element (M) can stripping in alkaline aqueous solution, therefore, the Plastic Bottle that has such vapor-deposited film at the internal surface container that can be used as mineral water or basic ion beverage etc. is in practicality.
In above-mentioned inorganic vapor-deposited film, carbon (C) concentration reduces to the block middle layer gradually from the interface side with substrate surface, and oxygen (O) concentration and metal (M) concentration raise gradually simultaneously.Therefore, near the part block middle layer in above-mentioned substrate-side tack coat has formed the compound zone of organic-inorganic that shows organic property and inorganic nature.In the present invention, preferably regulate the velocity of variation of each concentration of element, so that following formula is satisfied in the compound zone of such organic-inorganic:
0.2＜C/M＜1.8
1.5≤O/M，
And the bound energy of metallic element (M) is in the scope than the low 0.1eV～0.7eV of mean value of the metallic element (M) in the above-mentioned block middle layer.That is, by forming the compound zone of the organic-inorganic that satisfies such condition, vapor-deposited film shows excellent thermotolerance.For example, when the internal surface of Plastic Bottle forms such vapor-deposited film, at high temperature keep this bottle for a long time or when heat is filled content liquid in this bottle, can produce the stripping of metallic element in content liquid hardly, can avoid thickness to reduce effectively and follow the reduction of the gas barrier property of its generation.Therefore, the container of usefulness is sold in the Plastic Bottle that has a vapor-deposited film that has formed so compound zone of organic-inorganic at the internal surface heating that is particularly suitable as tea etc.
Description of drawings
Fig. 1 illustrates vapor-deposited film of the present invention that embodiment 1 obtains figure at the bound energy of the elementary composition and silicon of thickness direction.
Fig. 2 is the figure that the structure of the plasma processing apparatus that is used to form vapor-deposited film of the present invention is shown.
Fig. 3 is the concentration of element of vapor-deposited film on thickness direction and the figure of the bound energy of silicon that comparative example 1 is shown.
Fig. 4 be C/O that the vapor-deposited film surface is shown than and the figure of the relation of thickness reduction.
Fig. 5 be C/Si that the vapor-deposited film surface is shown than and the figure of the relation of thickness reduction.
Fig. 6 illustrates the figure of the O/Si on vapor-deposited film surface than the relation of (oxidisability) and thickness reduction.
Fig. 7 is illustrated in the figure that the vapor-deposited film (experimental example 1) that has the compound zone of organic-inorganic in the tack coat distributes at the composition of the silicon of thickness direction, oxygen, carbon.
Fig. 8 is a vapor-deposited film that Fig. 7 is shown at the element of the carbon of thickness direction and the silicon figure than (C/Si).
Fig. 9 is a vapor-deposited film that experimental example 1,2 and comparative experiments example 1,2 be shown and the element of carbon and silicon is in the figure of difference of metallic element (Si) bound energy of the choke film (being equivalent to the block middle layer) in the zone (the compound zone of organic-inorganic) of 1.0～1.8 scope than (C/Si).
Figure 10 illustrates the figure of the vapor-deposited film of experimental example 1 in the bound energy distribution of the elementary composition and metallic element (Si) of thickness direction.
Figure 11 illustrates the figure that the vapor-deposited film of experimental example 3 distributes at the composition of the silicon of thickness direction, oxygen, carbon.
Figure 12 illustrates the figure of the vapor-deposited film of experimental example 3 in the bound energy distribution of the elementary composition and metallic element (Si) of thickness direction.
Embodiment
Fig. 1 with reference to accompanying drawing.Fig. 1 be pattern the figure of elementary composition (M, O, the C) of the vapor-deposited film of measuring by X ray photoelectricity spectrum analysis of the present invention (vapor-deposited film that embodiment 1 particularly described later makes) is shown, this vapor-deposited film is divided into sealer X, block middle layer Y and these 3 zones of tack coat Z from the outside surface side to substrate surface.Promptly, vapor-deposited film of the present invention is formed on the matrix surface of regulation by using organometallic compound and oxidizing gas as the plasma CVD method of reactant gases, in this vapor-deposited film, the metallic element (M), oxygen (O) and the carbon (C) that derive from above-mentioned organometallic compound distribute as shown in Figure 1, according to by these 3 kinds of concentration of element that the element benchmark is represented, be divided into 3 above-mentioned zones.In addition, in Fig. 1, show silicon (Si) as metallic element (M).
In Fig. 1, the tack coat Z that is formed on the matrix surface side is that (C) concentration is the above zones of 5 element %, and this zone is organic property height and the zone that shows high flexibility.That is, the inorganic nature height of the metal oxide layer (the block middle layer of narrating below is suitable therewith) that forms by plasma CVD, and oxygen block height, but flexibility is low sometimes, lacks the cohesiveness with matrix.Yet, the flexibility height of the tack coat that organic property is high is also good with the cohesiveness of matrix.Therefore,, can avoid the reduction of cohesiveness or tack effectively, show extra high tack so that cohesiveness for plastic matrix by form the high tack coat Z of organic property at matrix surface.
In addition, the preferred carbon concentration of this tack coat Z (C) increases more gradually to the matrix surface side more, with the interface side of matrix surface, it is particularly preferred on the tack that improves with matrix that carbon concentration (C) increases to 20 element % above.In addition, as shown in Figure 1, when making carbon concentration (C) approach more to increase gradually with the interface side of matrix surface, the concentration of metallic element (M) and oxygen (O) concentration reduce thereupon gradually.
(C) concentration that is formed on the block middle layer Y on the above-mentioned tack coat is less than 5 element %, and therefore, in this zone, the total concn (M+O) of metallic element (M) and oxygen (O) is more than the 95 element %.That is, this layer Y that is formed on the centre portions of vapor-deposited film is the layer that organic property is low, be imbued with inorganic nature, particularly to the block height of oxygen.For example, when using hexamethyldisiloxane silicoorganic compound such as (HMDSO) as organometallic compound, the block middle layer becomes the layer based on Si oxide.Therefore, vapor-deposited film of the present invention is useful in the field that requires gases such as oxygen, carbonic acid gas are had the wrapping material such as plastic containers of block particularly.
In addition, in such block middle layer Y, the oxidisability x of metallic element (M) must satisfy following condition:
1.8＜x≤2.4
This oxidisability x represent oxygen (O) with respect to the element of metallic element (M) than (O/M), when oxidisability x is above-mentioned scope, show high gas barrier property, oxidisability x is outside the above-mentioned scope time, gas barrier property reduces.
The sealer X that is positioned at the face side of vapor-deposited film is that (C) concentration is the above zones of 5 element %, and same with above-mentioned tack coat Z, the carbon amount is many, is imbued with organic property.In the present invention; each concentration of element, the oxidisability x of metallic element (M) and the bound energy of metallic element (M) in the vapor-deposited film surface that exists on this sealer X (particularly, position) dark apart from outside surface 0.3nm must satisfy all following conditions (a)～(c).
Condition (a):
Carbon (C) concentration ratio oxygen (O) concentration and metallic element (M) concentration height,
That is, C＞O and C＞M;
Condition (b):
The oxidisability x (that is, element is than O/M) of metallic element (M) is below 1.3;
Condition (c):
More than the little 1.0eV of mean value of the bound energy of metallic element (M) than the metallic element bound energy among the barrier zones Y of middle layer.
Promptly, above-mentioned condition is vapor-deposited film rich carbon in surface and the condition that obviously is imbued with organic property, by satisfying all these conditions, can significantly improve the water tolerance of vapor-deposited film, particularly can suppress the stripping of metallic element (M) in alkali aqueous solution effectively, even when these conditions had only one not satisfy, water tolerance can not be met, the stripping of metallic element (M) in alkali aqueous solution becomes remarkable.For example, by the experimental result of embodiment 1 described later and comparative example 1 as can be known, even satisfy condition (a) and (c), oxidisability x at the metallic element (M) on surface is 1.49, under 1.3 the situation of surpassing (under the situation of do not satisfy condition (b)), when vapor-deposited film is flooded certain hour in alkali aqueous solution, because the film reduction that the stripping of metallic element (Si) causes is 3.4nm (comparative example 1), relative therewith, when satisfying all conditions (a)～(c) (embodiment 1), the film reduction is 0.2nm, and the stripping of metallic element (Si) is significantly suppressed.Can think and show such excellent in water resistance by vapor-deposited film of the present invention the chances are owing to following reason: by satisfying all above-mentioned conditions (a)～(c); existing hardly becomes Sauerstoffatom (O) or the OH base (silanol group) that vapor-deposited film surface water tolerance reduces major cause, and such Sauerstoffatom or OH base the quilt fully sealer of thickness cover.
In addition; in vapor-deposited film of the present invention; preferably when above-mentioned condition (a)～(c) is satisfied on the vapor-deposited film surface as shown in Figure 1; in sealer X; carbon (C) concentration increases gradually to face side, and the concentration of metallic elements such as Si (M) and oxygen (O) concentration reduce thereupon gradually, for example; preferred carbon (C) concentration increases to more than the 40 element %, and preferred especially carbon (C) concentration is that the above zone of 40 element % exists with the thickness more than the 5nm.By forming the very high zone of carbon (C) concentration in face side in this wise; can poor water resistance, the block middle layer Y that is easy to generate the stripping of silicon metallic elements (M) such as (Si) be covered by the sealer X of adequate thickness; thereby the water tolerance of significantly improving; and block the infiltration of water fully, can avoid effectively because the reduction of the gas barrier property that moisture causes.
In addition, in the present invention, be appreciated that interface portion in each layer X, Y and Z adjacency as Fig. 1, each concentration of element changes in fact continuously.That is, in these interface portion, each concentration of element is dull continuously to be reduced or increases, and this means each layer X, Y and Z-shaped being integral, and does not form clear and definite interface between the layer of adjacency.Therefore, vapor-deposited film of the present invention can not produce between each layer and peel off, and weather resistance is extremely excellent, to gas and moisture demonstration blocks steady in a long-term such as oxygen.
Like this, in vapor-deposited film of the present invention, sealer X, block middle layer Y and tack coat Z all are not that the form with clear and definite layer exists, and do not have clear and definite interface at interlayer.Therefore, can not be to each regional thickness strict regulation, but the thickness of vapor-deposited film (total thickness that each is regional) is in 4 to 500nm scope usually, and block middle layer Y can have the above thickness of about 4.0nm, and tack coat Z can have the above thickness of about 0.2nm.
In addition, in the present invention,, preferably make the surface of sealer X become uneven surface in order to improve block to moisture.For example, by its average surface roughness Ra (JIS B0601) is adjusted to about 0.1 to 10.0nm, can further improve block to moisture.Forming such uneven surface can carry out by the following method: for example when forming vapor-deposited film, regulate the decompression degree that is used for glow discharge, carry out glow discharge under than higher pressure.
In above-mentioned the present invention, see that on the thermotolerance that improves vapor-deposited film it is extremely preferred forming the compound zone of organic-inorganic of satisfying prescribed condition in tack coat Z.
Figure 12 with reference to accompanying drawing.Figure 12 shows elementary composition (M, O, C) and the bound energy of metallic element (M) of the vapor-deposited film of measuring by X ray photoelectricity spectrum analysis (vapor-deposited film that experimental example 3 described later is made).In addition, in this vapor-deposited film,, omitted above-mentioned sealer X for the function in the compound zone of organic-inorganic is described.
Narrate as the front, in vapor-deposited film of the present invention, carbon concentration reduces to block middle layer Y gradually from the interface portion with substrate surface, and oxygen (O) concentration and metal (M) concentration increase gradually.That is, move to the metal-rich zone territory gradually from the carbon-rich zone territory.Therefore; as shown in figure 12; in tack coat Z; formation has the compound region alpha of organic-inorganic of organic property and inorganic nature; the part of removing sealer X in this region alpha outside surface side becomes the inorganic nature region beta that is imbued with inorganic nature; in this inorganic nature region beta, there is above-mentioned block middle layer Y.
In the present invention, the element of the above-mentioned compound region alpha of organic-inorganic satisfies the condition of following formula (1) and (2) than (O/M) than (C/M) and element:
0.2＜C/M＜1.8...(1)
1.5≤O/M...(2)
That is, if the compound region alpha of this organic-inorganic is compared with the above-mentioned inorganic nature region beta that contains block middle layer Y (C/M≤0.2), then the oxidisability (O/M) of metallic element (M) can be low slightly, but carbon (C) is many with respect to the amount (C/M) of metallic element (M).That is, the compound region beta of this organic-inorganic is not near the zone based on carbon that is present in the substrate surface, but is rich in the zone of organic property than inorganic nature region beta, shows organic property and inorganic nature.
In addition, the bound energy of the metallic element (M) of so compound region alpha of organic-inorganic is in the scope than the low 0.1eV～0.7eV of mean value of metallic element (M) bound energy of block middle layer Y.That is, will deduct by the mean value of the bound energy of the metallic element (M) among the Y of this block middle layer the compound region alpha of organic-inorganic metallic element (M) bound energy and the difference that obtains is called " with the bound energy in block middle layer poor (Δ M) ".That is, the bound energy of metallic element (M) and oxygen (O) is than the bound energy height of metallic element (M) with carbon (C).Therefore, more many in the compound region alpha of organic-inorganic of carbon (C) containing than the inorganic nature region beta, metallic element (M) bound energy becomes the value lower than inorganic nature region beta, but in the present invention, during the degree of bound energy poor (Δ M) in above-mentioned scope, in the compound region alpha of organic-inorganic, contain the high metal oxide of oxidisability.
As previously described,, there is the shortcoming of shortcoming flexibility, and lacks tack matrix though the block middle layer Y that is present in the inorganic nature region beta shows high gas barrier property.For example, matrix waits because of expanding when more or less being out of shape, and such inorganic nature zone X can not follow the variation of matrix, and the tack of result and matrix suffers damage, and produces the reduction of gas barrier property.Such unfavorable condition can be avoided by forming the above-mentioned tack coat Z that is rich in flexibility.In the present invention, be formed in the tack coat Z, can not damage the flexibility of tack coat by making the compound region alpha of the organic-inorganic that satisfies above-mentioned condition, and raising is to the tack of matrix, simultaneously, amazingly be the thermotolerance that has also realized vapor-deposited film so unexpected advantage that is improved.
For example, in as patent documentation 3 disclosed vapor-deposited films, be formed on the zone on substrate-side surface, its carbon concentration is high, and poor (Δ M) is in the scope above 0.7eV with the bound energy of gas barrier layer, do not show inorganic nature.Therefore, though flexibility height, to the tack excellence of matrix, there is the low problem of thermotolerance in this vapor-deposited film.Shown in the comparative experiments example as described later 1, when the internal surface of PET bottle forms such vapor-deposited film, when heat is filled content liquid in bottle, compare with the situation of at room temperature filling content liquid, metallic element (silicon) obviously increases to the stripping quantity of content liquid.In contrast, when the vapor-deposited film that forms the compound region alpha of organic-inorganic satisfy above-mentioned condition in tack coat is arranged on PET bottle internal surface (experimental example 1), thermotolerance is obviously high, even fill in heat under the situation of content liquid, the stripping quantity of metallic element (silicon) about equally, is few amount when at room temperature filling.
For improving stable on heating reason by forming the compound region alpha of such organic-inorganic, the inventor etc. are presumed as follows.That is, patent documentation 3 such many organic property zones (tack coat) of carbon content only are formed in the vapor-deposited film of substrate-side, fill or maintenance at high temperature by heat, move actively in organic property zone.Its result thinks that under the condition of high temperature metallic element (M) in the inorganic nature zone that forms (perhaps block middle layer) is free easily, for example stripping in the content liquid of bottle on organic property zone.Yet, in the present invention, in the compound region alpha of the organic-inorganic that in tack coat, exists, because the metallic element (M) of amount exists with the high form of oxidisability to a certain degree, therefore, the motion of the compound region alpha of organic-inorganic at high temperature is lower than inorganic nature region beta (or block middle layer Y), and compares with above-mentioned organic property zone, and is quite little.Therefore, under the condition of high temperature, metallic element (M) is difficult for breaking away from, and the result shows excellent thermotolerance.
In above-mentioned vapor-deposited film of the present invention, as shown in figure 12, in the compound regional Y of organic-inorganic, the bound energy of preferable alloy element (M) increases gradually from matrix side direction inorganic nature region beta, and the difference of the maximum value of the bound energy of metallic element (M) and minimum value is more than the 0.1eV.By satisfying such condition, the compound region alpha of organic-inorganic can be guaranteed the thickness (for example about 0.2～10nm) of appropriateness because its flexibility, can guarantee and matrix between high tack.In addition, do not form clear and definite interface between such region alpha and region beta, therefore, can not be created in situation about peeling off outside both interfaces, weather resistance is extremely excellent, and gas such as oxygen or moisture are also shown long-time stable gas barrier property.
In the present invention, the above-mentioned compound region alpha of organic-inorganic can be element satisfies following formula (1a) and condition (2a) than (O/M) than (C/M) and element zone.
1.0＜C/M＜1.8...(1a)
2.0≤O/M ...(2a)
It is more slightly than metallic element (M) that carbon (C) is contained in such zone, and the oxidisability (O/M) of metallic element (M) is in high level.That is,, can improve the tack that causes by above-mentioned flexibility and keep effect and thermotolerance to improve effect by forming organic property for than higher level and there is the compound region alpha of organic-inorganic of the high metal oxide of oxidisability.Particularly, when making the reduced thickness to 0.2 of the compound region alpha of the organic-inorganic～5.0nm left and right sides, keep effect and thermotolerance to improve this point of effect in the tack that can show regulation and see, extremely be preferably formed the compound region alpha of such organic-inorganic.
[matrix]
In the present invention,, can use the matrix of making by glass, various metals etc., but have choosing to use plastic basis material most as the matrix of above-mentioned vapor-deposited film to be formed.As such plastics, can be self known thermoplastic resin, for example new LDPE (film grade), high density polyethylene(HDPE), polypropylene, poly-1-butylene, poly(4-methyl-1-pentene); Or polyolefine such as the random or segmented copolymer between the alpha-olefin such as ethene, propylene, 1-butylene, 4-methyl-1-pentene; Cyclic olefin copolymer etc., and vinyl-vinyl compound copolymer such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer; Styrene resins such as polystyrene, acrylonitritrile-styrene resin, ABS, alpha-methyl styrene-styrol copolymer; Polyvinyl compound such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, polymethyl acrylate, polymethylmethacrylate; Polymeric amide such as nylon 6, nylon 6-6, nylon 6-10, Ni Long11, nylon 12; Thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, PEN; Polycarbonate, polyphenylene oxide etc.; Or Biodegradable resin such as poly(lactic acid); The perhaps resin arbitrarily in their mixture.
These matrixes can use with the form of film or sheet, in addition also can be with the form use of container such as bottle, cup, pipe or other moulding product.Particularly, as bottle, can enumerate the Biaxially stretched blow-molded bottle that forms by polyester such as polyethylene terephthalates.Certainly, the present invention also can be equally applicable to the cup or the biaxially-stretched film of above-mentioned polyester.
In addition, plastic substrate can be to be ectonexine with above-mentioned thermoplastic resin (preferred alkenes resinoid), and the multilayered structure thing that between these ectonexines, has the gas barrier property of oxygen absorption layer, form vapor-deposited film of the present invention by internal layer and/or superficies, can significantly improve the oxygen block at such multilayered structure thing.
[reactant gases]
In the present invention, use organometallic compound and oxidizing gas, as required, can also use hydrocarbon simultaneously with them as carbon source as reactant gases.
In the present invention, as organometallic compound, though preferably use silicoorganic compound, but get final product so long as react the material that forms metal oxide with oxidizing gas, be not limited to silicoorganic compound, for example can use various materials such as organo-aluminium compounds such as trialkylaluminium and organic titanic compound.As silicoorganic compound, can use organic silane compounds such as hexamethyldisilane, vinyl trimethylsilane, methyl-monosilane, diformazan machine silane, trimethyl silane, diethylsilane, propyl silane, phenyl silane, Union carbide A-162, vinyltriethoxysilane, vinyltrimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, phenyltrimethoxysila,e, methyltrimethoxy silane, Union carbide A-162; Octamethylcyclotetrasiloxane, 1,1,3, organosilicone compounds such as 3-tetramethyl disiloxane, hexamethyldisiloxane etc.In addition, except that these materials, can also use aminosilane, silazane etc.
Above-mentioned organo-metallic can be used separately, also can make up more than 2 kinds and use.In addition, can also use silane (SiH simultaneously with above-mentioned silicoorganic compound
4) or silicon tetrachloride.
As oxidizing gas, use oxygen or NO
x,, use argon gas or helium etc. as carrier gas.
As carbon source, except silicoorganic compound, organometallic compound, can also use CH
4, C
2H
4, C
2H
6, C
3H
8Deng hydrocarbon.
[formation of vapor-deposited film]
In the present invention, in containing the atmosphere of above-mentioned reactant gases, form vapor-deposited film on the surface of matrix by plasma CVD method.
In addition, so-called plasma CVD is to utilize gaseous plasma to carry out film growth, consist essentially of following technology: under reduced pressure the electric energy that produces with high electric field makes geseous discharge, the decomposition that contains unstripped gas, through in gas phase or at the chemical reaction on the matrix material of generation being deposited on the matrix.Plasmoid can realize by glow discharge, adopts the mode of this glow discharge, the known method that the direct current glow discharge of utilizing arranged, utilize the high frequency glow discharge method, utilize the method for microwave discharge etc.
Low-temperature plasma CVD has following advantage, thereby can easily be applicable to form vapor-deposited film on plastic substrate,
A. owing to utilized the direct decomposition of adopting the gas molecule of high-velocity electrons, therefore can easily the big unstripped gas disassociation of energy will be generated;
B. be in the electronic temp thermal unbalance state different with the gas ion temperature, that is, electronic temp is to have the high temperature of finishing the necessary energy of chemical reaction, and ion temperature is a low temperature, and low temperature process becomes possibility;
Even c. substrate temperature hangs down and also can form amorphous membrance relatively uniformly.
In the present invention, in order to form above-mentioned zone shown in Figure 1, must form vapor-deposited film.As such method, for example have by reactant gases and regulate or the methods such as output adjusting of glow discharge.
Adopt under the situation of reactant gases, for example compare with organometallic compound, in the feed rate of oxidizing gas after a little while, the oxygenolysis level of organometallic compound is low, forms polymkeric substance.The result can form the many zones of carbon amount, for example zone such as sealer X or tack coat Z.In addition, by comparing with organometallic compound, increase the feed rate of oxidizing gas, the oxygenolysis of organometallic compound is carried out up to high level, therefore forms metal oxide almost completely.The result can form the few zone of carbon amount, i.e. block middle layer Y.In addition, in order to form sealer X, can also supply with hydrocarbon as carbon source.
In addition, when forming each layer X～Z by conditioned reaction gas, each concentration of element changes continuously, at each interregional interface that do not generate, must consider the balance of the feed rate of the output of microwave and oxygen.
In addition; when adopting the output adjusting of glow discharge, if, then can form many sealer X of carbon amount or tack coat Z etc. to hang down the glow discharge that the output generation for example produces plasma body; if carry out glow discharge with height output, then can form the few block middle layer Y of carbon amount.
The method that should pass through the output variation is based on following principle.
For example, if illustrate, can consider to form silicon oxide layer through following reaction circuit by silicoorganic compound and oxidizing gas with organosilicon oxide.
(a) removing of hydrogen: SiCH
3→ SiCH
2
(b) oxidation: SiCH
2→ SiOH
(c) dehydrating condensation: SiOH → SiO
That is, if carry out glow discharge with height output, output more than for example 100W, then silicoorganic compound are reacted to the stage of (c) at one stroke, and the result forms oxygenolysis level height, block middle layer Y that the carbon amount is few.On the other hand, if with low output, for example about 20 to 80W carry out glow discharge, the SiCH that generates in (a) stage then
2Free radical react each other, generate the polymerizable organosilicon compound thing, the result forms carbon amount many sealer X or tack coat Z.
In addition, when forming each layer X～Z, not at each interregional generation interface, the output of glow discharge is regulated continuously changed for each concentration of element is changed continuously by the output of regulating glow discharge.
In the present invention, the glow discharge that is used for producing plasma body is carried out under high-frequency electric field or microwave electric field.When the matrix of handling is plastics, under high-frequency electric field, carry out under the situation of glow discharge, only condition is according to interelectrode distance etc. and different, can not stipulate without exception, but the glow discharge under above-mentioned high output area is preferably carried out under the output more than the 100W, under microwave electric field, carry out under the situation of glow discharge, the glow discharge under height output can be for 90W more than.
For example; in order to form the vapor-deposited film surface of satisfying above-mentioned condition (a)～(c); and then make as shown in Figure 1 the distribution of being distributed as of carbon (C) concentration among the sealer X etc.; preference is as after forming the block middle layer Y of thickness to a certain degree; the supply of stopped reaction gas; gas displacement atmosphere gas with organometallic compound begins glow discharge then.If carry out glow discharge under the state of reactant gases existing, then for example the oxidisability x on surface becomes than 1.3 height, and the water tolerance of vapor-deposited film has the possibility of reduction.
In addition, in the present invention, can adopt the method and the method that adopts glow discharge output of the feed rate of above-mentioned reactant gases by combination, in tack coat Z, form the above-mentioned compound region alpha of organic-inorganic, and on this region alpha, form the inorganic nature region beta that contains block middle layer Y.
For example, when using situation that hexamethyldisiloxane (HMDSO) forms vapor-deposited film, with O as example
2/ HMDSO (mol ratio) is about 8～12 amount ratio supply HMDSO and oxidizing gas, the formation of the vapor-deposited film that the reaction of beginning using plasma is carried out under low output simultaneously, slowly improve output again, can be formed on the vapor-deposited film that has the compound region alpha of organic-inorganic in the tack coat Z thus.At this moment, under the situation that adopts microwave, about 30W, begin glow discharge, slowly improve output, when reaching the output more than the 90W, in the inorganic nature region beta on the compound region alpha of organic-inorganic, the oxidisability that forms metallic element (Si) is the highest, and carbon (C) content is essentially zero block middle layer Y.In addition, adopt under the situation of high frequency, only condition is according to interelectrode distance etc. and different, can not stipulate without exception, but about 40W, begin glow discharge usually, slowly improve output again, finally reach the above output of 100W, can in the inorganic nature region beta, form block middle layer Y thus.
Adopt under any situation of microwave and high frequency, gradient or system film time by regulating output, can make organic and inorganic compound close region alpha and satisfy above-mentioned formula (1) and (2), perhaps satisfy formula (1a) and condition (2a).For example,, perhaps prolong the system film time, can make organic and inorganic compound close region alpha and satisfy above-mentioned formula (1) and (2), and can to make its thickness be about 0.2～10nm by making the output gradient ratio milder.In addition, by making the output gradient ratio rapider, perhaps shorten the system film time, can make organic and inorganic compound close region alpha becomes and satisfies formula (1a) and zone (2a), and for example, the thickness that can make so compound region alpha of organic-inorganic is about 0.2～5.0nm.But,, perhaps extremely shorten the system film time if the output gradient sharply arrives more than the necessary degree, then the thickness of the compound region alpha of organic-inorganic is little, transforms to the inorganic nature region beta immediately, therefore, for the thickness that makes region alpha is at least about 0.2nm, should regulate the gradient or the system film time of output.
[treatment unit]
In the present invention, the device that is used to form above-mentioned vapor-deposited film has: comprise matrix to be processed plasma processing chamber, be used for plasma processing chamber remain on decompression state exhaust system, be used for importing to processing in the plasma processing chamber with gas delivery system be used in plasma processing chamber, producing the hertzian wave importing system of plasma body with handling with gas.As an example of this device, the employing microwave plasma processing apparatus is an example, and its structure as shown in Figure 2.
In Fig. 2, the plasma processing chamber of representing as overall usefulness 10 constitutes by cyclic pedestal 12, cylindrical sidewall 14 with the top cover 16 of cylindrical sidewall 14 tops sealing.
Centre portions at ring-type pedestal 12 forms the 1st venting hole 20, and the cyclic recess 22 of the 1st venting hole 20 is surrounded in formation on pedestal 12, in addition, forms annular groove 24 around cyclic recess 22, and annular groove 24 is communicated with the 2nd venting hole 26.
In above-mentioned cyclic recess 22, taken in bottle bearing 30, this bottle bearing makes bottle 28 keep handstand state.As shown in Figure 2, embedded the head of the bottle 28 of handstand state in the bottle bearing 30, the head that remains on the bottle 28 in this bearing is communicated with the 1st venting hole 20, and the head that passes through bottle 28 from the 1st venting hole 20 inserts gas supply pipe 32 to the inside of bottle 28.
Cooling is set with gas supply hole 40 on top cover 16, thus, after the formation of vapor-deposited film finishes or in the formation at vapor-deposited film, cools off the bottom that is blown into the bottle 28 that in plasma processing chamber 10, keeps handstand state with gas, cool off.
In addition, in order to ensure the stopping property of plasma processing chamber 10, O shape ring 42 is set respectively at the interface of pedestal 12 and cylindrical sidewall 14 and the interface of cylindrical sidewall 14 and top cover 16.In addition, the O shape ring 42 be used for the inside and outside partition of bottle 28 also is set on bottle bearing 30.
In addition, be provided for sealing the shielding 44 of microwave in the 1st venting hole 20 on being formed on pedestal 12 and the 2nd venting hole 26 respectively.In addition, in order to seal microwave, pedestal 12, cylindrical sidewall 14 and top cover 16 all are metal.
Using plasma is handled when forming vapor-deposited film, at first, the bottle bearing 30 that keeps bottle 28 for handstand state is placed in the annular recessed portion 22 of pedestal 12, with suitable lifting device pedestal 12 is risen with this state, closely contact with cylindrical sidewall 14, as shown in Figure 2, constitute airtight and taken in the plasma processing chamber 10 of the bottle 28 of handstand state.
Then, gas supply pipe 32 is inserted into bottle 28 inside from the 1st venting hole 20, drives vacuum pump simultaneously,, thereby make the inner sustain vacuum state of bottle 28 by 20 exhausts of the 1st venting hole.At this moment, for prevent the bottle 28 since external pressure cause distortion, by vacuum pump by the 2nd venting hole 26 make the bottle 28 outsides plasma processing chamber 10 in become decompression state.
The decompression degree of bottle in 28 are to be imported to handle with gas and importing microwave by gas introduction tube 32 to produce the high decompression degree of glow discharge, for example can be 1～500Pa, the scope of preferred especially 5～50Pa.On the other hand, even the decompression degree in the plasma processing chamber 10 of bottle 28 outsides is to import microwave also not produce the decompression degree of glow discharge.
After arriving this decompression state, in bottle 28, import reactant gases, in plasma processing chamber 10, import microwave, produce the plasma body that obtains by glow discharge by microwave transmission parts 36 by gas supply pipe 32.Electronic temp in this plasma body is several ten thousand K, compares with the temperature hundreds of K of gas particle, exceeds about 2 orders of magnitude, is the thermal unbalance state, even for cryogenic plastic substrate, also can carry out Cement Composite Treated by Plasma effectively.
Above-mentioned reactant gases or the microwave output that is used for glow discharge are regulated as previously described; the vapor-deposited film that forms is followed successively by tack coat Z, block middle layer Y and sealer X from the bottle internal surface; it is elementary composition if measure by the X ray photoelectric analysis, then is result shown in Figure 1.In addition, in the end the stage, bring up to about 15～500Pa, can make the surface (being the vapor-deposited film surface) of sealer X be uneven surface, thereby improve block moisture by making the pressure in the bottle 28.
After the Cement Composite Treated by Plasma of stipulating, stop to handle with the importing of gas and the importing of microwave, import cooling gas from cooling with gas supply hole 40 simultaneously, make the inside and outside recovery normal pressure of bottle 28, the bottle 28 of plasma treatment is fetched into plasma processing chamber 10 outsides, thereby can have obtained forming the Plastic Bottle of target vapor-deposited film.
Plasma treatment time is according to the thickness of the film of the internal surface area of bottle to be processed, formation and handle with the kind of gas etc. and different, can not stipulate without exception, but stability from Cement Composite Treated by Plasma, each Plastic Bottle of 2 liters must be more than 1 second, though require the shortening time from the cost aspect, also can be the treatment time of minute level if desired.
Embodiment
With following Example the present invention is described, but is going up in all senses that the present invention is not limited to following Example.
1. the compositional analysis method in the film
The X ray photoelectricity light-dividing device (Quantum2000) that adopts PHI company to make, internally surface coverage the internal surface of body part of the vapor-deposited film composition separately of measuring silicon, oxygen, the carbon of film depth direction distribute and the bound energy of silicon.
In addition, silicon concentration and oxygen concn are with fused quartz (SiO
2) proofread and correct for benchmark, about thickness, for convenience's sake, adopt and fused quartz (SiO
2) same sputtering rate infers.
Represent with the measured value of acceleration voltage 2kV, sputter scope 3mm * 3mm, the position dark at each concentration of element on vapor-deposited film surface and silicon bound energy apart from film surface 0.3nm.
2. the alkali-proof evaluation of vapor-deposited film
At room temperature with 500ml basic solution (commercially available mineral water, pH7.3) be filled in internal surface has covered the PET bottle of vapor-deposited film, lid with the polypropylene manufacturing seals mouth cylindrical part, after under 55 ℃, the environment of 30%RH, preserving 28 days, with fluorescent x-ray analyzer (RigakuZSX) through the time measure silicon amount in the film, with under identical conditions, make through the time before the silicon amount of bottle compare, with the alkali-proof evaluation of the reduction of silicon amount as vapor-deposited film.The mean value of the silicon amount that each bottle measured in the position of 6 points along short transverse is as thickness.
3. stable on heating evaluation
In having covered the PET bottle of vapor-deposited film, internal surface fills 23 ℃ and 87 ℃ the distilled water of 500mL respectively, after taking care of 28 days under 55 ℃ the environment, measure silicon amount in the PET bottle solution by the inductively coupled plasma mass spectrometry analytical equipment, with the stripping quantity of silicon in pyrosol as stable on heating evaluation.
4. the evaluation of tack
Put into 2.5g dry ice in internal surface has covered the PET bottle of vapor-deposited film, cover plastics matter lid, keeping is 2 days under 55 ℃ environment.
By the rate of expansion (V2/V1 * 100) that the volume (V1) and the volume (V2) of PET bottle after the keeping of the PET bottle before the keeping are obtained the PET bottle, the result is owing to keeping expand into 102%.Then, (モ ダ Application コ Application ト ロ one Le company makes by oxygen transit dose determinator, OX-TRAN) measure the PET bottle and expand before and expand after oxygen transit dose (under the atmosphere of 37 ℃-100%RH), will expand the variation of the oxygen transit dose that causes as the evaluation of tack owing to the PET bottle.
(embodiment 1)
Use device shown in Figure 2, it has the metal mold round shape plasma processing chamber of microwave power supply, diameter 90mm, the height 500mm of frequency 2.45GHz, maximum output 1.2kW, with the evacuated oil rotation of treatment chamber vacuum pump, microwave is imported to rectangular waveguide the plasma processing chamber from vibrator.
As gas supply pipe, use the stainless steel gas supply pipe of the sintered compact with vesicular structure of external diameter 15mm, length 150mm, the bottle (PET bottle) that the polyethylene terephthalate of the round tube type of bore 28mm, stack shell diameter 64mm, height 206mm, internal volume 520ml is made is set on the bottle bearing, and making the outside vacuum tightness of bottle in the treatment chamber is that vacuum tightness is 10Pa in 7kPa, the bottle.
Under this state, in bottle, import the hexamethyldisiloxane (HMDSO) of 2.7sccm, the oxygen of 27sccm, make the pulse microwave vibration of 500W then by microwave oscillator, carry out Cement Composite Treated by Plasma.At this moment, change, form the vapor-deposited film that comprises tack coat Z, block middle layer Y by the duration of oscillation that makes microwave.Then, stop to supply with oxygen, after being replaced as HMDSO atmosphere in the bottle, form sealer X.The evaporation time of each layer is respectively 3 seconds (layer Z), 5 seconds (layer Y), 3 seconds (layer X).
After forming protective layer X, emptying, the system film of end vapor-deposited film.
For the vapor-deposited film that obtains, measure silicon, oxygen, carbon at the composition distribution of film depth direction and the bound energy of Si, be shown in Fig. 1.In addition, average silicon bound energy and average oxidisability x (element is than O/Si) are shown in table 1 with alkali resistance evaluation (film reduction) in the bound energy of each concentration of element on vapor-deposited film surface, oxidisability x, silicon, block middle layer Y.
(comparative example 1)
Adopt method similarly to Example 1 to carry out Cement Composite Treated by Plasma, form the vapor-deposited film that comprises tack coat Z, block middle layer Y.Then, stop to supply with oxygen, between 0.5 second, carry out the making of sealer X immediately and handle, then, emptying, the system film of end vapor-deposited film.
Silicon in this vapor-deposited film, oxygen, carbon are shown in Fig. 3 in the composition distribution of film depth direction and the bound energy of Si, and in addition, the result of each concentration of element on vapor-deposited film surface etc. and alkali resistance evaluation etc. is shown in table 1.
(comparative example 2)
The feed rate of the oxygen when forming sealer X except making is the 2.7sccm, to make vapor-deposited film similarly to Example 1, and carry out similarly to Example 1 analysis and evaluation.The results are shown in table 1.
(comparative example 3)
Except not forming sealer X, make vapor-deposited film similarly to Example 1, and carry out similarly to Example 1 analysis and evaluation.The results are shown in table 1.
Table 1
| Outside surface | The block middle layer | The film reduction | ||||||
| Concentration of element (%) | Silicon bound energy (eV) | Silicon average binding energy (eV) | O/Si oxidisability x | Nm (under 55 ℃, 30 |
||||
| C | O | Si | O/Si | |||||
| Embodiment | ||||||||
| 1 | 51.9 | 26.2 | 21.9 | 1.20 | 101.99 | 103.70 | 2.19 | 0.2 |
| Comparative example 1 | 37.9 | 37.2 | 24.9 | 1.49 | 102.51 | 103.53 | 2.48 | 3.4 |
| Comparative example 2 | 13.2 | 56.0 | 30.8 | 1.82 | 102.80 | 103.71 | 2.27 | 6.6 |
| Comparative example 3 | 2.4 | 65.5 | 32.1 | 2.04 | 103.37 | 103.70 | 2.21 | 13.6 |
By The above results as can be known, satisfy the good alkali resistance of vapor-deposited film demonstration of the embodiment of all above-mentioned conditions (a)～(c).
In addition, Fig. 4～6 show under various conditions the concentration ratio of outside surface of the bottle of making and the relation that film reduces.By these results as can be known: each concentration of element of outside surface satisfies C＞O, C＞Si, and oxidisability x 1.3 shows surface of good protection effect when following, and shows good alkali resistance.
The thermotolerance when forming organic inorganic compounding region alpha and the variation of tack in order to observe in tack coat X, experimental example and comparative experiments example below having carried out.
In these examples, omitted outermost sealer.In addition, in experimental example 1,2 and comparative experiments example 1,2, to be element be in the zone of 1.0～1.8 scopes than (C/Si) to the compound region alpha of organic-inorganic, and in experimental example 3, the compound region alpha of organic-inorganic is element is in 0.2～1.8 scope than (C/Si) zone.
[experimental example 1]
Use and embodiment 1 identical plasma processing apparatus and PET bottle, making the outside pressure of bottle in the treatment chamber is that 7kPa, bottle pressure inside are 10Pa, import the hexamethyldisiloxane (HMDSO) of 2.7sccm, the oxygen of 27sccm, make the pulse microwave vibration by microwave oscillator then, carry out Cement Composite Treated by Plasma.When this plasma body is handled, by making the Strength Changes of microwave, the compound region alpha of organic-inorganic and on form the inorganic nature region beta that comprises the choke film, then emptying finishes the system film of vapor-deposited film.(in addition, the choke film is equivalent to block of the present invention middle layer Y, is C concentration less than 5% zone.)
Microwave intensity that each is regional and plasma treatment time be respectively under 35W 3 seconds (the compound region alpha of organic-inorganic), under 600W 5 seconds (inorganic nature region beta).
In the above-mentioned film of the vapor-deposited film that obtains, the silicon, oxygen, the carbon that adopt the compositional analysis method to measure distribute as shown in Figure 7 at the composition of film depth direction.And the carbon of film depth direction and the element of silicon are than (C/Si) as shown in Figure 8.The result of compositional analysis, the element of carbon and silicon is in carbon in the compound region alpha of organic-inorganic of 1.0～1.8 scopes and silicon than (C/Si) element is 1.0～1.8 scope than (C/Si), the element of oxygen and silicon is than (O/Si), and promptly oxidisability is 2.2～2.4 scope.In addition, the element of carbon and silicon is below 0.2 than (C/Si) in the compound region alpha of organic-inorganic.
In addition, as shown in Figure 9 about the silicon (Si) in the compound region alpha of organic-inorganic and bound energy poor (Δ M) choke film (being equivalent to block middle layer Y).
The bound energy of the elementary composition and metallic element (Si) of film thickness direction distributes as shown in figure 10.
Above-mentioned vapor-deposited film is estimated thermotolerance and tack, and stable on heating evaluation is shown in table 2 with the scope of above-mentioned bound energy poor (Δ M), and in addition, the evaluation of tack is shown in table 3.
[experimental example 2]
Except microwave intensity and plasma treatment time are changed to respectively in 3 seconds (the compound region alpha of organic-inorganic) under the 45W, 5 seconds (inorganic nature region beta) under the 600W, with experimental example 1 similarly, be produced on the vapor-deposited film that has the inorganic nature region beta that comprises the choke film on the compound region alpha of organic-inorganic.
For the result of the compositional analysis of this vapor-deposited film, the element of carbon and silicon is in oxygen in the compound region alpha of organic-inorganic of 1.0～1.8 scopes and silicon than (C/Si) element is 2.2～2.5 scope than (O/Si).In addition, the element of carbon and silicon is that oxidisability is below 0.2 than (C/Si) in the inorganic nature region beta.
In addition, as shown in Figure 9 for the bound energy with the choke film of the silicon (Si) in the compound region alpha of organic-inorganic poor (Δ M).
Above-mentioned vapor-deposited film is estimated thermotolerance and tack, and stable on heating evaluation is shown in table 2 with the scope of above-mentioned bound energy poor (Δ M), and in addition, the evaluation of tack is shown in table 3.
[experimental example 3]
The plasma treatment time that makes the compound region alpha of organic-inorganic prolongs 5 seconds than experimental example 1, with experimental example 1 similarly, be produced on the vapor-deposited film that has formed the inorganic nature region beta that comprises the choke film on the compound region alpha of organic-inorganic.
In the above-mentioned film at this moment, the silicon, oxygen, the carbon that adopt the compositional analysis method to measure distribute as shown in figure 11 at the composition of film depth direction, and the bound energy of the elementary composition and metallic element (Si) of depth direction distributes as shown in figure 12.The result of compositional analysis, the element of carbon and silicon than (C/Si) be the element of oxygen in the compound region alpha of organic-inorganic of 0.2～1.8 scope and silicon than (O/Si), promptly oxidisability is 1.9～2.2 scope.In addition, the element of carbon and silicon is below 0.2 than (C/Si) in the inorganic nature region beta.
In addition, above-mentioned vapor-deposited film is estimated thermotolerance and tack, stable on heating evaluation is shown in table 2 for the element silicon bound energy in the compound region alpha of organic-inorganic with the scope of the bound energy of choke film poor (Δ M), and in addition, the evaluation of tack is shown in table 3.
[comparative experiments example 1]
Use device and the PET bottle same, import the HMDSO of 2.7sccm, under microwave intensity 35W, carry out 0.5 second Cement Composite Treated by Plasma, on PET bottle substrate, form coherent film (organic property zone) as unstripped gas with experimental example 1.Then, import 27sccm oxygen, under microwave intensity 600W, carry out 7.5 seconds Cement Composite Treated by Plasma, on above-mentioned coherent film, form the inorganic nature region beta that comprises the choke film.
The result of compositional analysis, the element of carbon and silicon is in the element of oxygen in the compound region alpha of organic-inorganic of 1.0～1.8 scopes and silicon than (O/Si) than (C/Si), and promptly oxidisability is 1.9～2.2 scope.In addition, the element of carbon and silicon is below 0.2 than (C/Si) in the inorganic nature region beta.
About bound energy silicon (Si) and the choke film poor (Δ M) in the compound region alpha of organic-inorganic as shown in Figure 9.
Above-mentioned vapor-deposited film is estimated thermotolerance, be shown in table 2 with the scope of above-mentioned bound energy poor (Δ M).
[comparative experiments example 2]
Except making microwave intensity is 600W, and forms for 8 seconds beyond organic property zone and the inorganic nature zone to amount to, and fully similarly makes vapor-deposited film with experimental example 1.The result of compositional analysis, the element of carbon and silicon is in the element of oxygen in the compound region alpha of organic-inorganic of 1.0～1.8 scopes and silicon than (O/Si) than (C/Si), and promptly oxidisability is 2.2～2.5 scope.In addition, the element of carbon and silicon is below 0.2 than (C/Si) in the inorganic nature region beta.
In addition, as shown in Figure 9 about the bound energy with the choke film of the silicon (Si) in the compound region alpha of organic-inorganic poor (Δ M).
Above-mentioned vapor-deposited film is estimated tack, be shown in table 3 with the scope of above-mentioned bound energy poor (Δ M).
Table 2
| Scope (eV) with the bound energy difference of choke film | Silicon stripping quantity (ppb) is following 28 days at 55 ℃ | ||
| 23 ℃ of fillings | 87 ℃ of fillings | ||
| Experimental example 1 | 0.1～0.55 | 85 | 81 |
| Experimental example 2 | 0.3～0.7 | 88 | 92 |
| Experimental example 3 | 0.3～0.55 | 87 | 91 |
| Comparative experiments example 1 | 0.5～0.9 | 105 | 175 |
In experimental example 3, the element in the compound region alpha of organic-inorganic is 0.2～1.8 scope than (C/Si).
As shown in Table 2, when the Si bound energy in the compound region alpha of organic-inorganic is in the scope of the low 0.1～0.7eV of bound energy in the resistivity air film (C concentration less than 5% zone) (, the bound energy difference is in the scope of 0.1～0.7eV the time), there is the composition of inorganic nature and organic property well with balance in the coherent film of substrate, shows good thermotolerance., with the scope of the bound energy of choke film poor (Δ M) when bigger than the scope of 0.1～0.7eV, with the coherent film of substrate be the center with the composition of organic property, poor heat resistance.
Table 3
| Scope (eV) with the bound energy difference of choke film | Oxygen transit dose (cc/ days/bottle) | ||
| Before the expansion | After the expansion | ||
| Experimental example 1 | 0.1～0.55 | 0.0015 | 0.0018 |
| Experimental example 2 | 0.3～0.7 | 0.0016 | 0.0018 |
| Experimental example 3 | 0.3～0.55 | 0.0016 | 0.0019 |
| Comparative experiments example 2 | 0.05～0.2 | 0.0016 | 0.0035 |
In experimental example 3, the element in the compound region alpha of organic-inorganic is 0.2～1.8 scope than (C/Si).
As shown in Table 3, when being in the scope of 0.1～0.7eV, there is the composition of inorganic nature and organic property well, shows good thermotolerance with balance in the coherent film of substrate with the scope of the bound energy of choke film poor (Δ M)., with the scope of the bound energy of choke film poor (Δ M) than the scope of 0.1～0.7eV hour, with the coherent film of substrate be the center with the composition of inorganic nature, tack is poor.
Claims (9)
1. vapor-deposited film, it is formed on matrix surface by using organometallic compound and oxidizing gas as the plasma CVD method of reactant gases, wherein,
With metallic element (M), oxygen (O) and 3 kinds of elements of carbon (C) of deriving from above-mentioned organometallic compound is benchmark, and it be the above matrix side tack coat of 5 element %, carbon concentration less than the block middle layer of 5 element % and carbon concentration is sealer more than the 5 element % that above-mentioned vapor-deposited film is divided into carbon concentration;
The carbon of above-mentioned sealer (C) concentration ratio oxygen (O) concentration and metallic element (M) concentration height, and surface at this sealer, the element of expression metallic element (M) oxidisability is below 1.3 than (O/M), and more than the little 1.0eV of mean value of the bound energy of metallic element (M) than the metallic element bound energy in the above-mentioned block middle layer;
In above-mentioned block middle layer, the element of expression metallic element (M) oxidisability is higher and be below 2.4 than (O/M) average specific 1.8.
2. wherein, there is organic inorganic compounding zone in the described vapor-deposited film of claim 1 in above-mentioned matrix side tack coat, and in the compound zone of this organic-inorganic, element satisfies following formula than (C/M) and element than (O/M):
0.2＜C/M＜1.8
1.5≤O/M，
And the bound energy of this metallic element (M) is in the scope than the low 0.1eV～0.7eV of mean value of the metallic element (M) in the above-mentioned block middle layer.
3. the described vapor-deposited film of claim 2 wherein, is removed above-mentioned sealer, and the element in the zone that exists on the compound zone of above-mentioned organic-inorganic satisfies following condition than (C/M):
C/M≤0.2。
4. wherein, there is organic inorganic compounding zone in the described vapor-deposited film of claim 1 in above-mentioned matrix side tack coat, and in the compound zone of this organic-inorganic, element satisfies following formula than (C/M) and element than (O/M):
1.0＜C/M＜1.8
2.0≤O/M，
And the bound energy of this metallic element (M) is in the scope than the low 0.1eV～0.7eV of mean value of the metallic element (M) in the above-mentioned block middle layer.
5. the described vapor-deposited film of claim 4 wherein, is removed above-mentioned sealer, and the element in the zone that exists on the compound zone of above-mentioned organic-inorganic satisfies following condition than (C/M):
C/M≤0.2。
6. the described vapor-deposited film of claim 2, wherein, the bound energy of the metallic element (M) in the compound zone of above-mentioned organic-inorganic increases gradually from the above-mentioned inorganic nature of matrix side direction zone, and the difference of the maximum value of the bound energy of metallic element (M) and minimum value is more than the 0.1eV.
7. the described vapor-deposited film of claim 1, wherein, above-mentioned organometallic compound is silicoorganic compound, metal (M) is silicon (Si).
8. the described vapor-deposited film of claim 1, wherein, above-mentioned matrix is plastics.
9. Plastic Bottle, it has formed the described vapor-deposited film of claim 1 at internal surface.
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| JP2005045015A JP4747605B2 (en) | 2005-02-22 | 2005-02-22 | Deposition film by plasma CVD method |
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| JP2005137982 | 2005-05-11 | ||
| JP137982/2005 | 2005-05-11 | ||
| PCT/JP2006/302426 WO2006090602A1 (en) | 2005-02-22 | 2006-02-07 | Vapor deposited film by plasma cvd method |
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| CN105579227B (en) * | 2013-09-27 | 2017-09-22 | 住友化学株式会社 | Stacked film, Organnic electroluminescent device, photoelectric conversion device and liquid crystal display |
| TWI666121B (en) * | 2013-09-27 | 2019-07-21 | 住友化學股份有限公司 | Laminated film, organic electroluminescence device, photoelectric conversion device, and liquid crystal display |
| CN112041262A (en) * | 2018-05-08 | 2020-12-04 | 罗伯特·博世有限公司 | Method for producing a base for an analysis cell for analyzing biochemical material and analysis cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006233234A (en) | 2006-09-07 |
| CN101163817B (en) | 2010-06-16 |
| JP4747605B2 (en) | 2011-08-17 |
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