JPH01168767A - Actinic radiation-curable coating composition - Google Patents

Abstract

PURPOSE:To attain improvements in printability, adhesion to a substrate and bending resistance, by producing a coating compsn. comprising as a principal component a vehicle comprising a solid resin dissolved in an actinic radiation- curable diluent obtd. by esterifying a particular polyhydric alcohol with (meth) acrylic acid and a particular fatty acid. CONSTITUTION:A coating compsn. comprising as a principal component a vehicle produced by dissolving a solid resin (b) which is soluble in an actinic radiation-curable diluent (a) and is substantially devoid of actinic radiation- curability in an actinic radiation-curable diluent (a) obtd. by esterifying a polyhydric alcohol having at least 4 alcoholic hydroxyl groups pre molecule and a hydroxyl equivalent of up to 50 with (meth)acrylic acid and a 6 C or higher fatty acid. Optionally, a photopolymn. initiator is added. For component (a), it is pref. that the molar ratio of the 6 C higher fatty acid to (meth)acrylic acid be up to 1/2.5.

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Field of Industrial Application) The present invention relates to an active energy ray-curable coating composition, and more specifically, it is cured by irradiation with ultraviolet rays or electron beams, and furthermore, The present invention relates to an active energy ray-curable coating composition that has excellent printability, adhesion to substrates, bendability, etc.

(Prior Art) In recent years, research on coating compositions curable with active energy rays has been actively conducted, and among them, printing inks,
Practical applications are progressing in fields such as clear faces, paints, adhesives, and photoresists. These are composed of radically polymerizable monomers and prepolymers that have radical polymerizability, and if necessary, radical polymerization initiators and pigments.The prepolymers include alkyd acrylate, alkyd acrylate,
Polyester acrylate, epoxy acrylate, urethane-modified acrylate, etc., and as monomers,
Bisphenol A alkylene oxide adduct diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, dipentaerythritol hexaacrylate alkylphenol alkylene oxide adduct monoacrylate, and the like were used.

Recently, printing and painting speeds have been increased, and in order to cope with this, active energy ray-curable coating compositions often use epoxy acrylate as a prepolymer, which cures quickly. However, epoxy acrylate has secondary hydroxyl groups and has little oil content, so it is used as a curable coating composition.

For example, when used in printing ink, it stains during printing.

Emulsification of ink often causes poor transfer.

Furthermore, the adhesion to the base material and bendability are also poor. For this reason, the actual situation is that the scope of application of these curable coating compositions has been narrowed. Prepolymers made by further reacting epoxy acrylate with lactone compounds are also known, but 1
hydroxyl groups, which often cause the problems described above.

(a) A compound obtained by using a trihydric alcohol such as trimethylolethane, trimethylolpropane, and trimethylolbutane as a polyol raw material and esterifying it with (meth)acrylic acid and a fatty acid.

(b) An ultraviolet curable ink whose main components are a solid resin soluble in (a) and (C) a photopolymerization initiator is known. At present, it is unsatisfactory and the scope of application is narrow.

"Structure of the Invention" (Means for Solving Problems) The present invention has been developed as a result of intensive research to improve these drawbacks.
We have now invented an active energy ray-curable coating composition that has excellent printability, adhesion to substrates, and bendability.In other words, 1. The present invention consists of (8) four or more alcoholic hydroxyl groups in one molecule. (b)(a ) is soluble in the active energy ray curable diluent and has substantially no active energy ray curability, and is used as the main component of the vehicle, and optionally contains a photopolymerization initiator. The present invention relates to an energy beam curable coating composition.

``The (al active energy ray-curable diluent) of the present invention has four or more alcoholic hydroxyl groups in one molecule.

Examples of the polyhydric alcohol having a hydroxyl equivalent of 50 or less include polypentaerythritol such as pentaerythritol, dipentaerythritol, and tripentaerythritol; polyglycerin such as diglycerin and triglycerin; ditrimethylolpropane.

Polymethylolpropanes such as tri-trimethylolpropane; inositol and the like and alkylene oxide adducts thereof; and the like, and these polyols can be used alone or in combination as necessary.

If a polyol having less than four alcoholic hydroxyl groups in one molecule is used, the curability of the active energy ray-curable composition deteriorates and the film strength decreases. Further, the use of a polyol having a hydroxyl equivalent of more than 50 also produces similar results.

Next, fatty acids having 6 or more carbon atoms include valeric acid, trimethylacetic acid, caproic acid, and n-hebutanoic acid.

Caprylic acid, capric acid, pelargonic acid, methoxyacetic acid, nonylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, hexadecenoic acid, oleic acid, linoleic acid, lilunic acid, eleostearic acid, seamaric acid and Vegetable oil fatty acids which are a mixture of these can be mentioned, and it is also possible to use a mixture of these if necessary.

Next, the resin used in the present invention is a solid resin.

It is necessary to be soluble in the active energy ray-curable diluent of the present invention, and examples thereof include alkyd resins, epoxy ester resins, petroleum resins, xylene resins, natural resin-modified phenol resins, ketone resins, and diallyl phthalate resins. .

Alkyd resins that can be used in the present invention include wood rosin, gum rosin, and water-added rosin as monobasic acids.

Rosins such as disproportionated rosin and tall oil rosin, the aforementioned fatty acids, benzoic acid, and t-butylbenzoic acid.

Monobasic acids such as benzoic acid derivatives such as 0-benzoylbenzoic acid can be used, and as polyols, glycols such as ethylene glycol, diethylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolhexane, Common polyols such as trivalent polyols such as glycerin and multimers thereof, pentaerythritol and multimers of pentaerythritol can be used.

Further, polyhydric carboxylic acids, that is, organic compounds having two or more carboxyl groups, include oxalic acid, malonic acid, succinic acid, alkylsuccinic acid, and glutaric acid.

Maleic acid or its acid anhydrides, fumaric acid, adipic acid, pimelic acid, speric acid, azelaic acid.

Sebacic acid, 03K-DASL-12,03K-DAS
L-20,03K-DASB-12,03K-DASB
-20,03K-DAUL-20,03K-DAUB-
20 (O5K series is Okamura Oil Co., Ltd. - Long Chain Dibasic M), aliphatic dicarboxylic acids such as dimer acids such as linseed oil fatty acids and tung oil fatty acids, and 0-phthalic acid.

Water-added 0-phthalic acid, hymic acid, methylhimic acid, diphenic acid, trimellitic acid, pyromellitic acid, naphthalic acid, benzophenonetetracarboxylic acid and their acid anhydrides, isophthalic acid.

Terephthalic acid, hemimellitic acid, trimesic acid, brenidic acid, merophantic acid, benzenepentacarboxylic acid.

Benzene hexacarboxylic acid, homophthalic acid, o, m.

Examples include aromatic polycarboxylic acids such as p-phenylene acetic acid and 0-phenylene acetic acid-β-propionic acid, and rosin dimer acid.

An alkyd resin is obtained by combining these raw materials as necessary and esterifying them.

Epoxy ester resins are polymers produced by the reaction and condensation of bisphenol A and epichlorohydrin, and commercially available products include Epicote 828° and Epicote 10.
01. Epicote 1004. Epicoat 1009 (both manufactured by Yuka Shell Epoxy ■) is available.Commercially available reaction products of novolac resin and epichlorohydrin include DEN431° and DEN438 (Dow Chemical ■).
), YDCN701°YDCN702. YDCN704
(Tobu Kasei @), etc. Other compounds having an epoxy ring and -base acids subjected to an esterification reaction can be used. As these basic acids, the general monobasic acids listed above as alkyd raw materials can be used.

Next, petroleum resins are polymers whose main component is C1 fraction, and commercially available products include Neopolymer (Megaga Kagaku@)),
Vetrozin (Mitsui Petrochemicals@), Vetcol (Toyo Soda), etc. are listed, and examples of polymers containing +C5 fraction as a main component include Neoresin (Megaga Kagaku ■). Examples of xylene resin include Nicanol (Mitsubishi Gas Chemical).

As the natural resin-modified phenolic resin, those commonly used in oil-based inks of conventional products can be used. A commercially available product is Tamanol (Arayo Kagaku Kogyo ■).

Examples include Tespol (Hitachi Polymer@) and Haliftal (Harima Kasei).

As a ketone resin, Hilac 80. llOH.

111.222 (Hitachi Chemical ■), Halon 80,110
(Honshu Chemical side). Further, examples of the diallyl phthalate resin include Guiso Sodabu (Osaka Soda ■).

Next, in the present invention, a photopolymerization initiator can be used if necessary. Examples of the photopolymerization initiator that can be used in the present invention include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-based aggravating agents such as α-acrylic benzoin, benzophenone, p-methylbenzophenone, p-chlorobenzophenone, and tetra Aryl ketone sensitizers such as chlorobenzophenone, methyl 0-benzoylbenzoate, acetophenone, and 4,4-bisdiethylaminobenzophenone.

Dialkylaminoarylketone sensitizers such as p-dimethylaminobenzophenone, isoamyl p-dimethylaminobenzoate, p-dimethylaminoacetophenone, polycyclic carbonyl sensitizers such as thioxanthone, xanthone and their halogen-substituted products, methylbenzyl ketal,
Known sensitizers such as benzyl ketal sensitizers such as ethyl benzyl ketal and isopropylbenzyl ketal can be used, and these sensitizers can be used alone or in appropriate combinations. Further, it is desirable that the amount of these photosensitizers in the composition is in the range of 1 to 30% by weight.

In the present invention, the above composition is used as a binder to form an active energy ray-curable ink composition.

The pigment is dispersed, but this method is not particularly limited, and it is possible to perform dispersion using a conventional method such as a three-roll mill or ball mill. Additives such as inhibitors can be used.

Furthermore, it is also possible to use other resins in combination within a range that does not inhibit the curing of the present invention.

This will be explained in detail below using an example. All parts in the examples indicate parts by weight.

Production Example 1 [Synthesis of solid resin] 65 parts of water-added rosin (Hypere, Arayo Chemical Industry Co., Ltd.) and O-benzoylbenzoic acid (SKP-10A, Seiko Chemical Co., Ltd.) were placed in a 4-bottle flask equipped with a condenser with a water separation tube and a stirrer. ), 11.9 parts of pentaerythritol (Koei Kagaku@), and 5 parts of mixed xylene were added, heated to 140°C while blowing N2 gas, and stirred.

Further heating was continued at 270°C for 6 hours, and the acid value was 1.
It was set as 8. Thereafter, the mixture was cooled to 190°C, 18.1 parts of hydrogenated phthalic anhydride (Rikazid TH, Shin Nippon Rika ■) was added, the temperature was further raised, and the mixture was reacted at 280°C for 4 hours.

The acid value was set to 15, and xylene was distilled off to obtain [Alkyd Resin 1].

This resin has an acid value of 14.6 Melting point: 122℃ (capillary method) Met.

Production Example 2 Into the same reaction apparatus as Production Example 1, 65 parts of hydrogenated rosin, 12.1 parts of pentaerythritol, and 5 parts of xylene were charged, N8
Heat to 140°C while blowing gas.

The mixture was stirred, heated to 270°C, and reacted at the same temperature for 7 hours.

The acid value was set to 19. It was cooled to 180°C, 17.9 parts of hydrogenated phthalic anhydride was added, heated again, and reacted at 280°C for 4 hours to reach an acid value of 14.8. When the temperature reached ℃, 10 parts of methyl isobutyl ketone was added, and the temperature was further raised to 100℃, and 10 parts of cyclohexane was added.
drop and mix. Next, 5 parts of 98% acrylic acid and p
-) 1 part of luenesulfonic acid.

Mix and add 0.01 part of hydroquinone, and heat to 100°C.
The mixture was reacted for 6 hours to give an acid value of 16. Thereafter, the mixture was stirred at 100° C. for 2 hours under reduced pressure of 50 mml (g).

Hatyl isoptyl ketone and cyclohexane were distilled off.

The obtained solid resin is referred to as [Alkyd Resin-2].

[Alkyd resin-2] Oxidation 13.4 Melting point: 102℃ (capillary method) Met.

Production Example 3 Epicoat 10 was prepared using the equipment used in Production Examples 1 and 2.
04 (Epoxy resin, oil-based shell epoxy resin) 50
1 part, 50 parts of hydrogenated rosin, and 5 parts of xylene were charged, and the temperature was raised to 130°C while blowing Nt gas.

Start dissolving and stirring, add 0.1 part of triethylamine, keep warm for 1 hour, then react at 200°C for 1 hour,
Further, the temperature was raised to 260°C, and the reaction was carried out for 9 hours while dehydrating.
At an acid value of 16, xylene was distilled off.

A solid resin was obtained. This resin [Eponester resin-1
].

Epon ester resin-1 is Oxidation 15.2 Melting point: 102℃ (capillary method) Met.

Example 1 [Production of active energy ray-curable ink vehicle] A vehicle was produced using the apparatus used in Production Examples 1 to 3. Add Aronix S-10 (manufactured by Toagosei Chemical Industry Co., Ltd.) active energy ray-curable diluent to a flask.

Add 60 parts of dipentaerythritol monolaurate-pentaacrylate and 0.1 part of hydroquinone.

N! While blowing a mixed gas of gas/air = 1/1.

Heat, stir, and bring to 100°C. [Alkyd resin 1]
Add 40 parts of (added in 5 times of 8 parts each).

Dissolved. This varnish will be referred to as varnish 1.

Similarly, Example 2 Aronix 5-10 and [alkyd resin]
2] The varnish made with varnish 2. 3. The varnish made with Aronix 5-10 and [Epon ester resin-1] is varnish. 4. Aronix 5-10 and Megata Neopolymer NP120 (petroleum resin manufactured by Megata Kagaku ■). The varnish made with Varnish 4 〃 5 The varnish made with Aronix 5-10 and Hilac 222 (Hitachi Chemical type ketone resin) is Varnish 5 〃 6 The varnish made with Aronix 5-10 and Guisodatsubu (sial rifthalate resin manufactured by Osaka Soda ■) The varnish created with Varnish 6 〃 7 Aronix 5-10 and Nikkanol HP12
Varnish 7 〃 8 Aronix S-19 (active energy ray-curable diluent dipentaerythritol monocaprylate pentaacrylate manufactured by Toagosei Chemical Co., Ltd.) and [alkyd resin] Varnish 8〃9 The varnish made with Aronisox S-6 (active energy ray-curable diluent pentaerythritol monostearate, triacrylate manufactured by Toagosei Kagaku Kogyo ■) and [alkyd resin-1] Varnish 9〃10 Aronixx 5A-2 (Toagosei Chemical Co., Ltd. Oil-based energy ray curable diluent diglycerin monocapronate triacrylate) and [Alkyd tree-1] Varnish 10〃11 Aronix 5A3 Varnish 11 was prepared from (tripentaerythritol monocaprinate monostearate hexaacrylate) and [alkyd resin = 1].

[Creation of ink]

65 parts of each varnish and 18 parts of Lionol Blue SM (base cyanine blue pigment manufactured by Toyo Ink) were milled and dispersed using a three-roll mill, and then each varnish and a reactive diluent were added to make a total of 100 parts. Tack 1 using
0-11. An ink was prepared by adjusting the flow to be 17 to 18, and ink 1 (11 to 11(1)) was obtained.

In addition, for each 100 parts of this ink, 2 parts of EAB (initiator manufactured by Odugaya Chemical), 3 parts of Irgacure 907 (sensitizer manufactured by Nippon Ciba Geigy), 1 part of Gatecure FAA (initiator manufactured by Daito Chemical), and 1 part of Kayacure DETX ( Mix in 2 parts of Nippon Kayaku sensitizer).

Inks 1 tz> to 11-m were obtained.

Comparative Example 1 After dispersing 60 parts of Lipoxy 5P1519X (epoxy acrylate manufactured by Showa Kobunshi Co., Ltd.) and 18 parts of Dionol Blue 5M in a three-roll mill, A-BPE-4 (manufactured by Shin Nakamura Chemical Co., Ltd., active energy ray-curable diluent, bisphenol) was dispersed. A, diacrylate of ethylene oxide adduct) and lipoxy 5P1519X, total 100 parts, tack 10.5.
As flow 16.8, comparative ink 1c1) was used.

In addition, the same initiator as in the example was added to 100 parts of this ink.

An aggravating agent was added to prepare comparative ink 1 (Kl).

Comparative Example 2 In the same manner as Comparative Example 1, comparative inks 2-31°, 2(Z
) was obtained.

Comparative Example 3 In the same manner as in Example 1, guiso tsubu and NK ester A were prepared.
Comparative Ink 3-, which was made into a varnish and an ink using -BPE-4 (diluent manufactured by Shin Nakamura Chemical Co., Ltd.).

Comparative Example 4 In the same manner as in Example 1, [Alkyd Resin 1], NK Ester A-TY (Shin Nakamura Chemical Diluent), 1 mol of coconut oil fatty acid of trimethylolpropane, and acrylic An ink was prepared using the reactant of 2 moles of acid, and comparative ink 4-m was prepared.
4 <z>.

The results of the evaluation of these inks are shown in the table.

Table-■ indicates ink 1-o) to 11(1) and Comparative Example 1
-(+) to 3(I) were printed on Maricoat (manufactured by Hokuetsu Paper Co., Ltd., coated paper for men) and Polyethicoat (polyethylene laminated paper, made by Potrasoji Co., Ltd.) using Heidel WORD-1 (offset printing machine manufactured by Heidelberg Co., Ltd.). , which was evaluated after being cured using a curtain beam type electron beam irradiation device.

Table -■ shows the evaluation results of UV curable ink.

"Effects of the Invention" The active energy ray-curable coating composition of the present invention is superior to conventionally known compositions in both printing effect and workability.

(Margin below)

Claims (1)

[Claims] 1. (a) A polyhydric alcohol having 4 or more alcoholic hydroxyl groups in one molecule and a hydroxyl equivalent of 50 or less, (meth)acrylic acid and a fatty acid having 6 or more carbon atoms. (b) A solid resin that is soluble in the active energy ray curable diluent of (a) and has substantially no active energy ray curability. An active energy ray-curable coating composition comprising a dissolved vehicle as a main component and optionally containing a photopolymerization initiator. 2. (a) The active energy ray according to claim 1, wherein the active energy ray curable diluent has a fatty acid having 6 or more carbon atoms in a molar ratio of 1/2.5 or less to (meth)acrylic acid. Curable coating composition. 3. The active energy ray-curable coating composition according to claim 1 or 2, wherein the solid resin (b) has a melting point in the range of 60°C to 160°C.