JP5790127B2 - Manufacturing method of laminate - Google Patents

Description

  The present invention relates to a method for producing a transfer body / transfer layer laminate by transferring a transfer layer to a transfer body using a transfer film in which a transfer layer containing a siloxane oligomer is laminated on a support film.

  In recent years, various substrates such as glass, metal, and crystal substrates have been used in semiconductor substrates such as liquid crystal display devices, solar cell substrates, and LEDs, but the surface of these substrates is required to be antistatic. It is required to form functional layers such as antireflection, antifouling, light scattering, and ELOG (epitaxial lateral overgrowth). In order to form a functional layer, it is conventionally known to apply a photocurable resin on a substrate, but a layer formed of a photocurable resin decomposes at a high temperature exceeding 250 ° C., The problem is that it cannot be processed at a high temperature because it is yellowed by ultraviolet rays, and heat resistance and light resistance in use cannot be obtained.

  On the other hand, a layer made of siloxane can be used and processed at a high temperature because decomposition and yellowing do not occur at a high temperature as compared with an ultraviolet curable resin. A method of forming a layer made of siloxane by a sol-gel method obtained by applying a solution containing silicon alkoxide to a base material and heating it is known (Patent Document 1).

  On the other hand, when forming a functional layer, the method of applying a solution to a base material may form a continuous uniform film on a rigid material such as glass or form a uniform layer on a curved surface. Since it is difficult, a method has been proposed in which a transfer film in which a functional layer is previously formed on a flexible support such as a film is used, and the functional layer is transferred to a transfer target (Patent Documents 2 and 3).

Japanese Patent No. 4079383 Japanese Patent No. 3750393 JP 2004-122701 A

  However, if the size of the transfer target is a large area of 3 cm □ or more, even if an attempt is made to transfer by forming a siloxane gel as a functional layer on a flexible support such as a film, the transfer cannot or cannot be performed. Since transfer is possible only in a very small part of the area, and scratches are likely to occur, there is a problem of impracticality.

  In view of the above-described problems, an object of the present invention is to provide a method for manufacturing a laminate that can form a uniform film continuously over a large area or can form a uniform layer on a curved surface.

The method for producing a laminate of the present invention for achieving the above-described object is as follows.
A first step of applying a solution containing a siloxane oligomer on a support film;
A second step of forming a transfer layer by removing the solvent from the solution applied on the support film, and forming a transfer film;
A third step of activating the transfer layer surface of the transfer film produced in the second step;
A fourth step of transferring the transfer layer to the transfer body by causing the transfer layer surface activated in the third step and the transfer target to face and contact with each other;
The method includes a fifth step of peeling the support film from the laminate composed of the transfer target / transfer layer / support film at the interface between the transfer layer and the support film.

  According to the present invention, a uniform laminate having few scratches even in a large area can be easily produced.

(A) It is a cross-sectional schematic diagram of the transfer film whose support film is flat. (B) It is the cross-sectional schematic diagram of the transfer film for forming the transfer layer which has uneven | corrugated shape by making the surface which contact | connects the transfer layer of a support film into uneven | corrugated shape previously. It is the schematic which shows the thickness of the transfer layer of the support film with an uneven | corrugated shape. It is a section schematic diagram of a decompression plasma device.

  Hereinafter, the manufacturing method of the laminated body of this invention is demonstrated in more detail, referring drawings.

  The transferred object and the transfer layer in the present invention are films having no crystal structure having a continuous siloxane bond as a main skeleton, and are obtained by a crosslinking reaction of a siloxane monomer or a siloxane oligomer. By forming a layer composed of a siloxane oligomer on a support such as a film and transferring the transfer layer to a transfer target, a film having a continuous siloxane bond can be easily obtained.

First, the transfer film used in the present invention will be described.
<Support for transfer film>
The film as a support for the transfer film used in the present invention (hereinafter referred to as a support film) is preferably a film having a thickness of 5 to 500 μm, more preferably 40 to 300 μm. If the thickness is less than 5 μm, the transfer layer may be transferred and the transfer target may not be accurately coated. On the other hand, when the thickness exceeds 500 μm, the support film becomes rigid and may not be able to follow the covering. The material of the support film is not particularly limited as long as it can withstand the solvent removal of the transfer layer and the heating during the transfer to the covering. For example, polyethylene terephthalate, polyethylene-2, 6-naphthalate, polypropylene Polyester resins such as terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene and polymethylpentene, cyclic polyolefin resins, polyamide resins, polyimide resins, polyether resins, polyesters Amide resin, polyether ester resin, acrylic resin, polyurethane resin, polycarbonate resin, or polyvinyl chloride resin can be used. , Transfer layer and the support releasability polyolefin resin or an acrylic resin from the viewpoint of both of the film is preferred.

Moreover, in order to make the surface of a support film into an appropriate state, the resin layer different from this film can also be laminated | stacked. Furthermore, in order to give coatability and releasability to the surface of the support film in contact with the transfer layer, a treatment for applying a base conditioner, a primer, a silicone-based or fluorine-based release coating agent, etc. Alternatively, a precious metal such as gold or platinum may be sputtered on the surface.
<Form of the surface of the support film on the side in contact with the transfer layer>
The surface on the side where the support film in the present invention is in contact with the transfer layer may be flat or uneven. That is, as shown in FIG. 1A, even if the boundary between the transfer film 1 and the transfer layer 2 is flat, the uneven shape 3 is formed at the boundary between the transfer film 1 and the transfer layer 2 as shown in FIG. There may be. In the case of the concavo-convex shape, it is possible to provide a coated body in which the outermost surface of the transfer layer in the transfer material / transfer layer laminate formed by transfer has a concavo-convex shape. The formation method of the uneven | corrugated shape of a support film is not specifically limited, It is possible to apply known manufacturing methods, such as a thermal imprint method, UV imprint method, coating, an etching.
<Transfer layer of transfer film>
In the transfer film used in the present invention, the transfer layer laminated on the support film contains a siloxane oligomer. The component of the transfer layer is the content of silicon atoms relative to the total number of carbon, oxygen, and silicon atoms measured by X-ray photoelectron spectroscopy (XPS) of silicon atoms (hereinafter sometimes referred to simply as the silicon atom content). Is preferably 5 to 33%, more preferably 8 to 30%. When the silicon atom content is less than 5%, the siloxane oligomer contained in the transfer layer has a small number of siloxane bonds and a high proportion of organic matter, so decomposition at high temperature and yellowing due to ultraviolet rays occur. When the silicon atom content exceeds 33%, the structure of the siloxane oligomer contained in the transfer layer becomes very close to glass, and the adhesion to the transfer target may be reduced. Moreover, it is preferable that the siloxane oligomer in a transfer layer is 50-99 mass%. By having such a specific configuration as the transfer layer, a transfer film having a transfer layer that does not undergo decomposition or yellowing at a high temperature unlike an ultraviolet curable resin can be obtained. In addition to the siloxane oligomer, the transfer layer has a mold release agent and leveling agent for the purpose of improving releasability from the support film and wettability, and adhesion and crack resistance to resin-based transferred materials. An acrylic resin or the like for improving the properties may be included.

  Here, the siloxane oligomer refers to a siloxane compound having two or more continuous siloxane bonds and including a polyorganosiloxane skeleton in the structure. In addition, the siloxane oligomer may partially include a silica structure having no organic functional group directly bonded to a silicon atom as a partial structure. The mass average molecular weight of the siloxane oligomer is not particularly limited, but is preferably 500 to 100,000 in terms of polystyrene measured by GPC. The siloxane oligomer is obtained by solidifying a polysiloxane sol synthesized by hydrolysis / polycondensation reaction of one or more kinds of organosilanes represented by the following general formula (1) where n = 0 to 3, by heating and pressing. Synthesized. In addition, the siloxane oligomer of the transfer layer used in the present invention is 5 to 100 mol% of n = 1 to 3 organosilane from the viewpoint of crack generation during the storage period of the transfer film and crack prevention in the heat treatment of the transfer article. It is preferable that it is obtained by polymerizing the monomer to contain.

(R1) _n- Si- (OR2) _4-n (1)
In the formula, R1 represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R1 may be the same or different. Good. R2 represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R2 may be the same or different. n represents an integer of 0 to 3.

  In the organosilane represented by the general formula (1), the alkyl group, alkenyl group and aryl group of R1 may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 3, 3 , 3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, [(3-ethyl3-oxetanyl) methoxy] propyl group, 3-aminopropyl group, 3 -A mercaptopropyl group and 3-isocyanatopropyl group are mentioned. Specific examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. Specific examples of the aryl group include phenyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4-hydroxy-5- (p -Hydroxyphenylcarbonyloxy) pentyl group, naphthyl group.

  In the organosilane represented by the general formula (1), the alkyl group, acyl group and aryl group of R2 may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, and n-hexyl group. Specific examples of the acyl group include an acetyl group, a propinoyl group, a butyroyl group, a pentanoyl group, and a hexanoyl group. Specific examples of the aryl group include a phenyl group and a naphthyl group.

  N in the general formula (1) represents an integer of 0 to 3. A tetrafunctional silane when n = 0, a trifunctional silane when n = 1, a bifunctional silane when n = 2, and a monofunctional silane when n = 3.

  Specific examples of the organosilane represented by the general formula (1) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyl. Triisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methyl Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3 , 3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) trifunctional silane such as ethyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi Setokishishiran, di n- butyl dimethoxy silane, difunctional silane, such as diphenyl dimethoxysilane, trimethyl methoxy silane, include monofunctional silanes, such as tri-n- butyl silane.

These organosilanes may be used alone or in combination of two or more. From the viewpoint of preventing cracks in the cured uneven layer and the flexibility of the transfer film, the trifunctional silane and the bifunctional silane are used. It is preferable to combine silanes. In addition, silica particles may be added to these siloxane sols in order to improve scratch resistance and hardness.
<First step: Application of transfer layer>
In the coating for forming the transfer layer, the solvent used for diluting the siloxane sol is not particularly limited as long as it has a solubility capable of obtaining a solution of a siloxane sol having an appropriate concentration, but repelling occurs on the film. From the viewpoint of difficulty, an organic solvent is preferable. For example, high boiling alcohols such as 3-methyl-3-methoxy-1-butanol, glycols such as ethylene glycol and propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl Ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, prop Ethers such as pyrene glycol monobutyl ether, diethyl ether, diisopropyl ether, di n-butyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, cyclo Ketones such as pentanone, cyclohexanone, 2-heptanone, 3-heptanone, amides such as dimethylformamide, dimethylacetamide, ethyl acetate, butyl acetate, ethyl cellosolve acetate, 3-methyl-3-methoxy-1-butanol acetate, etc. Esters, toluene, xylene, hexane, cyclohexane In addition to aromatic or aliphatic hydrocarbons such as mesitylene and diisopropylbenzene, γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like can be mentioned, but from the viewpoint of solubility and coatability of the siloxane oligomer, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, diisobutyl ether, di-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, methyl isobutyl Ketones, diisobutyl ketone and butyl acetate are preferred.

As a method for applying the siloxane sol, for example, gravure coating, roll coating, spin coating, reverse coating, bar coating, screen coating, blade coating, air knife coating, dip coating, and the like may be appropriately selected and applied.
<Thickness of transfer layer of transfer film>
The thickness of the transfer layer of the transfer film used in the present invention is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. When the thickness is less than 0.01 μm, repelling is likely to occur in the application of siloxane sol, which may cause a defect. On the other hand, if it is thicker than 10 μm, cracks may occur due to film stress when the transfer layer is cured. In addition, the thickness of a transfer layer is the thickness in a transfer film, Comprising: It is the thickness after drying of the following transfer layer. The thickness of the transfer layer becomes a boundary when the transfer film is cut with a microtome, and the cross section is imaged with a scanning electron microscope (hereinafter sometimes abbreviated as SEM) and divided into 5 equal parts in a direction perpendicular to the thickness. The average of the four points measured by observing the four points is taken as the thickness of the transfer layer. When the surface of the transfer layer and / or the boundary surface with the support film has an uneven shape, it is the portion where the transfer layer is thickest in the captured image. That is, with reference to FIG. 2, when placed horizontally with the surface opposite to the transfer layer of the support film facing down, the lowest position of the depression on the surface of the boundary with the transfer layer 2 on the support film 1 The distance between the surfaces of the transfer layer that are not in contact with the support film is the thickness 4 of the transfer layer (FIG. 2). The magnification of observation and measurement is 20000 times when the thickness of the transfer layer is less than 2 μm, 5000 times when it is 2 μm or more and less than 5 μm, and 2500 times when it is 5 μm or more.
<Second Step: Removal of Solvent from Transfer Layer>
After coating, the solvent is removed by heating or under reduced pressure. The heating temperature for removing the solvent is preferably 20 ° C. or higher and 180 ° C. or lower. When the heating temperature is lower than 20 ° C., a great amount of time is required. On the other hand, when heated to a temperature higher than 180 ° C., there is a possibility that the transfer film loses its flexibility due to crosslinking of siloxane due to heating, cracks may occur, or transferability to a transfer medium may be reduced. The decompression conditions for removing the solvent may be set as appropriate as long as the shape of the transfer film does not collapse, and the decompression is preferably performed to 10 kPa, and the solvent may be removed by heating at the same time as the decompression. In this way, after the transfer film is heated at 80 ° C. for 1 hour, the transfer film is dried to a point where no change is observed in the thickness of the transfer layer. Specifically, for example, a method of allowing to stand at a reduced pressure of 10 kPa for 5 minutes and then heating to 80 ° C. for 5 minutes can be mentioned.

  After the transfer layer is formed on the support film, the crosslinking reaction is allowed to proceed, whereby the hardness is increased, and the transfer layer can be prevented from being deformed or damaged before transfer, or the solvent resistance can be improved. Further, the cross-linking reaction in the in-plane direction of the film proceeds, so that the transfer layer can be prevented from tearing or coming off during transfer.

In addition, since the crosslinking reaction of siloxane proceeds through hydrolysis and dehydration condensation, the moisture generated by the dehydration condensation is removed by heating to allow the crosslinking reaction to proceed, or the aging allows sufficient time for the crosslinking reaction to proceed sufficiently. By doing so, the crosslinking reaction in the transfer layer can be promoted.
<Third step: Activation treatment of transfer layer surface>
In the present invention, the surface activation treatment in contact with the transfer target is specifically introducing oxygen atoms into the surface of the transfer layer. In transferring the transfer layer from the transfer film to the transfer target, it is considered that the hydroxyl group on the transfer target is related to the adhesion between the transfer target and the transfer layer. Therefore, it is considered that introduction of oxygen atoms to the surface of the transfer layer increases the reactivity of the transfer layer with the hydroxyl group on the transfer target and improves transferability.

  Examples of methods for activating the surface of the transfer layer that contacts the transfer target include plasma treatment, ultraviolet treatment, corona treatment, ozone treatment, and various other activation treatment methods. Plasma treatment is preferable because energy suitable for treatment can be obtained.

  Plasma treatment is a process in which a high voltage is applied between two opposing electrodes to generate an electric field, the gas existing between the electrodes is turned into plasma by the action of the electric field, and the object is processed with the plasmaized gas. It is. The gas to be added between the electrodes, that is, the processing gas is not particularly limited as long as oxygen to be introduced into the surface of the transfer layer is present and the atmosphere contains 5 to 100% oxygen. The pressure state at the time of processing may be under atmospheric pressure, reduced pressure, or vacuum state. However, since the deactivation of plasma gas can be suppressed, it is preferable to perform processing under reduced pressure or vacuum state. .

  Hereinafter, as an example, a schematic cross-sectional view of a low-pressure plasma apparatus is shown in FIG.

  The low-pressure plasma apparatus includes an upper electrode 5, a lower electrode 6 facing the upper electrode 5, a chamber 7, and an exhaust pump 8. The chamber 7 is a container that can maintain the internal airtightness, and since the inside is in a reduced pressure (vacuum) state, it is necessary to have a pressure resistance that can withstand a pressure difference between the inside and the outside. The chamber shown in FIG. 3 has a shape in which the upper electrode 5 is connected to the upper portion of the chamber and the lower electrode 6 is accommodated in the chamber.

  The chamber 7 is connected to an exhaust pump 8, and the inside of the chamber is decompressed (vacuum) by the exhaust pump 8. The exhaust pump 8 is, for example, a rotary oil pump, a turbo molecular pump, or the like. By reducing the pressure inside the chamber, the gas can be easily converted to plasma, or a reaction product generated by plasma processing is discharged out of the system. You can do it. When adjusting the plasma processing gas, the processing atmosphere can be changed by introducing a processing gas supply unit connected to the chamber 7.

  The upper electrode 5 and the lower electrode 6 face each other, and plasma can be generated by applying a high voltage between the electrodes. By disposing a plasma processing object between these electrodes and applying a high voltage, the surface can be processed.

  As a plasma processing method, first, the chamber 7 is opened under normal pressure, and a transfer film is placed on the lower electrode 6 with the processing surface facing the upper electrode 5. Thereafter, the upper electrode 5, the lower electrode 6 and the transfer film are sealed in the chamber 7, and the pressure is reduced. In a state where the pressure is stable, a high voltage is applied to the upper electrode 5 and the lower electrode 6 to generate plasma, and the surface is treated for a predetermined time.

The treatment time of the transfer layer surface is preferably 5 to 300 seconds, more preferably 10 to 120 seconds. If the treatment time is less than 5 seconds, the surface may not be sufficiently treated and transferability may not be recovered. On the other hand, when the treatment time exceeds 300 seconds, the transfer layer surface is plasma-etched, and the transfer layer is damaged and becomes fine irregularities.
<Fourth Step Transfer Method>
The transfer layer surface of the transfer film used in the present invention is brought into contact with the transfer object to form a laminate containing the transfer object / transfer layer / support film, and the transfer layer is pressed or pressurized and heated. Can be transferred to a transfer medium. Examples of the pressurization at the time of transfer include, but are not limited to, nip rolls and press machines. The pressure applied to the laminate of transferred object / transfer layer / support film is preferably 1 kPa to 50 MPa. If it is less than 1 kPa, transfer defects may occur, and if it exceeds 50 MPa, the uneven shape of the transfer film may be broken or the glass substrate may be damaged. Moreover, when pressurizing, a buffer material can also be used between the support film of this laminated body, a pressurization plate, a pressurization roll, etc. By using the cushioning material, the transfer layer can be transferred with high accuracy without biting air or the like. As the buffer material, fluorine rubber, silicon rubber, ethylene propylene rubber, isobutylene isoprene rubber, acrylonitrile butadiene rubber, or the like can be used. In addition, in order to sufficiently adhere the transfer layer to the transfer target, heating can be performed together with pressurization.

The fourth step of transferring the transfer layer from the transfer film to the transfer target is preferably performed immediately after the third step of activating the transfer layer surface, that is, within 48 hours after completion of the various activation processes. If time passes again after the transfer layer surface is activated in the third step, the activated transfer layer surface may be deactivated, and the effect of the transfer layer activation treatment may not be obtained.
<Fifth Step Removal of Support Film>
In order to transfer the transfer layer to the transfer medium to form a transfer body / transfer layer laminate, the support film of the transfer film is removed. The support film may be peeled before or after heat treatment after transfer, which will be described later. When the support film is peeled in advance before the heat treatment, it is peeled off at a press temperature or lower after the transfer. When the temperature at the time of peeling is equal to or higher than the press temperature, the shape of the transfer layer may be lost, or the peelability from the support film may be reduced. On the other hand, when the support film is removed after the heat treatment, the support film may be scattered during the heat treatment or baked on the powder. In such a case, the surface may be washed or air blown. Can be removed. Further, when the transfer film / transfer layer / support film laminate is present as a support film even after the heat treatment, the support film is peeled off at a heat treatment temperature or lower. When the peeling temperature exceeds the heat treatment temperature, the shape of the transfer layer may be destroyed.
<Heat treatment after transfer>
After the transfer, heat treatment may be performed in order to further promote the crosslinking reaction of the siloxane oligomer contained in the transfer layer to vitrify. The heat treatment temperature for vitrification can be appropriately set according to the heat resistance, chemical resistance and reliability required for the laminate.

  For example, the heat treatment temperature is preferably 150 to 1200 ° C., more preferably 180 to 800 ° C. when used as a protective film by transferring to an inorganic material such as a glass plate, or for imparting uneven shapes on the surface of the glass plate. Preferably, 200-400 degreeC is the most preferable. When heat treatment is performed at a temperature lower than 150 ° C., the crosslinking reaction does not proceed sufficiently, and sufficient vitrification cannot be achieved or the heat resistance may deteriorate. On the other hand, when heat treatment is performed at a temperature higher than 1200 ° C., cracks may occur or the uneven shape may collapse.

  On the other hand, when using a transfer layer transferred to a transfer object made of an inorganic material or a crystal material having a low etching rate as an etching resist film, the transfer layer needs to have a lower etching rate than the transfer object. For this purpose, it is effective to burn the organic components in the transfer layer to form a dense silicon dioxide film, and therefore the heat treatment temperature is preferably 700 to 1200 ° C. When the heat treatment temperature is lower than 700 ° C., the transfer layer is not sufficiently densified and may not be used as an etching resist film. At temperatures higher than 1200 ° C., cracks may occur in the transfer layer. By pre-baking at a temperature lower than the heat treatment temperature before the heat treatment, it is possible to prevent the irregular surface shape from being deformed by heat.

  The present invention will be specifically described based on examples, but the present invention is not limited to the examples.

(1) Preparation of Transfer Film A siloxane sol was applied to a 30 mm × 30 mm support film using a spin coater model number 1H-DX2 manufactured by Mikasa Corporation. Thereafter, the solvent was removed in an environment of 20 ° C. and 10 kPa to obtain a transfer film.

(2) Measurement of transfer layer thickness The transfer film was cut with a rotary microtome model RMS manufactured by Microtome Laboratories Co., Ltd., and the cross section was observed and measured with a miniSEM model ABT-32 manufactured by TOPCON. The magnification and the measurement method were the conditions described in the text.

(3) Evaluation of degree of progress of crosslinking reaction before plasma treatment The degree of progress of the crosslinking reaction was evaluated by solvent resistance.
A transfer film of 10 mm × 10 mm was immersed in 3.5 g of methyl ethyl ketone placed in a glass petri dish in a direction in which the transfer layer faces the petri dish bottom surface. After immersion for 1 minute, the transfer film was taken out, and the immersed methyl ethyl ketone and the transfer film were observed and evaluated. In addition, the evaluation criteria of the progress degree of a crosslinking reaction were defined and described as follows.
3: The transfer layer was in close contact with the support film without peeling.
2: The transfer layer was peeled off from the support film and existed as a film in methyl ethyl ketone.
1: The transfer layer was dissolved and could not be confirmed even in methyl ethyl ketone.

(4) Evaluation of transferability (4-1) Preparation of transferred object Dust adhering to the surface of a low alkaline glass model No. 1737 (50 mm x 50 mm, thickness 1.1 mm) manufactured by Corning, which is a transferred object, is removed with a blower. Then, in a state immersed in pure water, washing for 10 minutes at 45 kHz was repeated twice using a three-frequency ultrasonic cleaner No. VS-100III manufactured by AS ONE Corporation. Then, it plasma-processed for 5 minutes by 15000VAC using the Sakai Semiconductor Co., Ltd. tabletop vacuum plasma apparatus.

(4-2) Transfer method The transfer layer surface of a transfer film having a size of 30 mm × 30 mm is brought into contact with the glass substrate as the transfer target prepared in (4-1), and further, as a buffer material on the support film surface of the transfer film. “Kinyo Board (registered trademark)” model number F200 manufactured by Kinyo Co., Ltd. was laminated, pressed at a press temperature of 20 ° C. and a press pressure of 1.38 MPa for 10 seconds, and then the support film was peeled off at room temperature.

(4-3) Transfer area ratio and transfer stability evaluation Of the three laminates produced by repeating the same experiment three times under the conditions of (4-2), the area of the laminate transferred with the largest area The transfer area ratio was calculated with a transfer film size of 30 mm × 30 mm as 100%. The evaluation criteria for the transfer area ratio were defined and described as follows.
5: Transfer area ratio 100%. Good transferability 4: Transfer area ratio of 90% to less than 100% 3: Transfer area ratio of 50% to less than 90% 2: Transfer area ratio of 10% to less than 50% 1: Transfer area ratio of 0% to less than 10% The stability evaluation criteria were defined and described as follows. Note that “equivalent” means that the transfer area ratio is classified into the same rank in the five-step evaluation.
3: All the transfer area ratios of the three laminates are the same 2: Of the three laminates, the two transfer area ratios are the same 1: All the transfer area ratios of the three laminates are different. ) Transfer Layer Appearance Evaluation Transfer layer appearance evaluation criteria were defined and evaluated as follows.
◎: No crack with a width of 2.0 μm or more and a length of 3 mm or more in the laminate ○: There are 1 to 3 cracks with a width of 2.0 μm or more and a length of 3 mm or more in the laminate ×: The width of the laminate is 2.0 μm There are four or more cracks having a length of 3 mm or more. [Example 1] A film having a thickness of 60 μm of “ZEONOR FILM (registered trademark)” model number ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin-based resin. After applying OCNL505 siloxane sol manufactured by Co., Ltd., the solvent was removed to obtain a transfer film having a transfer layer thickness of 4.76 μm. The obtained transfer film was aged in an environment of room temperature 20 ° C. and humidity 40% for 30 days, and then the surface of the transfer layer was subjected to plasma treatment at 15000 VAC for 20 seconds using a tabletop vacuum plasma apparatus model number YHS-R manufactured by Sakai Semiconductor Co., Ltd. Within 5 minutes after the plasma treatment, the transfer layer was transferred to obtain a laminate.

  [Example 2] A laminate was obtained in the same manner as in Example 1 except that the transfer layer was transferred 45 hours after the plasma treatment.

  [Example 3] A laminate was obtained in the same manner as in Example 1 except that the transfer layer was transferred 60 hours after the plasma treatment.

  [Example 4] A laminate was prepared in the same manner as in Example 1 except that the activation process of the transfer layer was an atmospheric pressure plasma treatment for 30 seconds using an atmospheric pressure plasma apparatus model S5000 manufactured by Sakai Semiconductor Co., Ltd. Obtained.

  [Example 5] A laminate was obtained in the same manner as in Example 4 except that the transfer layer was transferred 45 hours after the plasma treatment.

  [Example 6] A laminate was obtained in the same manner as in Example 4 except that the transfer layer was transferred 60 hours after the plasma treatment.

  [Example 7] Nippon Zeon Co., Ltd. “ZEONOR FILM (registered trademark)” model ZF14, 60 μm thick, is coated with OCNL505 siloxane sol manufactured by Tokyo Ohka Kogyo Co., Ltd. Removal was performed to obtain a transfer film having a transfer layer thickness of 4.91 μm. The obtained transfer film was heated with a hot plate at 120 ° C. for 1 hour, and then the surface of the transfer layer was subjected to plasma treatment at 15000 VAC for 20 seconds using a tabletop vacuum plasma apparatus model number YHS-R manufactured by Sakai Semiconductor Co., Ltd. Within 5 minutes after the plasma treatment, the transfer layer was transferred to obtain a laminate.

  [Example 8] A laminate was obtained in the same manner as in Example 7 except that the transfer layer was transferred 45 hours after the plasma treatment.

  [Example 9] A laminate was obtained in the same manner as in Example 7 except that the transfer layer was transferred 60 hours after the plasma treatment.

  [Example 10] On a film having a thickness of 60 μm of “ZEONOR FILM (registered trademark)” model ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, OCNL505 siloxane sol manufactured by Tokyo Ohka Kogyo Co., Ltd. Removal of the transfer film with a transfer layer thickness of 4.85 μm was obtained. Immediately after obtaining the transfer film, the surface of the transfer layer was subjected to plasma treatment at 15000 VAC for 20 seconds using a tabletop vacuum plasma apparatus model number YHS-R manufactured by Sakai Semiconductor. Within 5 minutes after the plasma treatment, the transfer layer was transferred to obtain a laminate.

  [Example 11] A laminate was obtained in the same manner as in Example 10 except that the transfer layer was transferred 45 hours after the plasma treatment.

  [Example 12] A laminate was obtained in the same manner as in Example 10 except that the transfer layer was transferred 60 hours after the plasma treatment.

  [Example 13] A laminate was obtained in the same manner as in Example 2 except that the thickness of the transfer layer was changed.

  [Example 14] A laminate was obtained in the same manner as in Example 3 except that the thickness of the transfer layer was changed.

  [Example 15] A laminate was obtained in the same manner as in Example 8 except that the thickness of the transfer layer was changed.

  [Example 16] A laminate was obtained in the same manner as in Example 11 except that the thickness of the transfer layer was changed.

  [Example 17] A laminate was obtained in the same manner as in Example 2 except that the thickness of the transfer layer was changed.

  [Example 18] A laminate was obtained in the same manner as in Example 8 except that the thickness of the transfer layer was changed.

  [Example 19] A laminate was obtained in the same manner as in Example 11 except that the thickness of the transfer layer was changed.

  [Example 20] A laminate was obtained in the same manner as in Example 2 except that the thickness of the transfer layer was changed.

  [Example 21] A laminate was obtained in the same manner as in Example 8 except that the thickness of the transfer layer was changed.

  [Example 22] A laminate was obtained in the same manner as in Example 2 except that the thickness of the transfer layer was changed.

  [Example 23] A "Zeonor film (registered trademark)" model ZF14 made by Nippon Zeon Co., Ltd., which is a cyclic polyolefin-based resin having a thickness of 60 μm, except that the surface was made into a blazed diffraction grating shape with a 556 nm pitch, A laminate was obtained in the same manner as in Example 2. The thickness of the transfer layer was 1.24 μm.

  [Comparative Example 1] OCNL505 siloxane sol manufactured by Tokyo Ohka Kogyo Co., Ltd. was applied to a 60 μm thick film of “ZEONOR FILM (registered trademark)” model ZF14 manufactured by ZEON Corporation, which is a cyclic polyolefin resin. An attempt was made to transfer the transfer layer as it was to the transfer target, but the transfer layer did not become a film and could not be transferred.

  [Comparative Example 2] An OCNL505 siloxane sol manufactured by Tokyo Ohka Kogyo Co., Ltd. was applied to a 60 μm thick film of “Zeonor Film (registered trademark)” model ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin. Removal was performed to obtain a transfer film having a transfer layer thickness of 2.68 μm. Immediately after obtaining the transfer film, an attempt was made to transfer the transfer layer to the transfer target without activating the surface of the transfer layer. However, the transfer layer remained on the support film, and a sufficient transfer area could not be obtained.

  [Comparative Example 3] An OCNL505 siloxane sol manufactured by Tokyo Ohka Kogyo Co., Ltd. was applied to a 60 μm thick film of “ZEONOR FILM (registered trademark)” model ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin. Removal of the transfer film with a transfer layer thickness of 3.25 μm was obtained. The obtained transfer film was aged in an environment of room temperature 20 ° C. and humidity 40% for 30 days, and then an attempt was made to transfer the transfer layer to the transfer material without activating the surface of the transfer layer. Thus, a sufficient transfer area could not be obtained.

  [Comparative Example 4] A film having a thickness of 60 μm of “ZEONOR FILM (registered trademark)” model ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, was coated with OCNL505 siloxane sol manufactured by Tokyo Ohka Kogyo Co., Ltd. Removal of the transfer film with a transfer layer thickness of 4.56 μm was obtained. After the obtained transfer film was heated on a hot plate at 120 ° C. for 1 hour, the transfer layer was transferred to the transfer target without activating the transfer layer surface, but the transfer layer remained on the support film, A sufficient transfer area could not be obtained.

  [Comparative Example 5] “Zeonor Film (registered trademark)” model ZF14 made by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin having a thickness of 60 μm, except that the surface is made into a blazed diffraction grating shape with a 556 nm pitch, A laminate was obtained in the same manner as in Comparative Example 4. The thickness of the transfer layer was 0.35 μm.

  Table 1 shows the transferability after plasma treatment of Examples 1 to 25 and Comparative Examples 1 to 5. In Examples 1, 2, 4, 5, 13, and 23, the transfer area ratio, stability, and appearance were very good. In Examples 3, 6, 10, 11, 14, and 15, both the transfer area ratio and stability were good, and the appearance was very good. In Examples 7 and 8, the transfer area ratio and appearance were very good, and the stability was good. In Example 9, transferability was good and appearance was very good, but stable transferability was not obtained. In Example 12, the transferability was generally good and the appearance was very good, but stable transferability was not obtained. Example 16 Transferability was generally good and appearance was very good, but stable transferability was not obtained. In Example 17, transferability was very good, and stability and appearance were good. In Examples 18, 19, and 21, the transferability was generally good, and the appearance and stability were good. In Example 22, transferability was generally good, but stable transferability was not obtained, and cracks were also confirmed in appearance. In Comparative Example 1, the transfer layer could not be transferred as a film due to the presence of the solvent. Comparative Examples 2 to 4 hardly transferred, resulting in the transfer layer remaining on the support film.

1: support film 2: transfer layer 3: uneven shape on support film 4: transfer layer thickness 5: upper electrode 6: lower electrode 7: chamber 8: exhaust pump

Claims (4)

A first step of applying a solution containing a siloxane oligomer on a support film;
A second step of forming a transfer layer by removing the solvent from the solution applied on the support film, and forming a transfer film;
A third step of activating the transfer layer surface of the transfer film produced in the second step by plasma treatment ;
A fourth step of transferring the transfer layer to the transfer body by causing the transfer layer surface activated in the third step and the transfer target to face and contact with each other;
A laminate consisting of the transfer material / transfer layer / support film, see contains a fifth step of peeling off the support film at the interface between the transfer layer supporting film,
A method for producing a laminate using a transfer film, wherein the transfer layer has a thickness of 0.01 to 10 μm . The manufacturing method of the laminated body of Claim 1 which implements a 4th process within 48 hours after implementation of the 3rd process of activating a transfer layer on a transfer film. The manufacturing method of the laminated body of Claim 1 or 2 which implements a 3rd process, after making the crosslinking reaction of the transfer layer of the transfer film produced at the said 2nd process advance. The manufacturing method of the laminated body in any one of Claims 1-3 which has an uneven | corrugated surface shape in the outermost surface of a transfer layer.

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