JP2018197378A - Method of manufacturing laminate - Google Patents

Abstract

To provide a method of manufacturing a laminate which can suppress the yellowing of the thin film layer.SOLUTION: The present invention relates to a method which uses a plasma chemical vapor deposition method to manufacture a laminate comprising a substrate F and a thin film layer deposited on at least one surface of the substrate F. The method includes arranging the substrate F on a pair of film deposition rolls 17, 18, supplying a film deposition gas G comprising a raw material gas and a reactant gas between the pair of film deposition rolls 17, 18, and decomposing and reacting the raw material gas and the reactant gas by plasma discharge occurring between the rolls 17, 18 to thereby deposit a thin film layer on at least one surface of the substrate, the raw material gas being an organic silane compound, and a b* value in an L*a*b* color space of the manufactured laminate being 6 or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for manufacturing a laminate by a plasma chemical vapor deposition method.

  The gas barrier film can be suitably used as a packaging container suitable for filling and packaging articles such as foods and drinks, cosmetics, and detergents. In recent years, a laminate having a gas barrier property has been proposed in which a plastic film or the like is used as a base material and a thin film layer such as silicon oxide, silicon nitride, silicon oxynitride, or aluminum oxide is laminated on one surface of the base material. . For example, Patent Document 1 discloses that a thin film layer is formed on a plastic film by a chemical vapor deposition method (CVD method) such as a plasma chemical vapor deposition method using an organic silicon compound gas and an oxygen gas as raw materials. A laminate obtained in this way is disclosed.

JP 2008-179102 A

However, in the conventional method, the thin film layer may be yellowed. In particular, the present invention may limit the use for electronic devices such as organic EL elements and organic thin film solar cells that require transparency. Found.
Therefore, the objective of this invention is providing the manufacturing method of the laminated body which can suppress yellowing of a thin film layer.

［式中、Ｒ^１は水素原子、アルキル基、シクロアルキル基、アラルキル基、アルコキシ基、ヒドロキシル基、アリール基を示し、Ｒ^２はアルキレン基を示し、Ｒ^３はアルキル基を示し、ｘは１〜４の整数を示す］
で表される化合物である、［２］又は［３］に記載の方法。
［５］反応ガスは酸素を含む、［１］〜［４］のいずれかに記載の方法。
［６］一対の成膜ロール間に供給される反応ガスの体積流量Ｖ_２と原料ガスの体積流量Ｖ_１との流量比（Ｖ_２／Ｖ_１）は、原料ガスに含まれるアルコキシアルキル基含有シラン化合物を完全酸化させるために必要な、反応ガスの体積流量Ｖ_０２と原料ガスの体積流量Ｖ_０１との最小流量比（Ｖ_０２／Ｖ_０１）をＰ_０としたとき、０．９５Ｐ_０〜０．３Ｐ_０である、［２］〜［５］のいずれかに記載の方法。
［７］前記工程において、基材の帯電量は５ｋＶ以下である、［１］〜［６］のいずれかに記載の方法。 As a result of intensive studies in order to solve the above problems, the present inventors have completed the present invention. That is, the present invention includes the following.
[1] A method for producing a laminate comprising a substrate and a thin film layer laminated on at least one surface of the substrate using a plasma chemical vapor deposition method,
A base material is disposed on a pair of film forming rolls, a film forming gas containing a raw material gas and a reactive gas is supplied between the pair of film forming rolls, and the raw material gas and the reactive gas are generated by plasma discharge generated between the rolls. In the L * a * b * color space of the laminate to be produced, comprising the step of laminating and reacting and laminating a thin film layer on at least one surface of the substrate. The b * value is 6 or less.
[2] A method for producing a laminate comprising a substrate and a thin film layer laminated on at least one surface of the substrate using a plasma chemical vapor deposition method,
A base material is disposed on a pair of film forming rolls, a film forming gas containing a raw material gas and a reactive gas is supplied between the pair of film forming rolls, and the raw material gas and the reactive gas are generated by plasma discharge generated between the rolls. And a step of laminating a thin film layer on at least one surface of the base material, and the source gas contains an alkoxyalkyl group-containing silane compound.
[3] According to [1] or [2], the source gas and the reactive gas are decomposed and reacted by plasma discharge generated by supplying power of 50 Hz to 500 kHz between a pair of film forming rolls to which a magnetic field is applied. The method described.
[4] The alkoxyalkyl group-containing silane compound has the following formula (1):

[Wherein, R ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, a hydroxyl group or an aryl group, R ² represents an alkylene group, R ³ represents an alkyl group, and x represents 1 Represents an integer of ~ 4]
The method as described in [2] or [3] which is a compound represented by these.
[5] The method according to any one of [1] to [4], wherein the reaction gas contains oxygen.
[6] The flow rate ratio (V ₂ / V ₁ ) between the volume flow rate V _{2 of the} reaction gas supplied between the pair of film forming rolls and the volume flow rate V ₁ of the source gas is an alkoxyalkyl group contained in the source gas. When the minimum flow rate ratio (V ₀₂ / V ₀₁ ) between the volume flow rate V ₀₂ of the reaction gas and the volume flow rate V ₀₁ of the raw material gas necessary for complete oxidation of the silane compound is P ₀ , 0.95 P ₀ to 0.3P ₀ the method according to any one of [2] to [5].
[7] The method according to any one of [1] to [6], wherein in the step, the charge amount of the base material is 5 kV or less.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body by which the yellowing of the thin film layer was suppressed can be obtained. Thereby, the visibility of the display using this laminated body improves.

It is a schematic diagram which shows an example of the manufacturing apparatus used for this invention.

  The present invention is a method for producing a laminate including a base material and a thin film layer laminated on at least one surface of the base material using a plasma chemical vapor deposition method. In this method, a base material is disposed on a pair of film forming rolls, a film forming gas containing a source gas and a reaction gas is supplied between the pair of film forming rolls, and a material gas is generated by plasma discharge generated between the rolls. And a step (A) in which a thin film layer is laminated on at least one surface of the base material by decomposing and reacting with the reactive gas.

[Base material]
The base material comprises a resin. Examples of the resin include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP) and cyclic polyolefin; polyamide resins; polycarbonate resins; polystyrene resins; Alcohol resin; saponified ethylene-vinyl acetate copolymer; polyacrylonitrile resin; acetal resin; polyimide resin. Among these resins, since they have high heat resistance and a small linear expansion coefficient, polyester resins or polyolefin resins are preferable, and polyester resins such as PET or PEN are more preferable. These resins can be used alone or in combination of two or more. For the purpose of smoothing or the like, the surface of these resins may be coated with another resin and used as a substrate. In addition, when the light transmittance of the laminate is not regarded as important, for example, a base material may be formed using a composite material in which a filler, an additive, or the like is added to the resin.

  Although the thickness of a base material is suitably set in consideration of the stability at the time of manufacturing a laminated body etc., since conveyance of a base material is easy also in a vacuum, it is preferable that it is 5-500 micrometers. Furthermore, since the thin film layer is formed using the plasma chemical vapor deposition method (plasma CVD method), since the discharge is performed through the base material, the thickness of the base material is more preferably 50 to 200 μm, and 50 to 100 μm. It is particularly preferred that In addition, in order to improve the adhesive force with the thin film layer to form, a base material may perform the surface activation process for cleaning the surface. Examples of the surface activation treatment include corona treatment, plasma treatment, and flame treatment.

  A layer different from the thin film layer, for example, a curable organic layer may be laminated on one side or both sides of the substrate. In this case, in the step (A), a thin film layer may be laminated on another layer.

  Below, an example of the method of laminating | stacking an organic layer on the single side | surface or both surfaces of a base material is demonstrated.

The organic layer is stacked by a method including the following step (i).
(I) A step of applying at least one organic substance selected from the group consisting of an acrylate resin, an acrylate monomer, and an acrylate oligomer on a substrate to obtain a coating film When the organic substance contains an acrylate monomer or an acrylate oligomer, a step ( Preferably it includes ii).
(Ii) Step of curing the coating film to obtain a cured film The coating film obtained in step (i) can be an organic layer, or the cured film obtained in step (ii) can be an organic layer. it can.

  The method for applying the organic substance is not particularly limited, but includes a spin coating method, a spray coating method, a blade coating method, a dip coating method, a roller coating method, a wet coating method using a land coating method, or a vapor deposition method. Any of the dry coating methods can be used.

  When applying the organic substance, the organic substance may be dissolved in a solvent. Examples of the solvent used include nonpolar solvents such as xylene, hexane, and cyclohexane, aprotic polar solvents such as toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, DMAc, DMF, γ-butyrolactone, NMP, and DMSO, methanol, ethanol, Examples include protic polar solvents such as isopropanol, diacetone alcohol, and water, and halogen solvents such as chloroform, dichloromethane, and carbon tetrachloride.

  The organic layer contains an acrylate resin. The acrylate resin is preferably a photocurable resin. The photocurable resin is a resin that starts to be polymerized by ultraviolet rays, electron beams, or the like and cures.

  The organic layer may contain a resin other than the acrylate resin to the extent that the effect is not impaired. Specific examples include polyester resins, isocyanate resins, ethylene vinyl alcohol resins, vinyl-modified resins, epoxy resins, phenol resins, urea melamine resins, styrene resins, and alkyl titanates. May be included.

  As the acrylate resin, it is preferable to use a resin containing a structural unit derived from an acrylic monomer having a (meth) acryloyl group as a main component. Here, the “main component” means that the content of the component is 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more with respect to the mass of all components of the organic layer. . Examples of the acrylate resin include acrylate resin, urethane acrylate resin, polyester acrylate resin, epoxy acrylate resin, and polyol acrylate resin. The acrylate resin is preferably an ultraviolet curable acrylate resin, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, or an ultraviolet curable polyol acrylate resin. Here, (meth) acryloyl means acrylate or methacrylate.

  As the acrylate resin, when the temperature change of the elastic modulus of the organic layer surface is evaluated by a rigid pendulum type physical property tester, the temperature at which the elastic modulus of the organic layer surface decreases by 50% or more is preferably 150 ° C. or higher. .

  The organic material may contain one or more of an inorganic filler, an organic filler, and an organic-inorganic composite filler for the purpose of improving the slipperiness of the substrate placed on the film forming roll. Among these, an inorganic filler is preferable because of good optical characteristics and wear resistance, and an inorganic oxide filler is particularly preferable from the viewpoint of improving surface hardness and controlling the refractive index. Specific examples include silica, zirconia, titania, alumina, and the like, and one or more of these may be included.

  The organic substance may contain a photopolymerization initiator for the purpose of facilitating the initiation of photopolymerization. Examples of the photopolymerization initiator include benzophenone and derivatives thereof, benzyldimethyl ketals, α-hydroxyalkylphenones, hydroxyketones, aminoalkylphenones, and the like. Specifically, Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, etc.), Darocure series (for example, Darocur TPO, commercially available from Ciba Specialty Chemicals) Darocur 1173, etc.), Quantacure PDO, Ezacure series (eg, Ezacure TZM, Ezacure TZT, etc.) commercially available from Sartomer, Inc. can be used.

  The organic matter may contain additives other than the filler and the photopolymerization initiator, such as the acrylate resin, to the extent that the performance of the laminate in the present invention is not impaired. Examples of the additive include a leveling agent, a viscosity modifier, an antioxidant, a bluing agent, a dye, and UVA.

  Although it does not specifically limit about the thickness of an organic layer, From a viewpoint of reducing defects, such as uniformity of the thickness of an organic layer, and a crack, 500 nm-5 micrometers are preferable, and, as for the thickness of an organic layer, 1 micrometer-3 micrometers are more preferable.

[Deposition gas]
The film forming gas includes a source gas and a reactive gas.

(Raw material gas)
The source gas contains an organosilane compound. The organosilane compound is preferably an alkoxyalkyl group-containing silane compound containing at least one alkoxyalkyl group. By including an alkoxyalkyl group in the source gas, yellowing of the formed thin film layer can be effectively suppressed. Examples of the alkoxyalkyl group include a methoxymethyl group, a methoxyethyl group, a methoxy-n-propyl group, a methoxy-i-propyl group, a methoxy-n-butyl group, a methoxy-i-butyl group, a methoxy-sec-butyl group, Methoxy-tert-butyl group, ethoxymethyl group, ethoxyethyl group, ethoxy-n-propyl group, ethoxy-i-propyl group, ethoxy-n-butyl group, ethoxy-i-butyl group, ethoxy-sec-butyl group, Ethoxy-tert-butyl group, n-propoxymethyl group, n-propoxyethyl group, n-propoxy-n-propyl group, n-propoxy-i-propyl group, n-propoxy-n-butyl group, n-propoxy- i-butyl group, n-propoxy-sec-butyl group, n-propoxy-tert-butyl group, -Propoxymethyl group, i-propoxyethyl group, i-propoxy-n-propyl group, i-propoxy-i-propyl group, i-propoxy-n-butyl group, i-propoxy-i-butyl group, i-propoxy -Sec-butyl group, i-propoxy-tert-butyl group, n-butoxymethyl group, n-butoxyethyl group, n-butoxy-n-propyl group, n-butoxy-i-propyl group, n-butoxy-n -Butyl group, n-butoxy-i-butyl group, n-butoxy-sec-butyl group, n-butoxy-tert-butyl group, i-butoxymethyl group, i-butoxyethyl group, i-butoxy-n-propyl Group, i-butoxy-i-propyl group, i-butoxy-n-butyl group, i-butoxy-i-butyl group, i-butoxy-sec-butyl group, i-butyl group X-tert-butyl group, sec-butoxymethyl group, sec-butoxyethyl group, sec-butoxy-n-propyl group, sec-butoxy-i-propyl group, sec-butoxy-n-butyl group, sec-butoxy- i-butyl group, sec-butoxy-sec-butyl group, sec-butoxy-tert-butyl group, tert-butoxymethyl group, tert-butoxyethyl group, tert-butoxy-n-propyl group, tert-butoxy-i- Linear or branched C ₁ -1 such as propyl group, tert-butoxy-n-butyl group, tert-butoxy-i-butyl group, tert-butoxy-sec-butyl group, tert-butoxy-tert-butyl group ₆ alkoxy _{C 1-6} alkyl group, and preferably a linear or branched _{C 1-4} A Lucoxy C _1-4 alkyl group. Among these, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, and an ethoxyethyl group are more preferable from the viewpoint that yellowing of the formed thin film layer can be more effectively suppressed. These alkoxyalkyl groups can be used alone or in combination of two or more. In addition, the alkoxyalkyl group-containing silane compound may contain other arbitrary substituents as long as it contains one or more alkoxyalkyl groups.

（式中、Ｒ^１は水素原子、アルキル基、シクロアルキル基、アラルキル基、アルコキシ基、ヒドロキシル基、アリール基を示し、Ｒ^２はアルキレン基を示し、Ｒ^３はアルキル基を示し、ｘは１〜４の整数を示す）
で表される化合物が好ましい。 The alkoxyalkyl group-containing silane compound has the following formula (1):

(Wherein R ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, a hydroxyl group, or an aryl group, R ² represents an alkylene group, R ³ represents an alkyl group, and x represents 1 Represents an integer of ~ 4)
The compound represented by these is preferable.

In the formula (1), R ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, a hydroxyl group, or an aryl group. Examples of the alkyl group include straight chain or branched chain such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, and tert-butyl group. _Examples thereof include a C _1-6 alkyl group, preferably a methyl group or an ethyl group. Examples of the cycloalkyl group include C _5-8 cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Examples of the aralkyl group include C _7-14 aralkyl groups such as a benzyl group and a phenethyl group. Examples of the alkoxy group include linear or branched methoxy groups, ethoxy groups, n-propoxy groups, i-propoxy groups, n-butoxy groups, i-butoxy groups, sec-butoxy groups, tert-butoxy groups, and the like. Examples thereof include a C _1-6 alkoxy group. Examples of the aryl group include C _6-12 aryl groups such as a phenyl group, an alkylphenyl group (such as a methylphenyl group and a dimethylphenyl group), a biphenyl group, and a naphthyl group, and a phenyl group is preferable. Among these, from the viewpoint of suppressing yellowing of the thin film layer, alkyl groups such as a methyl group and an ethyl group are preferable.

In the formula (1), examples of the alkylene group for R ² include a methylene group, an ethylene group, a trimethylene group, a propylene group, an n-butylene group, an i-butylene group, a sec-butylene group, and a tert-butylene group. From the viewpoint of suppressing yellowing of the thin film layer, a methylene group and an ethylene group are preferable. Examples of the alkyl group of R ³ include the alkyl groups exemplified above as R ¹ , and a methyl group and an ethyl group are preferable from the viewpoint of suppressing yellowing of the thin film layer.

In said Formula (1), x is an integer of 1-4, Preferably it is an integer of 1-3, More preferably, it is 1 or 2, More preferably, it is 1. When x is 1 or 2, the (R ¹ ) bonded to Si may be the same or different substituents. When x is 2 to 4, (R ² —O—R ³ ) may be the same or different substituents.

  Specific examples of preferable compounds represented by the formula (1) include, for example, tetra (methoxymethyl) silane, (methoxymethyl) trimethylsilane, di (methoxymethyl) dimethylsilane, methyltri (methoxymethyl) silane, tetra (ethoxy Methyl) silane, (ethoxymethyl) trimethylsilane, di (ethoxymethyl) dimethylsilane, methyltri (ethoxymethyl) silane, tetra (methoxyethyl) silane, (methoxyethyl) trimethylsilane, di (methoxyethyl) dimethylsilane, methyltri ( Methoxyethyl) silane, tetra (ethoxyethyl) silane, (ethoxyethyl) trimethylsilane, di (ethoxyethyl) dimethylsilane, methyltri (ethoxyethyl) silane, (methoxymethyl) triethylsilane, di (methoxy) Methyl) diethylsilane, ethyltri (methoxymethyl) silane, (ethoxymethyl) triethylsilane, di (ethoxymethyl) diethylsilane, ethyltri (ethoxymethyl) silane, (methoxyethyl) triethylsilane, di (methoxyethyl) diethylsilane, ethyltri (Methoxyethyl) silane, (ethoxyethyl) triethylsilane, di (ethoxyethyl) diethylsilane, ethyltri (ethoxyethyl) silane and the like. These compounds can be used alone or in combination of two or more. Of these, (methoxymethyl) trimethylsilane, (ethoxymethyl) trimethylsilane, and (methoxyethyl) trimethylsilane are preferred from the viewpoint of effectively suppressing yellowing of the formed thin film layer, and (methoxymethyl) trimethylsilane is preferred. Is more preferable.

（式中、Ｒ^４〜Ｒ^１５はそれぞれ独立して、水素原子、アルキル基、シクロアルキル基、アラルキル基、アルコキシ基、ヒドロキシル基、アリール基、ビニル基を示し、ｐは０又は１を示し、ｑは２〜４を示す）
で表される化合物が挙げられる。 Moreover, the silane compound which does not contain an alkoxyalkyl group can also be used as an organic silane compound. Such compounds include, for example, the following formulas (2) to (4):

(Wherein R ^{4 to} R ¹⁵ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, a hydroxyl group, an aryl group, or a vinyl group, p represents 0 or 1, q represents 2 to 4)
The compound represented by these is mentioned.

In the formulas (2) to (4), examples of the alkyl group, cycloalkyl group, aralkyl group, alkoxy group, and aryl group of R ^{4 to} R ¹⁵ include those exemplified above as R ¹ . Among these, an alkyl group and an alkoxy group are preferable. q is 2 to 4, preferably 3. In the formula (4), R ¹⁴ and R ¹⁵ bonded to different Si may be the same or different.

  Specific examples of preferable compounds represented by the formulas (2) to (4) include, for example, hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, and hexamethyl. Disilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclo Examples include tetrasiloxane. These compounds can be used alone or in combination of two or more.

(Reactive gas)
As the reaction gas, a gas that reacts with the raw material gas to become an inorganic compound such as oxide or nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. The reaction gas preferably contains oxygen. As the reaction gas for forming the nitride, for example, nitrogen or ammonia can be used. These reaction gases can be used alone or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a reaction gas for forming a nitride are used. Can be used in combination.

  The film forming gas may contain a carrier gas as necessary in order to supply the source gas and the reaction gas between the pair of film forming rolls. Further, the film-forming gas may contain a discharge gas as required in order to generate plasma discharge. As the carrier gas and the discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon, and hydrogen can be used.

[Production method]
The present invention includes a step (A) of forming a thin film layer on at least one surface of the substrate by plasma enhanced chemical vapor deposition (plasma CVD method).

  In the step (A), the film forming gas is supplied to a space between a pair of film forming rolls on which the base material is disposed, and the supplied film forming gas is plasma-discharged to decompose the source gas and the reaction gas. And by making it react, a thin film layer is formed in the at least one surface of the said base material.

  The film forming roll has a function of generating discharge plasma of a film forming gas between a pair of film forming rolls. Such a pair of film forming rolls may be connected to a plasma generating power supply so as to supply electric power between the film forming rolls and function as a pair of counter powers for plasma discharge. The plasma generating power source can generate discharge plasma between the film forming rolls, more specifically, between the film forming rolls. As a power source for generating plasma, a known power source can be used as appropriate, and since plasma CVD can be performed more efficiently, an AC power source that can alternately reverse the polarity of a pair of film forming rolls, etc. Is preferably used. A medium frequency, for example, 50 Hz to 500 kHz, preferably 1 kHz to 300 kHz, more preferably 1 kHz to 200 kHz, can be supplied between the pair of film forming rolls. When the intermediate frequency is in the above range, damage to the film forming roll due to generation of an excessive amount of heat can be suppressed. The applied power can be 100 W to 10 kW, preferably 100 W to 5 kW. When the applied power is equal to or higher than the lower limit value, generation of particles can be suppressed, and when the applied power is equal to or lower than the upper limit value, damage to the film forming roll due to generation of excessive heat can be suppressed.

  Each of the pair of film forming rolls is preferably provided with a magnetic field forming device fixed so as not to rotate even if the film forming roll rotates. The magnetic field forming apparatus can apply a magnetic field to the pair of film forming rolls, and simultaneously form a thin film layer on the surface of the substrate disposed on each film forming roll, so that the film forming rate can be doubled. A known magnetic field forming apparatus may be used as appropriate.

  The pressure for generating the discharge plasma between the pair of film forming rolls can be appropriately selected according to the type of the raw material gas, and is preferably 0.1 to 50 Pa, more preferably 0.1 to 30 Pa. In the case of a low pressure CVD method, the pressure in the space is preferably 0.1 to 10 Pa, more preferably 0.1 Pa to 8.0 Pa.

  A known roll can be appropriately used as the film forming roll, but from the viewpoint of more efficiently forming a thin film layer, the pair of film forming rolls preferably have the same diameter. From the viewpoint of the above, it is preferably 5 to 10 cm. The pair of film forming rolls are preferably arranged so that their central axes are substantially parallel, in particular parallel, on the same plane. By arranging in this way, a thin film layer can be simultaneously formed on the surface of the substrate arranged in each film forming roll, so the film forming rate can be doubled and a thin film layer having the same structure can be formed. . Furthermore, since it is possible to deposit a thin film layer on the surface of the substrate in one film forming roll and further deposit a thin film layer in the other film forming roll, the thin film layer can be formed efficiently. it can.

  The conveyance speed of the substrate conveyed by the film forming roll or the like can be appropriately selected according to the type of source gas and the space pressure between the pair of film forming rolls, preferably 0.1 to 100 m / min, more preferably 0. 3 to 20 m / min. Generation | occurrence | production of the flaw resulting from the heat | fever in a base material can be suppressed as a conveyance speed is more than the said lower limit, and it can suppress that the thickness of a thin film layer becomes too thin as it is below the said upper limit.

Preferably, SiO ₂ or SiO _x C _y (0 <x <2, 0 <y <2) is generated by the decomposition reaction of the raw material gas containing the alkoxyalkyl group-containing silane compound and the reaction gas to form a thin film layer. . In the present invention, since the source gas preferably contains an alkoxyalkyl group-containing silane compound, SiO _x C _y (0 <x <2, 0 <y <2) in which yellowing is suppressed can be formed. Here, in the step (A), the ratio of the raw material gas and the reactive gas supplied to the space between the pair of film forming rolls is such that the raw material gas and the reactive gas are completely reacted (the raw material gas is completely oxidized). Therefore, it is preferable not to exceed the reaction gas ratio that is theoretically required. This is because, when the alkoxyalkyl group-containing silane compound contained in the source gas is completely oxidized, a SiO ₂ layer is formed, and a SiO _{x Cy} layer is not formed, that is, an unoxidized carbon atom in the silane compound Is not taken into the thin film layer, which is disadvantageous from the viewpoint of gas barrier properties. On the other hand, when the ratio of the reaction gas is too small, carbon atoms that have not been oxidized are excessively taken into the thin film layer, and the transparency of the thin film layer may be lowered. For this reason, the flow rate ratio (V ₂ / V ₁ ) between the volume flow rate V _{2 of the} reaction gas supplied between the pair of film forming rolls and the volume flow rate V ₁ of the raw material gas contains the alkoxyalkyl group contained in the raw material gas. When the minimum flow rate ratio (V ₀₂ / V ₀₁ ) between the volume flow rate V ₀₂ of the reaction gas and the volume flow rate V ₀₁ of the raw material gas necessary for complete oxidation of the silane compound is P ₀ , it is preferably 0.95 P _{0 to} 0.30P ₀ , more preferably 0.80P _{0 to} 0.40P ₀ , and still more preferably 0.70P _{0 to} 0.50P ₀ . When the flow rate ratio V ₂ / V ₁ is less than or equal to the above upper limit, in the thin film layer, it is possible to effectively suppress a decrease in transparency due to excess carbon atoms derived from the alkoxyalkyl group-containing silane compound, and the flow rate ratio V ₂ / V. _{When 1} is equal to or more than the lower limit, in the thin film layer, it is possible to effectively suppress a decrease in gas barrier properties due to an excessive amount of carbon atoms derived from the alkoxyalkyl group-containing silane compound.

The minimum flow rate ratio P ₀ (V ₀₂ / V ₀₁ ) is obtained as follows. For example, when (methoxymethyl) trimethylsilane [(CH ₃ ) ₃ Si—CH ₂ OCH ₃ ] is used as the source gas and oxygen is used as the reaction gas, the following reaction formula ( i):
_{(CH 3) 3 Si-CH} 2 OCH 3 + 9O 2 → 5CO 2 + 7H 2 O + SiO 2 (i)
Reaction takes place and SiO ₂ is produced. In such a reaction, the amount of oxygen for completely oxidizing 1 mol of (methoxymethyl) trimethylsilane is 9 mol. Therefore, the minimum flow rate ratio P ₀ is V ₀₂ / V ₀₁ = 9.

  The flow rate of the source gas is preferably 10 to 1000 sccm, more preferably 20 to 500 sccm, still more preferably 30 to 100 sccm, based on 0 ° C. and 1 atmospheric pressure. The flow rate of the reaction gas is preferably 10 to 10000 sccm, more preferably 100 to 1000 sccm, and more preferably 200 to 500 sccm on the basis of 0 ° C. and 1 atmospheric pressure.

  In the step (A), the charge amount of the base material is 5 kV or less, preferably 4 kv or less, more preferably 3 kv or less. When the amount is not more than the above upper limit value, it is possible to prevent dust from adhering to the base material and to suppress a decrease in gas barrier properties due to the occurrence of pinhole defects in film formation. Furthermore, the occurrence of spark discharge can also be prevented, and a reduction in gas barrier properties due to damage to the substrate can be suppressed. In addition, it is preferable that the charge amount of the base material on at least a later-described feed roll is in the above range.

  Moreover, what laminated | stacked the thin film layer previously on the single side | surface or both surfaces of a base material may be used for a process (A). In the step (A), it is preferable to form a thin film layer by a roll-to-roll method from the viewpoint of productivity.

  Since the present invention is a manufacturing method by plasma chemical vapor deposition using a predetermined film-forming roll containing an organic silane compound, preferably an alkoxyalkyl group-containing silane compound as a raw material, the yellowing of a thin film layer is suppressed. A laminate having a good gas barrier property can be produced efficiently. For this reason, the laminated body obtained by this invention can be utilized for electronic device uses, such as an organic EL element and an organic thin film solar cell by which transparency is especially calculated | required.

  In the step (A), in addition to the film forming roll, a feed roll, a plurality of transport rolls, and a take-up roll can be used to transport the substrate. When the base material transported from the feed roll is transported by the transport roll and the film forming roll, a thin film layer is formed on the surface when passing through the film forming roll. The laminated body (or laminated film) obtained by this is wound up by a winding roll. Known feed rolls, transport rolls, and take-up rolls can be used. Further, a known gas supply pipe or the like may be used to supply the film forming gas to the space between the pair of rolls. In order to perform plasma discharge of the film forming gas under the above pressure, it is preferable to arrange at least the film forming roll and the gas supply pipe in a vacuum chamber or the like.

  Hereinafter, the manufacturing method according to an embodiment of the present invention will be described with reference to FIG. 1, but the present invention is not limited to the embodiment according to FIG. 1.

  FIG. 1 is a schematic view showing an example of a manufacturing apparatus used in the present invention, and is a schematic view of an apparatus for forming a thin film layer by a plasma chemical vapor deposition method. In FIG. 1, the dimensions and ratios of the constituent elements are adjusted as appropriate for easy viewing of the drawing. For this reason, a dimension, a ratio, etc. can be changed suitably.

  1 includes a feed roll 11, a take-up roll 12, transport rolls 13 to 16, a first film forming roll 17, a second film forming roll 18, a gas supply pipe 19, a plasma generating power source 20, and electrodes. 21, an electrode 22, a magnetic field forming device 23 installed inside the first film forming roll 17, and a magnetic field forming device 24 installed inside the second film forming roll 18.

  Among the components of the manufacturing apparatus 10, at least the first film forming roll 17, the second film forming roll 18, the gas supply pipe 19, the magnetic field forming apparatus 23, and the magnetic field forming apparatus 24 are used for manufacturing a laminate (laminated film). In a vacuum chamber (not shown). This vacuum chamber is connected to a vacuum pump (not shown). The pressure inside the vacuum chamber is adjusted by the operation of the vacuum pump.

  When this apparatus is used, the discharge of the film forming gas supplied from the gas supply pipe 19 to the space between the first film forming roll 17 and the second film forming roll 18 is controlled by controlling the plasma generating power source 20. Plasma can be generated, and plasma CVD film formation can be performed by a continuous film formation process using the generated discharge plasma.

  The feed roll 11 is arranged in a state where the base material F before film formation is wound up, and the base material F is sent out while being unwound in the longitudinal direction. Moreover, the winding roll 12 is provided in the edge part side of the base material F, winds up pulling the base material F after film-forming was performed, and accommodates in roll shape. The first film-forming roll 17 and the second film-forming roll 18 extend in parallel and face each other.

  Both rolls are made of a conductive material and convey the substrate F while rotating. It is preferable to use the 1st film-forming roll 17 and the 2nd film-forming roll 18 with the same diameter, and a diameter is 5 cm-100 cm. The first film-forming roll 17 and the second film-forming roll 18 are insulated from each other and connected to a common plasma generation power source 20. When an AC voltage is applied from the plasma generating power source 20, an electric field is formed in the space SP between the first film forming roll 17 and the second film forming roll 18. The plasma generation power source 20 preferably has an applied power of 100 W to 10 kW, and an AC frequency of preferably 50 Hz to 500 kHz.

  The magnetic field forming device 23 and the magnetic field forming device 24 are members that form a magnetic field in the space SP, and are stored in the first film forming roll 17 and the second film forming roll 18. The magnetic field forming device 23 and the magnetic field forming device 24 are fixed so as not to rotate together with the first film forming roll 17 and the second film forming roll 18 (that is, the relative posture with respect to the vacuum chamber does not change). .

  The magnetic field forming device 23 and the magnetic field forming device 24 are arranged around the center magnets 23a and 24a extending in the same direction as the extending directions of the first film forming roll 17 and the second film forming roll 18 and the center magnets 23a and 24a. It has annular outer magnets 23b and 24b arranged extending in the same direction as the extending direction of the first film forming roll 17 and the second film forming roll 18 while being enclosed. In the magnetic field forming device 23, magnetic lines (magnetic field) connecting the central magnet 23a and the external magnet 23b form an endless tunnel. Similarly, in the magnetic field forming device 24, the magnetic field lines connecting the central magnet 24a and the external magnet 24b form an endless tunnel.

  A discharge plasma of the film forming gas is generated by the magnetron discharge in which the magnetic field lines intersect with the electric field formed between the first film forming roll 17 and the second film forming roll 18. That is, as will be described in detail later, the space SP is used as a film formation space for performing plasma CVD film formation, and a surface that does not contact the first film formation roll 17 and the second film formation roll 18 on the substrate F (film formation). A thin film layer in which a deposition gas is deposited via a plasma state is formed on the surface).

  In the vicinity of the space SP, there is provided a gas supply pipe 19 for supplying a film deposition gas G containing a plasma CVD source gas and reaction gas into the space SP. The gas supply pipe 19 has a tubular shape extending in the same direction as the extending direction of the first film forming roll 17 and the second film forming roll 18, and the space SP is opened from openings provided at a plurality of locations. A film forming gas G is supplied to the substrate. In FIG. 1, the state in which the film forming gas G is supplied from the gas supply pipe 19 toward the space SP is indicated by arrows.

  As the source gas and the reactive gas, the source gas and the reactive gas exemplified above are used, and the flow rate and ratio thereof can also be selected from the ranges exemplified above. Note that the film forming gas may contain the carrier gas and the discharge gas. The pressure in the vacuum chamber (degree of vacuum), that is, the pressure in the space SP is preferably 0.1 to 50 Pa. The power of the electrode drum of the plasma generator is preferably 100 W to 10 kW. The conveyance speed (line speed) of the substrate F is preferably 0.1 to 100 m / min.

In the manufacturing apparatus 10, film formation is performed on the base material F as follows. That is, a thin film layer is formed on the surface of the substrate F. First, prior to film formation, a pretreatment may be performed so that outgas generated from the substrate F is sufficiently reduced. The amount of outgas generated from the base material F can be determined using the pressure when the base material F is mounted on a manufacturing apparatus and the inside of the apparatus (inside the chamber) is decompressed. For example, if the pressure in the chamber of the manufacturing apparatus is 1 × 10 ⁻³ Pa or less, it can be determined that the amount of outgas generated from the substrate F is sufficiently reduced.

  Examples of a method for reducing the amount of outgas generated from the substrate F include vacuum drying, heat drying, drying by a combination thereof, and drying by natural drying. Regardless of the drying method, in order to promote the drying of the inside of the base material F wound up in a roll shape, the roll is rewinded (unwinded and wound) repeatedly during the drying, and the whole base material F is obtained. Is preferably exposed to a dry environment.

  The vacuum drying is performed by putting the base material F in a pressure-resistant vacuum vessel and evacuating the vacuum vessel using a decompressor such as a vacuum pump. The pressure in the vacuum vessel during vacuum drying is preferably 1000 Pa or less, more preferably 100 Pa or less, and even more preferably 10 Pa or less. The exhaust in the vacuum vessel may be continuously performed by continuously operating the decompressor, and intermittently by operating the decompressor intermittently while managing the internal pressure so that it does not exceed a certain level. It is good also to do. The drying time is preferably at least 8 hours or more, more preferably 1 week or more, and further preferably 1 month or more.

  Heat drying is performed by exposing the base material F to an environment of room temperature or higher. The heating temperature is preferably room temperature to 200 ° C., more preferably room temperature to 150 ° C. At a temperature exceeding 200 ° C., the substrate F may be deformed. Moreover, when an oligomer component elutes from the substrate F and precipitates on the surface, defects may occur. The drying time can be appropriately selected depending on the heating temperature and the heating means used.

  Any heating means may be used as long as it can heat the substrate F to room temperature to 200 ° C. under normal pressure. Among the generally known apparatuses, an infrared heating apparatus, a microwave heating apparatus, and a heating drum are preferably used. An infrared heating device is a device that heats an object by emitting infrared rays from an infrared ray generating means. A microwave heating device is a device that heats an object by irradiating microwaves from microwave generation means. A heating drum is a device that heats a drum surface by heat conduction by heating the drum surface and bringing an object into contact with the drum surface.

  The natural drying is performed by placing the base material F in a low humidity atmosphere and maintaining the low humidity atmosphere by passing dry gas (dry air, dry nitrogen). When performing natural drying, it is preferable to arrange a desiccant such as silica gel together in a low-humidity environment where the substrate F is arranged. The drying time is preferably 8 hours or more, more preferably 1 week or more, and further preferably 1 month or more. These dryings may be performed separately before the substrate F is mounted on the manufacturing apparatus, or may be performed in the manufacturing apparatus after the substrate F is mounted on the manufacturing apparatus. As a method of drying after mounting the base material F on the manufacturing apparatus, the inside of the chamber can be decompressed while the base material F is sent out and conveyed from the feed roll. Moreover, the roll to pass shall be provided with a heater, and it is good also as heating this roll as the above-mentioned heating drum by heating a roll.

  Another method for reducing outgas from the substrate F is to form an inorganic film on the surface of the substrate F in advance. Examples of the film formation method for the inorganic film include physical film formation methods such as vacuum vapor deposition (heating vapor deposition), electron beam (Electron Beam, EB) vapor deposition, sputtering, and ion plating. The inorganic film may be formed by a chemical deposition method such as thermal CVD, plasma CVD, or atmospheric pressure CVD. The influence of outgas may be further reduced by subjecting the base material F having an inorganic film formed on the surface to a drying treatment by the above-described drying method.

  Next, a vacuum chamber (not shown) is set in a reduced pressure environment and applied to the first film forming roll 17 and the second film forming roll 18 to generate an electric field in the space SP. At this time, since the magnetic field forming device 23 and the magnetic field forming device 24 form the above-described endless tunnel-like magnetic field, by introducing the film forming gas, the magnetic field and the electrons emitted into the space SP are used. Then, a discharge plasma of a doughnut-shaped film forming gas is formed along the tunnel. Since this discharge plasma can be generated at a low pressure in the vicinity of several Pa, the temperature in the vacuum chamber can be in the vicinity of room temperature.

  On the other hand, since the temperature of electrons captured at high density in the magnetic field formed by the magnetic field forming device 23 and the magnetic field forming device 24 is high, discharge plasma is generated due to collision between the electrons and the deposition gas. That is, electrons are confined in the space SP by a magnetic field and an electric field formed in the space SP, so that high-density discharge plasma is formed in the space SP. More specifically, a high-density (high-intensity) discharge plasma is formed in a space that overlaps with an endless tunnel-like magnetic field, and a low-density (low-density) in a space that does not overlap with an endless tunnel-like magnetic field. A strong (intensity) discharge plasma is formed. The intensity of these discharge plasmas changes continuously.

  When the discharge plasma is generated, a large amount of radicals and ions are generated and the plasma reaction proceeds, and a reaction between the source gas contained in the film forming gas and the reactive gas occurs. For example, as described above, the alkoxyalkyl group-containing silane compound, which is a raw material gas, reacts with oxygen, which is a reaction gas, to cause an oxidation reaction of the alkoxyalkyl group-containing silane compound.

  Here, in a space where high-intensity discharge plasma is formed, a large amount of energy is imparted to the oxidation reaction, so that the reaction is likely to proceed, and a complete oxidation reaction of the alkoxyalkyl group-containing silane compound can be caused mainly. On the other hand, in a space where a low-intensity discharge plasma is formed, the reaction is difficult to proceed because there is little energy given to the oxidation reaction, and an incomplete oxidation reaction of the alkoxyalkyl group-containing silane compound can be caused mainly.

In the present specification, the “complete oxidation reaction of an alkoxyalkyl group-containing silane compound” means that the reaction between the alkoxyalkyl group-containing silane compound and oxygen proceeds, and the alkoxyalkyl group-containing silane compound has the above reaction formula (i ) And oxidative decomposition to SiO ₂ , water and carbon dioxide.

Further, in the present specification, the "incomplete oxidation reaction of alkoxy group-containing silane compound", without the alkoxyalkyl group-containing silane compound is complete oxidation reaction, SiOxCy (0 containing carbon in the SiO ₂ without structure < It means that the reaction is such that x <2, 0 <y <2).

As described above, in the manufacturing apparatus 10, the discharge plasma is formed in a donut shape on the surfaces of the first film forming roll 17 and the second film forming roll 18. The base material F transported on the surface alternately passes through the space where the high-intensity discharge plasma is formed and the space where the low-intensity discharge plasma is formed. Therefore, the surface of the base material F that passes through the surfaces of the first film-forming roll 17 and the second film-forming roll 18 contains a large amount of SiO ₂ generated by the complete oxidation reaction (referred to as a H _a1 layer or a H _a2 layer). in, including many SiOxCy caused by incomplete oxidation reaction layer _{(the H b1} layer or _{H b2} layer) is formed is sandwiched. For example, a laminate composed of a base material F / HA layer (H _a1 layer / H _b1 layer / H _a1 layer) / HB layer (H _a2 layer / H _b2 layer / H _a2 layer) in the order of lamination. Is formed.

  In addition to these, high-temperature secondary electrons are prevented from flowing into the base material F due to the action of the magnetic field, so that high power can be input while the temperature of the base material F is kept low, and high-speed film formation is achieved. Is done. Film deposition mainly occurs only on the film-forming surface of the base material F, and the film-forming roll is covered with the base material F and is not easily soiled.

  In one embodiment, the laminate produced according to the present invention has at least an HA layer and an HB layer. First, it is preferable to form the HB layer after forming the HA layer on the substrate side. When forming the HB layer, it is preferable to form the film at a temperature higher than the temperature of the film surface at the time of forming the HA layer. As a method for controlling the temperature of the film surface, 1. Lower the pressure during film formation in the vacuum chamber. 2. Increase the applied power from the plasma generating power source. 3. Reduce the flow rate of source gas (and the flow rate of reaction gas). 4. Decrease the conveyance speed of the substrate F 5. Raise the temperature of the film forming roll itself. For example, the frequency of the power source for generating plasma during film formation may be lowered. Select one of these conditions 1-6, fix other conditions, optimize the selected conditions, and may form a film so as to have an appropriate temperature during film formation, The film may be formed by changing two or more of these conditions and optimizing the film so as to obtain an appropriate temperature during film formation. Note that the conditions 1 to 4 and 6 are preferably optimized within the above-mentioned range. Regarding the condition 5 above, the surface temperature of the first film-forming roll 17 and the second film-forming roll 18 is preferably −10 to 80 ° C. In this way, the film formation conditions are defined, and a laminated body can be formed by forming a thin film layer on the surface of the substrate by plasma CVD using discharge plasma.

[Laminate]
The laminated body obtained by this invention contains a base material and the thin film layer laminated | stacked on the at least one surface of this base material. Since this laminated body has suppressed the yellowing of the thin film layer in a manufacture process, transparency is favorable and it has favorable gas barrier property. For this reason, it can utilize suitably for electronic device uses, such as an organic EL element and an organic thin film solar cell.

  Since the laminate obtained by the present invention has little or no yellowing (yellowishness), the b * value in the L * a * b * color space, which is an index showing yellowing (yellowishness), is preferably 6 or less. More preferably, it is 3 or less, More preferably, it is 1.5 or less. In addition, b * value shows the value measured using the spectrophotometer used for the measurement of the object color based on JISZ8722.

  The thickness of the base material of the laminate is preferably 5 to 500 μm, more preferably 50 to 200 μm, and still more preferably 50 to 100 μm.

The thin film layer preferably comprises SiO ₂ and SiOxCy (0 <x <2, 0 <y <2). The thickness of the thin film layer is preferably 5 nm to 3000 nm, more preferably 10 nm to 2000 nm, and still more preferably 100 nm to 1000 nm. Gas barrier property improves that the thickness of a thin film layer is more than the said lower limit. Further, when the thickness of the thin film layer is not more than the above upper limit value, it is effective for reducing warpage, reducing coloring, suppressing deterioration of gas barrier properties when bent, and the like.

  When the laminate has a layer in which two or more thin film layers are laminated, the total thickness of the thin film layers is preferably 100 nm to 3000 nm. Gas barrier property improves that the total value of the thickness of a thin film layer is 100 nm or more. When the total thickness of the thin film layers is 3000 nm or less, a high effect of suppressing a decrease in gas barrier properties when bent is obtained. The thickness per thin film layer is preferably larger than 50 nm.

  Although a laminated body has a base material and a thin film layer, it may have a curable organic layer on another layer, for example, a thin film layer, as needed.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, the measurement of yellowing (yellowishness) in a laminated body was implemented in accordance with the following method.

[Measurement of yellowing]
Laminates 1 and 2 were cut to 5 cm × 5 cm, and the chromaticity was measured using a spectrocolorimeter (“Konica Minolta“ CM3700A ”, light source D65 manufactured by Konica Minolta, Inc.) used for measuring the object color in accordance with JIS Z 8722. b * values were measured.

[Example]
The laminated body 1 (laminated film 1) was manufactured using the manufacturing apparatus as shown in FIG. That is, a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films Ltd., trade name “Teonex Q65FA”) is used as a base material (base material F), and this is sent out. Mounted on the roll 11. A film-forming gas {source gas [(methoxymethyl) trimethylsilane] is formed in a space between the first film-forming roll 17 and the second film-forming roll 18 where an endless tunnel-like magnetic field is formed. And a reaction gas (oxygen gas mixed gas) are supplied to supply power to the first film forming roll 17 and the second film forming roll 18, respectively. In the meantime, plasma discharge was performed, and the substrate was conveyed from the delivery roll 11 via the first film-forming roll 17 and the second film-forming roll 18, and taken up by the take-up roll 12. The charge amount of the base material applied to the delivery roll 11 was 2 kv. This was repeated twice to obtain a laminate 1. The obtained laminate 1 had a b * value of 1.0, and the thickness of the thin film layer of the laminate 1 was 600 nm. A thin film was formed by plasma CVD under the following film formation conditions.

(Deposition conditions)
Supply amount of raw material gas: 50 sccm (0 ° C., 1 atm standard)
Supply amount of oxygen gas: 250 sccm (0 ° C., 1 atm standard)
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.5 m / min

In this embodiment, since the amount of oxygen for completely oxidizing 1 mol of trimethylsilane is 9 mol, the minimum flow rate ratio P ₀ is V ₀₂ / V ₀₁ = 9. Therefore, the flow rate ratio (V ₂ / V ₁ ) between the volume flow rate V ₂ of the reaction gas and the volume flow rate V ₁ of the raw material gas at this time was 0.56P ₀ .

[Comparative example]
A laminated body 2 (laminated film 2) was obtained in the same manner as in Example except that hexamethyldisiloxane was used instead of (methoxymethyl) trimethylsilane as a raw material gas. The charge amount of the base material applied to the delivery roll 11 was 2 kv. The obtained laminate 2 had a b * value of 7.0, and the thickness of the thin film layer of the laminate 2 was 600 nm.

As in the comparative example, when hexamethyldisiloxane [(CH ₃ ) ₃ Si—O—Si (CH ₃ ) ₃ ] is used as the source gas and oxygen is used as the reaction gas, the source gas, the reaction gas, The following reaction formula (ii):
_{(CH 3) 3 Si-O} -Si (CH 3) 3 + 12O 2 → 6CO 2 + 9H 2 O + 2SiO 2 (ii)
Reaction takes place and SiO ₂ is produced. In this reaction, since the amount of oxygen for completely oxidizing 1 mol of hexamethyldisiloxane is 12 mol, the minimum flow rate ratio P ₀ is V ₀₂ / V ₀₁ = 12. Therefore, the flow rate ratio (V ₂ / V ₁ ) between the volume flow rate V ₂ of the reaction gas and the volume flow rate V ₁ of the raw material gas at this time was 0.42P ₀ .

  It was confirmed that the laminate 1 obtained in the example has a significantly lower b * value than the laminate 2 obtained in the comparative example, that is, the yellowing is significantly less. Therefore, it was confirmed that the yellowing of the thin film layer in the laminate was significantly suppressed in the example as compared with the comparative example.

DESCRIPTION OF SYMBOLS 10 ... Manufacturing apparatus, 11 ... Sending roll, 12 ... Winding roll, 13-16 ... Conveyance roll, 17 ... 1st film-forming roll, 18 ... 2nd film-forming roll, 19 ... Gas supply pipe, 20 ... For plasma generation Power source, 23, 24 ... Magnetic field forming device, F ... Base material (film), SP ... Space (deposition space)

Claims (7)

A method for producing a laminate comprising a base material and a thin film layer laminated on at least one surface of the base material using plasma chemical vapor deposition,
A base material is disposed on a pair of film forming rolls, a film forming gas containing a raw material gas and a reactive gas is supplied between the pair of film forming rolls, and the raw material gas and the reactive gas are generated by plasma discharge generated between the rolls. In the L * a * b * color space of the laminate to be produced, comprising the step of laminating and reacting and laminating a thin film layer on at least one surface of the substrate. The b * value is 6 or less. A method for producing a laminate comprising a base material and a thin film layer laminated on at least one surface of the base material using plasma chemical vapor deposition,
A base material is disposed on a pair of film forming rolls, a film forming gas containing a raw material gas and a reactive gas is supplied between the pair of film forming rolls, and the raw material gas and the reactive gas are generated by plasma discharge generated between the rolls. And a step of laminating a thin film layer on at least one surface of the base material, and the source gas contains an alkoxyalkyl group-containing silane compound.   The method according to claim 1 or 2, wherein the raw material gas and the reactive gas are decomposed and reacted by plasma discharge generated by supplying electric power of 50 Hz to 500 kHz between a pair of film forming rolls to which a magnetic field is applied. The alkoxyalkyl group-containing silane compound has the following formula (1):

[Wherein, R ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, a hydroxyl group or an aryl group, R ² represents an alkylene group, R ³ represents an alkyl group, and x represents 1 Represents an integer of ~ 4]
The method of Claim 2 or 3 which is a compound represented by these.   The method according to claim 1, wherein the reaction gas contains oxygen. The flow rate ratio (V ₂ / V ₁ ) between the volume flow rate V _{2 of the} reaction gas supplied between the pair of film forming rolls and the volume flow rate V ₁ of the source gas is the same as that of the alkoxyalkyl group-containing silane compound contained in the source gas. When the minimum flow rate ratio (V ₀₂ / V ₀₁ ) between the volume flow rate V ₀₂ of the reaction gas and the volume flow rate V ₀₁ of the raw material gas necessary for complete oxidation is P ₀ , 0.95P _{0 to} 0.3P The method according to claim 2, which is _zero .   The method according to claim 1, wherein in the step, the charge amount of the base material is 5 kV or less.

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