Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
  • C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/12—Esters of phenols or saturated alcohols
  • C08F222/22—Esters containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks

Definitions

• the present invention relates to an amino group-containing polyfunctional (meth)acrylate composition, a novel method for producing an amino group-containing polyfunctional (meth)acrylate, and an ultraviolet curable inkjet ink and curable resin composition containing the composition. .
• Polyfunctional (meth)acrylates having three or more (meth)acryloyl groups are used, for example, in paints, inks, adhesives, pressure-sensitive adhesives, insulating films, protective films, light extraction layers, photo spacers, optical lenses, photoresists, etc. It is widely used as a raw material.
• Patent Document 1 discloses that in order to obtain high-quality (meth)acrylate from which the catalyst has been sufficiently removed, alcohol and monofunctional (meth)acrylate are combined using the following catalyst A and the following catalyst B.
• a method for producing (meth)acrylate is disclosed, which comprises performing a contact treatment with the following adsorbent C on the reaction product of transesterification when producing (meth)acrylate by transesterification. There is.
• Catalyst A cyclic tertiary amine having an azabicyclo structure or a salt thereof or a complex thereof, amidine or a salt thereof or a complex thereof, a compound having a pyridine ring or a salt thereof or a complex thereof, a phosphine or a salt thereof or a complex thereof, a tertiary diamine structure
• Catalyst B One or more compounds selected from the group consisting of compounds containing zinc.
• Adsorbent C one or more compounds selected from the group consisting of oxides and hydroxides containing at least one of magnesium, aluminum, and silicon.
• Patent Document 2 discloses that a compound represented by the following chemical formula 1 is capable of forming a strong structure equivalent to or higher than that of a high-viscosity polyfunctional acrylate while maintaining a low viscosity at the level of a monofunctional or bifunctional compound.
• a method for producing an acrylate compound by reacting trialkanolamine and acrylic acid chloride is disclosed.
• R is hydrogen or a methyl group
• n is an integer from 2 to 6.
• Patent Document 1 when a compound containing zinc is used as a catalyst when performing the transesterification reaction, a large amount of zinc is contained in the resulting polyfunctional (meth)acrylate, and it is difficult to purify it using an adsorbent. Even with treatment, it is difficult to remove zinc sufficiently.
• the zinc content in the polyfunctional (meth)acrylates can be reduced to 0.1 ppm or less (energy-dispersive It is extremely difficult to achieve a value below the detection limit by X-ray (EDX) analysis.
• the transesterification method described in Patent Document 1 not only has low production efficiency due to the long reaction time, but also contains monoesters and diesters as impurities other than zinc in the obtained polyfunctional (meth)acrylate. , and intermediates such as triesters, and oxides obtained by oxidizing polyfunctional (meth)acrylates. Intermediates such as monoesters, diesters, and triesters have a hydroxyl group in their molecules, so they have a high affinity for water and may cause negative effects (such as ion migration) in applications that require insulation.
• the trifunctional acrylate obtained contains chloride and chloride ions as impurities, so metals are They tend to have adverse effects (eg, corrosion of metals, etc.) in the applications in which they are used. Furthermore, the present inventor found that the trifunctional acrylate obtained by the production method described in Patent Document 2 has a problem of a high degree of coloration.
• An amino group-containing polyfunctional (meth)acrylate composition containing an amino group-containing polyfunctional (meth)acrylate represented by the following general formula (1), An amino group-containing polyfunctional (meth)acrylate composition, wherein the content of the amino group-containing polyfunctional (meth)acrylate is 95% by mass or more, and the Hazen unit color number (APHA) of the composition is 200 or less. .
• APHA Hazen unit color number
• R 1 , R 2 and R 3 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms
• R 4 and R 5 are each independently hydrogen or a methyl group
• R 6 is ( It is a meth)acryloyloxy group or an amino group containing a (meth)acryloyloxy group represented by the following general formula (2).
• R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms
• R 9 and R 10 are each independently hydrogen or a methyl group.
• R 1 , R 2 and R 3 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 4 is hydrogen or a methyl group.
• R 1 , R 2 and R 3 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 4 and R 5 are each independently hydrogen or a methyl group.
• R 1 , R 2 , R 3 , R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 4 is hydrogen or a methyl group.
• R 1 , R 2 , R 3 , R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 4 and R 5 are each independently a hydrogen or methyl group.
• R 1 , R 2 and R 3 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 11 is a hydroxy group or a hydroxy group-containing amino group represented by the following general formula (10). It is the basis.)
• R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms.
• R 1 , R 2 and R 3 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms
• R 4 and R 5 are each independently hydrogen or a methyl group
• R 6 is ( It is a meth)acryloyloxy group or an amino group containing a (meth)acryloyloxy group represented by the following general formula (2).)
• R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 9 and R 10 are each independently hydrogen or a methyl group.
• An ultraviolet curable inkjet ink comprising the amino group-containing polyfunctional (meth)acrylate composition according to [1] or [2]. [5]. A curable resin composition comprising the amino group-containing polyfunctional (meth)acrylate composition according to [1] or [2].
• the amino group-containing polyfunctional (meth)acrylate composition of the present invention contains the amino group-containing polyfunctional (meth)acrylate at a high purity of 95% by mass or more, and further contains metals, chlorides, and chloride ions. It contains less impurities such as intermediates such as monoesters, diesters, and triesters, and oxides obtained by oxidizing the amino group-containing polyfunctional (meth)acrylate. Therefore, the amino group-containing polyfunctional (meth)acrylate composition of the present invention has good storage stability and thermal stability, and does not have any adverse effects (for example, metal corrosion) in applications where metal is used.
• the amino group-containing polyfunctional (meth)acrylate composition of the present invention does not have any adverse effects (such as ion migration) in applications where insulation is required, and has a relatively low viscosity, so it has excellent handling and coating properties.
• the amino group-containing polyfunctional (meth)acrylate composition of the present invention has a small amount of impurities, so it has a Hazen unit color number (APHA) of 200 or less, a low degree of coloring, and high transparency.
• APHA Hazen unit color number
• the amino group-containing polyfunctional (meth)acrylate composition of the present invention is also characterized in that the Hazen unit color number (APHA) does not easily change over time.
• the amino group-containing polyfunctional (meth)acrylate which is the main component of the amino group-containing polyfunctional (meth)acrylate composition of the present invention, has a tertiary amino group, it can be polymerized by oxygen during polymerization. It is possible to suppress inhibition and promote the curing reaction. Since the amino group-containing polyfunctional (meth)acrylate composition of the present invention has the various characteristics described above, it can be used as an ultraviolet curable inkjet ink and a curable resin composition (for example, a photosensitive resin composition, a hard coat resin). It is suitably used as a monomer component or a crosslinking component to be incorporated into compositions, pressure-sensitive adhesive compositions, adhesive compositions, etc.
• a curable resin composition for example, a photosensitive resin composition, a hard coat resin
• the above-mentioned polyfunctional (meth)acrylate with high purity and low degree of coloring can be obtained without requiring purification treatments such as distillation, column chromatography, and adsorbent treatment.
• An amino group-containing polyfunctional (meth)acrylate can be produced.
• purification treatment is not essential, so the amino group-containing polyfunctional (meth)acrylate can be produced with high yield and production efficiency. Can be done.
• (meth)acrylate means acrylate and/or methacrylate
• (meth)acryloyl means acryloyl and/or methacryloyl
• (meth)acrylic acid means acrylic acid and/or methacrylic acid.
• the amino group-containing polyfunctional (meth)acrylate composition of the present invention contains 95% by mass or more of the amino group-containing polyfunctional (meth)acrylate represented by the following general formula (1), and has a Hazen unit color of the composition.
• the number (APHA) is 200 or less.
• R 1 , R 2 and R 3 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms
• R 4 and R 5 are each independently hydrogen or a methyl group
• R 6 is ( It is a meth)acryloyloxy group or an amino group containing a (meth)acryloyloxy group represented by the following general formula (2).
• R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms
• R 9 and R 10 are each independently hydrogen or a methyl group.
• R 1 , R 2 , R 3 , R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and an amino group-containing polyfunctional ( From the viewpoint of reducing the viscosity of the meth)acrylate composition, it is preferably an aliphatic hydrocarbon group having 2 to 8 carbon atoms, more preferably an aliphatic hydrocarbon group having 2 to 6 carbon atoms, and even more preferably An aliphatic hydrocarbon group having 2 to 4 carbon atoms, particularly preferably an aliphatic hydrocarbon group having 2 or 3 carbon atoms.
• the aliphatic hydrocarbon group may be linear or branched.
• Examples of the aliphatic hydrocarbon groups include -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -(CH 2 ) 4 -, -CH 2 CH( CH 2 CH 3 )-, -CH 2 CH(CH 3 )CH 2 -, -CH(CH 3 )CH 2 CH 2 -, -(CH 2 ) 5 -, -CH 2 CH(CH 2 CH 2 CH 3 )-, -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, -CH 2 C(CH 3 ) 2 CH 2 -, -(CH 2 ) 6 -, -CH 2 CH 2 CH(CH 2 CH 2 CH 3 )-, -CH 2 CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 2 CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 2 CH 3 )
• amino group-containing polyfunctional (meth)acrylate examples include triethanolamine tri(meth)acrylate, triisopropanolamine tri(meth)acrylate, and 1-[bis(2-hydroxyethyl)amino]-2-propanol tri(meth)acrylate.
• the amino group-containing polyfunctional (meth)acrylate composition of the present invention may contain one type or two or more types of the amino group-containing polyfunctional (meth)acrylate.
• the content of the amino group-containing polyfunctional (meth)acrylate is preferably 96% by mass or more, More preferably, it is 97% by mass or more.
• the content of the amino group-containing polyfunctional (meth)acrylate in the amino group-containing polyfunctional (meth)acrylate composition of the present invention can be determined by gas chromatography, and the measurement conditions are as described in the Examples below. The conditions are as described in .
• the Hazen unit color number is preferably 190 or less, more preferably 180 or less, and further 170 or less, further 160 or less, further 150 or less, further 140 or less, further 130 or less, further 120 or less, further 110 or less, further 100 or less, further 90 or less, further 80 or less, further 70 or less, further 60 or less, further 50 or less , more preferably 40 or less, further preferably 30 or less, further preferably 20 or less, and further preferably 10 or less.
• the Hazen unit color number is based on JIS K 0071-1: 2017 "Color test method for chemical products - Part 1: Hazen unit color number (platinum-cobalt scale)".
• the color of the amino group-containing polyfunctional (meth)acrylate composition is measured using a colorimeter and determined by a calibration curve prepared from a platinum-cobalt color standard solution.
• the amino group-containing polyfunctional (meth)acrylate composition of the present invention has the advantage that the amino When the group-containing polyfunctional (meth)acrylate is a trifunctional (meth)acrylate having three (meth)acryloyloxy groups, monoester body A1 represented by the following general formula (3) and the following general formula (The total content of the diester A2 represented by 4) is preferably 1% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.1% by mass or less, and especially Preferably it is 0.01% by mass or less.
• the monoester A1 and the diester A2 are intermediates produced when synthesizing the trifunctional (meth)acrylate.
• the amino group-containing polyfunctional (meth)acrylate composition of the present invention is characterized in that the amino group-containing polyfunctional (meth)acrylate is a tetrafunctional (meth)acrylate having four (meth)acryloyloxy groups.
• the total content of triester B4 represented by formula (8) is preferably 1% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.1% by mass or less. The content is particularly preferably 0.01% by mass or less.
• the monoester B1, the diester B2, the diester B3, and the triester B4 are intermediates produced when synthesizing the tetrafunctional (meth)acrylate.
• the amino group-containing polyfunctional (meth)acrylate composition of the present invention is a trifunctional (meth)acrylate having three (meth)acryloyloxy groups.
• the total content of triester B4 represented by is preferably 1% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.1% by mass or less, and particularly preferably is 0.01% by mass or less.
• monoester body A1, diester body A2, monoester body B1, diester body B2, diester body B3, and triester body B4 are used when synthesizing the trifunctional (meth)acrylate and the tetrafunctional (meth)acrylate.
• R 1 , R 2 and R 3 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 4 is hydrogen or a methyl group.
• R 1 , R 2 and R 3 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 4 and R 5 are each independently hydrogen or a methyl group.
• R 1 , R 2 , R 3 , R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 4 is hydrogen or a methyl group.
• R 1 , R 2 , R 3 , R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 4 and R 5 are each independently a hydrogen or methyl group.
• R 1 , R 2 , R 3 , R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 4 and R 9 are each independently a hydrogen or methyl group. be.
• R 1 , R 2 , R 3 , R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 4 , R 5 and R 9 are each independently hydrogen or It is a methyl group.
• the content of these intermediates can be determined by gas chromatography similarly to the content of the amino group-containing polyfunctional (meth)acrylate.
• the amino group-containing polyfunctional (meth)acrylate composition of the present invention has a chlorine atom content of 0.07% by mass from the viewpoint of suppressing adverse effects (for example, metal corrosion) in applications where metal is used. It is preferably at most 0.05% by mass, even more preferably at most 0.01% by mass, particularly preferably at most the detection limit by energy dispersive X-ray (EDX) analysis.
• the content of chlorine atoms can be determined by EDX analysis using an energy dispersive X-ray (EDX) analyzer, and the measurement conditions for EDX analysis are the conditions described in the Examples described below.
• the amino group-containing polyfunctional (meth)acrylate composition of the present invention can be produced, for example, by the method described in ⁇ Method for producing amino group-containing polyfunctional (meth)acrylate> below.
• the amino group-containing polyfunctional (meth)acrylate composition of the present invention contains the amino group-containing polyfunctional (meth)acrylate in high purity and has a low degree of coloring, so it can be used as an ultraviolet curable inkjet ink and a curable resin. It is suitably used as a monomer component or a crosslinking component incorporated into compositions (for example, photosensitive resin compositions, hard coat resin compositions, pressure-sensitive adhesive compositions, adhesive compositions, etc.).
• the method for producing an amino group-containing polyfunctional (meth)acrylate represented by the following general formula (1) of the present invention includes an alkanolamine compound represented by the following general formula (9) and (meth)acrylic anhydride. It includes a step of reacting.
• R 1 , R 2 and R 3 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, R 4 and R 5 are each independently hydrogen or a methyl group, and R 6 is ( It is a meth)acryloyloxy group or an amino group containing a (meth)acryloyloxy group represented by the following general formula (2).)
• R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 9 and R 10 are each independently hydrogen or a methyl group.
• R 1 , R 2 and R 3 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and R 11 is a hydroxy group or a hydroxy group-containing amino group represented by the following general formula (10). It is the basis.
• R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms.
• R 1 , R 2 , R 3 , R 7 and R 8 are each independently an aliphatic hydrocarbon group having 2 to 10 carbon atoms. From the viewpoint of reducing the viscosity of the target amino group-containing polyfunctional (meth)acrylate, it is preferably an aliphatic hydrocarbon group having 2 to 8 carbon atoms, more preferably an aliphatic hydrocarbon group having 2 to 6 carbon atoms. It is an aliphatic hydrocarbon group, more preferably an aliphatic hydrocarbon group having 2 to 4 carbon atoms, and particularly preferably an aliphatic hydrocarbon group having 2 or 3 carbon atoms. The aliphatic hydrocarbon group may be linear or branched.
• Examples of the aliphatic hydrocarbon groups include -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -(CH 2 ) 4 -, -CH 2 CH( CH 2 CH 3 )-, -CH 2 CH(CH 3 )CH 2 -, -CH(CH 3 )CH 2 CH 2 -, -(CH 2 ) 5 -, -CH 2 CH(CH 2 CH 2 CH 3 )-, -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, -CH 2 C(CH 3 ) 2 CH 2 -, -(CH 2 ) 6 -, -CH 2 CH 2 CH(CH 2 CH 2 CH 3 )-, -CH 2 CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 2 CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 2 CH 3 )
• alkanolamine compounds include triethanolamine, triisopropanolamine, 1-[bis(2-hydroxyethyl)amino]-2-propanol, 2-[bis(2-hydroxypropyl)amino]ethanol, N, Examples include N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine and N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine.
• One type of the alkanolamine compound may be used, or two or more types may be used in combination.
• the amount of (meth)acrylic anhydride to be used needs to be adjusted appropriately depending on the number of hydroxy groups in the alkanolamine compound used, but it is important to note that the amount of the monoester A1 which is an intermediate in the reaction mixture, the From the viewpoint of reducing the content of the diester A2, the monoester B1, the diester B2, the diester B3, and the triester B4, and from the viewpoint of improving the yield, the hydroxyl contained in the alkanolamine compound It is preferably 1.0 molar equivalent or more, more preferably 1.05 molar equivalent or more, and even more preferably 1.1 molar equivalent or more per molar equivalent of the group.
• the amount of (meth)acrylic anhydride to be used is determined per molar equivalent of hydroxy group possessed by the alkanolamine compound. It is preferably at most 1.5 molar equivalents, more preferably at most 1.4 molar equivalents, even more preferably at most 1.35 molar equivalents. In one embodiment of the present invention, the amount of (meth)acrylic anhydride used is preferably 1.0 to 1.5 molar equivalents, more preferably 1.05 to 1.4 molar equivalents, and even more preferably 1.1 molar equivalents. ⁇ 1.35 molar equivalent.
• a catalyst may be used from the viewpoint of promoting the reaction.
• the catalyst is not particularly limited, and any known catalyst can be used.
• the reaction is performed using (meth)acrylic anhydride as a raw material, the amino group-containing polyfunctional (meth)acrylate as a target product, and the monoester A1, diester A2, and monoester as intermediates. From the viewpoint of suppressing polymerization of B1, the diester B2, the diester B3, the triester B4, etc., it is preferable to carry out in the presence of a polymerization inhibitor (polymerization inhibitor).
• a polymerization inhibitor polymerization inhibitor
• polymerization inhibitor examples include 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl.
• the amount of the polymerization inhibitor used is not particularly limited, but may include the (meth)acrylic anhydride as the raw material, the amino group-containing polyfunctional (meth)acrylate as the target product, the monoester A1 as the intermediate, and the From the viewpoint of suppressing polymerization of the diester A2, the monoester B1, the diester B2, the diester B3, the triester B4, etc., 0.00 parts by mass is added to 100 parts by mass of the alkanolamine compound. It is about 0.001 to 1 part by mass.
• organic solvent may be used in the reaction.
• the organic solvent is not particularly limited, but is preferably an organic solvent that is inactive within the reaction system.
• organic solvents include aliphatic hydrocarbon solvents such as n-hexane, n-heptane, and n-octane; alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; aromatic solvents such as benzene, toluene, and xylene.
• Hydrocarbon solvents such as diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; organic chlorine solvents such as dichloromethane and 1,1-dichloroethane; Nitrile solvents such as acetonitrile and benzonitrile; Ester solvents such as ethyl acetate, butyl acetate, and gamma-butyrolactone; Amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; Organic phosphorus solvents such as triethyl phosphate; dimethyl Examples include organic sulfur solvents such as sulfoxide. These may be used alone or in combination of two or more.
• the amount of the organic solvent used is not particularly limited, but is usually about 1 to 100 parts by weight per 100 parts by weight of the total amount of raw material substrates.
• the order and method of charging each raw material are not particularly limited. It is preferable to charge an alkanolamine compound, a polymerization inhibitor, an organic solvent, etc. into a reactor, and then add (meth)acrylic anhydride dropwise into the reactor.
• the dropping rate of the (meth)acrylic anhydride is not particularly limited, but from the viewpoint of suppressing coloring of the amino group-containing polyfunctional (meth)acrylate that is the target product and from the viewpoint of improving the yield, the alkanolamine compound It is preferably at most 3 molar equivalents/hour, more preferably at most 2.5 molar equivalents/hour, per 1 molar equivalent.
• the dropping rate of (meth)acrylic anhydride is preferably 1 molar equivalent/hour or more, more preferably 1.5 mol per mol equivalent of the alkanolamine compound. equivalent/hour or more.
• the reaction temperature in the reaction is determined from the viewpoint of suppressing coloring of the amino group-containing polyfunctional (meth)acrylate that is the target product, and from the viewpoint of improving the yield.
• the temperature is preferably 30°C or lower, more preferably 25°C or lower.
• the reaction temperature in the reaction is preferably 0°C or higher, more preferably 5°C or higher, from the viewpoint of shortening the reaction time.
• the reaction time (including the time for dropping the (meth)acrylic anhydride) in the above reaction cannot be determined unconditionally as it varies depending on the raw materials, reaction temperature, etc.
• the heating time is preferably 7 hours or less, more preferably 6 hours or less, and still more preferably 5 hours or less. Further, the reaction is usually carried out until the reaction conversion rate reaches 95% or more.
• the reaction conversion rate can be confirmed by, for example, gas chromatography and liquid chromatography.
• the reaction may be carried out in either a flow system or a batch system.
• a washing step may be performed to remove the organic solvent, unreacted raw materials, by-products (for example, (meth)acrylic acid, etc.) from the reaction mixture.
• the amino group-containing polyfunctional (meth)acrylate obtained by the production method of the present invention contains impurities such as metals, chlorides and chloride ions, the monoester A1 as an intermediate, the diester A2, the monoester ester B1, the diester B2, the diester B3, the triester B4, and the oxidized oxide of the amino group-containing polyfunctional (meth)acrylate), and the degree of coloration is low. Therefore, there is no need to perform a separate purification step. However, in order to obtain the amino group-containing polyfunctional (meth)acrylate with higher purity and lower degree of coloring, a purification step may be performed.
• the purification method in the purification step is not particularly limited, and includes, for example, a distillation method, a recrystallization method, a column chromatography method, and an adsorbent treatment method.
• a distillation method examples include simple distillation, precision distillation, thin film distillation, and molecular distillation, and any of these methods can be employed.
• Purification may be performed by combining two or more types of purification methods.
• the purity is 95% by mass or more, furthermore, the purity is 96% by mass or more, and the Hazen unit color number (APHA) is 200 or less, 190 or less, or 180 or less, without performing a purification treatment.
• APHA Hazen unit color number
• the amino group-containing polyfunctional (meth)acrylate having an amino group of 10 or less can be produced with a yield of 85% or more, furthermore, a yield of 90% or more, and with high manufacturing efficiency.
• the purity is 97% by mass or more, and the Hazen unit color number (APHA) is 200 or less, 190 or less, 180 or less, 170 or less, or 160 or less.
• APHA Hazen unit color number
• a group-containing polyfunctional (meth)acrylate can be produced with a yield of 80% or more, and even more with a yield of 83% or more.
• the amino group-containing polyfunctional (meth)acrylate obtained by the production method of the present invention has high purity and a low degree of coloration, so it can be used in ultraviolet curable inkjet inks and curable resin compositions (for example, photosensitive It is suitably used as a monomer component or a crosslinking component blended into resin compositions, hard coat resin compositions, pressure-sensitive adhesive compositions, adhesive compositions, etc.).
• curable resin compositions for example, photosensitive It is suitably used as a monomer component or a crosslinking component blended into resin compositions, hard coat resin compositions, pressure-sensitive adhesive compositions, adhesive compositions, etc.
• the production method of the present invention allows the amino group-containing polyfunctional (meth)acrylate with high purity and low degree of coloring to be obtained, ) is generally not used. That is, since there is no risk of containing coloring components derived from other amine compounds, it is thought that the amino group-containing polyfunctional (meth)acrylate with a low degree of coloring can be obtained even if it
• the ultraviolet curable inkjet ink of the present invention contains at least the amino group-containing polyfunctional (meth)acrylate composition and a photopolymerization initiator.
• the ultraviolet curable inkjet ink of the present invention may contain other polymerizable monomers, sensitizers, sensitization aids, coloring materials (pigments, dyes), dispersants, slip agents (surfactants), wetting agents (if necessary, the composition may contain known components such as a humectant), a surface conditioner, an antioxidant, an ultraviolet absorber, a chelating agent, a pH adjuster, and a stabilizer.
• the curable resin composition of the present invention contains at least the amino group-containing polyfunctional (meth)acrylate composition and a polymer component (for example, an alkali-soluble resin, a curable resin, a base polymer, etc.).
• a polymer component for example, an alkali-soluble resin, a curable resin, a base polymer, etc.
• the curable resin composition include photosensitive resin compositions, hard coat resin compositions, pressure-sensitive adhesive compositions, and adhesive compositions.
• the curable resin composition of the present invention can be used in combination with other polymerizable monomers, radically polymerizable oligomers such as unsaturated polyesters, epoxy acrylates, urethane acrylates, and polyester acrylates, and polymerization initiators (photopolymerization initiators or thermal polymerization initiators). It may contain a photopolymerization initiation agent), a photopolymerization initiation auxiliary agent, a solvent, and the like as necessary.
• the curable resin composition of the present invention also includes fillers such as aluminum hydroxide, talc, clay, and barium sulfate, crosslinking agents, dyes, pigments, antifoaming agents, coupling agents, leveling agents, sensitizers, and release agents.
• fillers such as aluminum hydroxide, talc, clay, and barium sulfate, crosslinking agents, dyes, pigments, antifoaming agents, coupling agents, leveling agents, sensitizers, and release agents.
• fillers such as aluminum hydroxide, talc, clay, and barium sulfate, crosslinking agents, dyes, pigments, antifoaming agents, coupling agents, leveling agents, sensitizers, and release agents.
• Contains known additives such as molding agents, lubricants, plasticizers, stabilizers, antioxidants, ultraviolet absorbers, flame retardants, polymerization inhibitors, thickeners, tackifiers, and dispersants as necessary. You can.
• Examples of cured products obtained by curing the curable resin composition of the present invention include lenses (microlenses), photo spacers, partition materials, insulating films, protective films, hard coat layers, optical waveguide materials, and flattening films. Examples include a material, an adhesive layer, an adhesive layer, and the like.
• Example 1 A reactor equipped with a stirrer, a thermometer, and a dropping funnel was charged with 15.03 g (0.1 mol) of triethanolamine and 30.11 g of tetrahydrofuran. 50.04 g (0.4 mol) of acrylic anhydride was added dropwise into the reactor from the dropping funnel over 2 hours while adjusting the temperature in the reactor to 6 to 11°C using an ice bath. did. After the dropwise addition was completed, the reaction mixture was stirred for 2 hours while controlling the temperature at 11 to 30°C.
• the content of triethanolamine triacrylate was 96% by mass
• the content of triethanolamine diacrylate was 0.7% by mass
• the content of triethanolamine triacrylate was 0.7% by mass. No monoacrylates were detected.
• the measurement conditions for gas chromatography are as follows. The injection port was set at a heater temperature of 280°C, an FID was used as a detector, and the heater temperature was set at 290°C.
• the GC column used was HP-1 manufactured by Agilent.
• the Hazen unit color number (APHA) of the obtained crude product was 25. Furthermore, when we confirmed the change in APHA in the crude product over time under room temperature conditions, we found that the APHA in the crude product gradually increased over time. Specifically, the APHA after 20 days was 42, and the APHA after 30 days was The APHA after 46 and 63 days was 43, and the APHA of the crude product reached its maximum at 30 days and remained almost constant thereafter. From these results, it was found that the maximum value of APHA in the crude product was about 46.
• the Hazen unit color number is the crude product obtained in accordance with JIS K 0071-1:2017 "Color test method for chemical products - Part 1: Hazen unit color number (platinum-cobalt scale)"
• the color of the object was measured using a colorimeter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product number: COH7700), and determined by a calibration curve prepared from a platinum-cobalt color standard solution.
• the content of chlorine atoms was below the detection limit (10 ppm or less).
• the zinc content was below the detection limit (0.1 ppm or less), and the magnesium content was below the detection limit (100 ppm or less).
• the measurement conditions for EDX analysis are as follows. Measurement conditions for EDX analysis: He atmosphere, stock solution, sample container: polypropylene
• the obtained purified product When the obtained purified product was observed, it was found that the coloration was further reduced than that of the crude product. Further, the Hazen unit color number (APHA) of the obtained purified product was smaller than that of the crude product. Furthermore, when the change in APHA of the purified product over time under normal temperature conditions was confirmed, the APHA of the purified product gradually increased over time, but the value was smaller than that of the crude product.
• APHA Hazen unit color number
• Comparative example 1 A reactor equipped with a stirrer, a thermometer, and a dropping funnel was charged with 25.0 g (0.17 mol) of triethanolamine, 71.8 g (0.67 mol) of 2,6-lutidine, and 200 ml of tetrahydrofuran. The temperature inside the reactor was cooled to -5°C using an ice bath. A solution of 50.0 g (0.55 mol) of acrylic acid chloride dissolved in 150 ml of tetrahydrofuran was slowly dropped into the reactor from the dropping funnel over 2 hours. After the dropwise addition was completed, the temperature of the reaction mixture was raised to 24° C. and stirred for 1 hour.
• the temperature of the reaction mixture was raised to 65° C., and the mixture was stirred for 6 hours under reflux conditions of tetrahydrofuran.
• the reaction mixture was cooled to -5°C, a 10% aqueous sodium bicarbonate solution was added, and the organic layer was extracted using ethyl acetate. The organic layer was separated using a separatory funnel, and the separated organic layer was dried over magnesium sulfate. Thereafter, the organic solvent was distilled off from the organic layer under reduced pressure to obtain a crude product (crude triethanolamine triacrylate).
• the Hazen unit color number (APHA) of the purified product was measured using the same method and conditions as in Example 1, and the APHA of the purified product was 266.
• EDX analysis of the obtained purified product using an energy dispersive X-ray (EDX) analyzer revealed that the content of chlorine atoms was 0.079% by mass, and the content of zinc was 0.079% by mass. was below the detection limit (0.1 ppm or less), and the magnesium content was below the detection limit (100 ppm or less).
• the measurement conditions for EDX analysis are the same as in Example 1.
• the amino group-containing polyfunctional (meth)acrylate composition of the present invention can be used in ultraviolet curable inkjet inks and curable resin compositions (for example, photosensitive resin compositions, hard coat resin compositions, adhesive compositions, It is suitably used as a monomer component or a crosslinking component to be blended in (and adhesive compositions, etc.).
• curable resin compositions for example, photosensitive resin compositions, hard coat resin compositions, adhesive compositions, It is suitably used as a monomer component or a crosslinking component to be blended in (and adhesive compositions, etc.).

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