JP2013082833A - Active energy ray curable hard coat resin composition having gravure printability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable hard coat resin composition having gravure printability.SOLUTION: The active energy ray curable hard coat resin composition includes: a bifunctional urethane (meth)acrylate oligomer having two (meth)acrylate groups in one molecule thereof and having a weight average molecular weight of 1,000 to 100,000; a monofunctional (meth)acrylate monomer having one (meth)acrylate group in one molecule thereof and having a molecular weight of 1,000 or less; a multifunctional (meth) acrylate monomer having two or more (meth)acrylate groups in one molecule thereof and having a molecular weight of 2,000 or less; and colloidal silica having a surface modified with a photopolymerizable functional group, wherein when the resin composition is converted into a composition for printing having a nonvolatile content of 50 mass% or more by dissolving it in an organic solvent for a gravure ink, the viscosity of the composition for printing is 200 mPa s or less at room temperature.

Description

  The present invention relates to a hard coat resin composition used for forming a hard coat layer of a transfer sheet, and more particularly to an active energy ray-curable hard coat resin composition having gravure printability.

  A method of protecting or decorating the surface of an article such as a plastic part or an exterior part using a transfer sheet is conventionally known. For example, Patent Document 1 discloses a transfer sheet in which a transfer layer is formed on the surface of a base sheet as a support, and the transfer sheet is inserted into an injection mold and in-mold injection molded, and then the base sheet To obtain a decorated injection-molded body (injection molding simultaneous transfer) is described.

  The transfer sheet has a structure in which a transfer layer is provided on a base sheet as a support, and this transfer layer is transferred from the base sheet to the surface of the decorative article. The transfer layer transferred to the surface of the article to be decorated is a laminated body in which a resin or a pattern is laminated in a layer shape, and forms a protective coating or a decorative coating on the surface of the article.

  In applications where the protection function for decorative articles is important, a hard coat layer is provided on the outermost side of the transfer layer. The hard coat layer refers to a coating layer exhibiting high hardness. The hard coat layer has a thickness or a resin amount necessary to maintain hardness, and generally contains a crosslinked resin.

  Conventionally, the surface protection of the article to be decorated is generally performed as a whole, and the hard coat layer has been formed on the entire surface of the transfer sheet. However, the need for surface protection differs depending on the part of the article to be decorated. For example, a pattern formed on a part of the surface of the decorated article is easily noticeable when it is damaged, and surface protection is required, whereas a plain part of the decorated article is less necessary for surface protection. Further, for example, the edge or corner of the decorated article is easily worn or damaged, and surface protection is required, whereas the recessed or flat part of the decorated article is less necessary for surface protection.

  Recently, the means for expressing the appearance of articles has become more sophisticated, and changes over time such as scratches, abrasion or fading on the article surface have also been used as means for aesthetic expression, and the parts or patterns of the decorated article Accordingly, it is necessary to provide a difference in the degree of change in appearance over time.

  Thus, it is necessary to partially protect the surface of the article to be decorated, and the hard coat layer of the transfer sheet is required to be formed on a part of the surface of the transfer sheet as a pattern or a pattern background.

  Patent Document 2 discloses ionizing radiation containing a non-crosslinked thermoplastic acrylic resin and a prepolymer having two or more acryloyl groups or methacryloyl groups in one molecule, which are used to form a hard coat layer of a transfer sheet. A curable resin composition is described.

  After the diluted solvent is dried, the ionizing radiation curable resin composition of Patent Document 2 becomes a non-adhesive solid even in an uncured state (uncrosslinked state). Therefore, the crosslinkable resin layer formed from this resin composition can be passed through a printing machine before being crosslinked, and functional layers such as a pattern layer and an adhesive layer can be sequentially formed on the surface. It is. Moreover, the manufactured transfer sheet can be wound and stored and transported on a roll before the crosslinkable resin layer is crosslinked.

  However, the transfer sheet in which the crosslinkable resin layer is uncured has a problem that it is easily blocked in a state where it is wound around a roll. Since the transfer sheet is stored and distributed as a roll and is used after being drawn out from the roll, the storage stability and the feed stability in a state of being wound on the roll are important evaluation factors for performance.

  In addition, the ionizing radiation curable resin composition has a relatively large molecular weight of the constituent polymer. Therefore, in order to obtain a printing composition having a viscosity suitable for printing, it is diluted with a relatively large amount of an organic solvent. Therefore, it is necessary to reduce the nonvolatile content, and it is difficult to form a hard coat layer having a sufficient thickness using a gravure printing method. In fact, in Patent Document 2, in all specific examples of the transfer sheet, the hard coat layer is formed on the entire surface of the base sheet from an ionizing radiation curable resin composition diluted with an organic solvent using a coating method. Yes.

  In order to form a pattern on the surface of the sheet-like material with practical accuracy and industrial efficiency, it is necessary to use a gravure printing method. Therefore, the gravure printing suitability of the resin composition forming the pattern or the pattern background is It is an important evaluation factor.

WO97 / 40990 JP-A-7-314995

  The present invention solves the above-mentioned conventional problems, and an object of the present invention is to provide an active energy ray-curable hard coat resin composition having gravure printability.

The present invention relates to a bifunctional urethane (meth) acrylate oligomer having two (meth) acrylate groups in one molecule and having a mass average molecular weight of 1,000 to 100,000;
A monofunctional (meth) acrylate monomer having one (meth) acrylate group in one molecule and a molecular weight of 1000 or less;
A polyfunctional (meth) acrylate monomer having two or more (meth) acrylate groups in one molecule and a molecular weight of 2000 or less; and colloidal silica whose surface is modified with a photopolymerizable functional group;
An active energy ray-curable hard coat resin composition comprising:
When dissolved in an organic solvent for gravure ink to give a printing composition having a nonvolatile content of 50% by mass or more, the viscosity of the printing composition is 200 mPa · s or less at room temperature.
An active energy ray-curable hard coat resin composition is provided.

  In one certain form, the said polyfunctional (meth) acrylate monomer is contained in the amount of 10-30 mass% in a polymeric component, and the said colloidal silica is 3 in an active energy ray hardening-type hard coat resin composition. It is contained in an amount of ˜18% by mass.

  In one form, the formula

[Wherein, x is a mass part of colloidal silica with respect to 100 parts by mass of the polymerizable component, and y is mass% in the polymerizable component of the polyfunctional (meth) acrylate monomer. ]
The relationship is satisfied.

  In one form, the formula

[Wherein, x is a mass part of colloidal silica with respect to 100 parts by mass of the polymerizable component, and y is mass% in the polymerizable component of the polyfunctional (meth) acrylate monomer. ]
The relationship is satisfied.

  In one embodiment, the polyfunctional (meth) acrylate monomer is pentaerythritol triacrylate, pentaerythritol tetraacrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, caprolactone modified. Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, propylene oxide modified ditrimethylolpropane tri (meth) acrylate, ethylene oxide modified ditrimethylolpropane tri (meth) acrylate, caprolactone modified ditrimethylolpropane tri (meth) It is at least one selected from the group consisting of acrylates.

  In one certain form, the average particle diameter of the said colloidal silica is 5-200 nm.

  In one certain form, the hardness of the said hard-coat layer is 2H or more of pencil hardness.

  In one certain form, one of the said active energy ray hardening-type hard-coat resin compositions is used for forming a hard-coat layer as a design or a design background.

  The present invention also provides a transfer sheet having a hard coat layer made of a cured resin crosslinked by irradiating one of the active energy ray-curable hard coat resin compositions with active energy rays.

In one certain form, the said hard-coat layer is,
Printing one of the active energy ray-curable hard coat resin compositions on the surface of the base sheet by a gravure printing method to form a crosslinkable resin layer; and a transfer layer on the surface of the crosslinkable resin layer Before the functional layer is formed, a step of irradiating the crosslinkable resin layer with an active energy ray and curing it;
It is formed by the method of including.

  In one certain form, the said hard-coat layer is formed as a design or a design background.

The present invention also includes a step of printing one of the active energy ray-curable hard coat resin compositions on the surface of the base sheet by a gravure printing method to form a crosslinkable resin layer;
Before the functional layer of the transfer layer is formed on the surface of the crosslinkable resin layer, the crosslinkable resin layer is irradiated with active energy rays and cured to form a hard coat layer;
Forming a functional layer of the transfer layer on the surface of the base sheet or hard coat layer as a continuous process in the same production line by gravure printing;
A method for producing a transfer sheet is provided.

Further, the present invention is a step of feeding any one of the transfer sheets into the molding die in such a direction that the outer side is in contact with the die cavity surface;
Closing the mold and filling the mold with the molten resin so that the molten resin is in contact with the inner surface (that is, the adhesive layer side) of the transfer sheet;
Cooling the resin, opening the mold and taking out the injection molded article; and peeling the base sheet;
A method for decorating the surface of an injection molded body comprising

  If the active energy ray hardening-type hard coat resin composition of this invention is used, the hard coat layer of a transfer sheet can be formed as one of the processes of forming a functional layer using a gravure printing method. Moreover, the hard coat layer of the obtained transfer sheet of the present invention is excellent in hardness and blocking resistance. Furthermore, since the relatively expensive hard coat layer is formed only in the necessary portion, the transfer sheet of the present invention is excellent in economic efficiency.

It is sectional drawing which shows typically the structure of the transfer sheet which is one Embodiment of this invention. It is sectional drawing which shows typically the structure of the transfer sheet which is other embodiment of this invention. It is a schematic diagram which shows the structure of a general multicolor gravure rotary printing press. In the hard coat resin compositions of Examples 1 to 9 and Comparative Examples 4 and 9 to 12, the relationship between the weight% of the polyfunctional monomer in the polymerizable component and the mass part of colloidal silica with respect to 100 parts by mass of the polymerizable component. It is a graph to show.

Hard Coat Resin Composition The hard coat resin composition of the present invention is an active energy ray curable type. Active energy rays are easier to apply than heat, and the crosslinking rate of the resin composition is also fast. Therefore, when the active energy ray-curable hard coat resin composition is used, after forming a crosslinkable resin layer of the resin composition, the following is performed as a continuous process in the same production line on the surface of the crosslinkable resin layer. Even when the functional layer is formed, the crosslinkable resin can be crosslinked before the functional layer is laminated.

  In general, in order to continuously print various functional layers on a sheet, an off-the-shelf multicolor gravure rotary press as shown in FIG. 3 is used. The main flow of printing in such a machine is that after a sheet to be printed is continuously fed out from the unwinding unit 11, first, in the first printing unit of the multicolor gravure rotary printing unit 12, the ink pan 15 is placed on the surface. By passing the sheet between a rotating plate cylinder 14 supplied with ink and an impression cylinder 16 that applies pressure to the plate cylinder 14, the ink is transferred onto the sheet to form a printing layer, and then the sheet. The printing layer is dried by passing it through a drying unit 18 such as a steam drum, hot air, or cold air, then the sheet is sent to the next printing unit, and another printing layer is formed on the sheet in the same manner as the previous printing unit. The process is repeated several times while changing or not changing the printing layer forming surface of the sheet as necessary, and after all the printing layers are formed, the sheet is wound around the winding unit 13. In this machine, the tension is finely adjusted by a large number of guide rolls 17 for registration.

  At that time, normal functional layers containing a thermoplastic resin such as a pattern layer and an adhesive layer lose their fluidity and tackiness by passing through the drying unit 18 of each printing unit, but the conventional active energy ray curing. The crosslinkable resin layer made of the mold resin composition will remain fluid and sticky when dried to that extent. This is because the drying unit 18 has a low heating temperature and a length of only about 2 m. In addition, since the sheet passing speed in the drying unit 18 is matched to the printing speed of the printing layer, the time for which the crosslinkable resin layer is heated in the drying unit 18 is, for example, about 3 seconds when the speed is 40 m / min. It is only possible.

  Moreover, although the crosslinking rate of the conventional active energy ray-curable resin composition is faster than that of the thermosetting resin composition, it is called a printing interval when a plurality of functional layers are continuously printed on the same production line (ie, inline). Not fast enough to cure in a short time.

  As a result, after forming the crosslinkable resin layer of the active energy ray curable resin composition and forming the next functional layer on the surface of the crosslinkable resin layer as a continuous process in the same production line, the substrate once The ink of the crosslinkable resin layer formed on the sheet is transferred to the guide roll 17 of the printing machine, or the ink such as the pattern layer and the adhesive layer is not transferred well from the plate cylinder 14 onto the crosslinkable resin layer. On the contrary, a so-called back trap occurs in which the ink of the crosslinkable resin layer once formed on the base sheet is transferred to the plate cylinder 14 forming the pattern layer, the adhesive layer, and the like.

  Therefore, in order to form a hard coat layer from an active energy ray-curable resin composition in the same manner as a normal functional layer containing a thermoplastic resin using an existing multicolor gravure rotary printing press, an active energy ray is used. After forming the crosslinkable resin layer from the curable hard coat resin composition, before forming the functional layer on the surface of the crosslinkable resin layer, make sure that the crosslinkable resin layer does not have fluidity or adhesiveness. There is a need.

  Preferred active energy rays for crosslinking the hard coat resin composition of the present invention include, for example, an electron beam, an X-ray, an ultraviolet ray, a visible ray, etc., preferably a wavelength of 200 to 400 nm, more preferably 220 to 300 nm ultraviolet light. Examples of the ultraviolet light source include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, and an electrodeless lamp, and a high-pressure mercury lamp is preferably used.

  The hard coat resin composition of the present invention contains an oligomer having a vinyl group and a monomer having a vinyl group. These are polymerizable components of the hard coat resin composition of the present invention. The hard coat resin composition of the present invention contains colloidal silica whose surface is modified with a photopolymerizable functional group.

  By doing so, a low viscosity suitable for performing gravure printing is maintained before crosslinking, and sufficient hardness and toughness are provided as a hard coat layer after crosslinking.

  The oligomer having a vinyl group has a mass average molecular weight of 1,000 to 100,000, preferably 2,000 to 10,000, more preferably 2,000 to 7,000. When the mass average molecular weight of the oligomer having a vinyl group is less than 1000, the formed hard coat layer has low flexibility and is easily cracked during molding. On the other hand, if the mass average molecular weight exceeds 100,000, the viscosity of the printing composition becomes too high, and it becomes difficult to perform gravure printing.

  The oligomer having a vinyl group has 2 or more, preferably 2 to 4, more preferably 2 vinyl groups in one molecule. If the number of vinyl groups in one molecule is less than 2, the hardness of the hard coat layer is low and the protective function is insufficient, and if it exceeds 4, the flexibility of the hard coat layer is low and the hard coat layer tends to crack. .

  The oligomer having a vinyl group is preferably a (meth) acrylate oligomer. The (meth) acrylate group is excellent in reactivity and can crosslink the hard coat resin composition in a short time. Of these, urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and epoxy (meth) acrylate oligomers are particularly preferable. These are because relatively many types are distributed and are not only easily available, but also a hard coat layer having an excellent balance between flexibility and hardness is formed.

  Examples of the urethane (meth) acrylate oligomer include an oligomer obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyisocyanate oligomer obtained by reacting a polyol and a polyisocyanate. Here, examples of the polyol include alkylene polyols such as ethylene glycol, propylene glycol, cyclohexane dimethanol, and 3-methyl-1,5-pentanediol; polyether polyols such as polyethylene glycol and polypropylene glycol; Alternatively, a polyester polyol that is a reaction product of a polyether polyol and an acid component such as a dibasic acid such as adipic acid, succinic acid, hexahydrophthalic acid, or terephthalic acid or an anhydride thereof may be used. Examples of polyisocyanates include tolylene diisocyanate, xylylene diisocyanate, mesitylene diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, or polyfunctional isocyanate obtained by polymerizing these. It is done. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

  The urethane (meth) acrylate oligomer is preferably of the formula

[Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group, R ³ is a residue of a diisocyanate, R ⁴ is a residue of a diol, and n is an integer of 1 or more. is there. ]
It is a compound which has a structure shown by these.

  As the monomer having a vinyl group, a monofunctional monomer having one vinyl group or a mixture of the monofunctional monomer and a polyfunctional monomer having a plurality of vinyl groups can be used. As the monomer having a vinyl group, it is particularly preferable to use a mixture of a monofunctional monomer having one vinyl group and a polyfunctional monomer having a plurality of vinyl groups.

  By including a monofunctional monomer having a small molecular weight, the resin composition can have a low viscosity suitable property for gravure printing. In addition, by including a polyfunctional (meth) acrylate monomer having a plurality of reaction points, the resin composition can have a property suitable for gravure printing in which it is immediately cured by irradiation with an active energy ray. . Although it is possible to reduce the viscosity with only the polyfunctional monomer without containing the monofunctional monomer, the acrylic equivalent becomes too low when the polyfunctional monomer alone is mixed with the oligomer, and the flexibility of the hard coat layer formed is lost. Cracks during molding. Therefore, it is preferable to use what mixed the monofunctional monomer which has one vinyl group, and the polyfunctional monomer which has several vinyl groups as a monomer to mix.

The monofunctional monomer has a molecular weight of 1000 or less, preferably 500 or less. If the molecular weight of the monomer having a vinyl group exceeds 1000, the viscosity of the printing composition becomes too high, and it becomes difficult to perform gravure printing.

  The monofunctional monomer having a vinyl group is preferably a (meth) acrylate monomer. Preferred (meth) acrylate monomers have the formula

[Wherein, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group, an alkenyl group, an alkynyl group, a hydroxyalkyl group, an aminoalkyl, or the like, and is not particularly limited. R ⁶ may contain a functional group or the like. ]
It is a compound which has a structure shown by these.

  Among these, preferable monofunctional monomers are N-acryloyloxyhexaethylhexahydrophthalimide and 2-ethylhexylethylene oxide (EO) modified acrylate.

  The polyfunctional monomer having a vinyl group has a molecular weight of 2000 or less, preferably 1000 or less. If the molecular weight of the monomer having a vinyl group exceeds 2000, the viscosity of the printing composition becomes too high, and it becomes difficult to perform gravure printing.

  The polyfunctional monomer having a vinyl group has up to 6, preferably 2 to 6, more preferably 3 vinyl groups in one molecule. If the number of vinyl groups in one molecule exceeds 6, the flexibility of the hard coat layer will be low and it will be easy to crack during molding.

  The polyfunctional monomer having a vinyl group is preferably a (meth) acrylate monomer. Examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and neopentyl glycol. Di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (Meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethyl Propane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, propylene oxide modified ditrimethylolpropane tri (meth) acrylate, ethylene oxide Modified ditrimethylolpropane tri (meth) acrylate, prolactone modified ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate , Caprolactone-modified pentaerythritol tri (meth) ac Rate, pentaerythritol tetra (meth) acrylate, propylene oxide modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Propylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, propylene oxide modified dipentaerythritol hexa (Meth) acrylate, ethylene oxide modified dipipe Examples include antaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and tris ((meth) acryloxyethyl) isocyanurate. These may be used alone or in combination of two or more.

  Among these, preferred polyfunctional monomers are pentaerythritol triacrylate, pentaerythritol tetraacrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth). ) Acrylate, ditrimethylolpropane tri (meth) acrylate, propylene oxide modified ditrimethylolpropane tri (meth) acrylate, ethylene oxide modified ditrimethylolpropane tri (meth) acrylate, caprolactone modified ditrimethylolpropane tri (meth) acrylate.

  The mixing ratio of the monofunctional monomer and the polyfunctional monomer is 1:20 to 20: 1 by mass ratio, preferably 1:10 to 10: 1, more preferably 1: 5 to 5: 1. When the mixing ratio of the monofunctional monomer is lower than 1:20, the acrylic equivalent is too low, and the formed hard coat layer has low flexibility and is easily cracked during molding. If the mixing ratio of the monofunctional monomer is higher than 20: 1, the acrylic equivalent becomes too high, and the hard coat layer formed has insufficient hard coat properties.

  The compounding ratio of the oligomer having a vinyl group and the monomer having a vinyl group is 0.5 to 50 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the oligomer having a vinyl group. .

  If the amount of the monomer having a vinyl group is less than 0.5 parts by mass relative to 100 parts by mass of the oligomer having a vinyl group, the viscosity of the printing composition becomes too high, and it becomes difficult to perform gravure printing. When the said amount of the monomer which has a vinyl group exceeds 50 mass parts, the leveling of a printing composition will worsen and the printability with a gravure printing machine will worsen.

  The polyfunctional monomer having a vinyl group is contained in an amount of 10 to 30% by mass in the polymerizable component of the hard coat resin composition of the present invention. The polymerizable component here specifically refers to a bifunctional urethane (meth) acrylate oligomer, a monofunctional (meth) acrylate monomer, and a polyfunctional (meth) acrylate monomer. These polymerizable components are sometimes referred to as “hard coat inks”.

  When the content of the polyfunctional monomer having a vinyl group is less than 10% by mass in the polymerizable component of the hard coat resin composition of the present invention, the hardness of the obtained hard coat layer becomes insufficient and exceeds 30% by mass. And cracks are likely to occur during transfer of the hard coat layer.

  In addition, content of the component in the hard-coat resin composition of this invention is expressed on the basis of a non volatile matter (solid content).

  When the hard coat resin composition of the present invention is a photocurable type, it contains a photopolymerization initiator having radical initiating ability. Examples of the photopolymerization initiator include 2-benzyl-2-dimethylamino-1-(-4-morpholinophenyl) butanone, 2-methyl-1 [4-methylthiophenyl] -2-morpholinopropane-1- ON, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethyl) Benzoyl) -phenylphosphine oxide, 2,4-diethylthioxanthone and the like are used.

  Among these photopolymerization initiators, 1-hydroxy-cyclohexyl-phenyl-ketone and the like are preferable. The cross-linking speed of the hard coat resin composition is improved, and the cross-linkable resin layer can be cured by irradiating light even during a short period of time, which is the printing interval when printing multiple functional layers in-line. Because it becomes. Generally a photoinitiator is 0.1-10 mass parts with respect to 100 mass parts of hard-coat resin compositions of this invention, Preferably it is used in the range of 1-5 mass parts.

  When the hard coat resin composition of the present invention is an electron beam curable type, it is not necessary to contain a photopolymerization initiator.

  Colloidal silica whose surface is modified with a photopolymerizable functional group is produced, for example, by subjecting colloidal silica dispersed in a solvent and a silane compound having a photopolymerizable functional group to a hydrolytic condensation reaction. A method for producing colloidal silica whose surface is modified with a photopolymerizable functional group is known, and is described, for example, in JP-A-2006-249322.

  As colloidal silica dispersed in a solvent, methanol silica sol MA-ST, isopropyl alcohol silica sol IPA-ST, n-butanol silica sol NBA-ST, ethylene glycol silica sol EG-ST, xylene / butanol silica sol XBA-ST, ethyl cellosolve silica sol ETC -ST, Butyl cellosolve silica sol BTC-ST, Dimethylformamide silica sol DBF-ST, Dimethylacetamide silica sol DMAC-ST, Methyl ethyl ketone silica sol MEK-ST, Methyl isobutyl ketone silica sol MIBK-ST Commercial products can be used.

  Examples of the silane compound having a photopolymerizable functional group include β- (meth) acryloyloxyethylmethyldimethoxysilane, β- (meth) acryloyloxyethylmethyldiethoxysilane, and β- (meth) acryloyloxyethyldimethyl. Methoxysilane, β- (meth) acryloyloxyethyldimethylethoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, β- (meth) acryloyloxyethyltriethoxysilane, γ- (meth) acryloyloxypropyldimethylmethoxysilane , Γ- (meth) acryloyloxypropyldimethylethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acrylic Silane compounds having a (meth) acryloyl group such as liloyloxypropyltrimethoxysilane and γ- (meth) acryloyloxypropyltriethoxysilane;

  Silane compounds having an allyl group such as allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, γ-allylaminopropyltrimethoxysilane, γ-allylaminopropyltriethoxysilane;

  Silane compounds having a vinyl group such as vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane; and

  p-vinylphenylmethyldimethoxysilane, p-vinylphenylmethyldiethoxysilane, p-vinylphenyltrimethoxysilane, p-vinylphenyltriethoxysilane, o-vinylphenyltrimethoxysilane, m-vinylphenyltrimethoxysilane, etc. A silane compound having a styryl group can be used.

  The colloidal silica whose surface is modified with a photopolymerizable functional group is a colloidal silica whose surface is modified with at least one selected from the group consisting of (meth) acryloyl group, allyl group, vinyl group and styryl group. . Among these, colloidal silica whose surface is modified with a (meth) acryloyl group is particularly preferable.

  The amount of photopolymerizable functional group on the surface of colloidal silica is double bond equivalent (average molecular weight per one side chain radically polymerizable unsaturated group) or alicyclic epoxy equivalent (per one side chain alicyclic epoxy group). Average molecular weight) is preferably 100 to 3000 g / mol on average from the charged value, from the viewpoint of improving scratch resistance and abrasion resistance. A more preferable range is an average of 100 to 1200 g / mol, and a most preferable range is an average of 100 to 800 g / mol. When the amount of the photopolymerizable functional group on the surface of the colloidal silica is less than 100 g / mol, the photopolymerization reaction proceeds excessively and the flexibility of the hard coat layer is lost. As a result, cracks occur in the hard coat layer when the transfer sheet is used. If it exceeds 3000 g / mol, the photopolymerization reaction hardly proceeds. As a result, the hardness of the hard coat layer decreases.

  The colloidal silica has an average particle size of 5 to 200 nm or less, preferably 5 to 100 nm, and more preferably 5 to 50 nm. When the average particle diameter of the colloidal silica exceeds 200 nm, the transparency of the obtained hard coat layer is lowered. If the thickness is less than 5 nm, the resulting hard coat layer will not exhibit the effect of friction resistance.

  In the active energy ray-curable hard coat resin composition, the colloidal silica is 3 to 18 parts by weight, preferably 4 to 16 parts by weight, more preferably 5 to 12 parts by weight with respect to 100 parts by weight of the polymerizable component. Contained in an amount. If the content of the colloidal silica is less than 3 parts by mass, the hardness of the obtained hard coat layer becomes insufficient, and if it exceeds 18 parts by mass, cracks are likely to occur during transfer of the hard coat layer.

  When the colloidal silica content is less than 1.75 parts by mass with respect to 100 parts by mass of the polymerizable component, scumming tends to occur during printing of the active energy ray-curable hard coat resin composition. If the amount exceeds 2 parts by mass, the printability of the active energy ray-curable hard coat resin composition is lowered. Here, the background stain refers to a phenomenon in which the ink constituting the pattern layer adheres to a part not intended to form the pattern layer when the pattern layer is partially formed on the hard coat layer. Printability is a general term for the ease with which ink can be printed. Specifically, it is the appearance of abuzz due to the appearance of a faint appearance or the inclusion of many particles.

  In the active energy ray-curable hard coat resin composition, the preferred content of the colloidal silica varies depending on the content of the polyfunctional monomer having a vinyl group. Although the reason is not clear, it is considered that the polyfunctional monomer having a vinyl group forms a crosslinked structure, and thus affects the dispersion stability of the colloidal silica in the resin matrix of the hard coat layer.

  That is, it is preferable that the contents of both components satisfy the relationship of the above formula (1). If this relationship is not satisfied, the hardness of the resulting hard coat layer tends to be insufficient. Moreover, it is preferable that content of both components also satisfies the relationship of the said Formula (2). If this relationship is not satisfied, the curing shrinkage of the hard coat layer increases, and cracks are likely to occur during transfer.

  The hard coat resin composition of the present invention may contain an auxiliary agent usually used for gravure ink. Such auxiliaries include colorants, leveling agents, antifoaming agents, matting agents, waxes, release modifiers, antistatic agents, light stabilizers, antioxidants, ultraviolet absorbers, viscosity modifiers, photosensitizers. Etc.

  The hard coat resin composition of the present invention is produced by mixing the above components. When mixing the components, an organic solvent, the above-mentioned auxiliary agent, and the like may be added as necessary.

Transfer sheet Figure 1 is a sectional view schematically showing the structure of a transfer sheet which is an embodiment of the present invention. A transfer layer 2 is provided in contact with one surface of the base sheet 1. The base sheet 1 may have a release layer (not shown) on the surface serving as a boundary with the transfer layer.

  The transfer layer 2 has a surface forming layer 4 that forms the outermost surface of the transfer sheet together with the hard coat layer 3 and the hard coat layer 3 formed as a pattern or a pattern background, for example, on the surface of the base sheet. And it has the contact bonding layer 6 as needed. Although not shown, the transfer layer may include a colored layer, a design layer, an anchor layer, a metal thin film, and the like as necessary. In the present specification, regarding the layer structure of the transfer sheet, the side of the article to be decorated is referred to as the inner side, and the viewer side is referred to as the outer side.

  The hard coat layer 3 is formed by a gravure printing method using the hard coat resin composition. Specifically, first, the hard coat resin composition is dissolved in an organic solvent to prepare a printing composition having a predetermined nonvolatile content.

  The organic solvent used for preparing the printing composition is preferably a volatile organic solvent conventionally used in gravure ink. This is because they are excellent in volatility, and the crosslinkable resin layer can be easily dried even during a short time of printing interval when a plurality of functional layers are continuously printed in-line. Specific examples of organic solvents for gravure inks include aromatic solvents such as toluene and xylene having a boiling point of 80 to 120 ° C., alcohol solvents such as normal propyl alcohol and isopropyl alcohol, ketone solvents such as methyl ethyl ketone (MEK), An ester solvent such as ethyl acetate can be used. Preferred are toluene, MEK and the like.

  The non-volatile content of the printing composition is 50% by mass or more, preferably 60 to 80% by mass, more preferably 60% by mass. When the non-volatile content of the printing composition is less than 50% by mass, the drying rate of the crosslinkable resin layer becomes slow, and the thickness of the hard coat to be formed becomes insufficient. When the non-volatile content of the printing composition exceeds 80% by mass, the viscosity increases and it becomes difficult to perform gravure printing.

  The viscosity of the printing composition is 200 mPa · s or less, preferably 100 mPa · s or less, more preferably 20 to 70 mPa · s at room temperature. If the viscosity of the printing composition is outside the above range at room temperature, it is difficult to perform gravure printing.

  Next, gravure printing is performed on the surface of the base sheet using the printing composition as an ink. The part where the pattern of the printing composition is formed is a part of the surface of the decorative article that needs to be protected, for example, a part corresponding to a convex part, a corner part, or a pattern part. Thereafter, the organic solvent is dried, and the hardenable layer 3 is formed by curing the crosslinkable resin layer by irradiating active energy rays.

  The drying and cross-linking speed of the active energy ray-curable resin composition of the present invention is very fast, and it is heated and dried even during a short time of a printing interval when a plurality of functional layers are continuously printed in-line. It can be crosslinked by irradiation with active energy rays.

  Therefore, when a hard coat layer is formed from the active energy ray-curable resin composition of the present invention using a ready-made multicolor gravure rotary printing press in the same manner as a normal functional layer containing a thermoplastic resin, an active energy ray is obtained. After forming the crosslinkable resin layer from the curable hard coat resin composition, before forming the functional layer on the surface of the crosslinkable resin layer, make sure that the crosslinkable resin layer does not have fluidity or adhesiveness. be able to.

  The thickness of the hard coat layer thus cured is 3 to 100 μm, preferably 4 to 50 μm, more preferably 5 to 10 μm. When the thickness of the hard coat layer is less than 3 μm, the hard coat property becomes insufficient, and when it exceeds 100 μm, cracks occur during molding.

  The hardness of the hard coat layer thus cured is a pencil hardness of H or higher, preferably 2H or higher and 4H or lower.

  The surface forming layer 4 may be, for example, an anchor layer that improves adhesion to a coating layer that forms a film, a colored layer that provides color, or a layer on an inner surface thereof.

  FIG. 2 is a sectional view schematically showing the structure of a transfer sheet according to another embodiment of the present invention. The transfer layer 2 further has a pattern layer 5 partially formed on the inner surface of the surface forming layer.

  Unless otherwise specified, each functional layer other than the hard coat layer among the layers constituting the transfer layer can be formed by a method similar to the conventional method. Examples of conventional layer forming methods include gravure coating methods, roll coating methods, comma coating methods and other printing methods using gravure coating methods, roll coating methods, comma coating methods, gravure printing methods, screen printing methods, etc. There is.

  Preferably, the functional layers of the transfer layer such as the surface forming layer 4, the design layer 5, and the adhesive layer 6 are used as continuous processes in the same production line by a gravure printing method using an off-the-shelf multicolor gravure rotary printing press. , Formed on the surface of the base sheet or hard coat layer. For example, the functional layer of the transfer layer is formed by spreading ink or paint on the surface of an adjacent layer.

  When the functional layer of the transfer layer is an anchor layer, the resin contained in the ink or paint is polyvinyl resin, polyamide resin, polyester resin, acrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin , Cellulose ester resin, alkyd resin, vinyl chloride vinyl acetate copolymer resin, thermoplastic urethane resin, methacrylic resin, acrylate ester resin, chlorinated rubber resin, chlorinated polyethylene resin, and chlorinated polypropylene It is preferably at least one synthetic resin selected from the group consisting of a resin.

  When the functional layer of the transfer layer is a colored layer, a design layer, or a coating layer, the synthetic resin that serves as the binder for the functional layer includes polyvinyl resins, polyamide resins, polyester resins, acrylic resins, polyurethane resins, and polyvinyl resins. Acetal resin, polyester urethane resin, cellulose ester resin, alkyd resin, vinyl chloride vinyl acetate copolymer resin, thermoplastic urethane resin, methacrylic resin, acrylate resin, chlorinated rubber resin, polyethylene chloride It is preferable that it is at least 1 sort (s) of synthetic resin selected from the group which consists of a resin and a chlorinated polypropylene resin.

  Examples of the colorant for the colored layer, the design layer, or the coating layer include pigments and dyes. As the colorant, those of the kind conventionally used for coloring the transfer sheet are used as necessary. Specific examples of preferable colorants include (1) plant pigments such as indigo, alizarin, carsamine, anthocyanins, flavonoids, shikonin, (2) food pigments such as azo, xanthene, triphenylmethane, (3) loess, green soil, etc. Natural inorganic pigments, (4) inorganic pigments such as acrylic and urethane, and (5) calcium carbonate, titanium oxide, aluminum lake, mudder lake, and cochineal lake.

  Further, the adhesive layer is formed on a portion of the inner surface of the transfer sheet that is to be adhered to the decorative article. That is, when it is desired to bond the entire inner surface to the article to be decorated, an adhesive layer is formed on the entire surface. Moreover, when it is desired to adhere a part of the inner surface to the article to be decorated, an adhesive layer is formed on a part thereof.

  The constituent material of the adhesive layer is not particularly limited as long as sufficient adhesiveness to the article to be decorated can be obtained. When the adhesive layer is thermocompression bonded to the article to be decorated, a synthetic resin having heat sensitivity and pressure sensitivity may be appropriately selected as a constituent material of the adhesive layer.

  For example, when the constituent material of the surface portion of the article to be decorated is a polyacrylic resin, it is preferable to use a polyacrylic resin as the constituent material of the adhesive layer. For example, when the constituent material of the surface portion of the article to be decorated is a polyphenylene oxide copolymer, a polystyrene copolymer resin, a polycarbonate resin, a styrene resin, or a polystyrene blend resin, The polyacrylic resin, polystyrene resin, polyamide resin and the like having an affinity for these resins may be appropriately selected and employed.

  Further, for example, when the constituent material of the surface portion of the article to be decorated is a polypropylene resin, the constituent materials of the adhesive layer are chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, coumarone Indene resin can be used.

Article decoration method Articles can be decorated by hot roll transfer or in-mold molding using the transfer sheet of the present invention. For example, in heat roll transfer, first, the position of the transfer sheet is determined so that the pattern is arranged at a desired position of the object to be decorated in consideration of the position of the pattern present on the transfer sheet. Next, the inner surface (adhesive layer side) of the transfer sheet is superimposed on the surface of the object to be decorated, and heat and pressure are applied from the substrate sheet side of the transfer sheet using a transfer machine such as a roll transfer machine or an up-down transfer machine. . By doing so, the transfer sheet adheres to the surface of the object to be decorated, and the surface of the article is decorated.

  In in-mold injection molding, first, a transfer sheet is fed into a molding die. At that time, the direction of the transfer sheet is adjusted so that the outer side faces the mold cavity surface, and the position of the transfer sheet is determined in consideration of the position of the pattern existing on the transfer sheet. Decide to be placed.

  Next, the mold is closed, and the molten resin is placed in the mold so that the molten resin is in contact with the inner surface (that is, the adhesive layer side) of the transfer sheet, that is, the transfer sheet is sandwiched between the molten resin and the mold cavity surface. Fill the mold cavity. As a result, the molten resin is molded, and at the same time, the transfer sheet is bonded to the surface of the injection molded body. When the resin is cooled, the mold is opened, and the injection molded body is taken out, the transfer layer is adhered to the surface of the injection molded body, and the surface of the injection molded body is decorated. Finally, the base sheet is peeled off.

  The material of the object to be decorated is not particularly limited as long as it has been conventionally decorated with a transfer sheet, or can devise the components of the adhesive layer to adhere the transfer layer to the surface. Various synthetic resins, members made of metal, glass, wood, paper, and these coated and decorative objects are used as objects to be decorated.

  The present invention will be specifically described by the following examples, but the present invention is not limited thereto. In the examples, the amount represented by “part” or “%” is based on mass unless otherwise specified.

Example 1
Production of hard coat resin composition for printing 100 parts by mass of bifunctional urethane acrylate (average molecular weight: 2800, “Aronix M-1600” (trade name)) manufactured by Toagosei Co., Ltd. 10 parts by mass of N-acryloyloxyethylhexahydrophthalimide (“Aronix M-140” (trade name) manufactured by Toagosei Co., Ltd.), a monofunctional monomer, pentaerythritol triacrylate (Toagosei Co., Ltd.), a polyfunctional monomer “Aronix M-305” (trade name) manufactured by 30 parts by mass, 1 part by weight of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” (trade name) manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, and non-volatile content (Meth) acryloyl in an amount of 17% by mass relative to the surface 90 parts by mass of MEK was added as a solvent and colloidal silica modified with a group (average particle size 10-15 nm, “MEK-AC-2101” (trade name) manufactured by Nissan Chemical Industries, Ltd.), and stirred at room temperature for 30 minutes. . After 30 minutes, it was confirmed by visual inspection that the components were uniformly dispersed, and a printing composition was obtained. The nonvolatile content at this time was 62%, and the viscosity was 37 mPa · s.

Production of Transfer Film A biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was used as a base sheet. This substrate sheet was set in a gravure printing machine (Orient Sogaku Co., Ltd .: 10 color sorting gravure rotary printing machine, Fuji Machine Industry: 11 color sorting gravure rotary printing machine), and the resulting printing composition was used. A crosslinkable resin layer was partially formed at a position corresponding to a pattern to be formed later. This crosslinkable resin layer was dried in-line using a dryer and an ultraviolet irradiation device installed in a gravure printing machine, and then cured by irradiation with 300 mJ / cm ² ultraviolet rays. At that time, in the formulation of Example 1, the film thickness after curing was 6 to 7 μm, and the hard coat layer was completely cured.

  Thereafter, in-line, the anchor layer ink is printed on the entire inner surface of the base sheet on which the hard coat layer is formed and dried, the pattern layer ink is partially printed and dried at a position corresponding to the hard coat layer, and the adhesive layer. Ink was printed on the entire inner surface of the anchor layer on which the pattern layer was formed and dried to obtain a transfer film.

Manufacture of Decorated Article The obtained transfer film was placed in a mold and subjected to in-mold injection molding of a polycarbonate / ABS alloy resin to prepare a switch base for automobile interior. When the base sheet was removed and the surface was observed, a hard coat layer was formed in a portion corresponding to the design.

The formed hard coat layer was evaluated for the following performance. The evaluation results are shown in Table 1.
1. Pencil Hardness The pencil hardness of the hard coat layer arranged on the surface of the decorative molded product was measured by a method based on JIS K 5400.

2. Wear resistance Based on JIS K7204, using a Taber friction tester (wear wheel: CS-10, load: 1 Kg / arm, rotation speed: 500 rotations) manufactured by Yasuda Seiki Seisakusho Co., Ltd. The hard coat layer disposed on the surface was rubbed. Then, the number of rotations of the wear wheel until the hard coat layer was worn and penetrated was measured.

3. Scratch resistance In accordance with JIS-K5600, the substrate sheet of the transfer film was peeled off to expose the surface of the hard coat layer. The surface of the hard coat layer was rubbed back and forth 200 times at a speed of 120 reciprocations / min with a load of 150 g using steel wool. The surface after friction was visually observed and evaluated. The evaluation criteria are as follows.

4). Crack resistance A transfer sheet consisting of a base sheet and a hard coat layer formed on the entire surface of the base sheet is placed in a mold, and then a resin is injected into the mold so that the hard coat layer is integrated on the surface. A molded product of KEYDECK, which is a personal computer part, was obtained. The area of the surface where the hard coat layer of the obtained molded product exists is 120 cm ² . The surface of the hard coat layer was visually observed to evaluate the presence or absence of cracks. The evaluation criteria are as follows.

5. Printability A transfer sheet having a surface area of 100 cm ² was produced by printing a hard coat layer on the surface of the substrate sheet. The obtained transfer sheet was irradiated with white light using a fluorescent lamp from the base sheet side and visually observed from a distance of 30 cm to evaluate the presence or absence of defects such as unevenness and doctor streak. The evaluation criteria are as follows.

6). Soil-fouling property A transfer sheet having a surface area of 100 cm ² was obtained by forming a hard coat layer, a vapor deposition layer, and a pattern layer on the surface of the base sheet. The obtained transfer sheet was visually observed from a distance of 30 cm to evaluate the presence or absence of soiling. The evaluation criteria are as follows.

Examples 2-9 and Comparative Examples 4, 9-12
A hard coat layer was formed and evaluated in the same manner as in Example 1 except that the components and amounts used of the hard coat resin composition were changed as shown in Table 1. The results are shown in Table 1 for the examples and Table 2 for the comparative examples.

  Further, the position of each example was plotted with the weight% of the polyfunctional monomer in the polymerizable component in the hard coat resin composition as the vertical axis and the mass part of colloidal silica with respect to 100 parts by mass of the polymerizable component as the horizontal axis. . It shows in FIG. 4 with the boundary line of the area | region shown by Formula (1) and Formula (2).

Comparative Example 1
A hard coat layer was formed and evaluated in the same manner as in Example 1 except that instead of N-acryloyloxyethyl hexahydrophthalimide (“Aronix M-140” manufactured by Toagosei Co., Ltd.) was used as the monofunctional monomer. . The results are shown in Table 2.

Comparative Example 2
A hard coat layer was formed and evaluated in the same manner as in Example 1 except that instead of pentaerythritol triacrylate (“Aronix M-305” manufactured by Toagosei Co., Ltd.) was used as the polyfunctional monomer. The results are shown in Table 2.

Comparative Example 3
A hard coat layer was formed and evaluated in the same manner as in Example 1 except that a low molecular weight product (“M-1600” manufactured by Toagosei Co., Ltd.) was used as the bifunctional urethane acrylate oligomer. The results are shown in Table 2.

Comparative Example 5
A hard coat layer is formed and evaluated in the same manner as in Example 1 except that colloidal silica whose surface is not modified (average particle size: 10 to 15 nm, “MEK-ST” manufactured by Nissan Chemical Industries, Ltd.) is used. did. The results are shown in Table 2.

Comparative Example 6
A hard coat layer is formed in the same manner as in Example 1 except that colloidal silica whose surface is not modified (average particle size: 10 to 15 nm, “MEK-ST” manufactured by Nissan Chemical Industries, Ltd.) is used. evaluated. The results are shown in Table 2.

Comparative Example 7
A hard coat layer was formed and evaluated in the same manner as in Example 1 except that colloidal silica whose surface was not modified (average particle size: 10 to 15 nm, “MEK-AC” manufactured by Nissan Chemical Industries, Ltd.) was used. did. The results are shown in Table 2.

Comparative Example 8
A hard coat layer was formed and evaluated in the same manner as in Example 1 except that colloidal silica whose surface was not modified (average particle size: 10 to 15 nm, “MEK-AC” manufactured by Nissan Chemical Industries, Ltd.) was used. did. The results are shown in Table 2.

1 ... Base sheet,
2 ... transfer layer,
3 ... Hard coat layer,
4 ... surface forming layer,
5 ... design layer,
6 ... adhesive layer,
11 ... Unwinding part,
12 ... Multicolor gravure rotary printing part,
13 ... winding part,
14 ... plate cylinder,
15 ... Ink pan,
16 ... impression cylinder,
17 ... Guide roll,
18 ... Drying section,

Claims (13)

A bifunctional urethane (meth) acrylate oligomer having two (meth) acrylate groups in one molecule and having a mass average molecular weight of 1,000 to 100,000;
A monofunctional (meth) acrylate monomer having one (meth) acrylate group in one molecule and a molecular weight of 1000 or less;
A polyfunctional (meth) acrylate monomer having two or more (meth) acrylate groups in one molecule and a molecular weight of 2000 or less; and colloidal silica whose surface is modified with a photopolymerizable functional group;
An active energy ray-curable hard coat resin composition comprising:
When dissolved in an organic solvent for gravure ink to give a printing composition having a nonvolatile content of 50% by mass or more, the viscosity of the printing composition is 200 mPa · s or less at room temperature.
An active energy ray-curable hard coat resin composition.   The polyfunctional (meth) acrylate monomer is contained in the polymerizable component in an amount of 10 to 30% by mass, and the colloidal silica is contained in the active energy ray-curable hard coat resin composition in an amount of 3 to 18% by mass. The active energy ray-curable hard coat resin composition according to claim 1, which is contained in formula

[Wherein, x is a mass part of colloidal silica with respect to 100 parts by mass of the polymerizable component, and y is mass% in the polymerizable component of the polyfunctional (meth) acrylate monomer. ]
The active energy ray-curable hard coat resin composition according to claim 1 or 2, satisfying the relationship: formula

[Wherein, x is a mass part of colloidal silica with respect to 100 parts by mass of the polymerizable component, and y is mass% in the polymerizable component of the polyfunctional (meth) acrylate monomer. ]
The active energy ray-curable hard coat resin composition according to any one of claims 1 to 3, which satisfies the relationship:   The polyfunctional (meth) acrylate monomer is pentaerythritol triacrylate, pentaerythritol tetraacrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri ( From the group consisting of (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, propylene oxide modified ditrimethylolpropane tri (meth) acrylate, ethylene oxide modified ditrimethylolpropane tri (meth) acrylate, caprolactone modified ditrimethylolpropane tri (meth) acrylate The active enzyme according to any one of claims 1 to 4, which is at least one selected. Energy ray-curable hard coating resin composition.   6. The active energy ray-curable hard coat resin composition according to claim 1, wherein the colloidal silica has an average particle size of 5 to 200 nm.   The hardness of the hard coat layer is a pencil hardness of 2H or more, The active energy ray-curable hard coat resin composition according to any one of claims 1 to 6.   The active energy ray-curable hard coat resin composition according to any one of claims 1 to 7, which is used to form a hard coat layer as a design or a design background.   A transfer sheet having a hard coat layer made of a cured resin crosslinked by irradiating the active energy ray-curable hard coat resin composition according to claim 1 with active energy rays. The hard coat layer is
The active energy ray-curable hard coat resin composition according to claim 1 is printed on the surface of the base sheet by a gravure printing method to form a crosslinkable resin layer; and the crosslinkable resin layer A step of irradiating the crosslinkable resin layer with an active energy ray and curing the functional layer of the transfer layer on the surface of the transfer layer;
The transfer sheet according to claim 9, which is formed by a method comprising   The transfer sheet according to claim 9 or 10, wherein the hard coat layer is formed as a design or a design background. A step of printing the active energy ray-curable hard coat resin composition according to any one of claims 1 to 8 on the surface of the base sheet by a gravure printing method to form a crosslinkable resin layer;
Before the functional layer of the transfer layer is formed on the surface of the crosslinkable resin layer, the crosslinkable resin layer is irradiated with active energy rays and cured to form a hard coat layer;
Forming a functional layer of the transfer layer on the surface of the base sheet or hard coat layer as a continuous process in the same production line by gravure printing;
A process for producing a transfer sheet. The step of feeding the transfer sheet according to any one of claims 9 to 11 into the molding die so that the outer side is in contact with the die cavity surface;
Closing the mold and filling the mold with the molten resin so that the molten resin is in contact with the inner surface (that is, the adhesive layer side) of the transfer sheet;
Cooling the resin, opening the mold and taking out the injection molded article; and peeling the base sheet;
A method for decorating the surface of an injection molded body comprising

Images