JP2006181791A - Transfer material and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transfer material used for obtaining a laminated sheet, which has high surface hardness and an antistatic function, at a low cost. <P>SOLUTION: In the transfer material constituted by providing a transfer layer, which contains at least an antistatic hard coat layer and an adhesive layer, on a base film having a mold release layer so that the mold release layer and the antistatic hard coat layer come into contact with each other, a surfactant having an 8-30C straight chain hydrocarbon group is added to the antistatic hard coat layer as a component (a) so that the adhesive strength between the mold release layer and the antistatic hard coat layer becomes lower than that between the antistatic hard coat layer and the adhesive layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a transfer material having a base film having a release layer and a transfer layer provided thereon, and more particularly to a transfer material having a transfer layer having an antistatic hard coat layer.

  A hard coat layer is usually formed on the surface of a resin plate used for an optical member or the like. Such a hard coat layer is formed by applying a curable composition for a hard coat layer to a resin plate by a roll coat method or a dipping method and curing it. There is a problem that is low. Therefore, the transfer layer including the hard coat layer and the adhesive layer formed thereon is formed on the release layer of the base film having the release layer so that the hard coat layer is in contact with the release layer. A method of transferring a transfer layer to a resin plate using a transfer material is being used.

  By the way, the resin plate provided with such a hard coat layer is often required to have an antistatic function in order to prevent dust and the like from adhering to the surface. In general, as a method for imparting an antistatic function to a resin layer, it is known that a relatively low cost surfactant or a higher cost antistatic particle is blended in the resin layer (non-patent) Reference 1).

  Accordingly, one method for imparting an antistatic function to the hard coat layer constituting the transfer layer of the transfer material at low cost is to add a surfactant to the resin composition for forming the hard coat layer. However, when the resin composition for forming a hard coat layer to which a surfactant is added is coated on the release layer of the base film for transfer material, the surfactant is on the release layer side of the film of the curable composition. Since there is a tendency to be ubiquitous on the air interface side instead of the interface, the adhesion strength between the hard coat layer and the adhesive layer is lower than the adhesion strength between the release layer and the hard coat layer, and the transfer layer Sometimes it does not transfer as intended. Moreover, even if it transfers, there exists a problem that the antistatic ability of the hard coat layer surface of a transfer material is not enough. This is presumably because the concentration of the surfactant on the surface of the hard coat layer in contact with the release layer is not sufficient.

  For this reason, conventionally, in order to impart an antistatic function to the hard coat layer constituting the transfer layer of the transfer material, it has been achieved by adding conductive fine particles to the resin composition for forming the hard coat layer. Is the current situation (Patent Documents 1 and 2).

Plastics Vol. 49, no. 10 pp34-40 (1998) JP 7-175220 A JP 2003-231200 A

  However, in the method of adding conductive fine particles to the resin composition for forming a hard coat layer, high-performance antistatic performance can be imparted to the transfer layer of the transfer material, but it is necessary to add a relatively large amount of conductive fine particles. Therefore, there is a problem that it is difficult to reduce the manufacturing cost of the transfer material. Thus, a transfer material that can transfer a hard coat layer having a low cost, high surface hardness, and an antistatic function has been desired.

  The present invention is intended to solve the above-described problems of the prior art, and is to provide a transfer material that can obtain a laminate having high surface hardness and an antistatic function at low cost.

  In order to use a surfactant that has not been conventionally used for the purpose of imparting antistatic ability to the hard coat layer constituting the transfer layer of the transfer material at a low cost, the present inventors have separated it. In consideration of the fact that the mold layer is a polyolefin resin or a silicone resin, the inventors have found that the above-mentioned object can be achieved by using a surfactant having a specific substituent having affinity for them, and completed the present invention. I came to let you.

  That is, the present invention provides a transfer layer including at least an antistatic hard coat layer and an adhesive layer on a base film having a release layer so that the release layer and the antistatic hard coat layer are in contact with each other. The transfer material provided is charged so that the adhesive strength between the release layer and the antistatic hard coat layer is lower than the adhesive strength between the antistatic hard coat layer and the adhesive layer. Provided is a transfer material wherein the preventive hard coat layer contains a surfactant having a linear hydrocarbon group having 8 to 30 carbon atoms as component (a).

The present invention is also a laminate in which the transfer layer of the transfer material described above is transferred to the surface of the transfer object, the pencil hardness of the transfer layer surface is 3H or more, and the surface resistivity is 1 Provided is a laminate having a size of 0.0 × 10 ¹⁴ Ω / □ or less.

  In the transfer material of the present invention, the hard coat layer forming resin composition for forming the antistatic hard coat layer of the transfer layer has a specific affinity for a release layer made of a polyolefin resin or a silicone resin. A surfactant having the following substituent is blended. Therefore, when the resin composition for forming the hard coat layer is applied onto the release layer, the proportion of the surfactant present at the interface between the film of the resin composition for forming the hard coat layer and the release layer is increased, and the release is performed. The adhesive strength between the mold layer and the antistatic hard coat layer is made lower than the adhesive strength between the antistatic hard coat layer and the adhesive layer, and on the surface of the hard coat layer of the transfer layer after transfer. Good antistatic ability can be imparted.

  In the present invention, a transfer layer including at least an antistatic hard coat layer and an adhesive layer is provided on a base film having a release layer so that the release layer and the antistatic hard coat layer are in contact with each other. Antistatic so that the adhesive strength between the release layer and the antistatic hard coat layer is lower than the adhesive strength between the antistatic hard coat layer and the adhesive layer. The functional hard coat layer contains a surfactant having a linear hydrocarbon group having 8 to 30 carbon atoms as component (a). Here, “the adhesive strength between the release layer and the antistatic hard coat layer is lower than the adhesive strength between the antistatic hard coat layer and the adhesive layer” specifically means This means that when the transfer layer of the transfer material is transferred to the transfer target, it is peeled off between the release layer and the antistatic hard coat layer, and the transfer layer is transferred cleanly to the transfer target. To do. Such a condition necessarily indicates that the amount of the surfactant present on the surface of the antistatic hard coat layer after transfer is relatively increased. The surface resistance value on the surface of the preventive hard coat layer is reduced.

  The antistatic hard coat layer constituting the transfer layer of the transfer material of the present invention is a layer that is positioned on the outermost surface when the transfer layer of the transfer material of the present invention is transferred to a transfer target, Usually, the surfactant of the component (a) is mixed with a resin composition for forming a hard coat layer containing a thermosetting resin or a photocurable resin as a main component, and the film is formed and cured.

  Specific examples of the “linear hydrocarbon group having 8 to 30 carbon atoms” in the surfactant of component (a) include octyl group, nonyl group, decanyl group, undecanyl group, eicosenyl group, pentacocenyl group, triacontanil. Saturated linear hydrocarbon groups such as groups; 9-octadecenyl group, 9,12-octadienoyl group, 9,12,15-octatrienoyl group, 11-eicocenyl group, 5,8,11,14-eicosatetraenoyl Groups, unsaturated linear hydrocarbon groups such as 5,8,11,14,17-eicosapentaenoyl group, 13-docosenyl group, 5,8,11,14-docosahexaenoyl group, and the like. . Among them, an unsaturated hydrocarbon group having 10 to 30 carbon atoms is preferable, and specific examples include 9-octadecenyl group, 9,12-octadienoyl group, 9,12,15-octatrienoyl group, 11-eicocenyl group, 5, 8,11,14-eicosatetraenoyl group, 5,8,11,14,17-eicosapentaenoyl group, 13-docosenyl group, 5,8,11,14-docosahexaenoyl group, etc. And a 9-octadecenyl group is more preferred.

  The surfactant of component (a) is not particularly limited as long as it is a known surfactant having a straight chain hydrocarbon group having 8 to 30 carbon atoms. For example, sulfate type, sulfonic acid Anionic surfactants such as salt type, phosphate ester type, sulfosuccinate type, carboxylic acid type and sulfate ester type; cationic surfactants such as quaternary cation type, amine oxide type, pyridinium salt and amine salt Agent: Nonionic surfactant such as alkyl ether type, alkyl phenol type, ester type, ether ester type, monool polyether type, amide type; amphoteric interface such as betaine type, ether amine oxide type, glycine type, alanine type Anionic surfactants are particularly preferred, and among the anionic surfactants, carboxylic acid type, sulfosac Sulfonate types are particularly preferred.

  Specific examples of the sulfosuccinate type surfactant include monoalkyl sulfosuccinate or dialkyl sulfosuccinate lithium salt, sodium salt, ammonium salt, etc. Among them, monoalkyl sulfosuccinate sodium salt is more preferable. .

  The surfactant of component (a) may have a radical polymerizable group such as an ethylenically unsaturated bond. By using such a surfactant, an effect of improving durability can be obtained.

  The content of the surfactant of component (a) in the resin composition for forming a hard coat layer is preferably 0.01% by mass or more and 5% by mass, more preferably 0.1% by mass or more and 5% by mass.

  Further, the hard coat layer forming resin composition for forming the antistatic hard coat layer contains a thermosetting resin or a photocurable resin as a main component in addition to the surfactant of component (a). Furthermore, in order to improve the coating property, a diluent is usually contained.

  Specific examples of such thermosetting resins include melamine resins, silicone resins, epoxy resins, urethane resins, alkyd resins, acrylic resins, phenol resins, and the like, while specific examples of photocurable resins. Examples thereof include urethane acrylate resin, acrylic resin, and epoxy resin. Among these, urethane acrylate resins and acrylic photocurable resins having relatively high hardness and high productivity are more preferable.

  The diluent is not particularly limited as long as it is a diluent used in general resin coatings, but is not limited to ketone compounds such as acetone, methyl ethyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, methoxyacetate Ester compounds such as ethyl; ether compounds such as diethyl ether, ethylene glycol dimethyl ether, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, dioxane; aromatic compounds such as toluene and xylene; aliphatic compounds such as pentane and hexane; methylene chloride; Examples thereof include halogen-based hydrocarbons such as chlorobenzene and chloroform; alcohol compounds such as methanol, ethanol, normal propanol and isopropanol, and water. The amount of such a diluent used can be appropriately determined according to the thickness of the antistatic hard coat layer.

  Further, the surface shape on the transfer layer side of the base film having the release layer may be a concavo-convex shape on the release layer side surface of the antistatic hard coat layer in order to exhibit an antiglare function. Examples of the method for forming the concavo-convex shape include sand blasting the base film surface to be coated with the hard coat layer forming resin composition.

The antistatic hard coat layer is the outermost layer when the transfer layer of the transfer material of the present invention is transferred to the transfer target, and therefore when coated on glass at a film thickness of 5 μm. More preferably, the pencil hardness is 3H or higher. Further, the surface resistance value is preferably 1.0 × 10 ¹⁴ Ω / □ or less.

The adhesive layer constituting the transfer layer of the transfer material of the present invention is required to be capable of thermal transfer of the transfer layer to a transfer target, and preferably contains the following components (b) to (d). It is comprised from the thermoadhesive cured resin layer which consists of a resin composition.
(B) a thermoadhesive polymer;
(C) an ethylenically unsaturated compound that can be polymerized by active energy rays; and (d) a polymerization initiator. In this curable resin composition, the amount (parts by mass) of component (b) is (Awt), and the component ( When the blending amount (part by mass) of c) is (Bwt), it is preferably a curable resin composition satisfying the relationship of the following formulas (1) and (2). From the viewpoint of improving the mechanical properties of the used laminate, it is more preferable to satisfy the relationship of the following formulas (1a) and (2a).

  In the above formula, when the numerical value of “(Awt) / {(Awt) + (Bwt)}” is less than 0.1, an adhesive layer obtained when the curable resin composition is cured (that is, thermal bonding) The adhesive strength of the adhesive cured resin layer) becomes insufficient. On the other hand, if it exceeds 0.6, the content of the ethylenically unsaturated compound of component (c) is relatively decreased, and the mechanical properties of the adhesive layer may be lowered. There is. In addition, when the value of “(Bwt) / {(Awt) + (Bwt)}” is less than 0.4, the content of the ethylenically unsaturated compound of component (c) decreases, and the mechanical properties of the adhesive layer May decrease.

The curable resin composition has an average crosslink density of component (b) and component (c) as v (mol / liter (L)) from the viewpoint of improving thermal adhesion and hardness. When it does, it is preferable that the relationship of following formula (3) is further satisfied, and it is more preferable that the average (v) value of the crosslinking density is between 1 and 4.5. In addition, the value of the average (v) of the crosslinking density can be calculated according to the description in Patent Document: Japanese Patent Application Laid-Open No. 2004-2824 (paragraphs 0029 to 0034).

  Furthermore, the curable resin composition according to the present invention has an average value of the solubility parameter (sp value) of the component (b) and the component (c) from the viewpoint of improving the adhesion to the transferred body made of a methacrylic resin or the like. When δ is satisfied, the relationship of the following formula (4) is preferably satisfied, and the average value (δ) of the solubility parameter (sp value) is more preferably in the range of 9.5 to 10.5. The average value (δ) of the solubility parameter (sp value) can be calculated according to the description in Japanese Patent Application Laid-Open No. 2004-2824 (paragraphs 0040 to 0061).

  The component (b) thermoadhesive polymer used in the adhesive layer of the transfer layer constituting the transfer material of the present invention is a component for imparting thermal adhesiveness to the curable resin composition. Such a thermoadhesive polymer is not particularly limited as long as it can impart thermal adhesiveness to the cured resin layer. However, it is excellent in thermal adhesiveness, and with an ethylenically unsaturated compound of component (c) described later. From the viewpoint of excellent compatibility, it is preferably a thermoplastic polymer having a glass transition temperature (at least one in the case of having a plurality of glass transition temperatures) of 60 ° C. or higher and 180 ° C. or lower, and 80 ° C. or higher and 140 ° C. It is more preferable that it is the following thermoplastic polymer. The thermoplastic polymer is more preferably a water-insoluble thermoplastic polymer from the viewpoint of improving compatibility with the ethylenically unsaturated compound of component (c).

  Specific examples of such heat-adhesive polymers of component (b) include (meth) acrylic polymers, styrene polymers, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate, polyesters and rosin polymers, and Examples thereof include block copolymers and graft copolymers containing these polymer units. Of these, only one type may be used, or a plurality of types may be used in combination. As a criterion for selection of the thermoadhesive polymer of component (b), it is preferable to select one having an affinity for the material of the transfer target. For example, when transferring the transfer layer to the methacrylic resin plate, it is preferable to use a polymer mainly composed of methyl methacrylate units, and from the viewpoint of further improving the adhesion to the methacrylic resin plate, A (meth) acrylic polymer containing a hydroxyl group is more preferred.

  As the component (c) of the curable resin composition forming the adhesive layer constituting the transfer layer of the transfer material of the present invention, that is, as the ethylenically unsaturated compound polymerizable by active energy rays, the curable resin composition The cured resin layer is not particularly limited as long as it exhibits thermal adhesiveness. For example, it contains a compound having at least two ethylenic double bonds in the molecule, and is active energy in the presence of a polymerization initiator. Examples thereof include compounds that can be polymerized by irradiation with rays (for example, ultraviolet rays, visible light, electron beams, X-rays, etc.). Here, in this specification, acryloyl group or methacryloyl group is abbreviated as (meth) acryloyl group, acrylate group or methacrylate group is abbreviated as (meth) acrylate group, and acrylic acid or methacrylic acid is abbreviated as (meth) acrylic acid. Sometimes.

  Specific examples of the polymerizable ethylenically unsaturated compound of component (c) include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth). Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclo Pentenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxy Chill (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxy Ethyl (meth) acrylate, biphenoxyethyl (meth) acrylate, biphenoxyethoxyethyl (meth) acrylate, norbornyl (meth) acrylate, phenylepoxy (meth) acrylate, (meth) acryloylmorpholine, N- [2- (meth) Acryloylethyl] -1,2-cyclohexanedicarboximide, N- [2- (meth) acryloylethyl] -1,2-cyclohexanedicarbomido-1-ene, N- [2- (meth) acrylic Monofunctional (meth) acrylate monomers such as [Ilethyl] -1,2-cyclohexanedicarbomido-4-ene, γ- (meth) acryloyloxypropyltylimethoxysilane; N-vinylpyrrolidone, N-vinylimidazole, N -Vinyl monomers such as vinyl caprolactam, styrene, α-methylstyrene, vinyl toluene, allyl acetate, vinyl acetate, vinyl propionate, vinyl benzoate; 1,4-butanediol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol pivalic acid ester di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene Recall di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol-A-diglycidyl ether di (meth) acrylate, epoxy-modified bisphenol-A-diacrylate, ethylene oxide-modified bisphenol- Bifunctional (meth) acrylates such as A-di (meth) acrylate, ethylene oxide-modified diacrylate of 1,4-cyclohexanedimethanol, zinc di (meth) acrylate, bis (4- (meth) acrylthiophenyl) sulfide; Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol pen (Meth) acrylate, pentaerythritol hexa (meth) acrylate, tri (meth) acrylate of ethylene oxide-added trimethylolpropane, tetra (meth) acrylate of ethylene oxide-added ditrimethylolpropane, tri (meth) acrylate of propylene oxide-added trimethylolpropane ) Acrylate, tetra (meth) acrylate of propylene oxide-added ditrimethylolpropane, tetra (meth) acrylate of ethylene oxide-added pentaerythritol, tetra (meth) acrylate of propylene oxide-added pentaerythritol, dipentaerythritol penta (meth) acrylate, ethylene Oxide addition dipentaerythritol penta (meth) acrylate, propylene oxide addition Pentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added dipentaerythritol hexa (meth) ) Trifunctional or higher polyfunctional monomers such as acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl formal, 1,3,5-triacryloylhexahydro-s-hydrazine, isocyanuric acid EO-modified triacrylate; urethane Examples include oligoacrylates such as acrylates and ester acrylates. Of these, polyfunctional monomers having two or more functions are preferably used. These ethylenically unsaturated compounds can be used alone or in combination of two or more.

  Along with the polymerizable ethylenically unsaturated compound of component (c), if necessary, a vinyl ether, epoxy or oxetane compound that can be cationically polymerized in the presence or absence of a catalyst compound is used in combination. You can also

  Specific examples of vinyl ether compounds include ethylene oxide modified bisphenol-A-divinyl ether, ethylene oxide modified bisphenol-F-divinyl ether, ethylene oxide modified catechol divinyl ether, ethylene oxide modified resorcinol divinyl ether, ethylene oxide modified hydroquinone divinyl ether, Examples include ethylene oxide-modified 1,3,5, benzenetriol trivinyl ether.

  Specific examples of the epoxy compound include 1,2-epoxycyclohexane, 1,4-butanediol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylolpropane dichloride. Examples thereof include glycidyl ether, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, glycidyl ether of phenol novolac, and bisphenol A diglycidyl ether.

  Specific examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl- 3- (2-ethylhexyloxymethyl) oxetane and the like can be mentioned.

  Moreover, as a polymerization initiator of the component (d) of the curable resin composition that forms the adhesive layer constituting the transfer layer of the transfer material of the present invention, the type of active energy rays that are curing means (ultraviolet rays, visible light, It can be appropriately selected according to the electron beam or the like. Moreover, when performing photopolymerization, it is desirable to use a photoinitiator and to use together one or more known photocatalytic compounds selected from a photosensitizer, a photo accelerator and the like.

  Specific examples of the photopolymerization initiator include 2,2-dimethoxy-2-phenylacetone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4-diaminobenzophenone, Benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-oxanthone, camphorquinone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one and the like. Moreover, the photoinitiator which has at least 1 (meth) acryloyl group in a molecule | numerator can also be used.

  The content of the photopolymerization initiator in the curable resin composition is preferably 0.1% by weight or more and 10% by weight or less, more preferably in the solid content excluding the diluent (including components that solidify after curing). Is 3% by weight or more and 5% by weight or less.

  A photosensitizer may be blended with the photopolymerization initiator in the curable resin composition in order to promote photopolymerization. Specific examples of the photosensitizer include 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like. In the present invention, a photo accelerator may be used together with the photo polymerization initiator in order to promote photo polymerization. Specific examples of the photo accelerator include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and the like. it can.

  Further, when the adhesive layer constituting the transfer layer of the transfer material of the present invention is formed, in order to apply the curable resin composition as a thin film on the chargeable bird coat layer, the curable resin composition includes: Diluent can be added. In that case, the addition amount of a diluent can be suitably determined according to the layer thickness etc. of the target adhesive layer.

  The diluent that can be used in the curable resin composition for forming the adhesive layer is not particularly limited as long as it is a diluent used in general resin coatings, but ketone compounds such as acetone, methyl ethyl ketone, and cyclohexanone. Ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, methoxyethyl acetate; ether compounds such as diethyl ether, ethylene glycol dimethyl ether, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, dioxane; aroma such as toluene and xylene Aliphatic compounds; aliphatic compounds such as pentane and hexane; halogenated hydrocarbons such as methylene chloride, chlorobenzene and chloroform; alcohol compounds such as methanol, ethanol, normal propanol and isopropanol; Rukoto can.

  If necessary, the curable resin composition for forming the adhesive layer may further include an inorganic filler, a polymerization inhibitor, a color pigment, a dye, an antifoaming agent, a leveling agent, a dispersant, a light diffusing agent, and a plasticizer. In addition, an antistatic agent, a surfactant, a non-reactive polymer, a near-infrared absorbing material, and the like can be added as long as the effects of the present invention are not impaired.

  Moreover, the curable resin composition that forms the adhesive layer is prepared by uniformly mixing the components (b) to (d) described above and other components blended as necessary according to a conventional method. can do.

  As the base film having a release layer constituting the transfer material of the present invention, a film-like acrylic resin, polyethylene terephthalate, polycarbonate, polystyrene, styrene-acrylic copolymer, vinyl chloride resin, polyolefin, ABS (acrylonitrile-butadiene) -Styrene copolymer) and the like can be used. Moreover, as a mold release layer provided in a base film, the silicone resin layer widely used as a mold release layer, a polyolefin resin layer, especially a polyolefin resin layer, for example, a low density polyethylene layer, can be mentioned preferably.

  The transfer material of the present invention is obtained by laminating a transfer layer on the release layer of a base film having a release layer, and the transfer layer includes at least an antistatic hard coat layer and an adhesive layer. There is no particular limitation as long as it is a layer, but it is further an antireflection layer, an antiglare layer, a printing layer, a decorative layer such as a colored layer, a vapor deposition layer (conductive layer) made of a metal or a metal compound, a primer layer, an intermediate layer, an antibacterial layer A multilayer structure of three or more layers including the above may be used.

  Specific examples of the layer structure of the transfer layer include a hard coat layer / adhesive layer, a hard coat layer / intermediate layer / adhesive layer, a hard coat layer / picture layer / adhesive layer, a colored layer / hard coat layer / adhesive layer, and a reflective layer. Examples include a prevention layer / hard coat layer / adhesion layer.

  The thicknesses of the hard coat layer and the adhesive layer are not particularly limited, but are usually appropriately selected from the range of about 0.5 to 50 μm. 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 50 μm.

  The transfer material of the present invention can be produced according to a production method including the following steps (A) to (D).

Step (A)
A coating method using a roll used in an impregnation method, a relief printing method, a lithographic printing method, an intaglio printing, or the like, on the release layer of the base film having a release layer, a film of a resin composition for forming a hard coat layer It is formed by a spray method such as spraying on a base material, curtain flow coating or the like.

  In addition, when the diluent (solvent) is contained in the resin composition for hard-coat layer formation, it is preferable to remove a diluent beforehand before implementing the process (B) mentioned later. In this case, it is usually evaporated by heating. As the method, a heating furnace, a far infrared furnace, a super far infrared path, or the like can be used.

Process (B)
When the film made of the resin composition for forming a hard coat layer obtained in the step (A) is an active energy ray curable, the film is cured by irradiating with an active energy ray to be antistatic. A hard coat layer is formed. A wide range of active energy rays such as ultraviolet rays, visible rays, lasers, electron beams, and X-rays can be used. 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. Moreover, when a hardening component is thermosetting, an antistatic hard-coat layer is formed by heating more than hardening temperature using a heating furnace, a far infrared furnace, or a super far infrared furnace.

Process (C)
A film of a curable resin composition for forming an adhesive layer on an antistatic hard coat layer, a coating method using a roll used in an impregnation method, a relief printing method, a lithographic printing method, an intaglio printing, a base It is formed by a spray method such as spraying on the material, curtain flow coating, or the like.

  In addition, when the diluent (solvent) is contained in the curable resin composition for forming an contact bonding layer, it is preferable to remove a diluent previously before implementing the process (D) mentioned later. In this case, it is usually evaporated by heating. As the method, a heating furnace, a far infrared furnace, a super far infrared furnace, or the like can be used.

Process (D)
The film made of the curable resin composition obtained in the step (C) is cured by irradiating active energy rays in the same manner as in the step (B) to form an adhesive layer. Thereby, a transfer material is obtained in which a transfer layer composed of an antistatic hard coat layer and an adhesive layer is formed on the release layer of the base film having the release layer from the release layer side.

  Since the transfer material of the present invention described above has a specific surfactant at the interface between the release layer of the base film of the transfer material and the antistatic hard coat layer of the transfer layer, the release layer and the antistatic The adhesive strength between the adhesive hard coat layer is lower than the adhesive strength between the antistatic hard coat layer and the adhesive layer. Therefore, it can be satisfactorily peeled between the release layer of the base film and the antistatic hard coat layer of the transfer layer during the transfer operation. Moreover, since an antistatic hard coat layer that becomes the outermost surface after transfer can be provided, it can be advantageously used as a material for producing a laminate having an antistatic hard coat layer on the surface by a transfer method. it can. A preferable structure of such a laminate is a structure in which a transfer material such as a plastic material, a glass material, a metal material, or a wooden material is transferred from the adhesive layer side of the transfer layer of the transfer material of the present invention. . Such a laminate is transferred by bringing the adhesive layer of the transfer layer of the transfer material of the present invention into intimate contact with the transfer target and thermocompression bonding using a known hot press apparatus or hot roll laminating apparatus. Can be manufactured. Here, the heating temperature at the time of transfer varies depending on the type of transfer material and the material to be transferred, etc., but for example, when the base film of the transfer material is polyethylene terephthalate, it is preferably 80 ° C. to 180 ° C., and 120 ° C. to 170 ° ° C is more preferred. Furthermore, it is also preferable that the transfer object is brought into close contact with heating. For example, when the transfer object is an acrylic resin, the transfer object is preferably heated to 50 ° C. to 100 ° C., and heated to 60 to 90 ° C. It is more preferable. As for the pressure during transfer, the linear pressure is preferably 100 g / cm or more, and more preferably 1000 g / cm or more.

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

Reference Example 1 (Preparation of base resin composition for forming antistatic hard coat layer)
As a resin composition for forming a hard coat layer, urethane acrylate (trade name: Diabeam UK-6074 manufactured by Mitsubishi Rayon Co., Ltd.) 26.1 parts by mass, PMMA (trade name: manufactured by Parapet HR-L Kuraray Co., Ltd.) 2.9 parts by mass, light In order to form a hard coat layer by uniformly mixing 0.7 parts by mass of a polymerization initiator (trade name: Irgacure 184, manufactured by Ciba Geigy Japan Ltd.), 52.5 parts by mass of methyl ethyl ketone, and 17.5 parts by mass of n-hexane. The photocurable base resin composition was prepared.

Reference Example 2 (Preparation of curable resin composition for forming adhesive layer)
8.6 parts by mass of epoxy ester (trade name: M-600A, manufactured by Kyoeisha Chemical Co., Ltd.) and γ-methacryloyloxypropyltrimethoxysilane (trade name: KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.) as the curable resin composition for forming an adhesive layer. 7 parts by mass, epoxy-modified bisphenol A diacrylate (trade name: Biscote # 540, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 5.7 parts by mass, isocyanuric acid EO-modified triacrylate (trade name: Aronix M-315, manufactured by Toagosei Co., Ltd.) 2.9 Parts by weight, acrylic polyol (trade name: ACRICID A-814, manufactured by Dainippon Ink & Chemicals, Inc.) 5.8 parts by weight, photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Geigy Japan), methyl ethyl ketone 52. 4 parts by mass and 17.5 parts by mass of isopropyl alcohol are mixed uniformly. By, to prepare a bonding layer photocurable resin composition.

  In the obtained adhesive layer photocurable resin composition, the component belonging to component (b) is an acrylic polyol, and the component belonging to component (c) is an epoxy ester, γ-methacryloyloxypropyltrimethoxysilane, epoxy A modified bisphenol A diacrylate and an isocyanuric acid EO-modified triacrylate. With regard to the component (b) and the component (c), the former blending amount (parts by mass) is (Awt), and the latter blending amount (parts by mass) is (Bwt). ), The value of “(Awt) / {(Awt) + (Bwt)}” is 0.20, and the value of “(Bwt) / {(Awt) + (Bwt)}” is 0.80. The average crosslink density (v) was 1.70, and the average value (δ) of the solubility parameter (sp value) was 10.3.

Examples 1-4, Comparative Examples 1-3
A surfactant shown in Table 1 was added to the photocurable base resin composition obtained in Reference Example 1 to prepare a resin composition for forming a hard coat layer. The obtained resin composition for forming a hard coat layer was applied on a release-treated polyethylene terephthalate film (trade name: Ester film, manufactured by Toyobo Co., Ltd.) so that the dry thickness was 5 μm, and dried at 80 ° C. for 30 seconds. After that, the obtained coating film was cured by applying ultraviolet irradiation (conveyor speed: 1 m / min, distance between light source and irradiated object: 10 cm, manufactured by USHIO INC.) Twice to form an antistatic hard coat layer.

  On the obtained antistatic hard coat layer, the adhesive layer photocurable resin composition obtained in Reference Example 2 was applied to a dry thickness of 5 μm and dried at 80 ° C. for 30 seconds. The resulting coating film was cured by UV irradiation (conveyor speed: 1 m / min, distance between light source and irradiated object: 10 cm, manufactured by Ushio Inc.) to form an adhesive layer, thereby obtaining a transfer material. .

  The obtained transfer material is stacked on a 2 mm-thick polymethyl methacrylate plate from the transfer layer side, and they are heated and pressurized (conditions: plate temperature 80 ° C., roll speed 1 m / min, roll temperature 160 ° C.), and transferred. By peeling off the base film of the material, a laminate in which the transfer layer was transferred onto the polymethyl methacrylate plate was obtained.

  The obtained transfer material or laminate was evaluated for the following test items. The results obtained are shown in Table 1.

  Adhesiveness: The obtained laminate was cut with a cutter in a 1 mm-interval grid, and then evaluated according to JIS K5400. In addition, when the part peeled in the comparative example was observed with the optical microscope, peeling had arisen between the antistatic hard-coat layer and the contact bonding layer.

  Pencil hardness: It was evaluated according to JIS K5600-5-4 using a pencil scratch coating film hardness tester (manufactured by Toyo Seiki Co., Ltd.).

Surface resistivity: Evaluated according to JIS K-6911 using a digital electrometer (ultra-high resistance microammeter R8340 (manufactured by Advantest)) after storing the laminate for 1 week at 25 ° C. and 50% RH. did.

Table 1 Note * 1: Represents the mass ratio of the composition to the solid content * 2: Wako Pure Chemical Industries, Ltd. * 3: Product name Adeka Coal EC-4500, Asahi Denka Kogyo Co., Ltd. * 4: Product name Antox MS-2N Manufactured by Nippon Emulsifier Co., Ltd. * 5: Average molecular weight 400 Wako Pure Chemical Industries, Ltd.

  From the results of Table 1, Examples 1 to 4 using surfactants having an unsaturated linear hydrocarbon group having 17 or 18 carbon atoms or a saturated linear hydrocarbon group having 8 carbon atoms in the antistatic hard coat layer. In the case of the transfer material or laminate, it can be seen that good adhesion, good pencil hardness, and good surface resistivity are exhibited. In particular, the adhesion evaluation shows that the adhesive strength between the release layer and the antistatic hard coat layer is lower than the adhesive strength between the antistatic hard coat layer and the adhesive layer. . On the other hand, in the case of Comparative Examples 1 to 3 using a surfactant other than the surfactant having a linear hydrocarbon group having 8 to 30 carbon atoms, the adhesion, pencil hardness, and surface resistance are all insufficient. It turns out that it is a result.

Examples 5-9
To 28.6 parts by mass of the composition shown in Table 2, 1.4 parts by mass of a photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Geigy Japan Ltd.), 52.4 parts by mass of methyl ethyl ketone, and 17.5 parts by mass of isopropyl alcohol were added. A photocurable resin composition for an adhesive layer was prepared by mixing. Table 2 also shows the numerical values of “(Awt) / {(Awt) + (Bwt)}” and “(Bwt) / {(Awt) + (Bwt)}”, the photocurable resin composition for the adhesive layer. The cross-linking density (v (mol / L)) and the average value δ of the solubility parameter (sp value) between the thermoadhesive polymer and the polymerizable ethylenically unsaturated compound are shown.

  The resin composition for forming a hard coat layer obtained in Example 2 was applied on a release-treated polyethylene terephthalate film (trade name: Ester film, manufactured by Toyobo Co., Ltd.) so as to have a dry thickness of 5 μm, and 80 ° C. After drying for 30 seconds, the resulting coating film is cured by UV irradiation (conveyor speed: 1 m / min, distance between light source and irradiated object: 10 cm, manufactured by Ushio Inc.) twice to cure the coating film. Formed.

  On the obtained antistatic hard coat layer, the above-mentioned photocurable resin composition for adhesive layer was applied so as to have a dry thickness of 5 μm, dried at 80 ° C. for 30 seconds, and then obtained coating film Were irradiated with ultraviolet rays (conveyor speed: 1 m / min, distance between light source and irradiated object: 10 cm, manufactured by Ushio Inc.) and cured twice to form an adhesive layer, thereby obtaining a transfer material.

  Using the obtained transfer material, a laminate in which the transfer layer was transferred onto a polymethyl methacrylate plate in the same manner as in Example 1 was obtained. The obtained transfer material and laminate were tested and represented in the same manner as in Example 1. The obtained results are shown in Table 2. In addition, the glass transition temperature (Tg) of each polymer shown in Table 2 is a value measured by METTLER TA 4000.

Comparative Example 4
A curable resin composition comprising 30 parts by mass of urethane acrylate (trade name UK-3320HC, manufactured by Negami Kogyo Co., Ltd.), 1.5 parts by mass of a photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Geigy Japan Ltd.) and 68.5 parts by mass of methyl ethyl ketone. The product was coated on a release-treated polyethylene terephthalate film (trade name: Ester film, manufactured by Toyobo Co., Ltd.) so as to have a dry thickness of 5 μm, dried at 80 ° C. for 30 seconds, and then the resulting coating film was irradiated with ultraviolet rays. (Conveyor speed: 1 m / min, distance between light source and irradiated object: 10 cm, manufactured by Ushio Inc.) was cured twice to obtain a transfer material.

  The obtained transfer material is stacked on a 2 mm-thick polymethyl methacrylate plate from the transfer layer side, and they are heated and pressurized (conditions: plate temperature 80 ° C., roll speed 1 m / min, roll temperature 160 ° C.), and transferred. By peeling off the base film of the material, an attempt was made to obtain a laminate in which the transfer layer was transferred onto the polymethyl methacrylate plate, but the transfer layer was not transferred onto the polymethyl methacrylate plate. Therefore, separately, the above resin composition was applied onto a polymethyl methacrylate plate so that the solid content film thickness was 5 μm, dried at 80 ° C. for 30 seconds, and then the obtained coating film was irradiated with ultraviolet rays (conveyor). A speed of 1 m / min, a distance of 10 cm between the light source and the object to be irradiated, manufactured by Ushio Inc.) was performed twice and cured to obtain a laminate.

About the obtained transfer material or laminated body, it test-evaluated about the test item similar to Examples 5-10. The obtained results are shown in Table 2.

Table 2 Note:
* 6: Product name manufactured by Parapet HR-L Kuraray Co., Ltd. * 7: Product name Acridick A-814, manufactured by Dainippon Ink & Chemicals, Inc. * 8: Product name manufactured by Poly-Pale Eastman Chemical Co., Ltd. * 9: Epoxy-modified bisphenol-A -Diacrylate, trade name Viscoat # 540, manufactured by Osaka Organic Chemical Industry * 10: Trade name M315, manufactured by Toa Gosei Co., Ltd. * 11: Epoxy-modified phenoxyacrylate, trade name M600A, manufactured by Kyoeisha Chemical Co., Ltd. * 12: γ-acryloyloxy Propyltrimethoxysilane, trade name KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd. * 13: Dipentaerythritol hexaacrylate, trade name DPHA, manufactured by Nippon Kayaku Co., Ltd. * 14: trade name, UN-3320HC, manufactured by Negami Kogyo Co., Ltd. * 15: Transferable Z The value is a value measured by laminating on an acrylic plate.

  From the results of Table 2, in Examples 5 to 9 that satisfy all the requirements of the present invention, the surface hardness is higher than in the case of Comparative Example 4 that does not satisfy any of the requirements of the present invention, and antistatic It can be seen that it has excellent properties and adhesion. In the case of Example 10 where the blending ratio of (b) the heat-adhesive polymer and (c) the ethylenically unsaturated compound polymerizable by the active energy ray is not included in the preferred range of the present invention, the surface Although it is as excellent as Example 5-9 in the point of hardness or antistatic property, it turns out that it is inferior to them in the point of adhesiveness.

According to the transfer material of the present invention, a transfer layer including an antistatic hard coat layer having a high surface hardness and an antistatic function can be easily transferred onto the surface of a transfer object. Therefore, the laminate to which the transfer layer has been transferred is provided with an antistatic hard coat layer on the outermost surface, so that it can be advantageously used for optical members such as nameplates and display front plates.

Claims (4)

  A transfer material in which a transfer layer including at least an antistatic hard coat layer and an adhesive layer is provided on a base film having a release layer so that the release layer and the antistatic hard coat layer are in contact with each other. The antistatic hard coat layer so that the adhesive strength between the release layer and the antistatic hard coat layer is lower than the adhesive strength between the antistatic hard coat layer and the adhesive layer. A transfer material containing a surfactant having a straight chain hydrocarbon group having 8 to 30 carbon atoms as component (a). The adhesive layer comprises the following components (b) to (d):
(B) a thermoadhesive polymer;
(C) an ethylenically unsaturated compound that can be polymerized by active energy rays; and (d) a polymerization initiator, the amount (parts by mass) of component (b) being (Awt), and the amount of component (c) When (part by mass) is (Bwt), the following formulas (1) and (2)

The transfer material according to claim 1, wherein the transfer material is a heat-adhesive curable resin layer comprising a curable resin composition satisfying the above relationship.   The transfer material according to claim 2, wherein the component (b) the heat-adhesive polymer is a (meth) acrylic polymer containing a hydroxyl group. A laminate in which the transfer layer of the transfer material according to any one of claims 1 to 3 is transferred to the surface of a transfer object, wherein the pencil hardness of the antistatic hard coat layer on the surface of the transfer layer is 3H. A laminate having a surface resistivity of 1.0 × 10 ¹⁴ Ω / □ or less.