Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/06—Interconnection of layers permitting easy separation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin

Definitions

• the present invention relates to a transfer film with excellent peeling properties due to heating temperature and a method for producing the same.
• Polarizing plates are used in displays (liquid crystal, organic electroluminescence) used in flat-screen TVs, mobile phones, etc.
• the role of polarizing plates is to only let light passing in a certain direction through, and the performance of the display is greatly influenced by the performance of the polarizing plate.
• Polarizing plates generally consist of a polarizer made of a polyvinyl alcohol film that has iodine or dye adsorbed and aligned, and a protective film attached to the polarizer.
• Patent Document 1 proposes a transfer sheet that is composed of a support substrate, a release layer, and a resin layer as a method for transferring only a resin layer to a molded body, and uses a silicone acrylic resin as the main material, which forms a strong hardened film by forming silicone bridges in the release layer, and a polydimethylsiloxane copolymer as the secondary material, allowing the release layer and functional layer to be smoothly peeled off.
• Patent Document 2 proposes a laminate that is composed of a supporting substrate, a release layer, and a resin layer, and that can be transferred uniformly within the surface without impairing the appearance quality such as unevenness or transparency.
• Patent Document 3 states that a resin layer of 3 ⁇ m or more is preferable because it can suppress deformation due to shrinkage of the polarizer in the polarizing plate and the transmission of moisture in the air to the polarizer.
• the resin layer is 3 ⁇ m or thicker, it is considered preferable because it can suppress deformation due to shrinkage of the polarizer in the polarizing plate and the transmission of moisture in the air to the polarizer.
• this increases costs, and there is a growing demand for thinner polarizers.
• the object of the present invention is to provide a transfer film in which the UV-curable resin layer is a thin film and the UV-curable resin layer and the release layer can be easily peeled off even before and after high-temperature heating.
• the present invention has the following configuration.
• the release layer does not separate or remain within the release layer during the subsequent transfer film peeling process, and the transfer film itself does not suffer damage.
• FIG. 2 is a layer structure diagram of an example of a transfer film in which a release layer and an ultraviolet curable resin layer are laminated on a supporting substrate.
• the transfer film of the present invention has a release layer and an ultraviolet-curable resin layer on at least one surface of a supporting substrate, in this order from the supporting substrate side.
• the resin constituting the support substrate used in the transfer film of the present invention may be either a thermoplastic resin or a thermosetting resin, and may be a homogeneous resin, a copolymer, or a blend of two or more kinds.
• the resin constituting the support substrate is preferably one having good moldability, and from that point of view, a thermoplastic resin is more preferable.
• thermoplastic resins examples include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyimide resins, polyester resins, polycarbonate resins, polyarylate resins, polyacetal resins, polyphenylene sulfide resins, fluororesins such as tetrafluoroethylene resin, trifluoroethylene resin, trichloroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer, and vinylidene fluoride resin, acrylic resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, and polylactic acid resins.
• polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene
• alicyclic polyolefin resins examples include poly
• thermoplastic resin is preferably one that has sufficient extensibility and conformability. From the standpoint of strength and heat resistance, it is more preferable that the thermoplastic resin is polyester resin, polycarbonate resin, acrylic resin, or methacrylic resin.
• polyester resin is a general term for polymers in which ester bonds are the main bonding chains in the main chain, and is obtained by polycondensation of an acid component and its ester with a diol component.
• Specific examples include polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, and polybutylene terephthalate. These may also be copolymerized with other dicarboxylic acids and their esters or diol components as the acid component or diol component.
• polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferred in terms of transparency, dimensional stability, heat resistance, etc.
• the support substrate is preferably a transparent material with low birefringence, and from the viewpoint of low birefringence, cellulose ester and cyclic olefin are preferred.
• Commercially available norbornene-based polymers that can be used include Arton (manufactured by JSR Corporation), Zeonex, Zeonor (all manufactured by Zeon Corporation), and TOPAS (manufactured by Polyplastics Corporation).
• thermosetting resins examples include phenolic resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, polyurethane resin, polyimide resin, silicone resin, etc.
• the support substrate may also contain various additives, such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, heat stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, and doping agents for adjusting the refractive index.
• the support substrate may have either a single-layer structure or a multilayer structure.
• Various surface treatments can also be performed before forming the ultraviolet-curable resin layer described below.
• Examples of surface treatments include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high-frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment.
• glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment, and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.
• the surface of the supporting substrate can be provided in advance with multiple functional layers such as an easy-adhesion layer, an antistatic layer, an undercoat layer, and an ultraviolet absorbing layer.
• the supporting substrate is not particularly limited as long as it is possible to transfer the UV-curable resin layer, but it is preferable to use a supporting substrate having a release layer on the surface that comes into contact with the UV-curable resin layer.
• the material of the release layer is not particularly limited, but it is preferably formed from a resin composition for the release layer described later, and is preferably formed on the surface of the support substrate by coating, drying, and curing according to the method for producing the release layer described later.
• the release layer may be composed of a plurality of layers on the support substrate side from the viewpoint of imparting adhesion, antistatic properties, solvent resistance, etc.
• the thickness of the release layer is not particularly limited, but in terms of the in-plane uniformity, quality, and peeling force of the release layer, it is preferably 350 to 500 nm, and more preferably 400 to 450 nm.
• the release layer refers to a layer formed using a release layer resin composition.
• the release layer resin composition is preferably a release layer resin composition in which the peak intensity at 1118 cm ⁇ 1 of the release layer resin composition measured using FT-IR by the method described below is 1.5 times or more of the peak intensity at 0 hours after stirring of the release layer resin composition.
• the interlayer peel strength between the ultraviolet curable resin layer of the transfer film and the release layer is preferably 0.04 N/25 mm or more.
• the interlayer peeling force between the ultraviolet curable resin layer and the release layer of the transfer film after heating under the condition of 150 ° C. is preferably 0.04 N / 25 mm or more and 0.12 N / 25 mm or less.
• the haze of the adherend after peeling is preferably 0.50% or less. If the haze of the adherend after peeling exceeds 0.50%, the transparency of the adherend may decrease, and the visibility may be deteriorated, so that it may be difficult to use it as a product for this purpose.
• the occurrence of peeling between the adherend and the transfer film is reduced in the molding process and heating process after the transfer film is attached to the adherend, and further, in the subsequent peeling process, the transfer film can be peeled off well from the adherend, and it is more possible to set the haze of the adherend after peeling to the preferred range described above.
• the interlayer peeling force between the ultraviolet curable resin layer and the release layer of the transfer film is less than 0.04 N/25 mm, the transfer film may peel off from the adherend before the molding process or heating process after the transfer film is attached to the adherend.
• the transfer film may peel off from the adherend before the peeling process.
• the transfer film may not be peeled off well from the adherend in the peeling process, and the transfer film may not be peeled off, or even if it is peeled off, the haze of the adherend after peeling may not be in the above-mentioned preferred range.
• the resin composition for the release layer in the present invention is not particularly limited as long as the peak intensity at 1118 cm ⁇ 1 of the resin composition measured using FT-IR is 1.5 times or more the peak intensity when the composition for the release layer is left for 0 hours after stirring, but preferred are alkyd-based resins, polyolefin-based resins, long-chain alkyl group-containing resins, fluorine-based resins, silicone-based resins, mixed or copolymerized resins of organic and silicone resins, etc. Furthermore, a mixture of a melamine-based resin and a silicone-based resin is more preferred.
• the binder resin contains it.
• binder resins include urethane-based resins, acetal-based resins, polyamide-based resins, melamine-based resins, polyol resins, cellulose resins, and polyvinyl alcohol, and it is preferable to use urethane-based resins and acetal-based resins. Of these, polyol resins are more preferable.
• the peak at 1118 cm ⁇ 1 of the resin composition measured using FT-IR indicates an ether bond. If the peak intensity at 1118 cm ⁇ 1 of the resin composition for the release layer measured using FT-IR is less than 1.5 times the peak intensity of the resin composition for the release layer after stirring and leaving for 0 hours, the polymerization of the resin composition for the release layer may not be promoted, the peeling force of the transfer film may increase significantly after heating, and the release layer may be broken, separated into the ultraviolet curable resin layer, and remain, causing an increase in haze.
• the above problem can be solved by making the peak intensity at 1118 cm ⁇ 1 of the resin composition for the release layer measured using FT-IR 1.5 times or more the peak intensity of the resin composition for the release layer after stirring and leaving for 0 hours.
• the method for forming the release layer on the support substrate is not particularly limited, but it is preferable to form a coating layer by applying the release layer coating composition described below by a dip coating method, roller coating method, wire bar coating method, gravure coating method, or die coating method (U.S. Pat. No. 2,681,294 specification), etc., with the gravure coating method or die coating method being preferred.
• the coating layer applied onto the supporting substrate or the like is dried.
• Drying methods include heat transfer drying (contact with a hot object), convection heat transfer (hot air), radiation heat transfer (infrared rays), and others (microwaves, induction heating). Of these, in the manufacturing method of the present invention, a method using convection heat transfer or radiation heat transfer is preferred because it is necessary to precisely uniform the drying speed even in the width direction.
• a further curing operation may be performed by irradiating heat or energy rays.
• the temperature is preferably from room temperature to 200°C, and from the viewpoint of the activation energy of the curing reaction, more preferably from 100°C to 200°C, and even more preferably from 130°C to 200°C.
• EB rays electron beams
• UV rays ultraviolet rays
• examples of the type of ultraviolet lamp used when irradiating ultraviolet rays include discharge lamp type, flash type, laser type, and electrodeless lamp type.
• ultraviolet irradiation is preferably performed under conditions where the illuminance of ultraviolet rays is preferably 100 to 3,000 (mW/cm 2 ), more preferably 200 to 2,000 (mW/cm 2 ), and even more preferably 300 to 1500 (mW/cm 2 ), and ultraviolet irradiation is preferably performed under conditions where the integrated light amount of ultraviolet rays is preferably 100 to 3,000 (mJ/cm 2 ), more preferably 200 to 2,000 (mJ/cm 2 ), and even more preferably 300 to 1500 (mJ/cm 2 ).
• UV illuminance is the radiation intensity received per unit area, and varies depending on the lamp output, emission spectrum efficiency, diameter of the light-emitting bulb, design of the reflector, and the distance between the irradiated object and the light source. However, illuminance does not vary depending on the transport speed.
• the UV integrated light amount is the radiation energy received per unit area, and is the total amount of photons that reach the surface. The integrated light amount is inversely proportional to the radiation speed passing under the light source, and proportional to the number of irradiations and the number of lamps.
• a release layer on the support substrate by drying and curing the coating layer formed on the support substrate.
• the ultraviolet curable resin layer in the present invention refers to a layer formed on a release layer, which is a layer that can be peeled off and transferred from the release layer.
• the peelability judgment criteria are based on JIS K5600-5-6:
• the ultraviolet curable resin layer and the release layer, the supporting substrate, and the support substrate are evaluated by the cross-cut method described in 1999, and those classified as Class 4 or higher are deemed peelable, and those classified as Class 0 to 3 are deemed non-peeling.
• the transfer film is made up of all layers, including the material.
• the release layer If only one layer is formed on the release layer, that layer is the ultraviolet curing resin layer, and if two layers are formed on the release layer, In the case where more than one layer is formed, the two or more layers excluding the release layer are regarded as one ultraviolet curable resin layer.
• the transfer film of the present invention can be obtained by applying a coating composition for an ultraviolet-curable resin layer onto the release layer of the aforementioned support substrate, and then drying and curing the composition as necessary.
• a layer refers to a portion that can be distinguished from adjacent portions in the thickness direction from the surface side of the transfer film by having an interface in the thickness direction, and that has a finite thickness. More specifically, it refers to a portion that can be distinguished by the presence or absence of a discontinuous interface when the cross section of the transfer film is observed with an electron microscope (transmission type, scanning type) or optical microscope. Therefore, even if the composition changes in the thickness direction of the ultraviolet-curable resin layer, if there is no interface between them, it is treated as one layer.
• the transfer film of the present invention may be in either a planar state or a three-dimensional shape, so long as it has an ultraviolet-curable resin layer exhibiting the above-mentioned physical properties.
• the total thickness of the ultraviolet-curable resin layer is preferably 0.5 ⁇ m or more and 2.5 ⁇ m or less, and more preferably 1.5 ⁇ m or more and 2.0 ⁇ m or less. If the total thickness of the ultraviolet-curable resin layer is less than 0.5 ⁇ m, scratch resistance may decrease, and if it is thicker than 2.5 ⁇ m, problems such as increased costs may occur.
• the ultraviolet-curable resin layer may have other functions such as gloss, fingerprint resistance, moldability, design, scratch resistance, stain resistance, solvent resistance, anti-reflection, anti-static, electrical conductivity, heat reflection, near-infrared absorption, electromagnetic wave shielding, and easy adhesion.
• one or more layers may be formed on the ultraviolet-curable resin layer.
• an ultraviolet-curable resin layer having the above-mentioned functions, an adhesive layer, an electronic circuit layer, a printing layer, an optical adjustment layer, or other ultraviolet-curable resin layers may be provided.
• the method for producing a transfer film of the present invention is a method for forming a release layer and an ultraviolet-curable resin layer in this order on at least one surface of a supporting substrate, and is a method for producing a transfer film in which a release layer is formed on a supporting substrate using a resin composition for a release layer, the peak intensity of which at 1118 cm -1 measured using FT-IR is 1.5 times or more the peak intensity when the resin composition for a release layer is left for 0 hours after stirring (a leaving time of 0 hours is defined as within 0 hours, rounded off to the first decimal place, in "hours").
• the method for forming the ultraviolet-curable resin layer is preferably a manufacturing method in which a preferred ultraviolet-curable resin layer composition described later is applied onto the release layer of the preferred support substrate described above, and then dried and cured to form an ultraviolet-curable resin layer.
• the application method is not particularly limited, and can be appropriately selected from dip coating, roller coating, wire bar coating, gravure coating, die coating (US Pat. No. 2,681,294), and the like. It is important that the surface characteristics of the ultraviolet-curable resin layer satisfy the above-mentioned conditions, and the manufacturing method may be capable of forming an ultraviolet-curable resin layer whose resin composition varies in the thickness direction.
• the manufacturing method for the transfer film is preferably a method in which at least two or more types of ultraviolet-curable resin layer compositions are applied successively or simultaneously, and then dried and cured to form an ultraviolet-curable resin layer, and a manufacturing method for the transfer film in which at least two or more types of ultraviolet-curable resin layer compositions are applied simultaneously is more preferable.
• Drying involves drying the coating film applied onto a supporting substrate or the like. In addition to completely removing the solvent from the resulting transfer film, it is preferable for the drying process to involve heating the coating film.
• the heating method used in the drying process includes heat transfer drying (contact with a hot object), convection heat transfer (hot air), radiation heat transfer (infrared rays), and others (microwaves, induction heating). Of these, methods using convection heat transfer or radiation heat transfer are preferred, as it is necessary to precisely ensure uniform drying speed across the width.
• a further curing operation may be carried out by irradiating with heat or active energy rays.
• an electron beam (EB ray) and/or an ultraviolet ray (UV ray) are preferable.
• the oxygen concentration is as low as possible because oxygen inhibition can be prevented, and it is more preferable to cure under a nitrogen atmosphere (nitrogen purging).
• the oxygen concentration is high, the curing of the outermost surface is inhibited, the curing of the surface is weakened, and the toughness may be reduced.
• the type of ultraviolet lamp used for irradiating ultraviolet ray includes, for example, a discharge lamp type, a flash type, a laser type, an electrodeless lamp type, etc.
• the illuminance of ultraviolet ray is preferably 100 to 3,000 mW/cm 2 , more preferably 200 to 2,000 mW/cm 2 , and even more preferably 300 to 1500 mW/cm 2 .
• the ultraviolet irradiation is preferably performed under conditions where the cumulative amount of ultraviolet light is preferably 100 to 3,000 mJ/cm 2 , more preferably 200 to 2,000 mJ/cm 2 , and even more preferably 300 to 1,500 mJ/cm 2 .
• the illuminance of ultraviolet light is the irradiation intensity received per unit area, and varies depending on the lamp output, emission spectrum efficiency, diameter of the light-emitting bulb, design of the reflector, and the distance between the light source and the irradiated object. However, the illuminance does not vary depending on the conveying speed.
• the cumulative amount of ultraviolet light is the irradiation energy received per unit area, and is the total amount of photons that reach the surface. The cumulative amount of light is inversely proportional to the irradiation speed passing under the light source, and proportional to the number of irradiations and the number of lamps.
• composition for ultraviolet curable resin layer The method for producing the transfer film of the present invention is not particularly limited.
• the transfer film of the present invention can be produced by applying a composition for an ultraviolet-curable resin layer onto the release layer of the above-mentioned supporting substrate, and optionally It can be obtained through a drying and hardening process.
• UV-curable resin layer composition refers to a liquid consisting of a solvent and a solute, which can be applied to the aforementioned support substrate, volatilized and removed in the process of drying the solvent, and further cured as necessary to form an UV-curable resin layer.
• type of UV-curable resin layer composition refers to a liquid in which the type of solute that constitutes the UV-curable resin layer composition is different, even if only partially.
• the solute consists of resin or a material that can form it in the application process (hereinafter referred to as a resin precursor), particles, and various additives such as polymerization initiators, curing agents, catalysts, leveling agents, UV absorbers, and antioxidants.
• the resin precursor can be used by itself or by dissolving it in a solvent to prepare a coating composition for an ultraviolet-curable resin layer.
• the resin precursor refers to a material that can harden a coating film by volatilization of the solvent and polymerization or crosslinking reaction of itself. That is, the ultraviolet-curable resin layer of the transfer film of the present invention and the supporting substrate obtained by peeling the release film from the transfer film contain a cured product obtained by crosslinking the resin precursor.
• a material that can be polymerized by the action of active energy rays, either by itself or in combination with a photopolymerization initiator that can be cleaved by active energy rays, to harden the coating film is preferred.
• preferred resin precursors are polyfunctional (meth)acrylate monomers, (meth)acrylate oligomers, alkoxysilanes having (meth)acrylic groups, alkoxysilane hydrolysates having (meth)acrylic groups, alkoxysilane oligomers having (meth)acrylic groups, acrylic polymers having (meth)acrylic groups, urethane polymers having (meth)acrylic groups, epoxy polymers having (meth)acrylic groups, and silicone polymers having (meth)acrylic groups.
• polyfunctional acrylate monomers include polyfunctional acrylates having two or more (meth)acryloyloxy groups in one molecule and modified polymers thereof, and specific examples thereof include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol triacrylate hexanemethylene diisocyanate urethane polymer. These monomers can be used alone or in a mixture of two or more.
• Acrylic polymers having (meth)acrylic groups are preferably synthesized by polymerization reaction of polyfunctional acrylate monomers (e.g., polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate).
• polyfunctional acrylate monomers e.g., polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate.
• urethane polymers include melamine polyurethane.
• Silicone polymers are preferably co-hydrolyzates of silane compounds (e.g., tetraalkoxysilane, alkyltrialkoxysilane) and silane coupling agents having reactive groups (e.g., epoxy, methacryl).
• silane compounds e.g., tetraalkoxysilane, alkyltrialkoxysilane
• silane coupling agents having reactive groups e.g., epoxy, methacryl
• various polymers that do not contain unsaturated groups have
• a preferred ultraviolet-curable resin layer composition used to form the ultraviolet-curable resin layer in the present invention preferably contains a leveling agent. It is particularly preferred to configure region B with a leveling agent, which allows the peeling force to be designed within a suitable range while maintaining the function of the ultraviolet-curable resin layer.
• leveling agents include acrylic copolymers, silicone-based, and fluorine-based leveling agents.
• a particularly preferred leveling agent is a leveling agent containing a hexafluoropropylene group or a polyether group. If the leveling agent contains the above functional group, the coating quality and peeling force can be suitably designed.
• the ultraviolet-curable resin layer of the transfer film of the present invention may contain particle components.
• the particles may be either inorganic particles or organic particles, but inorganic particles are preferred from the viewpoint of scratch resistance.
• the number of types of inorganic particles is preferably 1 to 20.
• the number of types of inorganic particles is more preferably 1 to 10, and particularly preferably 1 to 4.
• “inorganic particles” also includes those that have been surface treated. This surface treatment refers to the introduction of a compound onto the particle surface by chemical bonding (including covalent bonding, hydrogen bonding, ionic bonding, van der Waals bonding, hydrophobic bonding, etc.) or adsorption (including physical adsorption and chemical adsorption).
• the type of inorganic particles is determined by the type of element constituting the inorganic particles, and in the case of performing some surface treatment, it is determined by the type of element constituting the particles before surface treatment.
• titanium oxide (TiO 2 ) and nitrogen-doped titanium oxide (TiO 2- xNx) in which part of the oxygen of titanium oxide is replaced with nitrogen, which is an anion are different types of inorganic particles because the elements constituting the inorganic particles are different.
• ZnO multiple particles
• ZnO multiple particles consisting of the same element, for example, only Zn and O
• ZnO multiple particles
• ZnO multiple particles
• ZnO multiple particles
• ZnO even if there are multiple particles with different number average particle diameters or different composition ratios of Zn and O, these are the same type of particles.
• even if there are multiple Zn particles with different oxidation numbers as long as the elements constituting the particles are the same (as long as all elements other than Zn are the same in this example), these are
• the particles present in the composition for the ultraviolet-curable resin layer used in the present invention are referred to as “particle material”, and the particles present in the ultraviolet-curable resin layer formed by applying the composition for the ultraviolet-curable resin layer to a process such as coating, drying, curing, or vapor deposition are referred to as "particle components".
• the inorganic particles are not particularly limited, but are preferably oxides, nitrides, borides, chlorides, carbonates, or sulfates of metals or metalloids. They may also be composite oxides containing two types of metals or metalloids, or may have a different element introduced between the lattice, a different element substituted for the lattice points, or lattice defects introduced.
• the inorganic particles are oxide particles formed by oxidizing at least one metal or semi-metal selected from the group consisting of Si, Al, Ca, Zn, Ga, Mg, Zr, Ti, In, Sb, Sn, Ba and Ce.
• the oxide is at least one metal oxide or semi-metal oxide selected from the group consisting of silica (SiO 2 ), aluminum oxide (Al 2 O 3 ), zinc oxide (ZnO), zirconium oxide (ZrO 2 ), titanium oxide (TiO 2 ), indium oxide (In 2 O 3 ), tin oxide (SnO 2 ), antimony oxide (Sb 2 O 3 ), and indium tin oxide (In 2 O 3 ).
• the composition for ultraviolet-curable resin layer used in the method for producing a transfer film of the present invention may contain a solvent, and it is preferable to contain a solvent in order to form a coating film uniformly in the plane and to gradually change the composition within one layer.
• the number of types of solvents is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1 to 4.
• solvent refers to a substance that is liquid at room temperature and pressure and can be almost completely evaporated during the drying process after application.
• the type of solvent is determined by the molecular structure that makes up the solvent.
• solvents that have the same elemental composition and the same type and number of functional groups but different bonding relationships structural isomers
• solvents that are not structural isomers but do not overlap exactly in any conformation in three-dimensional space are treated as different types of solvents.
• 2-propanol and n-propanol are treated as different solvents.
• the ultraviolet-curable polymerization initiator and catalyst are used to promote the curing of the ultraviolet-curable resin layer.
• the polymerization initiator those capable of initiating or promoting the polymerization, condensation or crosslinking reaction of the components contained in the composition for the ultraviolet-curable resin layer by anionic, cationic or radical polymerization reaction or the like are preferable.
• polymerization initiators, curing agents, and catalysts can be used.
• the polymerization initiators, curing agents, and catalysts can be used individually, or multiple polymerization initiators, curing agents, and catalysts can be used simultaneously.
• acid catalysts and thermal polymerization initiators can be used in combination.
• acid catalysts include aqueous hydrochloric acid, formic acid, and acetic acid.
• thermal polymerization initiators include peroxides and azo compounds.
• photopolymerization initiators include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, and amine compounds.
• crosslinking catalysts that promote the reaction of forming urethane bonds include dibutyltin dilaurate and dibutyltin diethylhexoate.
• composition for the ultraviolet-curable resin layer may also contain other crosslinking agents, such as a melamine crosslinking agent, such as alkoxymethylolmelamine, an acid anhydride crosslinking agent, such as 3-methyl-hexahydrophthalic anhydride, or an amine crosslinking agent, such as diethylaminopropylamine.
• a melamine crosslinking agent such as alkoxymethylolmelamine
• an acid anhydride crosslinking agent such as 3-methyl-hexahydrophthalic anhydride
• amine crosslinking agent such as diethylaminopropylamine.
• alkylphenone compound is preferred from the viewpoint of curability.
• alkylphenone compounds include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-phenyl)-1-butane, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-phenyl)-1-butane, 2-benzyl-2-dimethylamino-1-(4-mo Examples of such compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butane, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[
• ultraviolet absorbers, lubricants, antistatic agents, etc. may be added to the ultraviolet curable resin layer composition used to form the ultraviolet curable resin layer.
• ultraviolet absorbers include benzophenone-based, benzotriazole-based, oxalic acid anilide-based, triazine-based, and hindered amine-based ultraviolet absorbers.
• antistatic agents include metal salts such as lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, and calcium salts.
• an ultraviolet-curable resin layer by drying and curing the coating layer formed on the release layer.
• the transfer film of the present invention can be suitably used for protecting the surface of a molded body made of, for example, plastics or metal, taking advantage of its scratch resistance, conformability to surface shape, etc. Furthermore, the support substrate obtained by peeling the support substrate and the release layer from the transfer film of the present invention can be suitably used, for example, as a protective film for a molded body.
• the method for producing the support substrate in the present invention is not particularly limited.
• the support substrate in the present invention can be produced by producing the transfer film of the present invention and then peeling off only the ultraviolet-curable resin layer from the transfer film.
• the support substrate of the present invention can be suitably used, for example, as a protective film for a molded body.
• Release layer resin composition The following materials were mixed and diluted with a mixed solvent of methyl ethyl ketone and isopropyl alcohol (mixture ratio by mass: 50/50) to obtain a resin composition for a release layer having a solid content concentration of 5% by mass.
• ⁇ One-end carbinol modified reactive silicone oil (X-22-170DX Shin-Etsu Chemical Co., Ltd., solid content concentration 100% by mass): 1 part by mass ⁇ Both-end polyether modified reactive silicone oil (X-22-4952 Shin-Etsu Chemical Co., Ltd., solid content concentration 100% by mass): 5 parts by mass ⁇ Acrylic modified alkyd resin (Haliftar KV-905 Harima Chemical Co., Ltd., solid content concentration 53% by mass): 100 parts by mass ⁇ Isobutyl alcohol modified melamine resin (Melan 2650L Hitachi Chemical Co., Ltd., solid content concentration 60% by mass): 20 parts by mass ⁇ Paratoluenesulfonic acid: 5 parts by mass.
• composition for ultraviolet curable resin layer [Composition for ultraviolet curable resin layer] The following materials were mixed and diluted with methyl ethyl ketone to obtain a composition for an ultraviolet-curable resin layer having a solid content concentration of 20% by mass.
• Resin precursor A 190 parts by mass of a butyl acetate/ethyl acetate solution of a polymer acrylate resin ("Unidic" V-6850, DIC Corporation, solid content concentration 50% by mass).
• Resin precursor B urethane acrylate oligomer ("Shiko” UV3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass): 5 parts by mass Leveling agent (LINC-3A, manufactured by Kyoeisha Chemical Co., Ltd., solid content concentration 100% by mass): 1 part by mass ⁇ -hydroxyacetophenone type photopolymerization initiator: 3 parts by mass (“Omnirad (registered trademark)" 184, manufactured by IGM).
• a release layer was formed by the following method, thereby preparing a supporting substrate with a release layer.
• the transfer films of Examples 1 to 6 and Comparative Examples 1 to 6 were created using the above method.
• the method of creating the transfer films for each Example and Comparative Example, as well as the thicknesses of the release layer and UV-curable resin layer, are listed in Table 1.
• FT-IR analysis method The FT-IR analysis can be carried out using a Fourier transform infrared spectrophotometer (manufactured by Bruker, trade name "FT-IR TENSOR II") as a measuring device under the following conditions.
• Light source Globar (SiC) Detector: DLaTGS ⁇ Resolution: 4cm -1 Measurement range: 400 to 4000 cm -1 .
• a universal tensile tester (Intesco, model: 200X) was used to perform 180-degree peeling between the UV-curable resin layer and the release layer at a test speed of 300 mm/min, and the interlayer peel strength (N/25 mm) between the UV-curable resin layer and the release layer of the transfer film was measured.
• the laminated film After cutting the laminated film to a length of 25 mm, it was subjected to a heat treatment at 150°C for 5 minutes in a thermostatic chamber, and the interlayer peel strength (N/25 mm) between the UV-curable resin layer and the release layer of the transfer film after heating was measured using the same method as above.
• the cross section of the transfer film was cut into an ultra-thin section and observed with a TEM (transmission electron microscope) at an accelerating voltage of 100 kV (at a magnification of 10,000 to 300,000 times), and the thickness of the UV-curable resin layer was measured from the cross-sectional photograph. The thickness was measured at a portion where no protrusions existed on the surface. The thickness was measured at five points, and the average value was taken as the thickness of the UV-curable resin layer.

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• Decoration By Transfer Pictures (AREA)

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