JP4539840B2 - Photocurable resin composition and method for producing laminate using the same - Google Patents

Description

  The present invention relates to a photocurable resin composition and a laminate using the same, and more specifically, a pot life is long, and a low refractive index film that can be cured in a short time under mild conditions can be obtained. The present invention relates to a photocurable resin composition, a laminate using the same, and a method for producing the same.

  An antireflection function is cited as one of the required performances of the image display board. The general principle of the antireflection function is to provide a low refractive index layer on the surface of the high refractive index layer and use the difference in optical path between the light reflected by the high refractive index layer and the light reflected by the low refractive index layer. Thus, the reflected light is reduced by causing interference with each other.

  An antireflection function is cited as one of the required performances of the image display board. The general principle of the antireflection function is to provide a low refractive index layer on the surface of the high refractive index layer and use the difference in optical path between the light reflected by the high refractive index layer and the light reflected by the low refractive index layer. Thus, the reflected light is reduced by causing interference with each other.

  Conventionally, such an antireflection film is produced by using a dry coating method such as a vapor deposition method or a sputtering method. According to the dry coating method, it is possible to produce a uniform film, but there is a problem that the production cost is high because the production speed is low. Therefore, in recent years, as a method for producing an antireflection film at a lower cost, a function in which a wet coating method capable of forming a film in a short time on a release substrate under a milder condition than a dry coating method is used. Attention has been focused on a method of transferring a layer (transfer layer) to the surface of a transfer medium or pressure-sensitive transfer (that is, transfer method), and attempts have been made to use the transfer layer as an antireflection film.

  By the way, as a low refractive index material used for an antireflection film, a composition containing a fluorine-based compound or a silane-based compound is generally used in order to lower the refractive index.

  As a composition containing a fluorine compound, a composition containing a low molecular fluorine compound having a reactive group (Patent Document 1, Patent Document 2), an inert fluorine-containing polymer and a compound having a reactive group are included. What is contained has been proposed (Patent Document 3). Although not intended as a low-refractive index material, an acrylic elastomer having the same level of surface tension as a general low-refractive index material is a (meth) acrylic copolymer having a fluoroalkyl group and a reactive group. Coalescence has also been proposed (Patent Document 4). Further, in order to improve storage stability while being a low refractive index material, a material using a reactive fluorine-containing polymer having a fluorine atom in the main chain has been proposed (Patent Document 10).

  However, in the case of the resin composition of Patent Document 1 or Patent Document 2, since the intermolecular force of the contained fluorine compound is weak, a toxic fluorine compound may be volatilized when the resin composition is applied. In the case of the resin composition of Patent Document 3, although the possibility of volatilization of the inert fluorine-containing polymer after coating is reduced, a reactive group is obtained when attempting to obtain a film having a lower refractive index. There is a problem in that the amount of the compound having a relatively small amount is relatively reduced and the strength of the film itself is weakened. Moreover, when the acrylic elastomer of patent document 4 is used as a low refractive index film, it must be heated at the time of coating. Therefore, there is a risk of thermal deformation when the base material is plastic. Moreover, since it takes time to form a film under mild conditions, productivity may be reduced.

  On the other hand, as a resin composition containing a silane compound, a low molecular silane compound having a silyl group added with a photoacid generator (Patent Document 5), a combination of a fluorine-containing silicate compound and an acrylate ester (Patent Document 6) and a combination of hydrolyzate of organosilane and fluoropolymer (Patent Documents 7 to 9) have been proposed.

  However, the composition of Patent Document 5 has a problem that the alkoxysilane concentration is high, and it takes time to cure and the productivity is lowered. In addition, when a fluorine-containing silane compound is added to the composition of Patent Document 5 to form a low refractive index thin film, the intermolecular interaction of the fluorine compound is low. There was a problem that the risk of volatilization increased. In the case of the compositions of Patent Documents 6 to 9, since a catalyst such as water or acid during hydrolysis of the silane compound remains in the composition, there is a risk that precipitates are generated during storage. Furthermore, in the compositions of Patent Documents 7 to 9, since it is necessary to evaporate and remove a dehydrating agent such as ethyl orthoformate added in order to improve the storage stability, a treatment at a high temperature is required. The process for producing the fluoropolymer and the subsequent process for producing the hydrolyzate of organosilane are essential, and there is a problem that the production cost increases. In addition, since the silane compound or its hydrolyzate has a higher refractive index than that of the fluorinated copolymer, it has been difficult to lower the refractive index of the composition containing them.

  In addition, in the transfer method, in order to transfer the transfer layer onto the transfer material all at once, when the transferable antireflection layer of the transfer material is produced from the composition of Patent Documents 1 to 10 described above, the transfer material It is necessary to provide a low refractive index layer on the substrate and further provide a high refractive index layer on the low refractive index layer. However, a composition containing a compound containing a fluorine atom as described in Patent Documents 1 to 10 generally exhibits strong water repellency and oil repellency (Patent Document 8), and accordingly, a cured film comprising such a composition. In many cases, it is difficult to further stack another layer (for example, a high refractive index layer) thereon.

  Thus, a resin that can be prepared by a simple method, has a long pot life, can be cured in a short time under mild conditions, and can obtain a low refractive index film that can be laminated on a low refractive index layer. A composition was desired.

Japanese Patent Laid-Open No. 4-272788 JP 2000-17099 A JP-A-6-136062 Japanese Patent Laid-Open No. 2-182712 JP-A-8-302284 JP 2001-207120 A JP 2000-109694 A Japanese Unexamined Patent Publication No. 2000-167993 JP 2002-22905 A JP 2003-26732 A

  An object of the present invention is to obtain a low refractive index film that can be prepared by a simple method, has a long pot life, can be cured in a short time under mild conditions, and can be laminated on a low refractive index layer. It is providing the resin composition which can be performed.

  The inventors of the present invention can prepare a photocurable resin composition comprising a fluorine-containing acrylic polymer having a hydrolyzable silyl group and a photoacid generator by a simple method, has a long pot life, and is mild. The present invention was completed by finding that it can be cured under conditions and in a short time and that another high refractive index layer can be laminated on the low refractive index layer formed therefrom.

That is, the present invention includes the following components (A) and (B):
(A) a (meth) acrylic copolymer containing structural units represented by the following chemical formulas (I) and (II);

(In the formula (I), X is .R ¹ represents a hydrogen atom or a methyl group represents a fluoroalkyl group having 1 to 15 carbon atoms. However, carbon atoms part of ^{R 1} has the -CF ₂ H unit 1 Represents -15 fluoroalkyl groups.)

(In Formula (II), X represents a hydrogen atom or a methyl group. R ² represents a substituent having 1 to 20 carbon atoms and having at least one hydrolyzable alkoxysilyl group); B) A photoacid generator is included, the proportion of the structural unit represented by the chemical formula (I) in the component (A) is (X mol%), and the proportion of the structural unit represented by the chemical formula (II) is (Y mol%). A photocurable resin composition satisfying the relationship of the following formulas (1) and (2) is provided.

Moreover, this invention is a manufacturing method of the laminated body by which the cured resin layer was laminated | stacked on the base material, Comprising: The following processes (a) and (b):
(A) a step of forming a film of the above-mentioned photocurable resin composition on a substrate; and (b) curing and curing the resulting photocurable resin composition film by irradiating active energy rays. In a manufacturing method including a step of forming a resin layer, and as a specific embodiment thereof, in a manufacturing method of a transfer material having a release base film and a transfer layer including a cured resin layer provided thereon, the following steps (A ′) and (b ′):
(A ′) forming a film of the aforementioned photocurable resin composition on the surface of the release base film; and (b ′) irradiating the obtained photocurable resin composition film with active energy rays. To provide a method for producing a transfer material including a step of forming a cured resin layer.

  Further, the present invention is a laminate in which a cured resin layer is laminated on a substrate, and at least one of them is formed from the above-mentioned photocurable resin composition, and a specific embodiment thereof A transfer material having a release base film and a transfer layer provided thereon, wherein the transfer layer includes a cured resin layer made of the above-described photocurable resin composition. To do.

  The present invention also provides a transfer product, wherein the transfer layer of the transfer material described above is transferred onto the surface of the transfer object.

The photocurable resin composition of the present invention includes a fluorine-containing (meth) acrylic monomer unit having a —CF ₂ H unit and a (meth) acrylic monomer unit having a hydrolyzable silyl group. Since it contains a (meth) acrylic copolymer and a photoacid generator, it can be prepared by a simple method, has a long pot life, can be cured under mild conditions and in a short time, and is formed therefrom. Another high refractive index layer can be laminated on the low refractive index layer.

  Hereinafter, the present invention will be described in detail. In this specification, an acryloyl group or a methacryloyl group may be abbreviated as (meth) acrylate group, and acrylic acid or methacrylic acid may be abbreviated as (meth) acrylic acid.

The photocurable resin composition of the present invention includes the following components (A) and (B):
(A) a (meth) acrylic copolymer containing structural units represented by the following chemical formulas (I) and (II);

(In the formula (I), X is .R ¹ represents a hydrogen atom or a methyl group represents a fluoroalkyl group having 1 to 15 carbon atoms. However, carbon atoms part of ^{R 1} has the -CF ₂ H unit 1 Represents -15 fluoroalkyl groups.)

(In Formula (II), X represents a hydrogen atom or a methyl group. R ² represents a substituent having 1 to 20 carbon atoms and having at least one hydrolyzable alkoxysilyl group); B) A photoacid generator is included, the proportion of the structural unit represented by the chemical formula (I) in the component (A) is (X mol%), and the proportion of the structural unit represented by the chemical formula (II) is (Y mol%). A photocurable resin composition satisfying the relationship of the following formulas (1) and (2) is provided.

  In the above formula, when the value of “(X mol%) / {(X mol%) + (Y mol%)}” is less than 0.5, the cured resin film obtained from the photocurable resin composition The refractive index increases and a good antireflection function cannot be obtained, and when it exceeds 0.9, the content of the component (B) is relatively decreased, so that the film strength is decreased. In addition, when the value of “(Y mol%) / {(X mol%) + (Y mol%)}” exceeds 0.5, the content of the component (A) is relatively lowered, and the cured resin film The refractive index increases and a good antireflection function cannot be obtained, and if it is less than 0.1, the film strength decreases.

  Moreover, from the viewpoint of the refractive index and the surface hardness of the cured resin layer, the photocurable resin composition preferably further satisfies the following expressions (1a) and (2a).

  The (meth) acrylic copolymer comprising the structural units represented by the chemical formulas (I) and (II) of the component (A) constituting the photocurable resin composition of the present invention is a low refractive index curing that can be laminated. It is a component for obtaining a resin film and increasing the film strength, and it is soluble in non-halogen solvents used in general paints.

The structural unit of the chemical formula (I) constituting the (meth) acrylic copolymer of the component (A) contributes particularly to lowering the refractive index of the cured resin film. Here, X in the chemical formula (I) is a hydrogen atom or a methyl group, but is preferably a methyl group in order to keep the film strength high. R ¹ is a fluoroalkyl group having 1 to 15 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. However, in order to improve the wettability of the surface of the cured resin film and obtain a cured film that can be laminated, a part of the fluoroalkyl group is a fluoroalkyl group having 1 to 15 carbon atoms having a —CF ₂ H unit. There is a need to. In this case, if the ratio of the “fluoroalkyl group having 1 to 15 carbon atoms having a —CF ₂ H unit” in the entire “fluoroalkyl group having 1 to 15 carbon atoms” of R ¹ is too low, the effect of improving wettability is obtained. If it is not sufficient and is too high, the refractive index is difficult to decrease, so it is preferably 30 to 100 mol%, more preferably 50 to 100 mol%.

Preferable specific examples of the monomer containing a —CF ₂ H unit necessary for constituting the structural unit represented by the chemical formula (I) include 2,2,2-trifluoroethyl (meth) acrylate, 1H, 1H. , 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl ( And (meth) acrylate. Among them, 1H, 1H, 5H-octafluoropentyl (meth) acrylate (2,2,3,3,4,4,5,5,5-octafluoropentyl (meth) from the viewpoint of the film strength of the resulting cured resin film Acrylate) is particularly preferred.

Specific examples of the monomer that does not contain a —CF ₂ H unit that can be used as needed to constitute the structural unit represented by the chemical formula (I) include 2,2,2-trifluoroethyl ( Fluoroalkyl (meth) acrylate having a trifluoromethyl group at the terminal of an alkyl group such as (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate; fluorocycloalkyl (meth) acrylate; trifluoromethylcycloalkyl (Meth) acrylate etc. are mentioned.

On the other hand, the structural unit of the chemical formula (II) contributes to improving the cross-linking density of the cured resin film and improving the film strength. Here, X in the chemical formula (II) is a hydrogen atom or a methyl group, but is preferably a methyl group in order to keep the film strength high. R ² represents a substituent having 1 to 20 carbon atoms, preferably 3 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, and at least one, preferably 1 to 2 hydrolyzable alkoxysilyl groups. To express. The hydrolyzable alkoxysilyl group is not particularly limited as long as it is a known substituent capable of generating a silanol bond by hydrolysis.

  Specific examples of the monomer for constituting the structural unit represented by the chemical formula (II) include γ-methacryloyloxypropyltrimethoxysilane, (meth) acryloxypropyltriethoxysilane, (meth) acryloxypropylmethyldimethoxy. Examples include (meth) acryl silanes such as silane.

  The (meth) acrylic copolymer containing the structural units represented by the chemical formulas (I) and (II) can be obtained by polymerizing the above monomers. The structural unit represented by the chemical formula (II) can also be obtained by introducing a hydrolyzable silyl group into the polymer side chain using a known method. For example, 1) hydrosilylation reaction in which trialkoxysilane is added to an unsaturated double bond of a polymer side chain in the presence of a transition metal catalyst, and 2) a mercapto group or an amino group to the epoxy group of the polymer side chain. A method of addition reaction of alkoxysilanes, 3) a method of reacting an alkoxysilane having an isocyanate group with a hydroxy group of a polymer side chain, and silylating with a urethane bond can be used.

  The photopolymerizable resin composition of the present invention contains a photoacid generator as component (B). The photoacid generator decomposes upon irradiation with active energy rays and can act on the hydrolyzable silyl group in the (meth) acrylic copolymer of component (A) to cause a curing reaction. A compound capable of releasing an acidic active substance. Here, a wide range of active energy rays such as ultraviolet rays, visible rays, lasers, electron beams, and X-rays can be used, and among these, the use of ultraviolet rays is preferable from the practical aspect. Specific examples of the ultraviolet ray generation source include a low-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, and a metal halide lamp.

Examples of the photoacid generator of component (B) include onium salts and sulfonic acid derivatives. Here, the cation of the onium salt is an onium ion, and specific examples thereof include an onium ion composed of S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or -N≡N. . Specific examples of anions include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate ( SbCl ₆ ⁻ ), tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, perchlorate ion (ClO ₄ ⁻ ), trifluoromethanesulfonate ion (CF ₃ SO ₃ ⁻ ), Examples thereof include fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, trinitrobenzenesulfonate anion, and trinitrotoluenesulfonate anion. As the onium salt, various combinations of the above cation and anion can be used, but a combination of a sulfonium cation and a phosphonium anion having less toxicity and a high curing rate is preferable.

  Examples of sulfonic acid derivatives include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imide sulfonates, benzoin sulfonates, sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol, Examples include pyrogallol trisulfonates and benzyl sulfonates. Specific examples include diphenyldisulfone, ditosyldisulfone, bis (phenylsulfonyl) diazomethane, bis (chlorophenylsulfonyl) diazomethane, bis (xylylsulfonyl) diazomethane, phenylsulfonylbenzoyldiazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (t -Butylsulfonyl) diazomethane, 1,8-naphthalenedicarboxylic acid imide methyl sulfonate, 1,8-naphthalenedicarboxylic acid imide Tosyl sulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethyl sulfonate, 1,8-naphthalenedicarboxylic acid imide Camphor Sulfonate, Succinimide Phenyl sulfonate, Succinimide Tosyl sulfonate, Succinimide Trifluoromethyl sulfone Nate, succinimide camphorsulfonate, phthalimide trifluorosulfonate, cis-5-norbornene-endo-2,3-dicarboxylic acid trifluoromethylsulfonate, benzoin tosylate, 1,2-diphenyl-2-hydroxy Propyl tosylate, 1,2-di (4-methylmercaptophenyl) -2-hydroxypropyl tosylate, pyrogallol methylsulfonate, pyrogallol ethylsulfonate, 2,6-dinitrophenylmethyl tosylate, ortho-nitrophenylmethyl tosylate, para-nitrophenyl Tosylate and the like can be mentioned.

  The blending amount of the photoacid generator of the component (B) in the photocurable resin composition is determined based on the solid content of the photocurable resin composition excluding the diluent described later (solid components already before curing and after curing). The total of the components to be solid) is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass.

  Moreover, in order to improve the coating property, a diluent can be added to the photocurable resin composition. The addition amount of the diluent can be appropriately determined according to the thickness of the cured layer to be formed. For example, when the thickness of the hardened layer is about 0.1 μm, it is preferable that the coating is applied at a wet film thickness of 1.9 μm with a diluent of 94.75% by mass with respect to a solid content of 5.25% by mass.

  As the diluent, a diluent used in a general resin coating solution can be used. Specifically, for example, ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone; methyl acetate, ethyl acetate, acetic acid Ester compounds such as butyl, ethyl lactate and methoxyethyl acetate; ether compounds such as diethyl ether, ethylene glycol dimethyl ether, ethyl cellosolve, butyl cellosolve, phenyl cellosolve and dioxane; aromatic compounds such as toluene and xylene; pentane and hexane Aliphatic compounds; halogen-based hydrocarbons such as methylene chloride, chlorobenzene and chloroform; alcohol compounds such as methanol, ethanol, normal propanol and isopropanol.

  If necessary, the photocurable resin composition of the present invention may further include an inorganic filler, a polymerization inhibitor, a color pigment, a dye, an antifoaming agent, a leveling agent, a dispersing agent, a light diffusing agent, a plasticizer, and an antistatic agent. An agent, a surfactant, a non-reactive polymer, a near-infrared absorber, and the like can be added as long as the effects of the present invention are not impaired.

  The photocurable resin composition of the present invention is prepared by uniformly mixing the components (A) and (B) described above and other additive components blended as necessary according to a conventional method. can do.

  The photocurable resin composition of the present invention is a layer comprising a base material layer and a cured resin obtained by curing the photocurable resin composition of the present invention by coating on a substrate and photocuring (hereinafter, cured). It may be referred to as a resin layer). Such a laminate includes additional types such as the type, thickness, and physical properties of the substrate used, and the physical properties and thickness of the cured resin layer made of the photocurable resin composition, and an adhesive layer that is laminated as necessary. It can be used in a wide range depending on the type and properties of the thermoplastic layer, thermosetting layer, or photocurable layer. For example, it can be used as a low refractive index layer such as a transfer material or an antireflection material.

  The substrate of such a laminate is not particularly limited as long as it is plate-like or film-like, such as a metal substrate such as iron or aluminum, a glass substrate, a ceramic substrate, an acrylic resin, a polyester resin, or a polycarbonate. A resin base material etc. can be mentioned.

  Such a laminate can be manufactured by a manufacturing method including the following steps (a) and (b). Hereinafter, it demonstrates for every process.

Step (a)
First, a film of the photocurable resin composition of the present invention is formed on a substrate. As a film forming method, a known method such as an impregnation method, a relief printing method, a flat printing method, a coating method using a roll used in intaglio printing, a spray method of spraying on a substrate, a curtain flow coat, or the like is used. Can be used. When a diluent is contained in the photocurable resin composition, the coating film is preferably heated and dried in a heating furnace, a far infrared furnace, a super far infrared furnace, or the like.

  As the base material, a plate-like or film-like metal (iron, aluminum, etc.) substrate, a ceramic substrate including a glass substrate, a plastic substrate such as acrylic resin, PET, polycarbonate, a thermosetting resin substrate, etc. may be used. it can.

Step (b)
The photocurable film obtained in the step (a) is cured by irradiating with active energy rays such as ultraviolet rays, visible light, laser, electron beam, X-rays, etc. to form a cured resin layer. Thereby, the laminated body by which the cured resin layer which consists of a photocurable resin composition of this invention on the base material was laminated | stacked is obtained. In addition, as a light source when using an ultraviolet-ray, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp etc. are mentioned.

  The laminate obtained in this way is not limited to a two-layer structure of a base material and a cured resin layer, and a layer of a thermoplastic, thermosetting, or photocurable material may be provided in advance, or a cured layer You may provide again after formation.

  As described above, the photocurable resin composition of the present invention, the laminate having a cured resin layer comprising the photocurable resin composition, and the production method thereof have been described. However, as an example of preferred specific embodiments of these laminates and production methods, a transfer material and its The manufacturing method is shown below. In addition, the meaning of the term in them is as having already demonstrated.

  The transfer layer of the transfer material of the present invention has at least one cured resin layer composed of the above-described photocurable resin composition, and therefore may be a cured resin layer alone, but other low refractive index layers. Further, it may be a multilayer structure of two or more layers including a high refractive index layer, a polymer layer and the like.

  For example, the transfer layer can be used as an antireflection layer in combination with a high refractive index layer, another low refractive index layer, or the like depending on the purpose of use of the transfer material. It may also include a hard coat layer such as an acrylic or silicon type, a functional layer such as an antibacterial layer, a decorative layer such as a printing layer or a colored layer, a vapor deposition layer (conductive layer) made of a metal or a metal compound, a primer layer, or the like. it can.

  Specific examples of the layer structure of the transfer layer include a cured resin layer / hard coat layer, a cured resin layer / high refractive index layer / hard coat layer, and a cured resin layer / high refractive index layer / deposition layer / primer layer / hard coat. Layer, cured resin layer / high refractive index layer / primer layer / evaporation layer / primer layer / hard coat layer, cured resin layer / high refractive index layer / primer layer / hard coat layer, printing layer / cured resin layer / high refractive index Layer, decorative layer / cured resin layer / high refractive index layer, and the like.

  Although there is no restriction | limiting in particular in the film thickness of the said cured resin layer, Usually, it selects suitably from the range of about 0.5-20 micrometers. Further, the film thicknesses of the other layers are not particularly limited, but are usually appropriately selected from the range of about 0.1 to 10 μm.

  In order to form a cured resin layer from the photocurable resin composition, the film of the formed photocurable resin composition is subjected to ultraviolet light, visible light, α according to a known photocuring technique of a photopolymerizable resin. A wide range of active energy rays such as rays, β rays, γ rays, electron rays, and lasers can be used. Among these, it is preferable to use ultraviolet rays. Any light source such as a point light source, a line light source, and a surface light source can be used, but a line light source is generally used from the viewpoint of practicality. For example, an ultraviolet lamp is generally used as an ultraviolet ray generation source in terms of practicality and economy, and specific examples include a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, and a metal halide lamp. In addition, when using a point light source or a line light source, it may scan suitably so that a predetermined amount of light can be irradiated to the layer which consists of a photocurable resin composition.

  Since the transfer material has a release base film and the above-described transfer layer thereon, specific examples of the layer structure of the transfer material include a release base film / cured resin layer / hard coat layer, a release layer. Type base film / cured resin layer / high refractive index layer / hard coat layer, release base film / cured resin layer / high refractive index layer / deposition layer / primer layer / hard coat layer, release base film / cured resin layer / High refractive index layer / primer layer / evaporation layer / primer layer / hard coat layer, release base film / cured resin layer / high refractive index layer / primer layer / hard coat layer, release base film / print layer / cured resin layer / High refractive index layer, release base film / mounting layer / cured resin layer / high refractive index layer, and the like.

  The releasable base film used for the transfer material of the present invention is not particularly limited. For example, the releasable base film has a releasability that exhibits a surface tension of 40 dyn / cm or less at 20 ° C., and has a sufficient self-holding property. Any film can be used as long as it is a film used for an ordinary transfer material. Specific examples of the release base film according to the present invention include polyester films such as polyethylene terephthalate films, polyolefin films such as polyethylene films and polypropylene films, polycarbonate films, polyvinylidene fluoride films, polyvinyl fluoride films, polyhexafluoropropylene films, Fluorine-based resin films such as poly (heptafluoroisopropyl (meth) acrylate film), silicon-containing polymer films such as polyoxydimethylsilylene, polyoxymethylsilylene, polyoxydimethylsilylene-α, ω-dibutanoic acid, polyoxyvinylsilylene , Polystyrene film, polyamide film, polyamideimide film, polyvinyl chloride film, cellulose acetate film, etc. Resin films, paper such as cellophane paper, glassine paper, Japanese paper, composite films of these, and those subjected to release treatment.

  The thickness of the releasable base film is not particularly limited, but is usually preferably in the range of 4 to 150 μm, more preferably in the range of 12 to 100 μm, in order to suppress the occurrence of wrinkles and cracks, More preferably, it is in the range of 30-100 μm.

  When the mold release property of the mold release base film is insufficient, a mold release treatment can be further performed on at least one surface of the mold release base film. Such a release treatment can be performed by a known method by appropriately selecting a release polymer or wax. Examples of the treatment agent used for the release treatment include release waxes such as paraffin wax; release resins such as silicone resins, melamine resins, urea resins, urea-melamine resins, cellulose resins, and benzoguanamine resins. Molding resin; various surfactants, etc., alone or mixed with a solvent, etc., applied onto a releasable base film according to a normal printing method such as gravure printing, screen printing, or offset printing, and dried Furthermore, it can be formed by curing (heating, ultraviolet irradiation, electron beam irradiation, radiation irradiation) as necessary.

  As described above, the transfer material of the present invention can be provided with a primer layer between layers in a transfer layer having a multilayer structure. Such a primer layer is a coating layer of a composition mainly composed of a polymer component having good adhesion to both the layers in the transfer material of the present invention, and the thickness is preferably in the range of about 0.5 to 5 μm. Specific examples of the primer layer include layers of acrylic resin, vinyl acetate resin, melamine resin, polyester resin, urethane resin, and the like. These layers can be formed by, for example, dissolving the resin in a solvent, applying the resin by the printing method, and drying.

  The transfer material of the present invention can be produced according to a production method including steps (a ′) and (b ′) as described below.

Step (a ′)
On the release base film, the above-mentioned photocurable resin composition of the present invention is applied to form a film of the photocurable resin composition. The release base film and the photocurable resin composition are as described above.

Step (b ′)
The film of the photocurable resin composition obtained in the step (a ′) is irradiated with active energy rays as described above. Thereby, the film | membrane of a photocurable resin composition hardens | cures and becomes a cured resin layer. Thereby, the transfer material which has the cured resin layer formed by hardening the photocurable resin composition of this invention is obtained.

  The transfer material thus obtained is not limited to the two-layer structure of the release base film and the cured resin layer, and may be provided with a layer of thermoplastic, thermosetting, or photocurable material in advance, or You may provide again after hardened layer formation.

  The transfer material according to the present invention is capable of thermally transferring the transfer layer to the transfer material by heating the outermost surface layer in close contact with the transfer material. The shape and the like of the material to be transferred are not particularly limited, but preferred examples include commercially available resin sheets, films, glass plates, and the like. Moreover, when using for a display screen protection board etc., it is preferable that it is a resin sheet as a to-be-transferred material. Specific examples of such resins are not particularly limited as long as they are transparent at visible light wavelengths, but methacrylic resins such as polymethyl methacrylate (PMMA), polycarbonate resins, methyl methacrylate-styrene copolymers (MS resins) and the like are preferable. Used.

  The transfer material of the present invention can easily transfer a transfer layer to a surface of a transfer target such as an image display device or a helmet shield with good transfer efficiency at low cost. Accordingly, the obtained transfer product is a transfer product having a good appearance.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to this.

Reference Example 1 (Production of fluorinated acrylic polymer)
After adding methyl isobutyl ketone (40 g) and the polymerization monomer shown in Table 1 (20 g) to a 100 mL three-necked flask, the inside of the flask was purged with nitrogen, and azobisisobutyronitrile (40 mg) was added. The polymerization was carried out by stirring at 0 ° C. for 6 hours. After completion of the reaction, the reaction solution was dropped into hexane to precipitate a polymer, and the precipitated polymer was collected by filtration and dried in a vacuum dryer at room temperature for 12 hours to obtain a fluorine-containing acrylic polymer.

(Table 1 note)
* 1: 2,2,2-trifluoroethyl methacrylate (trade name Biscoat 3FM, manufactured by Osaka Organic Chemical Co., Ltd.)
* 2: 1H, 1H, 5H-octafluoropentyl methacrylate (trade name Biscote 8FM, manufactured by Osaka Organic Chemical Co., Ltd.)
* 3: 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate (Brand name Biscote 17FM, manufactured by Osaka Organic Chemical Co., Ltd.)
* 4: γ-Methacryloyloxypropyltrimethoxysilane (trade name KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 5: [Structural unit represented by chemical formula (I)] / ([Structural unit represented by chemical formula (I)] + [Structural unit represented by chemical formula (II)]) × 100 (mol%) To express

Reference Example 2 (Production of high refractive index resin composition)
Titanium fine particles (trade name HIT, manufactured by Nissan Chemical Co., Ltd.) 1.8% by mass, dipentaerythritol hexaacrylate (trade name: DPCA-60 manufactured by Nippon Kayaku Co., Ltd.) 1.2% by mass, photopolymerization initiator (trade name) : Irgacure 184 Ciba Specialty Chemicals Co., Ltd.) 0.15% by mass and 96.85% by mass of isopropanol were mixed to obtain a high refractive index resin composition.

Reference Example 3 (Production of hard coat resin composition for laminate)
12% by mass of dipentaerythritol hexaacrylate (trade name: DPCA-60 manufactured by Nippon Kayaku Co., Ltd.), 18% by mass of ethylene oxide-modified bisphenol A diacrylate (trade name: Biscote # 540, manufactured by Osaka Organic Chemical Industry Co., Ltd.), light A polymerization initiator (trade name: Irgacure 184 Ciba Specialty Chemicals) 1.5 mass% and methyl isobutyl ketone 68.5 mass% were mixed to obtain a hard coat resin composition for a laminate.

Reference Example 4 (Production of hard coat resin composition for transfer foil)
Ethylene oxide-modified bisphenol A diacrylate 5% by mass (trade name Biscote # 540, manufactured by Osaka Organic Chemical Industry Co., Ltd.), triazine triacrylate 2% by mass (trade name M315, manufactured by Toagosei Co., Ltd.), epoxy-modified phenoxy acrylate 4% by mass % (Trade name M600A, manufactured by Kyoeisha Chemical Co., Ltd.), γ-acryloyloxypropyltrimethoxysilane 4% by mass (trade name KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.), polymethyl methacrylate 5% by mass (trade name Parapet Kuraray Co., Ltd.) Co., Ltd.), 1% by mass of a photopolymerization initiator (trade name: Irgacure 184, manufactured by Nippon Ciba Geigy Co., Ltd.) and 79% by mass of methyl ethyl ketone were mixed to obtain a hard coat resin composition for transfer foil.

Examples 1-6, Comparative Examples 1-2
The hard coat resin composition shown in Reference Example 3 was applied on an acrylic resin plate having a thickness of 2 mm so that the dry film thickness was 10 μm, dried at 130 ° C. for 30 seconds, and then 80 W high-pressure mercury lamp (USHIO INC.) )) Was used to irradiate ultraviolet rays once by using a belt conveyor (conveyor speed 1 m / min, distance between light source and irradiated object), and the hard coat resin composition was cured to form a hard coat layer. Further, on this hard coat layer, the high refractive index resin composition shown in Reference Example 2 was applied to a dry film thickness of 0.1 μm, and a high refractive index layer was formed by the same method as the hard coat layer preparation conditions. . Further, on this high refractive index layer, the low refractive index resin composition shown in Table 2 was applied so that the dry film thickness was 0.1 μm, and the low refractive index layer was formed by the same method as the hard coat layer preparation conditions. Thus, a laminate composed of an acrylic resin plate / hard coat layer / high refractive index layer / low refractive index layer was obtained.

(Evaluation)
About the "storage stability" of the low refractive index resin composition used in each example and comparative example, the "reflectance" and "scratch resistance" of the low refractive index surface of the laminate of each example and comparative example, Table 2 shows the results obtained by testing and evaluating as described in the above.

The storage stability low refractive index resin composition was stored for 6 months in an environment of 50% humidity and 25 ° C., and then the appearance change and the curable change were evaluated according to the following criteria.
◎: No change in appearance and curability after storage for 6 months ○: No change in appearance and curability when stored for 3 months, but appearance and cure during storage for 3-6 months When there is a change in properties ×: When changes in appearance and curability have already been observed at the time of storage for 1 month

The 5 ° regular reflectance of the transfer layer of the reflectance laminate was measured, the minimum reflectance at 400 nm to 700 nm was measured, and evaluated according to the following criteria.
A: Minimum reflectance is less than 0.5%. O: Minimum reflectance is 0.5% or more and less than 1.0%. X: Minimum reflectance is 1.0% or more.

A stack of 12 scratch-resistant cheesecloths is attached to the tip of a metal rod having a diameter of 0.6 mm and brought into contact with the transfer layer of the laminate under a load of 1.6 kg. When the surface was reciprocated 150 times, whether or not the transfer layer was peeled off from the laminate was visually confirmed and evaluated according to the following criteria.
○: When the surface layer is not peeled ×: When the surface layer is peeled

(Table 2 Note)
* 6: See Reference Example 1 * 7: Trade name UN-3320HC, manufactured by Negami Kogyo Co., Ltd. * 8: 2,2,2-trifluoroethyl methacrylate (trade name Viscoat 3FM, manufactured by Osaka Organic Chemical Co., Ltd.)
* 9: 1,2-diphenyl-2-hydroxypropyl tosylate (trade name: CD-1012 manufactured by Sartomer Co., Ltd.)
* 10: Product name Irgacure 184 Ciba Specialty Chemicals Co., Ltd.

  From the results of Table 2, the low refractive index resin compositions prepared in Examples 1 to 6 show good storage stability, and the antireflection film using the cured film has low reflectance and good scratch resistance. It turns out that it showed sex. On the other hand, the low refractive index resin compositions prepared in Comparative Examples 1 and 2 had good storage stability, but had a problem in either reflectance or scratch resistance.

Examples 7 to 12, Comparative Examples 3 to 4 (production of transfer plate)
After coating the low refractive index resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 to a thickness of 1 μm on a 50 μm thick polyester film, each was dried at 130 ° C. for 30 seconds. Further, ultraviolet irradiation (80 W high pressure mercury lamp, speed 1 m / min, 1 pass) was performed to form a low refractive index layer. After coating the high refractive index resin composition shown in Reference Example 2 on the low refractive index layer so as to have a dry film thickness of 1 μm, it is dried at 130 ° C. for 30 seconds, and further irradiated with ultraviolet rays (80 W high pressure mercury lamp, speed 1 m / second). 1 pass), and a high refractive index layer was formed. Furthermore, on the high refractive index layer, the hard coat resin composition for transfer foil shown in Reference Example 4 was applied to a dry film thickness of 10 μm, dried at 130 ° C. for 30 seconds, and further irradiated with ultraviolet light (80 W high pressure) A transfer material composed of polyester film / cured resin layer (low refractive index layer) / high refractive index layer / hard coat layer was obtained by performing a mercury lamp, speed 1 m / min, 1 pass).

  The obtained transfer film was thermally transferred to a 2 mm thick polymethyl methacrylate plate (roll speed 1 m / min, roll temperature 160 ° C.), and the polyester film was peeled off to obtain a laminate. The obtained laminate was evaluated for scratch resistance and reflectance of the transfer layer in the same manner as in Example 1. The results are shown in Table 3.

(Table 3 note)
* 11: Not evaluated because the polyester film could not be peeled after thermal transfer * 12: Not evaluated because the high refractive index layer could not be laminated on the low refractive index layer

  From the results in Table 3, it can be seen that the antireflection films of Examples 7 to 12 transferred to the transfer target body exhibited low reflectance and good scratch resistance. On the other hand, in Comparative Examples 3 and 4, transfer was not possible in the first place, and evaluation was impossible.

The photocurable resin composition of the present invention can be prepared by a simple method, has a long pot life, and can obtain a low refractive index film that can be cured in a short time under mild conditions. Can be advantageously used for articles such as laminate foil, transfer foil, image display screen protection plate, helmet shield and the like.

Claims (8)

A photocurable resin composition for forming an antireflection film, comprising the following components (A) and (B):
(A) a methacrylic copolymer containing structural units represented by the following chemical formulas (I) and (II);

(In the formula (I), X is .R ¹ represents methyl group represents a fluoroalkyl group having 2 to 10 carbon atoms. However, the number of carbon 30 to 100 mol% of ^{R 1} has the -CF ₂ H unit 2 Represents 10 to 10 fluoroalkyl groups.)

(In Formula (II), X represents a methyl group. R ² represents a substituent having 3 to 10 carbon atoms and having one or two hydrolyzable alkoxysilyl groups); and (B ) Containing a photoacid generator,
When the proportion of the structural unit represented by the chemical formula (I) in the component (A) is (X mol%) and the proportion of the structural unit represented by the chemical formula (II) is (Y mol%), the following formulas (1a) and ( 2a)

The blending amount of the photoacid generator of component (B) in the photocurable resin composition for forming an antireflective film is 100 parts by mass of the solid content of the photocurable resin composition for forming an antireflective film The photocurable resin composition for anti-reflective film formation which is 0.1-15 mass parts with respect to this.




The photocurable resin composition for forming an antireflection film according to claim 1, wherein the structural unit represented by the chemical formula (I) is a structural unit derived from 1H, 1H, 5H-octafluoropentyl methacrylate. Component structural units in (A) represented by the chemical formula (II) is, .gamma.-methacryloyloxy propyl trialkoxysilane is a structural unit derived from claim 1 or 2 anti-reflection film forming photocurable resin composition according object. A laminate in which a cured resin layer is laminated on a substrate, wherein the cured resin layer is a layer formed from the photocurable resin composition for forming an antireflection film according to any one of claims 1 to 3. Laminate containing. A method for producing a laminate in which a cured resin layer is laminated on a substrate, the following steps (a) and (b):
(A) a step of forming a film of the photocurable resin composition for forming an antireflection film according to any one of claims 1 to 3 on a substrate; and (b) of the obtained photocurable resin composition. A manufacturing method comprising a step of curing a film by irradiating an active energy ray to form a cured resin layer. A transfer material comprising a release base film and a transfer layer provided thereon, a transfer resin comprising a photocurable resin composition for forming an antireflection film according to any one of claims 1 to 3, wherein the transfer layer is a cured resin. A transfer material comprising a layer. In a method for producing a transfer material having a release base film and a transfer layer including a cured resin layer provided thereon, the following steps (a ′) and (b ′):
(A ′) a step of forming a film of the photocurable resin composition for forming an antireflection film according to claim 1 on the surface of the release base film; and (b ′) the photocuring obtained. The manufacturing method of the transfer material including the process of making it harden | cure by irradiating an active energy ray to the film | membrane of a photosensitive resin composition, and forming a cured resin layer.   A transfer product, wherein a transfer layer of the transfer material according to claim 6 is transferred onto the surface of a transfer object.