JP6016009B2 - Transfer film, laminate and production method thereof - Google Patents

Description

 The present invention relates to a transfer film, a laminate, and a method for producing them.

  Transparent resins such as acrylic resins and polycarbonate resins are widely used as various materials such as industrial materials and building materials. Particularly in recent years, it has been used as a front plate for various displays such as CRT, liquid crystal television and plasma display from the viewpoint of transparency and impact resistance.

  In recent years, various functions have been required for the front plate. One of the required functions is an antireflection function.

  The antireflection function is a function for reducing the reflected light of an indoor fluorescent lamp or the like reflected on the front plate and displaying the image more clearly.

  As a method for imparting an antireflection function, for example, Patent Document 1 discloses a transfer film in which a low refractive index layer, a high refractive index layer, and an adhesive layer are sequentially laminated on a process paper so that the surface of the adhesive layer is in contact. There has been proposed a method of obtaining an optical functional film in which a layer having an antireflection function is laminated on the surface by peeling off the process paper after being laminated on the surface of the material film.

  However, if dirt adheres to the surface of the antireflection layer, the discoloration of the portion becomes conspicuous, leading to a decrease in the visibility of the image display member. Is required to be granted.

  Under such circumstances, for example, Patent Document 2 proposes an antireflection transfer film in which a release layer, an antifouling functional layer, an antireflection layer, and an adhesive layer are sequentially laminated on one surface of a plastic film. A laminate in which the transfer film is laminated on a transfer object such as a substrate, and then the release layer and the plastic film are peeled off, and an antireflection layer and an antifouling layer are sequentially laminated on the surface of the transfer object. Is obtained. However, since the release film on which the release layer was formed was used, the water repellency of the surface after transfer was not sufficient.

JP 2004-310,135 A JP 2003-103,680 A

  The object of the present invention is to provide a laminate having excellent appearance, antireflection properties and transparency, and having excellent antifouling properties, a method for producing the same, a transfer film capable of obtaining the laminate, and a method for producing the same. Is to provide.

The gist of the present invention is that the surface of the peeling film is at least one surface selected from a hydrophilic treatment and a treatment in which an organic solvent having a boiling point of 200 ° C. or less is applied and dried at a drying temperature of 80 to 130 ° C. A method for producing a transfer film (hereinafter referred to as “the present transfer film 1”) in which an antifouling layer is formed on the surface subjected to the surface treatment of the peeling film after the treatment is defined as a first invention.

Further, the gist of the present invention is that at least one selected from a hydrophilization treatment and an organic solvent having a boiling point of 200 ° C. or less and drying at a drying temperature of 80 to 130 ° C. is applied to the surface of the peeling film. Is a method for producing a transfer film (hereinafter referred to as “this transfer film 2”) in which an antifouling layer and a high refractive index layer are formed in this order on the surface of the release film that has been subjected to the surface treatment. A method for producing a transfer film in which the refractive index (n _KK ) of the high refractive index layer is 1.6 or more is defined as a second invention.

Further, the gist of the present invention is that at least one selected from a hydrophilic treatment and an organic solvent having a boiling point of 200 ° C. or less and drying at a drying temperature of 80 to 130 ° C. is applied to the surface of the peeling film. After performing the surface treatment, a transfer film in which an antifouling layer, a high refractive index layer and a medium refractive index layer are formed in this order on the surface of the peeling film (hereinafter referred to as “the present transfer film 3”). The refractive index (n _KK ) of the high refractive index layer is 1.6 or more, and the refractive index (n _CHK ) of the medium refractive index layer is 1.5 to 1.65. A method for producing a film is a third invention.

Further, the gist of the present invention is that the surface of the transfer film 1 on which the antifouling layer is formed is attached to the substrate directly or through another layer with a coating film for forming an adhesive layer. Together, the transfer film laminate 1 is formed, and then the adhesive layer is obtained from the coating film for forming the adhesive layer to form the transfer film laminate 1, and then the release film is peeled from the transfer film laminate 1. A method for manufacturing a laminate (hereinafter referred to as “the present laminate 1”) is a fourth invention.

Further, the gist of the present invention is that the surface of the transfer film 2 on which the high refractive index layer is formed is coated with a base material directly or through another layer with a coating film for forming an adhesive layer. The transfer film laminate 2 is formed by bonding, then the adhesive layer is obtained from the coating film for forming the adhesive layer, the transfer film laminate 2 is formed, and then the release film is peeled from the transfer film laminate 2 The manufacturing method of the laminated body (henceforth "this laminated body 2") to make is made into 5th invention.

Further, the gist of the present invention is that the surface on which the intermediate refractive index layer of the transfer film 3 is formed is coated with a base material directly or through another layer with a coating film for forming an adhesive layer. The transfer film laminate 3 is formed by bonding, then the adhesive layer is obtained from the coating film for forming the adhesive layer, and the transfer film laminate 3 is formed, and then the release film is peeled from the transfer film laminate 3 A manufacturing method of a laminated body (hereinafter referred to as “the present laminated body 3”) is referred to as a sixth invention.

  Since a laminate having excellent appearance, antireflection properties and transparency and having excellent antifouling properties can be obtained according to the present invention, the laminates 1 to 3 are image display members used outdoors, fingerprints, It is suitable as a front plate for cellular phones, portable information terminals, notebook personal computers, etc. to which sebum, foundations and the like easily adhere.

1 is a sectional view in the thickness direction of a medium refractive index layer when the medium refractive index layer is a metal oxide fine particle-containing layer, showing an embodiment of the present invention.

Peeling film The peeling film used in the present invention is a film to be peeled off after laminating the transfer film 1, 2 or 3 on the surface of a substrate described later, and is conventionally used as a peeling film for transfer. For example, an active energy ray transparent film can be used.

  The release film has a critical surface tension in that it has good film-forming properties without repelling defects (a phenomenon in which the substrate is exposed to a part of the coating film) when an organic solvent is applied to the surface of the release film. Is preferably an active energy ray-permeable film having a surface of 40 mN / m or more.

  In the present invention, the critical surface tension can be calculated from a Zisman plot. That is, several types of standard solutions having different surface tensions are prepared, and these standard solutions are dropped on the surface of the film, and the contact angle (θ) between the standard solution and the film surface is measured. The cos θ value is calculated from the obtained contact angle (θ), and the cos θ value and the surface tension value of the standard solution are plotted on a graph having the cos θ value and the surface tension as XY coordinates. The value of the surface tension at the intersection of the straight line connecting the Zisman plot) and the straight line indicated by cos θ = 1 is defined as the critical surface tension.

  Specific examples of the peeling film include a polyethylene terephthalate film (hereinafter referred to as “PET film”), a synthetic resin film such as a polycarbonate film, a polyamide film, and a polyamideimide film, and a composite film or a composite sheet thereof. And those obtained by laminating a release layer thereon.

  Among these, an aromatic polyester film represented by PET film, polyethylene naphthalate film (hereinafter referred to as “PEN film”), polybutylene terephthalate film, polybutylene naphthalate, polytrimethylene terephthalate, etc. is preferable. More preferred are films and PEN films.

  In the present invention, by using an aromatic polyester film as a release film, the monomer (A) containing a perfluoropolyether group and a nitrogen atom (hereinafter referred to as “monomer”) A) ").) Even if the antifouling layer-forming composition having a low content and a low refractive index is used, the water contact angle on the surface of the antifouling layer of the obtained laminate 1, 2, or 3 is It becomes possible to increase the triolein contact angle, and as a result, a large amount of the component for improving the scratch resistance can be added to the antifouling layer forming composition, and the antifouling layer of the present laminate 1, 2 or 3 can be added. It is preferable at the point which can make surface abrasion resistance favorable.

  The thickness of the peeling film is preferably 4 μm or more, more preferably 12 μm or more, and even more preferably 30 μm or more from the viewpoint of ease of production of the present transfer film 1, 2 or 3 free from wrinkles, cracks and the like. Further, the thickness of the peeling film is preferably 500 μm or less, more preferably 150 μm or less, and further preferably 120 μm or less in view of the production cost and ultraviolet transmittance of the transfer film 1, 2 or 3.

  In this invention, you may provide a peeling layer in the surface of the film for peeling in the range which does not deviate from the objective of this invention.

  As a release layer forming material for forming a release layer on the surface of the release film, a polymer or wax that forms a known release layer can be appropriately selected and used.

  As a method for forming the release layer, for example, a melamine-based, urea-based, urea-melamine-based, benzoguanamine-based resin, and a paint in which a surfactant is dissolved in an organic diluent solvent or water, gravure printing method, screen Examples thereof include a method in which the film is applied, dried or cured on the surface of the peeling film by a known printing method such as a printing method or an offset printing method.

The thickness of the release layer is usually about 0.1 to 3 μm. When the release layer has an appropriate thickness, it tends to be easily peeled off from the low refractive index film. Conversely, if the release layer is not too thick, the low refractive index film tends not to be detached from the release film before transfer.

Surface Treatment In the present invention, the surface of the release film is subjected to a surface treatment.

  Examples of the surface treatment include at least one treatment selected from a hydrophilic treatment and a treatment of applying and drying an organic solvent.

  Appearance of this laminate 1, 2 or 3 obtained by surface-treating the surface of the release film to which the antifouling layer-forming composition is applied before applying the antifouling layer-forming composition described later Can be good.

  Examples of the hydrophilic treatment include corona treatment, plasma treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, heat treatment, and oxidizing material coating treatment. Further, these processes may be combined. Among these, as the hydrophilization treatment, corona treatment and ultraviolet irradiation treatment are preferable from the viewpoint of improving the scratch resistance of the present laminate 1, 2 or 3.

  Examples of the corona treatment method include a treatment method using an ordinary corona treatment apparatus. An example of corona treatment is shown below.

  Using a corona treatment device with an electrically insulated belt and an electrode placed close to the top of the belt, high energy is applied to the electrode to cause corona discharge, and peeling is performed by passing a peeling film under the electrode on the belt. Corona treatment is applied to the film surface.

  The irradiation energy for the peeling film at this time is preferably 10 to 200 W · min / m. By setting the irradiation energy to 10 W · min / m or more, the adhesion between the peeling film and the antifouling layer tends to be good. Moreover, it exists in the tendency which can make the external appearance of a pollution protection layer favorable by making irradiation energy into 200 W * min / m or less. The clearance between the peeling film and the electrode is preferably 5 mm or less in order to stably generate corona discharge.

  Examples of the plasma treatment method include a treatment method using a normal plasma treatment apparatus, and a treatment method using an atmospheric pressure plasma treatment apparatus is preferable because it is easy in terms of operation.

  Examples of the plasma treatment method include a remote method and a direct method, but the direct method is preferable in that uniform treatment can be obtained.

  As an example of the atmospheric pressure plasma processing apparatus, a chamber is provided that includes a pair of counter electrodes each having an upper electrode and a lower electrode, and at least one electrode facing surface is covered with a dielectric.

  In the above apparatus, when the dielectric is coated on only one of the counter electrodes, the part where the plasma is generated is between the dielectric and the electrode, and the dielectric is coated on both of the counter electrodes Between the dielectrics. A peeling film is disposed between the counter electrodes of such a plasma processing apparatus, high frequency power is applied to the power supply unit to generate plasma between the counter electrodes, and the surface of the peeling film is plasma processed.

  The distance between the opposing surfaces of the counter electrode (shortest distance) is determined in consideration of the thickness of the peeling film, the thickness of the coated dielectric, the magnitude of the applied voltage, etc. In either case where only one side is covered with a dielectric or both sides of the counter electrode are covered with a dielectric, it is preferably 50 mm or less. When the shortest distance is 50 mm or less, uniform discharge plasma tends to be generated.

  The frequency of the high frequency power applied between the counter electrodes is preferably 1 kHz or more. Further, the frequency of the high frequency power applied between the counter electrodes is preferably 10 MHz or less, and more preferably 500 kHz or less.

The power surface density is preferably ² to 30 W / cm ² . As a frequency, it exists in the tendency for the deformation | transformation and deterioration at the time of the process of a peeling film to be suppressed at 1-500 kHz.

Moreover, it exists in the tendency which can suppress a deformation | transformation of the film for peeling by a plasma irradiation heat at a power surface density of 30 W / cm < ² > or less.

  In the present invention, the power surface density is a value obtained by dividing the power input between a pair of opposed electrodes by the surface area of one electrode in contact with plasma.

  Examples of the ultraviolet irradiation treatment method include the following methods.

  Examples of the light source used include a high-pressure mercury lamp, a metal halide lamp, and a fluorescent ultraviolet lamp.

  Examples of the environment for the ultraviolet irradiation treatment include an atmosphere of an inert gas such as nitrogen or argon.

  The oxygen concentration in the ultraviolet irradiation treatment is preferably 1,000 ppm or less, more preferably 500 ppm or less, and still more preferably 300 ppm or less.

Moreover, as irradiation conditions of an ultraviolet-ray, the irradiation conditions of the peak illumination intensity of 100-1,200 mW / cm < ² > and the integrated light quantity 100-1,200 mJ / cm < ² > are mentioned, for example.

  Examples of the treatment method for applying and drying the organic solvent include a method of drying the organic solvent after applying an organic solvent having a boiling point of 200 ° C. or less to the surface of the peeling film.

  Examples of the organic solvent having a boiling point of 200 ° C. or lower include 1-methoxy-2-propanol, toluene, xylene, butyl acetate, chloroform, methyl isobutyl ketone, isopropanol, and ethanol. Among these, 1-methoxy-2-propanol, toluene, and xylene are preferable from the viewpoint of good wettability to the release film.

  Examples of the method for applying an organic solvent to the surface of the release film include a casting method, a gravure coating method, a reverse gravure coating method, a vacuum slot die coating method, a roller coating method, a bar coating method, a spray coating method, and an air knife coating. Method, spin coating method, flow coating method, curtain coating method, film cover method and dipping method.

  The drying temperature of the organic solvent having a boiling point of 200 ° C. or lower is preferably 80 to 130 ° C. By setting the drying temperature within this temperature range, sufficient drying is performed, and the generation of film wrinkles due to drying tends to be small.

In the present invention, a hydrophilic treatment and a treatment for applying and drying an organic solvent may be combined. In this case, either process may be performed first. That is, a treatment for applying and drying an organic solvent may be performed after the hydrophilic treatment, or a hydrophilic treatment may be performed after the treatment for applying and drying the organic solvent.

Antifouling layer In the present invention, the antifouling layer is a layer formed on the surface of the release film on which the surface of the transfer film 1, 2 or 3 has been treated or on the surface of the laminate 1, 2 or 3.

  The thickness of the antifouling layer is preferably 10 nm or more, and more preferably 60 nm or more, from the viewpoint of the antifouling property and scratch resistance of the surface of the laminate 1, 2 or 3. Further, from the viewpoint of optical characteristics, 1.3 μm or less is preferable, 300 nm or less is more preferable, and 110 nm or less is still more preferable.

  The antifouling layer composition for forming the antifouling layer (hereinafter referred to as “antifouling layer forming composition”) is at least one curable selected from thermosetting and active energy ray curable. The thing which has is mentioned.

  As a component of the composition for antifouling layer formation, the monomer (A) shown below is mentioned, for example. The monomer (A) has a perfluoropolyether group and a nitrogen atom independently in the same compound.

  As a specific example of the monomer (A), for example, a triisocyanate (C) obtained by trimerizing diisocyanate (hereinafter referred to as “triisocyanate (C)”) and an active hydrogen-containing compound (D) are reacted. Monomer (A-1) obtained by this (hereinafter referred to as “monomer (A-1)”).

  Examples of the diisocyanate used to obtain the triisocyanate (C) include an isocyanate group bonded to an aliphatic skeleton, such as hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and dicyclohexylmethane diisocyanate. Examples thereof include diisocyanates in which an isocyanate group is bonded to an aromatic skeleton, such as diisocyanate and tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate.

  Examples of the active hydrogen-containing compound (D) include compounds containing active hydrogen such as a hydroxyl group.

  Specific examples of the active hydrogen-containing compound (D) include perfluoropolyether (D-1) having one active hydrogen (hereinafter referred to as “polyether (D-1)”), active hydrogen and carbon-carbon. And a monomer (D-2) having a double bond (hereinafter referred to as “monomer (D-2)”).

  Examples of the polyether (D-1) include compounds having a perfluoropolyether group and one hydroxyl group at one molecular end.

  Specific examples of the polyether (D-1) include compounds represented by the following formula (1).

（式中、Ｘはフッ素原子、Ｙ及びＺはそれぞれフッ素原子又はトリフルオロメチル基を示す。ａは１〜１６の整数、ｃは０〜５の整数、ｂ、ｄ、ｅ、ｆ及びｇは０〜２００の整数、並びにｈは０〜１６の整数である。）。

(In the formula, X represents a fluorine atom, Y and Z each represents a fluorine atom or a trifluoromethyl group. A represents an integer of 1 to 16, c represents an integer of 0 to 5, b, d, e, f and g represent An integer of 0-200, and h is an integer of 0-16.)

  In the formula (1), if the numerical values a to h are not too large, the molecular weight does not become too large, and the solubility in a diluting solvent tends to be good. On the other hand, if the numerical values of a to h are not too small, the antifouling property of the laminate 1 or 2 tends to be good.

  Examples of the monomer (D-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.

  In the present invention, “(meth) acryl” means “acryl” or “methacryl”.

  As a method for synthesizing the monomer (A-1), for example, the polyether (D-1) is reacted with one isocyanate group of the triisocyanate (C), and the monomer (D-2) is reacted with the remaining two isocyanate groups. It can be obtained by reacting. In this reaction, the triisocyanate (C) may be reacted with the polyether (D-1) and the monomer (D-2) simultaneously or sequentially.

  Specific examples of the monomer (A-1) include compounds represented by the following formula (2).

（式中、Ｗはパーフルオロポリエーテル基を表す。）
本発明においては、モノマー（Ａ）としては、本積層体１、２又は３の防汚性が良好である観点から、式（２）で示される化合物が好ましい。

(In the formula, W represents a perfluoropolyether group.)
In the present invention, the monomer (A) is preferably a compound represented by the formula (2) from the viewpoint of good antifouling properties of the present laminate 1, 2 or 3.

  As another example of the monomer (A), a compound (E) having an isocyanate group and one or two (meth) acryloyloxy groups in the same compound (hereinafter referred to as “compound (E)”). And a monomer (A-2) obtained by reacting perfluoropolyether (F) having at least one active hydrogen at the molecular terminal (hereinafter referred to as “perfluoropolyether (F)”) (hereinafter referred to as “perfluoropolyether (F)”). Monomer (A-2) ").

  A commercially available product can be used as the perfluoropolyether (F). Examples of the perfluoropolyether diol include FLUOROLINK D10H, FLUOROLINK D and FLUOROLINK D4000 (all trade names) manufactured by Solvay Solexis.

  As the compound (E), a commercially available product can be used. For example, Karenz BEI (1,1-bis (acryloyloxymethyl) ethyl isocyanate), Karenz AOI (2-acryloyloxyethyl isocyanate) manufactured by Showa Denko KK And Karenz M01 (2-methacryloyloxyethyl isocyanate) (both are trade names).

  As the monomer (A-2), for example, as a compound in which the isocyanate group of the compound (E) and the hydroxyl group of the perfluoropolyether (F) are bonded, one perfluoropolyether group and one or A compound having two vinyl groups (or (meth) acryloyloxy groups) independently, preferably a compound having two vinyl groups (or (meth) acryloyloxy groups) independently.

  Here, “independently” means that the perfluoropolyether group and the (meth) acryloyloxy group are not directly bonded.

  The content of the monomer (A) contained in the antifouling layer forming composition is preferably 10 parts by mass or more, more preferably 12 parts by mass or more in 100 parts by mass of the solid content in the antifouling layer forming composition. preferable. Moreover, as content of a monomer (A), 50 mass parts or less are preferable, and 30 mass parts or less are more preferable. If it is in said range, it exists in the tendency for the antifouling property and hardness of the surface of this laminated body 1, 2, or 3 to become favorable. That is, the water contact angle of the antifouling layer of the present laminate 1, 2 or 3 tends to be 90 degrees or more and the triolein contact angle is 55 degrees or more.

  Here, the solid content in the antifouling layer-forming composition refers to a component excluding the antifouling layer dilution solvent in the antifouling layer-forming composition described below.

  In the present invention, the composition for forming an antifouling layer may contain inorganic fine particles (B) depending on the purpose.

  The content of the inorganic fine particles (B) in the composition for forming an antifouling layer is preferably 25 parts by mass or more and 90 parts by mass or less in terms of the hardness of the present laminate 1, 2 or 3.

  The “fine particles” of the inorganic fine particles (B) indicate particles having an average particle diameter of about 1 to 200 nm. Moreover, an average particle diameter is the value measured with the particle size distribution analyzer SALD-7100 (made by Shimadzu Corp.).

  Specific examples of the inorganic fine particles (B) include colloidal silica, porous silica, hollow silica, magnesium fluoride and cryolite. These may use only 1 type and may use 2 or more types together.

  In the present invention, the anti-smudge layer can function as a low-refractive-index functional layer when the laminated body obtained has not only anti-stain properties but also anti-reflection performance.

  The refractive index of the antifouling layer in the case of the low refractive index functional layer may be lower than that of the layer in contact with the lower part of the antifouling layer in the present laminate 1, 2 or 3.

  The refractive index of the antifouling layer when it is a low refractive index functional layer is preferably 1.5 or less, more preferably 1.45 or less, and still more preferably 1.4 or less from the viewpoint of antireflection performance.

  When obtaining the said laminated body, a low-refractive-index component can be mix | blended in the composition for antifouling layer formation. The antifouling layer-forming composition preferably contains a fluorine atom-containing curable monomer so that the refractive index of the low refractive index functional layer is 1.5 or less.

  As the low refractive index component, for example, among the inorganic fine particles (B), it is preferable to use low refractive index fine particles having a refractive index of 1.5 or less. Further, as will be described later, silica fine particles are preferable from the viewpoint that the surface of the inorganic fine particles (B) can be easily hydrolyzed, and hollow silica is more preferable in that the refractive index is low and the reflectance is easily reduced.

  The refractive index of hollow silica is 1.20 to 1.40, which is lower than that of ordinary silica 1.45 to 1.47. Therefore, in order to reduce the refractive index of the antifouling layer in the present invention, it is preferable to use hollow silica.

  In the present invention, the refractive index is a value measured with a laser having a wavelength of 594 nm using a prism coupler (Model 2010 manufactured by Metricon Corporation).

  In the present invention, as the inorganic fine particles (B), the particle surface is hydrolyzed because the antifouling property of the surface of the present laminate 1, 2 or 3 is improved and the strength of the antifouling layer is improved. Those treated individually with a surface treatment agent such as a functional silane compound are preferred. Individual treatment means that the surface of the inorganic fine particles (B) is reacted only with a surface treatment agent such as a hydrolyzable silane compound, and compounds other than catalysts that contribute to hydrolysis and condensation reactions of acids and bases. This means that the surface of the inorganic fine particles (B) is treated in a state that does not contain.

  As the mixing ratio when the hydrolyzable silane compound is reacted with the surface of the inorganic fine particles (B), from the viewpoint of the antifouling property, scratch resistance or sweat resistance of the surface of the present laminate 1, 2 or 3, The amount of the inorganic fine particles (B) is preferably 30% by mass or more, and more preferably 40% by mass or more with respect to the total amount of the decomposable silane compound and the inorganic fine particles (B). Moreover, it is preferable that inorganic fine particles (B) are 80 mass% or less, and it is more preferable that it is 70 mass% or less.

  Examples of the hydrolyzable silane compound include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- ( (Meth) acryloxypropyltriethoxysilane, p-styryltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldiethoxy Examples include silane. These may use only 1 type and may use 2 or more types together.

  As the surface treating agent, a compound other than the hydrolyzable silane compound can be added in combination.

  Examples of the compound other than the hydrolyzable silane compound include known surfactants such as an anionic surfactant, nonionic surfactant, and cationic surfactant.

  As a method of treating the particle surface with a surface treatment agent such as a hydrolyzable silane compound, for example, a method of hydrolyzing a hydrolyzable silane compound in advance and then condensing the particle surface to a particle surface A method of simultaneously performing hydrolysis and condensation reaction of a surface treatment agent such as a hydrolyzable silane compound. When performing the above reaction, an acid, an alkali, a metal catalyst, or the like may be added as necessary.

  When the monomer (A) is contained as a composition for forming an antifouling layer, the monomer (A) has an unsaturated bond. Or the thing which has an unsaturated bond is a point from which the antifouling property of the antifouling layer of the surface of 3 becomes favorable.

  In the present invention, if necessary, a compound having at least two (meth) acryloyloxy groups in the molecule (hereinafter referred to as “crosslinking component for antifouling layer”) is added to the antifouling layer forming composition. May be.

  The content of the crosslinking component for the antifouling layer in the antifouling layer forming composition is preferably a solid content 100 of the antifouling layer forming composition in terms of scratch resistance on the surface of the laminate 1, 2 or 3. 0-30 mass parts is preferable in a mass part.

  Examples of the antifouling layer crosslinking component include esterified products obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or a derivative thereof, polycarboxylic acid or anhydride thereof, and polyhydric alcohol. Examples include esterified products obtained from (meth) acrylic acid or its derivatives.

  Specific examples of the esterified product obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or a derivative thereof include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol. Polyethylene glycol di (meth) acrylate such as di (meth) acrylate; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate Alkyl diol di (meth) acrylate such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra ( Examples include tri- or higher functional polyol poly (meth) acrylates such as (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, and tripentaerythritol hepta (meth) acrylate.

  In an esterified product obtained from a polyvalent carboxylic acid or its anhydride, a polyhydric alcohol, and (meth) acrylic acid or a derivative thereof, a combination of a polyvalent carboxylic acid or its anhydride, a polyhydric alcohol and (meth) acrylic acid ( Examples of polycarboxylic acid or anhydride / polyhydric alcohol / (meth) acrylic acid) include, for example, malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic acid, Malonic acid / glycerin / (meth) acrylic acid, malonic acid / pentaerythritol / (meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid / trimethylolpropane / (meth) acrylic acid, succinic acid Acid / glycerin / (meth) acrylic acid, succinic acid / pentaerythritol / (meth) acrylic Acid, adipic acid / trimethylolethane / (meth) acrylic acid, adipic acid / trimethylolpropane / (meth) acrylic acid, adipic acid / glycerin / (meth) acrylic acid, adipic acid / pentaerythritol / (meth) acrylic acid Glutaric acid / trimethylolethane / (meth) acrylic acid, glutaric acid / trimethylolpropane / (meth) acrylic acid, glutaric acid / glycerin / (meth) acrylic acid, glutaric acid / pentaerythritol / (meth) acrylic acid, Sebacic acid / trimethylolethane / (meth) acrylic acid, sebacic acid / trimethylolpropane / (meth) acrylic acid, sebacic acid / glycerin / (meth) acrylic acid, sebacic acid / pentaerythritol / (meth) acrylic acid, fumar Acid / Trimethylolethane / (Me ) Acrylic acid, fumaric acid / trimethylolpropane / (meth) acrylic acid, fumaric acid / glycerin / (meth) acrylic acid, fumaric acid / pentaerythritol / (meth) acrylic acid, itaconic acid / trimethylolethane / (meth) Acrylic acid, itaconic acid / trimethylolpropane / (meth) acrylic acid, itaconic acid / glycerin / (meth) acrylic acid, itaconic acid / pentaerythritol / (meth) acrylic acid, maleic anhydride / trimethylolethane / (meth) Acrylic acid, maleic anhydride / trimethylolpropane / (meth) acrylic acid, maleic anhydride / glycerin / (meth) acrylic acid and maleic anhydride / pentaerythritol / (meth) acrylic acid.

  Other examples of cross-linking components for the antifouling layer include trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, trimethylhexa 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, N per mole of polyisocyanate obtained by trimerization of diisocyanate such as methylene diisocyanate -Methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, 1,5,3-propanetriol-1,3-di Urethane (meth) acrylate obtained by reacting 3 mol or more of an acrylic monomer having active hydrogen such as meth) acrylate and 3-acryloyloxy-2-hydroxypropyl (meth) acrylate; tris (2-hydroxyethyl) isocyanuric acid And poly [(meth) acryloyloxyethylene] isocyanurates such as di (meth) acrylate or tri (meth) acrylate; epoxy poly (meth) acrylate; and urethane poly (meth) acrylate.

  Only 1 type may be used for the crosslinking component for antifouling layers, and 2 or more types may be used together.

  When the composition for forming an antifouling layer is an active energy ray-curable composition for forming an antifouling layer, a photoinitiator for the antifouling layer can be blended in the composition for forming an antifouling layer.

  Examples of the photoinitiator for the antifouling layer include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, 2,2-di Ethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2- Carbonyl compounds such as hydroxy-2-methyl-1-phenylpropan-1-one; sulfur compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide; and 2,4 6- trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide, phosphorus compounds such as benzo dichloride ethoxy phosphine oxide.

  The addition amount of the antifouling layer photoinitiator is 0.1 with respect to 100 parts by mass of the total solid content of the antifouling layer forming composition in terms of curability by ultraviolet irradiation of the antifouling layer forming composition. More than mass part is preferable, 0.5 mass part or more is more preferable, and 1 mass part or more is still more preferable. In addition, the amount of the photoinitiator for the antifouling layer is preferably 10 parts by mass or less, and more preferably 7 parts by mass or less from the viewpoint of improving the color tone of the antifouling layer.

  When the antifouling layer forming composition is a thermosetting antifouling layer forming composition, an antifouling layer thermosetting agent can be blended in the antifouling layer forming composition.

  Examples of the antifouling layer thermosetting agent include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, and 2,2′-azobis. Azo polymerization initiators such as-(2,4-dimethylvaleronitrile); and lauroyl peroxide, diisopropyl peroxydicarbonate, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl Examples thereof include organic peroxide polymerization initiators such as peroxyneodecanoate and t-hexyl peroxypivalate. These may use only 1 type and may use 2 or more types together.

  In the present invention, the antifouling layer-forming composition may contain various additives such as a slip property improver, a leveling agent, an ultraviolet absorber, and a light stabilizer such as HALS, if necessary.

  As a compounding quantity of an additive, 10 mass parts or less are preferable with respect to 100 mass parts of solid content of the composition for antifouling layer formation at the transparency point of an antifouling layer.

  In the present invention, in order to adjust the solid content concentration of the antifouling layer forming composition, a diluting solvent for the antifouling layer can be added to the antifouling layer forming composition.

  Examples of the antifouling layer dilution solvent include methyl ethyl ketone, methyl isobutyl ketone, isopropanol, ethanol, 1-methoxy-2-propanol, and 2,2,3,3-tetrafluoro-1-propanol.

  The solid content concentration of the antifouling layer forming composition is preferably 0.1 to 20% by mass. By setting the solid content concentration of the antifouling layer forming composition in the above range, the storage stability of the antifouling layer forming composition can be improved, and it tends to be easily controlled to a desired film thickness. .

  Examples of the method for forming the antifouling layer when obtaining the present transfer film 1, 2 or 3 include the following methods.

  First, the antifouling layer-forming composition is applied to the surface of the release film that has been subjected to the above-described surface treatment, and then dried to form a coating film of the antifouling layer-forming composition.

  Subsequently, the coating film of the obtained antifouling layer forming composition is cured to obtain an antifouling layer.

  Examples of the method for applying the antifouling layer forming composition to the surface of the surface-treated release film include the same method as the method for applying an organic solvent to the surface of the release film.

  As a method of curing the coating film of the antifouling layer forming composition, for example, when the antifouling layer forming composition is a thermosetting antifouling layer forming composition, a heat curing method may be mentioned. When the layer forming composition is an active energy ray-curable antifouling layer forming composition, an active energy ray curing method may be mentioned.

  When the composition for forming an antifouling layer is an active energy ray-curable composition for forming an antifouling layer, the active energy ray used for curing the composition for forming an antifouling layer includes, for example, an electron beam, Examples include radiation and ultraviolet rays.

  Examples of the light source when irradiating ultraviolet rays as active energy rays include a high-pressure mercury lamp, a metal halide lamp, and a fluorescent ultraviolet lamp. Irradiation with ultraviolet rays under an inert gas atmosphere such as nitrogen or argon is preferable because the surface curability of the composition for forming an antifouling layer is improved and the process passability is improved. The oxygen concentration is preferably 1,000 ppm or less, more preferably 500 ppm or less, and even more preferably 300 ppm or less.

Moreover, as active energy ray hardening conditions for hardening the active energy ray-curable antifouling layer forming composition, for example, peak illuminance of 100 to 1,200 mW / cm ² and integrated light quantity of 100 to 1,200 mJ / cm ^{2 are used.} The curing conditions are as follows. If it is this range, it exists in the tendency for the balance of antifouling performance and abrasion resistance to become favorable.

In the present invention, a high refractive index layer described later can be formed after the antifouling layer is formed on the surface of the surface-treated release film, but the antifouling layer before the high refractive index layer is formed is It may be a partially cured product obtained by curing a part of the composition for forming an antifouling layer as necessary, as well as a composition obtained by completely curing the composition for forming an antifouling layer.

High Refractive Index Layer In the present invention, a high refractive index layer having a higher refractive index than the antifouling layer is formed on the surface of the antifouling layer of the transfer film 1 in order to improve the antireflection function of the laminate 1. The transferred transfer film 2 can be obtained.

  Further, the present laminate 2 having a good antireflection function can be obtained by using the present transfer film 2.

  In the present invention, an intermediate refractive index layer having a lower refractive index than the high refractive index layer is formed on the surface of the high refractive index layer of the transfer film 2 in order to suppress interference patterns that are likely to occur in the laminate 2. This transfer film 3 can be obtained.

  Further, the present laminate 3 in which the occurrence of interference patterns is suppressed can be obtained by using the present transfer film 3.

The film thickness (d _KK ) of the high refractive index layer is preferably 0.5 to 10 μm from the viewpoint of the scratch resistance and antireflection performance of the surface of the laminate 2.

The refractive index (n _KK ) of the high refractive index layer is preferably higher than the antifouling layer and the adhesive layer in the laminate 2 from the viewpoint of suppressing the interference pattern.

The refractive index (n _KK ) of the high refractive index layer is preferably 1.6 or more, and more preferably 1.7 or more.

Moreover, it is preferable that the refractive index (n _KK ) of the high refractive index layer satisfies the following formula (3) from the viewpoint of suppressing the interference pattern on the surface of the laminate 3.
^{_{(N HC × n KK) 1/2}} - (n KK -n HC) / 8 ≦ n CHK ≦ (n HC × n KK) 1/2 + (n KK -n HC) / 8 ··· (3)
(In the above formula (3), n _HC represents the refractive index of the adhesive layer described later, n _KK represents the refractive index of the high refractive index layer, and n _CHK represents the refractive index of the medium refractive index layer described later.)
Examples of the method for forming the high refractive index layer include the following methods.

  First, a high refractive index layer composition for forming a high refractive index layer (hereinafter referred to as “high refractive index layer forming composition”) is laminated on the surface of the surface-treated release film. It coats on the surface of the dirty layer to form a coating film of the composition for forming a high refractive index layer.

  When the high refractive index layer-forming composition described later is contained in the high refractive index layer-forming composition, the high refractive index layer-diluting solvent is volatilized to coat the high refractive index layer-forming composition. A film can be formed.

  Next, the coating film of the obtained composition for forming a high refractive index layer is cured to obtain a high refractive index layer.

  Examples of the high refractive index layer forming composition include at least one selected from a thermosetting high refractive index layer forming composition and an active energy ray curable high refractive index layer forming composition.

  Specific examples of the composition for forming a high refractive index layer include a composition containing a compound having at least two (meth) acryloyloxy groups (hereinafter referred to as “crosslinking component for high refractive index layer”). .

  Examples of the crosslinking component for the high refractive index layer include the same as the crosslinking component for the antifouling layer.

  In the composition for forming a high refractive index layer, in order to obtain the present laminate 2 or 3 having excellent scratch resistance, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- It is preferable to contain aminosilanes such as (aminoethyl) -3-aminopropyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropyltriethoxysilane.

  As content of said aminosilane in the composition for high refractive index layer formation, in order to obtain the favorable abrasion resistance of this laminated body 2 or 3, solid content in the composition for high refractive index layer formation 100 masses The amount is preferably 1 part by mass or more based on the part, and preferably 30 parts by mass or less in order to obtain a good antireflection function.

  In the composition for forming a high refractive index layer, high refractive index metal oxide fine particles can be added in order to improve the strength of the high refractive index layer and to increase the refractive index of the high refractive index layer.

  The high refractive index metal oxide fine particles preferably have a refractive index of about 1.55 to 2.0.

  Specific examples of the high refractive index metal oxide fine particles include tin oxide, antimony-doped tin oxide (ATO), indium oxide, tin-doped indium oxide (ITO), zinc oxide, aluminum-doped zinc oxide, and antimony. Zinc acid and antimony pentoxide are preferred, and zirconium oxide is more preferred from the viewpoint of high refractive index and good transparency.

  The content of the high refractive index metal oxide fine particles in the high refractive index layer forming composition is such that the laminate 2 or 3 has good scratch resistance and antireflection function, so that the high refractive index layer forming composition can be used. 20 mass parts or more are preferable with respect to 100 mass parts of solid content in a composition, and 80 mass parts or less are preferable at the point which this laminated body 2 or 3 has a favorable antireflection function.

  Moreover, about high refractive index metal oxide fine particles, it is preferable to surface-treat with the same processing agent as the surface treating agent used when processing the surface of inorganic fine particles (B).

  As the mixing ratio of the high refractive index metal oxide fine particles and the hydrolyzable silane compound when the hydrolyzable silane compound is reacted as a surface treatment agent on the surface of the high refractive index metal oxide fine particles, the laminate 2 or 3 is used. From the viewpoint of scratch resistance and antireflection performance of the surface, it is preferable to contain 20 to 80% by mass of the high refractive index metal oxide fine particles in the total amount of the hydrolyzable silane compound and the high refractive index metal oxide fine particles. .

  Examples of the method for adjusting the refractive index of the high refractive index layer include a method of changing the blending ratio of the high refractive index layer crosslinking component and the high refractive index metal oxide fine particles. That is, if the content of the high refractive index metal oxide fine particles increases, the refractive index of the high refractive index layer increases. On the other hand, if the content of the high refractive index metal oxide fine particles decreases, the high refractive index layer The refractive index of the lowers.

  Further, instead of the high refractive index metal oxide fine particles, a high refractive index organic compound may be added to adjust the refractive index of the high refractive index layer to a desired value.

  Examples of the high refractive index organic compound include compounds having a sulfur atom, a bromine atom, an aromatic skeleton, or a fluorene skeleton in the molecule.

  Examples of the compound having an aromatic skeleton include NK ester A-LEN-10 and NK ester ABE-300 (both trade names) manufactured by Shin-Nakamura Chemical Co., Ltd.

  Examples of the compound having a fluorene skeleton include Ogsol EA200, EA1000, EA-F5003, EA-F5503 and EA-F5510 (all trade names) manufactured by Osaka Gas Chemical Co., Ltd.

  In the present invention, if necessary, an antistatic component can be added to the composition for forming a high refractive index layer to impart an antistatic function to the high refractive index layer.

If imparting an antistatic function to the high refractive index layer, the surface resistivity of the surface layer of the laminate 2 or 3 is preferably ¹⁰ 10 Ω / □ or less, more preferably 10 ⁸ Ω / □ or less.

  When the composition for forming a high refractive index layer is an active energy ray-curable composition for forming a high refractive index layer, a photoinitiator for the high refractive index layer may be blended in the composition for forming a high refractive index layer. it can.

  About the kind and addition amount of the photoinitiator for high refractive index layers, it can be set as the compound and addition amount similar to the photoinitiator for antifouling layers.

  Further, when the high refractive index layer forming composition is a thermosetting high refractive index layer forming composition, a high refractive index layer thermosetting agent may be blended in the high refractive index layer forming composition. it can.

  About the kind and addition amount of the thermosetting agent for high refractive index layers, it can be set as the compound and addition amount similar to the thermosetting agent for antifouling layers.

  In the present invention, the high refractive index layer-forming composition may contain various additives such as a slip improver, a leveling agent, an ultraviolet absorber, and a light stabilizer such as HALS, if necessary. .

  As a compounding quantity of an additive, 10 mass parts or less are preferable with respect to 100 mass parts of solid content in the composition for high refractive index layer formation at the point of transparency of a high refractive index layer.

  In the present invention, in order to adjust the solid content concentration of the composition for forming a high refractive index layer, a diluting solvent for the high refractive index layer can be added.

  The dilution solvent for the high refractive index layer may be used alone or in combination.

  The diluting solvent for the high refractive index layer preferably has a dielectric constant at 25 ° C. of 10.0 or less from the viewpoint of good storage stability of the composition for forming the high refractive index layer. By using the composition for forming a high refractive index layer that has been allowed to stand at room temperature for a long time (for example, 24 hours or longer), the laminate 2 or 3 having excellent scratch resistance can be obtained by setting the dielectric constant to 10.0 or less. It tends to be possible to obtain.

  In order to set the dielectric constant of the diluting solvent for the high refractive index layer to 10.0 or less, the dielectric constant may be 10.0 or less with a single diluting solvent, or by mixing a plurality of diluting solvents, the dielectric constant is 10.0. The following may be used. Examples of the diluent solvent having a dielectric constant of 10.0 or less alone include toluene (2.38), xylene (2.41), butyl acetate (5.02), and chloroform (4.9).

  In addition, as an example in which the dielectric constant of the high refractive index layer dilution solvent is 10.0 or less when a diluent solvent having a dielectric constant of 10.0 or less and a dilution solvent of 10.0 or more are combined to form a mixed dilution solvent, What added 45 mass% or more of toluene in the total amount of toluene and i-propanol is mentioned.

  As solid content concentration of the composition for high refractive index layer formation, 5-50 mass% is preferable. By setting the solid content concentration of the composition for forming a high refractive index layer within this range, the storage stability of the composition for forming a high refractive index layer can be improved, and the film thickness tends to be easily controlled. It is in.

  Examples of the method for applying the composition for forming a high refractive index layer on the surface of the antifouling layer include the same methods as the method for applying the composition for forming an antifouling layer on the surface of the surface-treated release film.

  Examples of the method for curing the coating film of the composition for forming a high refractive index layer include a heat curing method when the composition for forming a high refractive index layer is a composition for forming a high refractive index layer. In the case where the composition for forming a high refractive index layer is an active energy ray-curable composition for forming a high refractive index layer, an active energy ray curing method may be mentioned.

  When the composition for forming a high refractive index layer is an active energy ray-curable composition for forming a high refractive index layer, examples of the light source when irradiating ultraviolet rays as active energy rays include high pressure mercury lamps, metal halide lamps and fluorescent ultraviolet lamps. Is mentioned.

The curing conditions with active energy rays for curing the composition for forming a high refractive index layer include, for example, a peak illuminance of 200 to 1,000 mW / cm ² and an integrated light amount of 400 to 1,200 mJ in the presence of air. A curing condition of / cm ² is mentioned. If it is this range, it exists in the tendency for the adhesiveness with the antifouling layer in this laminated body 2 or 3 and the balance of the external appearance after the abrasion resistance of this laminated body 2 or 3 and a moisture resistance test to become favorable.

  If the energy of the active energy ray at the time of curing the composition for forming a high refractive index layer is too low, a moisture resistance test is performed such that it is allowed to stand for 24 hours or more in a high-temperature and high-humidity environment such as 80 ° C. and 85%. Then, a white bleed material such as powder spray is generated on the surface of the laminate 2 or 3, and the appearance may be deteriorated.

  In the present invention, in order to obtain the present laminate 2 or 3 having excellent scratch resistance, as a composition for forming a high refractive index layer, a monomer having at least two (meth) acryloyloxy groups in the molecule, aminosilane, A composition containing high refractive index metal oxide fine particles, a photoinitiator for a high refractive index layer and a diluent solvent for a high refractive index layer is preferred.

  In this invention, when hardening the coating film of the composition for high refractive index layer formation, the partially hardened | cured material of the composition for antifouling layer formation can be hardened together as needed.

  In the present invention, the intermediate refractive index layer described later can be formed after the high refractive index layer is formed on the surface of the antifouling layer. However, the high refractive index layer before the formation of the intermediate refractive index layer is highly refractive. Not only a composition obtained by completely curing the composition for forming a refractive index layer but also a partially cured product obtained by reacting and curing a part of the composition for forming a high refractive index layer as necessary.

  In the present invention, when the coating film of the composition for forming a high refractive index layer is formed on the surface of the antifouling layer, the interface strength between the antifouling layer and the high refractive index layer is improved, and this laminate 2 or 3 In order to improve the scratch resistance of the anti-smudge layer, the surface of the antifouling layer is subjected to hydrophilic treatment such as ultraviolet irradiation, electron beam irradiation, heat treatment, oxidant coating, corona treatment, and plasma treatment, and then a high refractive index layer is formed. It is preferable to obtain a high refractive index layer after applying the composition for use. As the hydrophilization treatment, corona treatment and plasma treatment are preferable from the viewpoint of improving the scratch resistance of the laminate 2 or 3.

Specific methods and conditions for the above-described hydrophilic treatment include, for example, the same methods and conditions as in the case of hydrophilizing the surface of the peeling film.

Medium Refractive Index Layer In the present invention, a medium refractive index having a lower refractive index than the high refractive index layer is formed on the surface of the high refractive index layer of the transfer film 2 in order to suppress interference patterns that are likely to occur in the laminate 2. It can be set as this transfer film 3 in which the layer was formed.

  Further, the present laminate 3 in which the occurrence of interference patterns is suppressed can be obtained by using the present transfer film 3.

  In the present invention, the medium refractive index layer is, for example, the surface of the high refractive index layer in the transfer film 3 or between the high refractive index layer and the adhesive layer described later, or the base material and the high refractive index layer in the laminate 3. Or a layer formed between another layer of the substrate having another layer such as an adhesive layer and the high refractive index layer.

The film thickness (d _CHK ) of the medium refractive index layer is preferably 30 nm or more, and more preferably 40 nm or more in terms of suppressing the interference pattern on the surface of the laminate 3. In addition, the film thickness (d _CHK ) of the medium refractive index layer is preferably 90 nm or less, and more preferably 80 nm or less.

The refractive index (n _CHK ) of the medium refractive index layer preferably satisfies the above formula (3) from the viewpoint of suppressing the interference pattern on the surface of the laminate 3.

The refractive index (n _CHK ) of the medium refractive index layer is preferably 1.5 to 1.65.

  Examples of the medium refractive index layer in the laminate 3 include a metal oxide fine particle-containing layer for a medium refractive index layer containing metal oxide fine particles for a medium refractive index layer.

  The refractive index of the middle refractive index layer can be adjusted by adding metal oxide fine particles for the middle refractive index layer to the composition for forming the middle refractive index layer, and the strength of the middle refractive index layer can be improved. There is a tendency to be able to.

  When the metal oxide fine particle-containing layer for the medium refractive index layer is used as the medium refractive index layer, the refractive index of the metal oxide fine particle-containing layer for the medium refractive index layer is preferably 1.5 to 1.65.

  Examples of the metal oxide fine particles for the medium refractive index layer include the same metal oxide fine particles blended in the composition for forming a high refractive index layer.

  Examples of the layer containing the metal oxide fine particles for the medium refractive index layer include, for example, a film central region where the metal oxide fine particles for the medium refractive index layer do not exist, and metal oxide fine particles for the medium refractive index layer on one side of the film central region. Film surface layer region (a1) is formed, and the film surface layer region (a2) in which the metal oxide fine particles for the medium refractive index layer are present on the other side of the film center region is formed. Is mentioned.

  As shown in FIG. 1, the film center region / membrane surface layer-containing layer includes a film center region thickness (Tbi and Tci), a film surface layer region (a1) thickness (Tai), and a film surface layer region (a2) thickness ( Tdi) satisfies the following formulas (4) to (7), and the metal oxide fine particles for medium refractive index layer are contained in the cross section in the thickness direction of the metal oxide fine particle content layer for medium refractive index layer. It is preferable that the total length (L) of the length (Li) of the central region of the film in the length of 1,200 nm in the vertical direction is 240 nm or more, preferably 480 nm or more with respect to the film thickness of the layer.

0.1T ≦ Tbi ≦ 0.4T (4)
Tai = 0.5T−Tbi (5)
0.1T ≦ Tci ≦ 0.4T (6)
Tdi = 0.5T-Tci (7)
As the metal oxide fine particles for the medium refractive index layer, for example, tin oxide, tin oxide doped with antimony (ATO), indium oxide, indium oxide doped with tin (ITO), zinc oxide, zinc oxide doped with aluminum, Examples include zinc antimonate and antimony pentoxide.

  As the metal oxide fine particles for the medium refractive index layer, those obtained by individually treating the particle surface with a surface treating agent such as a hydrolyzable silane compound according to the purpose can be used. Individual treatment means that the metal oxide fine particles for the medium refractive index layer are reacted only with a surface treatment agent such as a hydrolyzable silane compound, and other than catalysts that contribute to hydrolysis and condensation reactions of acids, bases, etc. This means that the surface of the metal oxide fine particles for the medium refractive index layer is treated in a state in which the above compound is not included.

  The mixing ratio when the hydrolyzable silane compound is reacted with the surface of the metal oxide fine particles for the medium refractive index layer is hydrolyzed in terms of scratch resistance and antireflection performance of the surface of the laminate 3. It is preferable that 20-80 mass% of metal oxide fine particles for medium refractive index layers are contained in the total amount of the conductive silane compound and the metal oxide fine particles for medium refractive index layer.

  As shown in FIG. 1, the above-described film central region includes a region combining Tb1 and Tc1, which is a central region of the film central region / film surface layer region-containing layer, a region combining Tb2 and Tc2, and Tbi and Tci. This is a region where the metal oxide fine particles for the medium refractive index layer do not exist.

  Tb1, Tb2, Tbi, Tc1, Tc2, and Tci indicate the thickness of the film center region from the center of the film center region / film surface layer region-containing layer to the interface between the film surface layer region and the film center region. Tbi and Tci each represent one region constituting the i-th film central region.

  The film surface layer region (a1) and the film surface layer region (a2) described above are regions formed on the respective surfaces of the film center region, and are regions where metal oxide fine particles for the medium refractive index layer are present.

  In the film surface layer region (a1) or the film surface layer region (a2), as the filling state of the metal oxide fine particles for the medium refractive index layer, the particles are densely packed as in the region of Ta2, Td1 or Tdi in FIG. And a state having a space not filled with particles in the film surface layer region (a1) or the film surface layer region (a2) like the region of Tai or Td2 in FIG.

  Ta1, Ta2, Tai, Td1, Td2, and Tdi indicate the thicknesses of the film surface layer region (a1) and the film surface layer region (a2). Tai and Tdi represent one region constituting the i-th film surface layer region (a1) and the film surface layer region (a2), respectively.

  Moreover, the structure of the cross section in the thickness direction of the metal oxide fine particle-containing layer for the medium refractive index layer can be observed using a transmission electron microscope for the cross section obtained by randomly cutting the cross section in the thickness direction of the laminate 3. .

  In the present invention, the intermediate refractive index layer within the cross section in the thickness direction at the site of the intermediate refractive index layer shown in the transmission electron micrograph of the cross section obtained by randomly cutting the cross section in the thickness direction of the laminate 3. Calculate the total length of the central region of the film where the metal oxide fine particles for the medium refractive index layer are not present at any arbitrary vertical length of 1,200 nm with respect to the thickness of the metal oxide fine particle-containing layer. Can do. Further, the thickness (Tbi and Tci) of the film center region from the center of the metal oxide fine particle-containing layer for the medium refractive index layer to the interface between the film surface layer region (a1) and the film surface layer region (a2) and the film center region, and the film The range of the thickness (Tai) of the surface layer region (a1) and the thickness (Tdi) of the film surface layer region (a2) can be measured.

  Examples of the medium refractive index layer composition for forming the middle refractive index layer (hereinafter referred to as “medium refractive index layer forming composition”) include, for example, a thermosetting medium refractive index layer forming composition and activity. Examples include at least one selected from the energy ray-curable composition for forming a medium refractive index layer.

  Specific examples of the composition for forming a medium refractive index layer include a composition containing a compound having at least two (meth) acryloyloxy groups (hereinafter referred to as “crosslinking component for medium refractive index layer”). .

  Examples of the cross-linking component for the medium refractive index layer include the same as the cross-linking component for the antifouling layer.

  The content of the metal oxide fine particles for the medium refractive index layer in the composition for forming the middle refractive index layer is such that the refractive index of the medium refractive index layer satisfies the formula (3) as long as the refractive index of the medium refractive index layer satisfies the above formula (3). 15 mass parts or more are preferable with respect to 100 mass parts of solid content in a thing, and 20 mass parts or more are more preferable. In addition, the content of the metal oxide fine particles for the medium refractive index layer in the composition for forming the medium refractive index layer is preferably 60 parts by mass or less from the viewpoint of obtaining the present laminate 3 having good transparency. Less than the mass part is more preferable.

  The metal oxide fine particles for the medium refractive index layer are preferably surface-treated with the same compound as the hydrolyzable silane compound used when the surface of the inorganic fine particles (B) is treated.

  The mixing ratio of the surface treatment compound when the hydrolyzable silane compound is reacted with the surface of the metal oxide fine particles for the medium refractive index layer is the scratch resistance and antireflection performance of the surface of the laminate 3. Furthermore, the hydrolyzable silane compound and the medium refractive index layer are formed in that an unevenly distributed layer structure having a film surface layer region (a1), a film center region and a film surface layer region (a2) is formed in the medium refractive index layer. The content of the metal oxide fine particles for the medium refractive index layer in the total amount of the metal oxide fine particles is preferably 50% by mass or more, and more preferably 60% by mass or more. Further, the content of the metal oxide fine particles for the medium refractive index layer in the total amount of the hydrolyzable silane compound and the metal oxide fine particles for the medium refractive index layer is the point of obtaining this laminate having good transparency. 80 mass% or less is preferable, and 70 mass% or less is more preferable.

  Examples of the method for adjusting the refractive index of the medium refractive index layer include the same method as the method for adjusting the refractive index of the high refractive index layer described above.

  In the present invention, the refractive index of the middle refractive index layer can be adjusted to a desired value by adding a middle refractive index organic compound to the composition for forming the middle refractive index layer as necessary.

  Examples of the medium refractive index organic compound include compounds having a sulfur atom, a bromine atom, an aromatic skeleton or a fluorene skeleton in the molecule, and from the viewpoint of good film forming properties of the medium refractive index layer forming composition. preferable.

  Examples of the compound having an aromatic skeleton include NK ester A-LEN-10 and NK ester ABE-300 (both trade names) manufactured by Shin-Nakamura Chemical Co., Ltd.

  Examples of the compound having a fluorene skeleton include Ogsol EA200, EA1000, EA-F5003, EA-F5503 and EA-F5510 (all trade names) manufactured by Osaka Gas Chemical Co., Ltd.

  The content of the medium refractive index organic compound in the medium refractive index layer forming composition is a solid content in the medium refractive index layer forming composition as long as the refractive index of the medium refractive index layer satisfies the above formula (3). 30 mass parts or more are preferable with respect to 100 mass parts per minute, and 40 mass parts or more are more preferable. Further, the content of the medium refractive index organic compound in the composition for forming a medium refractive index layer is preferably 80 parts by mass or less, and preferably 70 parts by mass or less from the viewpoint of obtaining the laminate 3 having good transparency. More preferred.

  When adjusting the refractive index using a medium refractive index organic compound as the medium refractive index layer forming composition, it is preferable to add a leveling agent from the viewpoint of suppressing repellency defects.

  Examples of the leveling agent include silicone-based, fluorine-based, and acrylic leveling agents, and an acrylic leveling agent is preferable from the viewpoint that the adhesive layer can be formed without repellency.

  Examples of the acrylic leveling agent include BYK361N, BYK350, BYK352, BYK354, BYK355, BYK356, BYK358N, BYK380N, BYK381, BYK392, and BYK394 manufactured by BYK Corporation.

  In the present invention, if necessary, an antistatic component can be added to the medium refractive index layer forming composition to impart an antistatic function to the medium refractive index layer.

If imparting an antistatic function to the intermediate refractive index layer, the surface resistivity of the surface layer of the laminate 3 is preferably ¹⁰ 10 Ω / □ or less, more preferably 10 ⁸ Ω / □ or less.

  When the composition for forming a medium refractive index layer is an active energy ray-curable composition for forming a medium refractive index layer, the composition for forming a medium refractive index layer may contain a photoinitiator for the medium refractive index layer. it can.

  About the kind and addition amount of the photoinitiator for middle refractive index layers, it can be set as the compound and addition amount similar to the photoinitiator for antifouling layers.

  When the composition for forming a medium refractive index layer is a thermosetting composition for forming a medium refractive index layer, a composition for forming a medium refractive index layer may contain a thermosetting agent for the medium refractive index layer. it can.

  About the kind and addition amount of the thermosetting agent for medium refractive index layers, it can be set as the compound and addition amount similar to the thermosetting agent for antifouling layer formation.

  In the present invention, the intermediate refractive index layer forming composition can be blended with various additives such as slip improvers, leveling agents, ultraviolet absorbers, and light stabilizers such as HALS, if necessary. .

  As a compounding quantity of an additive, 10 mass parts or less are preferable with respect to 100 mass parts of solid content in a middle refractive index layer formation composition at the transparency point of a middle refractive index layer.

  In the present invention, an aminosilane that can be added to the composition for forming a high refractive index layer as necessary in terms of obtaining the laminate 3 having excellent scratch resistance in the medium refractive index layer forming composition. You may add the same compound.

  In the present invention, in order to adjust the solid content concentration of the medium refractive index layer forming composition, a medium refractive index layer dilution solvent can be added to the medium refractive index layer forming composition.

  As the diluting solvent for the medium refractive index layer, when metal oxide fine particles for the medium refractive index layer are used in the medium refractive index layer forming composition, for example, toluene (volatilization rate: 240), butyl acetate (volatilization rate: 100) ), Methyl isobutyl ketone (volatilization rate: 165), 1-methoxy-2-propanol (volatilization rate: 66) and isopropanol (volatilization rate: 150).

  In the present invention, the diluting solvent for the medium refractive index layer is volatilized in that it forms an unevenly distributed layer structure having a film surface layer region (a1), a film center region, and a film surface layer region (a2) in the medium refractive index layer. Those containing a diluting solvent with a speed of 100 or less are preferred.

  The content of the diluting solvent having a volatilization rate of 100 or less is preferably 20% by mass or more, and more preferably 30% by mass or more in the diluting solvent for the medium refractive index layer. Further, the content of the diluting solvent having a volatilization rate of 100 or less is preferably 90% by mass or less and more preferably 80% by mass or less in order to dry in a short time, that is, in terms of increasing production efficiency.

  The solid content concentration of the medium refractive index layer forming composition is preferably 0.4 to 2% by mass. By setting the solid content concentration of the medium refractive index layer forming composition in the above range, the storage stability of the medium refractive index layer forming composition can be improved, and the film thickness tends to be easily controlled. It is in.

  Examples of the method for forming the middle refractive index layer include the following methods.

  First, a medium refractive index layer forming composition is applied to the surface of the obtained high refractive index layer to form a coating film of the medium refractive index layer forming composition.

  When the medium refractive index layer-forming composition contains a medium refractive index layer dilution solvent, the medium refractive index layer dilution solvent is volatilized to form a medium refractive index layer-forming composition coating film. Can be formed. The temperature for drying the diluting solvent for the medium refractive index layer is 50 ° C. from the viewpoint of forming an unevenly distributed layer structure having a film surface layer region (a1), a film center region and a film surface layer region (a2) in the medium refractive index layer. The above is preferable, and 60 ° C. or higher is more preferable. The temperature for drying the medium refractive index layer dilution solvent is preferably 140 ° C. or lower, more preferably 120 ° C. or lower. The time for drying the diluting solvent for the medium refractive index layer is preferably 30 seconds or more from the viewpoint of forming the unevenly distributed layer structure in the medium refractive index layer and removing the diluting solvent for the remaining medium refractive index layer. Is more preferable, and more preferably 1 minute 30 seconds or more. Moreover, as time to dry the dilution solvent for middle refractive index layers, from a viewpoint of productivity of this transfer film 3, 5 minutes or less are preferable and 3 minutes or less are more preferable.

  Next, the medium refractive index layer is obtained by curing the coating film of the medium refractive index layer forming composition.

  Examples of the method for applying the medium refractive index layer forming composition to the surface of the high refractive index layer include the same method as the method for applying the antifouling layer forming composition to the surface of the release film.

  Examples of the method of curing the coating film of the medium refractive index layer forming composition include a heat curing method when the medium refractive index layer forming composition is a thermosetting medium refractive index layer forming composition. In the case where the medium refractive index layer forming composition is an active energy ray-curable composition for medium refractive index layer, an active energy ray curing method may be mentioned.

  Method for curing active energy ray and composition for curing antifouling layer forming method using active energy ray when medium refractive index layer forming composition is active energy ray curable medium refractive index layer composition And the same methods and conditions as the curing conditions.

  In the present invention, when the coating film of the medium refractive index layer forming composition is cured, a partially cured product of the antifouling layer forming composition and a portion of the high refractive index layer forming composition, as necessary. At least one selected from cured products can be cured together.

  In the present invention, after forming the middle refractive index layer on the surface of the high refractive index layer of the transfer film 3, an adhesive layer described later can be formed as necessary. The medium refractive index layer before the adhesive layer is formed is not only a completely cured medium refractive index layer forming composition, but also part of the medium refractive index layer forming composition reacts as necessary. A cured partially cured product may be used.

  In the present invention, when the coating film of the medium refractive index layer forming composition is formed on the surface of the high refractive index layer, the interface strength between the high refractive index layer and the middle refractive index layer is improved, and this laminate 3 In order to improve the scratch resistance, the surface of the high refractive index layer can be subjected to discharge treatment such as corona treatment or plasma treatment.

Examples of the discharge treatment method and conditions include the same methods and conditions as the hydrophilic treatment methods and conditions during the formation of the high refractive index layer.

This transfer film 1-3
In the present transfer film 1, the surface of the release film is subjected to at least one surface treatment selected from a hydrophilic treatment and a treatment of applying and drying an organic solvent, and then the surface of the release film subjected to the surface treatment is prevented. It is a transfer film obtained by forming a dirty layer.

  In addition, the transfer film 2 is formed on the surface of the release film that has been surface-treated after at least one surface treatment of either a hydrophilic treatment or an organic solvent coating / drying process. This is a transfer film obtained by forming an antifouling layer and a high refractive index layer in this order.

  Further, the transfer film 3 is obtained by subjecting the surface of the release film to the surface of the release film that has been surface-treated after performing at least one surface treatment selected from a hydrophilic treatment and a treatment of applying and drying an organic solvent. 2 is a transfer film obtained by forming an antifouling layer, a high refractive index layer and a medium refractive index layer in this order.

  In this invention, a well-known protective film can be laminated | stacked on the surface which is not in contact with the film for peeling of this transfer film 1, 2, or 3 as needed.

  As a method for producing the present transfer film 3, for example, a metal oxide fine particle-containing layer is laminated in this order as an antifouling layer, a high refractive index layer, and a medium refractive index layer on at least one surface of a surface-treated release film. Examples include a method for producing a transfer film.

That is, after the antifouling layer is laminated on at least one surface of the surface-treated release film, the high refractive index layer is laminated, and then the metal oxide fine particles for the medium refractive index layer and the volatilization rate are formed on the surface of the high refractive index layer. The medium refractive index layer is laminated by drying the solvent at a temperature of 140 ° C. or lower after applying the metal oxide fine particle-containing composition for the medium refractive index layer, which contains a solvent containing 100% or less of a solvent of 20% by mass or more. Thus, the transfer film 3 is obtained.

Substrate The surface of the substrate used in the present invention has an antifouling layer, an antifouling layer and a high refractive index layer or an antifouling layer, a high refractive index layer and a medium refractive index layer in the transfer film 1, 2 or 3. Is formed by a transfer method.

  As a base material, a resin base material and an inorganic base material are mentioned, for example.

  Specific examples of the resin substrate include polymethyl methacrylate, a copolymer having a methyl methacrylate unit as a main constituent, a methacrylic resin such as a copolymer having an alkyl methacrylate unit as a main constituent, polystyrene, styrene-methyl Examples thereof include aromatic vinyl monomer unit-containing resins such as methacrylate copolymers, olefin resins such as cyclic polyolefins, polycarbonate resins such as polycarbonate (hereinafter referred to as “PC resins”), and multilayer materials of polycarbonate and different materials. .

  Specific examples of the inorganic substrate include glass.

  The base material may contain additives such as a colorant and a light diffusing agent as necessary. Further, the substrate may be transparent or opaque, but is preferably transparent from the viewpoint of performing ultraviolet irradiation from the substrate side.

In this invention, it does not specifically limit as thickness of a base material, The film-form thing or sheet-like thing of the thickness according to the objective can be selected.

This laminated body 1-3
The laminate 1 is a transfer film laminate in which the surface of the transfer film 1 on which the antifouling layer is formed is bonded to a substrate directly or through another layer with a coating film for forming an adhesive layer. It is obtained by forming the product 1, then obtaining the adhesive layer from the coating film for forming the adhesive layer to form the transfer film laminate 1, and thereafter peeling the release film from the transfer film laminate 1.

  Moreover, this laminated body 2 bonds the surface by which the high refractive index layer of this transfer film 2 was formed with the base material directly or through another layer for forming the adhesive layer. The transfer film laminate 2 is formed, then the adhesive layer is obtained from the coating film for forming the adhesive layer, the transfer film laminate 2 is formed, and then the release film is peeled off from the transfer film laminate 2 It is done.

  Furthermore, this laminated body 3 is a transfer film in which the surface on which the middle refractive index layer of the transfer film is formed is bonded to a substrate directly or via another layer with a coating film for forming an adhesive layer. It is obtained by forming the laminate 3 and then obtaining the adhesive layer from the coating film for forming the adhesive layer to form the transfer film laminate 3, and then peeling the release film from the transfer film laminate 3.

  In this laminate 2 or 3, the refractive index (Nx) of the antifouling layer, the refractive index (Nz) of the medium refractive index layer, and the refractive index (Ny) of the high refractive index layer satisfy the following formula (8).

Nx <Nz <Ny (8)
As thickness of this laminated body 1, 2, or 3, 0.2 mm or more is preferable at the point of the mechanical strength of this laminated body, and 10 mm or less is preferable at the point of productivity of this laminated body 1-3.

The thickness of the high refractive index layer of the present laminate in 3 _{(d KK),} the thickness of the medium refractive index layer _{(d CHK)} and refractive index of the adhesive layer _{(n HC)} is Equation (3) as well as the following formula (9) and It is preferable to satisfy (10). By satisfying these conditions, the interference pattern is suppressed and the surface of the laminate 3 having excellent scratch resistance tends to be obtained.
d _KK ≧ 500 nm (9)
90 nm ≧ d _CHK ≧ 30 nm (10)
In the present invention, the present laminate 1, 2 or 3 has a water contact angle of 90 ° or more and a triolein contact angle of 55 ° or more on the surface of the antifouling layer of this laminate 1, 2 or 3. Is preferred. By setting it as said antifouling layer, it exists in the tendency which can obtain this laminated body 1, 2, or 3 in which dirt, such as a fingerprint, sebum, and foundation, is not conspicuous.

Further, the antifouling layer of the present laminate 1, 2 or 3 is obtained in that the present laminate 1, 2 or 3 is suppressed in which the discoloration of the reflected color and the visibility reduction of the image display member are suppressed at the time of dirt adhesion. The water contact angle of the surface is preferably 95 degrees or more and the triolein contact angle is 60 degrees or more.

The coating film for forming the adhesive layer for forming the adhesive layer is a coating film for forming the adhesive layer described later.

  Examples of the coating film for forming the adhesive layer include a thermoplastic resin coating film for an adhesive layer containing a thermoplastic resin and a curable coating film for an adhesive layer containing an active energy ray-curable adhesive layer composition. Can be mentioned.

  When the coating film for forming the adhesive layer is a thermoplastic resin coating film for the adhesive layer, as the adhesive layer forming material used, for example, a thermoplastic resin in which a thermoplastic resin is dissolved in a diluent solvent for the thermoplastic resin Resin solutions can be used.

  Examples of the diluent solvent for the thermoplastic resin include methyl ethyl ketone, methyl isobutyl ketone, isopropanol, ethanol, 1-methoxy-2-propanol, and toluene.

  Examples of the thermoplastic resin for forming the thermoplastic resin coating film for the adhesive layer include acrylic resins, chlorinated olefin resins, vinyl chloride-vinyl acetate copolymers, maleic acid resins, and chlorinated rubber resins. Cyclized rubber resin, polyamide resin, coumarone indene resin, ethylene-vinyl acetate copolymer, polyester resin, polyurethane resin, styrene resin, butyral resin, rosin resin and epoxy resin It is done. These may use only 1 type and may use 2 or more types together.

  When the coating film for forming the adhesive layer is a curable coating film for the adhesive layer, for example, a composition similar to the crosslinking component for the antifouling layer can be used as the adhesive layer forming material to be used. .

  Only one type of active energy ray-curable adhesive layer composition may be used, or two or more types may be used in combination.

  As a photoinitiator added to the composition for active energy ray hardening adhesive layers, the thing similar to the photoinitiator used when mix | blending in the composition for antifouling layer formation is mentioned, for example. These may use only 1 type and may use 2 or more types together.

As a method for forming a coating film for forming an adhesive layer, for example, the surface of the antifouling layer, the high refractive index layer or the medium refractive index layer in the present transfer film 1, 2 or 3, or the present transfer film 1, 2 or 3 When laminating the substrate and the base material, the thermoplastic resin solution or the active energy ray is applied to the surface of the antifouling layer, the high refractive index layer, the medium refractive index layer or the surface of the base material in the transfer film 1, 2 or 3. The method of forming the thermoplastic resin coating film for contact bonding layers or the curable coating film for contact bonding layers by removing the dilution solvent for contact bonding layers after apply | coating the composition for curable contact bonding layers is mentioned.

Transfer film laminates 1-3
The transfer film laminate 1, 2 or 3 is used to form an adhesive layer on the surface of the transfer film 1, 2 or 3 on which the antifouling layer, high refractive index layer or medium refractive index layer is formed. It is obtained by laminating the coating film directly or through another layer.

  In the present invention, when a curable coating film for an adhesive layer is used as a coating film for forming an adhesive layer, the present transfer film 1, 2 or 3 is bonded to the substrate via the curable coating film for the adhesive layer. To obtain a transfer film laminate 1, 2 or 3.

  The coating film for forming the adhesive layer may be provided in advance on the transfer film 1, 2 or 3, or may be provided in advance on the substrate.

  In the present invention, when a curable coating film for an adhesive layer is used as a coating film for forming an adhesive layer, the transfer film laminate 1, 2, or 3 is irradiated with active energy rays to transfer film 1, It can be implemented via 2 or 3. Moreover, according to the shape of a base material, you may irradiate an active energy ray from the base material side as needed.

In the present invention, if necessary, the antifouling layer of the transfer film 1, 2 or 3, a high refractive index layer or a medium refractive index layer and an adhesive layer between the hard coat layer, a layer that absorbs a specific wavelength, etc. Can be formed.

Adhesive layer In the present invention, the adhesive layer is for adhering the transfer film 1, 2 or 3 and the substrate.

  In the present invention, when the adhesive layer is formed, the transfer film 1, 2 or 3 is incorporated in a state of being laminated on the surface of the antifouling layer, the high refractive index layer or the middle refractive index layer, In addition, any of the cases where an adhesive layer is formed between the transfer film 1, 2 or 3 and the substrate when the transfer film 1, 2 or 3 and the substrate are laminated may be used.

  In any of the above cases, the refractive index of the adhesive layer preferably satisfies the above formula (3) from the viewpoint of suppressing the interference pattern of the present laminate 1, 2 or 3.

  The refractive index (nHC) of the adhesive layer is preferably 1.45 to 1.56.

  Further, when the refractive index difference between the base material and the adhesive layer becomes large and the refractive interface clearly exists, light reflection occurs at the interface between the base material and the adhesive layer, which causes a new interference pattern. Therefore, in order to eliminate the refractive interface between the base material and the adhesive layer, it is preferable to sufficiently penetrate the adhesive layer into the base material or to suppress the refractive index difference between the base material and the adhesive layer to 0.03 or less.

  In the present invention, as a method for forming an adhesive layer, for example, when a thermoplastic resin solution in which a thermoplastic resin is dissolved in a diluent solvent for an adhesive layer is used as the adhesive layer forming material, the adhesive layer is formed by a known method. For example, a method for obtaining an adhesive layer by volatilizing a diluting solvent for use. Moreover, as an adhesive layer forming material, for example, when an active energy ray-curable adhesive layer composition diluted with an adhesive layer dilution solvent is used, after volatilizing the adhesive layer dilution solvent by a known method, The method of hardening on the conditions similar to the active energy ray hardening conditions at the time of hardening the composition for high refractive index layer formation is mentioned.

In the present invention, when an adhesive layer is formed using an active energy ray-curable composition, a partially cured product of a composition for forming an antifouling layer, for forming a high refractive index layer, if necessary. At least one of the partially cured product of the composition and the partially cured product of the medium refractive index layer forming composition can be cured together with the curing of the coating film for forming the adhesive layer.

Transfer film laminates 1 to 3
The transfer film laminate 1, 2 or 3 is a laminate in which the surface of the antifouling layer, high refractive index layer or medium refractive index layer of the present transfer film 1, 2 or 3 and the substrate are laminated via an adhesive layer. It is.

  As a method for producing the transfer film laminate 1, 2 or 3, a coating film for forming an adhesive layer on the antifouling layer, high refractive index layer or medium refractive index layer of the present transfer film 1, 2 or 3 is used. A method of obtaining the adhesive layer after laminating the formed film with the base material so that the surface on which the coating film for forming the adhesive layer of the transfer film 1, 2 or 3 is formed is in contact with the base material, or of the base material Any method of laminating the surface of the transfer film 1, 2 or 3 with the antifouling layer, the high refractive index layer or the middle refractive index layer of the transfer film 1, 2 or 3 may be used. .

  Examples of the method of laminating the substrate and the present transfer film 1, 2 or 3 include a method of pressure bonding with a rubber roll.

  In the pressure bonding, for example, the pressure bonding can be performed under a condition of 5 to 15 MPa. Moreover, it is preferable to heat the surface of the base material to laminate | stack at 40-125 degreeC. By setting the heating condition to this condition, the adhesion between the transfer film 1, 2 or 3 and the substrate can be improved, the hardness decrease due to excessive dissolution of the substrate is suppressed, and the adhesive layer It tends to suppress yellowing.

  The surface temperature of the base material when heating the base material can be adjusted by the set temperature of the heating unit, the heating time, and the like. Moreover, as a measuring method of the temperature of a base material, the method by a non-contact-type surface thermometer is mentioned, for example.

  In the present invention, if necessary, the antifouling layer, the high refractive index layer or the high refractive index layer which has been sufficiently cured by promoting the curing of the antifouling layer, the high refractive index layer or the medium refractive index layer during the above-described heating treatment, or A medium refractive index layer can be obtained.

  In the present invention, if necessary, in addition to the above treatment, active energy rays are irradiated to promote curing of the antifouling layer, the high refractive index layer or the medium refractive index layer, thereby sufficiently curing and preventing the contamination. A dirty layer, a high refractive index layer, or a medium refractive index layer can be obtained.

  In the present invention, in order to prevent air entrainment when laminating the substrate and the present transfer film 1, 2, or 3, a coating film for forming an adhesive layer using an excessive amount of the adhesive layer forming material is provided. It is preferable to obtain.

  When peeling the peeling film from the transfer film laminate 1, 2 or 3, for example, the peeling film can be peeled from the transfer film laminate 1, 2 or 3 by a known method at room temperature.

Hereinafter, the present invention will be described by way of examples. In addition, the abbreviations of the compounds used in Examples and Comparative Examples are as follows. In the following, “part” and “%” represent “part by mass” and “% by mass”, respectively.
“Thruria S”: Isopropyl alcohol (IPA) dispersion of hollow silica sol (solid content 20%) (trade name, manufactured by JGC Catalysts & Chemicals Co., Ltd.)
“KBM503”: 3-methacryloxypropyltrimethoxysilane (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.)
"Toluene": (Wako Pure Chemical Industries, Ltd.)
“DAC”: a solution of a fluorine group-containing polyether compound having a perfluoropolyether group and an active energy ray reactive group (manufactured by Daikin Industries, Ltd., solid concentration 20%, 2,2,3,3-tetrafluoro -1-propanol solution, trade name: OPTOOL DAC)
“M400”: Dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., trade name: Aronix M400)
“IRGACURE184”: 1-hydroxy-cyclohexyl-phenyl-ketone (trade name, manufactured by Ciba Japan Co., Ltd.)
“PGM”: 1-methoxy-2-propanol (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
"ZRT15WT% -E28": zirconia toluene dispersion (solid content 15%)
77% of zirconia fine particles in the total amount of KBM503 and zirconia fine particles (CIK Nanotech Co., Ltd., trade name)
“KBM602”: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.)
“DAROCUR TPO”: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name, manufactured by Ciba Japan Co., Ltd.)
“ZRT15WT% -E30”: Toluene dispersion of zirconia (solid content concentration: 15%) KBM503 and the ratio of zirconia fine particles in the total amount of zirconia fine particles 67% (product name, manufactured by CIK Nanotech Co., Ltd.)
“IPA”: i-propanol (Wako Pure Chemical Industries, Ltd.)
“U6HA”: urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Oligo U6-HA)
“C6DA”: 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscote # 230)
“M305”: Pentaerythritol triacrylate (manufactured by Toa Gosei Co., Ltd., trade name: Aronix M305)
The evaluation method implemented by this invention is shown below.
(1) Temperature of the substrate The surface temperature of the substrate was measured using a non-contact surface thermometer (manufactured by Chino Co., Ltd., handy type radiation thermometer IR-TA (trade name)), and the temperature of the substrate. It was.
(2) Total light transmittance and haze value Based on the measurement method shown by JIS K7361-1 using the Nippon Denshoku Industries Co., Ltd. HAZE METER NDH2000 (brand name), the total light transmittance of a laminated body is obtained. It measured and the haze value was measured based on the measuring method shown by JISK7136.
(3) Scratch resistance A circular pad with a diameter of 25.4 mm fitted with # 0000 steel wool was placed on the surface of the antifouling layer of the laminate, and 20 mm distance was scratched twice under a load of 2.0 kg. The difference between haze values before and after scratch (Δhaze) was determined from the following formula, and the number of scratches on the sample surface after the test was counted to evaluate the scratch resistance.
[Δhaze (%)] = [haze value after abrasion (%)] − [haze value before abrasion (%)]
(4) Anti-reflective property The surface of the laminate, on which the antifouling layer is not laminated, is roughened with sandpaper and then applied with a matte black spray as an evaluation sample, and a spectrophotometer (Hitachi, Ltd.) Product, product name: U-4000), and measuring the reflectance of the surface of the antifouling layer of the sample for evaluation in accordance with the measurement method shown in JIS R3106 at an incident angle of 5 ° and a wavelength of 380 to 780 nm. Then, the wavelength with the lowest reflectance (bottom wavelength) and the reflectance at the bottom wavelength (bottom wavelength reflectance) of the obtained reflectance curve were obtained.

Moreover, the presence or absence of a change in reflected color when a fingerprint was attached to the surface of the antifouling layer of the laminate was evaluated according to the following criteria.
(Double-circle): The change of reflected color was not recognized.
○: A slight change in the reflected color is observed.
X: Change in reflected color was observed.
(5) Antifouling property The antifouling property of the antifouling layer of the laminate was evaluated by the following water contact angle, triolein contact angle and oil-based ink wiping property.
(A) Water contact angle In an environment of 23 ° C. and 50% relative humidity, a drop of 0.2 μL of ion-exchanged water was dropped on the surface of the antifouling layer of the laminate, and a portable contact angle meter (Fibro system ab company) The contact angle between water and the antifouling layer was measured using a product, product name: PG-X) to determine the water contact angle.
(B) Triolein contact angle The triolein contact angle was calculated | required like the case of the water contact angle measurement except having used triolein instead of ion-exchange water.
(C) Oil-based ink wiping property Write a line with “My Name” (black) (trade name, manufactured by Sakura Crepas Co., Ltd.) as oil-based ink on the surface of the antifouling layer of the laminate. The product was wiped off with Nippon Paper Crecia Co., Ltd. (trade name), and the wiping of the oil-based ink at that time was visually evaluated according to the following criteria.
A: Completely wiped off by wiping 5 times.
○: A trace of a line remains slightly after wiping 5 times.
X: Part or all of the oil-based ink remains adhered after wiping 5 times.
(6) Adhesiveness In accordance with JIS K5600-5-6, evaluation of peeling of 25 square grids was carried out at four locations, and the number of squares remaining without peeling in 100 squares was used to prevent the laminate. The adhesion of the dirty layer was evaluated.
(7) Film thickness of each layer A sample having a width of 100 nm was cut out with a microtome in the thickness direction of the laminate, and a cross section of the laminate was observed with a transmission electron microscope (JEM-1010 (trade name) manufactured by JEOL Ltd.). The film thickness of each layer was measured.
(8) Sweat resistance An artificial sweat solution was prepared according to Method A of the dyeing fastness test for sweat of JIS L0848.

The laminate was cut into a size of 50 × 50 mm to obtain a sample for evaluation. Next, the absorbent cotton was cut into a size of 30 × 30 mm, placed on the sample for evaluation, and using an injector, artificial sweat was dripped onto the absorbent cotton to wet the absorbent cotton. The sample was left in a constant temperature and humidity machine at a temperature of 45 ° C. and a relative humidity of 95% for 96 hours and then taken out. After the surface of the laminate was washed with water, the sweat resistance was evaluated by visual evaluation according to the following criteria.
○: No discoloration was observed.
X: Discoloration was recognized.
(9) Refractive index measurement The refractive index of the antifouling layer, the high refractive index layer, the middle refractive index layer or the adhesive layer in the 594 nm laser was measured using a prism coupler (manufactured by Metricon Corporation, model 2010).
(10) Interference pattern The presence or absence of an interference pattern was evaluated on the surface of the laminate by visual observation by five persons under a three-wavelength fluorescent tube (manufactured by Toshiba Corporation, trade name: Mellow 5 40W) according to the following criteria.
A: The interference pattern is not visible even when the angle is changed.
○: The interference pattern appears thin when the angle is changed.
Δ: The interference pattern looks prominent when the angle is changed. ×: The interference pattern appears prominent without changing the angle.
(11) Film center region thickness (Tbi and Tci) in the middle refractive index layer, film surface layer region (a1) thickness (Tai), film surface layer region (a2) thickness (Tdi), and film center region length A sample having a width of 100 nm was cut out with a microtome in the thickness direction of the body (thickness Tnm).

  Using a transmission electron microscope (JEM-1010 (trade name) manufactured by JEOL Ltd.), the distribution state of the metal oxide fine particles in the medium refractive index layer was photographed with respect to the thickness direction cross section of the above sample. .

  A schematic diagram of the state of distribution of metal oxide fine particles in the photograph of the cross section in the thickness direction of the obtained sample is shown in FIG.

In the photograph, the total length of the length (Li) of the central region of the film in which the metal oxide fine particles do not exist at a length of 1200 nm in the vertical direction with respect to the film thickness of the middle refractive index layer in the cross section in the thickness direction. (L) was calculated. For example, in FIG. 1, in the sample cross-sectional length of 1,200 nm, the film center region thickness (Tbi and Tci) satisfying the expressions (4) and (6) and the film surface layer area (a1) thickness ( Tai) and the thickness (Tdi) of the membrane surface layer region (a2), and the total length of L1, L2, L3, and L4 at these measured locations (D1, D2, D3 outside the scope of the present invention) And the length excluding the portion of D4) is the total length (L) of the length (Li) of the central region of the film where the metal oxide fine particles are not present.
(12) Appearance Appearance was observed by irradiating light from the edge of the laminate with an edge light in a dark room. Appearance defects are observed as black and white shading when irradiated with edge light.
A: Appearance defect is not recognized.
○: Slightly poor appearance is recognized.
(Triangle | delta): Appearance defect is recognized dimly. X: A remarkable appearance defect is recognized.
[Production Example 1] Production of silica sol (1) A 4-necked flask reaction vessel equipped with a stirrer and a cooling tube was charged with 63 g of sulria S, which is a hollow silica sol dispersion, and then 12 g of KBM503 was added.

  Thereafter, 4.4 g of water and 0.1 g of a 0.01 mol / l hydrochloric acid aqueous solution were sequentially added while stirring and heated at 80 ° C. for 2 hours.

  Next, the reaction system was put under reduced pressure to distill volatile components until the solid content concentration reached 40%, and then 38 g of toluene was added and heated at 80 ° C. for 2 hours.

  Thereafter, the reaction system was reduced in pressure to distill volatile components until the solid concentration reached 60%, and further heated at 80 ° C. for 2 hours to produce silica sol (1) in which the surface of the hollow silica particles was treated. .

  Silica sol (1) was a cloudy liquid with a solid content of 60%.

  In addition, solid content concentration calculated | required by calculation from the mass difference before and behind drying by heating and drying silica sol (1) for 3 days in an 80 degreeC environment.

Moreover, the ratio (%) of the inorganic fine particles in the silica sol (1) was obtained from the mass ratio of the inorganic fine particles to 100 parts in total of KBM503, which is the hydrolyzable silane compound used, and the solid content of the Sururia S.
[Formulation Example 1] Preparation of Antifouling Layer-Forming Composition (1) As the antifouling layer-forming composition, the antifouling layer-forming composition (1) shown in Table 1 was prepared in an environment at 25 ° C.

［調合例２］高屈折率層用組成物（１）の調合
高屈折率層用組成物として、表２に示す高屈折率層用組成物（１）を２５℃の環境下で調合した。

[Formulation Example 2] Preparation of High Refractive Index Layer Composition (1) As a high refractive index layer composition, the high refractive index layer composition (1) shown in Table 2 was prepared in an environment of 25 ° C.

［調合例３］中屈折率層用組成物（１）の調合
中屈折率層用組成物として、表３に示す中屈折率層用組成物（１）を２５℃の環境下で調合した。

[Formulation Example 3] Preparation of Medium Refractive Index Layer Composition (1) As the medium refractive index layer composition, the medium refractive index layer composition (1) shown in Table 3 was prepared in an environment of 25 ° C.

［実施例１］
厚さ１００μｍのＰＥＴフィルム（（株）東洋紡、商品名：Ａ４１００）の表面を以下の条件でコロナ処理し、表面処理剥離用フィルムを得た。

[Example 1]
The surface of a PET film having a thickness of 100 μm (Toyobo Co., Ltd., trade name: A4100) was subjected to corona treatment under the following conditions to obtain a film for surface treatment peeling.

  As the corona treatment device, a corona treatment device POLYDYNE (trade name) manufactured by Navitas Co., Ltd. was used. Moreover, the electrode made from SUS of thickness 1mm and length 260mm was used as an electrode.

  Corona treatment by passing the peeling film placed on the conveyor belt with the PET side up and passing through the lower part of the electrode at a film-electrode gap of 3 mm, an applied voltage of 11.6 kV and a peeling film conveyance speed of 2.0 m / min. Carried out. The irradiation energy for the peeling film was 100 W · min / m.

  The antifouling layer-forming composition (1) was allowed to stand for 30 minutes in an environment at 25 ° C. on the corona-treated surface of the PET film, and then applied using a No. 10 bar coater. It was dried for 5 minutes and at 150 ° C. for 1 minute to form a coating film of the composition for forming an antifouling layer.

Next, the PET film on which the coating film for the antifouling layer forming composition was laminated was placed at a position 20 cm below the 9.6 kW high-pressure mercury lamp (output setting 100%) under a nitrogen stream. The coating film of the antifouling layer forming composition was cured by passing at a speed of 5 m / min to obtain a transfer film on which the antifouling layer was laminated. The integrated light quantity at this time was 400 mJ / cm ² and the peak illuminance was 260 mW / cm ² .

  U6HA 10 parts, C6DA 30 parts, M305 30 parts, and M400 30 parts as the adhesive layer forming material on the surface of acrylite EX001 (Mitsubishi Rayon Co., Ltd. methacrylic resin board, product name) having a thickness of 2 mm as a base material And the surface of the antifouling layer through the coating film for forming the adhesive layer formed using the composition for active energy ray-curable adhesive layer obtained by mixing DAROCUR TPO Was laminated so as to be in contact with the substrate, and then heated to 60 ° C. to obtain a transfer film laminate.

The above transfer film laminate was heated at 60 ° C. for 60 seconds and then passed through a PET film at a speed of 2.5 m / min at a position 20 cm below a metal halide lamp with an output of 9.6 kW. The coating film for forming the adhesive layer was cured to form an adhesive layer, and a transfer film laminate was obtained. As the curing conditions of the coating film for forming the adhesive layer, the integrated light amount was 570 mJ / cm ² and the peak illuminance was 220 mW / cm ² . The adhesive layer had a refractive index of 1.52.

  Next, the PET film was peeled from the transfer film laminate to obtain a laminate.

  The thickness of the adhesive layer in the obtained laminate was 13 μm, and the thickness of the antifouling layer was 100 nm. Further, the total light transmittance of the laminate was 93.8%, the haze value was 0.1%, and the transparency was excellent.

  The Δhaze after the scratch test on the surface of the antifouling layer of the laminate was 0.24%, and the number of scratches was 5. Moreover, the adhesiveness of the antifouling layer of a laminated body and a base material was favorable.

  As for the sweat resistance of the surface of the antifouling layer of the laminate, no discoloration was observed. The bottom wavelength of the antifouling layer of the laminate was 620 nm, and the bottom wavelength reflectance was 2.0%.

  Furthermore, even if a fingerprint was attached to the surface of the antifouling layer of the laminate, no change in the reflected color was observed. In the evaluation of the interference pattern, no interference pattern was confirmed even when the angle was changed.

  The water contact angle on the surface of the antifouling layer of the laminate was 105 degrees, and the triolein contact angle was 65 degrees. Moreover, the oil-based ink wiping property on the surface of the antifouling layer of the laminate was at a level that could be completely wiped by wiping five times.

When the appearance of the laminate was observed, a slight appearance defect was recognized.
[Example 2]
The surface of a 100 μm-thick PET film (Toyobo Co., Ltd., trade name: A4100) is 4.5 m / min at a position 20 cm below a 9.6 kW high-pressure mercury lamp (output setting 100%) under air. The film was made to pass through and subjected to hydrophilic treatment by ultraviolet irradiation treatment to obtain a film for surface treatment peeling.

Two high-pressure mercury lamps were lit. The integrated light quantity at this time was 800 mJ / cm ² and the peak illuminance was 260 mW / cm ² .

  A transfer film and a laminate were produced in the same manner as in Example 1 except that the above hydrophilization treatment was used instead of the corona treatment. Table 4 shows the obtained results.

［実施例３］
厚さ１００μｍのＰＥＴフィルム（（株）東洋紡、商品名：Ａ４１００）の表面にＰＧＭを１０号バーコーターを用いて塗布し、８０℃で１．５分間及び１２０℃で１分間乾燥させて表面処理剥離用フィルムを得た。

[Example 3]
PGM was applied to the surface of a 100 μm thick PET film (Toyobo Co., Ltd., trade name: A4100) using a No. 10 bar coater, and dried at 80 ° C. for 1.5 minutes and 120 ° C. for 1 minute for surface treatment. A release film was obtained.

A transfer film and a laminate were produced in the same manner as in Example 1 except that the above organic solvent was applied and dried instead of the corona treatment. Table 4 shows the obtained results.
[Example 4]
The surface of a 100 μm-thick PET film (Toyobo Co., Ltd., trade name: A4100) was subjected to corona treatment in the same manner as in Example 1, and then coated and dried in the same manner as in Example 3 to remove the surface-treated release film. Got.

A transfer film and a laminate were produced in the same manner as in Example 1 except that the above surface treatment peeling film was used. Table 4 shows the obtained results.
[Example 5]
The surface of a PET film having a thickness of 100 μm (Toyobo Co., Ltd., trade name: A4100) was subjected to the same ultraviolet irradiation treatment as in Example 2, and then applied and dried in the same manner as in Example 3 to remove the surface treatment. A film was obtained.

A transfer film and a laminate were produced in the same manner as in Example 1 except that the above surface treatment peeling film was used. Table 4 shows the obtained results.
[Example 6]
After coating and drying PGM on the surface of a PET film having a thickness of 100 μm (Toyobo Co., Ltd., trade name: A4100) in the same manner as in Example 3, it was subjected to corona treatment in the same manner as in Example 1 and subjected to surface treatment peeling film Got.

A transfer film and a laminate were produced in the same manner as in Example 1 except that the above surface treatment peeling film was used. Table 4 shows the obtained results.
[Example 7]
After PGM was applied to the surface of a 100 μm thick PET film (Toyobo Co., Ltd., trade name: A4100) and dried in the same manner as in Example 3, UV irradiation treatment was performed in the same manner as in Example 2 for surface treatment peeling. A film was obtained.

A transfer film and a laminate were produced in the same manner as in Example 1 except that the above surface treatment peeling film was used. Table 4 shows the obtained results.
[Example 8]
In the same manner as in Example 1, a transfer film on which an antifouling layer was laminated was obtained. Subsequently, the surface of the antifouling layer of the transfer film was subjected to corona treatment in the same manner as in Example 1.

  Further, the composition for forming a high refractive index layer (1) was left on the surface of the antifouling layer treated with corona for 30 minutes in an environment of 25 ° C., and then applied using a No. 10 bar coater. And dried at 150 ° C. for 1 minute to form a coating film of the composition for forming a high refractive index layer.

Next, the laminate on which the coating film of the composition for forming a high refractive index layer was formed was 4.5 m / min at a position 20 cm below a 9.6 kW high-pressure mercury lamp (output setting 100%) under air. The coating film of the composition for forming a high refractive index layer was cured by passing it at a speed of 1 to obtain a laminate in which the high refractive index layer was laminated. Two high-pressure mercury lamps were lit. The integrated light quantity at this time was 800 mJ / cm ² and the peak illuminance was 260 mW / cm ² .

  Further, the medium refractive index layer-forming composition (1) was left on the surface of the high refractive index layer for 30 minutes in an environment of 25 ° C., and then applied using a No. 10 bar coater, and then applied at 80 ° C. for 1.5 minutes and 120 The coating film of the composition for forming a medium refractive index layer was formed by drying at 0 ° C. for 1 minute.

Next, the laminate on which the coating film of the composition for forming a medium refractive index layer was formed was 4.5 m / min at a position 20 cm below a high-pressure mercury lamp (output setting 100%) of 9.6 kW under air. The film of the composition for forming a medium refractive index layer is cured by passing the film at a speed of 2 to obtain a transfer film in which an antifouling layer, a high refractive index layer and a medium refractive index layer are sequentially laminated on the surface of the peeling film. It was. The integrated light quantity at this time was 400 mJ / cm ² and the peak illuminance was 260 mW / cm ² .

  Active energy ray-curable adhesive layer obtained by mixing U6HA 10 parts, C6DA 30 parts, M305 30 parts, M400 30 parts and DAROCUR TPO as the adhesive layer forming material on the surface of the intermediate refractive index layer of the obtained transfer film The composition for coating was applied using a No. 10 bar coater to form a coating film for forming an adhesive layer.

  The above transfer film was laminated on the surface of acrylite EX001 having a thickness of 2 mm as a base material heated to 60 ° C. through a coating film for forming an adhesive layer, and a transfer film laminate was obtained. .

The above transfer film laminate was heated at 60 ° C. for 60 seconds and then passed through a PET film at a speed of 2.5 m / min at a position 20 cm below a metal halide lamp with an output of 9.6 kW. The coating film for forming the adhesive layer was cured to form an adhesive layer, and a transfer film laminate was obtained. As the curing conditions of the coating film for forming the adhesive layer, the integrated light amount was 570 mJ / cm ² and the peak illuminance was 220 mW / cm ² .

  Next, the PET film was peeled from the transfer film laminate to obtain a laminate.

The thickness of the adhesive layer in the obtained laminate was 13 μm. Table 4 shows the obtained results.
[Example 9]
The same surface-treating release film as in Example 3 was used. Other than that was carried out similarly to Example 8, and obtained the laminated body. Table 4 shows the obtained results.
[Example 10]
The same surface treatment release film as that used in Example 4 was used. Other than that was carried out similarly to Example 8, and obtained the laminated body. Table 4 shows the obtained results.
[Example 11]
The same surface-treating release film as that used in Example 6 was used. Other than that was carried out similarly to Example 8, and obtained the laminated body. Table 4 shows the obtained results.
[Comparative Example 1]
A PET film (Toyobo Co., Ltd., trade name: A4100) having a thickness of 100 μm was used as a peeling film, and no surface treatment was performed. Other than that was carried out similarly to Example 1, and obtained the laminated body. The results obtained are shown in Table 5.

  Since the surface of the peeling film was not subjected to a hydrophilization process or a process of applying / drying an organic solvent, poor appearance was observed in the obtained laminate.

T: Thickness Ta1: Thickness Ta2 of first film surface region (a1): Thickness of second film surface layer region (a1) Tai: Thickness of i-th film surface layer region (a1) Tb1: First film center region Thickness Tb2: thickness of second film center region Tbi: thickness of i-th film center region Tc1: thickness of first film center region Tc2: thickness of second film center region Tci: i-th film center region Thickness Td1: thickness of the first film surface area (a2) Td2: thickness of the second film surface area (a2) Tdi: thickness of the i-th film surface area (a2) L1: thickness of the first film center area Length L2: Length of the second film central region L3: Length of the third film central region L4: Length of the fourth film central region Li: Length of the i-th film central region

Claims (7)

The surface of the release film is subjected to at least one surface treatment selected from a hydrophilic treatment and an organic solvent having a boiling point of 200 ° C. or less and dried at a drying temperature of 80 to 130 ° C., and then the release film. A method for producing a transfer film, wherein an antifouling layer is formed on the surface subjected to the surface treatment.   The method for producing a transfer film according to claim 1, wherein the hydrophilization treatment is at least one selected from a corona treatment and an ultraviolet irradiation treatment. The method for producing a transfer film according to claim 1 or 2 , wherein the peeling film is an aromatic polyester film. The method for producing a transfer film according to claim 3 , wherein the aromatic polyester film is a polyethylene terephthalate film or a polyethylene naphthalate film. The surface of the release film is subjected to at least one surface treatment selected from a hydrophilic treatment or an organic solvent having a boiling point of 200 ° C. or less and dried at a drying temperature of 80 to 130 ° C., and then the release film. A transfer film manufacturing method in which an antifouling layer and a high refractive index layer are formed in this order on the surface subjected to the surface treatment , wherein the refractive index (n _KK ) of the high refractive index layer is 1.6 or more. A method for producing a film . The surface of the release film is subjected to at least one surface treatment selected from a hydrophilic treatment or an organic solvent having a boiling point of 200 ° C. or less and dried at a drying temperature of 80 to 130 ° C., and then the release film. A method for producing a transfer film in which an antifouling layer, a high refractive index layer, and a medium refractive index layer are formed in this order on the surface subjected to the surface treatment , wherein the refractive index (n _KK ) of the high refractive index layer is 1. A method for producing a transfer film, which is 6 or more, wherein the refractive index (n _CHK ) of the medium refractive index layer is 1.5 to 1.65 . After obtaining the transfer film in the manufacturing method according to any one of claims 1 to 6, the antifouling layer is formed side surface of the transfer film, a coating for forming an adhesive layer directly or A transfer film laminate is formed by laminating with a base material via another layer, and then an adhesive layer is obtained from a coating film for forming an adhesive layer to form a transfer film laminate, and then the transfer film laminate The manufacturing method of the laminated body which peels the film for peeling from.

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