阅读说明：本技术 液膜形成装置、液膜形成方法及合成高分子膜的制造方法 (The manufacturing method of liquid film forming device, liquid film forming method and synthetic polymeric membrane ) 是由 二宫郁雄 林秀和 泽井一辉 于 2018-03-27 设计创作，主要内容包括：装置(50)具有：吹出口(51),其以雾的形式喷出液体；液体供应装置(52),其将液体供应到吹出口；筒状的内侧罩部(53),其划定吹出口；外侧罩部(54),其配置在内侧罩部的外侧；吸入口(55),其由内侧罩部和外侧罩部划定；以及气体吸引装置(56),其通过吸入口来吸引气体。吹出口在第1方向上的长度大于在与第1方向正交的第2方向上的吹出口的长度,吹出口在向基材的外周面(100s)以雾的形式喷出液体时,以第1方向实质上与基材的轴向平行的方式朝向外周面。气体吸引装置构成为吸引流量比包含从吹出口以雾的形式喷出的液体的气体的流量多的气体。(Device (50) includes blow-off outlet (51), and liquid is sprayed in the form of mist；Liquid supplying apparatus (52), supplies liquid to blow-off outlet；The inside cover portion (53) of tubular delimit blow-off outlet；Outside cover portion (54) configures in the outside in inside cover portion；Suction inlet (55) delimited by inside cover portion and outside cover portion；And gas suction device (56), gas is attracted by suction inlet.Length of the blow-off outlet on the 1st direction is greater than the length of the blow-off outlet on 2nd direction orthogonal with the 1st direction, blow-off outlet is when the outer peripheral surface (100s) to substrate sprays liquid in the form of mist, in the 1st direction mode substantially parallel with the axial direction of substrate towards outer peripheral surface.Gas suction device is configured to the gas more than the flow for the gas for attracting flow-rate ratio to include the liquid sprayed in the form of mist from blow-off outlet.)

1. a kind of liquid film forming device is the device for forming liquid film on the outer peripheral surface of cylindric or cylindric substrate, special Sign is, comprising:

Blow-off outlet, sprays liquid in the form of mist, and length of the above-mentioned blow-off outlet on the 1st direction is greater than and above-mentioned 1st direction The length of above-mentioned blow-off outlet on the 2nd orthogonal direction, it is above-mentioned when spraying aforesaid liquid in the form of mist to above-mentioned outer peripheral surface Blow-off outlet is in above-mentioned 1st direction mode substantially parallel with the axial direction of above-mentioned substrate towards above-mentioned outer peripheral surface；

Aforesaid liquid is supplied to above-mentioned blow-off outlet by liquid supplying apparatus；

The inside cover portion of tubular delimit above-mentioned blow-off outlet；

Outside cover portion configures in the outside of above-mentioned inside cover portion；

At least one suction inlet delimited by above-mentioned inside cover portion and above-mentioned outside cover portion, comprising with above-mentioned blow-off outlet above-mentioned the It is adjacent and in the part that above-mentioned 1st side upwardly extends on 2 directions；And

Gas suction device attracts gas by above-mentioned at least one suction inlet,

Above-mentioned gas suction device is configured to attract flow-rate ratio to include the aforesaid liquid sprayed in the form of mist from above-mentioned blow-off outlet Gas flow more than gas.

2. liquid film forming device according to claim 1,

The average diameter of the aforesaid liquid sprayed in the form of mist from above-mentioned blow-off outlet is 20 μm or less.

3. liquid film forming device according to claim 1 or 2,

Above-mentioned blow-off outlet penetrates through on the 3rd direction vertical with above-mentioned 1st direction and above-mentioned 2nd direction.

4. according to claim 1 to liquid film forming device described in any one in 3,

Also there are multiple nozzles in above-mentioned blow-off outlet, above-mentioned multiple nozzles are arranged along above-mentioned 1st direction, are sprayed in the form of mist Aforesaid liquid out.

5. liquid film forming device according to claim 4,

Above-mentioned multiple nozzles are ultrasonic nozzle.

6. liquid film forming device according to claim 4 or 5,

Configure to the above-mentioned high infraversion malposition of multiple nozzles.

7. according to liquid film forming device described in any one in claim 4 to 6,

The squit hole angle relative to horizontal direction that above-mentioned multiple nozzles are configured to adjacent nozzle is mutually different.

8. according to claim 1 to liquid film forming device described in any one in 7,

It is configured to when spraying aforesaid liquid in the form of mist to above-mentioned outer peripheral surface, above-mentioned inside cover portion and above-mentioned outside cover portion energy Not with above-mentioned periphery face contact.

9. according to claim 1 to liquid film forming device described in any one in 8,

Be configured to inside cover portion change when spraying aforesaid liquid in the form of mist to above-mentioned outer peripheral surface, above-mentioned with it is above-mentioned The distance of outer peripheral surface and/or above-mentioned outside cover portion are at a distance from above-mentioned outer peripheral surface.

10. according to claim 1 to liquid film forming device described in any one in 9,

It is configured to when spraying aforesaid liquid in the form of mist to above-mentioned outer peripheral surface, it can be by above-mentioned inside cover portion and above-mentioned periphery The shortest distance in face and above-mentioned outside cover portion and the shortest distance of above-mentioned outer peripheral surface are set to 30mm or less.

11. according to claim 1 to liquid film forming device described in any one in 10,

Above-mentioned gas suction device is configured to attract the gas of the aforesaid liquid comprising spraying in the form of mist from above-mentioned blow-off outlet Flow, the gas of 9 times or more and 15 times of flows below.

12. according to claim 1 to liquid film forming device described in any one in 11,

Also there is rotatable support structure body, above-mentioned rotatable support structure body so that above-mentioned substrate axially substantially upper and horizontal direction Parallel mode supports above-mentioned substrate, and above-mentioned substrate can be made to rotate around the axis of above-mentioned substrate.

13. a kind of liquid film forming method is the method in the outer peripheral surface formation liquid film of cylindric or cylindric substrate, feature It is, includes:

Process (a), Xiang Shangshu outer peripheral surface spray liquid in the form of mist；And

Process (b) attracts the gas on the periphery of above-mentioned outer peripheral surface；

Above-mentioned operation (b) includes the process carried out simultaneously with above-mentioned operation (a), the stream of the gas attracted in above-mentioned operation (b) Amount ratio includes that the flow of the gas of the aforesaid liquid sprayed in the form of mist in above-mentioned operation (a) is more.

14. liquid film forming method according to claim 13,

The average diameter of the aforesaid liquid sprayed in the form of mist in above-mentioned operation (a) is 20 μm or less.

15. liquid film forming method described in 3 or 14 according to claim 1,

Viscosity of the aforesaid liquid sprayed in the form of mist in above-mentioned operation (a) at 23 DEG C is 20cP or less.

16. liquid film forming method described in any one in 3 to 15 according to claim 1,

The aforesaid liquid that is sprayed in the form of mist in above-mentioned operation (a), by maximum bubble pressure method find out at 23 DEG C Dynamic surface tension when surface lifetime is 100ms is 31mN/m or more.

17. liquid film forming method described in any one in 3 to 16 according to claim 1,

Also include: process (c) is being configured with above-mentioned base in a manner of the axially substantially upper and horizontal direction parallel for making above-mentioned substrate In the state of material, rotate above-mentioned substrate centered on the axis of above-mentioned substrate.

18. liquid film forming method according to claim 17,

In above-mentioned operation (c), the rotation speed of above-mentioned substrate is more than 0rpm and 20rpm or less.

19. liquid film forming method described in any one in 3 to 18 according to claim 1,

It is formed with a thickness of 2 μm of liquid films below.

20. a kind of manufacturing method of synthetic polymeric membrane is to manufacture synthesis macromolecule using cylindric or cylindric mold The method of film, above-mentioned mold have porous alumina layer, and above-mentioned porous alumina layer has the moth ocular structure of reversion on surface, on It is 20nm or more and less than 500nm's that the moth ocular structure for stating reversion, which has the two-dimentional size when watching from normal to a surface direction, The manufacturing method of multiple recess portions, above-mentioned synthetic polymeric membrane is characterized in that, includes:

Process (A), prepares above-mentioned mold and machined object；

Process (B) assigns the 1st resin comprising uv curing resin to the surface of above-mentioned machined object；

Process (C), using liquid film forming device described in any one in claim 1 to 12 or by claim 13 to Liquid film forming method described in any one in 19 assigns the 2nd resin comprising fluorochemical monomer to the surface of above-mentioned mold；With And

Process (D) makes above-mentioned 1st resin and above-mentioned 2nd the resin phase between surface of the above-mentioned mold with above-mentioned machined object Mutually in the state of contact, by irradiating ultraviolet light to above-mentioned 1st resin and above-mentioned 2nd resin, and make above-mentioned 1st resin and above-mentioned 2nd resin solidification.

Technical field

The present invention relates to the manufacturing methods of liquid film forming device, liquid film forming method and synthetic polymeric membrane.

Background technique

In order to reduce surface reflection, the transmission amount of light is improved, usually to showing dress used in television set, portable phone etc. It sets, the optical elements such as camera lens implement antireflection technique.The reason is that for example, being incident on the boundary of air and glass in such as light In the case where interface of the case where face such light by the different medium of refractive index, the transmission amount of light can be due to Fresnel reflection etc. And it reduces, visual identity decline.

In recent years, it as antireflection technique, is formed in substrate surface and the concave-convex period is controlled into the wavelength (λ for visible light =380nm~780nm) method of subtle relief pattern below attracts attention (referring to patent document 1~3).Constitute performance The two-dimentional size of the protrusion of the relief pattern of anti-reflective function is 10nm or more and less than 500nm out.

This process employs the principle of so-called moth eye the eyes of moth (Moth-eye) structure, by making relative to entering The refractive index for being mapped to the light of substrate is continuously changed to the folding of substrate along concave-convex depth direction from the refractive index of incident medium Until penetrating rate, so that inhibition is wanted to prevent the reflection of the wavelength region of reflection.

Moth ocular structure can play the small antireflection effect of incident angle dependency in addition to having in big wavelength region Other than advantage, also has many advantages, such as to can be applied to numerous materials, relief pattern can be formed directly into substrate.Its result It is that can provide high performance antireflection film (or antireflective surfaces) with low cost.

As the manufacturing method of the antireflection film (or antireflective surfaces) with moth ocular structure, present applicant is opened Method (such as the patent document 2 using the anodic oxidation porous alumina layer as obtained from aluminium is carried out anodic oxidation is sent out With 3).

By utilizing anodic oxidation multiaperture pellumina, the mould for forming moth ocular structure on surface can be easily manufactured Have (hereinafter referred to as " the ophthalmically acceptable mold of moth ".).In particular, working as anodizing of aluminium film as recorded in patent document 2 and 3 Surface as former state when being used as mold, the effect for reducing manufacturing cost is big.The table of the ophthalmically acceptable mold of moth of moth ocular structure will be formed The structure in face is known as " the moth ocular structure of reversion ".In particular, when ophthalmically acceptable using cylindric moth as described in patent document 5 When mold, moth ocular structure can be efficiently manufactured by roll-to-roll mode.

In the specification of the present application, " mold " includes mold used in various processing methods (punching press, casting), sometimes Referred to as pressing mold.In addition, can be used for printing (including nano print).

As documented by patent document 4, present applicant is developed with anti-reflective function and soil resistance (example Such as, hydrophobicity, oleophobic property, the erasing easiness of grease, marresistance, sliding easiness) excellent synthetic polymeric membrane.

In order to refer to, all disclosures of patent document 1 to 5 are quoted to this specification.

Summary of the invention

Problems to be solved by the invention

The research of inventor according to the present invention, when the soil resistance for manufacturing patent document 4 by roll-to-roll mode is excellent Synthetic polymeric membrane when, fabrication yield can decline sometimes.It is high that the excellent synthesis of soil resistance is manufactured by roll-to-roll mode The method of molecular film by surface (outer peripheral surface) of the spray coating method to the cylindric or cylindric ophthalmically acceptable mold of moth for example comprising being assigned The process of resin.In this process, cause under fabrication yield since resin disperses to the periphery of the ophthalmically acceptable mold of moth sometimes Drop.Detailed content will be aftermentioned.

The process that the problem is not limited to the excellent synthetic polymeric membrane of manufacture soil resistance, is in addition also not necessarily limited to ophthalmically acceptable using moth The process of mold.The process for forming liquid film for the outer peripheral surface in cylindric or cylindric substrate is common problem.

The object of the present invention is to provide a kind of outer peripheral surface formation liquid being able to suppress in cylindric or cylindric substrate The device and method of the decline of fabrication yield in the process of film and provide a kind of synthesis using this device or method The manufacturing method of polymeric membrane.

The solution to the problem

The liquid film forming device of embodiments of the present invention is formed on the outer peripheral surface of cylindric or cylindric substrate The device of liquid film, above-mentioned liquid film forming device include blow-off outlet, liquid are sprayed in the form of mist, above-mentioned blow-off outlet is in the 1st side Upward length be greater than 2nd direction orthogonal with above-mentioned 1st direction on above-mentioned blow-off outlet length, to above-mentioned outer peripheral surface with When the form of mist sprays aforesaid liquid, the above-mentioned blow-off outlet side substantially parallel with the axial direction of above-mentioned substrate with above-mentioned 1st direction Formula is towards above-mentioned outer peripheral surface；Aforesaid liquid is supplied to above-mentioned blow-off outlet by liquid supplying apparatus；The inside cover portion of tubular, Delimit above-mentioned blow-off outlet；Outside cover portion configures in the outside of above-mentioned inside cover portion；At least one suction inlet, by above-mentioned inside Cover portion and above-mentioned outside cover portion delimited, comprising adjacent and prolong on above-mentioned 1st direction on above-mentioned 2nd direction with above-mentioned blow-off outlet The part stretched；And gas suction device, attract gas, above-mentioned gas suction device by above-mentioned at least one suction inlet It is configured to the gas more than the flow for the gas for attracting flow-rate ratio to include the aforesaid liquid sprayed in the form of mist from above-mentioned blow-off outlet.

In certain embodiment, the average diameter of the aforesaid liquid sprayed in the form of mist from above-mentioned blow-off outlet be 20 μm with Under.

In certain embodiment, above-mentioned blow-off outlet is on 3rd direction vertical with above-mentioned 1st direction and above-mentioned 2nd direction Perforation.

In certain embodiment, also there are multiple nozzles in above-mentioned blow-off outlet, above-mentioned multiple nozzles are along above-mentioned 1st side To arrangement, aforesaid liquid is sprayed in the form of mist.

In certain embodiment, above-mentioned multiple nozzles are ultrasonic nozzles.

In certain embodiment, configure to above-mentioned multiple high infraversion malpositions of nozzle.

In certain embodiment, squit hole angle relative to horizontal direction that above-mentioned multiple nozzles are configured to adjacent nozzle It spends mutually different.

In certain embodiment, above-mentioned liquid film forming device be configured to sprayed in the form of mist to above-mentioned outer peripheral surface it is above-mentioned When liquid, above-mentioned inside cover portion and above-mentioned outside cover portion can not be with above-mentioned periphery face contacts.

In certain embodiment, above-mentioned liquid film forming device be configured to change to above-mentioned outer peripheral surface in the form of mist When spraying aforesaid liquid, above-mentioned inside cover portion is with above-mentioned outer peripheral surface at a distance from and/or above-mentioned outside cover portion and above-mentioned outer peripheral surface Distance.

In certain embodiment, above-mentioned liquid film forming device be configured to sprayed in the form of mist to above-mentioned outer peripheral surface it is above-mentioned It, can be by the shortest distance and above-mentioned outside cover portion of above-mentioned inside cover portion and above-mentioned outer peripheral surface and above-mentioned outer peripheral surface when liquid The shortest distance be set to 30mm or less.

In certain embodiment, above-mentioned gas suction device is configured to attract comprising spraying in the form of mist from above-mentioned blow-off outlet The flow of the gas of aforesaid liquid out, 9 times or more and 15 times of flows below gas.

In certain embodiment, above-mentioned liquid film forming device also has rotatable support structure body, above-mentioned rotatable support structure Body supports above-mentioned substrate in a manner of the axially substantially upper and horizontal direction parallel for making above-mentioned substrate, and can make above-mentioned substrate around The axis of above-mentioned substrate rotates.

The liquid film forming method of embodiments of the present invention is the outer peripheral surface formation liquid in cylindric or cylindric substrate The method of film includes: process (a), Xiang Shangshu outer peripheral surface spray liquid in the form of mist；And process (b), attract above-mentioned periphery The gas on the periphery in face；Above-mentioned operation (b) includes the process carried out simultaneously with above-mentioned operation (a), is attracted in above-mentioned operation (b) Gas flow-rate ratio include in above-mentioned operation (a) in the form of mist spray aforesaid liquid gas flow it is more.

In certain embodiment, the average diameter of the aforesaid liquid sprayed in the form of mist in above-mentioned operation (a) is 20 μ M or less.

In certain embodiment, viscosity of the aforesaid liquid sprayed in the form of mist in above-mentioned operation (a) at 23 DEG C For 20cP or less.

In certain embodiment, in above-mentioned operation (a) in the form of mist spray aforesaid liquid, pass through most bulla pressure The dynamic surface tension when surface lifetime at 23 DEG C that method is found out is 100ms is 31mN/m or more.

In certain embodiment, above-mentioned liquid film forming method also includes: process (c), so that the axial direction of above-mentioned substrate is real In the state of being configured with above-mentioned substrate with the mode of horizontal direction parallel in matter, above-mentioned substrate is made centered on the axis of above-mentioned substrate Rotation.

In certain embodiment, in above-mentioned operation (c), the rotation speed of above-mentioned substrate be more than 0rpm and 20rpm with Under.

In certain embodiment, above-mentioned liquid film forming method is formed with a thickness of 2 μm of liquid films below.

The manufacturing method of the synthetic polymeric membrane of embodiments of the present invention is come using cylindric or cylindric mold The method for manufacturing synthetic polymeric membrane, above-mentioned mold have porous alumina layer, and above-mentioned porous alumina layer has anti-on surface The moth ocular structure turned, the moth ocular structure of above-mentioned reversion have the two-dimentional size when being watched from normal to a surface direction be 20nm with Upper and multiple recess portions less than 500nm, the manufacturing method of above-mentioned synthetic polymeric membrane includes: process (A), prepare above-mentioned mold and Machined object；Process (B) assigns the 1st resin comprising uv curing resin to the surface of above-mentioned machined object；Process (C), using any one above-mentioned liquid film forming device or by any one above-mentioned liquid film forming method, to above-mentioned mold Surface assign include fluorochemical monomer the 2nd resin；And process (D), make above-mentioned 1st resin and above-mentioned 2nd resin upper It states in the state of contacting with each other between mold and the surface of above-mentioned machined object, by above-mentioned 1st resin and above-mentioned 2nd resin Ultraviolet light is irradiated, and makes above-mentioned 1st resin and above-mentioned 2nd resin solidification.

Invention effect

A kind of embodiment according to the present invention, it is possible to provide outer peripheral surface being able to suppress in cylindric or cylindric substrate Form the device and method of the decline of the fabrication yield in the process of liquid film and the synthesis height using this device or method The manufacturing method of molecular film.

Detailed description of the invention

Fig. 1 is the schematical of liquid film forming method for illustrating embodiments of the present invention and liquid film forming device 50 Figure.

Fig. 2 is the schematical of liquid film forming method for illustrating embodiments of the present invention and liquid film forming device 50 Figure, shows the section along the A-A ' line in Fig. 1.

Fig. 3 is the schematical of liquid film forming method for illustrating embodiments of the present invention and liquid film forming device 50 Figure.

Fig. 4 is the schematical figure of an example for illustrating the composition of liquid film forming device 50.

Fig. 5 be when spraying liquid for illustrating the outer peripheral surface 100s to substrate 100A in the form of mist, substrate 100A with The schematical perspective view of the configuration relation of liquid film forming device 50.

Fig. 6 is the schematical side view when watching liquid film forming device 50 from the direction parallel with the axial direction of substrate 100A Figure.

Fig. 7 is to show the item extended in a circumferential direction caused by the liquid film for the outer peripheral surface 100s for being formed in substrate 100A The uneven figure of line shape.

Fig. 8 is the schematical figure of an example for illustrating the composition of liquid film forming device 50.

Fig. 9 is the schematical section of the method for illustrating to manufacture synthetic polymeric membrane 36 by roll-to-roll mode Figure.

(a) of Figure 10~(e) is the schematical sectional view for illustrating the manufacturing method of the ophthalmically acceptable mold 100A of moth.

(a) of Figure 11~(c) is the knot of the manufacturing method and synthetic polymeric membrane 36 for illustrating synthetic polymeric membrane 36 The schematical sectional view of structure.

Figure 12 is to schematically show the concentration of element of the fluorine (F) and nitrogen (N) of synthetic polymeric membrane 36 in a thickness direction Variation (depth distribution (depth profile)) figure.

Figure 13 is the schematical section of the method for illustrating to manufacture synthetic polymeric membrane 36 by roll-to-roll mode Figure.

Figure 14 is for illustrating to lead to the problem of in the case where manufacturing synthetic polymeric membrane 36 by roll-to-roll mode Schematical sectional view.

Figure 15 is for illustrating to lead to the problem of in the case where manufacturing synthetic polymeric membrane 36 by roll-to-roll mode Schematical sectional view.

Specific embodiment

Referring to Fig.1 1 and Figure 12 come illustrate synthetic polymeric membrane record in patent document 4, that soil resistance is excellent and its Manufacturing method.

Firstly, referring to Fig.1 1 come illustrate patent document 4 synthetic polymeric membrane 36 manufacturing method and synthetic polymeric membrane 36 structure.(a) of Figure 11~(c) is the knot of the manufacturing method and synthetic polymeric membrane 36 for illustrating synthetic polymeric membrane 36 The schematical sectional view of structure.

In addition, as described later, the liquid film forming method or liquid film forming device of embodiments of the present invention can be suitble to use In the process for for example forming synthetic polymeric membrane 36.Therefore, 1~Figure 13 is carried out about synthetic polymeric membrane referring to Fig.1 36 explanation is also applied for high using the synthesis of the liquid film forming method or liquid film forming device manufacturing of embodiments of the present invention One example of molecular film.

As shown in (c) of Figure 11, synthetic polymeric membrane 36 has multiple protrusion 36p on surface.Multiple protrusion 36p are constituted Moth ocular structure.Here, synthetic polymeric membrane 36 is formed on basement membrane 42.Film 30 shown in (c) of Figure 11 have basement membrane 42, with And it is formed in the synthetic polymeric membrane 36 on basement membrane 42.When being watched from the normal direction of synthetic polymeric membrane 36, protrusion 36p's Two-dimentional size D_pIn the range of more than 20nm and less than 500nm.Here, " the two-dimentional size " of protrusion 36p refers to from table The area equivalent diameter (the comparable diameter of a circle of area with protrusion 36p) of protrusion 36p when the normal direction viewing in face.Example Such as, in the case where protrusion 36p is cone, the two-dimentional sizableness of protrusion 36p is in the diameter of the bottom surface of circular cone.In addition, convex The typical adjacent spacing of portion 36p is from D_intFor more than 20nm and 1000nm or less.As illustrated by (c) of Figure 11, protrusion 36p is closely aligned, and there is no the feelings of gap (for example, the bottom surface portions of circular cone be overlapped) between adjacent protrusion 36p Under condition, the two-dimentional size D of protrusion 36p_pWith adjacent spacing from D_intIt is equal.The typical height D of protrusion 36p_hFor 50nm or more and Less than 500nm.The thickness t of synthetic polymeric membrane 36_sIt is not particularly limited, as long as the height D than protrusion 36p_hIt is big.

Synthetic polymeric membrane 36 includes fluorine element, fluorine containing ratio consecutive variations in a thickness direction, with the side protrusion 36p Fluorine containing ratio is higher than the distribution (profile) with the fluorine containing ratio of the protrusion side 36p opposite side.Fluorine containing ratio refers to such as fluorine member Plain concentration.

Synthetic polymeric membrane 36 has anti-reflective function, and soil resistance is (for example, be attached to the eye-catching difficulty of the grease on surface The erasing easiness and marresistance of degree, grease) it is excellent.

In order to make synthetic polymeric membrane 36 show excellent anti-reflective function, preferably surface does not have flat part, convex Portion 36p is closely aligned.Additionally, it is preferred that protrusion 36p be from air side towards 42 side of basement membrane and sectional area (be orthogonal to incident light The parallel section in the face of line, such as the section parallel with the face of basement membrane 42) increased shape, such as cone.In addition, in order to press down The interference of light processed arranges protrusion 36p randomly, so that its no regularity.However, according to the use of synthetic polymeric membrane 36 The difference on way, these features it is not necessary to.For example, protrusion 36p is not necessarily to be closely aligned, alternatively, it is also possible to regularly arranged.

Illustrate the manufacturing method of synthetic polymeric membrane 36.

Firstly, preparing the ophthalmically acceptable mold 100 of moth.The ophthalmically acceptable mold 100 of moth has porous alumina layer, above-mentioned porous oxygen on surface Changing aluminium layer to have the two-dimentional size when watching from normal to a surface direction is 20nm or more and less than multiple recess portions of 500nm. Multiple recess portions constitute the moth ocular structure of reversion.The ophthalmically acceptable mold 100 of moth for example can be by using side documented by patent document 3 Anodizing of aluminium and etching is repeated to obtain in method.The manufacturing method of the ophthalmically acceptable mold 100 of moth will be described in more detail below.

Next, assigning lower-layer resin (sometimes referred to as " the 1st resin " to the surface of basement membrane 42 as shown in (a) of Figure 11.) 36a'.Resin (sometimes referred to as " the 2nd tree in upper layer is assigned on the moth ocular structure of the reversion possessed by the ophthalmically acceptable mold 100 of moth Rouge ".)36b'.

Lower-layer resin 36a ' is for example able to use acrylic resin (acrylate monomer).In addition, in the present specification, Monomer is that the typical example of the raw material as light-cured resin provides, it is not excluded that oligomer.Lower-layer resin 36a ' example It such as include uv curing resin.Lower-layer resin 36a ' can not be fluorine-containing, can also be fluorine-containing, preferably the fluorine of lower-layer resin 36a ' Containing ratio is lower than the fluorine containing ratio of upper layer resin 36b '.Lower-layer resin 36a ' for example passes through intaglio printing mode or slit die mode To assign.Also slit coater or rod coater etc. can be used to assign.It is imparted to the lower layer when surface of basement membrane 42 The thickness of resin 36a ' is, for example, 3 μm~30 μm, such as preferably 5 μm~7 μm.The viscosity of lower-layer resin 36a ' is, for example, 50cP ~200cP, such as preferably 100cP.

Basement membrane 42 is, for example, PET (polyethylene terephthalate) film or TAC (triacetyl cellulose) film.

Upper layer resin 36b ' has fluorochemical monomer 38.Fluorochemical monomer 38 is, for example, fluoroacrylic resin.Fluorochemical monomer 38 Such as with fluorine-containing hydrocarbon chain 38c and acrylate-based 38t, acrylate-based 38t is at its end.Fluorine-containing hydrocarbon chain 38c also can wrap Ether-containing key.Solidify it is preferred that fluorochemical monomer 38 is irradiated by ultraviolet light.Upper layer resin 36b ' for example passes through spray coating method, intaglio printing Mode or slit die mode assign.Also slit coater or rod coater etc. can be used to assign.Using spraying In the case where method, such as using ultrasonic nozzle, two-fluid spray nozzle, swirl nozzle (swirl nozzle) or electrostatic atomiser, Resin 36b ' in upper layer is assigned on the ophthalmically acceptable mold 100 of moth.The thickness of upper layer resin 36b ' when being imparted on the ophthalmically acceptable mold 100 of moth There is no special lower limit, preferably more than 5 μm, for example, more than 0 μm and 3 μm hereinafter, more preferably 2 μm or less.Upper layer resin The viscosity of 36b ' is, for example, 1cP~100cP.In the case where assigning upper layer resin 36b ' by spray coating method, preferred upper layer tree The viscosity of rouge 36b ' is for example 100cP at 23 DEG C hereinafter, more preferably 20cP or less.

Upper layer resin 36b ' for example also has reactive diluent.Reactive diluent is for example able to use 4- acryloyl Quinoline.The chemical structural formula of the 4- acryloyl morpholine as shown in [chemical formula 1], 4- acryloyl morpholine has acryloyl group (H₂C =CH-C (=O) -), there is nitrogen.

[chemical formula 1]

In the case where lower-layer resin 36a ' includes solvent, before process shown in (b) such as Figure 11, carry out making solvent The process (such as heat treatment) of evaporation.In the case that on upper layer, resin 36b ' includes solvent, for example, in (b) institute of such as Figure 11 Before the process shown, the process (such as heat treatment) for evaporating solvent is carried out.It is preferred that lower-layer resin 36a ' and upper layer resin 36b ' does not include solvent.If lower-layer resin 36a ' and upper layer resin 36b ' does not include solvent, can reduce using solvent institute The cost of cost and the load foul smell etc. of when (such as using) in terms of environment.Moreover, being able to suppress the work for evaporating solvent Cost, the place etc. that sequence the time it takes, the device for evaporating solvent are spent.

Fluorine-containing list in the case where the lower-layer resin 36a ' of synthetic polymeric membrane 36 contains solvent, in the resin 36b ' of upper layer Body 38 has the tendency that being easy to mix with lower-layer resin 36a ', therefore, worries that fluorine element is difficult to be biased to the convex of synthetic polymeric membrane 36 The portion side 36p.In the case where the lower-layer resin 36a ' of synthetic polymeric membrane 36 contains solvent, if the drying of solvent is insufficient, Then worry that the close property of basement membrane 42 and synthetic polymeric membrane 36 (underclad portion 36a) declines.

In particular, manufacturing synthetic polymeric membrane 36, preferably upper layer resin to use the cylindric ophthalmically acceptable mold 100 of moth 36b ' does not include solvent.The viscosity of upper layer resin 36b ' not comprising solvent is for example preferably 100cP or less.

The ophthalmically acceptable mold 100 of moth is also possible to be carried out demoulding processing.That is, can also assign upper layer resin 36b ' it Before, release agent is assigned to the moth ocular structure of the reversion of the ophthalmically acceptable mold of moth 100.It is handled when implementing demoulding to the ophthalmically acceptable mold of moth 100 When, the fluorine-containing hydrocarbon chain 38c of fluorochemical monomer 38 can be demolded agent and draw over to one's side, the fluorine element of ophthalmically acceptable 100 side of mold of the moth of top section 36b Containing ratio may be got higher.

Then, as shown in (b) of Figure 11, ultraviolet light is irradiated in the state that basement membrane 42 is pressed into moth ophthalmically acceptable mold 100 (UV).When basement membrane 42 is pressed into the ophthalmically acceptable mold 100 of moth, lower-layer resin 36a ' contacts with each other with upper layer resin 36b ', and Interface is mutually mixed.When basement membrane 42 is pressed into the ophthalmically acceptable mold 100 of moth, due to lower-layer resin 36a ' and upper layer resin 36b ' It is not yet cured, therefore, not will form specific interface between lower-layer resin 36a ' and upper layer resin 36b '.In lower-layer resin In the state that 36a ' is mixed with upper layer resin 36b ', ultraviolet light, lower layer tree are irradiated to lower-layer resin 36a ' and upper layer resin 36b ' Rouge 36a ' and upper layer resin 36b ' are cured.

Due to being cured, as shown in (c) of Figure 11, fluorochemical monomer 38 reacts with reactive diluent.Fluorochemical monomer 38 also react with other acrylate monomers (including the acrylate monomer contained by lower-layer resin).To third after reaction The appended drawing reference of olefin(e) acid ester group 38t marks (r), indicates that reaction has terminated.Later, by making the ophthalmically acceptable mold 100 of moth from basement membrane 42 Separation, to form the synthetic polymeric membrane for having transferred the moth ocular structure of reversion of the ophthalmically acceptable mold 100 of moth on the surface of basement membrane 42 36.Protrusion 36p possessed by synthetic polymeric membrane 36, two-dimentional size D_p, height D_hAnd adjacent spacing is from D_intDepending on closing The shape of the recess portion of the ophthalmically acceptable mold 100 of moth used in manufacture at polymeric membrane 36.

Synthetic polymeric membrane 36 for example includes underclad portion 36a, mainly has lower-layer resin；And top section 36b mainly has upper layer resin.The fluorine containing ratio of top section 36b is higher than the fluorine containing ratio of underclad portion 36a.On upper layer Specific interface is not formed between part 36b and underclad portion 36a.

Since the top section 36b of synthetic polymeric membrane 36 has fluorochemical monomer 38, it is attached to synthetic polymeric membrane The greases such as 36 fingerprint are difficult to extend.Therefore, it even if the greases such as fingerprint are attached on synthetic polymeric membrane 36, is also not easy eye-catching. Moreover, synthetic polymeric membrane 36 can easily wipe the greases such as the fingerprint of attachment.Due to can easily wipe grease, The worry that protrusion 36p is destroyed is also few.The excellent scratch resistance of synthetic polymeric membrane 36.

Figure 12 is to schematically show the concentration of element of the fluorine (F) and nitrogen (N) of synthetic polymeric membrane 36 in a thickness direction Variation (depth distribution) figure.The horizontal axis of Figure 12 indicates the surface (table with multiple protrusion 36p away from synthetic polymeric membrane 36 Face) depth (depth of normal direction), the longitudinal axis indicate each element concentration of element (at%).

As shown in figure 12, depth of the fluorine element concentration of synthetic polymeric membrane 36 on the surface away from synthetic polymeric membrane 36 becomes When big, continuously (slowly) change from the fluorine element concentration of top section 36b to the fluorine element concentration of underclad portion 36a.Nitrogen When concentration of element is also that the depth on the surface away from synthetic polymeric membrane 36 becomes larger, from the nitrogen concentration of top section 36b to The nitrogen concentration of underclad portion 36a continuously (slowly) changes.

It is also possible to when the depth on the surface away from synthetic polymeric membrane 36 becomes larger, each element concentration moves closer under Concentration of element in layer resin.The face of synthetic polymeric membrane 36, surface with multiple protrusion 36p opposite side is (sometimes referred to as For " face of 42 side of basement membrane ".) composition it is substantially identical as the composition of lower-layer resin.Here, synthetic polymeric membrane 36, basement membrane The composition in the face of 42 sides refers to the composition of the part in face in synthetic polymeric membrane 36, constituting 42 side of basement membrane.For example, synthesis is high The concentration for the nitrogen that molecular film 36,42 side of basement membrane face is included refers in synthetic polymeric membrane 36, composition basement membrane 42 The concentration for the nitrogen that the part in the face of side is included.Such as, it is believed that in synthetic polymeric membrane 36 from the face of 42 side of basement membrane The thickness t of synthetic polymeric membrane 36 is arrived in normal direction_sAt least 1/5 until in the range of, have it is identical with lower-layer resin Composition.Therefore, the composition in the face of 42 side of basement membrane in order to obtain, as long as the composition in measurement such as above range.

Pair it can be seen that from the face of 42 side of basement membrane of synthetic polymeric membrane 36 in the normal side of synthetic polymeric membrane 36 To the thickness t of synthetic polymeric membrane 36_sFor example, at least 1/5 until in the range of upper layer resin be substantially absent included Ingredient and there is the reason of composition identical with lower-layer resin to be illustrated.As referring to Fig.1 1 it is above-mentioned as, synthesis high score In the manufacturing process of sub- film 36, when basement membrane 42 is pressed into the ophthalmically acceptable mold 100 of moth, lower-layer resin 36a ' and upper layer resin 36b ' It contacts with each other.Although the two near it has a common boundary phase counterdiffusion and mix, ingredient that upper layer resin 36b ' is included, particularly It is whole that fluorine element can't be diffused into lower-layer resin 36a '.This is because fluorine element, which has, wants to be present in ophthalmically acceptable 100 side of mold of moth Tendency.If short from the time that lower-layer resin 36a ' and upper layer resin 36b ' contacts with each other until irradiating ultraviolet light, expand Scattered degree may further become smaller.It contacts with each other until irradiating ultraviolet light from lower-layer resin 36a ' and upper layer resin 36b ' Time be, for example, 3 seconds~5 seconds.

The variation of the concentration of element of each element of synthetic polymeric membrane 36 in a thickness direction is certainly not limited to the example of diagram Son.For example, in the example in the figures, although underclad portion 36a does not have element silicon and fluorine element, under arbitrarily selecting The concentration of element of the material of layer resin, element silicon and fluorine element can change.Lower-layer resin also can have fluorine system lubricant And/or silicone base lubricant.When upper layer resin has reactive diluent, top section 36b is for example with nitrogen and third Enoyl-.

The present inventor, which has studied through roll-to-roll mode, manufactures the excellent synthetic polymeric membrane 36 of soil resistance.This Invention inventors have found that in the case where manufacturing synthetic polymeric membrane 36 by roll-to-roll mode, fabrication yield sometimes It can decline.Referring to Fig.1 3, Figure 14 and Figure 15 come illustrate the inventors found that the problem of.Figure 13 is for illustrating to pass through Roll-to-roll mode manufactures the schematical sectional view of the method for synthetic polymeric membrane 36.Figure 14 and Figure 15 is for illustrating logical The schematical sectional view for crossing roll-to-roll mode to lead to the problem of in the case where manufacturing synthetic polymeric membrane 36.

3 illustrate the method that synthetic polymeric membrane 36 is manufactured by roll-to-roll mode referring to Fig.1.

Firstly, preparing the cylindric or cylindric ophthalmically acceptable mold 100A of moth.The ophthalmically acceptable mold 100A of moth has porous on surface Alumina layer 14, it is 20nm or more and not that porous alumina layer 14, which has the two-dimentional size when watching from normal to a surface direction, To multiple recess portion 14p of 500nm.Multiple recess portion 14p constitute the moth ocular structure of reversion.The ophthalmically acceptable mold of cylindric or cylindric moth The manufacturing method of 100A will be described in more detail below.

The ophthalmically acceptable mold 100A of moth is for example configured to the axially substantially upper and horizontal direction of the ophthalmically acceptable mold 100A of moth (with vertical side To vertical direction) it is parallel.Figure 13 is schematical sectional view when from the axial viewing of the ophthalmically acceptable mold 100A of moth.Figure 14 and Figure 15 is also same.

Next, as shown in figure 13, being pressed into surface in the basement membrane 42 that surface is had been assigned to lower-layer resin 36a ' and being assigned It has given in the state of the ophthalmically acceptable mold 100A of moth of upper layer resin 36b ' (that is, making lower-layer resin 36a ' and upper layer resin 36b ' In In the state of contacting with each other between the ophthalmically acceptable mold 100A of moth and the surface of basement membrane 42), to lower-layer resin 36a ' and upper layer resin 36b ' irradiates ultraviolet light (UV), so that lower-layer resin 36a ' and upper layer resin 36b ' be made to solidify.

Basement membrane 42 is unreeled from let off roll (not shown), later, is assigned using the surface to basement membrane 42 such as such as slit coater Give lower-layer resin 36a '.As shown in figure 13, basement membrane 42 is supported by support roller 46 and 48.Support roller 46 and 48 has rotating mechanism, Basement membrane 42 is carried.Support roller 46 is the pressure carried for having been assigned the basement membrane 42 of lower-layer resin 36a ' to surface Roller, support roller 48 are for will have the basement membrane 42 of the synthetic polymeric membrane 36 after solidifying to shell from the ophthalmically acceptable mold 100A of moth on surface From roller.The ophthalmically acceptable mold 100A of moth, support roller 46 and support roller 48 are respectively with rotation corresponding with the transporting velocity of basement membrane 42 Speed is rotated along direction shown in arrow in Figure 13.

It is excellent in order to which the surface (outer peripheral surface) to the cylindric or cylindric ophthalmically acceptable mold 100A of moth assigns upper layer resin 36b ' Choosing uses spray coating method.Spray coating method is suitable for roll-to-roll mode due to that easily can form uniform liquid film in curved surface. In addition, spray coating method for example with material required for the easily controllable thickness for being formed by liquid film, the liquid film for formation (herein Resin material) amount it is few, be able to suppress for the cost of device setting and the advantages that space.

Here, as shown in figure 13, being sprayed in the form of mist from spray nozzle 92 to the outer peripheral surface of the ophthalmically acceptable mold 100A of moth Layer resin 36b '.There can also be multiple spray nozzles 92 along the axial alignment of the ophthalmically acceptable mold 100A of moth.Such as it is supplied from liquid Device 93 (referring to Fig.1 4) supplies upper layer resin 36b ' to spray nozzle 92.Spray nozzle 92 is to the periphery of the ophthalmically acceptable mold 100A of moth The part that in face, basement membrane 42 is not pressed sprays upper layer resin 36b ' in the form of mist.In the example in the figures, spraying spray Mouth 92 is arranged below vertical direction (direction vertical with horizontal direction) relative to the ophthalmically acceptable mold 100A of moth, from spray nozzle 92 Spray upper layer resin 36b ' angle be compared with horizontal direction more up.In addition, in the example in the figures, ultraviolet light (UV) from The upside of the ophthalmically acceptable mold 100A of moth is irradiated.Such as exposure device is square in the vertical direction relative to the ophthalmically acceptable mold 100A configuration of moth. But the configuration of spray nozzle 92 and exposure device is not limited to example illustrated.Spray nozzle 92 also can be set ophthalmically acceptable in moth Above the vertical direction of mold 100A, from spray nozzle 92 to the more downwardly direction ejection upper layer resin compared with horizontal direction 36b'.In this case, for example, exposure device configuration is below the vertical direction of the ophthalmically acceptable mold 100A of moth, ultraviolet light (UV) It can the irradiation below the vertical direction of the ophthalmically acceptable mold 100A of moth.

After solidifying lower-layer resin 36a ' and upper layer resin 36b ', by the way that the ophthalmically acceptable mold 100A of moth is divided from basement membrane 42 From to form the synthetic polymeric membrane for having transferred the moth ocular structure of reversion of the ophthalmically acceptable mold 100A of moth on the surface of basement membrane 42 36.The not shown work beam of basement membrane 42 that surface is formed with synthetic polymeric membrane 36 batches.It can also be formed with by surface The basement membrane 42 of synthetic polymeric membrane 36 from moth ophthalmically acceptable mold 100A separation and then it is secondary synthetic polymeric membrane 36 is irradiated it is ultraviolet Line.

The surface of synthetic polymeric membrane 36 has nanometer made of the nano surface structure reversion by the ophthalmically acceptable mold 100A of moth Surface texture.By the nano surface structure of the ophthalmically acceptable mold of appropriate adjustment moth, can manufacture with desired Nanosurface knot The synthetic polymeric membrane of structure.

Lower-layer resin 36a ' is not limited to uv curing resin, and also may include can be by the photocuring of visible-light curing Property resin.

The research of inventor according to the present invention is passing through spray coating method to the cylindric or cylindric ophthalmically acceptable mold 100A of moth Outer peripheral surface 100s assign upper layer resin 36b ' process in, sometimes due to upper layer resin 36b ' disperses to periphery and causes to manufacture Decrease in yield.As shown in figure 14, when spraying upper layer resin 36b ' in the form of mist from spray nozzle 92, upper layer resin 36b ' It disperses sometimes along the outer peripheral surface 100s of the ophthalmically acceptable mold 100A of such as moth to periphery.Think the week in the ophthalmically acceptable mold 100A of moth Enclose, as the ophthalmically acceptable mold 100A of moth, support roller 46 and support roller 48 rotation and can generate shown in the arrow in Figure 15 like that Air-flow.Think that the upper layer resin 36b ' sprayed in the form of mist can multiply the air-flow and be diffused into week of the ophthalmically acceptable mold 100A of moth It encloses.Also shown in Figure 15 indicate the ophthalmically acceptable mold 100A of moth, support roller 46 and support roller 48 direction of rotation arrow.In In example illustrated, the direction of rotation of the flowing and the ophthalmically acceptable mold 100A of moth that there is the gas sprayed from spray nozzle 92 is combined And form the tendency of the strong air-flow flowed along the periphery of the ophthalmically acceptable mold 100A of moth towards 46 side of support roller.In addition, in moth Between ophthalmically acceptable mold 100A and support roller 46, close to each other with the surface of the surface of the ophthalmically acceptable mold 100A of moth and support roller 46 The position that mode is rotated generates especially strong air-flow.Even in addition, around not along the ophthalmically acceptable mold 100A of moth In the case where the roller of rotation, it is also possible to generate the liquid sprayed in the form of mist from spray nozzle 92 as shown in figure 14 along moth eye It is dispersed with the outer peripheral surface 100s of mold 100A to periphery such problems.

As described above, the thickness of the upper layer resin 36b ' when being imparted on the ophthalmically acceptable mold 100A of moth is preferably more than 5 μm, example For example more than 0 μm and 3 μm hereinafter, more preferably 2 μm or less.In order to form this thin liquid film, it is preferable to use spray coating method.Upper layer Resin 36b ' is sprayed in the form of mist as mist (mist), therefore, is easy the air-flow on the periphery by the ophthalmically acceptable mold 100A of moth Influence, be easy to disperse.In particular, in order to be formed on the ophthalmically acceptable mold 100A of moth with a thickness of 2 μm of resin 36b ' in upper layer below, Such as preferably 20 μm or less of average diameter as the upper layer resin 36b ' that mist is sprayed in the form of mist from spray nozzle 92.

In the above content, it illustrates that upper layer resin 36b ' is imparted to cylindric or cylindric moth eye using spray coating method The problem of being declined in the process of the outer peripheral surface 100s of mold 100A, fabrication yield.The problem is not limited to manufacture soil resistance The process of excellent synthetic polymeric membrane, in addition, being also not necessarily limited to the process using the ophthalmically acceptable mold of moth.For in cylindric or cylinder The process that the outer peripheral surface of the substrate of shape forms liquid film is common problem.

Illustrate the liquid film forming method and liquid film forming device of embodiments of the present invention referring to the drawings.In addition, The present invention is not limited to embodiments illustrated below.In the following figures, has the function of substantially the same constituent element Sometimes it is indicated by common appended drawing reference, and the description thereof will be omitted.

Referring to Fig.1, Fig. 2 and Fig. 3 come illustrate embodiments of the present invention, cylindric or cylindric substrate outer The method (sometimes referred to as " liquid film forming method " of circumferential surface formation liquid film.) and cylindric or cylindric substrate outer peripheral surface Form the device (sometimes referred to as " liquid film forming device " of liquid film.).Fig. 1, Fig. 2 and Fig. 3 are for illustrating implementation of the invention The liquid film forming method of mode and the schematical figure of liquid film forming device 50, Fig. 2 shows cutting along the A-A ' line in Fig. 1 Face.Fig. 1 and Fig. 3 is schematical sectional view when from the axial viewing of substrate 100A.

The liquid film forming method of embodiments of the present invention includes: process (a), to the outer of cylindric or cylindric substrate Circumferential surface sprays liquid in the form of mist；And process (b), attract the gas on the periphery of outer peripheral surface.Process (b) includes and process (a) process carried out simultaneously.The flow-rate ratio of the gas attracted in process (b) includes to be sprayed in the form of mist in process (a) Liquid gas flow it is more.

The liquid film forming method of embodiment according to the present invention can inhibit the liquid sprayed in the form of mist to disperse to week Side.The liquid film forming method of embodiment according to the present invention, is able to suppress the outer peripheral surface in cylindric or cylindric substrate Form the decline of the fabrication yield in the process of liquid film.

Attracting the gas on the periphery of outer peripheral surface while the outer peripheral surface to substrate sprays liquid in the form of mist, So as to inhibit to make in the form of mist spray liquid be diffused into surrounding air-flow generation.Embodiment according to the present invention Liquid film forming method, without being contacted with substrate, it will be able to the liquid sprayed in the form of mist be inhibited to spread to surrounding.

The liquid film forming method of embodiments of the present invention in the case where being used for roll-to-roll mode, can also for example wrap Contain: process (c), in the state of being configured with substrate in a manner of the axially substantially upper and horizontal direction parallel for making substrate, with base Substrate is rotated centered on the axis of material.In process (c), the rotation speed of substrate be for example preferably more than 0rpm and 20rpm with Under.

The liquid film forming method of embodiments of the present invention can be also suitably used for roll-to-roll mode.Embodiments of the present invention Liquid film forming method does not have to contact the liquid for being just able to suppress and spraying in the form of mist with substrate to surrounding diffusion, therefore, fits yet Share in in rotation substrate spray liquid in the form of mist the case where.In addition, in roll-to-roll mode, due to mist Form spray upper layer resin process be comprising other process (for example, assigning the process of lower-layer resin to the surface of basement membrane, shining The process etc. of penetrating ultraviolet light) a series of processes among carry out, therefore, be suitble to the liquid film shape using embodiments of the present invention At method.In roll-to-roll mode, for example it is difficult to by the surface of the ophthalmically acceptable mold of moth from other support rollers, other equipment separate and Keep its closed.In addition, in roll-to-roll mode, the ophthalmically acceptable mold of moth is rotation, therefore, if it is desired to using with the ophthalmically acceptable mold of moth The a part of closed of surface is then worried the surface that can injure the ophthalmically acceptable mold of moth by the cover component of contact.

The liquid film forming method of embodiments of the present invention is able to use liquid film forming device 50 for example to carry out.

As depicted in figs. 1 and 2, liquid film forming device 50 is on the outer peripheral surface 100s of cylindric or cylindric substrate 100A Form liquid film.Cylindric or cylindric substrate is, for example, the ophthalmically acceptable mold of moth.In order to simple, to cylindric or cylindric substrate Mark appended drawing reference identical with the ophthalmically acceptable mold 100A of moth.

Liquid film forming device 50 includes blow-off outlet 51, and liquid is sprayed in the form of mist；Liquid supplying apparatus 52, will Liquid is supplied to blow-off outlet 51；The inside cover portion 53 of tubular delimit blow-off outlet 51；Outside cover portion 54 is configured in inside cover The outside in portion 53；Suction inlet 55 delimited by inside cover portion 53 and outside cover portion 54；And gas suction device 56, pass through Suction inlet 55 attracts gas.

As shown in Fig. 2, length Li1 of the blow-off outlet 51 in the 1st direction (x-axis direction in figure) is greater than with the 1st direction just The length Li2 for the blow-off outlet 51 on the 2nd direction (the y-axis direction in figure) handed over.In the outer peripheral surface 100s to substrate 100A with mist Form when spraying liquid, blow-off outlet 51 is in the 1st direction mode substantially parallel with the axial direction of substrate 100A towards outer peripheral surface 100s.In Fig. 1, substrate 100A is configured in the axial direction of the substrate 100A mode substantially parallel with the 1st direction.In Fig. 1 and Fig. 2 In, xyz orthogonal coordinate system is shown for liquid film forming device 50, but liquid supplying apparatus 52 and gas suction device 56 are not It is limited to this.In the example in the figures, inside cover portion 53 and outside cover portion 54 are and the 3rd side that is orthogonal to the 1st direction and the 2nd direction The tubular extended roughly in parallel to (the z-axis direction in figure).But the extending direction of inside cover portion 53 and outside cover portion 54 It can not be substantially parallel with the 3rd direction.

Suction inlet 55 includes adjacent and in the 1st direction (in figure on the 2nd direction (the y-axis direction in figure) with blow-off outlet 51 X-axis direction) on the part 55m that extends.

Here, having delimited 1 suction inlet 55 by inside cover portion 53 and outside cover portion 54.In this embodiment, including blow-off outlet 51 and suction inlet 55 section in, inside cover portion 53 is surrounded by outside cover portion 54.In this embodiment, suction inlet 55 is in the 1st direction (figure In x-axis direction) on length Lo1 be greater than length Li1 of the blow-off outlet 51 on the 1st direction, suction inlet 55 the 2nd direction (figure In y-axis direction) on length Lo2 be greater than length Li2 of the blow-off outlet 51 on the 2nd direction.But inside cover portion 53 and outside The shape of cover portion 54 and their configuration relation are not limited to the content of diagram.It can also be by inside cover portion 53 and outside cover portion 54 delimit 2 or more suction inlets.

Gas suction device 56 is configured to the gas for attracting flow-rate ratio to include the liquid sprayed in the form of mist from blow-off outlet 51 Gas more than the flow of body.

It is arranged along the 1st direction and as shown in Fig. 2, liquid film forming device 50 also has for example in blow-off outlet 51 with mist Multiple nozzles 57 of form ejection liquid.In addition, liquid film forming device 50 also has for example in suction inlet 55 is connected to gas Multiple suction ports 58 of suction device 56.As shown in Figure 1, for example, nozzle 57 connects via interconnecting piece 67 and liquid supplying apparatus 52 It connects.For example, suction port 58 is connect via interconnecting piece 65 with gas suction device 56.

According to liquid film forming device 50, the outer peripheral surface to cylindric or cylindric substrate can be inhibited to spray in the form of mist Liquid disperse to periphery.The liquid film forming method of embodiment according to the present invention, is able to suppress cylindric or cylindric Substrate outer peripheral surface formed liquid film process in fabrication yield decline.

It include the gas of the liquid sprayed in the form of mist from blow-off outlet 51 making gas suction device 56 attract flow-rate ratio Gas more than the flow of body, so that the liquid sprayed in the form of mist be inhibited to spread along the outer peripheral surface 100s of substrate 100A. In Fig. 1, by the flowing for the gas for having added the arrow of oblique line to indicate that gas suction device 56 is attracted by suction inlet 55, by hollow Arrow indicate the flowing of the gas of liquid comprising spraying in the form of mist from blow-off outlet 51, on the outside of the arrow expression of blacking The flowing of the gas in the outside of cover portion 54.Include what is sprayed in the form of mist from blow-off outlet 51 to the outer peripheral surface 100s of substrate 100A The gas of liquid is attracted after the outer peripheral surface 100s for reaching substrate 100A from suction inlet 55, therefore, it can be inhibited along outer Circumferential surface 100s diffusion.In particular, in length Li1 of the blow-off outlet 51 on the 1st direction relative to the length Li2 on the 2nd direction Depth-width ratio (Li1/Li2) it is big in the case where, the contribution of the air-flow of the gas attracted from the part 55m in suction inlet 55 is big.This It is because the part 55m in suction inlet 55 is adjacent and along substrate on the circumferencial direction of substrate 100A with blow-off outlet 51 100A's is axially extending.Moreover, generate between cover portion 54 and substrate 100A has from the outside of outside cover portion 54 inwardly on the outside The air-flow of flowing, this can also inhibit the liquid sprayed in the form of mist to spread along outer peripheral surface 100s.From blow-off outlet 51 with mist The liquid that form sprays is sprayed in the form of mist with the gases by mist.As mist from blow-off outlet 51 in the form of mist The average diameter of the liquid of ejection is, for example, 20 μm or less.

As shown in Fig. 2, it is preferred that blow-off outlet 51 is in 3rd direction (the z-axis side in figure vertical with the 1st direction and the 2nd direction To) on penetrate through.This is because being continuously generated above-mentioned air-flow during spraying liquid in the form of mist, It is preferred that the air pressure in blow-off outlet 51 is kept constant.In addition, efficiently attracting gas by suction inlet 55 from by gas suction device 56 From the perspective of body, preferably suction inlet 55 is not penetrated through on the 3rd direction.In the example in the figures, liquid film forming device 50 also has There are the bottom surface sections 62 of the side opposite with the side substrate 100A of covering suction inlet 55.Bottom surface sections 62 with do not cover blow-off outlet 51 with The mode of the opposite side in the side substrate 100A is formed.

Illustrate the positional relationship of substrate 100A Yu liquid film forming device 50 referring to Fig. 3.

The positional relationship of substrate 100A and liquid film forming device 50 for example depending on the top of the squit hole from nozzle 57 to The outer peripheral surface 100s of the shortest distance wd of the outer peripheral surface 100s of the ophthalmically acceptable mold 100A of moth, inside cover portion 53 and the ophthalmically acceptable mold 100A of moth Shortest distance dm1, the shortest distance dm2 of outer peripheral surface 100s of outside cover portion 54 and the ophthalmically acceptable mold 100A of moth etc..In Fig. 3 also Illustrate the outer peripheral surface 100s of on the direction that inside cover portion 53 is extended with tubular, inside cover portion 53 Yu the ophthalmically acceptable mold 100A of moth Distance dv1 and cover portion 54 is extended with tubular on the outside direction on, outside cover portion 54 and the ophthalmically acceptable mold 100A of moth it is outer The distance dv2 of circumferential surface 100s.In addition, length on the direction that inside cover portion 53 is extended with tubular, inside cover portion 53 is set For Li3, length on direction that cover portion 54 on the outside is extended with tubular, outside cover portion 54 is set as Lo3.

Liquid film forming device 50 does not have to contact with the outer peripheral surface 100s of substrate 100A, it will be able to inhibit to spray in the form of mist Liquid disperse to periphery.Liquid film forming device 50 is for example configured to spray in the form of mist to the outer peripheral surface 100s of substrate 100A Out when liquid, inside cover portion 53 and outside cover portion 54 can not be contacted with the outer peripheral surface 100s of substrate 100A.

The result of study of the present inventor as hereinafter described is such, is inhaled by regulating gas suction device 56 The flow and inside cover portion 53 of the gas drawn, outside cover portion 54 can control at a distance from substrate 100A from outside cover portion 54 The air-flow (arrow of the blacking in Fig. 1) that flows inwardly of outside.By control be so that from the outer side of outside cover portion 54 to The speed (flow velocity) of the air-flow of inside flowing has suitable value and since the unevenness of flow velocity caused by the difference of position becomes smaller, energy The liquid for enough the outer peripheral surface 100s to cylindric or cylindric substrate 100A being inhibited to spray in the form of mist disperses to periphery, and And liquid film can be formed uniformly in the outer peripheral surface 100s of substrate 100A.For example, if inwardly from the outside of outside cover portion 54 The flow velocity of the air-flow of flowing is insufficient, then can not inhibit dispersing for the liquid sprayed in the form of mist, but if the flow velocity mistake of air-flow Greatly, then it is formed by liquid film there may be unevenness.In addition, embodiments of the present invention are not limited to the condition illustrated.It can be according to packet The scale (size) of system containing substrate, the characteristic of the liquid sprayed in the form of mist, is formed the size of the substrate of formation liquid film The appropriate adjustments such as the thickness of liquid film.

Liquid film forming device 50 is for example also configured to, and is sprayed in the form of mist to the outer peripheral surface 100s of substrate 100A When liquid, it can change at a distance from the outer peripheral surface 100s of inside cover portion 53 and substrate 100A or outside cover portion 54 and substrate 100A Outer peripheral surface 100s distance at least one party.For example, outside cover portion 54 includes cylinder in aftermentioned example shown in Fig. 9 Shape portion 54a, extends roughly in parallel with inside cover portion 53；And sliding part 54s, the substrate of cylindrical portion 54a is set The end of the side 100A can be slided along cylindrical portion 54a.By sliding sliding part 54s along cylindrical portion 54a, cunning can be changed At a distance from the outer peripheral surface 100s of dynamic portion 54s and substrate 100A, thus, it is possible to change the outer peripheral surface of outside cover portion 54 and substrate 100A The distance of 100s.

In addition, as shown in figure 3, inside cover portion 53 and outside cover portion 54 can also be supported by supporting table 66.In the example of diagram In son, nozzle 57 is also supported by supporting table 66.Supporting table 66 also can have wheel (castor) 68.If inside cover portion 53 and outer Side cover portion 54 is arranged in supporting table 66, then can easily adjust them at a distance from substrate 100A.If supporting table 66 has There is wheel 68, then can further be easy to carry out adjusting.In addition, by making inside cover portion 53 and outside cover portion 54 by supporting table 66 Support can be easily moved inside cover portion 53 and outside cover portion 54, also, can also obtain cutting down for liquid film shape to be arranged At device 50 space the advantages of.In addition, the diagram of liquid supplying apparatus 52 and gas suction device 56 is omitted in Fig. 3.

The research of inventor according to the present invention, for example, if being configured to the gas that gas suction device 56 is attracted Flow is 9 times or more and 15 times of the flow of the gas of the liquid comprising being sprayed in the form of mist from blow-off outlet 51 hereinafter, then can The liquid for enough the outer peripheral surface 100s to cylindric or cylindric substrate 100A being inhibited to spray in the form of mist disperses to periphery, and And liquid film can be formed uniformly in the outer peripheral surface 100s of substrate 100A.If the gas that gas suction device 56 is attracted Flow is then sprayed in the form of mist less than 9 times of flow of the gas of the liquid comprising being sprayed in the form of mist from blow-off outlet 51 Liquid can be attached to outside cover portion 54 outside.If the flow for the gas that gas suction device 56 is attracted be more than comprising from 15 times of the flow of the gas for the liquid that blow-off outlet 51 is sprayed in the form of mist are then formed in the outer peripheral surface 100s's of substrate 100A Liquid film can generate unevenness.

The present inventor has used the liquid film forming device 50 of Fig. 3 and structure shown in Fig. 4 to have studied suitable suction Drainage flow.Fig. 4 is the schematical figure of an example for illustrating the composition of liquid film forming device 50.

Ultrasonic nozzle (manufacture of Sono-Tek society, ProductName: vortex) is used as nozzle 57.As shown in figure 4, blowing out In mouth 51, it is configured with 15 nozzles 57 (referring to figure 5 and figure 6 to high infraversion malposition.If a=53 ° of angle, θ, θ b=in Fig. 6 62°.).In suction inlet 55,8 suction ports 58 are each provided in the two sides of blow-off outlet 51.Inside cover portion 53 and outside cover portion 54 Size, inside cover portion 53, outside cover portion 54 and substrate distance dv1, dv2, shortest distance dm1, dm2 it is as follows.

Li1=1420mm, Li2=107mm, Li3=152mm

Lo1=1442mm, Lo2=213mm, Lo3=189mm

DL1=50mm, dL2=8mm

Dm1=15.2mm, dm2=22.5mm

Dv1=25mm, dv2=25mm

Here, inside cover portion 53 configures the center of cover portion 54 on the outside on the 1st direction, configured outside on the 2nd direction The center in side cover portion 54.Suction inlet 55 is formed in a manner of surrounding inside cover portion 53.Also shown in Fig. 4 suction inlet 55 The width dL2 for the part that 1st side upwardly extends and width dL1 in the part that the 2nd side upwardly extends.

The length of used substrate 100A in the axial direction is 1600mm, and the diameter of bottom surface is 300mm.It is sprayed in the form of mist Out when liquid, the shortest distance wd of the outer peripheral surface 100s of the top of nozzle 57 and substrate 100A be 110.45mm.

The flow of gas comprising the liquid sprayed in the form of mist from blow-off outlet 51 is set as 2m³/min.Pass through setting Valve between suction port 58 and gas suction device 56, the flow for the gas for attracting gas suction device 56 become Change.It is 17.3m in the flow for the gas that gas suction device 56 is attracted³In the case where/min, the liquid of ejection in the form of mist Body is attached to the outside of outside cover portion 54, is 30.9m in the flow for the gas that gas suction device 56 is attracted³The case where/min Under, the liquid film for being formed in the outer peripheral surface 100s of substrate 100A generates unevenness.In the stream for the gas that gas suction device 56 is attracted Amount is 24.3m³In the case where/min, it is able to suppress the liquid sprayed in the form of mist and disperses to periphery, further, it is possible in substrate The outer peripheral surface 100s of 100A is formed uniformly liquid film.

In addition, the present inventor according to the flow velocity of the sectional area of suction inlet 55 and the air-flow by suction inlet 55 it Product, estimates the flow for the gas that gas suction device 56 is attracted.The sectional area of suction inlet 55 is set as Lo1 × dL2 ×2.It is less than the width in the part that the 1st side upwardly extends due to the width dL1 in the part that the 2nd side upwardly extends of suction inlet 55 Spend dL2, therefore sectional area out approximate like this.It is set as in Fig. 4 by the flow velocity of the air-flow of suction inlet 55 by hollow arrow Shown in the average value of value that measures at 24 positions.The measurement of flow velocity use (KANOMAX is manufactured, ProductName: ANEMOMASTER airspeedometer 6006-00).By the valve being arranged between suction port 58 and gas suction device 56, make gas The flow for the gas that suction device 56 is attracted is changed with 4 kinds of situations, has estimated the attraction flow under various situations, and result is 17.3m³/min、24.3m³/min、30.9m³/ min and 42m³/min.In addition, being estimated as 42m³The case where/min is to make valve The case where door standard-sized sheet.The case where making valve wide open, by different methods to the attraction flow of gas suction device 56 into Estimation is gone, result 44m³/ min has obtained substantially the same value.Thus, the properness of above-mentioned estimation is confirmed that. It is performance and setting according to gas suction device 56 between suction port 58 and gas suction device 56 as different methods The pressure loss of piping estimate the attraction flow of gas suction device 56.

The research of inventor according to the present invention is preferably spraying liquid to the outer peripheral surface 100s of substrate 100A in the form of mist When body, the shortest distance dm1's and outside cover portion 54 and substrate 100A of the outer peripheral surface 100s of inside cover portion 53 and substrate 100A The shortest distance dm2 of outer peripheral surface 100s is smaller respectively.As described later, when the outer peripheral surface 100s's of inside cover portion 53 and substrate 100A When the shortest distance dm2 of the outer peripheral surface 100s of shortest distance dm1 and outside cover portion 54 and substrate 100A are big, due to position The unevenness of flow velocity becomes larger caused by difference.According to above-mentioned result of study, liquid film forming device 50 is for example preferably configured as It, can be respectively by the outer of inside cover portion 53 and substrate 100A when spraying liquid in the form of mist to the outer peripheral surface 100s of substrate 100A The shortest distance dm2 of the outer peripheral surface 100s of the shortest distance dm1 and outside cover portion 54 and substrate 100A of circumferential surface 100s are set as 30mm is hereinafter, more preferably be configured to be set as 25mm or less.

The present inventor measures in multiple positions from outside cover portion 54 under the experimental system different from Fig. 4 The flow velocity for the air-flow that outside is flowed inwardly has investigated the degree of its difference.Such as in Fig. 4 as shown in hollow arrow Like that, change measurement position along the side of outside cover portion 54 extended in the 1st direction (x-axis direction in figure), investigate gas The variation of the flow velocity of stream.Here, suction port 58 is provided only with 1, the distance away from suction port 58 is different according to measurement position.Root According to the measurement of the present inventor, if by the shortest distance dm1 of inside cover portion 53 and the outer peripheral surface 100s of substrate 100A, with And the shortest distance dm2 of the outer peripheral surface 100s of outside cover portion 54 and substrate 100A are set as 30mm, then the flow rate dependant of air-flow in away from The distance (such as being inversely proportional at a distance from away from suction port 58) of suction port 58, the more close then flow velocity of the distance away from suction port 58 are bigger. In contrast, if by the shortest distance dm1 of inside cover portion 53 and the outer peripheral surface 100s of substrate 100A and outside cover portion 54 with The shortest distance dm2 of the outer peripheral surface 100s of substrate 100A is set as 10mm, even if the distance then away from suction port 58 changes, flow velocity Variation also very little.That is, the speed for the air-flow that the outside from outside cover portion 54 can be made to flow inwardly is substantial constant.This Outside, it is believed that the preferred scope of the shortest distance dm1 and dm2 for example change according to the scale (size) of the system comprising substrate.

Liquid film forming device 50 can be also suitably used for roll-to-roll mode.Liquid film forming device 50 does not have to contact with substrate 100A, Just be able to suppress in the form of mist spray liquid to surrounding spread, therefore, suitable for in rotation substrate 100A with The form of mist sprays the case where liquid.In addition, in roll-to-roll mode, the process due to spraying upper layer resin in the form of mist is In the system comprising other process (for example, assigning the process of lower-layer resin, the process for irradiating ultraviolet light etc. to the surface of basement membrane) It is carried out among column process, therefore, is suitble to use liquid film forming device 50.In roll-to-roll mode, for example it is difficult to which moth is ophthalmically acceptable The surface of mold separates from other support rollers, other equipment and keeps its closed.In addition, in roll-to-roll mode, the ophthalmically acceptable mold of moth It is rotation, therefore, if worrying to injure using the cover component contacted with the ophthalmically acceptable mold of moth by a part of closed of surface The surface of the ophthalmically acceptable mold of moth

Patent document 6 discloses the substrate board treatment of the cleaning for flat substrate.At the substrate of patent document 6 Reason device includes jetting nozzle, sprays treatment fluid (such as cleaning solution) to substrate；And 2 attraction nozzles, configuration are being sprayed The two sides of delivery nozzle attract the treatment fluid of the cleaning for substrate together with the gas of surrounding.The substrate of patent document 6 Processing unit removes the foreign matter of attachment on the surface of the substrate by making the surface collision of cleaning solution and substrate, carries out to substrate clear It washes.The substrate board treatment of patent document 6, which passes through to have, attracts nozzle, is able to suppress the treatment fluid of the cleaning for substrate again It is attached to substrate and causes substrate contamination.In addition, from the viewpoint of the cleaning treatment for efficiently carrying out substrate, preferably from ejection The speed of nozzle to the cleaning solution that the surface of substrate sprays is larger, such as compared with jetting nozzle is single fluid nozzle, more preferably Jetting nozzle is two-fluid spray nozzle.

In contrast, liquid film forming device 50 is to form liquid film as mesh using the outer peripheral surface in cylindric or cylindric substrate 's.Therefore, in liquid film forming device 50, liquid film is equably preferably assigned from the outer peripheral surface to cylindric or cylindric substrate From the perspective of come adjust in the form of mist spray liquid speed and direction.As possessed by liquid film forming device 50, The nozzle 57 that liquid is sprayed in the form of mist, for example, being able to use ultrasonic nozzle, two-fluid spray nozzle, swirl nozzle or quiet EFI mouth etc..

[about nozzle]

Ultrasonic nozzle is the spraying spray by way of being atomized the liquid into the vibration of ultrasonic wave and being sprayed in the form of mist Mouth.Two-fluid spray nozzle is the spray nozzle of mode that the compressed air and liquid that will be divided into 2 systems are mixed and sprayed. By using ultrasonic nozzle, so that the mist sprayed in the form of mist can be made compared with the case where using two-fluid spray nozzle Average diameter become smaller.Such as the average diameter of the mist sprayed in the form of mist by ultrasonic nozzle is several μm~tens μm left sides It is right.In addition, liquids and gases are not pressurized in ultrasonic nozzle, therefore, it is able to suppress the liquid sprayed in the form of mist Body disperses, rebounds.It is also preferred that ultrasonic nozzle from the viewpoint of coated efficiency.Such as the liquid sprayed in the form of mist Coated efficiency is 60% or more in two-fluid spray nozzle, and in ultrasonic nozzle is 95% or more.

Also it is able to use swirl nozzle.By using swirl nozzle, spiral helicine air-flow can be generated, therefore can be on one side Drop convolution is set to be imparted to the outer peripheral surface of substrate on one side.At this point, impact when drop can be made to reach the outer peripheral surface of substrate Become smaller, therefore, the drop in the outer peripheral surface splashing of substrate can be reduced.In addition, the formation of liquid film can also use electrostatic atomiser. Electrostatic atomiser is the spray nozzle in a manner of spraying the drop of electrification in the form of mist.For example, by the surface of substrate and spray Apply voltage between mouth, liquid droplet charged can be made, and drop is efficiently made to be attached to the surface of substrate.Using electrostatic atomiser come with The coated efficiency for the liquid that the form of mist sprays is such as 98%.

The research of inventor according to the present invention is, it is preferable to use ultrasonic nozzle, particularly preferred use can generate spiral The ultrasonic nozzle of the air-flow of shape.Detailed result of study will be aftermentioned.

[liquid suitable for mist]

The present inventor, which has studied, is able to use ultrasonic nozzle (manufacture of Sono-Tek society, ProductName: vortex) Carry out the characteristic of the liquid of mist.

3 kinds of different liquid (water, A liquid and B liquid) is used as to the liquid sprayed in the form of mist, determines mist (mist Change) state it is whether stable.The flow of liquid is set as 3ml/min, and electric power is set as 1~3W.

The characteristic for determining result and each liquid has been shown in table 1.The viscosity of each liquid, static surface tension, Yi Jidong The measurement of state surface tension is carried out at 23 DEG C.

Viscosity is the TV25 type viscosimeter (ProductName: TVE-25L) that is manufactured using Dong Ji industry companies come what is measured.

Static surface tension is measured using percolation flow velocity method.Percolation flow velocity method is in cylinder with constant pressure Filled object object is compressed, according to relational expression: l²/ t=(r γ cos θ)/2 η are come object when determining to be measured with water The method of surface tension.In above-mentioned relation formula, l indicates the seepage flow height of water, and t indicates the time, and r indicates filled object Capillary radius, γ indicate surface tension, η indicate water viscosity, θ indicate contact angle.Surface tension is smaller, indicates to contact Angle is bigger, and hydrophobicity is higher.

Dynamic surface tension is found out by maximum bubble pressure method.Using automatic dynamic surface tensiometer, (BP-D5, coordinate boundary The manufacture of face scientific company) measure maximum when continuously generating bubble from the probe (tubule) being inserted into each liquid (coating fluid) Pressure (most bulla pressure), has found out surface tension.Specifically, measuring, there are the time limits (to generate newly from tips of probes Time of the time point at interface until becoming maximum bubble pressure；Otherwise referred to as " surface lifetime ".) be 100ms in the case where table The value of face tension.

[table 1]

As shown in table 1, spray pattern is stablized in water and A liquid, but unstable in B liquid.Although A liquid and B liquid have base The static surface tension of identical value in sheet, but the stability by mist is variant.Know the static state of liquid Surface tension is not contributed by the stability in the case where mist.And it knows in the feelings that vortex is used as to ultrasonic nozzle Under condition, about the liquid sprayed in the form of mist, such as preferably its by maximum bubble pressure method find out 23 DEG C of surface longevity Dynamic surface tension when life is 100ms is 31mN/m or more.In addition, about the liquid sprayed in the form of mist, such as preferably It is 20cP or less in 23 DEG C of viscosity.

[configuration of nozzle]

Illustrate the configurations of multiple nozzles 57 possessed by liquid film forming device 50 referring to figure 5 and figure 6.Fig. 5 is for saying When the bright outer peripheral surface 100s to substrate 100A sprays liquid in the form of mist, substrate 100A and liquid film forming device 50 configuration The schematical perspective view of relationship, Fig. 6 are when watching liquid film forming device 50 from the direction parallel with the axial direction of substrate 100A Schematical side view.In fig. 5 and fig., for the ease of viewing, the diagram of inside cover portion 53 and outside cover portion 54 is omitted.

As shown in figure 5, liquid film forming device 50 for example also have rotatable support structure body 59, rotatable support structure body 59 with Make axially substantially upper and horizontal direction parallel the mode supporting base material 100A of substrate 100A, and substrate 100A can be made around substrate The axis of 100A rotates.

As shown in figure 5, when spraying liquid in the form of mist to the outer peripheral surface 100s of substrate 100A, multiple nozzles 57 and base Material 100A's is approximately axially arranged in parallel.As shown in Figure 5 and Figure 6, multiple nozzles 57 are preferably with the height of adjacent nozzle 57 Mutually different mode configures.That is, the preferred high infraversion malposition of multiple nozzles 57 configure.In addition, multiple more preferably configurations of nozzle 57 It is mutually different for the squit hole angle relative to horizontal direction of adjacent nozzle 57.It is more in Fig. 5 and example shown in fig. 6 The 1st nozzle 57a and the 2nd nozzle 57b that a nozzle 57 has height mutually different.2nd nozzle 57b matches compared to the 1st nozzle 57a Set side in the vertical direction.The position of position and the 2nd nozzle 57b that the 1st nozzle 57a is illustrated in Fig. 6 is in the vertical direction Poor Δ v and poor Δ h in the horizontal direction.In addition, the squit hole of the 1st nozzle 57a and the 2nd nozzle 57b is relative to level side To angle it is mutually different.The squit hole of 2nd nozzle 57b angle, θ b relative to horizontal direction is greater than the ejection of the 1st nozzle 57a Hole angle, θ a relative to horizontal direction.1st nozzle 57a and the 2nd nozzle 57b are alternately configured.

The research of inventor according to the present invention, if the height of adjacent nozzle 57 is identical, the spray of adjacent nozzle 57 Angle relative to horizontal direction of portalling is identical, then as shown in fig. 7, sometimes the outer peripheral surface 100s's for being formed in substrate 100A Liquid film generates the unevenness of the striated extended in a circumferential direction.Fig. 7 is the outer peripheral surface 100s shown being formed in substrate 100A The uneven figure of the striated extended in a circumferential direction that generates of liquid film.The research of inventor according to the present invention, this Line shape does not change all in accordance with position, the quantity of nozzle 57, such as is accordingly formed with the interval of adjacent nozzle 57. Additionally, there are the rotation speed of substrate 100A is more fast, it is more prone to produce the uneven tendency of striated.If be configured to adjacent Nozzle 57 height it is mutually different, then can the outer peripheral surface 100s to substrate 100A equably assign from multiple nozzles 57 with mist The liquid that form sprays inhibits the uneven formation of striated.

As shown in table 2, the present inventor has studied the configuration of multiple nozzles 57 and the rotation speed of substrate 100A.This Outside, experiment herein is carried out in the case where no attraction for carrying out gas.

[table 2]

As shown in table 2, change the configuration of multiple nozzles 57 and the rotation speed of substrate 100A, the outer peripheral surface of Xiang Jicai 100A 100s sprays liquid in the form of mist, and whether investigation has been formed uniformly liquid film in outer peripheral surface 100s.It is multiple in condition A and B Nozzle 57 arranges on straight line.At condition A, liquid film produces unevenness, but when making the rotation speed of substrate 100A become smaller (item Part B) when, liquid film does not generate unevenness.In addition, liquid film does not produce when the high infraversion malposition of multiple nozzles 57 is arranged (condition C) It is raw uneven.

[liquid-feeding pump]

The liquid supplying apparatus 52 for supplying liquid to blow-off outlet 51 is for example holding comprising the container for storing liquid and configuration Liquid-feeding pump between device and blow-off outlet 51.The conduit that liquid-feeding pump is for example set to container and links container and blow-off outlet 51.From From the perspective of the outer peripheral surface 100s of substrate 100A is formed uniformly liquid film, the flow for the liquid preferably supplied from liquid-feeding pump Time dependence is small.For example, it is preferable to use small liquid-feeding pump of not pulsing or pulse.Also it can be used without valve arrangement Pump.

Liquid flow sensor is arranged between the container and liquid-feeding pump of storage liquid in the present inventor (manufacture of Sensirion Co., Ltd company, ProductName: SLI-2000), measures the flow for the liquid supplied from liquid-feeding pump Time dependence.Syringe pump (M Co., Ltd. inato concept is manufactured, ProductName: MCIP-BOi) is being used as liquid-feeding pump In the case where supplying liquid (flow: 5ml/min), produce about with the pulsation for the period in 4 seconds.In contrast, by tube pump (M Co., Ltd. inato concept manufacture, ProductName: MCRP204 type) is used as liquid-feeding pump to supply (the flow: 5ml/ of liquid Min in the case of), pulsation is not almost generated.

[gas suction device]

Illustrate an example of the composition of liquid film forming device 50 referring to Fig. 8.Fig. 8 is for illustrating liquid film forming device The schematical figure of one example of 50 composition.

The gas suction device 56 for attracting gas by suction inlet 55 is, for example, to attract fan 56.As shown in figure 8, liquid film shape It is for example also included at device 50 separator (not shown), liquid (including mist) is removed from the gas that suction inlet 55 attracts Fall；And discharge case (drain tank) 72, store the liquid isolated from gas by separator.Fan 56 is attracted to pass through Gas after removing liquid by separator is discharged to for example outdoor by filter 73.For example, every in multiple suction ports 58 One suction port 58 is connected with piping 71a, and piping 71a is connected to piping 71b.The internal diameter for being piped 71b can be greater than piping 71a's Internal diameter.Multiple piping 71a can also be connected in 1 piping 71b.From multiple suction ports 58 attract gas by piping 71a, 71b is sent to separator and discharge case 72, and is sent to and attracts fan 56.It can also be in piping 71a and/or piping 71b setting The valve (not shown) of the flow for the gas for thering is regulating gas suction device 56 to be attracted.

Liquid film forming device 50, which can also have, to be contacted with inside cover portion 53 and the Liquid acquisition in blow-off outlet 51 is arranged in Portion 61 (referring to Fig. 9).The research of inventor according to the present invention, it is attached if lasting for hours the ejection liquid in the form of mist Mist in inside cover portion 53 may be flowed along inside cover portion 53.In particular, if blow-off outlet 51 is in the 3rd direction (figure In z-axis direction) on penetrate through, then be attached to inside cover portion 53 mist sometimes along inside cover portion 53 flow, become drop It falls.When liquid film forming device 50 also has liquid-receivable section 61, it will be able to prevent this drop from falling.In liquid-receivable section 61 are for example connected with pipe or conduit (not shown), and the drop in liquid-receivable section 61 will be received by pipe or conduit by, which being configured to, returns It receives.

Liquid film forming device 50 can also have the liquid-receivable section of a part of the side substrate 100A of covering blow-off outlet 51 64 (referring to Fig. 9).Liquid-receivable section 64 is for example formed by metal material.The research of inventor according to the present invention, such as Fig. 9 institute Show, in the case where carrying out the manufacture of synthetic polymeric membrane by roll-to-roll mode, is sprayed in the form of mist if lasted for hours Liquid out, then mist is attached to the part of the side substrate 100A of outside cover portion 54 sometimes, is attached to the drop of outside cover portion 54 It is attached to support roller 48 sometimes.The research of inventor according to the present invention, it is believed that when by support roller 48 by basement membrane 42 from moth When ophthalmically acceptable mold 100A is removed, electrostatic can be generated on the surface of basement membrane 42, thus, the drop for being attached to outside cover portion 54 can adhere to In support roller 48.Since liquid film forming device 50 has liquid-receivable section 64, so that dispersing for this drop is inhibited.

[manufacturing method of synthetic polymeric membrane]

As described above, the liquid film forming device or liquid film forming method of embodiments of the present invention also can be used in synthesis height The manufacturing method of molecular film.The liquid film forming device or liquid film forming method of embodiments of the present invention can be suitable for antifouling The manufacturing method of the excellent synthetic polymeric membrane of property.Illustrate the synthetic polymeric membrane of embodiments of the present invention referring to Fig. 9 Manufacturing method.Fig. 9 is the schematical section of the method for illustrating to manufacture synthetic polymeric membrane 36 by roll-to-roll mode Figure.Fig. 9 is sectional view when from the axial viewing of the ophthalmically acceptable mold 100A of moth.About the synthesis illustrated with 1~Figure 13 referring to Fig.1 The common item of the manufacturing method of polymeric membrane 36, omits the description sometimes.In addition, to the composition with substantially the same function Element marks common appended drawing reference, and the description thereof will be omitted.

The manufacturing method of the synthetic polymeric membrane of embodiments of the present invention is come using cylindric or cylindric mold The method for manufacturing synthetic polymeric membrane, above-mentioned mold have porous alumina layer, and above-mentioned porous alumina layer has anti-on surface The moth ocular structure turned, the moth ocular structure of above-mentioned reversion have the two-dimentional size when being watched from normal to a surface direction be 20nm with Upper and multiple recess portions less than 500nm.The manufacturing method of the synthetic polymeric membrane of embodiments of the present invention includes: process (A), Prepare mold and machined object；Process (B) assigns the 1st resin comprising uv curing resin to the surface of machined object； Process (C) uses the liquid film forming device of embodiments of the present invention or the liquid film forming side of embodiment through the invention Method assigns the 2nd resin comprising fluorochemical monomer to the surface of mold；Process (D), make the 1st resin and the 2nd resin mold with In the state of contacting with each other between the surface of machined object, ultraviolet light is irradiated to the 1st resin and the 2nd resin, to make the 1st resin With the 2nd resin solidification.

The manufacturing method of the synthetic polymeric membrane of embodiment according to the present invention can inhibit under fabrication yield Drop, and the excellent synthetic polymeric membrane of soil resistance can be manufactured by roll-to-roll mode.

For example, the top of the squit hole of nozzle 57 is connected with the center 100o of the ophthalmically acceptable mold 100A of moth as shown in figure 9, setting Straight line with straight line angulation that the center 100o of the ophthalmically acceptable mold 100A of moth is connected with the center 48o of support roller 48 be θ n.The center 46o of support roller 46 can for example be located at the center 48o of the center 100o of the ophthalmically acceptable mold 100A of moth and support roller 48 On connected straight line.

The liquid film forming device or liquid film forming method of embodiments of the present invention can be not limited to above-mentioned synthesis high score The manufacturing method of sub- film come using.For example, the liquid sprayed in the form of mist can be surface treating agent, release agent etc. and be imparted to The well known a variety of materials on the surface of mold.In addition, for example, present applicant International Publication No. 2018/012340 In preparation method 3 among the manufacturing method for the synthetic polymeric membrane recorded in number, to the surface of mold assign comprising release agent (such as Release agent comprising the fluorochemical monomer with photoreactive group) resin.Embodiment party of the invention can be used in this process The liquid film forming device or liquid film forming method of formula.It, will be in International Publication No. 2018/012340 all disclosures in order to refer to Appearance is quoted to this specification.

[manufacturing method of the ophthalmically acceptable mold of moth]

0 (a)~(e) illustrates the manufacturing method of the ophthalmically acceptable mold 100A of moth referring to Fig.1.(a) of Figure 10~(e) is to be used for Illustrate the schematical sectional view of the manufacturing method of the ophthalmically acceptable mold 100A of moth.

Firstly, preparing mold substrate 10 as shown in (a) of Figure 10 and being used as mold substrate, mold substrate 10 includes cylindrical shape Aluminium base 12, be formed in aluminium base 12 surface inorganic material layer 16 and the aluminium film that is deposited on inorganic material layer 16 18。

As aluminium base 12, the purity using aluminium is 99.50mass% or more and less than 99.99mass%, rigid ratio Higher aluminium base.As the impurity that aluminium base 12 is included, preferably comprise from including iron (Fe), silicon (Si), copper (Cu), manganese (Mn), at least one kind of element selected in the group of zinc (Zn), nickel (Ni), titanium (Ti), lead (Pb), tin (Sn) and magnesium (Mg), especially It is preferred that Mg.The mechanism of formation pit (recess) in etching work procedure is local cell reaction, it is therefore preferable that using ideal situation Under be entirely free of the element more expensive than aluminium and be used as impurity element containing the Mg (standard electrode potential is -2.36V) as base metal Aluminium base 12.If the containing ratio of the element more expensive than aluminium be 10ppm hereinafter, if from the viewpoint of electrochemistry, it may be said that it is real The element is free of in matter.The containing ratio of Mg is preferably whole 0.1mass% or more, and even more preferably about 3.0mass% is below Range.Enough rigidity are unable to get if the containing ratio of Mg is less than 0.1mass%.On the other hand, if containing ratio becomes larger Then easily cause the segregation of Mg.Although even if formed the ophthalmically acceptable mold of moth surface near generate segregation in electrochemistry not at Problem, but Mg will form the form anode oxide film different from aluminium, thus will lead to bad.As long as the containing ratio root of impurity element It is suitably set according to the shape of aluminium base 12, thickness and size, and according to required rigidity.Such as passing through roll compacting In the case where processing the aluminium base 12 to make plate, the containing ratio of Mg is that about 3.0mass% is appropriate, and is squeezed out passing through Processing is come in the case where making the aluminium base 12 with stereochemical structures such as cylinders, the containing ratio of Mg is preferably 2.0mass% or less. If the containing ratio of Mg is more than 2.0mass%, extrusion processability can generally be reduced.

As aluminium base 12, such as using by JISA1050, Al-Mg alloy (such as JISA5052) or Al-Mg-Si It is the cylindric aluminum pipe that alloy (such as JISA6063) is formed.

It is preferred that the surface of aluminium base 12 was carried out lathe tool (bite) cutting.If aluminium base 12 remained on surface for example Abrasive grain, then the part existing for abrasive grain, is easy to turn between aluminium film 18 and aluminium base 12.Other than abrasive grain also there are recessed Convex position is easily locally connected between aluminium film 18 and aluminium base 12.If between aluminium film 18 and aluminium base 12 locally Conducting, it is likely that locally cause cell reaction between the impurity in aluminium base 12 and aluminium film 18.

Such as it is able to use tantalum oxide (Ta₂O₅₎Or silica (SiO₂) material as inorganic material layer 16.Inorganic material The bed of material 16 can for example be formed by sputtering method.In the case where tantalum oxide layers are used as inorganic material layer 16, tantalum oxide layers Thickness is, for example, 200nm.

The preferred 100nm or more of the thickness of inorganic material layer 16 and less than 500nm.If the thickness of inorganic material layer 16 less than 100nm, then aluminium film 18 can generate defect (mainly gap, i.e., intercrystalline gap) sometimes.In addition, if inorganic material layer 16 With a thickness of 500nm or more, then between aluminium base 12 and aluminium film 18 be easy insulate because of the surface state of aluminium base 12.In order to logical Cross and supply electric current from 12 side of aluminium base to aluminium film 18 to carry out the anodic oxidation of aluminium film 18, need aluminium base 12 and aluminium film 18 it Between circulating current.If using the structure of the inner face supply electric current from cylindric aluminium base 12, it is not necessary that aluminium film 18 is arranged Electrode, therefore anodic oxidation can be carried out throughout entire surface to aluminium film 18, and will not generate the progress with anodic oxidation And be difficult to supply electric current such problems, aluminium film 18 equably can be subjected to anodic oxidation throughout entire surface.

In addition, generally requiring extension film formation time to form thick inorganic material layer 16.If film formation time is elongated, Then the surface temperature of aluminium base 12 can unnecessarily rise, as a result, the film quality of aluminium film 18 deteriorates and generates defect (master sometimes If gap).If the thickness of inorganic material layer 16 less than 500nm, is also able to suppress the generation of this undesirable condition.

Aluminium film 18 is 99.99mass% by purity e.g. as documented by International Publication No. 2011/125486 The film (hereinafter sometimes referred to " high-purity aluminium film ") that above aluminium is formed.Aluminium film 18 is for example come using vacuum vapour deposition or sputtering method It is formed.The thickness of aluminium film 18 is preferably in the range of about 500nm or more and about 1500nm or less, and for example, about 1 μm.

In addition, also can replace high-purity aluminium film as aluminium film 18 and remembered using International Publication No. 2013/183576 The aluminium alloy film of load.Aluminium alloy film documented by International Publication No. 2013/183576 include aluminium, the metallic element other than aluminium with And nitrogen.In this specification, " aluminium film " is not only high-purity aluminium film, also includes documented by International Publication No. 2013/183576 Aluminium alloy film.

If the mirror surface that reflectivity is 80% or more can be obtained using above-mentioned aluminium alloy film.Constitute the crystalline substance of aluminium alloy film Average grain diameter when the normal direction viewing of the slave aluminium alloy film of grain is, for example, 100nm hereinafter, the maximum surface of aluminium alloy film is thick Rugosity Rmax is 60nm or less.The containing ratio of nitrogen contained by aluminium alloy film be, for example, 0.5mass% or more and 5.7mass% with Under.The difference of the standard electrode potential of the standard electrode potential and aluminium of metallic element other than aluminium contained by aluminium alloy film it is absolute Value is preferably 0.64V hereinafter, the containing ratio of the metallic element in aluminium alloy film is preferably 1.0mass% or more and 1.9mass% Below.Metallic element is, for example, Ti or Nd.But metallic element is without being limited thereto, can also be the standard electrode potential of metallic element Absolute value of the difference with the standard electrode potential of aluminium is 0.64V other metallic elements (such as Mn, Mg, Zr, V and Pb) below. Moreover, metallic element can also be Mo, Nb or Hf.Aluminium alloy film can also be containing two or more in these metallic elements.Aluminium closes Golden film is for example formed by DC (Direct Current, direct current) magnetron sputtering method.The thickness of aluminium alloy film is it is also preferred that in about In the range of 500nm or more and about 1500nm or less, for example, about 1 μm.

Then, as shown in (b) of Figure 10, by the surface 18s anodic oxidation of aluminium film 18, so that being formed has multiple recess portions The porous alumina layer 14 of (pore) 14p.Porous alumina layer 14 has porous layer with recess portion 14p and barrier layer is (recessed The bottom of portion (pore) 14p).The interval (distance between centers) of known adjacent recess portion 14p is approximately equivalent to the thickness of barrier layer 2 times of degree, it is substantially directly proportional to voltage when anodic oxidation.Final porous oxygen shown in (e) of the relationship for Figure 10 It is also set up for change aluminium layer 14.

Porous alumina layer 14 for example by acid electrolyte by surface 18s anodic oxidation and formed.It is formed more Electrolyte used in the process of porous aluminum oxide layer 14 is, for example, to include selected from including oxalic acid, tartaric acid, phosphoric acid, sulfuric acid, chromium Acid, citric acid, malic acid group in acid aqueous solution.For example, by using oxalic acid aqueous solution (concentration 0.3mass%, liquid temperature 10 DEG C) to apply surface 18s progress 55 second anodic oxidation of the voltage 80V to aluminium film 18, to form porous alumina layer 14.

Then, as shown in (c) of Figure 10, by contacting porous alumina layer 14 with the etchant of aluminium oxide to provide Amount be etched, so that the opening portion of recess portion 14p be expanded.It can be by adjusting the type, concentration and etching of etching solution Time controls etch quantity (that is, size and depth of recess portion 14p).As etching solution, such as it is able to use the phosphorus of 10mass% The aqueous solution or chromic acid phosphoric acid mixed aqueous solution of the organic acids such as acid or formic acid, acetic acid, citric acid or sulfuric acid.Such as use phosphorus Aqueous acid (10mass%, 30 DEG C) etch within 20 minutes.

Then, as shown in (d) of Figure 10, again by the partly anodic oxidation of aluminium film 18, to make recess portion 14p in depth side It grows up and porous alumina layer 14 is made to thicken.It is from the bottom of the recess portion 14p formed in the growth of this recess portion 14p Start, therefore the side of recess portion 14p becomes ladder-like.

Moreover, later as desired by contacting porous alumina layer 14 and further progress with the etchant of aluminium oxide Etching, thus by the aperture further expansion of recess portion 14p.As etching solution, herein it is also preferred that using above-mentioned etching solution, reality As long as identical etch bath is used in.

In this way, by the way that above-mentioned anodic oxidation process and etching work procedure to be alternately repeated a number of times to (such as 5 times: 5 time sun Pole oxidation and 4 etchings), to obtain the porous oxygen for the moth ocular structure for having with reversion as shown in (e) of Figure 10 Change the ophthalmically acceptable mold 100A of moth of aluminium layer 14.By being terminated with anodic oxidation process, the bottom of recess portion 14p can be formed as a little. That is, the mold for being capable of forming the sharp protrusion in top can be obtained.

(the thickness t of porous alumina layer 14 shown in (e) of Figure 10_p) having porous layer, (thickness is equivalent to the depth of recess portion 14p Spend D_d) and barrier layer (thickness t_b).Porous alumina layer 14, which has, inverts moth ocular structure possessed by synthetic polymeric membrane 34A Made of structure, therefore, sometimes to characterize its size corresponding parameter use identical mark.

Recess portion 14p possessed by porous alumina layer 14 is, for example, cone, it is possible to have stair-stepping side.It is preferred that Two-dimentional size (the area equivalent diameter of recess portion when being watched from normal to a surface direction) D of recess portion 14p_pMore than 20nm and not To 500nm, depth D_dFor 50nm or more and less than the degree of 1000nm (1 μm).Additionally, it is preferred that the bottom of recess portion 14p is sharp (bottommost become point).In the case where recess portion 14p is closely filled, if will be from the normal direction of porous alumina layer 14 The shape of recess portion 14p when viewing is assumed to be circle, then adjacent circle is mutually overlapping, forms saddle between adjacent recess portion 14p. In addition, when the recess portion 14p of conical shaped is adjacent in a manner of forming saddle, the two-dimentional size D of recess portion 14p_pWith adjacent Distance D_intIt is equal.The thickness t of porous alumina layer 14_pFor example, about 1 μm or less.

In addition, there are not anodized in aluminium film 18 under the porous alumina layer 14 shown in (e) of Figure 10 Aluminium residual layer 18r.It as needed, can also be by the substantially complete anodic oxidation of aluminium film 18, so that aluminium residual layer 18r is not present. For example, easily electric current can be supplied from 12 side of aluminium base in the case where inorganic material layer 16 is thin.

Antireflection film used in display panel for high-resolution, it is desirable that high uniformity, therefore preferably as it is above-mentioned that The selection of material, the mirror finish of aluminium base, the purity of aluminium film or the control of ingredient of sample progress aluminium base.On the other hand, In In the case where the synthetic polymeric membrane for manufacturing the purposes of not demanding uniformity, the manufacturing method of above-mentioned mold can be simplified. For example, can also be by the direct anodic oxidation in the surface of aluminium base.Even if additionally, it is believed that at this time because of the influence of impurity contained by aluminium base And pit is formed, local structure confusion also can be only generated in the moth ocular structure of finally obtained synthetic polymeric membrane 36, and The bactericidal effect of such as synthetic polymeric membrane 36 is hardly impacted.

According to the manufacturing method of above-mentioned mold, arrangement rule that be suitable for the production of antireflection film, recess portion can be manufactured The then low mold of property.In addition, the mold for being used to form the moth ocular structure with regularly arranged protrusion for example can be such as following system It makes.

As long as such as after being formed with a thickness of about 10 μm of porous alumina layer, by etching porous oxidation generated Aluminium layer removes, and anodic oxidation is then carried out under conditions of generating above-mentioned porous alumina layer.It is porous with a thickness of 10 μm Alumina layer can be formed by extending anodizing time.If generating relatively thick porous alumina layer in this way, and will The porous alumina layer removes, then not will receive the recessed caused by particle (grain) of the surface for being present in aluminium film or aluminium base Convex or machining deformation influence, is capable of forming the porous alumina layer with regularly arranged recess portion.In addition, choosing using chromic acid with The mixed liquor of phosphoric acid carrys out the removing of porous alumina layer.When being etched for a long time, it some times happens that galvanic corrosion, but chromium The mixed liquor of acid and phosphoric acid has the effect of inhibiting galvanic corrosion.

[nozzle selected]

Change the type of ultrasonic nozzle 57, makes synthetic polymeric membrane 36, and to made synthetic polymeric membrane 36 It is evaluated.Synthetic polymeric membrane 36 is made by referring to the method that Figure 13 illustrates.That is, not using implementation of the invention It is made in the case where the liquid film forming device and liquid film forming method of mode.

As shown in table 3, with frequency 120Hz using 3 kinds of ultrasonic nozzles (be that Sono-Tek company manufactures, ProductName: Vortex, AccuMist and Impact).Vortex generates spiral helicine air-flow.Such as in the feelings for spraying water in the form of mist Under condition, the mist that average diameter is 18 μm can be sprayed in the form of mist.But according to the viscous of the liquid sprayed in the form of mist The average diameter of degree, surface tension etc., mist may be different.The result of study for capableing of the condition of the liquid of mist is, for example, such as Referring to described in table 3.AccuMist and Impact does not generate spiral helicine air-flow.AccuMist can generate dotted spraying figure Case.Use the spraying width of Impact than having used the spraying width of AccuMist wide.

In table 3, in addition to the type of nozzle, pressure (psi), the electric power of the gas of ejection are also shown as spraying conditions (W), (mm), temperature, the flow (ml/min) of the liquid sprayed in the form of mist, scanning speed (mm/sec) at a distance from substrate And coating number.

" pressure of the gas of ejection " of table 3 is the pressure of the liquid sprayed in the form of mist and the gas of ejection.Here, 1psi=6894.76Pa.

" electric power " of table 3 is the electric power to ultrasonic nozzle supply.

" at a distance from the substrate " of table 3 is the top of ultrasonic nozzle and the shortest distance of the ophthalmically acceptable mold 100A of moth.

" temperature " of table 3 is to have carried out the temperature in spraying space, and " R.T " indicates room temperature.

" flow of liquid " of table 3 is the flow of the liquid sprayed in the form of mist.

" scanning speed " of table 3 is the movement speed of ultrasonic nozzle when carrying out liquid spray.

" the coating number " of table 3 is the coating number of upper layer resin 36b '.

In addition, the thickness of the lower-layer resin 36a ' when being imparted on basement membrane 42 is expressed as the " thickness of lower-layer resin in table 3 The thickness of degree ", the upper layer resin 36b ' when the surface that will be imparted to the ophthalmically acceptable mold 100A of moth is expressed as " thickness of upper layer resin ". And, further it is shown that the evaluation result of made synthetic polymeric membrane 36.Specific evaluation method will be aftermentioned.

[table 3]

As ultrasonic nozzle, Vortex has been used under condition 1, AccuMist has been used under condition 2~4, in item Impact has been used under part 5~7.It (is upper layer tree herein changing the liquid sprayed in the form of mist under condition 2~4 Rouge) flow, and assign the upper layer resin 36b ' of different-thickness and obtained synthetic polymeric membrane 36.Under condition 5~7, lead to The coating number for changing the liquid (the upper layer resin) and upper layer resin that spray in the form of mist is crossed, and assigns the upper layer of different-thickness Resin 36b ' has simultaneously obtained synthetic polymeric membrane 36.

As shown in table 3, the synthetic polymeric membrane 36 made in the case where Vortex to be used as to the condition 1 of ultrasonic nozzle (assigns The thickness of upper layer resin 36b ' when to the surface of the ophthalmically acceptable mold 100A of moth: 1.3 μm) there is hydrophobicity, also, it is oleophobic property, resistance to Scratch resistance, sliding easiness and the erasing easiness of grease are excellent.

Although will AccuMist be used as the lower synthetic polymeric membrane 36 made of condition 2 of ultrasonic nozzle with in item The upper layer resin 36b ' of the lower substantially the same thickness of synthetic polymeric membrane 36 (1.2 μm) made of part 1, but in hydrophobicity, oleophobic Property, marresistance, sliding easiness and grease erasing easiness in terms of it is poor.For this purpose, being to increase as condition 3 and 4 The thickness of the upper layer resin 36b ' assigned and make synthetic polymeric membrane 36, and evaluated.When increasing upper layer tree When the thickness of rouge 36b ', evaluation result is improved.The synthetic polymeric membrane 36 made under condition 4 (is imparted to the ophthalmically acceptable mold of moth The thickness of upper layer resin 36b ' when the surface of 100A: 4.5 μm) hydrophobicity, oleophobic property, marresistance, sliding easiness with And it is excellent in terms of the erasing easiness of grease, with 36 same degree of synthetic polymeric membrane made under condition 1.

The case where Impact is used as ultrasonic nozzle (condition 5~7), pass through the upper layer resin 36b ' that will be assigned Thickness increase to 5.4 μm (conditions 7), also obtained in hydrophobicity, oleophobic property, marresistance, sliding easiness and grease Erasing easiness in terms of with the synthetic polymeric membrane 36 of the production under condition 1 to same extent excellent synthetic polymeric membrane 36。

According to the above results it is found that in order to be efficiently obtained hydrophobicity, oleophobic property, marresistance, sliding easiness with And the excellent synthetic polymeric membrane of erasing easiness of grease, Vortex is preferably used as ultrasonic nozzle.

Each evaluation of made synthetic polymeric membrane 36 is following to be carried out.

Contact angle

Measure the static contact angle (sometimes referred to simply as " contact angle " of water and hexadecane.).Contact angle is using consonance circle The portable contact angle instrument (ProductName: PCA-1) of face scientific company manufacture passes through θ/2=arctan's (h/r) using the method for θ/2 Formula obtains.Here, θ indicates that contact angle, r indicate that the radius of drop, h indicate the height of drop." contact angle " of table 3 indicates The average value of the contact angle at 3 positions.Here, the measurement point as the 1st position, has selected the center portion of sample, as The measurement point at the 2nd position and the 3rd position has selected the measurement point 20mm or more away from the 1st position and has been located relative to the 1st 2 points of the position of the mutual point symmetry of the measurement point at a position measure.

Marresistance

Steel wool (SW) patience for having investigated made synthetic polymeric membrane 36, to the scratch resistance of synthetic polymeric membrane 36 Property is evaluated.Specifically, being applied in the steel wool (ProductName: #0000) manufactured to Japanese Steel Wool company The surface of synthetic polymeric membrane 36 is wiped in the state of defined load, the load of the time point of scar occurs in measurement.The load Value (value of " SW patience " in table 3) is bigger, then marresistance is more excellent.Specific wiping method is using new eastern scientific company The superficiality measuring machine (ProductName: 14FW) of manufacture wipes 10 back and forth with stroke amplitude 30mm, speed 100mm/s.In addition, It is to observe illumination 100lx (fluorescent lamp) in the environment of to judge by visual observation whether there is or not scar.

Slide easiness

The sliding easiness of synthetic polymeric membrane 36 is evaluated by the palpation of swab stick.◎ is used as evaluation index: non- Often be easy sliding, zero: be easy sliding, △: Hua get Dong, ×: cunning it is motionless.

The transparency

By the transparency for evaluating synthetic polymeric membrane 36 whether there is or not gonorrhoea.Specifically, at illumination 100lx (fluorescent lamp) In the environment of, the picture transmitted through synthetic polymeric membrane 36 is observed by visual observation, and having investigated seems no generation gonorrhoea.Refer to as evaluation Mark, uses zero: do not observe gonorrhoea, △: visual identity to slight gonorrhoea, ×: observe gonorrhoea.

The erasing easiness of grease

For the erasing easiness of grease, has rated and whether to be easily attached to the oil on the surface of synthetic polymeric membrane 36 It is wiped free of.Specifically, firstly, the Nivea skin cream (registered trademark) for manufacturing NIVEA KAO. Corp. SA is attached to each sample The surface of sample is placed 3 days in the environment of 25 DEG C of temperature, humidity 40%~60%.Later, using non-woven fabrics (KBSeiren Company's manufacture, ProductName: Savina (registered trademark)) each sample sample is wiped 50 times in one direction.In illumination 100lx In the environment of (fluorescent lamp), see whether to erase oil by visual observation.Use ◎ as evaluation index: spot is wiped completely Remove, zero: spot is wiped free of but not up to erasing, △ completely: most of spot is wiped free of, ×: spot is absolutely not wiped free of.

Y value

Measure the light reflectivity (Y value) of synthetic polymeric membrane 36.Specifically, making light source to the surface of the sample of each example It is irradiated from 5 ° of orientation of polar angle, measures the positive reflection rate of the sample of each example relative to each wavelength of incident light.Show in table 3 The reflectivity (Y value) of wavelength 550nm out.Reflectivity is the spectrophotometer (ProductName: V- manufactured using Japanese light splitting company 560) it is measured in the wave-length coverage of 250nm~850nm.The measurement of reflectivity is the basement membrane in support synthetic polymeric membrane 36 42 have attached the shape of the acrylic panel (ProductName: ACRYLITE (registered trademark) EX-502) of the black of Mitsubishi's Li Yang company manufacture It is carried out under state, illuminant-C is used as light source.

Mist degree

Measure the mist degree (diffusance) of synthetic polymeric membrane 36.Specifically, being using Japanese electric color industry strain formula meeting The haze meter NDH2000 measurement diffusion transmissivity and full light transmittance of society's manufacture, according to mist degree (%)=(diffusion transmissivity/ Full light transmittance) × 100 find out.

[1~embodiment of embodiment 8]

Hereinafter, showing 1~embodiment of embodiment 8.

By using the manufacturing method of 1~embodiment of embodiment 8 of condition shown in table 4, production has synthesis macromolecule The film 30 of film 36, and carry out the evaluation to made sample film.As long as not illustrating, the system of synthetic polymeric membrane 36 It is identical as the method illustrated referring to Fig. 4 and Fig. 9 to make method.Specifically, other than liquid film forming device 50, with patent document Embodiment 3 documented by 4 similarly makes film 30.Angle, θ n in Fig. 9 is set as 65 °.The bottom surface of support roller 46 and 48 it is straight Diameter is 210mm.As long as in addition, the composition of liquid film forming device 50 used and the ophthalmically acceptable mold 100A of moth do not illustrate, with ginseng The composition illustrated according to Fig. 4 is identical.Material used in the production of sample film described below, condition of cure and sample film Possessed moth ocular structure.

(basement membrane 42)

It has been carried out the PET film (ProductName: Cosmoshine (registrar of the Dongyang spinning company manufacture of easy bonding processing Mark) A4300)

(lower-layer resin 36a ')

Urethane acrylate (manufacture of chemical industrial company, the village Xin Zhong, ProductName: UA-7100): 31 weight %

Polyfunctional acrylic ester (manufacture of chemical industrial company, the village Xin Zhong, ProductName: ATM-35E): 40 weight %

Polyfunctional acrylic ester (manufacture of chemical industrial company, the village Xin Zhong, ProductName: A-TMM-3LM-N): 27.5 weights Measure %

Photoepolymerizationinitiater initiater (BASF AG's manufacture, ProductName: IRGACURE819): 1.5 weight %

(upper layer resin 36b ')

Fluorochemical monomer (manufacture of Daikin Industries company, fluorine system additive product name: OPTOOL DAC-HP): 10 weight %

Reactive diluent (amide-containing monomer (manufacture of KJ chemical company, ProductName: ACMO)): 90 weight %

(condition of cure)

The ophthalmically acceptable mold 100A of the moth for having been assigned upper layer resin 36b ' is being pressed into the lower layer tree being imparted on basement membrane 42 In the state of rouge 36a ', the UV lamp (ProductName: LIGHT HAMMAR6J6P3) that is manufactured using FusionUVsystems company from Ultraviolet light (exposure: 200mJ/cm is irradiated in 42 side of basement membrane²), solidify lower-layer resin 36a ' and upper layer resin 36b '.

(the moth ocular structure of sample film)

The shape of protrusion: coniform (hanging mitriform)

The adjacent spacing of protrusion is from (D_int): 200nm

Height (the D of protrusion_h): 200~250nm

In the assessment item shown in table 4, " the erasing easiness of grease " and " transparency " by with referring to table 3 illustrate The same method of method is evaluated.

" the dispersing for mist " of table 4 indicates whether be attached in the basement membrane 42 for being supported and being handled upside down by support roller 48 The result that layer resin is evaluated.As evaluation index, use zero: the basement membrane 42 in support roller 48 does not adhere to upper layer tree Rouge, △: the basement membrane 42 in support roller 48 be attached to a small amount of upper layer resin, ×: the basement membrane 42 in support roller 48 is attached with Upper layer resin.

" unevenness " of table 4 indicates the result for whether having color change to be evaluated sample film.If be endowed The thickness of upper layer resin has unevenness, then observes color change (unevenness of interference colours).Specifically, by the following method into Row evaluation.Firstly, the acrylic panel of black to be attached to the base of sample film by adhesive (Panac company manufactures, PDS1) Film 42.Also, in the environment of illumination 100lx (fluorescent lamp), from from polar angle of the normal to a surface direction at about 60 °, lead to The surface for crossing visually 36 side of synthetic polymeric membrane of observation sample film, to whether thering is color change to evaluate.As evaluation Index, zero: do not observe color change, △: visual identity to slight color change, ×: observe color change.

[table 4]

Embodiment 1

The flow of the liquid sprayed in the form of mist from blow-off outlet 51 (upper layer resin 36b ') is set as 3.0ml/min, it will The flow and pressure of gas comprising the liquid sprayed in the form of mist from blow-off outlet 51 are set as 2.0m³/ min and 0.03MPa.If The flow for the gas that gas suction device 56 is attracted is 18m³/min.The gas flowed inwardly from the outside of outside cover portion 54 Flow velocity be 2.0m/s.Flow velocity is set as in Fig. 4 the average value of the value of the measurement of 24 positions as shown in hollow arrow.By base The transporting velocity of film 42 is set as 2.0m/min, and the temperature of the ophthalmically acceptable mold 100A of moth is set as 30 DEG C, has made the sample of the length of 10m Film.The transporting velocity of basement membrane 42 corresponds to the rotation speed of moth ophthalmically acceptable mold 100A and support roller 46,48.If moth is ophthalmically acceptable The diameter of the bottom surface of mold 100 is set as 100d (m), then it represents that the 1rpm of revolution per minute is equivalent to (π × 100d) (m/ min).Therefore, the rotation speed of the ophthalmically acceptable mold 100A of moth in the manufacturing method of embodiment 1 is 2.12rpm.

In the manufacturing method of embodiment 1, mist can not be inhibited to disperse to periphery, in addition, obtained synthesis macromolecule The erasing easiness and the transparency of the grease of film 36 be not excellent, produces unevenness.

Embodiment 2