JP5434011B2 - Active energy ray-curable coating varnish composition excellent in antifouling property and printed matter thereof - Google Patents

Description

  The present invention relates to an active energy ray-curable coating varnish printed on the outermost layer of a package or the like, and further relates to a printed matter having excellent antifouling properties and particularly excellent fingerprint resistance.

  2. Description of the Related Art In recent years, research on coating active energy ray-curable coating varnish after printing color ink on various paper containers, commercial printing, and labels due to high quality and high quality of printed materials has been conducted.

  Regarding printed packages, when they are displayed at the storefront, they often adhere to fingerprints, sebum, sweat, etc. when they are picked up by hands, and the stains are not easy to remove once attached. The cosmetic properties are significantly impaired.

  For this reason, it is necessary to take measures to prevent the fingerprint from adhering, or to prevent smearing even if the fingerprint is attached.

  Therefore, as a means to solve these problems of dirt, as a method of forming an antifouling layer that has a performance that makes it difficult for dirt to adhere and easy to wipe off even if it adheres, mainly in optical materials (mainly display and touch panel) Various proposals have been made.

  For example, a method for forming a film containing an organic silane compound and a fluorine-based compound having a hydroxyl group and containing oil-repellent fluorine has been proposed (Japanese Patent Laid-Open Publication No. 2005-259542).

  Further, an antifouling and scratch resistant CRT filter in which a terminal silanol organopolysiloxane is coated on the surface of a substrate has been proposed (Japanese Patent Laid-Open No. 2002-260260).

  An antifouling and low-reflective plastic having an antireflection film composed of a mono- and disilane compound containing a polyfluoroalkyl group on the plastic surface and a halogen, alkyl or alkoxy silane compound has been proposed. (Patent Document 3)

  In addition, an optical member has been proposed in which a copolymer of perfluoroalkyl (meth) acrylate and a monomer having an alkoxysilane group is formed on an optical thin film mainly composed of silicon dioxide. (Patent Document 4)

  There has been proposed a method for providing a stain-inhibiting coating that makes the stain-inconspicuous coating non-greasy even if fingerprint stains are attached or makes the stain inconspicuous by making the coating of the stain-inhibiting coating oleophilic (Patent Document 5). )

As a means for solving the above-mentioned contamination problem, it mainly relates to optical member-related (mainly display / touch panel-related) applications, and Patent Documents 1 to 4 are techniques for making the surface oil-repellent. What is related to the present invention is to make the surface lipophilic. Moreover, in patent document 5, although it is a technique which makes a membrane | film | coat a new oil property, the further improvement is calculated | required by the present condition.
JP-A-11-217558 JP-A-4-338901 Japanese Patent Publication No. 6-29332 Japanese Patent Laid-Open No. 7-16940 Japanese Patent Laid-Open No. 13-353808

  The present invention relates to an active energy ray-curable coating varnish printed on the outermost layer of a package or the like, and relates to a printed matter having excellent antifouling property and particularly excellent fingerprint resistance.

  The present invention contains 0.1 to 5.0% by weight of the fatty acid ester represented by the general formula (1) (R1COO) nR2, and R1 of the fatty acid ester is 12 to 25 and R2 is 2 to 5 An active energy ray coating varnish characterized by using 70 to 90% by weight of an acrylate monomer having a surface tension of 32 to 38 mN / m and an active energy ray using the same The present invention relates to a printed matter obtained by coating a curable coating varnish.

  The present invention makes it possible to provide an active energy ray-curable coating varnish excellent in fingerprint resistance and a printed matter excellent in fingerprint resistance.

  By including a fatty acid derivative that is similar to the sebum component, the attached fingerprint (sebum) component gets wet on the coating varnish film, which makes the fingerprint itself inconspicuous and makes it possible to prevent contamination. .

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

As an example of the composition of the active energy ray-curable composition used in the present invention,
(A) Non-reactive resin 0 to 20% by weight
(B) Photopolymerizable acrylate monomer and oligomer 50 to 90% by weight
(C) Photoinitiator, photoauxiliary 1-20% by weight
(D) Fatty acid derivative 0.1 to 5% by weight
(E) Other additives 0 to 10% by weight
Is mentioned.

Among these, (b) 75 to 85% by weight of photopolymerizable acrylate monomer and oligomer
(C) Photoinitiator, photoauxiliary 10 to 15% by weight
(D) Fatty acid ester 1 to 3% by weight
(E) Other additives 1 to 5% by weight
Is good.

  In the present invention, the non-reactive resin does not have a radical polymerizable double bond. Examples of the non-reactive resin include polyester resin, acrylic resin, styrene-acrylic resin, petroleum resin, urethane resin, and the like. Thermosetting resins such as plastic resins, epoxy resins, and amino resins having no radically polymerizable double bond in the molecule are also used.

  In the present invention, the (b) photopolymerizable acrylate monomer and oligomer refer to monofunctional or polyfunctional (meth) acrylates, and the acrylate monomer having a surface tension of 32 to 38 mN / m is in the range of 50 to 90% by weight. Used in.

  Monofunctional monomers include 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 ( Examples thereof include benzyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, and tricyclodecane monomethylol (meth) acrylate.

  Polyfunctional (meth) acrylates include 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, hydroxypivalyl hydroxypivalate di (meth) acrylate (commonly called manda), Hydroxypivalyl hydroxypivalate dicaprolactonate di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di Addition of (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 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) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol prop Tricaprolactonate tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, diglycerin tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tetracaprolactonate, tetra (meth) acrylate, ditrimethylolethane tetra (meth) acrylate, ditrimethylolbutanetetra (meta) ) Acrylate, ditrimethylol hexane tetra (meth) acrylate, ditrimethylol octane tetra (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, and the like can be used.

  Among the monomers, acrylate monomers having a surface tension of 32 to 38 mN / m include tripropylene glycol diacrylate (surface tension 32.4 mN / m), trimethylolpropane triacrylate (surface tension 36.4 mN / m), PO Examples thereof include modified glycerol triacrylate (surface tension 35.4 mN / m).

  If a monomer having a surface tension of less than 32 mN / m is used, the surface uniformity of the fatty acid ester is greatly reduced, and sebum becomes conspicuous as a surface state, and fingerprint resistance cannot be obtained. Moreover, if a monomer of 38 mN / m or more is used, the solubility of the fatty acid ester in the coating varnish becomes poor, and the coating varnish becomes cloudy and cannot be used.

  The surface tension described above is measured by the Wilhelmey method using an automatic surface tension meter (CBVP-Z type) manufactured by Kyowa Interface Science Co., Ltd.

  As the photoinitiator (c) used in the present invention, as a 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 system initiation , Thioxanthone, 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.

  (C) The photoinitiator is used in the range of 1 to 20% by weight in the composition with respect to 100% by weight of the composition.

The fatty acid ester (d) used in the present invention is mainly a fatty acid ester represented by the general formula (R1COO) nR2 (1).
(In the formula, each R1 represents a C12 to C25, R2 represents a saturated or unsaturated linear or branched aliphatic hydrocarbon group having 2 to 5 carbon atoms)
In the case of an unsaturated aliphatic hydrocarbon group, it may have at least one double bond and / or triple bond in the molecule. These fatty acid esters are preferably used alone or as a mixture.

  The fatty acid ester is a fatty acid ester in which R1 represents an alkyl group or alkenyl group having 12 to 25 carbon atoms and R2 represents an alkyl group having 2 to 5 carbon atoms in the general formula (1). The fatty acid ester is preferably a simple substance or a mixture of fatty acid esters derived from vegetable oils and fats, but other synthetic methods can also be used.

  As said fatty acid ester, what was produced | generated by esterification of a fatty acid and alcohol can be used, for example. Fatty acids used for the production of the fatty acid ester are palm oil, palm oil, palm kernel oil, khair oil, red rice seed oil, rice seed oil, basket seed oil, guava seed oil, grapefruit seed oil, Fatty acids derived from plants such as white rice seed oil, white rice seed oil, peanut seed oil, potato seed oil, and habiwa seed oil. These fatty acids are generally composed of a plurality of fatty acids. Therefore, they can be separated and purified by a known method and used alone or in combination.

  Examples of the alcohol that reacts with the fatty acid to produce the fatty acid ester represented by the general formula (1) include alcohols having an alkyl group having 2 to 5 carbon atoms. Examples of the alcohol include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerin, amyl alcohol, and the like.

  Examples of the method for producing the fatty acid ester include a method by a direct esterification reaction by a reaction between the fatty acid and an alcohol, a method by an ester exchange reaction synthesized from an ester and an alcohol or an ester and a fatty acid, or an ester and an ester, A method by a direct esterification reaction is preferable, such as a method by reaction of acyl and alcohol, and a method by reaction of epoxide and fatty acid. In the method based on the above direct esterification reaction, the fatty acid and the alcohol are mixed, and an appropriate azeotropic dehydrating agent such as toluene or xylene is added and heated, so that the reaction proceeds while distilling water. As the catalyst, Bronsted acid such as sulfuric acid and p-toluenesulfonic acid, Lewis acid such as zinc oxide, activated alumina, titanium oxide, and tetraisopropyl titanate are used.

  The whole fatty acid ester contains 0.1 to 5.0% by weight of the whole. If it is 0.1% by weight or less, the fingerprint resistance is not sufficiently exhibited, and if it is 5% by weight or more, the solubility in the acrylate monomer is poor and tends to be separated.

  On the other hand, various additives for the purpose of anti-friction, anti-blocking, slip, anti-scratch and dark reaction can be used as (e) other additives in the composition. An agent, an antistatic agent, a surfactant, an antifoaming agent, a polymerization inhibitor and the like may be added. However, the said additive is limited to the thing which does not impair the lipophilicity of the coating varnish surface.

  EXAMPLES The present invention will be specifically described as examples, but the present invention is not limited to the following examples. Hereinafter, the numbers in the table indicate% by weight.

  An active energy ray-curable coating varnish composition was prepared according to the following formulation.

The manufacturing method of the active energy ray-curable coating varnish is heated at a temperature of 50 ° C. and dissolved by stirring (Table 1).

As photopolymerization acrylate monomer 1, trimethylolpropane triacrylate (surface tension 36.4 mN / m), as photopolymerization acrylate monomer 2, tripropylene diacrylate (surface tension 32.4 mN / m), photopolymerization acrylate monomer 3 In this case, PO-modified glycerol triacrylate (surface tension: 35.4 mN / m) and 1-hydroxycyclohexyl phenyl ketone as a photocleavable initiator are used. The fatty acid ester 1 uses stearic acid triglyceride, and the fatty acid ester 2 uses oleic acid triglyceride (triolein).

  Here, the photopolymerized acrylate monomer 4 is lauryl acrylate (surface tension 28.3 mN / m), and the photopolymerized acrylate monomer 5 is polyethylene glycol diacrylate (surface tension 41.8 mN / m). As a photocleavable initiator. 1-hydroxycyclohexyl phenyl ketone is used. Stearic acid amide is used as the fatty acid ester 3, stearic acid monoglyceride is used as the fatty acid ester 4, and silicone oil is used as the additive 1.

(Fingerprint resistance evaluation method)
As an artificial sebum, the contact angle is measured as the wettability between the fatty acid triglyceride (triolein) and the active energy ray-curable coating varnish film, and the effect is confirmed.

The active energy ray-curable overcoat varnish shown in Table 1 and Table 2 was applied to Hokuetsu Maricoat (Hokuetsu Paper Coated Ball) with a bar coater, and Example Samples 1 to 5 and Comparative Samples 1 to 4 were 160 W / A high-pressure mercury lamp (ozone type) having an intensity of cm was placed on a conveyor at 30 cm / min for 10 cm under the lamp and cured. 0.25 microliters of artificial sebum liquid (triolein) was dripped with respect to each film | membrane obtained, and the wettability was evaluated by the contact angle.

In Table 3, when Examples 1-4 and Comparative Examples 1-5 are compared, if the wettability with the contact angle is less than 10 degrees after 20 seconds, the artificial sebum liquid is inconspicuous and is inconspicuous as a fingerprint. In the case of 10 degrees or more, the artificial sebum fluid is repelled and becomes granular and can be clearly confirmed visually, and is also conspicuous as a fingerprint. As mentioned above, in Examples 1-4 corresponding to the present invention, it became possible to provide an active energy ray-curable coating varnish excellent in fingerprint resistance and a printed matter excellent in fingerprint resistance.

Claims (2)

0.1 to 5.0% by weight of the fatty acid ester represented by the general formula (1)
and
An active energy ray-curable coating varnish comprising 50 to 90% by weight of an acrylate monomer having a surface tension of 32 to 38 mN / m .
General formula (1)
(R1COO) ₃ R2
(In the formula, each R1 represents a C12 to C25, R2 represents a saturated or unsaturated linear or branched aliphatic hydrocarbon group having 2 to 5 carbon atoms) Claim 1 Symbol placement of the active energy ray-curable coating varnish formed by coating on the substrate a printed material.