JP6900172B2 - Active energy ray-curable resin composition - Google Patents

Description

The present invention relates to an active energy ray-curable resin composition. More specifically, the present invention relates to an active energy ray-curable resin composition that gives a cured product having excellent transparency and high hardness.

The active energy ray-curable resin composition is applied to, for example, ink applications, has features that it can reduce the environmental load because it does not use a solvent, and can improve productivity due to quick-drying due to active energy ray curing, and is suitable for industrial applications. Widely used.
In recent years, among active energy ray-curable inks, printing by the inkjet method capable of high-design and high-definition printing has attracted attention, and has begun to be widely used for printing for sign displays and packages.

As a method of achieving both a low viscosity of the active energy ray-curable ink and a coating film hardness after curing, a method of using a composition containing caprolactone-modified dipentaerythritol hexaacrylate (for example, Patent Document 1), for a polyfunctional monomer A method using a compound to which an alkylene oxide is added (for example, Patent Document 2) has been proposed.

Japanese Unexamined Patent Publication No. 2013-2566659 Japanese Unexamined Patent Publication No. 2014-169360

However, in both methods of Patent Documents 1 and 2, the ink viscosity can be reduced by the polyfunctional monomer-modified composition and the ejection stability is excellent, but the coating film hardness is lowered due to the decrease in the cross-linking density of the coating film after curing. There is a problem that it decreases.
An object of the present invention is to provide an active energy ray-curable resin composition that provides a cured product having low viscosity, high hardness, and high transparency, which is applicable to inkjet inks.

The present inventors have arrived at the present invention as a result of studies for achieving the above object.
That is, the present invention is a hydrolyzed condensate (A) containing an inorganic alkoxide (a1) and a hydroxyethyl acrylamide and / or a polyethylene glycol mono (meth) acrylate having 35 or less carbon atoms as a constituent monomer, monofunctional unsaturated. An active energy ray-curable resin composition containing a monomer (B), a polyfunctional (meth) acrylate (C), and a photopolymerization initiator (D).
The monofunctional unsaturated monomer (B) contained in the active energy ray-curable resin composition is a monofunctional (meth) acrylate (B1) having 3 to 35 carbon atoms, N, N-dimethylacrylamide, diacetoneacrylamide, and the like. At least one monomer selected from the group consisting of hydroxyethyl acrylamide and acryloyl morpholine.
The content of the hydrolyzed condensate (A) contained in the active energy ray-curable resin composition is the same as that of the hydrolyzed condensate (A) contained in the active energy ray-curable resin composition. Based on the total weight of the saturated monomer (B), it is 10-61% by weight,
The content of the monofunctional unsaturated monomer (B) contained in the active energy ray-curable resin composition is the same as that of the hydrolyzed condensate (A) contained in the active energy ray-curable resin composition. 39-90% by weight, based on the total weight of the unsaturated monomer (B).
The content of the polyfunctional (meth) acrylate (C) contained in the active energy ray-curable resin composition is the same as that of the hydrolysis condensate (A) contained in the active energy ray-curable resin composition. The active energy ray-curable resin composition (X) is 10 to 100% by weight based on the total weight of the functional unsaturated monomer (B).

The active energy ray-curable resin composition (X) of the present invention has the following effects.
(1) It has a low viscosity and is particularly excellent in ejection stability from an inkjet nozzle.
(2) The cured product has excellent scratch resistance (surface hardness).
(3) The cured product has excellent transparency.

<Inorganic alkoxide (a1)>
Examples of the inorganic alkoxide (a1) in the present invention include silane alkoxide, titanium alkoxide, zirconium alkoxide, hafnium alkoxide, zinc alkoxide, aluminum alkoxide, gallium alkoxide, indium alkoxide, germanium alkoxide, tin alkoxide and the like.

Of these, from the viewpoint of hardness, silane alkoxide, titanium alkoxide, zirconium alkoxide, aluminum alkoxide are preferable, and silane alkoxide is more preferable.

<Monofunctional unsaturated monomer (B)>
Examples of the monofunctional unsaturated monomer (B) in the present invention include a monofunctional (meth) acrylate (B1) having 3 to 35 carbon atoms and a nitrogen atom-containing monofunctional unsaturated monomer (B2).

(B1) Monofunctional (meth) acrylate having 3 to 35 carbon atoms:
(Meta) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 4-n- Butylcyclohexyl (meth) acrylate, Bornyl (meth) acrylate, Isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate , 4-Bromobutyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene mono (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2- (2- (2-) Methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, phenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (Meta) Acrylate, Glycidyl (Meta) Acrylate, Tetrahydrofurfuryl (Meta) Acrylate, Cyclic Trimethylol Propaneformal Acrylate, 1,4 Cyclohexanedimethanol Monoacrylate, 2-Hydroxyethyl (Meta) Acrylate, 3-Hydroxypropyl (Meta) ) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, polyethylene glycol (PEG) mono (meth) acrylate;

(B2) Nitrogen atom-containing monofunctional unsaturated monomer:
Vinylamine, N-methylvinylamine, N-ethylvinylamine, N-propylvinylamine, Nn-butylvinylamine, Nt-butylvinylamine, N-butoxymethylvinylamine, N-isopropylvinylamine, N -Methylol vinylamine, N, N-dimethylvinylamine, N, N-diethylvinylamine, N-vinylmorpholine, allylamine, N-methylallylamine, N-ethylallylamine, N-propylallylamine, N-n-butylallylamine, N-t-butylallylamine, N-butoxymethylallylamine, N-isopropylallylamine, N-methylolallylamine, N, N-dimethylallylamine, N, N-diethylallylamine, N-allylmorpholine, N-vinylpyrrolidone, vinylformamide, N, N-dimethylacrylamide, diacetoneacrylamide, hydroxyethylacrylamide, acryloylmorpholin;

Among these monofunctional unsaturated monomers (B), a monofunctional unsaturated monomer having one hydroxyl group is preferable from the viewpoint of hardness, and hydroxyethyl acrylamide and PEG mono (meth) acrylate are more preferable. ..

In the hydrolyzed condensate (A) in the present invention, the inorganic alkoxide (a1) and a monofunctional (unsaturated monomer (B) are referred to as constituent monomers [hereinafter, may be referred to as constituent units]]. ..
The hydrolyzed condensate (A) preferably has an unsaturated group from the viewpoint of the hardness of the cured product, and more preferably has an unsaturated group derived from (B). The unsaturated group concentration derived from (B) is preferably 0.5 to 6.0 mmol / g, more preferably 0.7 to 5.5 mmol / g, and particularly preferably 1.2 to 5.0 mmol / g. is there.
The unsaturated group can be quantified by the method described below.

The unsaturated group contained in (A) preferably has a structure represented by the following general formula (1).

［式中、Ｒ¹はＨまたは炭素数１〜３のアルキル基；Ｒ²は単官能不飽和モノマー（Ｂ）から、１個の水酸基を除いた残基；ＸはＳｉ、Ｚｒ、Ｔｉ、またはＳｎを表す。］

[In the formula, R ¹ is H or an alkyl group having 1 to 3 carbon atoms; R ² is a residue obtained by removing one hydroxyl group from the monofunctional unsaturated monomer (B); X is Si, Zr, Ti, or Represents Sn. ]

The molar ratio [(a1) / (B)] of (a1) and (B) constituting (A) is preferably 50/50 to 95/5 from the viewpoint of transparency and hardness of the cured product. It is preferably 55/45 to 90/10, particularly preferably 60/40 to 85/15.

(A) in the present invention is preferably a hydrolyzed condensate (A1) and / or a particulate hydrolyzate (A2) having a weight average molecular weight (Mw) of 500 to 20,000.

The weight average molecular weight [hereinafter abbreviated as Mw] of the hydrolyzed condensate (A1) is preferably 20,000 or less, more preferably 15,000 or less, and particularly preferably 10,000 or less. The Mw is preferably 500 or more, more preferably 700 or more, and particularly preferably 1,000 or more. The weight average molecular weight is measured by GPC and is subject to the following measurement conditions.

<GPC measurement conditions>
GPC model: Waters Alliance 2695, Waters column: TSKgel Super H4000 +
TSKgel Super H3000 +
TSKgel Super H2000 +
Guardcolum Super HL, Tosoh Co., Ltd. Solvent: Tetrahydrofuran (THF)
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard)
POLYSTYRENE), manufactured by Tosoh Corporation

The volume average particle size (Dv) of the particulate hydrolyzed condensate (A2) is preferably 1 μm or less, and more preferably 0.7 μm or less from the viewpoint of the active energy ray-curable resin composition (X) described later. , Especially preferably 0.4 μm or less.
Further, (Dv) is preferably 0.005 μm or more, more preferably 0.01 μm or more, and particularly preferably 0.02 μm or more, from the viewpoint of thixotropy of the active energy ray-curable resin composition (X) described later. .. The volume average particle size (Dv) is measured by a light scattering particle size distribution measuring device.

The hydrolyzed condensate (A) in the present invention preferably contains the inorganic alkoxide (a1) and water in the monofunctional unsaturated monomer (B) in a molar ratio of (a1) and (water) [ (A1) / (water)] is preferably 2 to 200, more preferably 5 to 150, particularly preferably 10 to 100 from the viewpoint of transparency and hardness, by carrying out a hydrolysis reaction and a condensation reaction. Can be manufactured.
Further, in the production method, in the above reaction, (A) which is (A1) may be obtained by the step of first producing the (A1). Further, the reaction (sol-gel reaction) may be further carried out to obtain (A) which is (A2).
In the above production method, it can be estimated that it is obtained as a solution according to (B) of (A), and is mainly a solution in the case of (A1) and a (dispersion) solution in the case of (A2).

A catalyst (b) may be used in the above reaction for the purpose of accelerating the reaction. For example, as an acid catalyst, an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, maleic acid, acetic acid, methanesulfonic acid, paratoluenesulfonic acid or the like may be used. Examples of the organic acid and alkali catalyst include aliphatic amines such as hexylamine and octylamine, alicyclic amines such as cyclohexylamine and cyclopentylamine, aromatic amines such as aniline and diphenylamine, and heterocyclic amines such as morpholine.

Examples of the organic solvent used in the solgel method include alcohol solvents such as methanol, ethanol and 2-propanol, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl acetate and isobutyl acetate. Of these, an alcohol solvent is preferable, and ethanol is more preferable.

The unsaturated group concentration (mmol / g) of (A) is measured by the following method.
(1) Separation and purification of hydrolyzed condensate (A) <hydrolyzed condensate (A1)>
The hydrolyzed condensate (A1) is separated and purified using a preparative GPC. The preparative GPC shall be performed under the following conditions.

<GPC measurement conditions>
-GPC model: Waters Alliance 2695, manufactured by Waters-Column: GPC K-2001 + GPC K2002 +
GPC K2002.5 + GPC K-2003 +
GPCK-2004 + GPC K-LG, manufactured by Showa Denko KK ・ Solvent: Chloroform ・ Detector: Refractive index detector ・ Reference material: Standard polystyrene (TSK standard)
POLYSTYRENE), manufactured by Tosoh Corporation

<Particulate Hydrolyzate (A2)>
Weigh 0.5 g of the sample, add it to a 1 ml centrifuge tube, and add a desktop ultracentrifuge [model "Optima MAX-XP", manufactured by Beckman Coulter Co., Ltd., the same applies hereinafter. ] Is used to centrifuge at 150,000 rpm for 30 minutes. After centrifugation, remove the supernatant, add 0.5 ml of acetone, and centrifuge again under the same conditions. After repeating the above operation 5 times, the precipitate is taken out and dispersed in 20 ml of acetone to prepare a (A) dispersed acetone solution. The solid content in this acetone solution is calculated from the following formula, where about 1.0 g of the sample is weighed in a petri dish (W1) and dried at room temperature for 90 minutes, and the residual weight is (W2).

Solid content (% by weight) = (W2) x 100 / (W1)

(2) Calculation of unsaturated group concentration (mmol / g) The unsaturated group concentration (mmol / g) is calculated from the iodine value measured by the following method.
<Iodine value measurement method>
The hydrolyzed condensate (A) purified by the above method is precisely weighed to a solid content of 0.3 g, placed in a 500 mL iodine flask, 10 mL of chloroform and Wyeth's reagent (7.9 g of iodine trichloride and 8.7 g of iodine). Add glacial acetic acid to make 1 L) and leave it in the dark for 1 hour to react. To the above solution, add 20 mL of 10% potassium iodide solution and 100 g of water, and titrate with 0.1 N sodium thiosulfate standard solution using 1% starch solution as an indicator. At the same time, a blank test is also performed, the iodine value Y can be calculated from the following formula, and the unsaturated group concentration (mmol / g) can be calculated from the iodine value.
Iodine value: Y = (BA) x f x 1.269 / S
A: Number of ml of 0.1 mol / l sodium thiosulfate standard solution required for this test B: Number of ml of 0.1 mol / l sodium thiosulfate standard solution required for blank test f: 0.1 mol / l sodium thiosulfate Titer of standard solution.
S: Sampling amount (g)

Unsaturated group concentration (mmol / g) = Y / 25.38

<Active energy ray-curable resin composition (X)>
The active energy ray-curable resin composition (X) of the present invention contains the hydrolyzed condensate (A), a monofunctional unsaturated monomer (B), and a photopolymerization initiator (D) described later.
The (X) can be particularly preferably used for inkjet ink applications.

From the viewpoint of hardness and transparency, the content of the active energy ray-curable resin composition (X) based on the total weight of (A) and (B) is preferably 10 to 50% by weight. (B) is 50 to 90% by weight, (D) is 0.1 to 10% by weight, more preferably (A) is 20 to 40% by weight, (B) is 60 to 80% by weight, (D). Is 0.2 to 8% by weight.

<Photopolymerization initiator (D)>
The photopolymerization initiator (D) in the present invention includes a phosphine oxide compound (D1), a benzoylformate compound (D2), a thioxanthone compound (D3), an oxime ester compound (D4), a hydroxybenzoyl compound (D5), and a benzophenone. Examples thereof include compound (D6), ketal compound (D7), α-aminoalkylphenone compound (D8) and the like.

Examples of the phosphine oxide compound (D1) include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

Examples of the benzoyl format compound (D2) include methyl benzoyl format.

Examples of the thioxanthone compound (D3) include isopropyl thioxanthone and the like.

Examples of the oxime ester compound (D4) include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-). Methylbenzoyl) -9H-carbazole-3-yl]-, 1 (O-acetyloxime)) and the like can be mentioned.

Examples of the hydroxybenzoyl compound (D5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, benzoin alkyl ether and the like.

Examples of the benzophenone compound (D6) include benzophenone and the like.

Examples of the ketal compound (D7) include benzyldimethyl ketal and the like.

Examples of the α-aminoalkylphenone compound (D8) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one.

Among these photopolymerization initiators (D), (D1), (D5), and (D8) are preferable from the viewpoint of hardness, and bis (2,4,6-trimethylbenzoyl)-is more preferable. Phenylphosphine oxide, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one.

The active energy ray-curable resin composition (X) of the present invention may contain a polyfunctional (meth) acrylate (C), if necessary, as long as the effects of the present invention are not impaired. Examples of the polyfunctional (meth) acrylate (C) include polyfunctional (meth) acrylates having at least two, preferably 3 to 6 (meth) acryloyl groups. The hardness can be increased by using two or more (meth) acrylates in the molecule.
The content of (C) is preferably 10 to 100% by weight, more preferably 20 to 90% by weight, based on the total weight of (A) and (B), from the viewpoint of curability and transparency. Is.

Examples of the polyfunctional (meth) acrylate (C) include di (meth) acrylate (C1), trivalent or higher (meth) acrylate (C2), polyester (meth) acrylate (C3), and urethane (meth) acrylate (C4). , Epoxy (meth) acrylate (C5), (meth) acryloyl group-modified butadiene polymer (C6), (meth) acryloyl group-modified dimethylpolysiloxane polymer (C7).

Di (meth) acrylate (C1):
Polyoxyalkylene (alkylene has 2 to 4 carbon atoms) [molecular weight 106 or more and number average molecular weight (hereinafter, number average molecular weight by gel permeation chromatography (GPC) method is abbreviated as Mn) 3,000 or less] Di (meth) acrylate (C11)
Di (meth) acrylates of polyethylene glycol (Mn400), polypropylene glycol (Mn200) and polytetramethylene glycol (Mn650);

Di (meth) acrylate (C12) of a divalent phenol compound alkylene oxide (hereinafter, "alkylene oxide" is abbreviated as AO) (2 to 30 mol) adduct:
For example, AO adducts of divalent phenol compounds [monocyclic phenol (catechol, resorcinol, hydroquinone, etc.), condensed polycyclic phenol (dihydroxynaphthalene, etc.), bisphenol compounds (bisphenol A, -F, -S, etc.)] Di (meth) acrylate of EO4 mol adduct, di (meth) acrylate of PO4 mol adduct of dihydroxynaphthalene, 2 mol of EO (ethylene oxide) of bisphenol A, -F and -S, and PO (propylene oxide) 4 Each di (meth) acrylate of the molar adduct, etc.];

Di (meth) acrylate (C13) of an aliphatic dihydric alcohol having 2 to 30 carbon atoms:
For example, neopentyl glycol and 1,6-hexanediol di (meth) acrylates;

Di (meth) acrylate (C14) of an alicyclic-containing divalent alcohol having 6 to 30 carbon atoms:
For example, di (meth) acrylate of dimethylol tricyclodecane, di (meth) acrylate of cyclohexanedimethanol and di (meth) acrylate of hydrogenated bisphenol A;

Trivalent or higher (meth) acrylate (C2):
Poly (meth) acrylates of polyhydric alcohols having 3 to 40 carbon atoms and their AO adducts, such as trimethylolpropane tri (meth) acrylates, tri (meth) acrylates of glycerin, EO3 mol and PO3 mol of trimethylolpropane. Tri (meth) acrylate of each tri (meth) acrylate of glycerin, EO3 mol of glycerin and tri (meth) acrylate of PO3 mol adduct, tri (meth) acrylate of pentaerythritol, tetra (meth) acrylate of pentaerythritol, EO4 mol of pentaerythritol addition Tetra (meth) acrylate of things, penta (meth) acrylate of dipentaerythritol, hexa (meth) acrylate of dipentaerythritol;

Polyester (meth) acrylate (C3) [other than (C1) and (C2) above]:
A polyester acrylate having a molecular weight of 150 or more and Mn 4,000 or less having a plurality of ester bonds and 5 or more acryloyl groups obtained by esterification of a polyvalent carboxylic acid, a polyhydric alcohol, and an ester-forming acryloyl group-containing compound.

Examples of the above polyvalent carboxylic acid include aliphatic [for example, a reaction product of malonic acid, maleic acid (anhydride), adipic acid, sebacic acid, succinic acid, and acid anhydride (reaction product of dipentaerythritol and maleic anhydride). Etc.)], alicyclic [eg cyclohexanedicarboxylic acid, tetrahydro (maleic anhydride) phthalic acid, methyltetrahydro (maleic anhydride) phthalic acid] and aromatic polyvalent carboxylic acids [eg isophthalic acid, terephthalic acid, phthalic acid (anhydride), Trimellitic acid (anhydride), pyromellitic acid (anhydride)].

Urethane (meth) acrylate (C4) [other than (C1) and (C2) above]:
Urethane (meth) acrylate having a molecular weight of 400 or more and Mn 5,000 or less having a plurality of urethane bonds and two or more acryloyl groups obtained by a urethanization reaction with a polyisocyanate, a polyol, or a hydroxyl group-containing (meth) acrylate;

Corresponding polyisocyanates include, for example, aliphatic polyisocyanates [hexamethylene diisocyanate, etc.], aromatic (lipid) group polyisocyanates [2,4- and / or 2,6-tolylene diisocyanate, 1,5-naphthalenediocyanate, xyli Range isocyanate, etc.], alicyclic polyisocyanate [isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), etc.] can be mentioned.
Examples of the polyol include ethylene glycol, 1,4-butanediol, neopentyl glycol, polyether polyol, polycaprolactone polyol, polyester polyol, polycarbonate polyol, polytetramethylene glycol and the like.
Examples of the hydroxyl group-containing (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

Epoxy (meth) acrylate (C5) [other than (C1) and (C2) above]:
Epoxy (meth) acrylate with a molecular weight of 400 or more and Mn 5,000 or less obtained by the reaction of a multivalent (2 to 4 valent) epoxide and (meth) acrylic acid;

(Meta) Acryloyl group-modified butadiene polymer (C6) [other than (C1) and (C2) above]:
Polybutadiene poly (meth) acrylates (Mn500-500,000) having (meth) acryloyl groups in the main chain and / or side chains;

(Meta) Acryloyl group-modified dimethylpolysiloxane polymer (C7) [other than (C1) and (C2) above]:
Mn 300-20,000 dimethylpolysiloxane poly (meth) acrylates having a (meth) acryloyl group in the main chain and / or side chains].

The above (C1) to (C7) may be used alone or in combination of two or more. Of these (C1) to (C7), (C2) to (C7) are preferable from the viewpoint of hardness of the cured product, (C2) and (C4) are more preferable, and (C2) is particularly preferable. ..

The active energy ray-curable resin composition (X) of the present invention may contain various additives as necessary as long as the effects of the present invention are not impaired.
Examples of the additive include pigments, plasticizers, organic solvents, dispersants, defoamers, thixotropy-imparting agents (thickeners), slip agents, antioxidants, hindered amine light stabilizers and ultraviolet absorbers.

<Cured product>
The cured product of the present invention is a cured product of the active energy ray-curable resin composition (X). The (X) can be cured by irradiating with active energy rays (ultraviolet rays, electron beams, X-rays, etc.), for example.
When used as an active energy ray-curable resin composition for inkjet ink, it is printed by an inkjet printing machine and then cured by irradiating it with active energy rays (ultraviolet rays, electron beams, X-rays, etc.). , Printed matter can be obtained.
The film thickness is usually 0.5 to 300 μm as the film thickness after curing and drying. From the viewpoint of curability, the preferable upper limit is 250 μm, and from the viewpoint of hardness, the preferable lower limit is 1 μm.

Examples of the base material include those made of resins such as methyl methacrylate (co) polymer, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose and polycycloolefin.

The active energy rays in the present invention include ultraviolet rays, electron beams, X-rays, infrared rays and visible rays. Of these active energy rays, ultraviolet rays and electron beams are preferable from the viewpoint of curability and resin deterioration.

When the active energy ray-curable resin composition (X) of the present invention is cured by ultraviolet rays, various ultraviolet irradiation devices [for example, ultraviolet irradiation devices [model number "VPS / I600", manufactured by Fusion UV Systems Co., Ltd.]] are used. Can be used.
Examples of the lamp used include a UV-LED lamp and a metal halide lamp. The dose of ultraviolet rays is preferably a flexible viewpoint of curability and cured product of a composition 10~10,000mJ / cm ^2, more preferably from 100~5,000mJ / cm ^2.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified,% indicates a weight% and a part indicates a weight part.

<Manufacturing example 1>
In a reaction vessel equipped with a stirrer, a cooling tube and a thermometer, hydroxyethyl acrylamide (B-1) [trade name: HEAA, manufactured by KJ Chemicals Co., Ltd.] 65.0 parts, water 0.01 parts, hydrochloric acid [reagent] , The same applies hereinafter] 0.01 parts are charged and stirred for 30 minutes, then 35.0 parts of silicate tetra-n-ethoxide (a1-1) [trade name: TEOS, manufactured by Tokyo Chemical Industry Co., Ltd.] are charged and 65 ° C. After reacting with (A-1) for 2 hours, ethanol was distilled off under reduced pressure to obtain a solution of the hydrolyzed condensate (A-1) by (B-1) [content of (A-1): 61% by weight]. It was.
The unsaturated group concentration of (A-1) was 5.5 mmol / g, and the weight average molecular weight (Mw) was 1814.
The molar ratio [(a1) / (B)] constituting (A) was 45/55.

<Manufacturing Examples 2-5>
Hydrolyzed condensates (A-2) to (A-5) (B) in the same manner as in Production Example 1 except that the inorganic alkoxide (a1), hydrochloric acid, ethanol, and water shown in Table 1 were subjected to the respective parts. ) Was obtained. The results are shown in Table 1.

The raw materials used in Table 1 are as follows.
(A1-1):
Silicate tetra-n-ethoxide [Product name: TEOS, manufactured by Tokyo Chemical Industry Co., Ltd.]
(A1-2):
Titanium tetra-n-ethoxide [trade name: B-1, manufactured by Nippon Soda Co., Ltd.]
(B-1):
Hydroxyethyl acrylamide [trade name: HEAA, manufactured by KJ Chemicals Co., Ltd.]
(B-2):
Monoacrylate of polyethylene glycol (PEG, number average molecular weight 200) [Product name: Blemmer AE-200, manufactured by NOF CORPORATION]
(B-3): Acryloyl morpholine [Product name: ACMO, manufactured by KJ Chemicals Co., Ltd.]
(B-4): Diacetone acrylamide [Product name: Diacetone acrylamide, manufactured by Nippon Kasei Chemical Company Limited]

<Manufacturing example 6>
85.6 parts of ethanol, 0.6 parts of water and 0.1 part of triethylamine were charged in a reaction vessel equipped with a stirrer, a cooling tube and a thermometer, and the temperature was raised to 65 ° C. while stirring for 30 minutes. After reaching 65 ° C., 13.6 parts of the hydrolyzed condensate (A-1) obtained in Production Example 1 (B-1), which was previously charged in the dropping funnel, was added in the entire amount over 60 minutes. After the completion of charging, stirring was continued at 65 ° C. for 180 minutes to carry out a sol-gel reaction.
After the reaction, the pressure inside the reaction vessel was reduced and ethanol and water were distilled off to obtain a solution (B) of the hydrolyzed condensate (A-6) [content 58% by weight of (A-6)].
The unsaturated group concentration of (A-6) was 6.3 mmol / g, and the volume average particle size was 0.2 μm.
The molar ratio [(a1) / (B)] constituting (A) was 45/55.

<Manufacturing example 7>
In Production Example 6, a solution of the hydrolyzed condensate (A-7) according to (B) was obtained in the same manner as in Production Example 6 except that the preparation (parts by weight) shown in Table 2 was followed. The results are shown in Table 2.

<Comparative manufacturing example 1>
Commercially available inorganic oxide fine particles [trade name "coloidal silica MEK-ST" particle size 10-15 nm MEK (methyl ethyl ketone) 40% solution, manufactured by Nissan Chemical Industry Co., Ltd.] 100 parts of dipentaerythritol pentaacrylate (B-1) 60 The parts were mixed and MEK was distilled off with an evaporator to obtain a solution of the hydrolyzed condensate (ratio A-1) by (B-1) [content of (ratio A-1) 40% by weight]. ..
The volume average particle diameter of (ratio A-1) was 0.5 μm.

<Example 1>
In a reaction vessel equipped with a stirrer, a cooling tube and a thermometer, 100 parts of the (B-1) solution of the hydrolyzed condensate (A-1) obtained in Production Example 1 was added to pentaerythritol triacrylate [trade name: Neomer EA-300, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 10 parts, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (D-2) [Product name " Irgacure 907 ", manufactured by BASF Ltd.] 2.0 parts was added, and the mixture was mixed and stirred at 65 ° C. until uniform to obtain an active energy ray-curable resin composition (X-1).

<Examples 2 to 7, Comparative Example 1>
In Example 1, each active energy ray-curable resin composition (X) was obtained in the same manner as in Example 1 except that the amount charged (parts by weight) was according to Table 3. The performance of each active energy ray-curable resin composition (X) was evaluated by the method described later. The results are shown in Table 3.

The raw materials used in Table 3 are as follows.
(C-1): Pentaerythritol triacrylate
[Product name: Neomer EA-300, manufactured by Sanyo Chemical Industries, Ltd.]
(C-2): Trimethylolpropane triacrylate
[Product name: NK Ester A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.]
(D-1): 2,4,6-trimethylbenzoyldiphenylphosphine oxide
[Product name "Lucillin TPO", manufactured by BASF Ltd.]
(D-2): 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one [trade name "Irgacure 907", manufactured by BASF Limited]
(D-3): 1-Hydroxycyclohexylphenyl ketone
[Product name "Irgacure 184", manufactured by BASF Ltd.]

<Curing film making method>
PET film with a thickness of 100 μm [trade name “Cosmo Shine A4300”, manufactured by Toyobo Co., Ltd.] Using a bar coater on one side of the base material, apply it so that the film thickness after drying and curing is 5 μm, and at 60 ° C. After drying for 3 minutes, UV irradiation device [model number "VPS / I600", manufactured by Fusion UV Systems Co., Ltd. same as below. ], A film having a cured film on the surface of the base film was prepared by irradiating with ultraviolet rays at 300 mJ / cm ^2. The performance of the obtained film was evaluated by the following methods <1> to <3>.

<1> Evaluation of haze (transparency of film) Based on JIS-K7105, total light transmittance measuring device [trade name "haze-gard"
Haze was measured using "dual" BYK gardener Co., Ltd.].

<2> Evaluation of total light transmittance (transparency of film) For the test piece, a total light transmittance measuring device [trade name "haze-garddual", manufactured by BYK gardener Co., Ltd.] is used in accordance with JIS-K7105. The total light transmittance (%) was measured using.

<3> Evaluation of pencil hardness (film hardness) Pencil hardness was measured according to JIS K-5400. The pencil hardness was evaluated according to the following criteria.
<Evaluation criteria>
⊚: 2H or more ○: H
Δ: F
×: HB or less

<4> Evaluation of discharge stability (viscosity)
Using an inkjet printer device [trade name "Material Printer DMP-2831", manufactured by FUJIFILM Global Graphic Systems Co., Ltd.], the applied voltage is such that the droplet volume of one drop is 10 pl and the droplet speed is 6 m / sec. Was adjusted and continuously discharged. The temperature of the head was adjusted to 60 ° C. Ten minutes after the start of ejection, the number of nozzles in which ejection failure occurred among the 16 nozzles mounted was counted, and the ejection stability was evaluated.
<Evaluation criteria>
◯: 0 nozzles with defective discharge Δ: 1 nozzle with defective discharge ×: 2 or more nozzles with defective discharge

From the results in Table 3, the active energy ray-curable resin composition (X) of the present invention imparted excellent discharge stability (low viscosity) as compared with the comparative one, and the active energy ray-curable resin composition (X) was (the active energy ray-curable resin composition). It can be seen that the cured product of X) is imparted with excellent surface hardness and transparency.

The active energy ray-curable resin composition (X) of the present invention has a low viscosity and imparts excellent scratch resistance and transparency to the cured product. It can be suitably applied to various applications of the active energy ray-curable resin, particularly an inkjet ink application, and is extremely useful.

Claims (10)

A hydrolyzed condensate (A) containing an inorganic alkoxide (a1) and a hydroxyethyl acrylamide and / or a polyethylene glycol mono (meth) acrylate having 35 or less carbon atoms as a constituent monomer , a monofunctional unsaturated monomer (B), and many. An active energy ray-curable resin composition containing a functional (meth) acrylate (C) and a photopolymerization initiator (D).
The monofunctional unsaturated monomer (B) contained in the active energy ray-curable resin composition is a monofunctional (meth) acrylate (B1) having 3 to 35 carbon atoms, N, N-dimethylacrylamide, diacetoneacrylamide, and the like. At least one monomer selected from the group consisting of hydroxyethyl acrylamide and acryloyl morpholine.
The content of the hydrolyzed condensate (A) contained in the active energy ray-curable resin composition is the same as that of the hydrolyzed condensate (A) contained in the active energy ray-curable resin composition. Based on the total weight of the saturated monomer (B), it is 10-61% by weight,
The content of the monofunctional unsaturated monomer (B) contained in the active energy ray-curable resin composition is the same as that of the hydrolyzed condensate (A) contained in the active energy ray-curable resin composition. 39-90% by weight, based on the total weight of the unsaturated monomer (B).
The content of the polyfunctional (meth) acrylate (C) contained in the active energy ray-curable resin composition is the same as that of the hydrolysis condensate (A) contained in the active energy ray-curable resin composition. The active energy ray-curable resin composition (X) which is 10 to 100% by weight based on the total weight of the functional unsaturated monomer (B). The active energy ray-curable resin composition according to claim 1, wherein the molar ratio [(a1) / (B)] of (a1) and (B) constituting the (A) is 50/50 to 95/5. (X). The active energy ray-curable resin composition according to claim 1 or 2, wherein the unsaturated group concentration of (A) is 0.5 to 6.0 mmol / g. The invention according to any one of claims 1 to 3, wherein the (A) is a hydrolyzed condensate (A1) having a weight average molecular weight (Mw) of 500 to 20,000 and / or a particulate hydrolyzed condensate (A2). Active energy ray-curable resin composition. Claim 1 in which the inorganic alkoxide (a1) is at least one selected from the group consisting of silane alkoxide, zirconium alkoxide, titanium alkoxide, hafnium alkoxide, zinc alkoxide, aluminum alkoxide, gallium alkoxide, indium alkoxide, germanium alkoxide and tin alkoxide. 4. The active energy ray-curable resin composition according to any one of 4. The active energy ray-curable resin composition according to any one of claims 1 to 5, wherein the content (D) based on the total weight of (A) and (B) is 0.1 to 10% by weight. The active energy ray-curable resin composition according to any one of claims 1 to 6, which is used for inkjet ink. A cured product obtained by curing the active energy ray-curable resin composition (X) according to any one of claims 1 to 7. Claims 1 to 7 include a step of reacting an inorganic alkoxide (a1) with water in a monofunctional unsaturated monomer (B) in the presence of a catalyst (b) to form a hydrolyzed condensate (A1). The method for producing an active energy ray-curable resin composition (X) according to any one. The method for producing an active energy ray-curable resin composition (X) according to claim 9, further comprising a step of further sol-gel-reacting the hydrolyzed condensate (A1) to obtain a particulate hydrolyzed condensate (A2).