JP2013208796A - Transfer film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer film for applying a thin-film transfer layer formed of a siloxane composition to a large-area and high-rigidity substrate to be transferred uniformly without defects through a simple production process.SOLUTION: A transfer film includes, on a support film, a transfer layer composed of a siloxane composition containing a siloxane. The siloxane composition shows a ductility factor of 0.40-0.99 when a triangular-pyramid indenter is pushed into a 2 μm-thick layer of the siloxane composition at a load of 1 mN.

Description

  The present invention relates to a transfer film for transferring a thin-film siloxane layer excellent in heat resistance and light resistance to a large-area transfer object without a defect by a simple manufacturing process.

  In recent years, various substrates such as a glass substrate, a metal substrate, and a crystal substrate have been used as a semiconductor substrate such as a liquid crystal display device, a solar cell substrate, and an LED. In order to form functional layers such as antistatic, antireflection, antifouling, light scattering, a power generation layer, and a light emitting layer on these substrates, appropriate processing on the substrate surface is required. As a conventional processing method, it is known that a photocurable resin is applied onto a substrate, but a layer formed of the photocurable resin is decomposed at a high temperature exceeding 250 ° C. or yellowed by ultraviolet rays. Therefore, there are problems in that processing at a high temperature is impossible and heat resistance and light resistance in use cannot be obtained.

  On the other hand, a layer made of siloxane has a property that does not cause decomposition or yellowing at a high temperature as compared with an ultraviolet curable resin, and thus can be used or processed at a high temperature. As a method for forming a film made of siloxane, a sol-gel method is known in which a solution containing silicon alkoxide is applied to a substrate and heated to obtain a siloxane film (Patent Document 1). In addition, a pattern is formed by resist using a method of applying a solution containing silicon alkoxide on a substrate and then pressing and solidifying the mold (Patent Document 2), or a resin having a siloxane structure imparted with ultraviolet curability. Thus, a method of forming a siloxane film having a concavo-convex shape with high heat resistance and light resistance (Patent Document 3) is also known.

  On the other hand, a transfer method is known as a method for easily forming a large-area film (Patent Document 4). In general, the transfer method is a method of forming a film to be a functional layer on a support and copying the functional layer onto a substrate. In the formation of the functional layer, by applying a transfer method, a large area can be processed uniformly, or a laminate such as a decorative board with a pattern can be processed at a time.

Japanese Patent No. 4079383 Japanese Patent No. 3750393 JP 2006-154037 A JP 2002-293094 A

  When forming a functional layer by transferring a layer using the transfer method, especially if the substrate to be transferred is highly rigid, such as glass or metal, bubbles are introduced between the substrate and the transfer layer. There is a problem that transfer defects such as omission of the transfer layer and peeling from the substrate are likely to occur due to intrusion or failure of the transfer layer to follow the substrate. In response to such problems, measures have been taken to increase the film thickness, or to mix or laminate flexible resins. However, when a layer made of siloxane having both heat resistance and light resistance is used as a functional layer, the siloxane serving as the transfer layer shrinks due to condensation, so that it is easy to generate cracks due to stress, so the film thickness cannot be increased. . Furthermore, it is difficult to laminate and mix the resins when forming a high transmittance film while maintaining high heat resistance and light resistance.

  In view of the above-described problems, an object of the present invention is to provide a transfer film for uniformly and easily transferring a thin transfer layer made of a siloxane composition on a transfer film to a rigid substrate. is there.

  The transfer film of the present invention that achieves the above-described object is a transfer film having a transfer layer made of a siloxane composition containing siloxane on a support film, wherein the siloxane composition is made of the siloxane composition having a thickness of 2 μm. When the triangular pyramid indenter is pushed into the layer with a load of 1 mN, it has a plasticity ratio of 0.40 to 0.99.

  According to the present invention, a thin transfer layer made of a siloxane composition on a transfer film can be easily transferred onto a highly rigid substrate.

The cross section of a transfer film is shown, (a) is a schematic sectional view of a transfer film in which a transfer layer is formed on a flat support film, and (b) is a transfer layer on a support film having an uneven surface. It is a schematic sectional drawing of the transfer film formed. It is a schematic sectional drawing of the indenter used for a plasticity rate measurement. It is a schematic perspective view of the Berkovich indenter used for a plasticity rate measurement. It is a schematic characteristic figure which shows the load / unloading profile in a plasticity rate measurement. It is a schematic perspective view of a plasticity rate measurement sample in which a transfer layer is formed by droplet development on a soda lime glass substrate. It is a schematic sectional drawing which shows the transfer film by which a transfer layer is formed on the support film which has an uneven | corrugated shaped surface.

  Hereinafter, the transfer film of the present invention will be described in more detail with reference to the drawings.

[Support film]
The thickness of the support film used for the transfer film is preferably 5 to 500 μm, and more preferably 40 to 300 μm. If the thickness is less than 5 μm, the transfer layer may be twisted when transferred, and the transfer target may not be properly coated. On the other hand, if the thickness exceeds 500 μm, the support film becomes rigid and may not be able to deform following the surface of the transfer target. The material of the support film is not particularly limited as long as it can withstand removal of the solvent when forming the transfer layer and heat when transferring the transfer layer to the transfer target. For example, polyethylene terephthalate, polyethylene- Polyester resins such as 2,6-naphthalate, polypropylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene and polymethylpentene, cyclic polyolefin resins, polymethyl methacrylate, polyacryl Acrylic resins such as methyl acid, polyamide resins, polyimide resins, polyether resins, polyester amide resins, polyether ester resins, polyurethane resins, polycarbonate resins, or polychlorinated resins Nyl-based resin can be used, but the coating property of the coating liquid for forming the siloxane composition as the transfer layer (hereinafter also referred to as “siloxane composition coating liquid”) and the release of the transfer layer and the support film From the viewpoint of achieving compatibility, polyolefin resins and acrylic resins are preferable.

  A laminated film can also be applied as the support film. 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 process of sputtering a noble metal such as gold or platinum may be performed.

[Surface morphology of support film]
The surface on the side where the support film is in contact with the transfer layer may be flat or uneven. That is, as shown in FIG. 1 (a), the boundary between the support film 2 and the transfer layer 3 may be flat across the entire surface of the support film, or the transfer with the support film 2 as shown in FIG. 1 (b). There may be a concavo-convex shape portion 4 across the entire surface of the support film at the boundary of the layer 3. Furthermore, the shape of the boundary between the support film 2 and the transfer layer 3 may have both a flat portion and an uneven shape portion 4. The formation method of the uneven | corrugated shaped part 4 is not specifically limited, It is possible to apply known methods, such as a thermal imprint method, UV imprint method, coating, an etching.

[Transfer layer]
The transfer layer is made of a siloxane composition. The siloxane composition is a composition containing a crosslinkable polymer having a siloxane bond as a main skeleton, and is a precursor material of a crosslinkable polymer having a siloxane bond as a main skeleton (hereinafter also referred to as “siloxane”). It is preferable to contain what is obtained by the condensation reaction of a siloxane monomer and / or a siloxane oligomer, and may also contain these precursor materials. The crosslinkable polymer having a siloxane bond as the main skeleton can be vitrified by causing a crosslinking reaction to proceed by heat treatment because the Si—OH bond derived from the general formula (1) described later remains. it can. The crosslinkable polymer having a siloxane bond as the main skeleton preferably does not have a crystal structure.

  A siloxane oligomer refers to a siloxane compound having a polyorganosiloxane skeleton having two or more continuous siloxane bonds 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 weight 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 preferably synthesized by hydrolysis and polycondensation reaction using one or more organosilanes represented by the following general formula (1) as monomers. In addition, 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 obtained by polymerizing a monomer containing 5 to 100 mol% of n = 1 to 3 organosilane. Is more preferable.

_{^{(R 1) n -Si- (OR}} 2) 4-n (1)
(In the formula, R ¹ 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 R ¹ are the same or different. R ² 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 R ² may be the same. (N may represent an integer of 0 to 3).

In the organosilane represented by the general formula (1), the alkyl group, alkenyl group and aryl group of R ¹ 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-ethyl-3-oxetanyl) methoxy] propyl group, 3-aminopropyl group, A 3-mercaptopropyl group and a 3-isocyanatopropyl group are exemplified. 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 R ² 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. Further, when the hydrolysis / polycondensation reaction using these organosilanes as monomers is carried out in the presence of silica particles, siloxane containing silica particles can be formed. The siloxane composition containing silica particles can impart scratching properties to the transfer layer or improve the hardness.

  The siloxane composition used in the transfer layer may contain a release agent or leveling agent for the purpose of improving releasability from the support film and wettability, and improving crack resistance. An acrylic resin or the like may be included for the purpose of improving the adhesion when the transfer object is a resin material.

[Plastic modulus of transfer layer]
The transfer layer is formed from a siloxane composition having an adjusted plasticity rate. Specifically, when a 2 μm-thick transfer layer is formed on a glass substrate using a siloxane composition, the plasticity ratio measured when a triangular pyramid indenter is pushed into this layer with a load of 1 mN is 0. It is preferably formed from a siloxane composition that is 40 to 0.99. When the plasticity ratio is less than 0.40, even when the transfer layer is pressed against the transfer target during transfer, the surface that is in close contact with the transfer target due to unloading is in a state before pressing due to the elasticity of the transfer layer. There is a risk that it will be recovered and transfer will not be possible due to insufficient contact with the transfer target. On the other hand, when the plasticity ratio is larger than 0.99, even if the transfer layer is pressed against the transfer target, it cannot follow the roughness of the surface of the transfer target, or air is trapped, resulting in transfer defect. May occur.

<Measurement method of plastic modulus>
The plasticity ratio can be measured using an indenter. The indenter is an apparatus as shown in FIG. 2, and a minute indenter 5 is pushed into the transfer layer 3 as a measurement object, and the material physical properties are evaluated from the pushing depth and pressure history (FIG. 4). .

  In the measurement of the plasticity ratio, as shown in FIG. 3, a Barkovich indenter 5 having a triangular interval of 115 ° and made of a regular triangular pyramid type diamond tip is used.

  Loading and unloading are performed at a constant speed of 0.0225 mN / sec. After loading up to a maximum load of 1 mN, unloading is performed to 0.1 mN, and a load-displacement profile as shown in FIG. 4 is obtained. .

From the load-displacement profile obtained by measurement, the ratio of the maximum indentation depth (h _max ) 10 at the maximum load 1 mN and the indentation recovery depth (h _c ) 11 at the indentation pressure 0.1 mN after unloading. The indicated plasticity ratio ξ _r = h _c / h _max is calculated.

When the transfer layer is made of a completely elastic body, the unloaded h _c completely returns to the state before the measurement, so the plasticity ratio becomes zero. On the other hand, when the transfer layer exhibits a completely plastic property, h _c does not return to the state before the measurement even after unloading, so the plasticity ratio is 1. If the maximum indentation depth (h _max ) 10 exceeds 1 μm, the transfer layer may be broken or peeled off, or the measurement indenter may penetrate the transfer layer to measure the change of the substrate. A remeasurement shall be performed. If it exceeds 1 μm even after re-measurement, change the measurement conditions so that the maximum indentation depth (h _max ) is 10 to 0.7-1 μm and unloads to 10% of the maximum load. And measure again.

[Method of forming transfer layer]
As a method for forming a transfer layer on a support film, a transfer method in which the transfer layer is once formed on a substrate different from the support film and then transferred onto the support film, or a siloxane composition dissolved in a solvent is used. Examples include direct coating methods in which the coating liquid is directly coated on a support film and then dried, but the thickness of the transfer layer (hereinafter also referred to as “film thickness”) is easy to adjust, such as the thickness of the support film. Since it is difficult to be affected, it is preferable to use a direct coating method.

  The solvent used for dissolving the siloxane composition is not particularly limited as long as it has solubility capable of obtaining a solution of the siloxane composition having an appropriate concentration to be used for coating, but it is difficult to cause repellency on the film. From the viewpoint, an organic solvent is preferable. For example, high boiling point 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, propylene 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 Ethers such as tellurium and dipropylene glycol dimethyl ether, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and 3-heptanone, amides such as dimethylformamide and dimethylacetamide, acetic acid Esters such as ethyl, butyl acetate, ethyl acetate, ethyl cellosolve acetate, 3-methyl-3-methoxy-1-butanol acetate, aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, cyclohexane, mesitylene, diisopropylbenzene In addition, γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc. can be mentioned. 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 ketone, diisobutyl ketone and butyl acetate are preferred.

  For example, gravure coating, roll coating, spin coating, reverse coating, bar coating, screen coating, blade coating, air knife coating, dip coating, etc. are appropriately selected as a method for applying a coating solution of a siloxane composition dissolved in a solvent. And apply.

  When the transfer layer is formed to have a thickness of 2 μm on the glass substrate, the plasticity ratio measured when the triangular pyramid indenter is pushed into the transfer layer with a load of 1 mN is 0.40 to 0.99. Examples of the method include a method in which the transfer layer is laminated on the support film and then heated to advance the crosslinking of siloxane, or the crosslinking of the siloxane is advanced by plasma treatment or UV ozone treatment. When the network structure grows three-dimensionally, deformation of the entire film is less likely to occur due to the movement of the resin being restricted or the slippage between the molecular chains being suppressed. Conceivable. In addition, the degree of crosslinking of the siloxane composition can be appropriately adjusted by changing the type and ratio of the organic functional group of the crosslinkable polymer having a siloxane bond as the main skeleton in the siloxane composition. For example, when many organic functional groups are introduced, it is considered that the behavior like an organic substance can be caused. In addition, when an organic functional group having a large steric hindrance is introduced, it is considered that the cross-linking reaction is difficult to proceed, so that plastic properties can be imparted.

[Thickness of transfer layer]
The thickness of the transfer layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. When the transfer layer is thinner than 0.01 μm, repelling is likely to occur in the application of the coating solution of the siloxane composition, and uneven thickness is likely to occur, which may cause a defect. On the other hand, if the transfer layer 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 operation was completed in the lamination process of a transfer layer. The thickness of the transfer layer is measured by cutting the transfer film with a microtome and reading the cross section from an image taken with a scanning electron microscope (hereinafter also referred to as “SEM”). When the transfer layer does not have a concave-convex shape as shown in FIG. 1B, the thickness of the imaging cross section at four locations that become boundaries between sections when the imaging cross section is divided into five equal parts in the direction orthogonal to the thickness. The thickness of the transfer layer is the average of the four thickness measurement results. When the boundary surface between the surface of the transfer layer and the support film has an uneven shape as shown in FIG. 1B, the portion where the transfer layer is thickest in the captured image is taken as the thickness of the transfer layer. That is, with reference to FIG. 6, when the support film 2 is placed horizontally with the surface opposite to the transfer layer 3 facing down, the deepest position of the recess on the boundary surface with the transfer layer 3 on the support film 2 The distance between the (lowermost part) and the outermost surface (uppermost part) of the transfer layer is the transfer layer thickness 13.

[Transfer method]
A method for transferring a transfer layer to a transfer medium using a transfer film will be described. The surface of the obtained transfer film on the transfer layer side is brought into contact with the transfer target to form a laminate, and the transfer layer can be transferred to the transfer target by applying pressure or pressurizing and heating. Examples of the pressing method at the time of transfer include, but are not limited to, a nip roll and a press machine. The pressure applied to the laminate 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 mold film may be broken or the glass substrate may be damaged. Moreover, when pressurizing, a buffer material can be interposed between the support film of the laminate and a pressure plate, a pressure roll, or the like. 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.

[Post-transfer processing]
After the transfer, high-temperature heat treatment can also be performed in order to advance the crosslinking of siloxane contained in the transfer layer to vitrify. The object to be subjected to the high temperature heat treatment may be a three-layer laminate of support film / transfer layer / transfer object or a two-layer laminate of transfer layer / transfer object from which the support film has been peeled off. When the support film is peeled in advance in order to produce a two-layer laminate of transfer layer / transfer object, it is preferable to peel at a pressing 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. The temperature of the high-temperature heat treatment for vitrifying the siloxane composition can be appropriately set according to the heat resistance, chemical resistance, and reliability required for the laminate. For example, the processing temperature for transferring to an inorganic material such as a glass plate to form a protective film, or for imparting uneven shapes on the surface of the glass plate is preferably 150 to 1000 ° C, more preferably 180 to 800 ° C. Preferably, 200-400 degreeC is more preferable. When the treatment is performed at a temperature lower than 150 ° C., the condensation does not proceed sufficiently, and there is a possibility that the solidification cannot be sufficiently achieved or the heat resistance is deteriorated. On the other hand, when heat treatment is performed at a temperature higher than 1000 ° C., cracks may occur or the uneven shape may collapse. In addition, when the transfer layer is transferred to an object to be transferred made of an inorganic material or a crystal material having a low etching rate and used as an etching resist film, the organic component in the transfer layer is burned to form a dense silicon dioxide film. Since it is effective to do, it is preferable that the heat processing temperature is 700-1200 degreeC. When the processing temperature is less than 700 ° C., the transfer layer is not sufficiently densified and may not be used as an etching resist film, and at a temperature higher than 1200 ° C., cracks may occur in the transfer layer. In the high temperature heat treatment, pre-baking at a temperature lower than the high temperature heat treatment temperature before the treatment can 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) Measurement of plasticity ratio of transfer layer Using an indenter shown in FIG. 2, the physical properties of the transfer layer were measured by the method described below, and the plasticity ratio ξ _r was calculated. The measurement was carried out at five different points in the same sample, and the average value of ξ _r obtained from each measurement was taken as the plastic ratio of the transfer layer.

  On a UFF-standard soda lime glass substrate (hereinafter, also referred to as “soda lime glass substrate”) manufactured by Nippon Sheet Glass Co., Ltd. having a thickness of 1.1 mm, the layer to be measured is 15 mm under the same conditions as the respective examples and comparative examples. It was formed to have a thickness of 2 μm in an area of × 15 mm. When the material for forming the layer to be measured is liquid, a frame 12 having an area of 15 mm × 15 mm as shown in FIG. 5 is produced on the soda lime glass substrate 9 and a solution for forming the layer to be measured is formed in the center thereof. Dripping developed. Thereafter, an appropriate treatment such as removal of the solvent was performed to form a measured layer. When the material for forming the layer to be measured is not liquid but is formed on the support film, the material for forming the layer to be measured is formed on the soda lime glass substrate 9 with a prescribed film. It was produced by transferring to a thickness.

  The outermost surface of the layer to be measured thus obtained was flat enough to detect the outermost surface of the sample with the measurement indenter.

  Thereafter, the soda lime glass substrate on which the flat transfer layer was produced was fixed to the measurement stage of the indenter.

  As shown in FIG. 3, the indenter is a regular triangular pyramid pyramid type Barkovic indenter 5 as shown in FIG. 3, and loading and unloading are performed at a constant speed of 0.0225 mN / sec, up to a maximum load of 1 mN. After loading, the load was unloaded to 0.1 mN to obtain a load-displacement profile (eg, FIG. 4).

The plasticity ratio ξ _r was calculated from the load-displacement profile thus obtained.

(2) Production of Transfer Film A siloxane composition coating solution was applied to a 30 mm × 30 mm □ support film so as to have the thickness of each transfer layer shown in Table 2, and the coating property was evaluated. When the thickness was 5 μm or less, the spin coater model number 1H-DX2 manufactured by Mikasa Co., Ltd. was used, and when the transfer layer thickness exceeded 5 μm, the coating was performed using the Baker applicator. Then, the transfer film was obtained by solvent removal and surface treatment.

(3) 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.

  If the transfer layer does not have irregularities as shown in FIG. 1 (b), observe and measure 4 points that become boundaries when divided into 5 equal parts in the direction orthogonal to the thickness, and transfer the average of 4 points The layer thickness was taken.

  When the surface of the transfer layer and / or the boundary surface with the support film has a concavo-convex shape as shown in FIG. 1B, the portion where the transfer layer is thickest in the captured image, that is, the support in FIG. The distance between the deepest position (lowermost part) of the recess on the boundary surface with the transfer layer 3 on the film 2 and the outermost surface (uppermost part) of the transfer layer was defined as the transfer layer thickness 13. The magnification of observation and measurement was 20000 times when the transfer layer thickness 13 was 0.01 to 2 μm, 5000 times when 2 μm to 5 μm, and 2500 times when 5 μm to 10 μm.

(4) Transferability of transfer layer and evaluation of transfer defects Immediately after the transfer film was produced, the transfer layer was transferred to a transfer target under the following conditions, and the transferability was evaluated from the transfer area ratio.

(4-1) Preparation of Transferred Body After removing dust adhering to the surface of the low alkaline glass model No. 1737 (30 mm × 30 mm, thickness 1.1 mm) manufactured by Corning, which is the transfer body, by immersion in pure water In this state, the cleaning was repeated twice at 45 kHz for 10 minutes using a three-frequency ultrasonic cleaner model number VS-100III manufactured by AS ONE Corporation. Thereafter, plasma was irradiated for 5 minutes at 15000 VAC using a tabletop vacuum plasma apparatus manufactured by Sakai Semiconductor Co., Ltd.

(4-2) Transfer Method The surface of the transfer layer of a 20 mm × 20 mm transfer film is brought into contact with the glass substrate prepared in (4-1) as a transfer target, and is further applied to the support film surface of the transfer film as a buffer material. A model No. F200 was laminated and 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 Layer Appearance Evaluation The transfer area ratio was calculated based on the area transferred to the transfer medium under the above conditions, with the transfer film size 20 mm × 20 mm being 100%. The evaluation criteria for the transfer area ratio were defined and described as follows.
A: Transfer area ratio 100%. Good transferability.
○: Transfer area ratio of 90% or more and less than 100%.
Δ: Transfer area ratio of 10% or more and less than 90%.
X: Transfer area ratio of 0% or more and less than 10%.

[Example 1]
OCNL505 14000 manufactured by Tokyo Ohka Kogyo Co., Ltd., which is a methylsiloxane polymer solution as a coating solution for the siloxane composition, is dropped on a soda lime glass substrate and allowed to stand in an environment of 20 ° C. and 10 kPa for 3 minutes. A layer was formed. The obtained plasticity ratio was 0.80.

  “ZEONOR FILM” (registered trademark) model number ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, is coated with OCNL505 14000 on a film having a thickness of 60 μm, and left to stand at 20 ° C. and 10 kPa for 3 minutes to transfer film. Got. The thickness of the transfer layer of the obtained transfer film was 4.09 μm.

[Example 2]
A transfer film was obtained in the same manner as in Example 1 except that the thickness of the transfer layer of the transfer film was 0.14 μm.

[Example 3]
A transfer film was obtained in the same manner as in Example 1 except that the thickness of the transfer layer of the transfer film was 0.012 μm.

[Example 4]
A transfer film was obtained in the same manner as in Example 1 except that the thickness of the transfer layer of the transfer film was 9.85 μm.

[Example 5]
“Zeonor film” model number ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, is transferred in the same manner as in Example 1 except that the surface of the film having a thickness of 60 μm is formed into a prism shape having a pitch of 5 μm and a height of 2.5 μm. A film was obtained. The thickness of the transfer layer of the obtained transfer film was 3.69 μm.

[Example 6]
A transfer film was prepared in the same manner as in Example 1 except that the surface of the ZEONOR FILM model number ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, and a 60 μm thick film surface was formed into a moth-eye shape with a pitch of 250 nm and a height of 250 nm. Obtained. The thickness of the transfer layer of the obtained transfer film was 2.14 μm.

[Example 7]
OCNL505 14000 manufactured by Tokyo Ohka Kogyo Co., Ltd. was dropped on a soda lime glass substrate as a coating solution for the siloxane composition and heat treated at 90 ° C. for 30 minutes to form a measured layer made of siloxane. The obtained plasticity ratio was 0.64.

  OCNL505 14000 was coated on a “Zeonor film” model ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, with a thickness of 60 μm and treated at 90 ° C. for 30 minutes to obtain a transfer film. The thickness of the transfer layer of the obtained transfer film was 2.18 μm.

[Example 8]
A transfer film was obtained in the same manner as in Example 7 except that the thickness of the transfer layer of the transfer film was 0.31 μm.

[Example 9]
A transfer film was obtained in the same manner as in Example 7 except that the thickness of the transfer layer of the transfer film was 8.67 μm.

[Example 10]
A transfer film was obtained in the same manner as in Example 7 except that the thickness of the transfer layer of the transfer film was 0.018 μm.

[Example 11]
OCNL505 14000 manufactured by Tokyo Ohka Kogyo Co., Ltd. was dropped on a soda lime glass substrate as a coating solution for the siloxane composition, and heat treated at 90 ° C. for 1 hour to form a measured layer made of siloxane. The resulting plastic modulus was 0.42.

  OCNL505 14000 was coated on a “Zeonor film” model ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, and a film having a thickness of 60 μm, and treated at 90 ° C. for 1 hour to obtain a transfer film. The thickness of the transfer layer of the obtained transfer film was 4.26 μm.

[Example 12]
A transfer film was obtained in the same manner as in Example 11 except that the thickness of the transfer layer of the transfer film was 1.85 μm.

[Example 13]
OCNL505 14000 manufactured by Tokyo Ohka Kogyo Co., Ltd. is dropped on a soda lime glass substrate as a coating solution for the siloxane composition, heat treated at 90 ° C. for 1 hour, and further, a tabletop vacuum plasma apparatus model number YHS-R manufactured by Sakai Semiconductor Co., Ltd. is used. Then, plasma treatment was performed at 15000 VAC for 20 seconds to form a measurement layer made of siloxane. The obtained plasticity ratio was 0.56. “Zeonor film” model number ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, is coated with OCNL505 14000 on a film with a thickness of 60 μm, heat-treated at 90 ° C. for 1 hour, and then a tabletop vacuum plasma device model manufactured by Sakai Semiconductor Co., Ltd. Using YHS-R, plasma treatment was performed at 15000 VAC for 20 seconds to obtain a transfer film. The thickness of the transfer layer of the obtained transfer film was 1.45 μm.

[Example 14]
OCNL505 14000 manufactured by Tokyo Ohka Kogyo Co., Ltd. is dropped on a soda lime glass substrate as a coating solution for the siloxane composition, heat treated at 90 ° C. for 1 hour, and a tabletop light surface treatment device PL16-110 manufactured by Sen Special Light Source Co., Ltd. Then, a UV ozone treatment was performed for 1 minute to form a measurement layer made of siloxane. The obtained plasticity ratio was 0.40. OCNL505 14000 was applied to a “Zeonor film” model ZF14 made by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, with a thickness of 60 μm, and heat transfer and UV ozone treatment were performed in the same procedure as above to obtain a transfer film. The thickness of the transfer layer of the obtained transfer film was 1.79 μm.

[Example 15]
As a coating liquid for the siloxane composition, HARS-10 manufactured by Colcoat Co., Ltd., which is an alcoholic silica solution, is dropped on a soda lime glass substrate, and left to stand in an environment of 20 ° C. and 10 kPa for 3 minutes. A layer was formed. The plasticity ratio obtained was 0.77.
HAS-10 was applied to a "Zeonor film" model ZF14 made by Nippon Zeon Co., Ltd., which is a cyclic polyolefin-based resin, and a film having a thickness of 60 μm, and left to stand in an environment of 10 kPa at 20 ° C. for 3 minutes to obtain a transfer film. . The thickness of the transfer layer of the obtained transfer film was 2.22 μm.

[Example 16]
A transfer film was obtained in the same manner as in Example 15 except that the thickness of the transfer layer of the transfer film was 0.28 μm.

[Example 17]
A transfer film was obtained in the same manner as in Example 15 except that the thickness of the transfer layer of the transfer film was 0.021 μm.

[Example 18]
A transfer film was prepared in the same manner as in Example 15 except that the surface of the ZEONOR FILM model number ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, and a 60 μm thick film surface was formed into a moth-eye shape with a pitch of 250 nm and a height of 250 nm. Obtained. The thickness of the transfer layer of the obtained transfer film was 0.63 μm.

[Example 19]
A coating solution of a siloxane composition obtained by dissolving polyphenylsilsesquioxane SR-23 manufactured by Konishi Chemical Industry Co., Ltd. in propylene glycol monomethyl ether acetate to a solid content of 20% is dropped onto a soda lime glass substrate. The layer to be measured was placed in an environment of 20 ° C. and 10 kPa for 3 minutes to form a measurement layer made of siloxane. The obtained plasticity ratio was 0.93.

  A coating solution of the above-mentioned siloxane composition obtained by dissolving SR-23 was applied to a “Zeonor film” model ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, and a film having a thickness of 60 μm. The transfer film was obtained by allowing to stand for 3 minutes in the environment. The thickness of the transfer layer of the obtained transfer film was 4.97 μm.

[Example 20]
A transfer film was obtained in the same manner as in Example 19 except that the thickness of the transfer layer of the transfer film was 0.37 μm.

[Example 21]
A transfer film was obtained in the same manner as in Example 19 except that the thickness of the transfer layer of the transfer film was 9.97 μm.

[Example 22]
A transfer film was obtained in the same manner as in Example 19 except that the thickness of the transfer layer of the transfer film was 0.075 μm.

[Example 23]
A coating solution of a siloxane composition obtained by dissolving polyphenylsilsesquioxane SR-23 manufactured by Konishi Chemical Industry Co., Ltd. in propylene glycol monomethyl ether acetate to a solid content of 20% is dropped onto a soda lime glass substrate. This was developed and heat treated at 120 ° C. for 1 hour to form a measured layer made of siloxane. The obtained plastic modulus was 0.89. A coating solution of the above siloxane composition obtained by dissolving SR-23 was applied to a “Zeonor film” model number ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin-based resin, and a thickness of 60 μm. A transfer film was obtained by heat treatment for a period of time. The thickness of the transfer layer of the obtained transfer film was 4.65 μm.

[Example 24]
A transfer film was obtained in the same manner as in Example 23 except that the thickness of the transfer layer of the transfer film was 0.85 μm.

[Example 25]
A coating solution of a siloxane composition having a solid content of 20% obtained by polycondensation of methyltrimethoxysilane is dropped on a soda lime glass substrate, and left in an environment of 20 ° C. and 10 kPa for 3 minutes. A layer to be measured was formed. The obtained plasticity ratio was 0.71.

  Apply the coating solution of the above siloxane composition to a film with a thickness of 60 μm, “ZEONOR FILM” model ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, and let stand in an environment of 20 ° C. and 10 kPa for 3 minutes for transfer. A film was obtained. The thickness of the transfer layer of the obtained transfer film was 4.96 μm.

[Example 26]
A transfer film was obtained in the same manner as in Example 25 except that the thickness of the transfer layer of the transfer film was 0.29 μm.

[Example 27]
A coating solution of a siloxane composition having a solid content of 20% obtained by copolymerization of methyltrimethoxysilane and phenyltrimethoxysilane is dropped on a soda lime glass substrate and left in an environment of 20 ° C. and 10 kPa for 3 minutes. Thus, a measurement layer made of siloxane was formed. The resulting plastic modulus was 0.86.

  Apply the coating solution of the above siloxane composition to a film with a thickness of 60 μm, “ZEONOR FILM” model ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, and let stand in an environment of 20 ° C. and 10 kPa for 3 minutes for transfer. A film was obtained. The thickness of the transfer layer of the obtained transfer film was 4.02 μm.

[Example 28]
A transfer film was obtained in the same manner as in Example 27 except that the thickness of the transfer layer of the transfer film was 0.25 μm.

[Example 29]
A coating solution of a siloxane composition having a solid content of 20% obtained by copolymerization of methyltrimethoxysilane and phenyltrimethoxysilane is dropped on a soda lime glass substrate and heat-treated at 120 ° C. for 1 hour to form siloxane. A layer to be measured was formed. The obtained plastic modulus was 0.83.

  A coating film of the above siloxane composition was applied to a “Zeonor film” model number ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin-based resin, and a thickness of 60 μm, and heat-treated at 120 ° C. for 1 hour to obtain a transfer film . The thickness of the transfer layer of the obtained transfer film was 3.91 μm.

[Example 30]
A transfer film was obtained in the same manner as in Example 29 except that the thickness of the transfer layer of the transfer film was 0.18 μm.

[Example 31]
A coating solution of a siloxane composition having a solid content of 20% obtained by copolymerization of methyltrimethoxysilane and tetramethoxysilane is dropped on a soda lime glass substrate and left in an environment of 20 ° C. and 10 kPa for 3 minutes. Thus, a measurement layer made of siloxane was formed. The obtained plasticity ratio was 0.62.

  Apply the coating solution of the above siloxane composition to a film with a thickness of 60 μm, “ZEONOR FILM” model ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, and let stand in an environment of 20 ° C. and 10 kPa for 3 minutes for transfer. A film was obtained. The thickness of the transfer layer of the obtained transfer film was 4.25 μm.

[Example 32]
A transfer film was obtained in the same manner as in Example 31 except that the thickness of the transfer layer of the transfer film was 0.34 μm.

[Example 33]
A coating liquid of a siloxane composition having a solid content of 20% obtained by copolymerizing methyltrimethoxysilane, dimethylditrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane was dropped on a soda lime glass substrate, The measurement layer made of siloxane was formed by allowing to stand in an environment of 20 ° C. and 10 kPa for 3 minutes. The obtained plasticity ratio was 0.91.

  Apply the coating solution of the above siloxane composition to a film with a thickness of 60 μm, “ZEONOR FILM” model ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, and let stand in an environment of 20 ° C. and 10 kPa for 3 minutes for transfer. A film was obtained. The thickness of the transfer layer of the obtained transfer film was 6.25 μm.

[Example 34]
A transfer film was obtained in the same manner as in Example 33 except that the thickness of the transfer layer of the transfer film was 0.13 μm.

[Comparative Example 1]
OCNL505 14000 manufactured by Tokyo Ohka Kogyo Co., Ltd. was dropped onto a soda lime glass substrate as a coating solution for the siloxane composition and heat treated at 120 ° C. for 1 hour to form a measured layer made of siloxane. The obtained plasticity ratio was 0.37.

  OCNL505 14000 was applied to a film having a thickness of 60 μm, “ZEONOR FILM” manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, and heat-treated at 120 ° C. for 1 hour to obtain a transfer film. The thickness of the transfer layer of the obtained transfer film was 3.27 μm.

[Comparative Example 2]
A transfer film was prepared in the same manner as in Comparative Example 1 except that the surface of the ZEONOR FILM model number ZF14 made by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, and a 60 μm thick film surface was formed into a moth-eye shape with a pitch of 250 nm and a height of 250 nm. Obtained. The thickness of the transfer layer of the obtained transfer film was 1.92 μm.

[Comparative Example 3]
A layer to be measured was formed in the same manner as in Example 14 except that the UV ozone treatment time using a tabletop light surface treatment apparatus PL16-110 manufactured by Sen Special Light Source Co., Ltd. was set to 10 minutes. The obtained plasticity ratio was 0.34.

  Moreover, the transfer film was obtained like Example 14 except having made UV ozone treatment time into 10 minutes. The thickness of the transfer layer of the obtained transfer film was 3.92 μm.

[Comparative Example 4]
As a coating solution for the siloxane composition, HASCO-10 manufactured by Colcoat Co., Ltd. was dropped on a soda lime glass substrate and heat treated at 90 ° C. for 1 hour to form a measured layer made of siloxane. The obtained plasticity ratio was 0.38.

  HAS-10 was applied to a “Zeonor film” model ZF14 manufactured by Nippon Zeon Co., Ltd., which is a cyclic polyolefin resin, with a thickness of 60 μm, and a heat-treated transfer film was obtained at 90 ° C. for 1 hour. The thickness of the transfer layer of the obtained transfer film was 1.96 μm.

[Comparative Example 5]
A layer to be measured was formed in the same manner as in Comparative Example 4 except that the heat treatment temperature was 120 ° C. The plasticity ratio obtained was 0.29.
Further, a transfer film was obtained in the same manner as in Comparative Example 4 except that the heat treatment temperature was 120 ° C. The transfer layer thickness of the transfer film was 1.57 μm.

[Comparative Example 6]
A layer to be measured was formed in the same manner as in Example 25 except that the heat treatment temperature was 120 ° C. The plasticity ratio obtained was 0.31.

  Further, a transfer film was obtained in the same manner as in Example 25 except that the heat treatment temperature was 120 ° C. The transfer layer thickness of the transfer film was 4.20 μm.

[Comparative Example 7]
A layer to be measured was formed in the same manner as in Example 31 except that the heat treatment temperature was 120 ° C. The resulting plastic modulus was 0.26.

  Moreover, the transfer film was obtained like Example 31 except having made heat processing temperature into 120 degreeC. The transfer layer thickness of the transfer film was 1.55 μm.

  Tables 1 and 2 show the results of confirming the transferability of the transfer films prepared in Examples 1 to 34 and Comparative Examples 1 to 7.

  While Examples 1 to 34 all showed good transferability, Comparative Examples 1 to 7 could not be transferred because the transfer layer had elastic properties.

  The transfer film according to the present invention can be widely used for transferring a siloxane layer as a functional layer to a liquid crystal display device, a solar cell substrate, a semiconductor substrate such as an LED, or the like.

DESCRIPTION OF SYMBOLS 1 Transfer film 2 Support film 3 Transfer layer 4 Uneven shape part 5 Indenter 6 Load cell 7 Piezoelectric actuator 8 Gap sensor 9 Glass substrate 10 Maximum indentation depth (h _max )
11 Indentation recovery depth (h _c )
12 Frame 13 Transfer layer thickness

Claims (2)

  A transfer film having a transfer layer made of a siloxane composition on a support film, wherein the siloxane composition has a triangular pyramid indenter with respect to a layer made of the siloxane composition having a thickness of 2 μm under the load conditions specified in this specification. A transfer film having a plasticity ratio of 0.40 to 0.99 when pressed. The transfer film according to claim 1, wherein the transfer layer has a thickness of 0.01 μm to 10 μm.

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