JP2008138268A - Method for producing substrate having thin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin film-fitted substrate having excellent adhesion between a thin film and a substrate, optical properties and productivity, and having various functions. <P>SOLUTION: In the method for producing a thin film-fitted substrate where, using a thin film deposition device at least comprising: (A) a substrate carrying means; (B) a sputtering means provided along the circumference of the substrate carrying means; and (C) a plasma generating means provided separately from the sputtering means along the circumference of the substrate carrying means, a vapor-deposited film is deposited on a substrate by a sputtering means, thereafter, the vapor-deposited film and plasma generated by the plasma generating means are brought into reaction, so as to deposit a thin film, as the substrate, a molded body of a resin composition comprising: (a) an acrylic resin; and (b) an aliphatic polyester-based resin 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 thin film forming apparatus having a sputtering means and a plasma generation means provided along the periphery of the substrate transport means disclosed in Patent Document 1, vapor deposition of a vapor deposition material such as metal and deposition film The continuous reaction method significantly reduces the time required for film formation, can form various compound thin films such as oxides, nitrides, hydrides, and carbides, and even on curved substrates. Since a thin film with a sufficient thickness can be formed with good reproducibility, this is a preferable thin film forming method.

  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.

Patent No. 3064301

  The present invention uses a thin film forming apparatus having a sputtering means and a plasma generating means provided along the periphery of the substrate transport means, and uses a thin film forming method for continuously performing vapor deposition and the reaction of the vapor deposition film. It is an object to form a thin film with high adhesion on a plastic substrate without performing surface treatment or formation of an adhesion layer on the substrate.

  The present inventors have earnestly studied a thin film forming method in which vapor deposition and a reaction between the deposited films are continuously performed by using a thin film forming apparatus having a sputtering unit and a plasma generating unit provided along the periphery of the substrate transfer unit. As a result of investigation, when a molded product of a resin composition containing an acrylic resin and an aliphatic polyester resin is used as a plastic substrate, the surface of the plastic substrate is not required even if surface treatment or adhesion layer formation is not performed on the substrate in advance. The inventors have found that a thin film having high adhesion can be formed, and have reached the present invention.

That is, the present invention
Using a thin film forming apparatus having at least the following (a) to (c), after forming a deposited film on a substrate by sputtering means, the deposited film and the plasma generated by the plasma generating means are reacted to form a thin film. A method for manufacturing a substrate with a thin film to be formed, the method using a molded body of a resin composition containing an acrylic resin (a) and an aliphatic polyester resin (b) as a substrate;
(A) Substrate transport means,
(A) Sputtering means provided along the periphery of the substrate transport means;
(C) Plasma generating means provided apart from the sputtering means along the periphery of the substrate transport means.

  According to the present invention, using a thin film forming apparatus having a sputtering means and a plasma generation means provided along the periphery of the substrate transport means without performing surface treatment or adhesion layer formation on the substrate in advance. By continuously performing the reaction between the vapor deposition and the vapor deposition film, a thin film with high adhesion can be formed on the plastic substrate. Therefore, the optical properties and productivity are excellent by a simple method, and various functions (antireflection, conductivity, It is possible to provide a substrate with a thin film having electromagnetic wave shielding properties, near-infrared absorbing properties, ultraviolet ray cutting properties, high surface hardness properties, 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 apparatus used in the present invention will be described.

  In the present invention, the substrate is attached to the substrate transporting means so that the thin film forming surface faces the sputtering means and the plasma generating means, and sputtering means for depositing a deposition material, followed by the material deposited on the substrate, It passes under plasma generating means for forming plasma for reaction.

The substrate transport means in the thin film forming apparatus used in the present invention is not particularly limited. Specifically, the serial translation type substrate transport means, the rotary cylindrical drum support, and the continuous winding wound around the rotary cylindrical drum. Examples thereof include a substrate conveying means disclosed in Patent Document 1 such as a moving belt.

The sputtering means in the thin film forming apparatus used in the present invention is not particularly limited as long as the target material can be vapor-deposited. For example, a planar magnetoelectric tube or a CNAG rotating magnetoelectric tube can be used. In particular, the linear magnetron enhanced sputtering apparatus disclosed in Patent Document 1 can be preferably used.
The target material, that is, the vapor deposition material deposited on the substrate by sputtering means is not limited, and examples thereof include silicon, tantalum, niobium, tin, indium, and titanium.

The plasma generated by the plasma generating means in the thin film forming apparatus used in the present invention collides with the material deposited by sputtering on the substrate to form a compound with this material.
Accordingly, the plasma generating means is not particularly limited as long as it can form plasma for forming a compound by reacting with a vapor deposition material, and for example, a plasma magnet or the like capable of forming DC or RF plasma is used. be able to. In particular, the linear magnetron ion source device disclosed in Patent Document 1 can be preferably used.
There is no limitation on the plasma to be generated, but plasma of reactive gas such as oxygen, nitrogen, hydrogen, carbon oxide is particularly preferable.

  In the thin film forming apparatus used in the present invention, it is preferable that the substrate carrying means, the sputtering means, and the plasma generating means are provided in the vacuum chamber.

  The sputtering unit and the plasma generation unit are provided so as to be separated from each other along the outer side, the inner side, or both of the periphery of the substrate transfer unit. Therefore, the elongate zone for vapor deposition and the elongate zone for reaction are completely physically separated. When the same magnetron cathode is used for the sputtering means and the plasma generating means, the vapor deposition is performed by lowering the partial pressure of the active gas (oxygen etc.) of the sputtering means, while the partial pressure of the active gas of the plasma generating means is increased. Thus, a strong reaction plasma that generates a reaction such as oxidation is generated.

  By using a plurality of sputtering means and plasma generating means, it is possible to increase the deposition rate and the types of substances to be deposited.

Moreover, there is no limitation on the structure of the sputtering means and the plasma generating means, and various structures can be employed in order to deposit various substances separately, sequentially or simultaneously and to react, for example, oxidize. For example, two sputtering means and two plasma generation means are selectively disposed and operated sequentially, and tantalum deposition and oxidation, titanium deposition and oxidation are sequentially performed, and Ta ₂ O ₅ and TiO ₂ stacked alternately. This layer can be formed quickly.

  In the present invention, by adjusting the electric power applied to the cathode of the sputtering means and the substrate transport speed (rotation speed in the case of the rotary cylindrical drum type transport means), 1 is used when the substrate passes under the sputtering apparatus. A deposited film having a thickness equal to or larger than the atomic layer can be formed. Furthermore, by providing a sputtering means for depositing two or more different metals and adjusting the power to each cathode, it is possible to efficiently produce a desired ratio of the deposited alloy film. For example, by adjusting the ratio of electric power to the cathode of each sputtering means, a NiCr thin film having a desired ratio can be formed from a Ni and Cr sputtering means over a wide area. Further, by generating oxygen gas plasma by the plasma generating means, a complex oxide thin film such as barium copper yttrium oxide known as a superconductor material can be formed.

  In the present invention, a thin film can be rapidly and uniformly formed on a flat substrate or a curved substrate having a large volume by using a rotating cylindrical drum as the substrate transport means. In particular, by providing a double rotating planetary gear mounting structure, which will be described later, a thin film can be uniformly formed over the entire periphery of a substrate having a complicated shape such as a tube or polyhedron.

  Further, by using a serial translation type substrate transport means, a thin film can be quickly and uniformly deposited on a large and flat substrate.

In the case of metal deposition, the deposition rate per input electric power is high, and the deposition and heat are diffused on the surface of a large number of substrates and a large substrate transport means. In addition, since the substrate is not heated so much, a coating can be rapidly formed even on a low melting point plastic substrate.
In comparison, in the conventional reactive oxide sputtering method, the film formation rate is 10 angstrom / second or less regardless of the target, but according to the method of the present invention, about 100 for Ta ₂ O _5. Film formation rates of -150 angstroms / second and about 100 angstroms / _second for SiO ₂ can be achieved.

Next, the substrate in the present invention will be described.
In the present invention, the substrate means a thin film formed body, the shape thereof is not limited, and a film having a flat and / or curved surface, a sheet, a plate, an uneven plate, a curved plate, Tubes etc. are included.

  The 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 the group of acrylic acid esters such as 2-ethylhexyl acrylate, which can be used alone or in combination.
Among these, a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and another monomer 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, alkyl acrylates are particularly preferred because of their excellent thermal decomposition resistance and high fluidity during molding of methacrylic resins obtained by copolymerizing these. .

  These can be used alone or in combination of two or more.

  The amount of alkyl acrylates used when methyl acrylate is copolymerized with methyl methacrylate is preferably 0.1% by weight or more from the viewpoint of heat decomposability, 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.

  Among the alkyl acrylates, in particular, methyl acrylate and ethyl acrylate can improve the fluidity during the molding process just by copolymerizing a small amount of 0.1 to 1% by weight with methyl methacrylate. This is most preferable because it can be obtained remarkably.

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- Organic peroxides such as 2-ethylhexanoate can be used.
In particular, when the polymerization is carried out at a high temperature of 90 ° C. or higher, solution polymerization is common, so that the peroxide has a 10-hour half-life temperature of 80 ° C. or higher and 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.

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 composed of a polycondensate of an aliphatic polyvalent carboxylic 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.

The polylactic acid-based 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, neopentyl glycol, glycerin, trimethyl Aromatic propane, pentaerythritol, bisphenol A, polyhydric alcohols such as aromatic polyhydric alcohol obtained by addition reaction of bisphenol with ethylene oxide, 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, for example, “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 range of the acrylic resin (a) and the aliphatic polyester. From 0.1 to 99.9 parts by weight with respect to the total amount of 100 parts by weight of the resin (b) in terms of adhesion to the thin film, photoelastic coefficient, retardation, strength, heat resistance, etc. Is more preferably 20 parts by weight or more and 95 parts by weight or less, and particularly 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 _x -n _y
Here, n _x is a refractive index for light having a polarization plane in the direction of elongation parallel to the direction, n _y is the refractive index for light having a polarization plane in the stretching direction perpendicular to the 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 −10 × 10 ⁻¹² / Pa or more and 9 × 10 ⁻¹² / Pa or less, and −5 × 10 ⁻¹² / Pa or more and 5 × 10 ⁻¹² / Pa. It is particularly preferred that The photoelastic coefficient can be controlled to such a value by adjusting the blending ratio of the acrylic resin (a) and the aliphatic polyester resin (b).

Furthermore, arbitrary resin components and additives can be blended in the resin composition used for the substrate of the present invention in accordance with various purposes within a range that does not significantly impair the effect.
As resin components that may be optionally blended, 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, mineral oils; antioxidants such as hindered phenol 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 a hydrolysis inhibitor and other ingredients as described above, and melt kneading. Can be manufactured.

A preferred form of the substrate in the present invention includes a film and a sheet.
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 stretched uniaxially in the machine flow direction and uniaxially stretched in the direction perpendicular to the mechanical flow direction. A biaxially stretched film can also 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 schematic perspective view and a horizontal sectional view, respectively, of a specific example of a thin film forming apparatus according to the present invention. The thin film forming apparatus 10 includes a vacuum chamber 11 connected to a suitable vacuum pump system 12 shown in FIG. The vacuum pump system evacuates the vacuum chamber 11 through an exhaust port 13 and includes a cryopump or other suitable vacuum pump or combination thereof.
The thin film forming apparatus 10 includes a cage-type drum 14 as a substrate transfer means, and this drum is rotatably mounted around a shaft 16 and is attached to a cylindrical side surface on which various shapes and sizes of substrates 15 are mounted. have. The substrate 15 is disposed outwardly toward the sputtering means spaced apart around the outer peripheral surface of the drum, or inwardly toward the sputtering means spaced apart along the inner peripheral surface of the drum, It can be mounted directly on the drum 14.

  The device 10 may be provided with one or more double-rotation planetary gear attachment devices 25 in combination with or in place of the drum 14, as shown in FIG. This double-rotation planetary gear device may be provided only on the drum, or may be provided in combination with a single-rotation (not planetary-rotation) substrate 15 attached to the drum. This planetary gear device mounts a tubular substrate 18 and imparts a double rotational motion thereto. The sun gear 19 rotates the attached planetary gear 21 around the rotation shaft 21A and the rotation shaft 16A of the sun gear. In the example of FIG. 3, the planetary gear 21 is connected to a series of gears 22, which are attached to a shaft and rotate around its axis 22A. On the other hand, the tubular substrate 18 is attached to the planetary gear support shaft, and rotates around the shaft 22A together with the shaft. When the drum 14 and the sun gear 19 are rotated along the reversible path 16P around the shaft 16A by the planetary gear mounting device, the planetary gear 21 is rotated along the path 21P around the shaft 21A. 22 is converted into a rotational motion of the tubular substrate 18 along the path 18P around the axis 22A. This double rotational movement of the sun gear 19 and the planetary gear 21 enhances the ability to uniformly form a thin film on the entire substrate having a complicated shape such as a tubular shape.

  In the apparatus 10, a plurality of sputtering means and plasma generating means are arranged around the outer peripheral surface of the drum 14. In one example, the sputtering means 26 deposits a material such as silicon on the substrate, the sputtering means 27 causes another material such as tantalum to be deposited on the deposition substrate, and the plasma generating means 28 generates a gas plasma such as oxygen to generate a gas plasma on the substrate. The deposited film is converted into an oxide by reacting with the deposited film. In this way, by rotating the drum 14 and selectively operating the sputtering means and the plasma generating means 26, 27 and 28, the metal and / or its oxide is selectively combined on the substrate in any combination. Can be formed.

For example, by rotating the drum 14 and sequentially operating each means in the order of 26, 28, 27, 28, the thin film forming apparatus 10 forms a silicon layer having a thickness of several atoms and oxidizes the silicon to SiO ₂ . Then, a tantalum layer with a thickness of several atoms can be deposited and the tantalum can be oxidized to Ta ₂ O ₅ . This procedure can be repeated and modified as needed to form a precisely controlled thickness SiO ₂ and Ta ₂ O ₅ composite optical coating.

  As the plasma generating means 28, the same means as the sputtering means 28 and 27 may be used except that the gas of the sputtering means 28 and 27 is changed from argon to oxygen.

An oxide dielectric thin film or the like can be formed by using a linear magnetron enhanced sputtering apparatus 30 for the sputtering means 26 and / or 27 and another type of apparatus for the plasma generating means 28. Alternatively, the same type of linear magnetron enhanced sputtering apparatus 30 with baffle plates can be used for 27 and the plasma generating means 28. In any case, the sputtering means and the plasma generating means are housed in separate partial pressure regions or chambers, and the substrate passes alternately under them by a continuously rotating drum.
When a linear magnetron enhanced sputtering apparatus 30 with a baffle plate is used for both sputtering and plasma generation, the apparatus 30 uses a metal target such as silicon, tantalum, niobium, tin, indium, titanium, and the like in the vacuum chamber 10. It can be operated at a relatively high power density in an oxygen atmosphere. The linear magnetron enhanced sputtering apparatus 30 used as the sputtering means 26 and 27 performs the deposition at a high speed by operating under a relatively low reactive gas (oxygen) partial pressure. Such a low oxygen partial pressure can be realized by supplying an inert gas such as argon from the manifold 37. On the other hand, the linear magnetron sputtering apparatus 30 used as the plasma generating means 28 operates under a relatively high reactive gas partial pressure to perform vapor deposition on the transfer substrate at a very low speed, and at a high speed the vapor deposition film. Oxidize. This very low rate deposition has little effect on the overall deposition rate, so it is highly reactive to promote the reaction between the oxygen in the chamber and the deposited film without affecting the overall control. Plasma can be generated. As a result, a relatively low oxygen partial pressure can be used as a whole, which increases the stability and deposition rate of the sputtering means. Such reactive sputtering methods can form reproducible thin films that are vapor deposited at high speed, fully oxidized, and have good optical properties.

  A specific example of another thin film forming apparatus is shown in FIG. The apparatus 60 includes a pair of cryopumps (vacuum pumps) 12-12 positioned on opposite sides of the vacuum chamber, and a plurality of silicon sputtering means 26 facing outwardly provided on the inside of the drum 14 serving as a substrate transfer means. And a tantalum sputtering means 27 and an inward plasma generation (oxidation) means 28 provided outside the drum 14. The thin film forming apparatus includes a planetary gear substrate mounting drive device 25 in order to uniformly expose the periphery of a substrate having a shape such as a tube to both the inner sputtering means and the outer plasma generating means. With this planetary gear substrate mounting apparatus, a plurality of silicon sputtering means, tantalum sputtering means, and plasma generation (oxidation) means, formation of silicon and tantalum layers and oxidation of these layers can be performed on a large number of substrates at high speed. it can. For example, a composite layer composed of SiO 2 and Ta 2 O 5 operates a plurality of silicon sputtering means 26 at the same time, then activates the plasma generation (oxidation) means 28 in the upper right of FIG. The plasma generation (oxidation) means 28 at the lower left of FIG.

  Yet another specific example is shown in FIG. The apparatus 65 includes a pair of vacuum pump systems 12-12 and four rotating drums or substrate transfer means 14, each of which includes a silicon sputtering apparatus 26, a tantalum sputtering means 27, and a plasma generation (oxidation) means. 28.

Yet another specific example is shown in FIG. This apparatus 70 applies the thin film forming method of the present invention to a flexible sheet substrate. This apparatus 70 is a single layer without causing the problem of a rise in substrate temperature and a low deposition rate, which has been a problem when a thin film of dielectric material or the like is conventionally deposited on a roll of a flexible substrate. Alternatively, a multilayer dielectric thin film is deposited by sputtering at a high speed.
The apparatus 70 includes a rotating drum 14A, an inner rewinding roll 71, and an inner winding roll 72, which jointly rewind a flexible sheet or substrate transport belt 73 that is a substrate. The material is unwound from the roll 71, continuously moved around the drum 14 </ b> A, passed under the sputtering means 26 and 27, and the plasma generating means 28, and taken up on the inner take-up roll 72.
Using this apparatus 70, a thin film can be formed on the flexible sheet substrate 73 itself or on the substrate 15 mounted on a substrate transport belt.

  When forming a multilayer film in the apparatus 70, the flexible sheet or substrate transport belt 73 is rewound and the thin film forming process is repeated.

An example of operation of the thin film forming apparatus having the above-described rotary type substrate transfer means will be described.
First, the substrate is attached around a drum which is a rotary substrate transfer means. Next, the vacuum chamber is evacuated to, for example, 1 × 10 ⁻⁶ torr, and drum rotation at a predetermined speed is started. Next, a sputtering gas (for example, argon) is circulated through the inlet manifold and power is supplied to the cathode from the attached power source to start the sputtering apparatus. Until the deposition is started, the shutter of the sputtering means is closed to prevent the deposition. After starting the sputtering means, the plasma generating means 40 is started. Oxygen or other desired reactive gas or mixture thereof is introduced from the inlet manifold, and power is supplied from the power source to start the plasma generating means. When the operating state of the sputtering means and the plasma generating means is stable, that is, the power, the gas flow rate and the gas pressure are stable, and the drum is operated at a constant rotational speed to enable stable deposition and oxidation, the sputtering means and By selectively listening to the shutter of the plasma generating means, desired deposition and oxidation can proceed.
For example, four sputtering means and oxidation plasma generation means are arranged around the drum 14 in the order of metal 1 sputtering means, oxidation plasma generation means, metal 2 sputtering means and oxidation plasma generation means, and the shutter is opened. The following thin film can be obtained by the combination.
1. Metal 1 deposition, oxidation, metal 2 deposition, oxidation → metal 1 oxide on metal 1;
2. Metal 1, metal 2, oxidation-> metal 2 oxide on metal 1;
3. Metal 1, oxide, metal 2 → metal 1 on metal 1 oxide 2;
4). Metal 2, metal 1, oxidation → metal 1 oxide on metal 2;
5. Metal 1, oxide, metal 1 → metal 1 on metal 2 oxide;
6). Metal 1 and metal 2 simultaneously (ie, simultaneously opening the shutter of the metal 1 sputtering means and the shutter of the metal 2 sputtering means) → mixture of metal 1 and metal 2;
7). Simultaneous oxidation of metal 1 and metal 2 → Mixed oxide of metal 1 and metal 2

By using a plurality of sputtering means, it is possible to form innumerable combinations of multilayer thin films from various substances.
When forming a mixture of two or more metals and / or other materials, keep the shutter of the sputtering means open and adjust the power, pressure, aperture size and / or number of one of them. The deposition amount ratio of the metal (substance) to the other metal (substance) can be changed.
In general, the thickness of the layer of any compound or mixture is determined by the length of time that the shutter of the sputtering means is open.

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

Next, a thin film forming apparatus having serial translation type substrate transfer means will be described.
FIG. 7 is a schematic view of a thin film forming apparatus having serial translation type substrate transfer means suitable for forming a thin film on a flat substrate. The device 80 has the advantage of being able to coat very large, flat substrates over the aforementioned rotary mold. The apparatus 80 has three basic chambers: a loading vacuum chamber 81, a vacuum processing chamber 82, and a removal vacuum chamber 83. Each chamber is provided with an independent pump system 84 and an independent high vacuum valve 86. The vacuum processing chamber 82 can be isolated from the loading and removal vacuum chambers by vacuum locks 87 and 88. The substrate is loaded into the apparatus through the vacuum lock 87 of the loading vacuum chamber 83, that is, the door 89, and removed from the apparatus through the vacuum lock 91 of the removal vacuum chamber 83. The chamber, whose cross section is shown in FIG. 7, is a thin, flat box that can be mounted horizontally or vertically.

  Substrate transfer means such as endless conveyor belts 92, 93, 94 are provided in the chamber.

  The loading conveyor 92 is used to move the substrate at position 95 from the loading vacuum chamber 81 through a vacuum lock 87 to position 96 in the vacuum processing chamber 82. The vacuum processing chamber conveyor 93 transports the substrate to the position 97 through the sputtering means, the plasma generation means 101-104 in the direction of the entrance position 95 to 99 quickly at a constant speed and to the position 97. In the direction, return to position 96. The removal conveyor 94 receives the substrate by a vacuum lock 88 and carries it into the removal vacuum chamber 83. According to circumstances, a conveyor may be arranged outside the loading vacuum chamber 81 and the removal vacuum chamber 83 so that the substrate can be sent to the loading vacuum chamber 81 and the substrate can be taken out of the removal vacuum chamber 83. Can do.

As described above, the vacuum processing chamber 82 includes four chambers including the outer plasma generating means 101, the intermediate or inner sputtering means 102 and 103, and the plasma generating means 104.
A baffle plate 106 is provided between the sputtering means 102 and 103 and the plasma generation means 101 and 104 to insulate them.

  The sputtering means and the plasma generating means are set so as to form elongated deposition zones and reaction zones along the transport directions 99 and 100, and these zones are larger than the substrate in the width direction of the substrate transport means.

In the example shown in FIG. 8, the vacuum processing chamber 82A has a sputtering means and a plasma generation means arranged in two upper and lower stages instead of the sputtering means and the plasma generation means arranged in a row 107 as in the apparatus 80 of FIG. I have. In the configuration shown in FIG. 8, a thin film can be formed on both sides of the substrate 96 simultaneously, and one side of each of the two substrates attached back to back can be coated simultaneously.
FIG. 9 shows another example 80B comprising a vacuum processing chamber 82 and a loading vacuum chamber 81 that also functions as a removal vacuum chamber. This example can be used when a separate loading and removal vacuum chamber cannot be provided due to cost or space concerns.
FIG. 10 illustrates a third example 80C that includes a loading vacuum chamber 81, a removal vacuum chamber 83, and a vacuum processing chamber 82B consisting of two independent processing chambers 82-82 separated by a vacuum lock 109. Show. This example is useful in order to improve the throughput of the entire apparatus or when the reaction in the two rows 107-107 of the sputtering means and the plasma generating means must be highly insulated.

An operation example of the serial translation type thin film forming apparatus of FIGS. 7 to 10 will be described.
Initially, the vacuum locks or doors 87, 88, and 91 are closed and the removal vacuum chamber 83 is evacuated to a background pressure of about ^10-6 torr. The substrate 92 is then loaded into the loading vacuum chamber 81 through the vacuum lock 89, and then the vacuum lock 89 is closed and the loading vacuum chamber is evacuated, typically to 10 ⁻⁶ torr. The lock 87 is then opened, the substrate is fed into position 96 in the vacuum processing chamber 82, the lock 87 is closed, and argon is introduced into the sputtering means 102 and 103. Next, electric power is supplied to the cathodes of the sputtering means 102 and 103, and sputtering of the metal M 1 by the sputtering means 102 and metal M 2 by the sputtering means 103 is started. During this period, the shutters of the sputtering means 102 and 103 are kept closed until the sputtering state is stabilized. Next, a reactive gas such as oxygen is put into the plasma generating means 101 and 104, and an appropriate bias voltage is applied to the plasma generating means to operate.

  In order to start the thin film formation, a shutter covering the opening of the sputtering means 102 is opened, and the substrate 96 is fed to the position 97 in the direction 99 at a constant speed, and then returned to the position 96 in the opposite direction 100. In general, the transport speed and sputtering conditions are adjusted so that a deposited film not exceeding three atomic layers is deposited by one transport and an oxide of about 20 Å is formed by one reciprocal transport. This forward and reverse transport cycle is repeated until the desired thickness of metal M1 oxide is formed on the substrate. When it is formed, the shutter of the sputtering means 102 is closed.

  Next, a shutter covering the sputtering means 103 is opened, and the above-described process is repeated to deposit a metal M2 layer to a desired thickness. The two metal oxide deposition steps can be repeated until the desired multilayer combination is deposited on the substrate. Further, by closing the shutter of the plasma generating means when the substrate passes through the row 107 of the sputtering means and the plasma generating means, a metal M1 and / or M2 layer can be provided (that is, the metal is oxidized). Can be formed without).

After the desired thin film is formed, the pressure in the removal vacuum chamber 83 is increased to a pressure equivalent to the pressure in the vacuum processing chamber 82. The vacuum lock 88 is opened, and the substrate 97 on which the thin film is formed is carried into a position 98 in the vacuum chamber 83 for removal. The vacuum lock 88 is closed and the vacuum chamber 83 for removal is raised to atmospheric pressure. The lock 91 is then opened so that the substrate at position 94 can be removed from the removal vacuum chamber.
In the apparatus 80 having the serial translation type substrate transfer means, the loading of the new substrate into the loading vacuum chamber 81 and the removal of the previously processed substrate from the removal vacuum chamber 83 are synchronized with the thin film formation process. It is also possible to operate in continuous mode.

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 According to the following standards. A tape peeling test was performed, 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> About used raw materials and films <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. Add 0.0294 parts by weight of cyclohexane and 0.115 parts by weight of n-octyl mercaptan and mix 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). And 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, a plastic substrate (film) having the composition shown in Table 1 at a processing temperature of about 60 ° C. or less under the following conditions while appropriately turning on / off the sputtering means 1 and the sputtering means 2. An optical multilayer film was formed thereon. The results are shown in Table 1.

  In this apparatus, the diameter of the drum is 29 inches, the rotation speed is 48 rpm, the sputtering means and the plasma generation means use an aperture having an insulating baffle with a width of 5 inches, and the sputtering means has a width of 5 inches. I used the target.

Target of sputtering means 1: Titanium Target of sputtering means: Silicon Gas of sputtering means 1: Argon 600 sccm
Gas of sputtering means 2: argon 600 sccm
Power of sputtering means 1: 5 kW
Power of sputtering apparatus 2: 5 kW
Operation of plasma generating means: 5 amp, 100 sccm O ₂
Firing after film formation: None

As shown in Table 1, each substrate has a very thin (100 nm thick) film composed of a plurality of TiO ₂ layers and SiO ₂ layers 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. This was far superior to the case of using a molded body of acrylic resin alone.
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 used in Examples 1 to 6 and Comparative Example 1, a plastic substrate having a composition shown in Table 2 with an ITO film formed in a low temperature process of about 50 ° C. or lower under the following conditions without using one sputtering means ( Film). The results are shown in Table 2.

Sputtering means target: indium and tin oxide Sputtering means gas: Argon 600 sccm
Power of sputtering means: 5 kW
Operation of plasma generator: 5 amps, 100 sccm O ₂

  Each substrate was formed with a thin (100 nm thickness) ITO film having a very high total light transmittance and a low surface resistance. The film had a QWOT (Quarter Wave Optical Thickness; 1/4 wavelength optical thickness) of 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. This was far superior to the case of using a molded body of acrylic resin alone. 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.

  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), liquid crystal display (LCD), polarizing plate, plasma display, various optical filters, other organic EL displays, field emission displays ( FED), surface conduction electron emission display (SED), and can be attached to and incorporated in various displays such as rear projection televisions, and can be used as glasses, optical waveguides, various window materials, and the like.

It is a perspective view of an example of the thin film formation apparatus which can be used in this invention. It is a horizontal sectional view of an example of the thin film forming apparatus which can be used in the present invention. It is a perspective view of the drum of an example of the thin film forming apparatus which can be used in this invention. It is a horizontal sectional view of other examples of a thin film forming device which can be used in the present invention. It is a horizontal sectional view of other examples of a thin film forming device which can be used in the present invention. It is a horizontal sectional view of other examples of a thin film forming device which can be used in the present invention. It is explanatory drawing of another example of the thin film forming apparatus which can be used in this invention. It is explanatory drawing of another example of the thin film forming apparatus which can be used in this invention. It is explanatory drawing of another example of the thin film forming apparatus which can be used in this invention. It is explanatory drawing of another example of the thin film forming apparatus which can be used in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Thin film formation apparatus 11 Vacuum chamber 12 Vacuum pump system 13 Exhaust port 14 Drum (substrate conveyance means)
14A Rotating drum 15 Substrate 16 Drum shaft 16A Sun gear rotating shaft 18 Tubular substrate 19 Sun gear 21 Planetary gear 21A Planetary gear rotating shaft 22 Gear 25 Planetary gear mounting drive device 26, 27 Sputtering means 28 Plasma generating means 30 Linear magnetron Enhanced sputtering apparatus 31 Cathode 32 Baffle plate 34 Target 37 Manifold 40 Linear magnetron plasma generating means 60, 65, 70 Thin film forming apparatus 71 Inner winding roll 72 Inner winding roll 73 Flexible sheet substrate or conveyor belts 80, 80A, 80B 80C Thin film forming apparatus 81 Vacuum chamber for loading 82, 82A Vacuum processing chamber 83 Vacuum chamber for taking out 86 Vacuum valve 87, 88, 91 Vacuum lock 92, 93, 94 Conveyor belt 101, 102, 103, 104 Ttaringu means, a plasma generating means 106 baffles

Claims (7)

Using a thin film forming apparatus having at least the following (a) to (c), after forming a deposited film on a substrate by sputtering means, the deposited film and the plasma generated by the plasma generating means are reacted to form a thin film. A method for manufacturing a substrate with a thin film to be formed, the method using a molded body of a resin composition containing an acrylic resin (a) and an aliphatic polyester resin (b) as a substrate;
(A) Substrate transport means,
(A) Sputtering means provided along the periphery of the substrate transport means;
(C) Plasma generating means provided apart from the sputtering means along the periphery of the substrate transport means.   Forming at least two layers of thin films, each thin film comprising a first metal, a second metal, an oxide of the first metal, an oxide of the second metal, a mixture of the first and second metals, and The manufacturing method of the board | substrate with a thin film of Claim 1 containing at least 1 sort (s) of the mixed oxide of a 1st and 2nd metal.   2. The plasma generated by the plasma generating means changes the material deposited by the sputtering means into at least one of an oxide, a nitride, a hydride, a sulfide, a carbon-containing compound, or a mixture. The manufacturing method of the board | substrate with a thin film of description.   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.

Images