JP2008208154A - Active energy ray curable composition and printed material and molded decorative sheet material produced by using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray curable composition to form a soft and tough coating film, a printed material durable to molding, and a moldable decorative sheet material printable by offset printing. <P>SOLUTION: The invention provides an active energy ray curable coating varnish containing a non-reactive resin having a cyclohexane structure or a cyclohexane structure and free from radically reactive double bond and a mono- to tri-functional (meth)acrylate monomer as essential components in an active energy ray curable composition, a printed material produced by using the varnish, and a molded decorative sheet material produced by molding the printed material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an active energy ray-curable composition used for a molded product such as a product dummy exhibit of a vending machine, a printed material using the composition, and a molding process by drawing such as vacuum molding or pressure molding. It is related with the decorated decorative sheet molding.

  Active energy ray-curable compositions are used in various industrial fields. However, in recent years, the issues (performance) required for active energy ray curable compositions are curling of printed matter caused by cure shrinkage, removal of strain stress, formation of flexible and tough films, and excellent molding. It has changed to workability.

  The most widely used method for suppressing curing shrinkage is to mix an additive such as an inorganic filler. However, the use of such inorganic additives reduces the mechanical strength of the binder polymer, the adhesion to the printing interface, the transparency of the cured film, etc., as well as the printing process by increasing the viscosity of the composition. This is not a complete solution, including a decrease in workability.

  On the other hand, as a system that does not rely on additives or the like, monomers utilizing ring-opening polymerization have been proposed. It has been proposed that the polymerizable non-shrinkable monomer is preferably a cationic polymerizable monomer among radical polymerizable, cationic polymerizable and anionic polymerizable. There is Non-Patent Document 1 as a known document of this polymerizable non-shrinkable monomer. However, there are still few types of materials that can be put to practical use, and it is not practical as a solution to the problem of the present application.

  Further, Patent Document 1 discloses a colored ink for an insert molding molded article and an insert molding molded article having a urethane acrylate oligomer and a heterocyclic monofunctional monomer or a cyclic monofunctional monomer as essential components. Patent Document 2 describes a hetero-cycloaliphatic monofunctional monomer and an ultraviolet curable coloring ink containing a thermoplastic resin soluble in the monomer as an essential component.

  With regard to this urethane oligomer or urethane resin, a compound suitable for the application is prepared and used by combining a hard segment and a soft segment with an isocyanate compound as a core. Various proposals have been made on the segment material that enhances the softness. However, the use of compounds having properties due to stronger intermolecular interactions such as urethane oligomers and urethane resins, in mixed compositions or colored compositions, is extremely lacking in system stability.・ Practical restrictions will be imposed, and materials that are more stable in practical use will be required.

  This urethane oligomer or urethane resin tends to dissolve in dampening water on offset printing, which is a printing method that forms images using dampening water, making it difficult to ensure suitability during printing. is there.

Any of the disclosed techniques is a method of imparting flexibility, but the current situation is that further improvement is still required.
JP 2003-145573 A JP 2004-314552 A Author Endo and Fumio Mita, “Radical Ring-Opening Polymerizable Monomer (-Possibility of Application to Polymerized Non-Shrinkable Materials)” (No.32 Annual Meeting of the Adhesion Society of Japan 36-49 (1994)

  An object of the present invention is to provide a printed material that forms a flexible and tough film in an active energy ray-curable composition and can withstand molding. In addition, the elements required for the ink composition in the printing process are very diverse, and the ink cured film after printing not only satisfies the required characteristics such as molding processing suitability, but also can withstand the printing process, that is, printability. (Offset printing suitability) is good, and it is necessary to be a practicable / practical composition.

  The present invention is based on the total ink composition, (a) 1 to 50% by weight of a non-reactive resin having no monomer-soluble radical polymerizable double bond, (b) 1 to 3 functional (meta) The present invention relates to an active energy ray-curable composition comprising 1) to 50% by weight of acrylate monomer and 5 to 55% by weight of (c) pigment as essential components.

  In the present invention, the active energy is characterized in that (a) the non-reactive resin having no monomer-soluble radical polymerizable double bond is a polyester resin having a cyclohexene structure or a cyclohexane structure. The present invention relates to a wire curable composition.

  Furthermore, this invention relates to the printed matter characterized by printing by said active energy ray hardening-type composition.

  Further, the present invention relates to a printed matter characterized in that printing is performed with an offset.

  Furthermore, the present invention relates to a decorative sheet molded product obtained by molding the above-described printed material by a drawing process such as vacuum molding or pressure molding.

  According to the present invention, a printed matter can be obtained by offset printing. Furthermore, even if this printed matter is molded, cracks and the like do not occur, and it is possible to provide a good molded product.

  That is, the active energy ray-curable composition of the present invention is flexible and tough, and the stress generated in the cured film during curing is relaxed by the cyclohexene structure or the cyclohexane structure, which cannot be achieved with other compounds. Because it forms a film, it has workability such as bending and drawing. In addition to the stability of the composition itself, it has not only the stability of the composition itself but also the workability in the printing process, particularly the offset printability used under severe conditions.

  In the present invention, the compound having the required performance has arrived at the cyclohexene structure or the cyclohexane structure described in the claims. The compounds of these structures are chair-shaped, funa-shaped, or twisted, and are considered to be the factors that have the effect achieved by the present invention even when compared with the corresponding phenyl ring.

  Hereinafter, the active energy ray-curable composition according to the present invention will be described in more detail.

  The active energy rays used in the present invention are mainly ultraviolet rays and electron beams, but are not necessarily limited thereto.

As the composition of the active energy ray-curable composition used in the present invention,
(A) Non-reactive resin having no monomer-soluble radically polymerizable double bond 1 to 50% by weight
(B) 1 to 3 functional (meth) acrylate monomer 1 to 50% by weight
(C) Pigment (organic pigment / inorganic pigment) 5 to 55% by weight
Photoinitiator, photoauxiliary 5 to 15% by weight
Additive 1-10% by weight
Is mentioned.

  The non-reactive resin having no monomer-soluble radically polymerizable double bond is particularly a polyester resin having a cyclic structure, and preferably having a carboxyl group in the molecule. This polyester resin relieves rapid curing shrinkage. Further, it preferably has a carboxyl group in the molecule and contains a cyclohexene or cyclohexane structure in the resin.

  In the present invention, the monomer solubility of the non-reactive resin having no monomer-soluble radically polymerizable double bond means that the monomer is soluble in a trifunctional (meth) acrylate monomer, but when the number of functional groups increases, Since the polarity becomes high and the solubility of the non-reactive resin or the like is lowered, the trifunctional acrylate monomer (trimethylolpropane triacrylate and glycerin triacrylate) is dissolved in a certain ratio or more. The solubility of a certain ratio or more means that 10 g (10% by weight) of a non-reactive resin is added to 90 g of trimethylolpropane triacrylate or glycerin triacrylate, dissolved at 100 ° C. for 1 hour, and brought to room temperature (25 ° C.). Both solutions of two types of acrylate monomers (trimethylolpropane triacrylate, glycerin triacrylate) shall not be cloudy. However, when it is difficult to determine when 10 g of the non-reactive resin is added to 90 g of the two types of acrylate monomers listed above and observed, 15 g to 5 g of the non-reactive resin is added to the front and rear (85 g to 95 g of the acrylate monomer. 15 wt% to 5 wt%))) and confirm that the unreacted resin is dissolved by 10 wt% or more.

  Examples of the alcohol used for synthesizing the polyester resin which is a non-reactive resin having no radically polymerizable double bond which is soluble in the monomer of the present invention include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, hydrogenated bisphenol A, hydrogenated bisphenol F, cyclohexane-1,2-diol, cyclohexanedimethanol, glycerin, trimethylol You may use 1 type (s) or 2 or more types of polyhydric alcohols, such as ethane, a trimethylol propane, and a trishydroxymethylaminomethane.

  In order to further enhance the toughness of the cured film and post-processing suitability such as drawing and bending, hydrogenated bisphenol A, hydrogenated bisphenol F, and cyclohexanedimethanol containing a cyclohexane structure are preferred.

  Acid components include phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, and hept One or more polybasic acids such as acid, hymic anhydride, maleic anhydride, fumaric acid, itaconic acid, trimellitic anhydride, methylcyclohexeric carboxylic anhydride, pyromellitic anhydride can be used. In addition, monobasic acids such as benzoic acid, fatty acids such as array acid, linseed oil fatty acid and soybean oil fatty acid can be used.

  In order to further enhance the toughness of the cured film and post-workability such as drawing and bending, tetrahydrophthalic anhydride having a cyclohexene structure and hexahydrophthalic anhydride having a cyclohexane structure are preferable.

  It is a non-reactive resin that does not have a radical-polymerizable double bond that is monomer-soluble according to the present invention, that is, a non-crosslinked polyester resin is cured in addition to other resins, reactive oligomers, and monomer solubility used together. From the viewpoint of securing the balance of physical properties of the film, if the weight average molecular weight (Mw) is 1000 or less, the cured film is weak, and if it is 10,000 or more, the solubility in the monomer is inferior, so 1000-10000, preferably 2000-6000. The range of is good.

  The non-reactive resin having no monomer-soluble radically polymerizable double bond according to the present invention is used in the range of 1 to 50% by weight, preferably 5 to 30% by weight, based on 100% by weight of the composition. is there.

  Furthermore, in this invention, 1-3 functional (meth) acrylate monomer is used, this 1-3 functional (meth) acrylate monomer has an ethylenically unsaturated double bond, and is 100 weight% of compositions. And used in the range of 1 to 50% by weight. Examples of this monomer include alkyl (having 1 to 18 carbon atoms) (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and octyl (meth) acrylate. , Dodecyl (meth) acrylate, stearyl (meth) acrylate, and (meth) acrylate, isobonyl of alkylphenol ethylene oxide adducts such as benzyl (meth) acrylate, butylphenol, octylphenol or nonylphenol or dodecylphenol (Meth) acrylate, hexyl (meth) acrylate, tricyclodecane monomethylol (meth) acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, acroylmo Folin, phenoxyethyl (meth) acrylate, cyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-acryloyloxyethyl phthalate, 2-acryloyloxypropyl phthalate, 2- Examples include acryloyloxyethyl-2-hydroxyethyl phthalate and 2-acryloyloxyethyl hexahydrophthalate.

  Furthermore, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di as bifunctional monomers (Meth) acrylate, tripropylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalyl hydroxypivalate di (meth-9 acrylate, hydroxypivalyl hydroxypivalate Dicaprolactonate di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,2-hexyldiol di (meth) acrylate , And the like 1,5-hexyl di (meth) acrylate, bisphenol A tetraethylene oxide adduct di (meth) acrylate, bisphenol F tetraethylene oxide adduct di (meth) acrylate.

  As trifunctional monomers, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolhexane tri (meth) Examples include acrylate, trimethylol ethane tri (meth) acrylate, trimethylol hexane tri (meth) acrylate, trimethylol octane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate.

  Further, as an acrylate monomer of the present invention, there is an alkylene oxide adduct (meth) acrylate of an aliphatic alcohol compound. As an alkylene oxide adduct (meth) acrylate monomer of an aliphatic alcohol compound, there is a mono- or poly (1-20 alkylene (C2-C20) oxide adduct (alkylene oxide) of an aliphatic alcohol compound.

  As a monofunctional monomer, an alkylene oxide adduct (meth) acrylate having 2 to 20 carbon atoms, such as methanol mono- or poly (1-20) alkylene (C2 to C20) oxide adduct (as alkylene oxide, ethylene oxide, propylene oxide, Examples include butylene oxide) (meth) acrylate, ethanol mono- or poly (1-20) alkylene (C2-C20) oxide adducts, and the like.

  Furthermore, as a bifunctional monomer, ethylene glycol mono- or poly (1-20) alkylene (C2-C20) oxide adduct (as alkylene oxide, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, diethylene glycol mono or poly ( 2-20) alkylene (C2 to C20) oxide adducts and the like are exemplified.

  Further, as a trifunctional monomer, glycerin poly (2-20) alkylene (C2-C20) oxide adduct (as alkylene oxide, ethylene oxide, propylene oxide, butylene oxide) tri (meth) acrylate, trimethylolpropane poly (2-20) ) Alkylene (C2 to C20) oxide adducts and the like are exemplified.

  As photoinitiators used in the present invention, as hydrogen abstraction type, benzophenone, p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4 '-Methyl-diphenyl sulfide, 2-isopropylthiocisanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, acetophenone / aryl ketone initiator, 4,4'-bis ( Diethylanino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, isoamyl p-dimethylaminobenzoate, p-dimethylaminoacetophenone-dialkylaminoaryl ketone initiator, Xanthone, and the like xanthone Part halogen-substituted and multi-ring carbonyl-based initiators.

  Further, as a cleavage type photoinitiator, benzoin, benzoin methyl ether, benzoin isopropyl ether, α-acrylbenzoyl benzoin series, benzyl, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, benzylmethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropyl Phenyl-2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 4- (2-acryloyloxyethoxy) phenyl-2-hydroxy-2-propyl Ketone And the like diethoxyacetophenone.

  Photoinitiators include triethanolamine, methyldiethanolamine, triisopropanolamine / aliphatic amine, 4,4′-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Examples thereof include isoamyl dimethylaminobenzoate and dibutylethanolamine.

  On the other hand, various additives for the purpose of anti-friction, anti-blocking, slip, anti-scratch, and dark reaction can be used as additives in the composition. Leveling agents and antistatic agents can be used as necessary. An agent, surfactant, antifoaming agent, polymerization inhibitor and the like may be added.

  As the coloring material of the present invention, a pigment is mainly used. As the pigment, white pigment such as titanium oxide, mineral furnace yellow, navel yellow, naphthol yellow S, hansa yellow G, quinoline yellow lake, permanent yellow NCG, Yellow pigments such as Tartrazine Lake, Indanthrene Brilliant Orange RK, Pirazone Orange, Vulcan Orange, Benzidine Orange G, Indanthrene Brilliant Orange GK and other orange pigments, Permanent Red 4R, Lionol Red, Pyrarozone Red, Watching Lettuce Calcium Red pigments such as salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, brilliant carmine 3B, first violet B, methyl Purple pigments such as iolet lake, bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, blue pigments such as first sky blue and indanthrene blue BC, pigment green Examples thereof include green pigments such as B, malachide green lake, and fine series green G, black pigments such as carbon black, acetylene black, run black, and aniline black, and extender pigments such as barite powder, barium carbonate, and benton.

  The pigment according to the present invention is used in the range of 5 to 55% by weight, preferably 10 to 30% by weight, based on 100% by weight of the composition.

  Examples of the printing method of the active energy ray-curable composition include offset printing, resin convex printing, flexographic printing, and screen printing. Especially used for offset printing. In this case, a high-definition, stable quality printed matter can be obtained, and it can be obtained with higher productivity than screen printing and can be used in this field. The composition of the present invention is particularly suitable. .

  The composition of the present invention is printed or applied mainly to a plastic film. Examples of the plastic film include a polyethylene film, a polypropylene film, a prestyrene film, a polyvinyl chloride film, a polyester film, an acrylic film, a urethane film, a polycarbonate film, and a film whose surface is treated.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “parts” and “%” mean “parts by mass” and “% by mass”. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography). Moreover, it illustrates about a standard active energy ray hardening-type varnish and ink composition here.

(Create ink varnish)
Mixing non-reactive resin with 1 to 3 functional acrylate monomers as reactive monomers and heating and heating with addition of polymerization inhibitor (upper limit temperature kept at 100 ° C)
5000 CPS ink varnishes were prepared at a resin ratio of 10 to 30% by weight.

(Creation of ink composition)
Next, the non-crosslinked resin of the present invention and a reactive monomer having a radical polymerizable bipolymer bond, a mixed varnish of an oligomer, the coloring pigment, a radical polymerization initiator, and other additives at a predetermined blending ratio, Stir and mix using a butterfly mixer, disperse so that the maximum particle size becomes 7.5 μm or less with 3 rolls, and prepare an ink composition, and adjust with a spread meter to achieve a certain viscosity standard. Each ink composition was prepared.

(Measurement of print samples for comparative evaluation)
Predetermined amounts of each ink composition prepared on a polyethylene sheet used for molding, using a RI tester (simple print transfer device) for printing and application to a predetermined dose with a 160 W / cm metal halide lamp The ink composition was cured to produce a comparative evaluation print sample.

The printed material is marked in 0.5 mm increments, and the printed material is placed on a hot plate heated to about 200 ° C. for 15 seconds. When the film surface becomes about 170 ° C. and softens, a tensile test is performed.
The tensile test is performed in three stages: 200% (mark interval 1.0 cm), 250% (mark interval 1.5 cm), and 300% (mark interval 2.0 cm). Confirm with Judgment.

(Evaluation of UV curing status of ink composition)
No crack: ◎
One crack point: ○
2-5 cracks: △
Many cracks: ×
If it is ○ or ◎, it can be used as a dummy can.

(Ink drying)
About ink drying property, it is cured with a fixed amount of color developing panel at a metal halide lamp 112W / cm1 lamp 30m / min, the panel is sticky to the touch, and scratch resistance is 5 levels in the nail scratch test. Perform an evaluation.
5 (excellent) ⇔ 1 (inferior)
If it is 3 or more, it can be used as a dummy can application.

  Table 1 shows the formulation of Examples 1 to 5, Table 2 shows the formulation of Comparative Examples 1 to 4, and Table 3 shows the evaluation results.

  In Table 1, as a non-reactive resin 1 (non-reactive resin 1) having no radical polymerizable double bond, a resin synthesized using hydrogenated BisA, tetrahydrophthalic anhydride, 1,6 hexanediol, Non-reactive resin 2 having no radical polymerizable double bond (non-reactive resin 2) includes a resin synthesized using cyclohexanedimethanol, tetrahydrophthalic anhydride and 1,6 hexanediol, radical polymerizable double bond As the non-reactive resin 3 having no bond (non-reactive resin 3), a resin synthesized using cyclohexanedimethanol, trimethylolpropane and adipic acid was used. The weight average molecular weights (Mw) of the synthesized non-reactive resins 1 to 3 were measured by GPC, and Mw = 2750 (non-reactive resin 1), Mw = 3100 (non-reactive resin 2), and Mw = 4720 (non-reactive), respectively. Resin 3) was obtained.

Monofunctional monomer is NK ester LA lauryl acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., bifunctional monomer is M-210 manufactured by Toa Gosei as an acrylate monomer, M-311 manufactured by Toa Gosei Co., Ltd. as an acrylate monomer, initiator is photocleavage Irgacure 907 manufactured by Ciba Geigy was used as a mold initiator.

In Table 2, the resin 4 was an epoxy resin (reactive resin) having a radical polymerizable double bond, and the resin 5 was a diallyl phthalate resin (reactive resin) having a radical polymerizable double bond. As the polyfunctional monomer 1, M-408 manufactured by Toagosei Co., Ltd., and as the polyfunctional monomer 2, KAYARAD DPHA manufactured by Nippon Kayaku was used. As the initiator, Irgacure 907 manufactured by Ciba Geigy was used as a photocleavable initiator.

  In Table 3, when Examples 1 to 5 and Comparative Examples 1 to 4 are compared, in Examples 1 to 5 corresponding to the present invention, from the elongation rate of the active energy ray-curable composition and the workability evaluation results, the mold processability It has been found that it is possible to provide a decorative resin sheet molded article having the above.

Claims (5)

  Based on the total ink composition, (a) 1 to 50% by weight of a monomer-soluble non-reactive resin having no radically polymerizable double bond, (b) 1 to 3 functional (meth) acrylate monomers An active energy ray-curable composition comprising 1 to 50% by weight and (c) a pigment containing 5 to 55% by weight as an essential component.   2. The active energy ray-curable type according to claim 1, wherein the monomer-soluble non-reactive resin having no radically polymerizable double bond is a polyester resin having a cyclohexene structure or a cyclohexane structure. Composition.   A printed matter, which is printed with the active energy ray-curable composition according to claim 1 or 2.   The printed matter according to claim 3 is printed with an offset.   A decorative sheet molding obtained by molding the printed matter according to claim 3 or 4 by drawing.