CN1198106A - Method of forming coating film - Google Patents

Method of forming coating film Download PDF

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Publication number
CN1198106A
CN1198106A CN97190996A CN97190996A CN1198106A CN 1198106 A CN1198106 A CN 1198106A CN 97190996 A CN97190996 A CN 97190996A CN 97190996 A CN97190996 A CN 97190996A CN 1198106 A CN1198106 A CN 1198106A
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China
Prior art keywords
coating
coating fluid
manufacture method
solid content
supporter
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CN97190996A
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Inventor
吉田达朗
渡边谦二
池田智之
伊藤哲也
后藤义隆
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JAPAN OIL AND GREASE Ltd
NOF Corp
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JAPAN OIL AND GREASE Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Apparatus (AREA)

Abstract

A method of continuously forming a coating film on a support having a large area with high productivity. The film can be an ultra-thin film having a uniform thickness. This method comprises coating continuously a coating solution having a solid content concentration of 0.05 to 40 wt.% to a support by using a gravure roll and forming a film having a dry thickness of 0.005 to 1 mu m.

Description

Method of forming coating film
Technical field
The present invention relates on supporters such as plastic sheeting, form continuously the method that superthin layer is filmed.
Background technology
If, then can give supporter with various functions in the ultrathin membrane coating of implementing on the supporter below the dry film thickness 1 μ m.For example, by be provided as antireflection film on the supporters such as plastic sheeting, be coated with solid formation branch, filming about dry film thickness 0.1 μ m, just can reduce the surface reflectivity of supporter.
The coating of ultrathin membrane in the past can be carried out with Vacuum Coating method, chemical reaction method (CVT), Plasma Polymerization, infusion process, spin-coating method, LB embrane method etc.Wherein Vacuum Coating method, CVT, Plasma Polymerization make solid formation divide the gasification back to be coated with on supporter.Therefore, coating must be carried out in enclosed system, the large tracts of land supporter be coated with difficulty, productivity is also low.On the other hand, infusion process, spin-coating method, LB embrane method can be coated with in open system, be difficult but carry out the coating of large tracts of land supporter, and can not produce continuously, thereby productivity is low.
As making large tracts of land supporter coating become the also high coating process of possibility, productivity, known have methods such as rolling method, gravure rubbing method.Yet these have method also not to be applied to the industry manufacturing of ultrathin membrane coating earlier.
Disclosure of the Invention
The purpose of this invention is to provide a kind of can on the large tracts of land supporter, the coating continuously thereby the high method of forming coating film that also can form the high ultrathin membrane of thickness homogeneity of productivity.
According to the present invention, can provide and make solid concentration with the gravure roller is that the coating fluid of 0.05～40% (weight) is coated on the supporter continuously, forms the method for forming coating film of filming of dry film thickness 0.005～1 μ m.
The accompanying drawing simple declaration
Fig. 1 is the spectral reflectance measured value of the antireflection film that shows that embodiment 1 obtains and the figure of theoretical value.
Fig. 2 is the spectral reflectance measured value of the antireflection film that shows that embodiment 2 obtains and the figure of theoretical value.
Fig. 3 is the spectral reflectance measured value of the antireflection film that shows that embodiment 3 obtains and the figure of theoretical value.
Fig. 4 is the spectral reflectance measured value of the antireflection film that shows that comparative example 1 obtains and the figure of theoretical value.
The better embodiment of invention
According to method of forming coating film of the present invention, at first, be solid concentration that the coating fluid of 0.05～40% (weight) is applied on the supporter continuously with the gravure roller.
The form of the coating fluid that uses in the method for forming coating film of the present invention so long as liquid material just is not particularly limited, comprises solution, dispersion liquid, colloidal solution (colloidal sol) or these admixture etc. Solid content in these forms is respectively solute. Dispersate or colloid. And liquid component is respectively solvent or decentralized medium. The concentration of solid content is 0.05～40% (weight), better is that 0.1～20% (weight), solid concentration reach the above person of 0.05% (weight) evaporation of liquid component is become easily in the coating fluid, and can make the dry film thickness of the filming homogeneous that becomes the following person of 40% (weight).
The composition that comprises in the solid content is not particularly limited, and can enumerate such as polymerisable monomer, polymer or these mixture etc.In addition, also can contain inorganic compound.
Described polymerizable thing monomer can be any in simple function polymerisable monomer, the multifunctional polymerisable monomer, better can enumerate such as (methyl) acrylic acid and alkane ester thereof; Unsaturated polyacid and alkane esters thereof such as fumaric acid, maleic acid, citraconic acid, mesaconic acid, itaconic acid, tetrahydrochysene phthalandione; Fatty acid vinyl ester; Phenylethylene; Vinyl alkyl ethers; Vinyl alkyl ketone etc.More particularly, better can enumerate (methyl) methyl acrylate, two (methyl) acrylic acid 1,6-hexylene glycol ester, six (methyl) acrylic acid dipentaerythrityl ether ester, (methyl) acrylic acid 2-(perfluoro capryl) ethyl ester, two (methyl) acrylic acid perfluoro capryl Propylene Glycol ester, four (methyl) acrylic acid 4,4,5,5-tetrafluoro octane-1,2,7,8-tetrol ester, the fumaric acid diisopropyl ester, vinyl acetate, propionate, styrene, AMS, allyl acetate, 12 carbon alkyl vinyl ether, triethylene glycol divinyl ether, ethenyl methyl ketone, vinyl ethyl ketone etc.
In solid content, contain under the situation of polymerisable monomer, also can add polymerization initiator in the lump.Polymerization initiator can suitably be selected according to the polymerisable monomer that uses, and can use such as azo type free base polymerization initiators such as azodiisobutyronitrile, azo bicyclohexane formonitrile HCN, azo two valeronitriles; Organic peroxide type free base polymerization initiators such as benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, peroxidating diacyl; Benzoin compounds such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether; Carbonyls such as benzophenone, acetophenone, Michler's keton; Azo-compounds such as azodiisobutyronitrile, azo dibenzo benzoyl; Photoepolymerizationinitiater initiaters such as the mixture of α-diketone and tertiary amine etc.The use amount of described polymerization initiator for polymerisable monomer 100 weight portions, is preferably 0.01～10 weight portion.
As described polymer, be not particularly limited, but better can enumerate the equal polymerization of described simple function polymerisable monomer or copolymer etc.As homopolymers, better can enumerate such as poly-((methyl) methyl acrylate), poly-((methyl) acrylic acid 2-(perfluoro capryl) ethyl ester), poly-(fumaric acid diisopropyl ester), polyvinyl acetate, polyvinyl proprionate, polystyrene, poly-(AMS), poly-allyl acetate, poly-12 carbon alkyl vinyl ether, polyvinyl methyl ketone, polyvinyl ethyl ketone etc.
As described inorganic compound, better can enumerate such as metal, metal oxide, metal sulfide, metal halide, silicon compound etc., specifically, be preferably subparticles such as zinc oxide, titanium oxide, magnesium fluoride, silica gel etc.
Polymerisable monomer, polymer or the inorganic compound content ratio for solid content is not particularly limited.Solid content all is that polymerisable monomer and/or polymer also are fine.
Can further cooperate additives such as antiseize paste, levelling agent, defoamer, surfactant, anti-colour splitting agent, dyestuff, pigment, ultra-violet absorber, antioxidant, polymerization inhibitor, metal packing in the solid content.The proportioning of these additives can be adjusted according to each additive.
Liquid component in the coating fluid is not particularly limited, but can consider the dissolubility of solid content or dispersiveness, the evaporation during to the wetability of supporter, coating etc. elects again.For example, can enumerate hexane, toluene, dimethylbenzene, trifluoromethylbenzene, Di Iso Propyl Ether, dichloroethanes, methyl ethyl ketone, butyl acetate, isopropyl alcohol, butanols etc.
In manufacture method of the present invention, the supporter as coating fluid will be coated with just is not particularly limited so long as can carry out the material of gravure coating, can use plastic sheeting or resin-coated paper etc. is arranged.As plastic sheeting, can enumerate such as polyethylene, polypropylene, polymethylpentene, PETG, polybutylene terephthalate (PBT), polymethyl methacrylate, polystyrene, Merlon, triacetyl cellulose, polyurethane, polysulfones, polyether sulfone, polyethers-ether ketone, polyvinyl acetate etc.
In the method for forming coating film of the present invention, coating process when coating fluid is coated with on supporter continuously, so long as used the coating process of gravure roller just to be not particularly limited, can take directly coating fluid to be applied to direct mode on the supporter, between gravure roller and supporter, dispose the methods such as hectograph mode of hectograph roller with the gravure roller.
As using the gravure roller in the coating, be not particularly limited, but be preferably several 10～300/cm of mesh, the degree of depth 5～500 μ m persons.Make the mesh number 300/below the cm, the degree of depth more than 5 μ m, can avoid the moistening thickness of filming thin excessively, become easily thereby make to film to form, can also avoid producing paint film defect because of coating fluid is under feeding.On the other hand, make the mesh number 10/more than the cm, the degree of depth is below 500 μ m, can prevent that the coating fluid feed is excessive, can also prevent between gravure roller or hectograph roller and supporter, to produce accumulating of coating fluid, thereby the homogeneity that had both improved the face that is coated with also makes the evaporation of liquid component become easy.Yet, even the mesh number and the degree of depth outside the scope of described regulation, also can reach receptible effect of the present invention.
The shape of mesh is not particularly limited on the gravure roller surface, can use the gravure roller of the mesh of Any shape such as pyramid, lattice type, bias type.
The spinning solution of gravure roller when coating fluid is applied on the supporter for the coating direction, can be any in positive rotation, the contrary rotation.The reasonable of gravure roller rotary speed and supporter coating speed is 0.001～500.Velocity ratio is to avoid making the moistening thickness of filming thin excessively more than 0.001, can also avoid producing because of coating fluid is under feeding paint film defect.Making velocity ratio is below 500, can prevent that the coating fluid feed is excessive, can also prevent to produce accumulating of coating fluid between gravure roller or hectograph roller and supporter, thereby the homogeneity that had both improved the face that is coated with also makes the evaporation of liquid component become easy.Yet, even velocity ratio outside the scope of described regulation, also can reach receptible effect of the present invention.
Coating fluid is the coating thickness after coating on the supporter just, and promptly moistening thickness is preferably 0.025～1000 μ m.Moistening thickness is reached to prevent more than the 0.025 μ m significantly to be difficult to form the situation that homogeneous is filmed, on the other hand, make the solvent evaporation become easy with next at 1000 μ m.In method of forming coating film of the present invention,, can easily regulate resulting dry film thickness of filming by selecting suitable gravure roller, suitably regulating the coating condition to regulate moistening thickness.Because the evaporation of liquid component begins immediately in filming after described coating fluid is coated with, thereby is difficult to directly measure moistening thickness of filming, but can calculate indirectly from the thickness of dry coating and the Volume Changes of coating fluid.For example, the Volume Changes of coating fluid can be obtained by the volume that coating fluid is contained in the container such as culture dish and measure before and after dry.And the coating fluid quantity of using from coating and the area of coating also can be calculated moistening thickness of filming.
In method of forming coating film of the present invention, described coating fluid is coated on the supporter, form filming of dry film thickness 0.005～1 μ m.After dry film thickness means liquid component evaporation, the perhaps thickness after liquid component evaporation under the situation that the coating fluid with the solid content that contains polymerisable monomer is coated with and polymerization end.The fluctuation degree of dry coating is not particularly limited, but its standard deviation can obtain industrial good goods at 25% of thickness mean value with interior person, thereby better.
In order to form filming of dry film thickness 0.005～1 μ m, can be with such as (moistening filming) the dry immediately method etc. of filming after the coating fluid coating.Drying means is not particularly limited, and can be set forth in the drying oven with gases such as the air of room temperature or the above temperature of room temperature or nitrogen to blow the method for filming etc.The drying of liquid component contains in solid content under the situation of polymerisable monomer, carries out more fortunately carrying out simultaneously before the polymerizing curable or with the polymerization sclerosis.Under the situation that does not contain polymerisable monomer, can before the coiling of filming, carry out.Different because of the use liquid component, the meeting that has is evaporation rapidly immediately after coating, needn't carry out drying steps specially in this case.
For filming that the coating fluid coating with the solid content that contains polymerisable monomer forms, the method for polymerisable monomer polymerization can suitably be selected according to the kind of polymerisable monomer from methods such as the irradiation of ultraviolet ray, electron beam isoreactivity energy-ray or heating.
According to method of forming coating film of the present invention, owing to adopt the gravure roller to be applied to the coating fluid of specific concentrations on the supporter continuously, thereby make coating become possibility to the large tracts of land supporter, can make the following ultrathin membrane of dry film thickness 1 μ m continuously, the productivity height.And, according to method of forming coating film of the present invention, can obtain thickness homogeneity height, industrial useful ultrathin membrane.And then, by selecting suitable gravure roller and suitably regulating coating condition, the dry film thickness that can easily regulate resultant ultrathin membrane.
Embodiment
Below illustrate in greater detail with embodiment, but the invention is not restricted to these embodiment.
Production Example 1
Mixing is as diacrylate (perfluoro capryl) Propylene Glycol ester (polymerisable monomer) 400g of solid content with as the trifluoromethylbenzene 4600g of liquid component, the coating fluid A of preparation solid concentration 8% (weight).
Production Example 2
Mixing is as poly-(acrylic acid 2-(perfluoro capryl) ethyl ester) 100g (polymer) of solid content with as the trifluoromethylbenzene 4900g of liquid component, the coating fluid B of preparation solid concentration 2% (weight).
Production Example 3
Mixing is as three acrylic acid three (methylol) propane ester (polymerisable monomer) 178g of solid content, as " DAROCUR 1116 " (trade name of polymerization initiator, the Merck corporate system, acetophenone compounds) 2g, inorganic compound " XBA-ST Silica Sol " (trade name, daily output chemical company system) 600g is (among the 600g, cataloid 180g as solid content, and be respectively 270g and 150g as the dimethylbenzene and the n-butanol of liquid component), as the toluene 4580g of liquid component, the coating fluid C of preparation solid concentration 6.72% (weight).
Production Example 4
Mixing is as diacrylate (perfluoro capryl) Propylene Glycol ester (polymerisable monomer) 2500g of solid content with as the trifluoromethylbenzene 2500g of liquid component, the coating fluid D of preparation solid concentration 50% (weight).
Production Example 5
Mixing is as poly-(acrylic acid 2-(perfluoro capryl) ethyl ester) (polymer) 0.5g of solid content with as the trifluoromethylbenzene 4999.5g of liquid component, the coating fluid E of preparation solid concentration 0.01% (weight).
Embodiment 1
Coating fluid A with Production Example 1 preparation is coated with by following condition on PET film support body.Use is as " Microgravure Coater " (trade name of gravure roller spreader, the smart machine corporate system of Kang Jing) with as " Microgravure Roller " (trade name of gravure roller, the smart machine corporate system of Kang Jing, the several 110/cm of mesh, the degree of depth 70 μ m).Coating speed is 20m/ minute, and Microgravure Roller was coated with rotary speed 10m/ minute on the contrary direction for the coating direction.In order after coating, to make the polymerisable monomer polymerization immediately,, obtained antireflection film F with the electron beam of electron beam irradiator (the rugged electric corporation system of rock) with accelerator voltage 125kV, beam electronic current 60mA irradiation absorption line amount 20M rad (rad).Coating fluid A to using in resulting antireflection film F and the coating has carried out the following various tests as evaluation test.
(a) spectral reflectance of antireflection film
Measure with the ultraviolet spectrometer (Japanese beam split corporate system U-best35) that 5 ° of normal reflection determinators are subsidiary.But with the coated face is the mensuration face, and the inside is measured with the rough back of sand paper mill, to cover its reflection.The result is illustrated among Fig. 1.In addition, the minimum of a value γ of spectral reflectance m(%), show γ mWavelength (blooming) λ m(μ m) lists in the table 1.
(b) volume ratio of solid content and coating fluid
Coating fluid 50ml is poured in the culture dish of radius 50mm, make liquid component evaporation after, with the electron beam of electron beam irradiator with accelerating potential 175kV, beam electronic current 5mA irradiation absorption line amount 5M rad.Measure the dry film thickness of resultant solid content, calculate the volume ratio of (coating fluid/solid content): V w/ V dThe results are shown in Table 1.
(c) refractive index of supporter and solid content
Measure the refractive index n of supporter respectively with abbe's refractometer (ア go Co., Ltd. system) 1Refractive index n with the solid content film that obtains by (b) 2The results are shown in Table 1.
(d) standard deviation of the average film thickness of antireflection film and fluctuation degree.
For antireflection film, when the refractive index of supporter is n 1, antireflection film refractive index be n 2, antireflection film thickness when being d, set up known following mathematical expression (1) and (2).But γ t, λ tBe respectively reflectivity minimum of a value, the blooming that calculates from following mathematical expression (1) and (2) theory.
γ t(％)＝((n 1-n 2 2)/(n 1+n 2 2)) 2×100?????(1)
λ t＝4×n 2×d????????????????????????????????(2)
If have on the surface of antireflection film concavo-convexly, then measure corresponding to the spectral reflectance mean value of thickness separately.Its result has obtained and theoretical value γ tDifferent measured value γ m, the accurate deviations of fluctuation scale that can obtain for thickness mean value from both departing from.The thickness mean value d of antireflection film AV, the fluctuation degree is with respect to d AVStandard deviation (%) and theoretical reflectivity γ tList in the table 1.In addition, the spectral reflectance of obtaining from theoretical formula is also illustrated in Fig. 1.
(e) moistening thickness
The V that (b) obtained w/ V dEqual moistening thickness d w/ dry film thickness d, the d that calculates wBe listed in the table 1.
Embodiment 2
Coating fluid B with Production Example 2 preparations is coated with by following condition on PET film support body.With gravure roller spreader similarly to Example 1, " Microgravure Roller " (the smart machine corporate system of Kang Jing, the several 90/cm of mesh, the degree of depth 100 μ m), have been used as the gravure roller.Coating speed is 20m/ minute, and Microgravure Roller is coated with rotary speed 20m/ minute on respect to the contrary direction of coating direction, and then blows 80 ℃ warm wind and carry out drying in the drying oven of length 2m, obtains antireflection film G.For resulting antireflection film G coating fluid B, carried out evaluation test similarly to Example 1.γ m, λ m, V w/ V d, n 1, n 2, d AV, γ tAnd d wMeasurement result list among table 1 and Fig. 2.But V w/ V dThe dried thickness former state of coating fluid is measured.
Embodiment 3
Coating fluid C with Production Example 3 preparations is coated with by following condition on PET film support body.With gravure roller spreader similarly to Example 1, " Microgravure Roller " (the smart machine corporate system of Kang Jing, the several 110/cm of mesh, the degree of depth 70 μ m), have been used as the gravure roller.Coating speed is 10m/ minute, and Microgravure Roller was coated with rotary speed 5m/ minute on the contrary direction with respect to the coating direction.In order to make the polymerisable monomer polymerization, use ultraviolet radiation device (the rugged electric corporation system of rock) irradiation 950mJ/cm after the coating immediately 2Ultraviolet ray, obtain antireflection film H.For resulting antireflection film H and coating fluid C, carried out evaluation test similarly to Example 1.γ m, λ m, V w/ V d, n 1, n 2, d AV, γ tAnd d wMeasurement result list among table 1 and Fig. 3.But V w/ V dBe after the coating fluid drying, to shine 950mJ/cm 2Ultraviolet ray, measure thickness then.
Comparative example 1
Coating fluid D with Production Example 4 preparations is coated with by following condition on PET film support body.With gravure roller spreader similarly to Example 1, " Microgravure Roller " (the smart machine corporate system of Kang Jing, the several 250/cm of mesh, the degree of depth 13 μ m), have been used as the gravure roller.Coating speed is 20m/ minute, and Microgravure Roller was coated with rotary speed 0.1m/ minute on the contrary direction with respect to the coating direction.In order to make the polymerisable monomer polymerization, use the electron beam of electron beam irradiator (the rugged electric corporation system of rock) after the coating immediately with accelerator voltage 125kV, beam electronic current 60mA irradiation absorption line amount 20M rad, obtain antireflection film I.For resulting antireflection film I and coating fluid D, carried out evaluation test similarly to Example 1.γ m, λ m, V w/ V d, n 1, n 2, d AV, γ tAnd d wMeasurement result list among table 1 and Fig. 4.But V w/ V dBe after the coating fluid drying, to shine 950mJ/cm 2Ultraviolet ray after measure thickness.
Comparative example 2
Coating fluid E with Production Example 5 preparations is coated with by following condition on PET film support body.With gravure roller spreader similarly to Example 1, " Microgravure Roller " (the smart machine corporate system of Kang Jing, the several 20/cm of mesh, the degree of depth 300 μ m), have been used as the gravure roller.Coating speed is 1m/ minute, and Microgravure Roller is coated with rotary speed 100m/ minute on respect to the contrary direction of coating direction, but the evaporation of liquid component is carried out insufficiently, does not obtain antireflection film.The volume of the coating fluid that is consumed from coating and the area of coated face have been calculated d wThe results are shown in Table 1.
Table 1
??γ m??(％) ??λ m(μm) ??V w/V d ????n 1 ????n 2 ??d AV??(μm) ??σ ?(％) ??γ t???(％) ????d w???(μm)
Embodiment 1 ??0.76 ??0.576 ???15.3 ??1.645 ??1.388 ??0.104 ??11 ???0.62 ???1.57
Embodiment 2 ??0.63 ??0.580 ???62.1 ??1.645 ??1.364 ??0.104 ??15 ???0.37 ???6.49
Embodiment 3 ??1.53 ??0.589 ???20.1 ??1.645 ??1.442 ??0.101 ??13 ???1.36 ???2.03
Comparative example 1 ??1.55 ??0.596 ???2.22 ??1.645 ??1.388 ??0.092 ??30 ???0.62 ???0.433
Comparative example 2 ???1100

Claims (10)

1. method of forming coating film comprises that being coated with solid concentration with the gravure roller continuously on supporter is the coating fluid of 0.05～40% (weight), forms filming of dry film thickness 0.005～1 μ m.
2. the described manufacture method of claim 1 wherein, when described coating, is used described coating fluid, is coated with moistening thickness 0.025～1000 μ m.
3. the described manufacture method of claim 1, wherein, the described accurate deviation of dry film thickness fluctuation scale of filming dry film thickness mean value 25% in.
4. the described manufacture method of claim 1, wherein, the mesh number of described gravure roller is that 10～300/cm, the degree of depth are 5～500 μ m.
5. the described manufacture method of claim 1, wherein, described gravure roller rotary speed is 0.001～500 with the ratio of the speed of the described supporter of coating.
6. the described manufacture method of claim 1, wherein, the solid content in the described coating fluid is the composition that contains polymerisable monomer.
7. the described manufacture method of claim 1, wherein, the solid content in the described coating fluid is the composition that contains polymer.
8. claim 6 or 7 described manufacture methods, wherein, the solid content in the described coating fluid further contains inorganic compound.
9. the described manufacture method of claim 6 wherein, after described coating fluid coating, is carried out the drying of liquid component in the described coating fluid and the polymerization of polymerisable monomer.
10. the described manufacture method of claim 7 wherein, after described coating fluid coating, is carried out the drying of liquid component in the described coating fluid.
CN97190996A 1996-05-29 1997-05-28 Method of forming coating film Pending CN1198106A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP13544996A JP3757467B2 (en) 1996-05-29 1996-05-29 Method for manufacturing antireflection film
JP135449/96 1996-05-29

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CN1198106A true CN1198106A (en) 1998-11-04

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EP (1) EP0857517B1 (en)
JP (1) JP3757467B2 (en)
KR (1) KR100246508B1 (en)
CN (1) CN1198106A (en)
DE (1) DE69714833T2 (en)
WO (1) WO1997045207A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
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JP4366864B2 (en) * 2000-12-27 2009-11-18 東洋製罐株式会社 Method of applying or printing paint or ink having glitter
JP2007044694A (en) * 2006-11-27 2007-02-22 Nippon Steel Corp Coating quality monitoring apparatus
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Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5359515A (en) * 1976-11-05 1978-05-29 Toyo Ink Mfg Co Concave pattern forming method
DE2861151D1 (en) * 1977-06-23 1981-12-24 Ici Plc Process and apparatus for coating a web
US4537811A (en) * 1978-04-24 1985-08-27 Energy Sciences, Inc. Electron beam irradiating process for rendering rough or topographically irregular surface substrates smooth; and coated substrates produced thereby
US4302486A (en) * 1978-12-28 1981-11-24 Burroughs Corporation Method of solvent coating with gravure roll in combination with sheathed elastomeric roll and apparatus
AU539577B2 (en) * 1980-04-08 1984-10-04 Wiggins Teape Group Limited, The Applying a coating to a web of sheet material
US4400414A (en) * 1981-04-07 1983-08-23 Milliken Research Corporation Process for imparting soil resistance to polyester-fiber-containing textile materials
US4548840A (en) * 1984-06-15 1985-10-22 Graham Magnetics Incorporated High speed coating
JPH01176478A (en) * 1987-12-29 1989-07-12 Kawasaki Steel Corp Applied film thickness control of strips
US5156904A (en) * 1990-05-18 1992-10-20 Hoechst Celanese Corporation Polymeric film coated in-line with polyethyleneimine
CA2122089A1 (en) * 1993-04-30 1994-10-31 Glen H. Bayer, Jr. Method and apparatus for applying a coating material to a receiving surface

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1795054B (en) * 2003-07-10 2010-12-15 日东电工株式会社 Process for producing coated sheet, optically functional layer, optically compensating plate, optical device and image display

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DE69714833T2 (en) 2002-12-05
KR100246508B1 (en) 2000-03-15
WO1997045207A1 (en) 1997-12-04
EP0857517A4 (en) 1999-05-19
JPH09314038A (en) 1997-12-09
EP0857517A1 (en) 1998-08-12
EP0857517B1 (en) 2002-08-21
DE69714833D1 (en) 2002-09-26
KR19990029035A (en) 1999-04-15

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