JP2017039917A - Curable composition for inkjet ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition for inkjet ink having low viscosity even without solvent, excellent in discharge property, further excellent in curability and excellent in adhesiveness, hardness and scratch resistance of a cured article of the composition, preferably an active energy ray curable composition for inkjet ink.SOLUTION: There is provided a curable composition for inkjet ink containing a (meth)acrylate composition (A) mainly containing glycerol tri(meth)acrylate, and a polymer in the (A) component of less than 30% by area% of polymer which is a value obtained by a gel permeation chromatography measurement and defined by a specific formula.SELECTED DRAWING: None

Description

The present invention relates to a curable composition for inkjet ink, and preferably to an active energy ray curable composition for inkjet ink, which can be used not only for two-dimensional printing but also for three-dimensional modeling, and belongs to these technical fields. .
In the present specification, “acryloyl group and / or methacryloyl group” is “(meth) acryloyl group”, “acrylate and / or methacrylate” is “(meth) acrylate”, “acrylic acid and / or methacrylic”. "Acid" is represented as "(meth) acrylic acid".

  Printing by an ink jet printer is a method in which ink is ejected from a nozzle and adhered to a recording material. Since the nozzle and the recording material are not in contact with each other, a curved surface or an irregular surface with irregular shapes is applied. Thus, good printing can be performed. For this reason, it is a printing method used not only in the commercial printing field but also in various industrial fields such as an electronic field such as a display and an electronic field.

Such inks for inkjet printing generally include aqueous dye inks using water as a main solvent and non-aqueous (oil-based) dye inks using an organic solvent as a main solvent.
However, when using conventional water-based dye inks in industrial applications, there are problems in drying speed after forming a printed film on a non-absorbing material such as a plastic film, adhesion of the printed film to a substrate (hereinafter simply referred to as “ It is referred to as “adhesiveness”) and durability such as scratch resistance, water resistance, and light resistance is insufficient.
On the other hand, since the oil-based dye ink uses a chromium complex dye containing a heavy metal such as chromium, there is a problem in terms of safety.

Therefore, as an ink composition that has improved the problems associated with these colorants, it contains substantially non-polymerizable solvents such as aqueous pigment and oil pigment inks using pigments as colorants, and organic solvents for dilution and dissolution. In addition, there has been proposed an active energy ray-curable inkjet ink that can cure and dry a printed film with an active energy ray such as ultraviolet rays. In recent years, utilization not only for two-dimensional printing but also for three-dimensional modeling has been promoted.
Since the active energy ray-curable inkjet ink composition cures the printed film with active energy rays, a printed film having relatively excellent durability can be obtained. However, although the composition is excellent in printing on an absorbent material such as paper used as a base material, it has a problem of poor adhesion to printing on a non-absorbent material such as a plastic film.

As an ink composition for improving the adhesion to a substrate, a composition in which various oligomers and an adhesive resin are added to the composition is known.
However, since the composition has a high viscosity, the head driving condition for obtaining a stable light emission property becomes narrow. In particular, in the case of reducing the droplet size, if ink having a high viscosity is ejected in a small droplet size, problems such as deterioration in landing accuracy and nozzle clogging have occurred.

As an ink composition that solves the above problems and has low viscosity and excellent adhesion, a compound having one (meth) acryloyl group such as isobornyl acrylate (hereinafter referred to as “monofunctional (meth) acrylate”) There is known an active energy ray-curable composition using a combination of (Patent Document 1).
However, such monofunctional (meth) acrylate as a main component has a problem that the composition has a strong odor and a high skin toxicity, and the curability and scratch resistance are lowered. Met

On the other hand, as a composition other than the above, an active energy ray-curable composition containing ethylene oxide-modified glycerin triacrylate and monofunctional (meth) acrylate is known (Patent Documents 2 and 3).
However, since the acrylate is a compound having an ethylene oxide chain, the composition has a problem that it is inferior in hardness and scratch resistance of a cured product of the composition.

JP 2010-235914 A JP 2005-162882 A JP 2011-132349 A

  The inventors of the present invention provide a curable composition for inkjet inks that has a low viscosity even when the composition is solvent-free, is excellent in ejection properties, is excellent in curability, and is excellent in adhesion, hardness, and scratch resistance of a cured product of the composition. In order to find a product, preferably an active energy ray-curable composition for ink-jet ink, intensive studies have been conducted.

In order to solve the above-described problem, a compound having two or more (meth) acryloyl groups (hereinafter referred to as “multiple”) having no ethylene oxide chain and high (meth) acryloyl group concentration as a component of the composition. Functional (meth) acrylate ”) is considered effective, and glycerol tri (meth) acrylate (hereinafter referred to as“ GLY-TA ”) is considered effective.
In order to industrially obtain GLY-TA, a production method by dehydration esterification of glycerin and acrylic acid can be considered. However, in the dehydration esterification reaction, since the reactivity of the secondary hydroxyl group is particularly low, a large amount of high molecular weight is formed and it is difficult to obtain industrially, and GLY-TA has not been distributed in the market. . For this reason, conventionally, the curable composition for inkjet ink containing GLY-TA is not known.

In order to solve the above problems, the present inventors have a curable composition for inkjet inks containing a specific GLY-TA, which has a low viscosity even in the absence of a solvent, excellent dischargeability, and excellent curability. It was found that the cured product had excellent adhesion, hardness and scratch resistance, and the present invention was completed.
Hereinafter, the present invention will be described in detail.

  According to the composition of the present invention, even in the absence of a solvent, the viscosity is low, the ejection property is excellent, the curability is excellent, and the cured product has excellent adhesion, hardness, and scratch resistance.

The present invention includes a (meth) acrylate mixture (A) (hereinafter referred to as “component (A)”) mainly composed of GLY-TA [glycerin tri (meth) acrylate]. Ink-jet ink whose molecular weight is a value obtained by gel permeation chromatography (hereinafter referred to as “GPC”) measurement and is less than 30% as area% of the high molecular weight defined by the following formula (1) The present invention relates to a curable composition for use.
High molecular weight area% = [(R−IL) / R] × 100 (1)
Symbols and terms in formula (1) are as described below.
Hereinafter, the component (A), other components, and methods of use will be described.

1. (A) component (A) component is a (meth) acrylate mixture which has GLY-TA as a main component.
In the present invention, the component (A) is mainly composed of GLY-TA, so that the high molecular weight component in the component (A) is a value obtained by GPC measurement, The area% of the high molecular weight body defined in 1) is less than 30%, preferably less than 25%, more preferably less than 20%.

High molecular weight area% = [(R−IL) / R] × 100 (1)
The symbols and terms in formula (1) mean the following.
-R: Total area of detection peaks in component (A)-I: Area of detection peaks including GLY-TA-L: Weight average molecular weight (hereinafter referred to as "Mw") than detection peaks including GLY-TA Total area of small detection peak In the present invention, Mw means a value obtained by converting the molecular weight measured by GPC based on the molecular weight of polystyrene using tetrahydrofuran (hereinafter referred to as “THF”) as a solvent. .

By setting the area% of the high molecular weight substance in the component (A) within this range, the composition can have a low viscosity, and a composition excellent in the hardness of the cured product can be obtained.
In addition, the molecular weight measured by GPC in the present invention means a value measured under the following conditions.
・ Detector: Differential refractometer (RI detector)
-Column type: Cross-linked polystyrene column-Column temperature: within 25-50 ° C-Eluent: THF

The component (A) is mainly composed of GLY-TA and preferably has a low hydroxyl value. Specifically, the hydroxyl value is preferably 60 mgKOH / g or less, more preferably 45 mgKOH / g or less.
By setting the hydroxyl value of the component (A) within this range, the composition can have a low viscosity, and a composition excellent in the hardness of the cured product can be obtained.
In the present invention, the hydroxyl value means the number of mg of potassium hydroxide equivalent to the hydroxyl group in 1 g of a sample.

(A) As a component, what is obtained by transesterifying glycerol and monofunctional (meth) acrylate is preferable.
As described above, in the production method in which glycerin and (meth) acrylic acid are subjected to a dehydration esterification reaction, the secondary hydroxyl group has low reactivity, so a large amount of high molecular weight is produced, and GLY-TA is produced industrially. Is difficult. On the other hand, according to the transesterification reaction between glycerin and monofunctional (meth) acrylate, it becomes possible to produce a (meth) acrylate mixture mainly composed of GLY-TA.

In the case of a transesterification reaction between glycerin and a monofunctional (meth) acrylate, a (meth) acrylate mixture is obtained. Specifically, in addition to GLY-TA, glycerin di (meth) acrylate and high molecular weight are obtained, and a small amount of glycerin mono (meth) acrylate is obtained depending on the production conditions.
Examples of the high molecular weight substance include, for example, a polyfunctional (meth) acrylate having a Michael addition type structure such as a compound in which a hydroxyl group of glycerin di (meth) acrylate is added to a (meth) acryloyl group of GLY-TA. Is mentioned.

  Hereinafter, regarding the method for producing the component (A) by transesterification, the method for producing the polyhydric alcohol, the monofunctional (meth) acrylate, the catalyst, and the component (A) will be described.

1-1. The polyhydric alcohol used as a raw material for the polyhydric alcohol (A) component is glycerin.
In the present invention, glycerin and a polyhydric alcohol other than glycerin (hereinafter referred to as “other polyhydric alcohol”) may be used in any combination as long as the effects of the present invention are not impaired. .
In addition, as a ratio when using a polyhydric alcohol together, 50 weight part or less is preferable with respect to 100 weight part of glycerol.

  Other polyhydric alcohols include aliphatic alcohols having at least two alcoholic hydroxyl groups in the molecule, alicyclic alcohols, aromatic alcohols, polyhydric alcohol ethers, and other functional groups and bonds in the molecule. For example, phenolic hydroxyl group, ketone group, acyl group, aldehyde group, thiol group, amino group, imino group, cyano group, nitro group, vinyl group, ether bond, ester bond, carbonate group, amide bond, imide bond, peptide bond , A urethane bond, an acetal bond, a hemiacetal bond, a hemiketal bond, and the like.

  Specific examples of the dihydric alcohol having two alcoholic hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, trimethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, Pentanediol, hexanediol, heptanediol, nonanediol, neopentylglycol, cyclohexanediol, cyclohexanedimethanol, dioxaneglycol, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-tert-butyldiethanolamine, N- Lauryl diethanolamine, stearyl diethanolamine, N-phenyldi Tanolamine, m-tolyldiethanolamine, p-tolyldiethanolamine, N, N′-bis (2-hydroxypropyl) aniline, N-nitrosodiethanolamine, N- (2-hydroxyethyl) lactamamide, N, N′-bis (2 -Hydroxyethyl) oxamide, 3-morpholino-1,2-propanediol, 2,6-pyridinedimethanol, 3- (dimethylamino) -1,2-propanediol, 3- (diethylamino) -1,2-propane Diol, alloxanthin dihydrate, (+)-N, N, N ′, N′-tetramethyl-L-tartaric acid diamide, (−)-N, N, N ′, N′-tetramethyl-D— Tartaric acid diamide, N-propyl-N- (2,3-dihydroxypropyl) perfluoro-n-octylsulfonamide, thymidine, Chloramphenicol, thiamphenicol, D-erythronolactone, methyl 4,6-O-benzylidene-α-D-glucopyranoside, phenyl 4,6-O-benzylidene-1-thio-β-D-glucopyranoside, 1 , 2: 5,6-di-O-isopropylidene-D-mannitol, 1,2-O-isopropylidene-α-D-xylofuranose, 2,6-di-O-palmitoyl-L-ascorbic acid, isosorbide And these alkylene oxide adducts, hydroquinone, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, thiobisphenol, bisphenol Lumpur P, bisphenol PH, alkylene oxide adducts of compounds having a phenolic hydroxyl group such as bisphenol TMC and bisphenol Z, alcohol having a carbonate bond, such as polycarbonate diol.

  Specific examples of the trihydric alcohol having three alcoholic hydroxyl groups include trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, hexanetriol, octanetriol, decanetriol, triethanolamine, triisopropanolamine. 1- [bis-2- (hydroxyethyl) amino] -2-propanol, D-panthenol, DL-panthenol, uridine, 5-methyluridine, cytidine, inosine, adenosine, leucomycin A3, leucomycin A4, leuco Mycin A6, leucomycin A8, clindamycin hydrochloride monohydrate, prednisolone, methyl β-D-arabinopyranoside, methyl β-L-fucopyranoside, methyl α-L-fucopyranoside, D-galactal, 4- Methoxyphenyl 3-O-allyl-β-D-galactopyranoside, 4-methoxyphenyl 3-O-benzyl-β-D-galactopyranoside, 1,6-anhydro-β-D-glucose, α- Chloralose, β-chloralose, 4,6-O-ethylidene-α-D-glucopyranose, D-glucal, 1,2-O-isopropylidene-α-D-glucofuranose, D-glucurono-6,3-lactone 2-deoxy-D-ribose, methyl β-D-ribofuranoside, D-(+)-ribono-1,4-lactone, methyl-β-D-xylopyranoside, 6-O-palmitoyl-L-ascorbic acid, 6 Examples include -O-stearoyl-L-ascorbic acid, 3-O-ethyl-L-ascorbic acid, and alkylene oxide adducts thereof.

  Specific examples of the tetrahydric alcohol having four alcoholic hydroxyl groups include ditrimethylolethane, ditrimethylolpropane, diglycerin, pentaerythritol, N, N, N ′, N′-tetrakis (2-hydroxyethyl) butanediamide, N, N, N ′, N′-tetrakis (2-hydroxypropyl) butanediamide, N, N, N ′, N′-tetrakis (2-hydroxyethyl) hexanediamide, N, N, N ′, N′-tetrakis (2-hydroxypropyl) hexanediamide, N, N, N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N-hexanoyl -D-glucosamine, N-valeryl-D-glucosamine, N-trifluoroacetyl-D- Lucosamine, N-benzoyl-D-glucosamine, 5-acetamido-N, N′-bis (2,3-dihydroxypropyl) -2,4,6-triiodoisophthalamide, spiramycin, clarithromycin, leucomycin A1 , Leucomycin A5, leucomycin A7, leucomycin A9, leucomycin A13, lincomycin hydrochloride monohydrate, diazolidinyl urea, D-(-)-arabinose, DL-arabinose, L-(+)-arabinose, meso -Erythritol, D-(+)-fucose, L-(-)-fucose, allyl α-D-galactopyranoside, methyl β-D-galactopyranoside, methyl α-D-galactopyranoside monohydrate Japanese, 4-methoxyphenyl β-D-galactopyranoside, 2-nitrophenyl β-D-ga Ctopyranoside, 4-nitrophenyl α-D-galactopyranoside, 4-nitrophenyl β-D-galactopyranoside, phenyl β-D-galactopyranoside, N-acetyl-D-galactosamine hydrate, D -(+)-Galactosamine hydrochloride, arbutin, 2-deoxy-D-glucose, esculin hemihydrate, D-(+)-glucono-1,5-lactone, D-glucuronamide, helicin, methyl α -D-glucopyranoside, methyl β-D-glucopyranoside hemihydrate, 4-methoxyphenyl β-D-glucopyranoside, 4-nitrophenyl β-D-glucopyranoside monohydrate, 4-nitrophenyl α-D- Glucopyranoside, nonyl β-D-glucopyranoside, n-octyl β-D-glucopyranoside, phenyl β-D-glucopyrano Hydrate, phlorizin hydrate, picaide, puerarin, N-acetyl-D-glucosamine, N-benzoyl-D-glucosamine, D-(+)-glucosamine hydrochloride, N-hexanoyl-D-glucosamine, N- Valeryl-D-glucosamine, L-(+)-gulonic acid γ-lactone, D-(−)-lyxose, L-(+)-lyxose, 3,4-O-isopropylidene-D-mannitol, methyl α- D-mannopyranoside, D-mannono-1,4-lactone, 4-methoxyphenyl α-D-mannopyranoside, N-acetyl-D-mannosamine monohydrate, D-(−)-ribose, L-ribose, D- (+)-Xylose, DL-xylose, L-(-)-xylose, D-araboascorbic acid, L-ascorbic acid, L-threitol and this Alkylene oxide adducts of al the like.

  Specific examples of the pentahydric alcohol having 5 alcoholic hydroxyl groups include tritrimethylolethane, tritrimethylolpropane, triglycerin, bis (2-hydroxyethyl) aminotris (hydroxymethyl) methane, and bis (2-hydroxypropyl). Aminotris (hydroxymethyl) methane, N, N, N ′, N ″, N ″ -pentakis (2-hydroxyethyl) diethylenetriamine, N, N, N ′, N ″, N ″ -pentakis (2 -Hydroxypropyl) diethylenetriamine, miglitol, erythromycin, azithromycin dihydrate, D-(+)-arabitol, DL-arabitol, L-(-)-arabitol, D-(-)-fructose, L-(+)- Fructose, D-(+)-galactose, L-(-)-galactose, β-D-glucose, D-(+)-glucose, L-(−)-glucose, D-glucose diethyl mercaptal, salicin, L-gulose, D-(+)-mannose, L-(−) − Mannose, ribitol, L-(−)-sorbose, D-tagatose, xylitol, sucralose, glyceryl ascorbate, and alkylene oxide adducts thereof can be mentioned.

  Specific examples of the polyhydric alcohol having 6 or more alcoholic hydroxyl groups include polytrimethylolethane, polytrimethylolpropane, polyglycerin, dipentaerythritol, tripentaerythritol, polypentaerythritol, iohexol, galactitol, D- Sorbitol, L-sorbitol, myo-inositol, scyllo-inositol, D-mannitol, L-mannitol, icariin, amygdalin, D-(+)-cellobiose, diosmine, 2-O-α-D-glucopyranosyl-L-ascorbic acid , Hesperidin, D-(+)-lactose monohydrate, lactulose, D-(+)-maltose monohydrate, D-(+)-melibiose monohydrate, methyl hesperidin, maltitol, naringin hydrate Thing Hesperidin dihydrochalcone hydrate, palatinose hydrate, rutin hydrate, D-(+)-sucrose, stevioside, D-(+)-turanose, D-(+)-trehalose (anhydrous), D-(+ ) -Trehalose dihydrate, D-(+)-meletitol hydrate, D-(+)-raffinose pentahydrate, rebaudioside A, stachyose, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin , Starch, polyvinyl alcohol, and these alkylene oxide adducts.

1-2. The monofunctional (meth) acrylate used as a raw material for the monofunctional (meth) acrylate (A) component is a compound having one (meth) acryloyl group in the molecule. For example, it is represented by the following general formula (1). Compounds.

In Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents an organic group having 1 to 50 carbon atoms.

Specific examples of R ² in the general formula (1) include methyl group, ethyl group, n- or i-propyl group, n-, i- or t-butyl group, n-, s- or t-amyl group. , Neopentyl group, n-, s- or t-hexyl group, n-, s- or t-heptyl group, n-, s- or t-octyl group, 2-ethylhexyl group, capryl group, nonyl group, decyl group , Undecyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, cetyl group, heptadecyl group, stearyl group, nonadecyl group, aralkyl group, seryl group, myricyl group, melicyl group, vinyl group, allyl group, methallyl group, crotyl group Group, 1,1-dimethyl-2-propenyl group, 2-methylbutenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 2-methyl-3-butenyl group, butene Group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, oleyl group, linol group, linolene group , Cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, 4-methylcyclohexyl group, 4-t-butylcyclohexyl group, tricyclodecanyl group, isobornyl group, adamantyl group, dicyclopentanyl group, dicyclopentenyl group Group, phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, 4-t-butylphenyl group, benzyl group, diphenylmethyl group, diphenylethyl group, triphenylmethyl group, cinnamyl group Naphthyl group, anthranyl group, methoxyethyl group, methoxyethoxyethyl group, methoxyethoxyethoxyethyl group, 3-methoxybutyl group, ethoxyethyl group, ethoxyethoxyethyl group, cyclopentoxyethyl group, cyclohexyloxyethyl group, cyclohexane Pentoxyethoxyethyl group, cyclohexyloxyethoxyethyl group, dicyclopentenyloxyethyl group, phenoxyethyl group, phenoxyethoxyethyl group, glycidyl group, β-methylglycidyl group, β-ethylglycidyl group, 3,4-epoxycyclohexylmethyl Group, 2-oxetanemethyl group, 3-methyl-3-oxetanemethyl group, 3-ethyl-3-oxetanemethyl group, tetrahydrofuranyl group, tetrahydrofurfuryl group, tetrahydropyranyl group, dioxazola Nyl group, dioxanyl group, N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group, N, N-dimethylaminopropyl group, N, N-diethylaminopropyl group, N-benzyl-N-methylaminoethyl group N-benzyl-N-methylaminopropyl group and the like.
Among these functional groups, R ² is an alkyl having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and 2-ethylhexyl. Group, alkoxyalkyl group such as 2-methoxyethyl group, 2-ethoxyethyl group and 2-methoxybutyl group, N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group, N, N-dimethylaminopropyl group A dialkylamino group such as N, N-diethylaminopropyl group is preferred.

In the present invention, these monofunctional (meth) acrylates can be used alone or in combination of two or more.
Among these monofunctional (meth) acrylates, carbon such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate Alkyl (meth) acrylates having an alkyl group of 1 to 8 and alkoxyalkyl (meth) acrylates such as 2-methoxyethyl acrylate, and N, N-dimethylaminoethyl (meth) acrylate are preferred, most of which are polyhydric alcohols (Meth) acrylate having an alkyl group having 1 to 4 carbon atoms, and an alkoxyalkyl (meth) acrylate having an alkyl group having 1 to 2 carbon atoms, which are easy to obtain, are preferable.
Furthermore, the alkoxyalkyl (meth) acrylate which has a C1-C2 alkyl group which promotes melt | dissolution of a polyhydric alcohol and shows very favorable reactivity is more preferable, and 2-methoxyethyl (meth) acrylate is especially preferable.
Furthermore, as monofunctional (meth) acrylate, acrylate is particularly preferable because of its excellent reactivity.

  (A) Although there is no restriction | limiting in particular in the usage rate of the polyhydric alcohol and monofunctional (meth) acrylate in the manufacturing method of component, 0.4% of monofunctional (meth) acrylate is used with respect to 1 mol of hydroxyl groups in polyhydric alcohol. -10.0 mol is preferable, More preferably, it is 0.6-5.0 mol. By making the monofunctional (meth) acrylate 0.4 mol or more, side reactions can be suppressed. Moreover, the production amount of GLY-TA can be increased and productivity can be improved by setting it as 10.0 mol or less.

1-3. As the transesterification catalyst in the method for producing the catalyst (A) component, conventionally known ones such as a tin-based catalyst, a titanium-based catalyst, and sulfuric acid can be used.
In this invention, it is preferable to use the following catalysts X and Y together as a catalyst at the point which can manufacture GLY-TA efficiently with a high yield.
Catalyst X: a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof (hereinafter referred to as “azabicyclo compound”), an amidine or a salt or complex thereof (hereinafter referred to as “amidine compound”), a compound having a pyridine ring, or One or more compound catalysts selected from the group consisting of salts or complexes thereof (hereinafter referred to as “pyridine compounds”) and phosphines or salts or complexes thereof (hereinafter referred to as “phosphine compounds”): a compound containing zinc.
Hereinafter, the catalyst X and the catalyst Y will be described.

1-3-1. Catalyst X
The catalyst X is one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, pyridine compounds, and phosphine compounds.
The catalyst X is preferably at least one compound selected from the group consisting of azabicyclo compounds, amidine compounds and pyridine compounds among the compound groups described above. These compounds are excellent in catalytic activity and can preferably produce the component (A), and also form a complex with the catalyst Y described later after completion of the reaction. Since the complex is hardly soluble in the reaction solution, it can be easily filtered and adsorbed. By this method, it can be easily removed from the reaction solution after completion of the reaction. In particular, the azabicyclo compound can be more easily removed by filtration, adsorption, and the like because the complex with the catalyst Y becomes hardly soluble in the reaction solution.
On the other hand, although the phosphine compound is excellent in catalytic activity, it is difficult to form a complex with the catalyst Y, or when the complex is formed, it is easily soluble in the reaction solution, and the phosphine compound in the reaction solution after the completion of the reaction. Since most of the compound or complex remains dissolved, it is difficult to remove from the reaction solution by a simple method such as filtration and adsorption. For this reason, the phosphine-based catalyst remains in the final product, thereby causing turbidity and catalyst precipitation during storage of the product, and increasing the viscosity or gelation over time. Problems may arise, and similar problems may occur when used as a component of a composition.

  Specific examples of the azabicyclo compounds include 1-azabicyclo [1,1,0] butane, 1,3-diazabicyclo [1,1,0] butane, 1-azabicyclo [2,1,0] heptane, 1,3 -Diazabicyclo [2,1,0] heptane, 1,4-diazabicyclo [2,1,0] heptane, 1-azabicyclo [2,2,0] hexane, 1,3-diazabicyclo [2,2,0] hexane 1-azabicyclo [2,1,1] hexane, 1,3-diazabicyclo [2,1,1] hexane, 1-azabicyclo [2,2,1] heptane, 1,3-diazabicyclo [2,2,1 ] Heptane, 1,4-diazabicyclo [2,2,1] heptane, 1-azabicyclo [3,2,0] heptane, 1,3-diazabicyclo [3,2,0] heptane, 1,4-diazabicyclo [ , 2,0] heptane, 1,6-diazabicyclo [3,2,0] heptane, 1,3-diazabicyclo [2,2,2] octane, 1-azabicyclo [3,2,1] octane, 1,3 -Diazabicyclo [3,2,1] octane, 1,4-diazabicyclo [3,2,1] octane, 1,5-diazabicyclo [3,2,1] octane, 1,6-diazabicyclo [3,2,1 ] Octane, 1-azabicyclo [4,1,1] octane, 1,3-diazabicyclo [4,1,1] octane, 1,4-diazabicyclo [4,1,1] octane, 1,5-diazabicyclo [4] , 1,1] octane, 1,6-diazabicyclo [4,1,1] octane, 1,7-diazabicyclo [4,1,1] octane, 1-azabicyclo [4,2,0] octane, 1,3 -Diazabi B [4,2,0] octane, 1,4-diazabicyclo [4,2,0] octane, 1,5-diazabicyclo [4,2,0] octane, 1,7-diazabicyclo [4,2,0] Octane, 1-azabicyclo [3,3,1] nonane, 1,3-diazabicyclo [3,3,1] nonane, 1,4-diazabicyclo [3,3,1] nonane, 1,5-diazabicyclo [3, 3,1] nonane, 1-azabicyclo [3,2,2] nonane, 1,3-diazabicyclo [3,2,2] nonane, 1,4-diazabicyclo [3,2,2] nonane, 1,5- Diazabicyclo [3,2,2] nonane, 1,6-diazabicyclo [3,2,2] nonane, 1,8-diazabicyclo [3,2,2] nonane, 1-azabicyclo [4,3,0] nonane, 1,3-diazabicyclo [4,3,0] Nonane, 1,4-diazabicyclo [4,3,0] nonane, 1,5-diazabicyclo [4,3,0] nonane, 1,6-diazabicyclo [4,3,0] nonane, 1,7-diazabicyclo [ 4,3,0] nonane, 1,8-diazabicyclo [4,3,0] nonane, 1-azabicyclo [4,2,1] nonane, 1,3-diazabicyclo [4,2,1] nonane, 1, 4-diazabicyclo [4,2,1] nonane, 1,5-diazabicyclo [4,2,1] nonane, 1,6-diazabicyclo [4,2,1] nonane, 1,7-diazabicyclo [4,2, 1] nonane, 1-azabicyclo [5,2,0] nonane, 1,3-diazabicyclo [5,2,0] nonane, 1,3-diazabicyclo [5,2,0] nonane, 1,4-diazabicyclo [ 5,2,0] nonane, 1,5-di Zabicyclo [5,2,0] nonane, 1,6-diazabicyclo [5,2,0] nonane, 1,7-diazabicyclo [5,2,0] nonane, 1,8-diazabicyclo [5,2,0] Nonane, 1-azabicyclo [5,1,1] nonane, 1,3-azabicyclo [5,1,1] nonane, 1,4-azabicyclo [5,1,1] nonane, 1,5-azabicyclo [5, 1,1] nonane, 1,6-azabicyclo [5,1,1] nonane, 1,7-azabicyclo [5,1,1] nonane, 1-azabicyclo [6,1,0] nonane, 1,3- Diazabicyclo [6,1,0] nonane, 1,4-diazabicyclo [6,1,0] nonane, 1,5-diazabicyclo [6,1,0] nonane, 1,6-diazabicyclo [6,1,0] Nonane, 1,7-diazabicyclo [6,1,0] no 1,8-diazabicyclo [6,1,0] nonane, 1-azabicyclo [7,1,0] decane, 1,9-diazabicyclo [7,1,0] decane, 1-azabicyclo [6,2, 0] decane, 1,8-diazabicyclo [6,2,0] decane, 1-azabicyclo [6,1,1] decane, 1,8-diazabicyclo [6,1,1] decane, 1-azabicyclo [5, 3,0] decane, 1,7-diazabicyclo [5,3,0] decane, 1-azabicyclo [5,2,1] decane, 1,7-diazabicyclo [5,2,1] decane, 1-azabicyclo [ 4,3,1] decane, 1,6-diazabicyclo [4,3,1] decane, 1-azabicyclo [4,2,2] decane, 1,6-diazabicyclo [4,2,2] decane, 1- Azabicyclo [5,4,0] undecane, 1 , 7-diazabicyclo [5,4,0] undecane, 1-azabicyclo [5.3.1] undecane, 1,7-diazabicyclo [5,3,1] undecane, 1-azabicyclo [5,2,2] undecane 1,7-diazabicyclo [5,2,2] undecane, 1-azabicyclo [4,4,1] undecane, 1,7-diazabicyclo [4,4,1] undecane, 1-azabicyclo [4,3,2 ] Undecane, 1,7-diazabicyclo [4,3,2] undecane, 1-azabicyclo [3,3,0] octane, 1-azabicyclo [4,3,0] nonane, quinuclidine, lupinan, lupinin, quinolizidine, 3 -Hydroxyquinuclidine, 3-quinuclidinone, quincholine, quincolidine, cinchonidine, cinchonine, quinidine, quinine, cupurein, warts In, swainsonine, castanospermine, mianserin, mirtazapine, canazine, Trager base, 1-azabicyclo [2,2,2] octane-3-carboxylic acid, triethylenediamine (also known as 1,4-diazabicyclo [2,2 , 2] Octane. Hereinafter referred to as “DABCO”), hexamethylenetetramine, 3-quinolidinone hydrochloride, 3-chloro-1-azabicyclo [2,2,2] octane hydrochloride, cinchonidine dihydrochloride, cinchonine hydrochloride hydrate, cinchonidine sulfate Dihydrate, hydroquinidine hydrochloride, cinchonine sulfate dihydrate, quinine hydrochloride dihydrate, quinine sulfate dihydrate, quinine phosphate, quinidine sulfate dihydrate, mianserin hydrochloride, 1 , 1 ′-(butane-1,4-diyl) bis [4-aza-1-azoniabicyclo [2,2,2] octane] dibromide, 1,1 ′-(decane-1,10-diyl) bis [4 -Aza-1-azoniabicyclo [2,2,2] octane] dibromide, bis (trimethylaluminum) -1,4-diazabicyclo [2,2,2] octane adduct, bismuthine, Nuclidine hydrochloride, 3-quinuclidinone hydrochloride, 3-hydroxyquinuclidine hydrochloride, DABCO hydrochloride, quinuclidine acetate, 3-quinuclidinone acetate, 3-hydroxyquinuclidine acetate, DABCO acetate, quinuclidine acrylic Acid salt, 3-quinuclidinone acrylate, 3-hydroxyquinuclidine acrylate, DABCO acrylate and the like.

  Specific examples of the amidine compound include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 1-allylimidazole, 1 , 8-diazabicyclo [5,4,0] undec-7-ene (hereinafter referred to as “DBU”), 1,5-diazabicyclo [4,3,0] non-5-ene (hereinafter referred to as “DBN”) N-methylimidazole hydrochloride, DBU hydrochloride, DBN hydrochloride, N-methylimidazole acetate, DBU acetate, DBN acetate, N-methylimidazole acrylate, DBU acrylate, DBN acrylate, phthalimide DBU etc. are mentioned.

  Specific examples of the pyridine compound include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-propylpyridine, and 4-propylpyridine. 4-isopropylpyridine, 4-tert-butylpyridine, 4-amylpyridine, 4- (1-ethylpropyl) pyridine, 4- (5-nonyl) pyridine, 2-vinylpyridine, 2,3-dimethylpyridine, 2 , 4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine, 3,5-diethylpyridine, N, N-dimethyl-4-amino Pyridine (hereinafter referred to as “DMAP”), 2,4,6-trimethylpyridine, 2,6-di-ter -Butylpyridine, N, N-dimethyl-2-aminopyridine, 4-piperidinopyridine, 4-pyrrolidinopyridine, 4-phenylpyridine, quinoline, 2-methylquinoline, 3-methylquinoline, 4-methylquinoline, 6-methylquinoline, 7-methylquinoline, 8-methylquinoline, isoquinoline, 1-methylisoquinoline, acridine, 3,4-benzoquinoline, 5,6-benzoquinoline, 7,8-benzoquinoline, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,6-dihydroxypyridine, 2- (hydroxymethyl) pyridine, 3- (hydroxymethyl) pyridine, 4- (hydroxymethyl) pyridine, 5-hydroxyisoquinoline, 2-methoxypyridine , 3-methoxypyridine, 4-methoxy Pyridine, 2,6-dimethoxypyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, 1,8-naphthyridine, 2,6-naphthyridine, 2,7-naphthyridine, 2,2′- Bipyridyl, 3,3′-bipyridyl, 4,4′-bipyridyl, 2,3′-bipyridyl, 2,4′-bipyridyl, 3,4′-bipyridyl, 4,4′-ethylenedipyridine, 1,3- Di (4-pyridyl) propane, 1,10-phenanthroline monohydrate, 2- (trimethylsilyl) pyridine, DMAP hydrochloride, DMAP acetate, DMAP acrylate, 1-methylpyridinium chloride, 1-propylpyridinium chloride, Borane-pyridine complex, borane-2-picoline complex, pyridinium paratoluenesulfonate, etc. .

  Examples of the phosphine compound include compounds having a structure represented by the following general formula (2).

[In Formula (2), R < ³ >, R < ⁴ > and R < ⁵ > are a C1-C20 linear or branched alkyl group, a C1-C20 linear or branched alkenyl group, carbon number 6 Means an aryl group of ˜24 or a cycloalkyl group of 5 to 20 carbon atoms. R ³ , R ⁴ and R ⁵ may be the same or different.
Represent. )

  Specific examples of the phosphine compound include triphenylphosphine, (S)-(−)-BINAP, (R)-(+)-BINAP, (±) -BINAP, 2,2′-bis (diphenylphosphino) Biphenyl, xanthophos, 4,6-bis (diphenylphosphino) phenoxazine, bis [2- (diphenylphosphino) phenyl] ether, (2-bromophenyl) diphenylphosphine, bis (pentafluorophenyl) phenylphosphine, diphenylphos Sodium finobenzene-3-sulfonate, diphenyl-1-pyrenylphosphine, diphenyl-2-pyridylphosphine, 4- (dimethylamino) phenyldiphenylphosphine, 1,1′-bis (diphenylphosphino) ferrocene, (R, R ′ ′)-2,2 ′ ′-bis (diphenyl) Phosphino) -1,1 ′ ′-biferrocene, (R) —N, N-dimethyl-1-[(S) -2- (diphenylphosphino) ferrocenyl] ethylamine, (S) —N, N-dimethyl-1 -[(R) -2- (diphenylphosphino) ferrocenyl] ethylamine, (R) -N, N-dimethyl-1-[(S) -1 ', 2-bis (diphenylphosphino) ferrocenyl] ethylamine, S) -N, N-dimethyl-1-[(R) -1 ′, 2-bis (diphenylphosphino) ferrocenyl] ethylamine, 4-diphenylphosphinomethylpolystyrene resin, (R)-(+)-2- Diphenylphosphino-2′-methoxy-1,1′-binaphthyl, (S)-(−)-2-diphenylphosphino-2′-methoxy-1,1′-binaphthyl, 2- (diphenylphosphite ) Benzoic acid, 4- (diphenylphosphino) benzoic acid, 2- (diphenylphosphino) benzaldehyde, (S)-(−)-5,5′-bis [di (3,5-xylyl) phosphino] -4 , 4′-bi-1,3-benzodioxole, (R)-(+)-5,5′-bis [di (3,5-xylyl) phosphino] -4,4′-bi-1, 3-benzodioxole, (S)-(+)-5,5′-bis [di (3,5-di-tert-butyl-4-methoxyphenyl) phosphino] -4,4′-bi-1 , 3-benzodioxole, (R)-(−)-5,5′-bis [di (3,5-di-tert-butyl-4-methoxyphenyl) phosphino] -4,4′-bi- 1,3-benzodioxole, (pentafluorophenyl) diphenylphosphine, (S)-(−)-5,5 ′ Bis (diphenylphosphino) -4,4′-bi-1,3-benzodioxole, (R)-(+)-5,5′-bis (diphenylphosphino) -4,4′-bi- 1,3-benzodioxole, tris (4-methoxyphenyl) phosphine, tri (p-tolyl) phosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tris (2,6-dimethoxyphenyl) ) Phosphine, triphenylborane-triphenylphosphine complex, triphenylphosphine borane, tris (pentafluorophenyl) phosphine, tris [3,5-bis (trifluoromethyl) phenyl] phosphine, tris (4-fluorophenyl) phosphine, Parastyryl diphenylphosphine, tetraphenylphosphonium bromide, methyl Riphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, methoxymethyltriphenylphosphonium chloride, benzyltriphenylphosphonium chloride, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, ethyltriphenylphosphonium acetate / acetic acid Complex, ethyltriphenylphosphonium iodo, tris (4-methoxy-3,5-dimethylphenyl) phosphine, (+)-DIOP, (−)-DIOP, 1,2-bis (diphenylphosphino) ethane, 1,3 -Bis (diphenylphosphino) propane, 1,2-bis (dimethylphosphino) ethane, 1,4-bis (diphenylphosphino) butane, 1,6-bis (diphenylphospho) Sufino) hexane, 1,5-bis (diphenylphosphino) pentane, bis (diphenylphosphino) methane, trans-1,2-bis (diphenylphosphino) ethylene, (S, S) -chilafos, (R, R ) -DIPAMP, (S, S) -DIPAMP, 1,2-bis [bis (pentafluorophenyl) phosphino] ethane, (2R, 3R)-(-)-Norphos, (2S, 3S)-(+)- Norphos, 2-butenyl (di-tert-butyl) phosphine, cyclohexyldiphenylphosphine, dicyclohexyl (1,1-diphenyl-1-propen-2-yl) phosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, diphenylpropylphosphine, 2- (Di-tert-butylphosphino Biphenyl, 2- (dicyclohexylphosphino) biphenyl, 2- (dicyclohexylphosphino) -2 '-(dimethylamino) biphenyl, 1- [2- (di-tert-butylphosphino) phenyl] -3,5-diphenyl -1H-pyrazole, di-tert-butylphenylphosphine, (4-dimethylaminophenyl) di-tert-butylphosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, ethyldiphenylphosphine, isopropyldiphenylphosphine Methyldiphenylphosphine, tricyclohexylphosphine, tri (2-furyl) phosphine, tri (2-thienyl) phosphine, tri-tert-butylphosphine, tricyclopentylphosphine, and the like.

  In this invention, these catalysts X can be used individually or in combination of 2 or more types. Among these catalysts X, quinuclidine, 3-quinuclidinone, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, DBN, DMAP, triphenylphosphine, tri (p-tolyl) phosphine, tri (m- (Tolyl) phosphine, tris (4-methoxyphenyl) phosphine, and tris (4-methoxy-3,5-dimethylphenyl) phosphine are preferable, and particularly, they exhibit good reactivity with most polyhydric alcohols and are easily available. 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, DMAP, triphenylphosphine, and tri (m-tolyl) phosphine are preferable.

  (A) Although the usage-amount of the catalyst X in the manufacturing method of a component does not have a restriction | limiting in particular, it is preferable to use 0.0001-0.5 mol of catalyst X with respect to 1 mol of hydroxyl groups in a polyhydric alcohol, More preferably, it is 0.0005-0.2 mol. By using 0.0001 mol or more of catalyst X, the production amount of the target polyfunctional (meth) acrylate can be increased, and by setting it to 0.5 mol or less, the production of by-products and the reaction solution Coloring can be suppressed, and the purification step after completion of the reaction can be simplified.

1-3-2. Catalyst Y
The catalyst Y is a compound containing zinc.
As the catalyst Y, various compounds can be used as long as they contain zinc, but organic acids zinc and zinc diketone enolate are preferable because of excellent reactivity.
Examples of the organic acid zinc include dibasic acid zinc such as zinc oxalate and a compound represented by the following general formula (3).

[In Formula (3), R < ⁶ > and R < ⁷ > are C1-C20 linear or branched alkyl groups, C1-C20 linear or branched alkenyl groups, C6-C24 An aryl group or a C5-C20 cycloalkyl group is meant. R ⁶ and R ⁷ may be the same or different.
As the compound of the formula (3), a compound in which R ⁶ and R ⁷ are linear or branched alkyl groups having 1 to 20 carbon atoms is preferable. In R ⁶ and R ⁷ , the linear or branched alkyl group having 1 to 20 carbon atoms is a functional group having no halogen atom such as fluorine and chlorine, and the catalyst Y having the functional group has a high yield. Is preferable because a polyfunctional (meth) acrylate can be produced.

  Examples of the zinc diketone enolate include compounds represented by the following general formula (4).

[In Formula (4), R < ⁸ >, R < ⁹ >, R < ¹⁰ >, R < ¹¹ >, R < ¹² > and R < ¹³ > are C1-C20 linear or branched alkyl groups, C1-C20 linear Or a branched alkenyl group, a C6-C24 aryl group, or a C5-C20 cycloalkyl group is meant. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different.

Specific examples of the compound containing zinc represented by the general formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octylate, zinc neodecanoate, zinc laurate, zinc myristate, Examples include zinc stearate, zinc cyclohexanebutyrate, zinc 2-ethylhexanoate, zinc benzoate, zinc t-butylbenzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and zinc methacrylate.
In addition, about these compounds containing zinc, when the complex with the hydrate, solvate, or catalyst X exists, this complex with the hydrate, solvate, and catalyst X is also component (A). It can be used as the catalyst Y in the production method.

  Specific examples of the compound containing zinc represented by the general formula (4) include zinc acetylacetonate, zinc acetylacetonate hydrate, bis (2,6-dimethyl-3,5-heptanedionato) zinc, bis (2,2,6,6-tetramethyl-3,5-heptanedionato) zinc, bis (5,5-dimethyl-2,4-hexanedionato) zinc and the like. In addition, about these compounds containing zinc, when the complex with the hydrate or solvate, or the catalyst X exists, this complex with the hydrate, the solvate, and the catalyst X is also component (A). It can be used as the catalyst Y in the production method.

As the organic acid zinc and zinc diketone enolate in the catalyst Y, the aforementioned compounds can be used directly, but these compounds can also be generated and used in the reaction system.
For example, zinc compounds such as metal zinc, zinc oxide, zinc hydroxide, zinc chloride and zinc nitrate (hereinafter referred to as “raw zinc compounds”) are used as raw materials. In the case of organic acid zinc, raw zinc compounds and organic acids are used. In the case of zinc diketone enolate, a method of reacting a raw material zinc compound with 1,3-diketone and the like can be mentioned.

  In this invention, these catalysts Y can be used individually or in combination of 2 or more types. Among these catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, and zinc acetylacetonate are preferable, and particularly shows good reactivity with most polyhydric alcohols and is easily available. Zinc acetate, zinc acrylate and zinc acetylacetonate are preferred.

  (A) Although there is no restriction | limiting in particular in the usage-amount of the catalyst Y in the manufacturing method of a component, It is preferable to use 0.0001-0.5 mol of catalyst Y with respect to 1 mol of total hydroxyl groups in a polyhydric alcohol, More preferably, it is 0.0005-0.2 mol. By using 0.0001 mol or more of catalyst Y, the production amount of the target polyfunctional (meth) acrylate can be increased, and by setting it to 0.5 mol or less, by-product formation and reaction solution Coloring can be suppressed, and the purification step after completion of the reaction can be simplified.

1-4. (A) Component Production Method Component (A) is produced by subjecting glycerol and a monofunctional (meth) acrylate to an ester exchange reaction in the presence of a transesterification catalyst.
As described above, the production method of the component (A) is preferably a production method using the catalysts X and Y in combination as a catalyst. The production method will be described below.

  (A) Although the usage-amount of the catalyst X and the catalyst Y in the manufacturing method of a component does not have a restriction | limiting in particular, It is preferable to use 0.005-10.0 mol of catalyst X with respect to 1 mol of catalyst Y, and more. Preferably it is 0.05-5.0 mol. By using 0.005 mol or more, the production amount of the target GLY-TA can be increased, and by making it 10.0 mol or less, the production of by-products and coloring of the reaction liquid are suppressed, and the reaction The purification step after completion can be simplified.

The combination of the catalyst X and the catalyst Y used in the present invention is preferably a combination of the catalyst X being an azabicyclo compound, the catalyst Y being a compound represented by the general formula (3), and the azabicyclo compound being DABCO. And a combination in which the compound represented by the general formula (3) is zinc acetate and / or zinc acrylate is most preferable.
In addition to obtaining GLY-TA with good yield, this combination is excellent in color tone after the completion of the reaction, and therefore can be suitably used for various industrial applications in which color tone is regarded as important. Furthermore, since the catalyst is available at a relatively low cost, it is an economically advantageous production method.

  The catalyst X and catalyst Y used in the present invention may be added from the beginning of the above reaction or may be added midway. Moreover, a desired use amount may be added all at once, or may be added in divided portions.

  (A) It is preferable that the reaction temperature in the manufacturing method of a component is 40-180 degreeC, More preferably, it is 60-160 degreeC. By setting the reaction temperature to 40 ° C. or higher, the reaction rate can be increased, and by setting it to 180 ° C. or lower, thermal polymerization of (meth) acryloyl groups in raw materials and products is suppressed, and coloring of the reaction liquid is performed. And the purification process after completion of the reaction can be simplified.

  The reaction pressure in the method for producing the component (A) is not particularly limited as long as the predetermined reaction temperature can be maintained, and may be performed in a reduced pressure state or in a pressurized state. Usually, it is 0.000001-10MPa (absolute pressure).

  In the manufacturing method of (A) component, the monohydric alcohol derived from monofunctional (meth) acrylate byproduces with progress of transesterification. Although the monohydric alcohol may be allowed to coexist in the reaction system, the transesterification reaction can be further promoted by discharging the monohydric alcohol out of the reaction system.

In the method for producing the component (A), the reaction can be carried out without using a solvent, but a solvent may be used as necessary.
Specific examples of the solvent include n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, diamyl. Hydrocarbons such as benzene, triamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, isopropyltoluene, decalin and tetralin; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diethyl acetal, dihexyl acetal , T-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, trioxane, dioxane, anisole, diphenyl ether Ethers such as tellurium, dimethylcellosolve, diglyme, triglyme and tetraglyme; crown ethers such as 18-crown-6; esters such as methyl benzoate and γ-butyrolactone; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone And ketones such as benzophenone; carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, and 1,2-butylene carbonate; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; ureas or derivatives thereof Ionic liquids such as phosphine oxides such as tributylphosphine oxide, imidazolium salts, piperidinium salts and pyridinium salts; silicon oil and water Etc.
Of these solvents, hydrocarbons, ethers, carbonate compounds and ionic liquids are preferred.
These solvents may be used alone, or two or more kinds may be arbitrarily combined and used as a mixed solvent.

  In the method for producing the component (A), an inert gas such as argon, helium, nitrogen and carbon dioxide may be introduced into the system for the purpose of maintaining a good color tone of the reaction solution, but a (meth) acryloyl group For the purpose of preventing polymerization of oxygen, an oxygen-containing gas may be introduced into the system. Specific examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like. As a method for introducing the oxygen-containing gas, there is a method in which the oxygen-containing gas is dissolved in the reaction solution or blown into the reaction solution (so-called bubbling).

In the manufacturing method of (A) component, it is preferable to add a polymerization inhibitor in the reaction liquid for the purpose of preventing the polymerization of the (meth) acryloyl group.
Specific examples of the polymerization inhibitor include hydroquinone, tert-butyl hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4-tert -Butylcatechol, benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine Organic polymerization inhibitors such as -1-oxyl, inorganic polymerization inhibitors such as copper chloride, copper sulfate and iron sulfate, and organic salt systems such as copper dibutyldithiocarbamate and N-nitroso-N-phenylhydroxylamine aluminum salt A polymerization inhibitor is mentioned.
A polymerization inhibitor may be added individually by 1 type, or may be added in combination of 2 or more types, may be added from the beginning of this invention, and may be added from the middle. Moreover, a desired use amount may be added all at once, or may be added in divided portions. Moreover, you may add continuously via a rectification column.
The addition ratio of the polymerization inhibitor is preferably 5 to 30,000 wtppm in the reaction solution, and more preferably 25 to 10,000 wtppm. By setting this ratio to 5 wtppm or more, the polymerization inhibition effect can be exerted, and by setting it to 30,000 wtppm or less, coloring of the reaction solution can be suppressed, and the purification step after completion of the reaction can be simplified. Moreover, the fall of the cure rate of the (A) component obtained can be prevented.

  Although the reaction time in the manufacturing method of (A) component changes with the kind and usage-amount of a catalyst, reaction temperature, reaction pressure, etc., it is 0.1 to 150 hours normally, Preferably it is 0.5 to 80 hours.

  (A) The manufacturing method of a component can be implemented by any method of a batch type, a semibatch type, and a continuous type. As an example of a batch system, a polyhydric alcohol, a monofunctional (meth) acrylate, a catalyst, and a polymerization inhibitor are charged into a reactor, and stirred at a predetermined temperature while bubbling oxygen-containing gas into the reaction solution. Then, it can implement by the method of producing | generating the target (A) component by extracting the monohydric alcohol byproduced with progress of transesterification from a reactor by predetermined | prescribed pressure.

For the reaction product obtained by the method for producing the component (A), it is preferable to carry out a separation / purification operation because the desired GLY-TA can be obtained with high purity.
Examples of the separation / purification operation include a crystallization operation, a filtration operation, a distillation operation, and an extraction operation, and these are preferably combined. Examples of the crystallization operation include cooling crystallization and concentration crystallization. Examples of the filtration operation include pressure filtration, suction filtration, and centrifugal filtration. Examples of the distillation operation include single distillation, fractional distillation, and molecular distillation. And steam distillation, and the extraction operation includes solid-liquid extraction and liquid-liquid extraction.
A solvent may be used in the separation and purification operation. Further, a neutralizing agent for neutralizing the catalyst and / or polymerization inhibitor used in the present invention, an adsorbing agent for adsorbing and removing, an acid and / or alkali for decomposing or removing by-products, a color tone Activated carbon for improving diatomaceous earth, diatomaceous earth for improving filtration efficiency and filtration speed, and the like may be used.

2. Inkjet inks curable composition The present invention relates to an ink jet inks curable composition containing the component (A).
The composition of the present invention is preferably used as a composition for inkjet ink because it has a low viscosity even in the absence of a solvent, is excellent in ejection properties, is excellent in curability, and is excellent in the adhesion, hardness and scratch resistance of the cured product. can do.

Furthermore, as a method for producing the composition, a (meth) acrylate mixture containing GLY-TA as a main component, obtained by subjecting glycerol and a monofunctional (meth) acrylate to a transesterification reaction in the presence of the catalysts X and Y. The manufacturing method of the composition including the process of manufacturing (A) is preferable.
According to the production method, the component (A) can be produced in a high yield, and since the high molecular weight product in the obtained component (A) is small, the viscosity is low and there are few impurities. This is preferable in that it can be excellent in physical properties.
What is necessary is just to follow the manufacturing method of above-described (A) component as the said process.
The method for producing the composition in the case of blending other components described later may be in accordance with a conventional method, and the component (A) and other components described later can be stirred and mixed as necessary.

As the viscosity of the composition, it is preferable that the viscosity of the composition is 5 to 200 mPa · s, more preferably at a temperature at the time of discharge (for example, 25 ° C. to 80 ° C.) in consideration of the discharge property in the ink jet system. It is 7-40 mPa * s, More preferably, it is 7-20 mPa * s.
By setting the viscosity of the composition to 5 mPa · s or more, it is possible to prevent a decrease in the followability of the discharge, and by setting it to 200 mPa · s or less, the discharge stability is excellent.
In addition, the viscosity in this invention means the value measured at the temperature at the time of discharge using an E-type viscometer.

The amount of water in the composition is preferably 5% by weight or less, and more preferably 1% by weight or less.
By reducing the water content to 5% by weight or less, the pigment dispersibility is prevented from being deteriorated, and the ink ejection stability with time deteriorates. At the same time, the coarse particles of the pigment increase, resulting in a decrease in saturation and color reproduction. It is possible to prevent the performance from being impaired.

The composition of the present invention contains (A) as an essential component, but various components can be blended depending on the purpose.
As other components, specifically, monofunctional (meth) acrylate [hereinafter referred to as “component (B)”], photopolymerization initiator [hereinafter referred to as “component (C)”], thermal polymerization initiator [hereinafter referred to as “component (B)”) , “Component (D)”, compounds having an ethylenically unsaturated group other than the components (A) and (B) (hereinafter referred to as “component (E)”), colorants (hereinafter referred to as “(F) ) Component ”, pigment dispersant agent (hereinafter referred to as“ component (G) ”), organic solvent, antioxidant, ultraviolet absorber, leveling agent, silane coupling agent, surface modifier, polymerization inhibitor, etc. Is mentioned.
Hereinafter, these components will be described.
In addition, the other component mentioned later may use only 1 type of the illustrated compound, and may use 2 or more types together.

1) Component (B) The component (B) is a monofunctional (meth) acrylate. (B) As a component, it can also mix | blend separately and can also be used as it is, without refine | purifying the monofunctional (meth) acrylate used by manufacture of (A) component.
As the component (B), the same compounds as those mentioned above as examples of the monofunctional (meth) acrylate can be used.
(B) Component other than the above-mentioned compounds includes 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, cyclic trimethylolpropane formal mono (meth) acrylate, and (meth) phenol adduct of alkylene oxide. Acrylate, Alkyl oxide alkylene oxide adduct (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, (meth) acrylic acid, Michael addition dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, phthalic acid Monohydroxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, butyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, benzy (Meth) acrylate (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, paracumylphenol alkylene oxide adduct Acrylate, orthophenylphenol (meth) acrylate, (meth) acrylate of alkylene oxide adduct of orthophenylphenol, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N- (2- (meth) acryloxyethyl) hexa Hydrophthalimide, N- (2- (meth) acryloxyethyl) tetrahydrophthalimide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N-formamide and the like can be mentioned.
Examples of the alkylene oxide adduct include ethylene oxide adduct, propylene oxide adduct, ethylene oxide and propylene oxide adduct, and the like.

As the component (B), among the compounds described above, isobornyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate (hereinafter referred to as “VEEA”). And cyclic trimethylolpropane formal mono (meth) acrylate.
In particular, when VEEA is used as component (B), since VEEA has a vinyl ether group, the composition used in combination with (meth) acrylate obtained by conventional dehydration esterification is said to have reduced storage stability. Had a problem. On the other hand, the component (A) obtained by the transesterification is excellent in storage stability even when VEEA is used in combination as the component (B).

The content ratio of the component (B) is preferably 0 to 90% by weight, more preferably 0 to 80% by weight in 100% by weight of the total amount of the curable components.
When the content ratio of the component (B) is 90% by weight or less, the curability of the composition is excellent, and it is possible to prevent the scratch resistance of the cured product from being lowered.
In the present invention, the “curable component” is a component that is cured by active energy rays or heat, means the component (A), and when it further includes the component (B), “(A) and ( “B) component” means “component (E)” or “(A), (B) and (E) component” when the component (E) described later is further included. .

2) Component (C) When the composition of the present invention is used as an active energy ray-curable composition and further used as an electron beam-curable composition, the component (C) (photopolymerization initiator) is not included. It is also possible to cure with an electron beam.
When the composition of the present invention is used as an active energy ray-curable composition, particularly when ultraviolet rays and visible rays are used as active energy rays, the component (C) is further added from the viewpoint of ease of curing and cost. It is preferable to contain.
When an electron beam is used as the active energy ray, it is not always necessary to add it, but a small amount can be added as necessary in order to improve curability.

Specific examples of the component (C) include benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl. ] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methylvinyl) phenyl] propanone, 2-hydroxy-1- [ 4- [4- (2-hydroxy-2-methyl-propionyl) benzyl] phenyl] -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- 4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole and the like Acetophenone compounds of
Benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1- [4- (4-benzoylphenylsulfanyl) phenyl ] -2-Methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone and 4-methoxy-4 ′ -Benzophenone compounds such as dimethylaminobenzophenone;
Such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. Acylphosphine oxide compounds; and thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2 -Yl-oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride and thioxanthone compounds such as fluorothioxanthone.
Examples of the compound other than the above include benzyl, methyl phenylglyoxylate, ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate, ethyl anthraquinone, phenanthrenequinone and camphorquinone.

Among these compounds, α-hydroxyphenyl ketones are preferable because they have good surface curability even in the case of thin film coating in the atmosphere. Specifically, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one is more preferred.
Also, when it is necessary to increase the thickness of the cured product, for example, when it is necessary to make it 50 μm or more, for the purpose of improving the curability inside the cured product, or when using an ultraviolet absorber or a pigment together In order to improve the curability of the composition, it is preferable to use a plurality of compounds selected from acylphosphine oxide compounds, thioxanthone compounds and aromatic ketone compounds in combination.
Preferred examples of the compound in this case include (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6) as the acylphosphine oxide compound. -Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like, and examples of the thioxanthone compound include 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, and the like. As aromatic ketone compounds, 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) butane-1-o , 2-dimethylamino-2- (4-methylbenzyl) -1- (4-4-morpholine-yl - phenyl) - butan-1-one, and the like.
In this case, the combination of the compounds is appropriately selected in consideration of the type of the curable component to be used, the light absorption region of the ultraviolet absorber or the pigment, and the light irradiation region of the active energy ray irradiation apparatus.

  As for the content rate of (C) component, 0.1-25 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1-20 weight part. (C) By making the ratio of a component 0.1 weight part or more, the photocurability of a composition can be made favorable and it can be excellent in adhesiveness, and it is 25 weight part or less, and hardened | cured material The internal curability can be improved, and the adhesion to the substrate can be improved.

3) Component (D) The component (D) is a thermal polymerization initiator, and when the composition is used as a thermosetting composition, the component (D) can be blended.
The composition of this invention can mix | blend a thermal-polymerization initiator and can also be heat-hardened.
Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.
Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl- , 5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5 -Di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butyl) Peroxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide P-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 Examples include 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide.
Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. Azodi-t-octane, azodi-t-butane and the like.
These may be used alone or in combination of two or more. Moreover, an organic peroxide can also be made into a redox reaction by combining with a reducing agent.

The amount of these thermal polymerization initiators used is preferably 10 parts by weight or less with respect to 100 parts by weight of the total amount of curable components.
When the thermal polymerization initiator is used alone, it may be carried out in accordance with conventional means of radical thermal polymerization. In some cases, it is used in combination with the component (C) (photopolymerization initiator), and after photocuring, the reaction rate is further increased. For the purpose of improving the temperature, thermosetting can also be performed.

4) Component (E) The component (E) is an ethylenically unsaturated compound other than the components (A) and (B), and is blended for the purpose of imparting various physical properties to the cured product.
Examples of the ethylenically unsaturated group in component (E) include (meth) acryloyl group, (meth) acrylamide group, vinyl group and (meth) allyl group, and (meth) acryloyl group is preferred.
In the following, “◯ functional” means a compound having ○ ethylenically unsaturated groups, and “polyfunctional” means a compound having 2 or more ethylenically unsaturated groups.

  Specific examples of the bifunctional (meth) acrylate compound include polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and tetramethylene glycol. Di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, di (meth) acrylate of bisphenol A alkylene oxide adduct, di (meth) acrylate of bisphenol F alkylene oxide adduct, butanediol di (meth) Examples include acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth) acrylate. In addition, epoxy (meth) acrylate having a bisphenol skeleton, polyether skeleton, polyalkylene skeleton, polyester skeleton, urethane (meth) acrylate having a polyether skeleton or a polycarbonate skeleton, and polyester (meth) acrylate may also be used. Can do.

Examples of the tri- or higher functional (meth) acrylate compound include various compounds as long as the compound has three or more (meth) acryloyl groups. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri- or tetra- Poly (poly) (meth) acrylates such as (meth) acrylate, ditrimethylolpropane tri- or tetra (meth) acrylate, diglycerin tri- or tetra (meth) acrylate, and dipentaerythritol tri-, tetra-, penta- or hexa (meth) acrylate ) Acrylate;
Tri (meth) acrylate of glycerin alkylene oxide adduct, tri- or tetra (meth) acrylate of pentaerythritol alkylene oxide adduct, tri- or tetra (meth) acrylate of ditrimethylolpropane alkylene oxide adduct, diglycerin alkylene oxide adduct Poly (meth) acrylates of polyol alkylene oxide adducts such as tri or tetra (meth) acrylate, dipentaerythritol alkylene oxide adduct tri, tetra, penta or hexa (meth) acrylate;
Tris (meth) acrylates of isocyanuric acid alkylene oxide adducts; and compounds having 3 or more (meth) acryloyl groups and hydroxyl groups, such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate Examples thereof include urethane (meth) acrylate that is a reaction product with polyisocyanate.
Examples of the alkylene oxide adduct include ethylene oxide adduct, propylene oxide adduct, ethylene oxide and propylene oxide adduct, and the like.
Examples of the organic polyisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated xylylene. Examples include diisocyanate, trimer of 4,4′-dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.

(E) It is preferable that the content rate of a component contains 0 to 60 weight% in the total amount of 100 weight% of a sclerosing | hardenable component, More preferably, it is 0 to 30 weight%.
(E) By making the content rate of a component 60 weight% or less, especially in the case of a polyfunctional ethylenically unsaturated compound, it can prevent that hardened | cured material becomes weak.

5) Component (F) The component (F) is a colorant, and examples of the colorant include pigments and dyes.
Examples of the pigment include organic pigments and inorganic pigments.
Specific examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, benzidine yellow and pyrazolone red; soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet and Permanent Red 2B; Alizarin, Indantron And derivatives from vat dyes such as thioindigo maroon; phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone organic pigments such as quinacridone red and quinacridone magenta; perylene organic pigments such as perylene red and perylene scarlet; Isoindolinone organic pigments such as indolinone yellow and isoindolinone orange; pyranthrone organic pigments such as pyranthrone red and pyranthrone orange Thioindigo organic pigments; condensed azo organic pigments; benzimidazolone organic pigments; quinophthalone organic pigments such as quinophthalone yellow; isoindoline organic pigments such as isoindoline yellow; and other pigments such as flavanthrone yellow and acylamide Examples include yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, and dioxazine violet.
Specific examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean curd (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, chromium oxide green, Examples thereof include cobalt green, amber, titanium black, and synthetic iron black. The carbon black exemplified as the filler can also be used as an inorganic pigment.
Various conventionally known compounds can be used as the dye.

  The content ratio of the component (F) may be appropriately set according to the purpose, but is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the curable components. It is.

6) Component (G) The component (G) is a pigment dispersant. When a pigment is used as the colorant of the composition of the present invention, it is preferable to incorporate the component (G).
The pigment dispersant is not particularly limited, and various pigment dispersants can be used.
Specific examples of usable pigment dispersants include amide compounds such as nonanoamide, decanamide, dodecanamide, N-dodecylhexamide, N-octadecylpropioamide, N, N-dimethyldodecanamide and N, N-dihexylacetamide. , Amine compounds such as diethylamine, diheptylamine, dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine, tributylamine and trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N, N, N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N′-tri (hydroxyethyl) -1,2-diaminoethane, N, N, N ′, N′-tetra (hydroxyethylpolyoxyethylene) -1,2 -Examples include amines having a hydroxy group such as diaminoethane, 1,4-bis (2-hydroxyethyl) piperazine, and 1- (2-hydroxyethyl) piperazine, and others such as nipecotamide, isonipecotamide, and nicotinamide. And the like.

  Furthermore, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts of (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid (Partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamides Phosphate salts: Amides obtained by reacting poly (lower alkyleneimine) with free carboxyl group-containing polyesters and salts thereof can be mentioned.

  As commercially available dispersants, Shigenox-105 (trade name, manufactured by Hakkol Chemical Co., Ltd.), Disperbyk-101, -130, -140, -170, -171, -182, -2001 [Above, manufactured by Big Chemie Japan Co., Ltd.], EFKA-49, -4010, -9900 (manufactured by EFKA CHEMICALS), Solsperse 12000, 13240, 13940, 17000, 20000, 24000GR, 24000SC, 27000, 28000, 33500 [above, manufactured by Zeneca Co., Ltd.], PB821, 822 [above, manufactured by Ajinomoto Fine Techno Co., Ltd.], and the like.

  The pigment dispersant is usually used at a ratio of 10 to 90 parts by weight, preferably 20 to 80 parts by weight, based on 100 parts by weight of the pigment.

  The inkjet ink containing the pigment of the present invention is produced by thoroughly dispersing the component (A), the pigment, and the pigment dispersant using an ordinary dispersing machine such as a bead mill. It is preferable to prepare a concentrated solution having a high pigment concentration in advance and then dilute with a monomer. Sufficient dispersion is possible even with dispersion by a normal disperser. Therefore, excessive dispersion energy is not required, and a large amount of dispersion time is not required. An ink having excellent properties is prepared.

7) Organic solvent The composition of the present invention does not substantially require a solvent, but may contain an organic solvent as needed for the purpose of adjusting the viscosity.
Organic solvents include ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetates such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, ethylene glycol monoacetate, propylene glycol monomethyl ether, butyl Examples include alcohols such as alcohol, and other commonly used organic solvents.

8) Antioxidant Antioxidant is mix | blended in order to improve durability, such as the heat resistance of a hardened | cured material, and a weather resistance.
Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
Examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. As what is marketed, Ade-20 Co., Ltd. AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80 etc. are mentioned.
Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphites and triaryl phosphites. Examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. Etc.
Examples of the sulfur-based antioxidant include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.
These may be used alone or in combination of two or more. Preferred combinations of these antioxidants include the combined use of phenolic antioxidants and phosphorus antioxidants, and the combined use of phenolic antioxidants and sulfurous antioxidants.
What is necessary is just to set suitably as content rate of antioxidant according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1-1 weight part. It is.
When the content ratio is 0.1 parts by weight or more, the durability of the composition can be improved. On the other hand, when the content ratio is 5 parts by weight or less, curability and adhesion can be improved.

9) Ultraviolet absorber An ultraviolet absorber is mix | blended in order to improve the light resistance of hardened | cured material.
Examples of the ultraviolet absorber include triazine ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole ultraviolet absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
What is necessary is just to set suitably as a content rate of a ultraviolet absorber according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1-1 weight part. It is. When the content ratio is 0.01% by weight or more, the light resistance of the cured product can be improved, and when it is 5% by weight or less, the curability of the composition is excellent. be able to.

10) Silane coupling agent A silane coupling agent is mix | blended in order to improve the interface adhesive strength of hardened | cured material and a base material.
The silane coupling agent is not particularly limited as long as it can contribute to improvement in adhesion to the substrate.

  Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3 -Aminopropyltrimethoxysilane, 3-mercaptopropylmethyldi Tokishishiran, 3-mercaptopropyltrimethoxysilane, and the like.

The blending ratio of the silane coupling agent may be appropriately set according to the purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component. .
When the blending ratio is 0.1 parts by weight or more, the adhesive strength of the composition can be improved. On the other hand, when the blending ratio is 10 parts by weight or less, it is possible to prevent the adhesive force from changing over time.

11) Surface modifier The composition of the present invention may be added with a surface modifier for the purpose of enhancing leveling properties during coating or for enhancing the slipping property of the cured product to enhance the scratch resistance. Good.
Examples of the surface modifier include a surface modifier, a surfactant, a leveling agent, an antifoaming agent, a slipperiness imparting agent, and an antifouling imparting agent, and these known surface modifiers can be used. .
Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specific examples include silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone polymers and oligomers having a silicone chain and a polyester chain, and fluorine polymers having a perfluoroalkyl group and a polyalkylene oxide chain. And a fluorine-based polymer and an oligomer having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
Further, for the purpose of increasing the slidability, a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group, in the molecule may be used.

  It is preferable that the content rate of a surface modifier is 0.01-1.0 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component. It is excellent in the surface smoothness of a coating film as it is the said range.

3. Application The present invention relates to a curable composition for inkjet ink, and can be used for various applications to which inkjet printing can be applied.
Specifically, printing, color filter pixels and black matrix formation, microlens formation, three-dimensional modeling, and the like can be given.
The composition of the present invention can be preferably used as an active energy ray-curable composition.

4). Method of Use As a method of using the composition of the present invention for printing by an ink jet method, a conventional method may be followed.
First, the composition is supplied to a printer head of an ink jet recording method or 3D ink jet printer, and discharged from the printer head onto a substrate.
Then, when the composition of this invention is an active energy ray hardening-type composition, active energy rays, such as an ultraviolet-ray or an electron beam, are irradiated to a printing surface. This quickly cures the composition on the print medium. In the case where the composition of the present invention is a thermosetting composition, the composition is discharged onto a substrate and then left at room temperature or heated.

  When there is a concern about an increase in the viscosity or fluidity of the composition due to a decrease in temperature, it is preferable to use a discharger in which a mechanism for decreasing the viscosity due to heating is incorporated in the head.

Examples of the substrate to which the composition of the present invention can be applied include various substrates conventionally used as the substrate, and specifically include paper, plastic, glass, metal and wood.
Examples of the paper include high-quality paper, coated paper, art paper, imitation paper, thin paper and thick paper, and various synthetic papers.
Plastics include polyester resins such as polyethylene terephthalate, acrylic resins such as polymethyl methacrylate, polyolefins such as polyethylene and polypropylene, polycarbonate, polystyrene, vinyl chloride resins (hard vinyl chloride, soft vinyl chloride), vinylidene chloride resins, polyvinyl alcohol, polyacrylonitrile. , Ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon, polylactic acid, cellophane and the like. Further examples include styrene foam and the like, and mixed or modified products of these plastics.
Examples of the metal include aluminum foil and stainless steel.

In the present invention, when plastic is used as the substrate, surface treatment such as corona treatment or plasma treatment that imparts a polar group to the substrate surface may be performed in order to improve adhesion. Corona treatment and plasma treatment are types of discharge treatment, and are treatments in which oxygen-containing groups are introduced on the surface of the polymer substrate. Among oxygenates, a polar group can be imparted to the substrate surface by introducing a carboxyl group or the like.
The composition of the present invention has a good affinity with a non-polar substrate such as polypropylene, and expresses a strong bond to a polar part generated by corona treatment or plasma treatment of the substrate, and has excellent adhesion Sex can be expressed.

What is necessary is just to set the film thickness of the hardened | cured material of a composition with respect to a base material suitably according to the objective.
As thickness of hardened | cured material, what is necessary is just to select according to the use of the base material to be used or the base material which has manufactured hardened | cured material, It is preferable that it is 1-30 micrometers, and it is more preferable that it is 1-20 micrometers. .

As the light source of the active energy ray, when irradiating ultraviolet rays, for example, a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet laser, an LED (light emitting diode), and sunlight can be used. . It is also possible to cure with an electron beam.
The composition of the present invention can be preferably cured by ultraviolet (UV-LED) irradiation using an LED as a light source. Inkjet printers using LEDs as light sources consume less power than conventional light sources, do not become hot during printing, have a longer lamp life, and can be made compact. It is preferably used.
The irradiation energy may be appropriately set according to the type and composition of the active energy ray. As an example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 5,000 mJ / cm ^2. Is preferable, and 200 to 1,000 mJ / cm ² is more preferable.

The example in the case of forming the pixel of a color filter using the active energy ray hardening-type composition in this invention is demonstrated.
In this case, as the composition, a composition having a plurality of colors for forming a pixel, specifically, three kinds of compositions having red, green, and blue colors are manufactured.
Using a composition having the first color, printing is performed on a substrate at a plurality of locations in a predetermined region by an inkjet method, and irradiation with active energy rays is performed to form a pixel having the first color.
Thereafter, using the composition having the second and third colors, the respective pixels are formed by the same operation.

The example in the case of manufacturing a molded object by three-dimensional modeling using the active energy ray hardening-type composition in this invention is demonstrated.
An example in which a three-dimensional modeling apparatus including a head and a stage is used will be described. The head includes an inkjet discharger and an ultraviolet irradiation device, and moves on the stage in the X-axis-Y-axis directions. The stage moves up and down in the Z-axis direction and descends to form.
Supply the composition to the head. Depending on the data shape, the composition is ejected while the head moves on the stage in the X-axis to Y-axis directions, prints the desired image, and is irradiated with ultraviolet rays by an ultraviolet irradiation device on the side of the head. The object is cured to form a single layer.
In this case, in addition to the inkjet ejector and the ultraviolet irradiation device as the head, when the head is further provided with a roller, the head is in the X-axis-Y-axis direction while ejecting the composition according to the data shape. It moves on the stage, prints the target image, and the head moves in the reverse direction of printing (return path). On the return path, the composition is cured by irradiating ultraviolet rays with an ultraviolet irradiation device on the side of the head while leveling the coated surface with a roller.
After this series of operations is completed, the stage is lowered, and in the same manner as described above, an image is printed according to the data shape, and the composition is cured by irradiating with ultraviolet rays to form one layer. This operation is performed a plurality of times to form a plurality of layers, and finally a three-dimensional molded body is manufactured.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
In the following, “parts” means parts by weight.

1. Production example
1) Production Example 1 ( Production of GLY-TA1 by transesterification method)
In a 1 liter flask equipped with a stirrer, a thermometer, a gas introduction tube, a rectification column and a cooling tube, 63.60 parts (0.69 mol) of glycerin and 700.99 parts of 5-methoxyethyl acrylate (5 .39 mol), 5.47 parts (0.05 mol) of DABCO as catalyst X, 8.94 parts (0.05 mol) of zinc acetate as catalyst Y, 1.56 parts of hydroquinone monomethyl ether (raw materials charged) The oxygen-containing gas (5% by volume of oxygen and 95% by volume of nitrogen) was bubbled into the liquid.
2-methoxyethanol and 2-methoxyethyl acrylate by-produced as the transesterification progresses while adjusting the pressure in the reaction system in the range of 110 to 760 mmHg while heating and stirring at a reaction liquid temperature of 105 to 130 ° C. Was extracted from the reaction system via a rectification column and a cooling tube. Further, 2-methoxyethyl acrylate in the same weight part as the extracted liquid was added to the reaction system as needed. 30 hours after the start of heating and stirring, the pressure in the reaction system was returned to normal pressure, and the extraction was completed. After cooling the reaction solution to room temperature and separating the precipitate by filtration, 1.0 part of KYOWARD 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd. and activated carbon (manufactured by Phutamura Chemical Co., Ltd.) are used for the filtrate. 1.0 parts of Dazai S (trade name)] was added and vacuum distillation was performed for 8 hours at a temperature of 70 to 95 ° C. and a pressure of 0.001 to 100 mmHg while bubbling dry air, and unreacted 2- A distillate containing methoxyethyl acrylate was separated. 2.0 parts of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.] was added to the kettle and subjected to pressure filtration, and the obtained filtrate was used as a purified product.
As a result of analyzing the composition of the purified product using a high performance liquid chromatograph equipped with a UV detector, it was confirmed that glycerin triacrylate was included as a main component (hereinafter referred to as “GLY-TA1”). The yield of the purified product was 90%. As a result of measuring the hydroxyl value of the purified product obtained according to the following method, it was 17 mgKOH / g. The results are shown in Table 1.

2) Production Examples 2 to 4 (Production of GLY-TA2 to 4 by transesterification method)
GLY-TA2 to 4 were produced in the same manner as in Production Example 1 except that the compounds shown in Table 1 below were used as catalysts X and Y. The results are shown in Table 1.

3) Method for evaluating purified product The high-molecular weight GPC area, the viscosity, and the hydroxyl value of the obtained purified product were measured according to the methods described below. The results are shown in Table 1.

(1) High molecular weight GPC area%
About the refinement | purification processed material obtained by the said manufacture example, area% of the high molecular weight body was computed by GPC measurement of the following conditions. The results are shown in Table 1.

◆ GPC measurement conditions and equipment: GPC system name manufactured by Waters Co., Ltd. 1515 2414 717P RI
-Detector: RI detector-Column: Guard column Shodex KFG (8 μm 4.6 × 10 mm) manufactured by Showa Denko KK, two types of this column Watergel HR 4E THF (7.8 × 300 mm) + styragel HR 1THF (7.8 × 300 mm)
Column temperature: 40 ° C
-Eluent composition: THF (containing 0.03% sulfur as internal standard), flow rate 0.75 mL / min-Calculation method of high molecular weight area (%) From GPC measurement results, based on the following formula (1) Calculated.
High molecular weight area% = [(R−IL) / R] × 100 (1)
The symbols and terms in formula (1) are as described above.

(2) Viscosity The viscosity of the purified product obtained was measured with an E-type viscometer (25 ° C.).

(3) Hydroxyl value An acetylating reagent is added to the obtained purified product and heat-treated in a hot tub. After allowing to cool, the acid was titrated with a potassium hydroxide ethanol solution using a phenolphthalein solution as an indicator to determine the hydroxyl value.

2) Comparative Production Example 1 ( Production of GLY-TA5 by dehydrated ester method)
In a flask equipped with a stirrer, a thermometer, a gas introduction tube, a rectifying column, a cooling tube and a water separator, 61.17 parts (0.66 mol) of glycerin and 172.18 parts (2.39 of acrylic acid) were obtained. Mol), 129.50 parts of toluene, 6.40 parts of 78% by weight sulfuric acid aqueous solution, 0.37 parts of copper sulfate (1000 wtppm with respect to the total weight of the charged raw materials), oxygen-containing gas (5 volumes of oxygen) %, Nitrogen 95% by volume) was bubbled into the liquid. The reaction system was stirred while being heated to reflux at a pressure of 370 mmHg, and water produced as a by-product with the progress of the dehydration esterification reaction was withdrawn from the reaction system via a rectification column and a cooling tube. During this time, the temperature of the reaction solution changed in the range of 80 to 90 ° C. After 6 hours from the start of heating and stirring, the heating of the reaction solution was completed, and the pressure in the reaction system was returned to normal pressure to complete the extraction.
After cooling the reaction solution to room temperature, 133 parts of toluene and 55 parts of water were added and stirred, and then allowed to stand to separate the lower layer (aqueous layer). Thereafter, 52 parts of a 20% aqueous sodium hydroxide solution was added to the upper layer (organic layer), stirred and allowed to stand, and the lower layer (aqueous layer) was separated. Thereafter, 38 parts of water was added to the upper layer (organic layer), stirred and allowed to stand, and the lower layer (aqueous layer) was separated. 0.018 parts of hydroquinone monomethyl ether is added to the upper layer (organic layer), and vacuum distillation is performed for 8 hours at a temperature of 60 to 90 ° C. and a pressure of 0.001 to 100 mmHg while bubbling dry air and contains toluene. The distillate was separated. 2.0 parts of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.] was added to the kettle and subjected to pressure filtration, and the obtained filtrate was used as a purified product.
As a result of analyzing the composition of the purified product using a high performance liquid chromatograph equipped with a UV detector, it was confirmed that glycerin triacrylate was contained (hereinafter referred to as “GLYTA5”). The yield of the purified product was 8%.
About the obtained refinement | purification processed material, according to the above-mentioned method, the high molecular weight GPC area, the viscosity, and the hydroxyl value were measured. The results are shown in Table 2.

2. Examples 1 to 8 and Comparative Examples 1 to 6 [active energy ray-curable composition for ink-jet ink (clear ink)]
1) Production of composition The compounds shown in Table 3 below were stirred and mixed in the proportions shown in Table 3 to produce an active energy ray-curable clear composition.
The obtained composition was used and evaluated as described later. The results are shown in Table 4.

The numbers in Table 3 mean the number of copies. The abbreviations in Table 3 mean the following.
(1) Component (B) · IBXA: Isobornyl acrylate, IBXA manufactured by Osaka Organic Chemical Industry Co., Ltd., 25 ° C viscosity 7.7 mPa · s
POA: Phenoxyethyl acrylate, Osaka Organic Chemical Co., Ltd. Viscoat # 192, 25 ° C. viscosity 8.7 mPa · s
VEEA: Vinyloxyethoxyethyl acrylate, VEEA manufactured by Nippon Shokubai Co., Ltd., 25 ° C. viscosity 3.65 mPa · s

(2) Component (E) TMPTA: trimethylolpropane triacrylate, Aronix M-309 manufactured by Toagosei Co., Ltd., 25 ° C. viscosity 90 mPa · s
EO-TMPTA: ethylene oxide 3 mol modified trimethylolpropane triacrylate, Aronix M-350 manufactured by Toagosei Co., Ltd., 25 ° C. viscosity 60 mPa · s

(3) Component (C) IRG907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, IRGACURE907 manufactured by BASF

2) Evaluation method
(1) Composition physical properties
(A) Viscosity The viscosity of the obtained composition was measured with an E-type viscometer (25 ° C.).

(I) Dischargeability The obtained composition was discharged at 25 ° C using an ink jet printer (DMP-2831 manufactured by FUJIFILM Dimatix Inc.) equipped with a head having a piezoelectric element that can be heated to 60 ° C. Inkjet ejection properties were evaluated at two levels.
In addition, since the inkjet head of a 3D inkjet printer is the same as that of the said inkjet pudding, the discharge property in a 3D inkjet printer substitutes by this evaluation.
○: The nozzle can be discharged without clogging.
X: The nozzle is clogged and cannot be discharged.

(2) Cured material properties
(C) Scratch resistance A polyethylene terephthalate film [manufactured by Toyobo Co., Ltd., Cosmo Shine A4300 (thickness: 100 μm) is used to obtain a film thickness of 2 μm. Hereinafter, referred to as “PET” and a polymethyl methacrylate film [manufactured by Kuraray Co., Ltd., Clarity HI 50-75 (thickness: 75 μm). (Hereinafter referred to as “PMMA”).
Using a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., the test specimen after application was irradiated with an irradiation energy of 800 mJ / cm ² per pass at an ultraviolet region (UV-A) intensity of about 500 nm at 500 mW / cm ² . It was conveyed in an air atmosphere on a conveyor adjusted so as to be irradiated with ultraviolet rays.
The obtained cured product was subjected to a rubbing test (load 500 g, 100 g reciprocating) using a nonwoven fabric (Bencot manufactured by Asahi Kasei), and the appearance was visually observed and evaluated according to the following three levels.
○: Not scratched △: Slightly scratched ×: Scratched

(D) Hardness The obtained composition was applied onto a 10 cm glass substrate with an inkjet printer similar to (A) so as to have a film thickness of 20 μm, and was irradiated with ultraviolet rays under the same conditions as in (C). .
When the hardness of the obtained cured product was measured using an ultra-micro hardness meter (manufactured by Fisher Instruments Co., Ltd., H-100C) under the condition that the maximum load of the Vickers indenter was 20 mN at room temperature. The universal hardness was evaluated.

(E) Adhesion to the substrate (PET, PMMA) of the cured product obtained in adhesion (c) was cut with a cutter knife in a 5 × 5 25 square pattern, and then a Nichiban cellophane tape was applied. The tape was peeled off vigorously at a peeling speed of about 1 cm / sec, and the number of squares on which the coating film remained was confirmed. In addition, the following criteria evaluated three steps.
○: 25 to 21 squares △: 20 to 10 squares ×: 10 squares or less

3) Evaluation results As is clear from the results of Examples 1 to 8, the composition of the present invention has a low viscosity, so that it is excellent in inkjet discharge properties, scratch resistance of the cured product, universal hardness, and substrate adhesion. It was excellent in properties.
On the other hand, since Comparative Example 1 is a composition containing GLY-TA4 containing 25% by mass or more of a high molecular weight substance, the inkjet dischargeability was poor. Comparative Examples 2 to 6 are compositions that do not contain the component (A) and contain polyfunctional acrylates other than the component (A). In Comparative Examples 2 and 3, the cured product has scratch resistance and adhesion to PMMA. In Comparative Examples 4 to 6, the universal hardness of the cured product was insufficient or inferior.

3. Examples 9 to 12 and Comparative Examples 7 to 9 [active energy ray-curable composition for ink-jet ink (colored ink)]
1) Manufacture of composition Among the compounds shown in Table 5 below, components other than component (B) are first mixed and dispersed with a bead mill to obtain a pigment dispersion, and then component (B) is stirred and mixed for activity. An energy ray curable coloring composition was produced.
The obtained composition was used and evaluated as described later. The results are shown in Table 6.

The numbers in Table 5 mean the number of copies. The abbreviations in Table 5 mean the following, except for the above.
(1) Component (F) FA5375: C.I. I. Pigment Blue 15: 3, DIC Co., Ltd. Fastogen Blue FA5375

(2) Component (G) -PB821: Pigment dispersant having basic functional group, Ajimoto Fine Techno Co., Ltd. Ajisper PB821

(3) Component (C) IRG819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, IRGACURE819 manufactured by BASF
TPO: diphenyl- (2,4,6-trimethylbenzoyl) -phosphine oxide, LUCIRIN TPO manufactured by BASF
DETX: 2,4-diethylthioxanthone, DETX-s manufactured by Nippon Kayaku Co., Ltd.

2) Evaluation method
(1) The composition physical viscosity was evaluated by the same method as in (a) except that the measurement temperature was 60 ° C.
About the discharge property, it evaluated by the method similar to the said (A) except heating at 60 degreeC. In addition, the discharge property in a 3D inkjet printer is substituted by this evaluation.
The curable, UV-LED irradiator manufactured Sentekku (Ltd.) equipped with a stage moving device (emission wavelength: 385 nm, peak intensity: 540 mW / cm ²⁾ at, so that one pass per 200 mJ / cm ² irradiation Then, the transfer was performed in an air atmosphere, and the number of passes until the surface tack was eliminated was obtained.

(2) Cured material properties
(F) Scratch resistance The obtained composition was applied to PET so as to have a film thickness of 2 μm using the same ink jet printer as (a), and 2) UV-irradiated under the same conditions as in (1), in an air atmosphere Then, it was transported.
The scratch resistance of the obtained cured product was evaluated by the same method as in (c) above.

(G) Hardness The obtained composition was coated on a 10 cm glass substrate with an ink jet printer similar to (a) so as to have a film thickness of 20 μm, and was irradiated with ultraviolet rays under the same conditions as in (f). .
The hardness of the obtained hardened | cured material was evaluated by the method similar to said (D).

(H) Adhesiveness The adhesiveness of the cured product obtained in (f) was evaluated by the same method as in (v) above.

3) Evaluation results As is clear from the results of Examples 9 to 12, the composition of the present invention has a low viscosity and thus is excellent in ink jet ejection properties, curability, scratch resistance of cured products, universal hardness and All of the substrate adhesion was excellent.
On the other hand, since Comparative Example 7 is a composition containing GLY-TA4 containing 25% by area or more of a high molecular weight substance, pigment dispersion without a solvent could not be performed. Moreover, since Comparative Examples 8-9 did not contain (A) component and contained polyfunctional acrylates other than (A) component, any of sclerosis | hardenability, abrasion resistance, and universal hardness was inferior.

  The composition of the present invention relates to a curable composition for inkjet ink, and preferably relates to an active energy ray curable composition for inkjet ink. The pixel and black matrix formation, microlens formation, and three-dimensional modeling can be used.

Claims (22)

It includes a (meth) acrylate mixture (A) containing glycerin tri (meth) acrylate as a main component, and the high molecular weight material in the component (A) is a value obtained by gel permeation chromatography measurement. A curable composition for inkjet inks having an area% of the high molecular weight substance defined by formula (1) of less than 30%.
High molecular weight area% = [(R−IL) / R] × 100 (1)
The symbols and terms in formula (1) mean the following.
-R: Total area of detection peaks in component (A)-I: Area of detection peaks containing glycerin tri (meth) acrylate-L: Detection with a weight average molecular weight smaller than that of detection peaks containing glycerin tri (meth) acrylate Total area of peak 2. The (A) component is a (meth) acrylate mixture containing glycerin tri (meth) acrylate as a main component, obtained by subjecting a compound having glycerin and one (meth) acryloyl group to a transesterification reaction. The curable composition for inkjet ink as described. The component (A) is mainly composed of glycerin tri (meth) acrylate obtained by transesterification of glycerin and a compound having one (meth) acryloyl group in the presence of the following catalysts X and Y. The curable composition for inkjet ink according to claim 2, which is a (meth) acrylate mixture.
Catalyst X: a kind selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof, and phosphine or a salt or complex thereof The above compound.
Catalyst Y: Compound containing zinc. The curable composition for a molding material according to claim 3, wherein the following compound is used as the catalyst X.
Catalyst X: One or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, and a compound having a pyridine ring or a salt or complex thereof. The curable composition for inkjet ink according to any one of claims 2 to 4, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate. The said catalyst Y is organic acid zinc or / and zinc diketone enolate, The curable composition for inkjet inks of any one of Claims 3-5. The curable composition for inkjet ink according to any one of claims 1 to 6, wherein the hydroxyl value of the component (A) is 60 mgKOH / g or less. The viscosity at the temperature at the time of discharge is 5-200 mPa * s, The curable composition for inkjet inks of any one of Claims 1-7. Furthermore, the curable composition for inkjet inks of any one of Claims 1-8 containing the compound (B) which has one (meth) acryloyl group. Furthermore, the compound (B) having one (meth) acryloyl group is included, and as the component (B), one (meth) acryloyl group used in the transesterification reaction present in the reaction solution after the reaction is completed. The curable composition for ink-jet ink according to any one of claims 2 to 9, wherein the compound is used as it is. Furthermore, the curable composition for inkjet inks of any one of Claims 1-10 containing a coloring agent. The curable composition for inkjet ink according to claim 11, wherein the colorant is a pigment and further contains a pigment dispersant. A curable composition for 3D inkjet printer ink comprising the composition according to any one of claims 1 to 12. The active energy ray hardening-type composition for inkjet ink containing the composition of any one of Claims 1-12. Furthermore, the active energy ray hardening-type composition for inkjet inks of Claim 14 containing a photoinitiator (C). An active energy ray-curable composition for 3D inkjet printer ink comprising the composition according to claim 15. The ultraviolet-ray (UV-LED) curable composition which uses LED for inkjet ink containing the composition of Claim 15 as a light source. A (meth) acrylate mixture (A) mainly composed of glycerin tri (meth) acrylate obtained by transesterification of glycerin and a compound having one (meth) acryloyl group in the presence of the following catalysts X and Y The manufacturing method of the curable composition for inkjet inks including the process of manufacturing.
Catalyst X: a kind selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof, and phosphine or a salt or complex thereof The above compound.
Catalyst Y: Compound containing zinc. The method for producing a curable composition for inkjet ink according to claim 18, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate. The catalyst X is one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, and a compound having a pyridine ring or a salt or complex thereof. The manufacturing method of the curable composition for inkjet inks in any one of Claim 18 or Claim 19. The method for producing a curable composition for ink-jet ink according to any one of claims 18 to 20, wherein the catalyst Y is an organic acid zinc or / and a zinc diketone enolate. (A) The manufacturing method of the curable composition for inkjet inks of any one of Claims 18-21 including the process of mixing a photoinitiator (C) after manufacturing a component.