JP2008163301A - 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 preliminarily printed print surface with an active energy ray-curable overprint varnish composition, irradiating active energy rays to cure the printed varnish composition, 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 printed surface prepared by preliminarily printing 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, a monofunctional monomer, and organic beads having preferably an average particle diameter of 2 to 30 μm, 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). Furthermore, it has been proposed to add a filler which is a kind of organic beads in order to protect the printing surface and improve the cosmetics (glossiness or matte) (Patent Documents 5 and 6).

Regarding a method for forming a printed sheet, 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.

On the other hand, as a filler, although cited in Non-Patent Document 1, there is no description of an overprint varnish composition that is an active energy ray-curable composition having the characteristics of the molding processability of the present invention.

On the other hand, in order to improve the cosmetic properties (glossiness or matting), in particular, Patent Document 6 describes a thermosetting composition as a coating agent for matting. Not enough.

Furthermore, a composition containing spherical urethane beads and an active energy ray-curable resin is described in Patent Document 7, and by including spherical urethane beads, flexibility and toughness can be improved. The moldability is not sufficient.
JP 2003-145573 A JP 2003-145574 A JP 2003-326591 A JP 2004-314552 A JP-A-8-3502 JP-T-2004-516357 Japanese Patent Publication No. WO2002 / 077058 "Functional filler overview" November 30, 2000, first edition, first edition, edited Filler workshop, publisher Takeshi Seno, publisher Technonet

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. Furthermore, in detail, the overprint varnish composition, which is an active energy ray-curable type, is printed on a preprinted printing surface, irradiated with active energy rays, and cured, and then the printed sheet is subjected to vacuum forming and pressure forming. An overprint varnish composition that is an active energy ray curable type and a printing sheet used in a method of producing a molded article by performing molding or vacuum / pressure forming, etc., and further produced by this printing sheet It is to provide a printed sheet molding.

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 printing surface preliminarily printed on a substrate sheet. The overprint varnish composition used is soluble in a monomer and has an average molecular weight of 70,000 or less. A methacrylic resin, a reactive urethane oligomer, a monofunctional monomer, and organic beads having an average particle size of 2 to 30 μm, and further comprising an active energy ray-curable overprint varnish composition It is.

  The present invention also relates to the overprint varnish composition described above, wherein the organic beads are (meth) acrylic resin beads or urethane resin beads.

  Furthermore, the present invention relates to the above overprint varnish composition, wherein the organic beads are (meth) acrylic resin beads and urethane resin beads.

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

Moreover, this invention relates to said overprint varnish composition characterized by the glass transition temperature of (meth) acrylic resin being 50-250 degreeC.

Furthermore, in the present invention, the glass transition temperature of the cured film of the reactive urethane oligomer is −60 ° C.
The present invention relates to the above-mentioned overprint varnish composition characterized by being at 10 ° C.

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

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

Furthermore, this invention relates to the printing sheet manufactured by printing said overprint varnish composition, irradiating an active energy ray, and making it harden | cure.

The present invention also relates to a printed sheet molded product produced by molding the above printed sheet.

Furthermore, the present invention relates to a printed sheet molded product, wherein the molding process is performed by a vacuum molding process, a pressure forming 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. Furthermore, it has become possible to provide a printed sheet and a printed sheet molded product having a cosmetic property, particularly a matte property.

  The present invention prints an active energy ray-curable overprint varnish composition on a printing surface that has been printed on a base material sheet in advance, and irradiates and cures the active energy rays to vacuum-form a printed sheet produced. The molding is performed by processing, pressure forming, vacuum pressure forming, 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.

  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, and examples include offset printing, gravure printing, screen printing, resin letterpress printing, ink jet printing, etc. The thickness of the printing layer is 10 μm or less, and more Preferably, it is 5 μm or less, 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
Organic beads with an average particle size of 2-30 μm 5-30% by weight
Other additives 1-20% by weight
Etc. are mentioned as preferred compositions.

  The (meth) acrylic resin soluble in the monomer used in the present invention and having an average molecular weight of 70,000 or less is a homopolymer or copolymer synthesized from monomers represented by (meth) acrylate, more preferably, The glass transition temperature is preferably 50 to 250 ° C., but it is an essential condition to be 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.

Furthermore, the organic beads used in the present invention preferably have a volume-based average particle diameter (D50) measured by a Cole counter method of 2 to 30 μm, more preferably 5 to 20 μm, and even more preferably 10 to 20 μm.

Further, the organic beads used in the present invention can improve flexibility and toughness, and also improve cosmetics, in particular, matteness. Furthermore, an organic filler as described in Non-Patent Document 1 may be used, and a thermoplastic resin bead is particularly preferable. Among them, acrylic resin fillers (beads) or urethane resin fillers (beads) are preferable. In addition, polyethylene, polypropylene, polyester, polystyrene, and melamine resin particles are listed as organic fillers (beads) and used in the present invention. Is possible. In the present invention, the acrylic resin beads are produced by using a monofunctional monomer, a polyfunctional monomer, a styrene monomer, or a derivative of a styrene monomer used when synthesizing a (meth) acrylic resin as described above. Poly (meth) acrylic resin beads and urethane resin beads (urethane resin particles) are preferred.

The content of the organic beads is preferably 5 to 30% as the composition of the overprint varnish composition that is an active energy ray curable type, and 15 to 30% is preferable in consideration of matting properties. If it is contained in an amount of more than 30%, the molding processability of the varnish is lowered, and if it is less than 5%, the effect of the inclusion is hardly recognized.

In addition, since the organic beads used in the present invention are easier to handle when they are close to spherical, the ratio of the shortest diameter / longest diameter of the organic beads when observed with a scanning electron beam (hereinafter true) The abbreviation of “sphericity” is preferably in the range of 0.6 to 1.0.

  In the present invention, as described above, the active energy ray-curable overprint varnish composition is printed or coated on the printing surface previously printed on the base sheet, and the active energy rays are applied. Irradiating to cure the active energy ray-curable overprint varnish composition to produce a printed sheet, and then vacuum forming, pressure forming or vacuum / pressure forming to produce a printed sheet molded product .

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”.

  Offset printing was performed on a transparent polyester resin sheet having a thickness of 0.5 mm using an ultraviolet curable offset ink (FDO New Series) manufactured by Toyo Ink Manufacturing Co., Ltd. (printing thickness of 2 μm or less).

Furthermore, 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.

Tables 1 and 2 on the printed surface of the polyester resin sheet printed with ink.
The overprint varnish composition, which is an active energy ray curable type produced by the above method, is printed (coated) by screen printing (printing thickness: 20 μm), and 10 m below 10 cm of a metal halide lamp having an intensity of 160 W / cm. / Min. On a conveyor, irradiated and cured to produce 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 a method for printing an overprint varnish composition on a printing surface on which a substrate sheet has been printed in advance, the overprint varnish composition used is soluble in a monomer and has an average molecular weight of 70000 or less (meth) acrylic An overprint varnish composition comprising a resin, a reactive urethane oligomer, a monofunctional monomer, and organic beads having an average particle diameter of 2 to 30 μm, and further comprising an active energy ray curable type.   2. The overprint varnish composition according to claim 1, wherein the organic beads according to claim 1 are (meth) acrylic resin beads or urethane resin beads.   2. The overprint varnish composition according to claim 1, wherein the organic beads according to claim 1 are (meth) acrylic resin beads and urethane resin beads.   The overprint varnish composition according to any one of claims 1 to 3, wherein the base sheet is a thermoplastic resin sheet.   The glass transition temperature of (meth) acrylic resin is 50-250 degreeC, The overprint varnish composition in any one of the Claims 1 thru | or 4 characterized by the above-mentioned. The overprint varnish composition according to any one of claims 1 to 5, wherein a glass transition temperature of a cured film of the reactive urethane oligomer is -60C to 10C.   The overprint varnish composition according to any one of claims 1 to 6, 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 6, wherein the ink used for pre-printing 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. A printed sheet molded product produced by molding the printed sheet according to claim 9. 11. A printed sheet molded article produced by performing the molding process according to claim 10 by a vacuum molding process, a pressure forming process, or a vacuum / pressure forming process.