JPH05140208A - Actinic radiation curable composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition improved in the wettability with a photocurable vehicle by using an inorganic pigment surface-treated with a specified water-insoluble bivalent cationic metal salt of an organic carboxylic acid as a pigment. CONSTITUTION:The objective actinic radiation curable composition contains a compound containing a radical-polymerizable double bond and a pigment, wherein an inorganic pigment surface-treated with a water-insoluble bivalent cationic metal salt of a double bond-terminated organic carboxylic acid is used as the pigment.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY In the active energy ray-curable composition according to the present invention, an inorganic pigment surface-treated with a compound having a terminal unsaturated double bond is an ultraviolet ray containing a photosensitive oligomer compound having an acryloyl group and a monomer. In addition, since the wetting of the vehicle such as the active energy ray curable printing ink or coating agent such as electron beam is very good, not only the printability or coating suitability is good but also the polymerization shrinkage of the polymerized cured coating film is suppressed. Based on this, it also has a function of alleviating the phenomenon of deterioration of the adhesiveness due to the occurrence of strain at the interface between the substrate and the coating film.

For example, a circuit pattern is printed on the surface of a wiring board by a screen printing method using an ultraviolet curable etching resist ink for a printed wiring board, which uses barium sulfate surface-treated as an inorganic pigment as described above. Compared with the case where untreated barium sulfate is used, the leveling property and the image reproducibility are good, and a tough coating film is formed. Therefore, it is necessary to produce an ink having excellent resist properties. Is possible.

Further, for example, when the surface-treated pigment as described above is applied to produce an electron beam curing type off-wheel ink, and printing is performed, the ink is emulsified by the fountain solution by the emulsification action of the pigment. Since it is extremely small, it shows good printability. Since it is an extremely useful inorganic pigment as described above, it can be applied to various fields-inks, paints, adhesives, dental composite resins, artificial marble and the like.

[0004]

2. Description of the Related Art Recently, in the printed wiring board industry, as the type of resist screen ink for forming a copper circuit pattern on the surface of a substrate, ultraviolet rays, so-called active energy ray-curable products are overwhelmingly more common than thermosetting products. Is coming. However, when a coating film is formed by curing with active energy rays, there is a drawback that the polymerization shrinkage occurs by about 10 to 15%, and therefore attempts to alleviate the decrease in the adhesiveness have been studied.

For example, when barium sulfate is used in an amount of 30 to 40% by weight as an inorganic extender pigment in a resist screen ink, the decrease in adhesion is alleviated. Currently, it is difficult to obtain an inorganic pigment suitable for an active energy ray-curable ink or paint on the market, so when using barium sulfate having a hydrophilic surface, which is usually available on the market,
It is necessary to use a dispersant together.

At this time, when about 10% by weight of a hydrophilic vinyl polymer such as polyvinylpyrrolidone is added to the ink as a dispersant, the wetting of the active energy ray-curable vehicle having an acryloyl group is improved,
There is a disadvantage that the water resistance of the cured coating film deteriorates.

Therefore, in the use of a printing ink using an inorganic pigment having an untreated surface, printability, adhesion of a coating film,
In order to improve various properties such as water resistance in general, it is necessary not only to adjust the type and amount of the inorganic pigment, the dispersant and other auxiliary agents for each use condition and application of the ink,
At present, the above-mentioned various physical properties are not always satisfactory. Thus, there has been a demand for new development of inorganic pigments having good dispersibility not only in the use of active energy ray-curable printing inks but also in the use of paints and adhesives.

[0008]

SUMMARY OF THE INVENTION The present invention has a terminal unsaturated double bond having a relaxation effect on the polymerization shrinkage of a coating film in order to solve various problems such as the complicated compounding operation as described above. It is intended to produce an active energy ray-curable composition having improved wettability to a photocurable vehicle by adding an inorganic pigment surface-treated with a water-insoluble organic carboxylic acid divalent metal salt. .

[0009]

The present invention is an active energy ray-curable composition containing a compound having a radical-polymerizable double bond and a pigment, the pigment being water-insoluble having a terminal unsaturated double bond. It relates to an active energy ray-curable composition, which is an inorganic pigment surface-treated with a divalent cation metal salt of an organic carboxylic acid.

The inorganic pigment surface-treated with the water-insoluble organic carboxylic acid divalent metal salt having a terminal unsaturated double bond, which is one constituent of the present invention, is an inorganic pigment produced by the following production method. Can be used.

That is, as the first method, calcium,
An aqueous solution containing a divalent cation such as strontium or barium (hereinafter referred to as a metal cation aqueous solution) and an aqueous solution containing an equimolar amount of a divalent anion such as a sulfate ion, a carbonate ion or an oxalate ion (hereinafter referred to as an anion When water-insoluble crystals are formed by stirring and mixing an aqueous solution), a water-soluble alkali salt such as lithium, potassium, sodium or ammonium of an organic carboxylic acid having a terminal unsaturated double bond is added to a reaction system. An inorganic pigment produced by coexisting with the water-insoluble organic carboxylic acid divalent metal salt having a terminal unsaturated double bond during production, which strongly adheres to the pigment surface to make the surface lipophilic and at the same time, crystallizes. And becomes an lipophilic inorganic pigment having a fine particle size.

As the second method, a water-soluble alkali salt of an organic carboxylic acid having a hydroxyl group is used instead of the water-soluble alkali salt of an organic carboxylic acid having a terminal unsaturated double bond. In addition to the inorganic pigment produced in the same manner as described above, a compound having a (meth) acryloyl group capable of reacting with a hydroxyl group, for example, an equimolar urethanization reaction product of a diisocyanate compound and a hydroxyalkyl (meth) acrylate or isocyanate ethyl By reacting a (meth) acrylate or the like with a hydroxyl group in an organic carboxylic acid chain present on the surface of the pigment, a lipophilic inorganic pigment having a fine particle size having a terminal unsaturated double bond on the surface of the pigment is obtained. It is achieved by forming.

As a means for coexisting an organic carboxylic acid alkali salt having a terminal unsaturated double bond or a hydroxyl group (hereinafter simply referred to as an organic carboxylic acid alkali salt), an organic carboxylic acid alkali salt is previously prepared in an anion aqueous solution. The salt may be allowed to coexist, and the mixed solution and the metal cation aqueous solution may be mixed by stirring, or the three types of aqueous solutions may be simultaneously mixed.

The concentration of the organic carboxylic acid alkali salt in the pigment formation reaction is usually about 0.001 to 0.1 mol, preferably 0.005 mol, per mol of the anion component solute of the pigment.
Although it can be used in an amount of up to 0.03 mol, it can be arbitrarily set depending on the application of ink, paint, adhesive, dental composite resin, artificial marble, etc. while observing the pigment dispersion effect. .

Examples of the organic carboxylic acid alkali salt include lithium, potassium, and organic carboxylic acids having the following terminal unsaturated double bond or hydroxyl group, depending on the application.
Alkali salts such as sodium and ammonium can be easily used.

Examples of the organic carboxylic acid having a terminal unsaturated double bond include compounds represented by the following general formulas (1) to (5).

[0017]

[Chemical 1]

(Wherein R ₁ represents a hydrogen atom or a CH ₃ group, R ₂ and R ₃ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, or R ₂ and R ₃ are formed together. (A hydrocarbon chain capable of representing a 6-membered hydrocarbon group, and X represents an alkylene group having 2 to 4 carbon atoms.)

[0019]

[Chemical 2]

(Here, R ₁ , R ₂ , R ₃ , X and the like have the same meanings as described above.)

[0021]

[Chemical 3]

(Here, R ₁ , X and the like have the same meanings as described above.)

[0023]

[Chemical 4]

(Here, R ₁ , X and the like have the same meanings as described above.)

[0025]

[Chemical 5]

(Here, n = 5 to 15.)

Further, as the organic carboxylic acid having a terminal unsaturated double bond, an organic compound obtained by addition of an isocyanate compound having a (meth) acryloyl group and an organic carboxylic acid having a hydroxy group by an NCO / OH group ratio of 1/1 is added. Unsaturated carboxylic acid etc. can be mentioned.

The organic carboxylic acid represented by the general formula (1), (2), (3) or (4) is, for example, a dibasic acid anhydride and a hydroxyalkyl (meth) acrylate in an equimolar ratio. It can be easily obtained by carrying out an addition reaction with. Examples of dibasic acid anhydrides include succinic anhydride, hexahydrophthalic anhydride, phthalic anhydride,
Tetrahydrophthalic anhydride, maleic anhydride, itaconic anhydride and the like can be mentioned. Examples of hydroxyalkyl (meth) acrylate compounds include hydroxyethyl methacrylate, hydroxyethyl acrylate,
Examples thereof include hydroxy (iso) propyl methacrylate, hydroxy (iso) propyl acrylate, hydroxybutyl methacrylate and hydroxybutyl acrylate.

Specific examples of the organic acid represented by the general formula (1) include β-methacryloyloxyethyl monosuccinate, β-acryloyloxyethyl monosuccinate, β-methacryloyloxyethyl monohexahydrophthalate and β. Specific examples of the acryloyloxyethyl monohexahydrophthalate and the organic acid represented by the general formula (2) include β-methacryloyloxyethyl monophthalate, β-acryloyloxyethyl monophthalate, and β-methacryloyl. Specific examples of oxyisopropyl monophthalate, β-acryloyloxyisopropyl monophthalate, and organic acids represented by the general formulas (3) and (4) include β-methacryloyloxyethyl monoitaconate and β- Acryloyloxyethyl monoitaconate, also general (5) As the specific examples of the organic acid represented by may be mentioned undecylenic acid.

Examples of the organic carboxylic acid having a hydroxyl group include dimethylolpropionic acid, 12-hydroxystearic acid, ricinoleic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, δ-hydroxyvaleric acid, ε-hydroxycaproic acid, p. -Hydroxyethyloxybenzoic acid etc. can be illustrated.

Further, as the isocyanate compound having a (meth) acryloyl group, in addition to isocyanate ethyl methacrylate and isocyanate ethyl acrylate,
The equimolar urethanization reaction product of a diisocyanate compound and the said hydroxyalkyl (meth) acrylate can be illustrated.

The diisocyanate compound includes toluylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, α, α, α ', α'-tetramethylxylylene diisocyanate. Etc. can be illustrated.

The organic carboxylic acid having a terminal unsaturated double bond is not limited to the above examples, and water 1
Any organic monobasic acid having a solubility of about 10 gr or less in 00 gr can be used.

If the amount is less than 1% by weight based on the pigment, an anionic surfactant may be used in combination with the organic carboxylic acid alkali salt to reinforce the lack of lipophilicity. By doing so, various properties such as dispersibility and gloss of the pigment can be adjusted.

When the anionic aqueous solution is an acidic aqueous solution such as sodium sulfate or when the reaction temperature is low, the lipophilicity of the pigment surface can be improved by salting out an organic carboxylic acid alkali salt or an anionic surfactant. Tends to lower. In such a case, salting out can be suppressed by allowing a small amount of a water-soluble organic solvent to coexist in the reaction system.

Examples of such water-soluble organic solvents are methyl lactate, ethyl lactate, acetone, methyl ethyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, 2-methoxyethyl alcohol, 2-ethoxyethyl alcohol and the like.

Further, in the present invention, when a pigment is produced according to each of the above methods, a trace amount of an aqueous solution of a coloring transition metal salt such as cobalt or manganese may be added and used immediately after the pigment is produced.

Examples of the compound having a radical-polymerizable double bond, which is one component of the present invention, include the following monomers and prepolymers. As the monomer, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 3-chloro-2-hydroxyethyl (meth) acrylate, methyl (meth) Acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, propyl (meth) acrylate, hydroxy (iso) propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, hydroxybutyl (meth) Acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) ) Acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth)
Acrylate, benzyl (meth) acrylate, (meth) alkylene oxide adduct of alkylphenol
Monofunctional monomers such as acrylate and cyclohexyl (meth) acrylate may be mentioned.

Further, as a bifunctional or higher functional monomer, 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 (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 hydroxypivale Todi (meth) acrylate, hexanediol (meth) acrylate, glycerin tri (meth) acrylate, diglycerin alkylene oxide tri (meth) acrylate, diglycerin tetra (meth) acrylate, diglycerin alkylene oxide tetra (meth) acrylate, trimethylol Propane tri (meth) acrylate, trimethylol propane alkylene oxide tri (meth) acrylate, ditrimethylol Ropane tetra (meth) acrylate, ditrimethylol propane alkylene oxide tetra (meth) acrylate, trimethylol ethane tri (meth) acrylate, ditrimethylol ethane tetra (meth) acrylate, trimethylol ethane alkylene oxide tri (meth) acrylate, ditrimethylol ethane alkylene Oxide tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A alkylene oxide di (meth)
Acrylate, bisphenol F alkylene oxide di (meth) acrylate, dihydroxybenzene alkylene oxide di (meth) acrylate, trihydroxybenzene alkylene oxide di (meth) acrylate, water-added bisphenol A di (meth) acrylate,
Examples thereof include water-added bisphenol F di (meth) acrylate, water-added bisphenol A alkylene oxide adduct di (meth) acrylate, and water-added bisphenol F alkylene oxide adduct di (meth) acrylate.

Other examples include lactone adduct monomers. That is, polyethylene glycol polylactonate di (meth) acrylate, polypropylene glycol polylactonate di (meth) acrylate, alkylene glycol polylactonate di (meth) acrylate, glycerin polylactonate tri (meth) acrylate, diglycerin polylactonate Tatra (meth) acrylate, trimethylolpropane polylactonate tri (meth) acrylate, ditrimethylolpropane polylactonate tetra (meth) acrylate, pentaerythritol polylactonate tri (meth) acrylate, pentaerythritol polylactonate tetra (meth) acrylate Acrylate, dipentaerythritol polylactonate, poly (meth) acrylates such as hexa (meth) acrylate It is. The lactone of the above monomer is a functional group-C of ester such as γ-butyrolactone, δ-valerolactone, ε-caprolactone.
It is a compound containing O-O- in the ring.

Further, an organic carboxylic acid having a terminal unsaturated double bond can be used as the monomer. Examples of the organic carboxylic acid having a terminal unsaturated double bond include, for example, the above-mentioned general formulas (1), (2), (3), (4),
In addition to the organic carboxylic acid represented by (5), acrylic acid,
Methacrylic acid, 3-acryloyloxypropionic acid, 2
-Hydroxyethyl (meth) acrylate and acid anhydride,
For example, succinic anhydride, phthalic anhydride, maleic anhydride,
Examples include trimellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, and an equimolar adduct with chlorendic anhydride. Furthermore, vinyl acetate, vinyl butyrate, vinyl benzoate, 2
Examples thereof include-, 3-, or 4-vinylpyridine, acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolacrylamide butyl ether.

Examples of the prepolymer include polyamide acrylate, polyester acrylate, epoxy acrylate, polyurethane acrylate and acrylated polyorganosiloxane.

The polyamide acrylate is represented by, for example, the general formula (6).

[0044]

[Chemical 6]

(Here, A is -O- or -NH
Represents-, at least two in one molecule are -NH-, R represents a divalent saturated aliphatic or unsaturated hydrocarbon group, and R ₁ represents a divalent saturated or unsaturated aliphatic group. Alternatively, it represents a cyclic hydrocarbon, R ₂ represents a hydrogen atom or an alkyl group, and n is an integer of 1 to 14. ) A diacrylic-modified (or dimethacryl-modified) polyamide poly (meth) acrylate and a general formula (7)

[0046]

[Chemical 7]

(Here, X represents a hydrogen atom or an acyl group, A represents —O— or —NH—, and at least two are —NH— in one molecule, and R is a divalent group. It represents a saturated or unsaturated aliphatic or cyclic hydrocarbon group, R ₁ represents a divalent aliphatic hydrocarbon group, R ₂ represents a hydrogen atom or an alkyl group, and n is an integer of 1 to 14. ) Diacryl-modified (or dimethacryl-modified) polyamide poly (meth) acrylate represented by

The polyester acrylate is, for example, an acrylic or methacrylic compound having an epoxy group in a polyester having two or more carboxyl groups derived from a polybasic acid or its anhydride and a polyhydric alcohol (eg, glycidyl (meth) acrylate). The polyester poly (meth) acrylate obtained by making it react can be mentioned.

Examples of the epoxy acrylate include bisphenol A type epoxy resin which is a condensation polymer of epichlorohydrin and bisphenol A, bisphenol F type epoxy resin which is a condensation polymer of epichlorohydrin and bisphenol F, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether. ,
1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, Eposizer W
An epoxy poly (meth) acrylate obtained by reacting an epoxy compound such as epoxidized oil such as -100 (manufactured by Dainippon Ink and Chemicals, Inc.) and epoxidized polybutadiene with (meth) acrylic acid can be mentioned.

As the polyurethane acrylate, for example, hydroxyl group-containing acrylic resin, hydroxyl group-containing organopolysiloxane resin, hydroxyl group-containing polyether, hydroxyl group-containing polyurethane, half ester of fatty acid and polyhydric alcohol,
Hydroxyl group-containing compounds such as castor oil include, for example, hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, xylylene diisocyanate and these diisocyanates and polyhydric alcohols. A compound having a hydroxyl group-containing terminal unsaturated double bond through a polyisocyanate such as a product containing a free isocyanate group by a reaction or a polymer of diisocyanate, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth ) Polyurethane poly (meth) acrylate obtained by reacting acrylate can be mentioned.

Examples of the acrylated polyorganosiloxane include, for example, Japanese Patent Publication No. 50-31041, US Pat. No. 4,348,454, and JP-A-55-112.
236, JP-A-60-215009,
JP-A-59-64669, JP-A-59-126
Mention may be made of the various acrylated polyorganosiloxanes disclosed in specification 478.

Examples of the radical polymerization initiator include the following substances. That is, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin initiators such as α-acrylbenzoin, benzophenone, p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, methyl ο-benzoylbenzoate, Arylketone initiators such as acetophenone, 4,4′-bisdiethylaminobenzophenone, isoamyl p-dimethylaminobenzoate, dialkylaminoarylketone initiators such as p-dimethylaminoacetophenone, thioxanthone, xanthone and halogen-substituted compounds thereof. Examples thereof include polycyclic carbonyl-based initiators.

As the coloring agent, solvent and additive, those generally used for inks, paints, adhesives, dental composite resins, artificial marble and the like can be used. As the additives, for example, plasticizer, defoaming agent, leveling improver, surfactant, anti-skin agent, drying regulator, flame retardant, anti-set off agent, lubricant, storage stabilizer (polymerization inhibitor), Etc. can be mentioned.

Examples of the organic polymer compound include diallylphthalate resin, polyvinylpyrrolidone, urethane resin, alkyd resin, polyester resin, epoxy resin, epoxy resin ester, acrylic resin, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-vinyl acetate copolymer. Coalesce, rosin ester, cellulose acetate butyrate, cellulose acetate propionate, phenol resin, petroleum resin, polyamide resin, nitrocellulose, chlorinated rubber, cyclized rubber, butyl rubber, melamine resin, urea resin,
Benzoguanamine resin, silicone resin, polybutadiene, etc. can be used.

The amount of the inorganic pigment surface-treated with the water-insoluble organic carboxylic acid divalent cation metal salt having a terminal unsaturated double bond used in the active energy ray-curable composition of the present invention is Although it may be optional depending on the physical properties or use of the composition, it is usually 0.1 based on the weight of the composition.
% To 90%. When the addition ratio is 0.1% or less, the effect of adding the inorganic pigment is not recognized, and when it is 90% or more, the adhesiveness of the paint to the plywood is deteriorated, for example, in the application of a sealing paint for plywood, which is preferable. Absent.

The active energy ray-curable composition obtained by the present invention is coated or printed on glass, plastic, paper, metal, stone (including ceramics), wood or other substrate, and is applied by irradiation with active energy rays. It is useful in applications such as curable paints, curable inks, and curable adhesives when curing or drying a film. When a solvent is used in the curable composition of the present invention, it is desirable to dry the coated article immediately before curing.

Any source can be used as the active energy ray for curing the active energy ray-curable composition of the present invention, and there is no particular limitation, and for example, mercury high pressure, medium pressure, low pressure lamp or super active fluorescent tube, Examples thereof include a light source such as a xenon lamp that emits short-wave light at a high rate or an active energy ray source such as an electron beam or X-ray.

[0058]

EXAMPLES The method of the present invention will be described in detail below with reference to examples and reference examples. In each example, parts and% mean parts by weight and% by weight.

Reference Example 1 150 ml of an aqueous solution of β-acryloyloxyethyl monophthalate having a concentration of 0.1 mol and 1000 ml of an aqueous solution of sodium sulfate having a concentration of 0.5 mol were heated to 75 ° C. and placed in a reaction vessel having a volume of 3000 ml. Charge. Then, 1100 ml of a 0.5 molar aqueous barium chloride solution, which is also heated to 75 ° C., is poured into this while stirring. Stirring is continued for 60 minutes to carry out the reaction, the resulting suspension is washed with water and filtered off, and the water-containing cake is dried at 60 ° C. for 48 hours to obtain lipophilic modified barium sulfate having good wettability with phenoxyethyl acrylate.

The average particle diameter of the obtained barium sulfate was 0.
2 microns. The wettability with an ultraviolet (hereinafter referred to as UV) curable vehicle was also better than that of a commercially available barium sulfate.

Reference Example 2 500 ml of an aqueous solution containing 0.4 molar sodium sulfate and 0.008 molar sodium 12-hydroxystearate was kept at 80 ° C. and the volume was 2000 m.
Charge into a 1 l reaction vessel. 500 ml of a 0.408 molar barium chloride aqueous solution at the same temperature was poured into this under stirring and the reaction was carried out for 1 hour. The obtained suspension is washed with water and filtered, and the water-containing cake is dried at 60 ° C. for 48 hours. 100 g of the obtained powder is dispersed in 250 ml of ethyl acetate, kept at 60 ° C., and charged into a reaction vessel having a volume of 1000 ml. To this, 250 ml of an ethyl acetate solution of 0.01 mol concentration of isophorone diisocyanate mono-β-hydroxyethyl acrylate (Artresin UN-2100A manufactured by Negami Kogyo Co., Ltd.) is injected under stirring and the reaction is carried out for 24 hours. The obtained suspension was filtered, and the residue was dried at 60 ° C. for 24 hours to obtain modified barium sulfate having good lipophilicity and good wettability with phenoxyethyl acrylate.

The resulting modified barium sulfate has an average particle size of 0.2 micron. Wetting to the UV curable vehicle was better compared to commercial barium sulphate.

Reference Example 3 Aqueous solution 50 containing 0.4 molar sodium sulfate and 0.008 molar sodium undecylenate
Keep 0 ml at 80 ° C. and load into a 2000 ml reaction vessel. To this, 500 ml of a barium chloride aqueous solution having the same temperature and a concentration of 0.408 is injected under stirring, and the reaction is carried out for 1 hour. The resulting suspension was washed with water and filtered to remove water cake.
After drying at 0 ° C. for 48 hours, a lipophilic modified barium sulfate having good wettability with phenoxyethyl acrylate was obtained.

The resulting modified barium sulfate has an average particle size of 0.2 micron. Wetting to the UV curable vehicle was better compared to commercial barium sulphate.

Reference Example 4 400 ml of water was put in a 3000 ml reaction vessel, kept at 40 ° C., and stirred. In this, 800 ml of 0.408 molar calcium chloride aqueous solution and 800 ml of an aqueous solution containing 0.4 molar sodium carbonate and 0.008 molar sodium undecylenic acid were kept at 40 ° C. at the same time and at a constant rate. , Add over 15 minutes. The mixture was further stirred for 20 minutes, the obtained suspension was washed with water and filtered, and the water-containing cake was dried at 60 ° C. for 48 hours to obtain modified calcium carbonate having good lipophilicity and good wettability with phenoxyethyl acrylate.

The modified calcium carbonate obtained has an average particle size of 0.1 micron. Wetting to the UV curable vehicle was better than commercial calcium carbonate.

Example 1 β-acryloyloxyethyl monophthalate surface-treated in Reference Example 1 Using barium sulfate, UV was prepared according to the following composition.
After producing a curable etching resist ink and printing it on a printed wiring board with a screen printer,
Using a UV irradiation device (manufactured by Eye Graphics Co., Ltd.) equipped with one watt / cm air-cooled high-pressure mercury lamp, the irradiation distance to the lamp is 11 cm, and the film is moved at a film moving speed of 1.5 m / min. When a film was formed and compared with a similarly prepared cured film using commercially available barium sulfate, it showed extremely excellent properties in various points such as gloss, hardness and corrosion resistance.

Modified barium sulfate prepared in Reference Example 1 30.0 parts β-type phthalocyanine blue 0.5 β-acryloyloxyethyl monohexahydrophthalate 61.3 1-hydroxycyclohexyl phenyl ketone 1.4 2-ethylanthra Quinone 0.3 Phenoxyethyl acrylate 2.0 Silicone KS66 2.0 Polyvinylpyrrolidone 2.5 Total 100.0 parts

Example 2 The following components were mixed with a premixer to form a paste, which was then kneaded with a three-roll mill to obtain an offset printing ink.

Byron 200 (linear polyester; manufactured by Toyobo Co., Ltd.) 10 parts Dicklight UE-8400 44 parts (epoxy acrylate; manufactured by Dainippon Ink and Chemicals, Inc.) 30 parts Aronix M8060 (oligoester acrylate; manufactured by Toagosei Co., Ltd.) Phthalocyanine blue (manufactured by Dainippon Ink and Chemicals, Inc.) 20 parts Modified barium sulfate prepared in Reference Example 2 5 parts Hydroquinone monomethyl ether 0.5 part

When the above printing ink was printed on a carton paper (UF coat made by Honshu Paper Co., Ltd.) by an offset rotary printing machine using an offset printing plate using a PS plate, the balance control between the ink and the dampening water was performed. It was easy to remove and the printability was good. Using an Electro-curtain CB150 / 15 / 10L type manufactured by Energy Science Co., Ltd., an electron beam irradiating device with an accelerating voltage of 165 KVA and an electron current of 2 mA is used to irradiate an electron beam of 20 KGy from the ink surface side in a nitrogen gas atmosphere of 20 ° C. As a result, a printed matter having good hardness and surface gloss was obtained.

Example 3 After mixing the following components, the mixture was thoroughly stirred and mixed for 20 minutes with a shaking paint conditioner to obtain a solution of the active energy ray-curable composition of the present invention.

Modified barium sulfate prepared in Reference Example 10 10 parts Trimethylolpropane triacrylate 20 parts Diethylene glycol diacrylate 14 parts Diclite UE8400 (Dainippon Ink and Chemicals) 14 parts Antistatic agent GAFAC RD-720 (Toho) 2 parts 1-hydroxycyclohexyl phenyl ketone 4 parts benzophenone 1 part isobutyl alcohol 28 parts methyl isobutyl ketone 7 parts

The resulting curable composition solution was applied to an untreated milky-white polyethylene terephthalate sheet to give a dry coating film thickness of 6
After coating with a bar coater to a thickness of μm, it was dried with hot air at 120 ° C. for 1 minute, and then a UV irradiation device (manufactured by Eye Graphics Co., Ltd.) equipped with a concentrating 120 watt / cm air-cooled high-pressure mercury lamp was used. When the irradiated distance was 11 cm and a cured film was formed by irradiating ultraviolet rays at a film moving speed of 1.5 m / min, the cured coating had good curability and film-forming property, and had good gloss and adhesion. A film was obtained.

The curable composition solution was stored at room temperature for one month, but no separation of the solution was observed due to the precipitation of barium sulfate. On the other hand, when preparing the curable composition solution,
The same procedure was repeated except that surface-untreated barium sulfate having an average particle size of 0.2 μm was used to prepare a curable composition solution of a comparative control example, and a cured film was formed in the same manner. Although the film forming property was good, when the solution was stored at room temperature, barium sulfate was precipitated in one day, and the solution was completely separated.

Example 4 The following components were mixed with a premixer to form a paste, which was then kneaded with a three-roll mill to obtain an electron beam curable adhesive.

2,2-bis (4-acryloxydiethoxyphenyl) propane 45 parts Aronix M1300 (urethane acrylate; manufactured by Toagosei Kagaku) 45 parts Modified calcium carbonate prepared in Reference Example 4 5 parts Cyanine blue 5 parts

The resulting adhesive was applied to treated OPP film 1
After coating with a bar coater at a coating amount of 0 g / m ² , it is attached to an aluminum foil, accelerating voltage of 165 KV and electron current of 2
When a 20 KGy electron beam was irradiated by a mA electron beam irradiation device, the bonded product was firmly bonded. Speed 2 at room temperature
T-type peel strength at 00mm / min is 50-100g / 15mm
Met. On the other hand, a bonded product was prepared in the same manner as described above by using untreated fine powder calcium carbonate (average particle size 0.1 micron) chemically formed according to Reference Example 4 instead of 5 parts of the modified calcium carbonate. Under the same conditions as above.
When the mold was peeled off, the peeling strength was 20 to 40 g / 15.
mm, and the peel strength was poor.

[0079]

According to the present invention, an inorganic pigment surface-treated with a water-insoluble organic carboxylic acid divalent metal salt having a terminal unsaturated double bond has improved wettability with an active energy ray curable vehicle. Therefore, when applied to various active energy ray-curable inks, paints, adhesives, dental composite resins, artificial marble, etc., gloss, hardness,
It has extremely excellent physical properties such as chemical resistance and adhesiveness.

Claims (1)

[Claims] 1. An active energy ray-curable composition containing a compound having a radical-polymerizable double bond and a pigment, wherein the pigment has a water-insoluble organic carboxylic acid divalent cation metal having an unsaturated terminal double bond. An active energy ray-curable composition, which is an inorganic pigment surface-treated with a salt.