JP2008138267A - Method for producing thin film-deposited substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin film-deposited substrate having excellent adhesion between a thin film and a substrate, optical properties and productivity, and having various functions. <P>SOLUTION: The method for producing a thin film-deposited substrate where a thin film is formed by a thin film formation process, comprises: a stage (1) where the substrate is installed in the surface of a cylindrical support, and the cylindrical support is rotated; a stage (2) where a sputtering system provided around the cylindrical support is operated during the rotation of the cylindrical support, so as to deposit a material on the substrate; and a stage (3) where, simultaneously with the stage of depositing the material on the substrate, an ion source apparatus provided separately from the sputtering system along the circumference of the cylindrical body is operated, so as to form the gas plasma of reactive gas, and the material deposited on the substrate and the reactive gas are reacted, as the substrate, the molded body of a resin composition containing: an acrylic resin (a); and an aliphatic polyester based resin (b) is used. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a plastic substrate with a thin film having excellent adhesion between the substrate and the thin film.

Recently, various functional plastic substrates are used in the electric / electronic field, the automobile field, and the like.
For example, in the thin display market represented by a liquid crystal television, for example, there is an increasing demand to obtain clearer images at a lower price as the market scale increases. What is important for realizing this is a functional plastic substrate represented by various optical films and sheets. In this functional plastic substrate, various thin films are formed on the surface of the plastic substrate for the purpose of imparting functions, thereby realizing advanced functions (optical characteristics, conductivity, etc.), productivity, durability, and the like.

  Various methods are known for forming a thin film on such a substrate.

  Among them, by using a sputtering apparatus and an ion source apparatus provided around the rotating cylindrical substrate support disclosed in Patent Document 1, chemical reactions such as deposition of substances and the like and oxidation of deposited films are performed. Is a preferable thin film forming method because a dense thin film can be formed on a substrate with good reproducibility, and a thin film having a uniform thickness can be formed on substrates of various shapes. It is.

  However, when this method is applied to a plastic substrate, there is a problem that the adhesion between the thin film and the substrate becomes insufficient and the thin film is peeled off. In order to make up for the lack of adhesion, surface treatment is performed on the substrate or a thin film is formed after forming an adhesion layer. However, such a method has a problem in productivity.

Japanese Patent No. 2695514

  The present invention uses a sputtering apparatus and an ion source apparatus provided around a rotating cylindrical substrate support, and uses a method in which deposition of a substance, oxidation of a deposited film, and the like are performed alternately in succession, It is an object to form a thin film with high adhesion without performing surface treatment or formation of an adhesion layer on a plastic substrate.

  The present inventors have earnestly devised a method for alternately and alternately depositing a substance and oxidizing a deposited film by using a sputtering apparatus and an ion source apparatus provided around a rotating cylindrical substrate support. As a result of investigation, when a molded body of a resin composition containing an acrylic resin and an aliphatic polyester resin is used as a plastic substrate, a thin film with high adhesion can be obtained without performing surface treatment or forming an adhesion layer in advance. The inventors have found that it can be formed and have arrived at the present invention.

That is, this invention is a manufacturing method of the board | substrate with a thin film which forms a thin film with the thin film formation method containing the following processes (1)-(3), Comprising: Acrylic resin (a) and aliphatic polyester-type resin are used as a board | substrate. A method for producing a substrate with a thin film using a molded product of the resin composition comprising (b);
(1) A step of installing a substrate on a cylindrical support and rotating the cylindrical support;
(2) A step of depositing a substance on the substrate by operating a sputtering device provided around the cylindrical support during rotation of the cylindrical support,
(3) Simultaneously with the step of depositing a substance on the substrate, a reactive plasma gas plasma is formed by operating an ion source device provided apart from the sputtering device along the periphery of the cylindrical support. And reacting the material deposited on the substrate with the reactive gas.

  According to the present invention, it is possible to deposit a substance using a sputtering device and an ion source device provided around a rotating cylindrical substrate support without performing surface treatment or adhesion layer formation on a plastic substrate in advance. And a thin film with excellent adhesion can be formed by the method of alternately and alternately oxidizing the deposited film, etc., so various functions (antireflection, conductivity, electromagnetic shielding, near infrared absorption, It becomes possible to provide a substrate with a dense thin film having ultraviolet cutting properties, high surface hardness, gas barrier properties, antifouling properties, and the like.

  Hereinafter, the present invention will be specifically described.

  In the present invention, thin films that exhibit various functions are formed on a plastic substrate. Examples of such functions include antireflection properties, electrical conductivity, electromagnetic wave shielding properties, near infrared ray absorption properties, ultraviolet ray cutting properties, high surface hardness properties, gas barrier properties, and antifouling properties.

  First, a thin film forming method will be described.

  In the thin film forming method of the present invention, the substrate mounted on the cylindrical support is reacted with (a) at least one sputtering apparatus for depositing the substance and (a) the substance deposited on the substrate. Alternately pass under the at least one ion source device forming a reactive gas plasma for forming a thin film.

The type of the sputtering apparatus used in the present invention is not limited, and for example, a planar magnetoelectric tube or a CNAG rotating magnetoelectric tube can be used. In particular, the sputtering apparatus disclosed in Patent Document 1 can be preferably used.
There is no limitation on the material to be deposited on the substrate by a sputter device, but a metal is preferable, and examples thereof include silicon, tantalum, niobium, tin, indium, and titanium.

The ion source device used in the present invention is not particularly limited as long as it can form reactive gas plasma. For example, a planar magnetoelectric tube or the like can be used. In particular, the ion source device disclosed in Patent Document 1 can be preferably used.
Moreover, as a kind of reactive gas, oxygen, nitrogen, hydrogen, gaseous carbon oxide, etc. are mentioned, for example.

  The sputter device and the ion source device are installed along the circumference of the cylindrical support so as to be separated from each other, and completely separate the zone for the deposition of the material and the zone for the reaction. When the same magneto-electric tube cathode is used for the sputtering device and the ion source device, the reactive gas (for example, oxygen) of the sputtering device is lowered to deposit the material, while the reactive gas of the ion source device is used. It is preferable to generate a plasma having high reactivity for oxidation or the like by increasing the partial pressure of.

In the thin film forming method of the present invention, the substrate and each device can be installed inside or outside (or both) of the cylindrical support. Further, by using a plurality of sputtering devices and ion source devices, the deposition rate can be increased and the number of materials for film formation can be increased.
Each device can be provided in a chamber and can be operated separately, sequentially or simultaneously for reactions such as material deposition and oxidation. For example, in order to quickly and alternately form Ta ₂ O ₅ and SiO ₂ layers, four apparatuses can be provided to sequentially perform tantalum deposition, oxidation, silicon deposition, and oxidation.

  In the thin film formation method of the present invention, one or more atomic layers are deposited each time the substrate passes under the sputtering device by adjusting the relationship between the cathode power of the sputtering device and the rotation speed of the substrate. Can do. Furthermore, by adding cathodes of other materials and adjusting the power to each cathode, an alloy deposited film can be effectively formed at a desired ratio. For example, a NiCr thin film can be formed at a desired ratio from a cathode of Ni and Cr over a wide area simply by adjusting the relative power to the cathode. Furthermore, if a material vapor deposition film is oxidized by an ion source device, a thin film of oxide such as barium copper yttrium known as a superconducting material can be formed.

Next, the substrate in the present invention will be described.
In the present invention, the substrate refers to a member having a flat and / or curved surface, such as a film, a sheet, a plate, an uneven plate, a curved plate, and a tube.

  The plastic substrate used in the present invention is obtained by molding a resin composition containing an acrylic resin (a) and an aliphatic polyester resin (b).

  In the present invention, the acrylic resin refers to a polymer compound containing a polymer of acrylic acid, methacrylic acid and derivatives thereof.

Specific examples of the acrylic resin (a) in the present invention include methacrylic acid esters such as cyclohexyl methacrylate, t-butylcyclohexyl methacrylate, and methyl methacrylate; methyl acrylate, ethyl acrylate, butyl acrylate, and isopropyl acrylate. And those obtained by polymerizing one or more monomers selected from acrylic acid esters such as 2-ethylhexyl acrylate, which may be used alone or in admixture of two or more.
Among these, a homopolymer of methyl methacrylate or a copolymer with other monomers is preferable.

Examples of monomers copolymerizable with methyl methacrylate include alkyl methacrylates other than methyl methacrylate; alkyl acrylates; aromatic vinyl compounds such as styrene, vinyl toluene and α-methyl styrene; acrylonitrile, Vinyl cyanides such as methacrylonitrile; maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; unsaturated carboxylic acid anhydrides such as maleic anhydride; unsaturated acids such as acrylic acid, methacrylic acid and maleic acid Is mentioned.
Among these monomers that can be copolymerized with methyl methacrylate, acrylic acid alkyl esters are particularly excellent in heat decomposability and have high fluidity during molding of methacrylic resins obtained by copolymerizing these. preferable.
These can be used alone or in combination of two or more.

  When alkyl methacrylates are copolymerized with methyl methacrylate, the amount of alkyl acrylates used is preferably 0.1% by weight or more from the viewpoint of thermal decomposition resistance, and 15 from the viewpoint of heat resistance. It is preferable that it is below wt%. The content is more preferably 0.2% by weight or more and 14% by weight or less, and particularly preferably 1% by weight or more and 12% by weight or less.

  As alkyl acrylates, the effect of improving fluidity at the time of molding described above is remarkably obtained only by copolymerizing methyl acrylate and ethyl acrylate with a small amount of methyl methacrylate such as 0.1 to 1% by weight. Therefore, it is preferable.

The weight average molecular weight of the acrylic resin (a) is preferably 50,000 to 200,000. The weight average molecular weight is preferably 50,000 or more from the viewpoint of the strength of the molded product, and preferably 200,000 or less from the viewpoint of molding processability and fluidity. A more preferable range is 70,000 to 150,000.
In the present invention, isotactic polymethacrylate and syndiotactic polymethacrylate can be used simultaneously.

As a method for producing the acrylic resin (a), for example, generally used polymerization methods such as cast polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, and anionic polymerization can be used. It is preferable to avoid the introduction of minute foreign substances as much as possible. From this viewpoint, bulk polymerization or solution polymerization without using a suspending agent or an emulsifier is desirable.
When solution polymerization is performed, a solution prepared by dissolving a mixture of monomers in an aromatic hydrocarbon solvent such as toluene or ethylbenzene can be used. In the case of polymerization by bulk polymerization, the polymerization can be started by irradiation with free radicals generated by heating or ionizing radiation as is usually done.

As the initiator used in the polymerization reaction, any initiator used in radical polymerization can be used. For example, azo compounds such as azobisisobutylnitrile, benzoyl peroxide, lauroyl peroxide, t-butylperoxy An organic peroxide such as -2-ethylhexanoate can be used.
In particular, when polymerization is carried out at a high temperature of 90 ° C. or higher, solution polymerization is common, so that the 10-hour half-life temperature is 80 ° C. or higher and a peroxide that is soluble in the organic solvent used, An azobis initiator is preferred. Specifically, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, cyclohexane peroxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 1, Examples thereof include 1-azobis (1-cyclohexanecarbonitrile) and 2- (carbamoylazo) isobutyronitrile.
These initiators are preferably used in the range of 0.005 to 5% by weight, for example.

As the molecular weight regulator used as necessary in the polymerization reaction, any of those used in radical polymerization can be used. For example, mercaptan compounds such as butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-ethylhexyl thioglycolate are particularly preferable. As mentioned.
These molecular weight regulators are added in a concentration range such that the polymerization degree of the acrylic resin (a) is controlled within a preferable range.

Examples of the aliphatic polyester-based resin (b) of the present invention include, for example, a polymer mainly composed of an aliphatic hydroxycarboxylic acid and a polycondensate of an aliphatic polycarboxylic acid and an aliphatic polyhydric alcohol. And the like.
In the present invention, the main constituent means that the constituent occupies 50% by weight or more.
Specific examples of the polymer mainly containing an aliphatic hydroxycarboxylic acid include polyglycolic acid, polylactic acid, poly-3-hydroxybutyric acid, poly-4-hydroxybutyric acid, poly-4-hydroxyvaleric acid, and poly-3-hydroxyhexane. Specific examples of the polymer mainly comprising a polycondensate of an aliphatic polycarboxylic acid and an aliphatic polyhydric alcohol include polyethylene adipate, polyethylene succinate, polybutylene adipate, and the like. Examples include polybutylene succinate.
These aliphatic polyesters can be used alone or in combination of two or more.

Among these aliphatic polyester resins (b), a polymer containing hydroxycarboxylic acid as a main constituent component is preferable, and a polylactic acid resin is particularly preferably used.
In the present invention, the polylactic acid-based resin is a polymer containing L-lactic acid and / or D-lactic acid as a main constituent component.

In the polylactic acid-based resin, the constituent molar ratio of the L-lactic acid unit and the D-lactic acid unit is preferably 100% for both the L-form and the D-form, and either the L-form or the D-form is preferably 85% or more. More preferably, one is 90% or more, and more preferably one is a 94% or more polymer. In the present invention, poly-L lactic acid mainly composed of L-lactic acid and poly-D lactic acid mainly composed of D-lactic acid can be used simultaneously.
The polylactic acid-based resin may be copolymerized with a lactic acid derivative monomer other than L-form or D-form or other components copolymerizable with lactide. Examples of such components include dicarboxylic acids, polyhydric alcohols, and hydroxycarboxylic acids. Examples include acids and lactones.
The polylactic acid resin can be polymerized by a known polymerization method such as direct dehydration condensation or ring-opening polymerization of lactide. Moreover, it can also be made high molecular weight using binders, such as polyisocyanate, as needed.
The weight average molecular weight range of the polylactic acid-based resin is preferably 30,000 or more from the viewpoint of mechanical properties, and preferably 1,000,000 or less from the viewpoint of processability. More preferably, it is 50,000-500,000, Most preferably, it is 100,000-280,000.

  In addition, the polylactic acid resin may contain 0.1 to 30% by weight of a copolymer component other than lactic acid as long as the object of the present invention is not impaired. Examples of such other copolymer component units include polyvalent carboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones, and the like. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , Azelaic acid, sebacic acid, dodecanedioic acid, fumaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium sulfoisophthalic acid Polyvalent carboxylic acids such as ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglycol, glycerin, trimethyl Aromatic polyhydric alcohol in which ethylene oxide is added to ethylene propane, pentaerythritol, bisphenol A, bisphenol; polyhydric alcohols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; glycolic acid, 3- Hydroxycarboxylic acids such as hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid, hydroxybenzoic acid; glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, Lactones such as β- or γ-butyrolactone, pivalolactone, and δ-valerolactone can be used. These copolymer components can be used alone or in combination of two or more.

  As a method for producing the aliphatic polyester resin (b), a known polymerization method can be used. Particularly, for a polylactic acid resin, a direct polymerization method from lactic acid, a ring-opening polymerization method via lactide, or the like is employed. be able to. Specifically, Hidehito Tsuji, “Polylactide” in Biopolymers Vol. 4 (Wiley-VCH 2002) PP129-178 and Japanese National Patent Publication No. 05-504731 can be preferably used.

  In the present invention, by adding a hydrolysis resistance inhibitor, it is possible to suppress a decrease in molecular weight due to hydrolysis of the aliphatic polyester resin (b) component, and for example, a decrease in strength can be suppressed. Examples of such hydrolysis resistance inhibitors include compounds having reactivity with the carboxylic acid and hydroxyl group that are terminal functional groups of the aliphatic polyester resin (b), such as carbodiimide compounds, isocyanate compounds, and oxozoline compounds. . In particular, carbodiimide compounds having one or more carbodiimide groups in the molecule (including polycarbodiimide compounds) can be melt-kneaded well with the aliphatic polyester resin (b), and hydrolysis is suppressed by adding a small amount of 3% by weight or less. This is preferable because it is possible.

As a carbodiimide compound (including a polycarbodiimide compound) having one or more carbodiimide groups in the molecule, for example, an organic phosphorus compound or an organometallic compound is used as a catalyst, and various polymer isocyanates are used at a temperature of about 70 ° C. or higher. And those which can be synthesized by subjecting to a decarboxylation condensation reaction in a solvent-free or inert solvent.
As the polycarbodiimide, those produced by various methods can be used. Basically, a conventional method for producing polycarbodiimide (US Pat. No. 2,941,956, Japanese Patent Publication No. 47-33279, J. Pat. Chem. 28, 2069-2075 (1963), Chemical Review 981, Vol. 81 No. 4, p619-621) can be used.
Examples of the organic diisocyanate that is a raw material for producing polycarbodiimide include aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate and mixtures thereof. Specifically, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2, Mixture of 4-tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate Sulfonates, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl isocyanate, and 1,3,5-triisopropylbenzene 2,4-diisocyanate.

  The preferred amount of the hydrolysis resistance inhibitor is 0.01 to 50 parts by weight of the hydrolysis resistance inhibitor with respect to 100 parts by weight of the acrylic resin (a) component and the aliphatic polyester resin (b) component. It is preferable. 0.01 weight or more is preferable from the viewpoint of expression of the hydrolysis resistance suppressing effect, and 50 weight part or less is preferable from the viewpoint of optical characteristics. A more preferable range is a range of 0.01 to 30 parts by weight, and a further preferable range is 0.1 to 30 parts by weight.

  In the present invention, the ratio (parts by weight) of the acrylic resin (a) in the resin composition containing the acrylic resin (a) and the aliphatic polyester resin (b) is the acrylic resin (a) and the aliphatic polyester resin. From the viewpoint of adhesion to the thin film, photoelastic coefficient, retardation, strength, heat resistance, etc., the total amount of (b) is 100 parts by weight or more and 0.1 to 99.9 parts by weight. The amount is preferably 20 parts by weight or more and 95 parts by weight or less, more preferably 40 parts by weight or more and 90 parts by weight or less.

The substrate of the present invention preferably has a photoelastic coefficient of −13 × 10 ⁻¹² / Pa or more and 12 × 10 ⁻¹² / Pa or less. The photoelastic coefficient is a coefficient representing the ease with which birefringence changes due to external force, and is described in various literatures (for example, Chemical Review, No. 39, 1998 (published by the Academic Publishing Center)) and is defined by the following formula: Is done.
C _R [/ Pa] = Δn / σ _R
Here, σ _R is extensional stress [Pa], Δn is birefringence when stress is applied, and Δn is defined by the following equation.
Δn = n ₁ −n ₂
Here, n ₁ is a refractive index for light having a polarization plane in a direction parallel to the extension direction, and n ₂ is a refractive index for light having a polarization plane in a direction perpendicular to the extension direction.
The closer the value of the photoelastic coefficient is to zero, the smaller the change in birefringence due to external force, which means that the change in birefringence designed for each application is small, and the optical characteristics are excellent.

The value of the photoelastic coefficient of the substrate is more preferably from −10 × 10 ⁻¹² (/ Pa) to 9 × 10 ⁻¹² (/ Pa), more preferably from −5 × 10 ⁻¹² (/ Pa) to 5 × 10. ^-12 (/ Pa) or less is particularly preferable. Controlling the photoelastic coefficient to such a value can be performed by the blending ratio of both the acrylic resin (a) and the aliphatic polyester resin (b).

Furthermore, the resin composition used for the substrate of the present invention can be blended with arbitrary resin components and additives depending on various purposes within a range that does not significantly impair the effect.
Examples of resin components that may be optionally blended include polyolefins such as polyethylene and polypropylene; styrene resins such as polystyrene and styrene acrylonitrile copolymers; polyamides, polyphenylene sulfide, polyether ether ketone, polyesters other than aliphatic, polysulfones, Examples thereof include thermoplastic resins such as polyphenylene oxide, polyimide, polyetherimide, and polyacetal; and thermosetting resins such as phenol resin, melamine resin, silicone resin, and epoxy resin. One or more types can be used.

  The additive is not particularly limited as long as it is generally used for blending resins and rubber-like polymers. Inorganic fillers, pigments such as iron oxides; lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide; mold release agents; paraffinic process oil, naphthenic process oil, Softeners and plasticizers such as aromatic process oils, paraffins, organic polysiloxanes, and mineral oils; Antioxidants such as hindered phenolic antioxidants and phosphorus heat stabilizers; Hindered amine light stabilizers; benzotriazoles Examples include ultraviolet absorbers; flame retardants; antistatic agents; reinforcing agents such as organic fibers, glass fibers, carbon fibers, and metal whiskers; colorants and other additives.

  The manufacturing method of the resin composition used for the board | substrate of this invention is not restrict | limited in particular, A well-known method can be utilized. For example, using a melt kneader such as a single screw extruder, twin screw extruder, Banbury mixer, Brabender, various kneaders, etc., if necessary, adding an anti-hydrolysis inhibitor and the above-mentioned other components to melt knead Can be manufactured.

Examples of the form of the substrate in the present invention include films and sheets.
The method for molding the substrate is not particularly limited, and the substrate is molded by a known method such as injection molding, sheet molding, blow molding, injection blow molding, inflation molding, extrusion molding, foam molding, cast molding, or the like. Secondary processing molding methods such as pressure forming and vacuum forming can also be used. Of these, extrusion molding and cast molding are preferably used.
At this time, for example, an unstretched film or sheet can be extruded by using an extruder equipped with a T die, a circular die, or the like. When a molded product is obtained by extrusion molding, a material in which various resin components, additives and the like are previously melt-kneaded can be used, or can be molded through melt-kneading during extrusion molding. In addition, by using a solvent common to various resin components, for example, a solvent such as chloroform, methylene dichloride, etc., after dissolving the various resin components, it is possible to cast-mold an unstretched film or sheet by cast drying and solidifying. .
Further, if necessary, an unstretched film or sheet can be uniaxially stretched in the mechanical flow direction and uniaxially stretched in the direction orthogonal to the mechanical flow direction. In addition, a biaxially stretched film and sheet can be produced by stretching by a sequential biaxial stretching method of roll stretching and tenter stretching, a simultaneous biaxial stretching method by tenter stretching, a biaxial stretching method by tubular stretching, or the like.

Next, a specific example of the thin film forming method will be described with reference to schematic views.
1 and 2 are a simplified schematic perspective view and a cross-sectional view of a thin film forming apparatus 10 that can be used in the present invention, respectively. The apparatus 10 includes a housing 11 that forms a vacuum processing chamber and is coupled to a suitable vacuum pump system 12 shown in FIG. The vacuum pump system includes a cryogenic pump or other suitable vacuum pump or combinations thereof for evacuating the vacuum chamber through the exhaust port 13.
The apparatus 10 also includes a cage-like drum 14 that is mounted for rotation about an axis 16 and that has a cylindrical side that is adapted to mount substrates 15 of various shapes and sizes. The substrate 15 can be directly mounted on the drum 14 such that the outer surface or the inner surface of the substrate 15 faces a sputter apparatus that is spaced along the outer periphery or inner periphery of the drum.

  Further, in the apparatus 10, a plurality of magnetoelectric tube increasing sputtering apparatuses 30 and ion source apparatuses 30 are located around the outer periphery of the drum 14. In one example, silicon is deposited using a sputtering device 26, tantalum is deposited using a sputtering device 27, and oxygen is reacted with a material deposited on a substrate by an ion source device 28 to form a material layer (single layer or multilayer). ) To oxides. In this manner, substantially any desired combination of materials and / or their oxides can be achieved by rotating the drum 14 and selectively operating the sputter and ion source devices 26, 27, and 28. It can be selectively formed on a substrate.

For example, by rotating the drum 14 and continuously operating the sputtering devices 26 and 27 while operating the ion source device 28, the device 10 forms a silicon layer having a thickness of several atoms on the substrate. the to silicon oxidized to SiO _2, tantalum can be oxidized to the Ta ₂ O ₅ followed by forming a tantalum layer having a thickness of several atoms. This sequence can be repeated or changed as needed to form a composite optical thin film of precisely controlled thickness SiO ₂ and Ta ₂ O ₅ layers.

An operation example of the thin film forming apparatus 10 will be described.
First, the substrate is mounted on the periphery of a cylindrical support. The vacuum sealed chamber is then evacuated to, for example, 1 × 10 ⁻⁶ torr, and the drum starts to rotate at the selected speed. Next, the sputtering apparatus is operated by flowing a putter gas (typically argon) from the inlet manifold and supplying power from the power supply source to the cathode. Before starting the deposition of the substance, the shutter of the sputtering apparatus is closed so that the deposition does not start. The operation of the ion source device is started simultaneously with the start of the operation of the sputtering device.

Supply a stable and selected power, gas flow and pressure to the sputter and ion source devices and use the drum to operate at the rotational speed required to supply the selected deposition and oxidation rate, and selectively release the shutter. Opening provides the desired deposition and oxidation sequence.
For example, assuming that four sputter devices and ion source devices are located around the periphery of drum 14 in the order of metal 1 sputter device, ion source device, metal 2 sputter device and ion source device, a combination of shutter apertures. Thus, the following thin film is obtained.
1. Metal 1 deposition and oxidation; metal 2 deposition and oxidation → metal 1 oxide over metal 1 oxide (ie, metal 1 sputtering device shutter and ion source device shutter together, then metal 2 deposition Open the shutter of the spatter device and the shutter of the ion source device together)
2. Metal 1; metal 2 and oxidation-> metal 2 oxide on metal 1 3. Metal 1 and oxidation; Metal 2 → Metal 2 on Metal 1 oxide
4). Metal 2; metal 1 and oxidation → metal 1 oxide on metal 2 5. Metal 2 and oxidation; metal 1 → metal 1 on metal 2 oxide
6). Metal 1 and metal 2 simultaneously (ie, simultaneously opening the metal 1 sputtering device and the metal 2 cathode shutter) → a layer of a mixture of metal 1 and metal 2;
7). Metal 1 and metal 2 and oxidation (the shutters of the metal 1 and metal 2 sputtering device and ion source device are opened together) → the mixed oxide of metal 1 and metal 2.

By using a plurality of sputtering apparatuses, it is possible to form a multilayer thin film of various materials in a virtually infinite combination.
When forming a mixture of two or more metals and / or other substances, keep the shutter of the sputter device open and adjust the power, pressure, aperture size and / or number of the sputter device. It is preferable to change the ratio of the metal to the other metal. In general, the thickness of the layer, whether a compound or a mixture, is determined by the length of time that the shutter of the related sputtering apparatus is opened.

For example, a thin film whose composition changes continuously in a direction perpendicular to the plane of the substrate, and thus a thin film whose optical properties change continuously can be formed. The composition distribution is obtained by continuously or periodically changing the power supplied to the sputtering apparatus, or by continuously changing the opening of the sputtering apparatus or the opening of the shutter.

Next, the present invention will be described by way of examples.
Next, the evaluation method and plastic substrate used in the examples will be described.
<1> Evaluation Method <1-1> Measurement of Visibility Reflectivity The following measuring machine was used.
Measuring machine: Photo diode array spectrophotometer “MultiSpec-1500” manufactured by Shimadzu Corporation
<1-2> Measurement of total light transmittance It carried out using the following measuring machines.
Measuring machine: Integral sphere type spectral transmittance measuring machine “DOT-3C” manufactured by Murakami Color Research Laboratory Co., Ltd.
<1-3> Measurement of surface resistance value It measured using the following measuring machines.
Measuring machine: Mitsubishi Chemical Corporation contact type surface resistance meter "MCP-T360"
<1-4> Measurement of adhesion of thin film to substrate A tape peeling test was performed according to the following standards, and the ratio (%) of the area where the thin film remained (the area where peeling did not occur) was measured. When all the thin film remains (when there is no peeling), it becomes 100%, and when all peels, it becomes 0%. The larger this value, the better the result. (In the standard, it is classified into 6 stages, and the state with no peeling of classification 0 corresponds to 100%, and the peeling state of classification 6 corresponds to 0%.)
Standard: JIS K5600-5-6
<1-5> Molecular weight of resin used for substrate GPC [GPC-8020 manufactured by Tosoh, detection RI, column Shodex K- manufactured by Showa Denko
805,801 connection], the solvent was chloroform, the measurement temperature was 40 ° C., and the weight average molecular weight was calculated in terms of commercially available standard polystyrene.

<2> Raw materials used, film preparation <2-1> Acrylic resin (a) (methyl methacrylate / methyl acrylate copolymer) (P-1)
1,1-di-t-butylperoxy-3,3,5-trimethyl was added to a monomer mixture consisting of 89.2 parts by weight of methyl methacrylate, 5.8 parts by weight of methyl acrylate, and 5 parts by weight of xylene. 0.0294 parts by weight of cyclohexane and 0.115 parts by weight of n-octyl mercaptan were added and mixed uniformly.
This solution is continuously supplied to a sealed pressure resistant reactor having an internal volume of 10 liters, polymerized with stirring at an average temperature of 130 ° C. and an average residence time of 2 hours, and then continuously sent to a storage tank connected to the reactor. The volatile matter is removed under a certain condition, and further transferred to the extruder in a molten state. The acrylic resin (a) is a methyl methacrylate / methyl acrylate copolymer (P-1) ) Was obtained.
The copolymer (P-1) had a methyl acrylate content of 6.0% by weight and a melt flow rate value of 230 g, 3.8 kg load measured in accordance with ASTM-D1238 was 1.0 g / It was 10 minutes.
<2-2> Aliphatic polyester resin (b) (polylactic acid) (P-2)
Polylactic acid (copolymer of L-lactic acid and D-lactic acid) which is an aliphatic polyester resin (b) by ring-opening polymerization of lactide using a tin-based catalyst according to the method described in JP-T-05-504731 A pellet of (P-2) was obtained.
The obtained polylactic acid (P-2) had a weight average molecular weight of 176,000.
<2-3> Substrate P-1 and P-2 pellets are placed in a hopper of a Technobel T-die mounting extruder (KZW15TW-25MG-NH type / width 150 mm T-die mounting / lip thickness 0.5 mm). 2 was dry blended at a composition ratio shown in FIG. Extrusion was carried out by adjusting the cylinder temperature of the extruder and the temperature of the T die, and films were obtained under the stretching conditions shown in Tables 1 and 2 with a stretching machine.
Tables 1 and 2 show the composition, molding conditions, stretching conditions, and thickness of the obtained film.

[Examples 1 to 6 and Comparative Example 1]
A substrate with an antireflection coating was obtained by the following method.
Using the apparatus shown in FIGS. 1 and 2, an optical multilayer film was formed on a plastic substrate (film) having the composition shown in Table 1 under the conditions shown below while appropriately turning on / off the sputtering apparatus 1 and the sputtering apparatus 2. . The results are shown in Table 1.

Target of the sputter device 1: Target of the niobium sputter device 2: Gas of the silicon sputter device 1: Argon 300 sccm
Sputtering device 2 gas: Argon 300 sccm
Power of the sputter device 1: 7 kW
Power of the sputter device 2: 7 kW
Ion source device operation: 5 amps, 100 sccm O ₂
Firing after film formation: None

As shown in Table 1, each substrate has a thin (100 nm thick) film composed of a plurality of layers of Nb ₂ O ₅ and SiO ₂ that give very high total light transmittance and low visibility reflectance. Been formed. And in Examples 1-6 using the molded object of the resin composition containing acrylic resin (a) and aliphatic polyester-type resin (b) as a board | substrate, the adhesiveness with respect to the board | substrate of a thin film is a comparative example. The acrylic resin (a) was much better than a single molded body.
Thus, in the present invention, an excellent antireflection thin film could be directly formed on the substrate without performing surface treatment of the substrate or formation of an adhesion layer.

[Examples 7 to 12 and Comparative Example 2]
A substrate with an ITO film was obtained by the following method.
Using the apparatus shown in FIGS. 1 and 2, an optical film made of ITO was formed on a plastic substrate (film) having the composition shown in Table 2 under the following conditions without using one sputtering apparatus. The results are shown in Table 2.

Sputter device target: Indium and tin oxide Sputter device gas: Argon 300 sccm
Power of sputter device: 7kW
Ion source device operation: 5 amps, 100 sccm O ₂

Each substrate was formed with a thin (100 nm thick) ITO film having a high total light transmittance and a low surface resistance. The film was composed of one layer, and QWOT (Quarter Wave Optical Thickness; 1/4 wavelength optical thickness) was 20 nm. And in Examples 7-12 which used the molded object of the resin composition containing acrylic resin (a) and aliphatic polyester-type resin (b) as a board | substrate, the adhesiveness with respect to the board | substrate of a thin film is a comparative example. The acrylic resin (a) was much better than the case of using a single molded body.
Thus, in the present invention, a good ITO film could be directly formed on the substrate without performing surface treatment of the substrate or formation of an adhesion layer.

  The substrate with a thin film produced according to the present invention is excellent in optical characteristics and productivity, and has various functions (antireflection, conductivity, electromagnetic wave shielding, near infrared absorption, ultraviolet cut, high surface hardness, gas barrier) Since the thin film having a good adhesion and antifouling property is attached to the substrate with good adhesion, a cathode ray tube (CRT), a liquid crystal display (LCD), a polarizing plate, a plasma display, various optical filters, other organic EL displays, a field emission display ( FED), surface conduction electron emission display (SED), rear projection television and other various displays can be used by being incorporated or used as glasses, optical waveguides, various window materials and the like.

1 is a simplified schematic perspective view of a thin film forming apparatus that can be used in the present invention. It is a simplified schematic cross-sectional view of a thin film forming apparatus that can be used in the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Thin film forming apparatus 11 Housing 12 Vacuum pump system 13 Exhaust port 14 Drum 15 Substrate 26, 27 Sputter device 28 Ion source device 30 Sputter device or ion source device

Claims (7)

A method for manufacturing a substrate with a thin film, in which a thin film is formed by a thin film forming method including the following steps (1) to (3), wherein the resin includes an acrylic resin (a) and an aliphatic polyester resin (b) as a substrate: A method for producing a substrate with a thin film using a molded article of the composition;
(1) A step of installing a substrate on a cylindrical support and rotating the cylindrical support;
(2) A step of depositing a substance on the substrate by operating a sputtering device provided around the cylindrical support during rotation of the cylindrical support,
(3) Simultaneously with the step of depositing a substance on the substrate, a reactive plasma gas plasma is formed by operating an ion source device provided apart from the sputtering device along the periphery of the cylindrical support. And reacting the material deposited on the substrate with the reactive gas.   The manufacturing method of Claim 1 in which the said thin film contains at least 1 sort (s) selected from an oxide, nitride, hydride, sulfide, a carbon-containing compound, a metal, an alloy, and those composite materials.   The manufacturing method according to claim 2, wherein the thin film contains at least one selected from metals, metal oxides, metal nitrides, and other reacted metal compounds.   The said resin composition contains 0.1-99.9 weight part of acrylic resin (a) with respect to 100 weight part of total amounts of acrylic resin (a) and aliphatic polyester-type resin (b). The manufacturing method of any one of 1-3.   The method according to any one of claims 1 to 4, wherein the acrylic resin (a) is a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and another monomer.   The manufacturing method according to any one of claims 1 to 5, wherein the aliphatic polyester-based resin (b) is a polymer mainly composed of hydroxycarboxylic acid.   The production method according to claim 6, wherein the aliphatic polyester resin (b) is a polylactic acid resin.

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