JP2008163304A - Active energy ray-curable overprint varnish composition, printed sheet and printed sheet molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable overprint varnish composition used in a method for printing a substrate sheet with an active energy ray-curable overprint varnish composition, irradiating active energy rays to cure the printed varnish composition, and then subjecting the produced printed sheet to a molding processing such as vacuum molding processing, air pressure molding processing, or vacuum-air pressure molding process to produce the molded article, to provide a printed sheet, and to provide a printed sheet molded article produced from the printed sheet. <P>SOLUTION: This active energy ray-curable overprint varnish composition used in a method for printing an overprint varnish composition on a substrate sheet is characterized in that the used overprint varnish composition comprises a (meth)acrylic resin soluble in a monomer and having an average molecular weight of ≤70,000, a reactive urethane oligomer, and a monofunctional monomer, and is an active energy ray-curing type. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to an overprint varnish composition that is an active energy ray curable type, a printed sheet produced using the composition, and a printed sheet molded product.

In recent years, it has been proposed to variously form and process printing sheets subjected to printing or the like, particularly plastic sheets subjected to printing or the like, and among them, thermoplastic resin sheets (Patent Documents 1 to 3).
4).

Patent Document 1 describes an insert-molding molded product and an ultraviolet curable coloring ink used for decorating the molded product. In this method, a printed sheet that has been printed is heated and softened, and a predetermined plastic resin molded product is produced by vacuum forming or pressure forming. In these steps, the ink to be printed may peel off or crack from the printing sheet, which is a base sheet, and must be able to withstand this. This patent document 1 is an ultraviolet curable color ink, which is different from the heat-resistant ink containing the cited solvent (patent document 5), but is a color ink, requires a pigment, and depends on the printing method. Since it is printed thick, peeling or cracks (cracks) are likely to occur on the printed surface.

Patent Document 2 also describes an insert molding molded product and a manufacturing method thereof. The ultraviolet curable colored ink used is the same as that of Patent Document 1, and the performance is improved by providing a binder layer on the ultraviolet curable colored ink. Depending on the printing method of the ultraviolet curable color ink used in Patent Document 2, peeling or cracking (crack) or the like occurs on the printed surface, as in Patent Document 1.

Furthermore, Patent Document 3 also describes an ultraviolet curable colored ink used for decorating an insert molding molded product and a molded product. However, the ultraviolet curable colored ink basically used in Patent Documents 1 and 2 is the same, and in this molding process, similarly, peeling or cracks (cracks) are likely to occur on the printed surface.

Moreover, in patent document 4, the ultraviolet curable coloring ink used for the molded article produced by vacuum forming, pressure forming, or vacuum-pressure forming of the printing sheet printed without insert molding is used. Are listed. However, as it is, depending on the printing method, printing is performed thickly, so that the printed surface is likely to be peeled off or cracked.

Further, in Patent Documents 1 to 4, it is considered that peeling or cracking or the like is likely to occur because printing (coating) is not performed with an overprint varnish as in the present invention in order to protect the printed surface. It is done.
JP 2003-145573 A JP 2003-145574 A JP 2003-326591 A JP 2004-314552 A JP-A-8-3502

An object of the present invention is to provide an overprint varnish composition which is an active energy ray-curable composition, a printed sheet produced using the composition, and a molded article produced by molding the printed sheet. More specifically, an overprint varnish composition that is an active energy ray curable type is printed on a base sheet, irradiated with an active energy ray, and cured to produce a printed sheet that is formed by vacuum forming, pressure forming, or vacuum. An overprint varnish composition and a printing sheet, which are active energy ray-curable types, used in a method of producing a molded product by performing a molding process using a pressure molding process or the like, and further, a printing sheet molding produced from this printing sheet To provide things.

The present inventor has solved the above-mentioned problem and does not cause peeling or cracking (cracking) or the like on the printed surface, and is an active energy ray-curable overprint varnish composition, and a printed sheet produced using the same The present inventors have found a molded product manufactured by molding a sheet and completed the present invention.

  That is, the present invention relates to a method for printing an overprint varnish composition on a substrate sheet, wherein the overprint varnish composition used is soluble in a monomer and has an average molecular weight of 70000 or less (meth) acrylic resin, reaction The present invention relates to an overprint varnish composition comprising a functional urethane oligomer and a monofunctional monomer and further being an active energy ray curable type.

  Furthermore, the present invention relates to the above overprint varnish composition, wherein the base sheet is a thermoplastic resin sheet.

The present invention also relates to the above overprint varnish composition, wherein the glass transition temperature of the (meth) acrylic resin is 50 to 250 ° C.

  Furthermore, the glass transition temperature of the cured film of the reactive urethane oligomer is −60 ° C. to 10 ° C. or lower, and the present invention relates to the overprint varnish composition described above.

  The present invention also relates to a method for printing an overprint varnish composition, wherein the overprint varnish composition is printed on a printing surface that has been previously printed on a substrate sheet. Is.

  Furthermore, the present invention relates to the above overprint varnish composition, wherein the ink used for printing in advance on the substrate sheet is a solvent type.

  In addition, the present invention relates to the overprint varnish composition described above, wherein the ink used for printing in advance on the substrate sheet is of an active energy ray curable type.

  Furthermore, the present invention relates to a printed sheet produced by printing the above-described overprint varnish composition, irradiating with active energy rays and curing the composition.

  Moreover, this invention relates to the printing method of the printing method of said overprint varnish composition, after printing an overprint varnish composition, irradiating an active energy ray and making it harden | cure.

  Furthermore, the present invention relates to a printed sheet molded article produced by molding the above printed sheet.

  The present invention also relates to a printed sheet molded product, wherein the molding process is performed by a vacuum molding process, a compressed air molding process, or a vacuum / pressure forming process.

According to the present invention, it is possible to provide a printed sheet having a good printed surface without causing peeling or cracking (crack) or the like on the printed surface, and a molded product produced by molding the printed sheet. It was.

  The present invention relates to a printing sheet produced by printing an overprint varnish composition that is an active energy ray curable type on a substrate sheet, irradiating and curing the active energy ray, and performing vacuum forming processing, pressure forming processing, or vacuum pressure forming. The molding process is performed by molding process or the like to manufacture a molded product.

  As the base material sheet, a plastic sheet, among them, a thermoplastic resin sheet is preferable in consideration of the subsequent molding process. Examples of the thermoplastic resin used in the thermoplastic resin sheet include polystyrene resin, polycarbonate resin, polyvinyl chloride resin, polyester resin, etc., but the ease of printing on the base sheet and various final molded products. Considering physical properties, polycarbonate resin and polyester resin are preferable, and polyester resin can be preferably used.

  In the present invention, before printing or coating the overprint varnish composition of the active energy ray curable type on the base sheet, it is possible to print it on the base sheet with a normal ink in advance.

  The ink used for printing on the base sheet can be any solvent type or active energy ray curable ink, but it is an ink in consideration of the subsequent molding process. For this reason, if the printing is performed thickly because it contains the pigment, the possibility of peeling or cracking of the printed surface increases. Any generally known printing method can be used, for example, offset printing, gravure printing, screen printing, resin relief printing, ink jet printing, etc. The thickness of the printing layer is 10 μm or less, More preferably, it is 5 μm or less, and more preferably 3 μm or less.

  Furthermore, an overprint varnish composition that is an active energy ray curable type is printed or coated on a printing surface that has been printed in advance on a substrate sheet, and the overprint varnish is irradiated with the active energy ray. The composition is cured to produce a printed sheet.

As the method of printing or coating the overprint varnish composition that is an active energy ray curable type, any generally known printing method can be used, for example, offset printing, gravure printing, screen printing, Resin letterpress printing, ink jet printing, etc. are mentioned, but considering the protection of the printing surface, and further prevention of peeling or cracking (crack), etc.,
Screen printing is preferred.

  In addition, when the active energy ray curable ink is selected as the ink to be printed on the base material sheet in advance, after printing the active energy ray curable ink, the present invention is not irradiated with the active energy ray. The active energy ray curable overprint varnish composition is printed or applied and then irradiated with active energy rays, and the active energy ray curable ink and the active energy ray curable overprint varnish composition are simultaneously applied. A curing method is also possible.

The composition of the overprint varnish composition that is an active energy ray curable type used in the present invention is a (meth) acrylic resin that is soluble in monomers and has an average molecular weight of 70000 or less.
5-20% by weight
Reactive urethane oligomer 5-30% by weight
Monofunctional monomer 20-70% by weight
Other additives 1-20% by weight
As a (meth) acrylic resin soluble in the monomer used in the present invention and having an average molecular weight of 70,000 or less, a homopolymer or copolymer synthesized using a monomer represented by (meth) acrylate as a raw material More preferably, the glass transition temperature is 50 to 250 ° C., but it is an essential condition that it is soluble in the monomer at the time of formulation.

  Monomers that are soluble in monomers and can be used as raw materials for (meth) acrylic resins having an average molecular weight of 70000 or less are alkyl (having 2 to 18 carbon atoms) (meth) acrylate, ethyl (meth) acrylate, butyl ( Meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tri Examples include cyclodecane monomethylol (meth) acrylate, (meth) acryloylmorpholine, etc. (above monofunctional monomer).

In addition, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, butylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalylhydroxypivalate di (meth) acrylate (commonly called manda), hydroxypivalylhydroxypivalate dica Prolactonate di (meta)
Acrylate, 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,2-hexadecanediol di (meth) acrylate, 2 -Methyl-2,4-pentanediol di (meth) acrylate, bisphenol A tetraethylene oxide adduct di (meth) acrylate, bisphenol F tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol A tetraethylene oxide adduct Di (meth) acrylate, water-added bisphenol F tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol A di (meth) acrylate, water-added bisphenol F di (meth) acrylate, glycerin tri (meth) Chlorate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctanetri (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diglycerin tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tetracaprolactonate, tetra (meth) acrylate, ditri Methylolethanetetra (meth) acrylate, ditrimethylolbutanetetra (meth) acrylate, ditrimethylolhexaneteto (Meth) acrylate, ditrimethyloloctanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, Tripentaerythritol octa (meth) acrylate or the like (above polyfunctional monomer) can also be used.

The reactive urethane oligomer used in the present invention has an ethylenically unsaturated double bond.

  Furthermore, the reactive urethane oligomer used in the present invention preferably has an average molecular weight of 5000 or more.

Further, the glass transition temperature of the cured film of the reactive urethane oligomer is preferably −60 to 10 ° C., more preferably −60 to −10 ° C., and further preferably −60 to −30 ° C.

The reactive urethane oligomer is preferably used at 5 to 30% in the composition of the overprint varnish composition, more preferably 10 to 20%. In the case of 5% or less, the effect on the cohesive force is not exhibited. On the other hand, when it is 30% or more, the film of the overprint varnish composition is hardened.

Moreover, as a monofunctional monomer used for this invention, alkyl (carbon number is 2-18).
) (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
There are hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecane monomethylol Examples include (meth) acrylate, (meth) acryloylmorpholine, phenoxyethyl (meth) acrylate and the like.

  In the present invention, as described above, an active energy ray-curable overprint varnish composition is printed on or coated on the base sheet, and the active energy rays are irradiated. A certain overprint varnish composition is cured to produce a printed sheet, and then the printed sheet is subjected to vacuum forming, pressure forming, or vacuum / pressure forming to produce a printed sheet.

In the present invention, the glass transition temperature is measured by raising the temperature of the test piece from room temperature at a rate of 10 ° C./min, measuring the amount of thermal expansion in the heat direction with a thermal analyzer, and before and after the glass transition temperature. A tangent line was drawn on the curve, and the measurement was performed by the TMA method for obtaining the glass transition temperature (or Tg when omitted) from the intersection of the tangent lines.

In the present invention, the glass transition temperature is measured by increasing the temperature of the test piece from room temperature at a rate of 10 ° C./min, measuring the amount of thermal expansion in the thickness direction with a thermal analyzer, and before and after the glass transition temperature. A tangent line was drawn on the curve, and the measurement was performed by the TMA method for obtaining the glass transition temperature (or Tg when omitted) from the intersection of the tangent lines.

The average molecular weight of the present invention represents a weight average molecular weight and was measured by GPC (Gel Permeation Chromatography). The following apparatus, column, detector and solvent were used in the measurement.
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSKgel SuperHM-H
Detector: RI
Solvent: THF (tetrahydrofuran)

In the present invention, the active energy ray curable type mainly indicates an ultraviolet ray or electron beam curable type, and in the case of the ultraviolet ray curable type, a photoinitiator is required.

Examples of photoinitiators used in the present invention include hydrogen abstraction type initiators such as benzophenone, p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4 Arylbenzoic initiators such as benzoyl-4′-methyl-diphenyl sulfide, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4 diethylthioxanthone, 2,4 dichlorothioxanthone, acetophenone, 4,4′-bis (
Diethylamino) benzophenone, 4,4′-bis (dimethylamino) benzophenone,
Examples include dialkylaminoaryl ketone initiators such as isoamyl p-dimethylaminobenzoate and p-dimethylaminoacetophenone, thioxanthone, xanthone-based and halogen-substituted polycyclic carbonyl-based initiators, and the like. Further, as photocleavable initiators, benzoin such as benzoin, benzoin methyl ether, benzoin isopropyl ether, α-acrylobenzoin, benzyl, Irgacure 907 (2-methyl-2-morpholino (4-thiol produced by Ciba Specialty Chemicals) Methylphenyl) propan-1-one)
Irgacure 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone manufactured by Ciba Specialty Chemicals), Irgacure 651 (benzyl methyl ketal manufactured by Ciba Specialty Chemicals), Irgacure 184 (Ciba Specialty) Chemicals 1-hydroxycyclohexyl phenyl ketone), Darocur 1173 (Ciba Specialty Chemicals 2-hydroxy-2-methyl-1-phenylpropan-1-one), (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-
2-propyl) ketone, ZLI3331 (Ciba Specialty Chemicals 4- (2-
(Acryloyl-oxyethoxy) phenyl-2-hydroxy-2-propylketone, diethoxyacetophenone, Esacure KIP100 (manufactured by Ramberty), Lucillin TP
Examples include O (manufactured by BASF), BTTB (manufactured by NOF Corporation), CGI1700 (manufactured by Ciba Specialty Chemicals), and the like.

Moreover, a photoinitiator auxiliary agent can also be used in combination with a photoinitiator. As the photoinitiator aid, tertiary amines which are hydrogen donors are used. Specifically, aliphatic amines such as triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Aromatic amines such as isoamyl acid can be mentioned, and triethanolamine, methyldiethanolamine, dibutylethanolamine, triisopropanolamine, and 4,4′-diethylaminobenzophenone are preferable.

In the present invention, the photoinitiator is used in an amount of 0.1% to 30%, preferably 5 to 15%, in the composition of the overprint varnish composition which is an active energy ray curable type.

Additives used in the present invention include, for example, plant waxes such as carnauba and wax, animal waxes such as whale wax and lanolin, for the purpose of friction resistance, anti-blocking, slip, scratch resistance, and defoaming. Hydrogenation of mineral waxes such as montan, petroleum waxes such as paraffin and microcrystalline (natural waxes), synthetic hydrocarbon waxes such as sazol and polyethylene, silicone additives such as silicone oil or silicone acrylate, and hardened castor oil In addition, amide waxes such as wax and fatty acid amide, ketones, amines, imides, ester compounds, and polytetrafluoroethylene (synthetic wax) can be used.

EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the present invention, “part” represents “part by weight”, and “%” represents “% by weight”.

The overprint varnish composition which is an active energy ray hardening type was produced by the prescription (Table 1: Examples 1-5, Table 2: Comparative Examples 1-3) shown in the following tables. The method for producing the overprint varnish composition is as follows. After the acrylic resin and the initiator were dissolved in the monofunctional monomer, all other raw materials were added and mixed by a mixer.

  On the transparent 0.5 mm thick polyester resin sheet, the active energy ray-curable overprint varnish composition prepared according to Table 1 and Table 2 was printed (coated) by screen printing (print thickness 20 μm), A place 10 cm below one metal halide lamp having an intensity of 160 W / cm was placed on a conveyor of 10 m / min, irradiated and cured to prepare a printed sheet.

The state when the printed surface (coated surface) of the obtained printing sheet was rubbed with a cotton cloth was visually evaluated (
Curability test).
[Evaluation]
A: No change.
○: Scratches are observed on a part of the printed surface (coated surface), but peeling cannot be observed.
Δ: Peeling is observed on a part (less than 50%) of the printed surface (coated surface).
X: Peeling is observed on part (50% or more) or all of the printed surface (coated surface).

Further, the obtained printing sheet was folded at 90 ° with the printing surface (coating surface) as a table, and the degree of peeling and cracking (cracking) was observed with a 50 times magnifier (moldability aptitude test).
[Evaluation]
(Double-circle): Peeling and a crack (crack) are not observed.
○: No peeling is observed, but some cracks are observed.
Δ: Peeling is hardly observed (somewhat observed), but further cracks (cracks)
C) is also observed.
X: Peeling is observed and cracks are also observed.

  The evaluation results are shown in Table 3.

Using the printing sheet produced using the overprint varnish composition of the present invention, which is an active energy ray-curable composition of the present invention, which is an example of Table 3, the printed sheet molding produced is printed on its surface (coating surface). ) Does not peel or crack (crack), etc.
Both peeling and cracks are observed. In the present invention, an overprint varnish composition that is an active energy ray curable composition excellent in curability and moldability, a printed sheet produced using the composition, and a molded article produced by molding the printed sheet Things can now be provided.

Claims (11)

  In the method of printing an overprint varnish composition on a base sheet, the overprint varnish composition used is soluble in a monomer and has an average molecular weight of 70000 or less (meth) acrylic resin, reactive urethane oligomer and simple substance. An overprint varnish composition containing a functional monomer and further being an active energy ray curable type.   The overprint varnish composition according to claim 1, wherein the base sheet is a thermoplastic resin sheet. The glass transition temperature of the (meth) acrylic resin is 50 to 250 ° C, The overprint varnish composition according to claim 1 or 2. The overprint varnish composition according to any one of claims 1 to 3, wherein a glass transition temperature of the cured film of the reactive urethane oligomer is -60C to 10C or less.   5. The method of printing an overprint varnish composition according to any one of claims 1 to 4, wherein the overprint varnish composition is printed on a printing surface previously printed on a substrate sheet. .   The overprint varnish composition according to any one of claims 1 to 4, wherein the ink used for printing in advance on the substrate sheet according to claim 1 is a solvent type.   The overprint varnish composition according to any one of claims 1 to 4, wherein the ink used for printing in advance on the substrate sheet according to claim 1 is an active energy ray-curable ink.   A printed sheet produced by printing the overprint varnish composition according to claim 1, irradiating with active energy rays and curing.   The printing method of the overprint varnish composition printing method according to claim 5, wherein the overprint varnish composition is printed and then irradiated with active energy rays and cured.   A printed sheet molded product produced by molding the printed sheet according to claim 8 or 9.   11. A printed sheet molded article produced by performing the forming process according to claim 10 by vacuum forming, pressure forming, or vacuum / pressure forming.