CN113853397A - Urethane (meth) acrylate, neutralized product thereof, photocurable resin composition, and liquid composition - Google Patents

Urethane (meth) acrylate, neutralized product thereof, photocurable resin composition, and liquid composition Download PDF

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CN113853397A
CN113853397A CN202080036783.2A CN202080036783A CN113853397A CN 113853397 A CN113853397 A CN 113853397A CN 202080036783 A CN202080036783 A CN 202080036783A CN 113853397 A CN113853397 A CN 113853397A
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acrylate
meth
urethane
component
diisocyanate
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CN113853397B (en
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石田久宪
畠中瑞生
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Negami Chemical Industrial Co Ltd
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Negami Chemical Industrial Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

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Abstract

A urethane (meth) acrylate according to an embodiment of the present invention is a reaction product of an amino alcohol component (a) having 1 hydroxyl group and 1 or more tertiary amino groups, a diisocyanate component (B), and a (meth) acrylate component (C) having 1 or more hydroxyl groups, the (meth) acrylate component (C) containing dipentaerythritol poly (meth) acrylate (C1) having 1 or more hydroxyl groups, and the urethane (meth) acrylate having a weight average molecular weight of 1000 or more.

Description

Urethane (meth) acrylate, neutralized product thereof, photocurable resin composition, and liquid composition
Technical Field
The present invention relates to a urethane (meth) acrylate, a neutralized product thereof, a photocurable resin composition, and a liquid composition.
The present application claims priority based on Japanese application laid out in Japanese patent application No. 2019-142964, 8/2 in 2019, the contents of which are incorporated herein by reference.
Background
As the photocurable resin, a urethane (meth) acrylate having a urethane bond and a (meth) acryloyl group is known. When a urethane (meth) acrylate is used, the urethane (meth) acrylate is generally diluted with an organic solvent or a reactive diluent. In recent years, it has been studied to dilute urethane (meth) acrylate with water to make it water-soluble.
As an aqueous composition containing a urethane (meth) acrylate, the following compositions are proposed.
(1) An emulsion coating material composition prepared from at least one monomer selected from (meth) acrylates of mono-or polypentaerythritol, a urethane poly (meth) acrylate compound having at least 2 radically polymerizable unsaturated double bonds in 1 molecule, a photopolymerization initiator, a radically polymerizable surfactant, and water (patent document 1).
(2) A photocurable resin composition comprising a polyfunctional urethane acrylate having an oxyalkylene group and a carboxyl group neutralized with an amino compound, a photopolymerization initiator, and water (patent document 2).
(3) An aqueous active energy ray-curable resin composition obtained by producing a carboxyl group-containing urethane (meth) acrylate in the presence of a water-soluble reactive diluent having a water mixing ratio of 100 wt% or more, converting the carboxyl group of the urethane (meth) acrylate into an amine salt, and then adding water to emulsify the amine salt (patent document 3).
(4) A water-dispersible curable resin composition obtained by dispersing at least 1 curable oligomer selected from urethane acrylate and epoxy acrylate in a water solvent in the presence of a reactive emulsifier (patent document 4).
(5) An active energy ray-curable emulsion composition which contains an ethylenically unsaturated monomer and in which a polyfunctional oligomer having 3 to 30 radical-polymerizable unsaturated groups is dispersed in an aqueous solvent in the presence of a polyfunctional reactive surfactant which is a urethane (meth) acrylate compound using a polyalkylene glycol derivative (patent document 5).
Documents of the prior art
Patent document
Patent document 1: japanese unexamined patent publication Hei 9-137081
Patent document 2: japanese unexamined patent publication No. Hei 11-209448
Patent document 3: japanese unexamined patent publication No. Hei 11-279242
Patent document 4: japanese laid-open patent publication No. 2000-159847
Patent document 5: japanese laid-open patent publication No. 2008-303258
Disclosure of Invention
Problems to be solved by the invention
The compositions of patent documents 1 to 5 are all aqueous dispersions, not aqueous solutions, and are insufficient in homogeneity.
The purpose of the present invention is to provide a urethane (meth) acrylate which exhibits water solubility when neutralized, and a neutralized product thereof.
Another object of the present invention is to provide a photocurable resin composition that contains a water-soluble urethane (meth) acrylate and can be solubilized in water, and a liquid composition using the same.
Means for solving the problems
The present invention has the following aspects.
[1] A urethane (meth) acrylate which is a reaction product of an aminoalcohol component (A) having 1 hydroxyl group and 1 or more tertiary amino groups, a diisocyanate component (B), and a (meth) acrylate component (C) having 1 or more hydroxyl groups,
the (meth) acrylate component (C) comprises dipentaerythritol poly (meth) acrylate (C1) having 1 or more hydroxyl groups,
the urethane (meth) acrylate has a weight average molecular weight of 1000 or more.
[2] The urethane (meth) acrylate according to the above [1], wherein the amino alcohol component (A) is at least 1 selected from the group consisting of 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol and 2- (dibutylamino) ethanol.
[3] The urethane (meth) acrylate according to the above [1] or [2], wherein the diisocyanate component (B) is at least 1 selected from the group consisting of an alicyclic diisocyanate compound and an aliphatic diisocyanate compound.
[4] The urethane (meth) acrylate according to any one of the above [1] to [3], wherein the diisocyanate component (B) is at least 1 selected from isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.
[5] A neutralized product obtained by neutralizing a tertiary amino group based on the aminoalcohol component (A) in the urethane (meth) acrylate according to any one of [1] to [4] with a carboxylic acid.
[6] A photocurable resin composition comprising the neutralized product of [5] and a photopolymerization initiator.
[7] The photocurable resin composition according to [6], further comprising a monomer having a polymerizable unsaturated bond.
[8] The photocurable resin composition according to [7], wherein the monomer comprises dipentaerythritol hexa (meth) acrylate.
[9] The photocurable resin composition according to [8], wherein a hydroxyl value of a mixture of the dipentaerythritol poly (meth) acrylate (C1) and the dipentaerythritol hexa (meth) acrylate is 80mgKOH/g or more.
[10] A liquid composition comprising the photocurable resin composition according to any one of [6] to [9] and water.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a urethane (meth) acrylate which exhibits water solubility when neutralized, and a neutralized product thereof can be provided.
The present invention also provides a photocurable resin composition which contains a water-soluble urethane (meth) acrylate and can be made water-soluble, and a liquid composition using the same.
Detailed Description
In the present specification, "(meth) acryloyl group" is a generic name of acryloyl group and methacryloyl group.
"(meth) acrylate" is a generic term for both acrylates and methacrylates.
"urethane (meth) acrylate" is a (meth) acrylate having a urethane bond.
"Poly (meth) acrylate" is a (meth) acrylate having 2 or more (meth) acryloyl groups.
The "weight average molecular weight" (hereinafter, also referred to as "Mw") is a value in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC).
The "hydroxyl value" is the amount of potassium hydroxide required to acetylate hydroxyl groups in a sample, and to neutralize acetic acid used for acetylation, expressed in milligrams relative to 1.0g of the sample, is a standard indicating the content of hydroxyl groups in the sample. Hydroxyl value was measured according to JIS K0070: 1992.
Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.
[ urethane (meth) acrylate ]
A urethane (meth) acrylate (hereinafter, also referred to as "present urethane (meth) acrylate") according to an embodiment of the present invention is a reaction product of an aminoalcohol component (a) (hereinafter, also referred to as "component a"), a diisocyanate component (B) (hereinafter, also referred to as "component B"), and a (meth) acrylate component (C) having 1 or more hydroxyl groups (hereinafter, also referred to as "component C").
The reaction product contains units based on the component (A), units based on the component (B), and units based on the component (C).
< component (A) >
(A) The component (A) has 1 hydroxyl group and 1 or more tertiary amino groups in the molecule.
(A) The number of tertiary amino groups contained in the component (a) is preferably 1 from the viewpoint of water solubility.
The component (A) includes, for example, (R)1)2-N-R2The compounds represented. Here, R is1Represents an alkyl group, R2Represents hydroxyalkyl. 2 of R in the formula1May be the same or different.
R1The polymer may be linear or branched. R1The carbon number of (b) is preferably 1 to 4 from the viewpoint of water solubility.
R2The polymer may be linear or branched. R2The carbon number of (b) is preferably 1 to 4 from the viewpoint of water solubility.
The component (a) is preferably at least 1 selected from the group consisting of 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol and 2- (dibutylamino) ethanol from the viewpoint of water solubility.
(A) The component (A) may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
< ingredient (B) >
The component (B) may be any compound having 2 isocyanate groups (-N ═ C ═ O) in the molecule, and examples thereof include: aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds.
Examples of the aliphatic diisocyanate compound include: hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, methylene diisocyanate, ethylene diisocyanate, butylene diisocyanate, propylene diisocyanate, octadecylene diisocyanate, 1, 4-tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 10-decamethylene diisocyanate.
Examples of the alicyclic diisocyanate compound include: 4,4 '-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2, 4 (or 2,6) -diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, dimer acid diisocyanate, 1, 3-cyclohexylene diisocyanate, 4' -methylene-bis (cyclohexyl isocyanate).
Examples of the aromatic diisocyanate include: toluene diisocyanate, 4 ' -diphenylmethane diisocyanate, xylylene diisocyanate, xylene diisocyanate, dianisidine diisocyanate, phenyl diisocyanate, halogenated phenyl diisocyanate, 1, 5-naphthalene diisocyanate, polymethylene polyphenylene diisocyanate, naphthalene diisocyanate, 3-phenyl-2-ethylene diisocyanate, cumene-2, 4-diisocyanate, 4-methoxy-1, 3-phenylene diisocyanate, 4-ethoxy-1, 3-phenylene diisocyanate, 2,4 ' -diisocyanate diphenyl ether, 5, 6-dimethyl-1, 3-phenylene diisocyanate, 4 ' -diisocyanate diphenyl ether, toluene diisocyanate, xylene diisocyanate, 4, xylene diisocyanate, Benzidine diisocyanate, 9, 10-anthracene diisocyanate, benzyl 4,4 '-diisocyanate, 3' -dimethyl-4, 4 '-diisocyanate diphenylmethane, diphenyl 2, 6-dimethyl-4, 4' -diisocyanate, diphenyl 3,3 '-dimethoxy-4, 4' -diisocyanate, 1, 4-anthracene diisocyanate, phenylene diisocyanate.
The above-mentioned diisocyanate compound may be a biuret compound, an uretate compound, an adduct compound or an allophanate compound.
The component (B) is preferably at least 1 selected from the group consisting of an alicyclic diisocyanate compound and an aliphatic diisocyanate compound, from the viewpoint of suppressing yellowing.
Among the above, at least 1 selected from the group consisting of isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate is preferable.
(B) The component (A) may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
< ingredient (C) >
(C) Component (C) contains dipentaerythritol poly (meth) acrylate (C1) (hereinafter, also referred to as "compound (C1)") having 1 or more hydroxyl groups.
The compound (C1) is a compound in which 2 or more and 5 or less hydroxyl groups among 6 hydroxyl groups of dipentaerythritol are substituted with (meth) acryloyloxy groups. Specifically, there may be mentioned: dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. These compounds (C1) may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
(C) Component (C) preferably contains at least 1 selected from compounds having 2 or more hydroxyl groups, i.e., dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, and dipentaerythritol tetra (meth) acrylate, as the compound (C1), from the viewpoint of water solubility of the neutralized product of the present urethane (meth) acrylate. The larger the number of hydroxyl groups, the more the amount of tertiary amino groups introduced per 1 molecule of the present urethane (meth) acrylate increases, and the higher the water solubility of the neutralized product.
A compound having 2 or more hydroxyl groups and dipentaerythritol tetra (meth) acrylate may also be used in combination as the compound (C1).
(C) Component (C) may further contain a (meth) acrylate having 1 or more hydroxyl groups in addition to the compound (C1). Examples of the (meth) acrylate include: dipentaerythritol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, pentaerythritol di-or tri (meth) acrylate.
The proportion of the compound (C1) to the total mass of the component (C) is preferably 90 mass% or more, more preferably 95 mass% or more, and may be 100 mass%.
The urethane (meth) acrylate has a tertiary amino group derived from the component (A).
The content of the tertiary amino group in the present urethane (meth) acrylate is preferably 0.1 to 6% by mass, more preferably 0.2 to 3% by mass, in terms of the proportion of the nitrogen atom in the tertiary amino group to the total mass of the present urethane (meth) acrylate. When the ratio of the nitrogen atom is not less than the lower limit, the water solubility of the neutralized product of the urethane (meth) acrylate is further excellent. When the ratio of nitrogen atoms is not more than the above upper limit, a cured product having high surface hardness and excellent abrasion resistance and hard coating properties can be easily obtained. The proportion of the nitrogen atoms is determined by calculating the addition ratio.
The urethane (meth) acrylate has a polymerizable unsaturated bond (carbon-carbon double bond) because it has a (meth) acryloyl group derived from the component (C).
The double bond equivalent of the urethane (meth) acrylate is preferably 125 to 250g/mol, more preferably 130 to 200 g/mol. When the double bond equivalent is not less than the lower limit, a cured product having high surface hardness and excellent abrasion resistance and hard coating properties can be easily obtained. If the double bond equivalent is less than the above upper limit, the flexibility is further excellent.
"double bond equivalent" refers to the mass of each 1 mole of double bonds in a compound.
When the number of moles of the component (C) required for producing 1g of the present urethane (meth) acrylate is α mol and the number of polymerizable unsaturated bonds contained in the molecule of the component (C) 1 is β, the double bond equivalent weight is calculated from 1/(α × β).
When a plurality of compounds different in the number of polymerizable unsaturated bonds ((number of (meth) acryloyl groups)) are used in combination as the component (C), β is a weighted average value calculated from the number of polymerizable unsaturated bonds possessed by each compound and the presence ratio (molar ratio) of each compound. The presence ratio of each compound was determined from the addition ratio.
The present urethane (meth) acrylate has Mw of 1000 or more, preferably 1500 or more.
The Mw of the present urethane (meth) acrylate is preferably 10000 or less, and more preferably 2500 or less.
The Mw of the urethane (meth) acrylate is preferably 1000 to 10000, more preferably 1500 to 2500.
< method for producing urethane (meth) acrylate >
The present urethane (meth) acrylate can be produced by reacting (urethanizing) the component (a), (B), and (C). When these components are reacted, the hydroxyl groups of the components (A) and (C) and the isocyanate groups of the component (B) form urethane bonds, thereby producing the present urethane (meth) acrylate.
The reaction temperature of the carbamation reaction is, for example, 50 to 150 ℃ and further 60 to 100 ℃.
The reaction time of the carbamation reaction varies depending on the reaction temperature, the presence or absence of the catalyst, or the type of the catalyst, and is, for example, 6 to 48 hours, and further 12 to 36 hours.
The ratio of each component in the urethanization reaction can be appropriately selected in consideration of the number of hydroxyl groups of the components (a) and (C), physical properties after synthesis, and the like.
(B) The ratio (NCO/OH) of the number of isocyanate groups in component (A) to the total number of hydroxyl groups in component (C) is, for example, 0.5 to 2.
(A) The proportion of the component (C) to the total mass of the component (a), the component (B), and the component (C) is preferably 3 to 30% by mass, and more preferably 3 to 15% by mass.
(B) The proportion of the component (C) to the total mass of the component (a), the component (B), and the component (C) is preferably 7 to 40% by mass, and more preferably 10 to 30% by mass.
(C) The proportion of the component (C) to the total mass of the component (a), the component (B), and the component (C) is preferably 60 to 90% by mass, and more preferably 65 to 85% by mass.
(A) The proportion of the component (C) to the total mass of the components (a) and (C) is preferably 3 to 40% by mass, and more preferably 5 to 20% by mass.
The urethanization reaction can be carried out in the presence of dipentaerythritol hexa (meth) acrylate (hereinafter, also referred to as "dph (m) a").
Compound (C1) is generally produced by esterification of dipentaerythritol with (meth) acrylic acid, and is produced in the form of a mixture with dph (m) a. The mixture may contain a plurality of compounds (C1) having different amounts of (meth) acryloyl groups.
If the above-mentioned urethanization reaction is carried out using a mixture of the compound (C1) and dph (m) a, dph (m) a having no hydroxyl group does not react with the (B) component but remains directly, thereby obtaining a mixture of the present urethane (meth) acrylate and dph (m) a. Dph (m) a in the mixture is not reacted but remains as it is when the present urethane (meth) acrylate in the mixture is neutralized, and therefore can be used as a monomer of the photocurable resin composition.
The hydroxyl value of the mixture of the compound (C1) and DPH (M) A is preferably 80mgKOH/g or more. The higher the hydroxyl number of the mixture, the lower the proportion of DPH (M) A. Dph (m) a alone is not water-soluble, but if the hydroxyl value of the mixture of the compound (C1) and dph (m) a is 80mgKOH/g or more, a mixture of the present urethane (meth) acrylate and dph (m) a is obtained from the mixture, and the mixture of the present urethane (meth) acrylate and dph (m) a obtained by neutralizing the present urethane (meth) acrylate in the mixture easily becomes water-soluble.
The upper limit of the hydroxyl value of the mixture of the compound (C1) and DPH (M) A is not particularly limited, and is, for example, 130 mgKOH/g.
The above-mentioned urethanization reaction is preferably carried out in the presence of a catalyst from the viewpoint of shortening the reaction time. As the catalyst, a known urethanization catalyst can be used, and examples thereof include: organic metal compounds such as dibutyltin acetate, dibutyltin dilaurate and dioctyltin dilaurate; and basic compounds such as triethylenediamine and triethylamine.
The amount of the catalyst to be used can be appropriately adjusted depending on the activity of the catalyst to be used, and is preferably 0.01 to 0.50% by mass, more preferably 0.03 to 0.30% by mass, and still more preferably 0.05 to 0.25% by mass, based on the total mass of the components (a) and (C).
The urethanization reaction is preferably carried out in the presence of a thermal polymerization inhibitor from the viewpoint of suppressing the progress of the reaction of the (meth) acryloyl group. As the thermal polymerization inhibitor, known thermal polymerization inhibitors can be used, and examples thereof include: 2, 6-di-tert-butyl-p-cresol and 4-methoxyphenol.
The amount of the thermal polymerization inhibitor to be used may be appropriately adjusted depending on the activity of the thermal polymerization inhibitor to be used, and is preferably 0.01 to 1.5% by mass, more preferably 0.03 to 1.0% by mass, and still more preferably 0.03 to 0.8% by mass, based on 100% by mass of the reactive product.
In the urethanization reaction, it is preferable that substantially all isocyanate groups in the component (B) are reacted with the component (a) or the component (C).
Measuring the infrared absorption spectrum of the reaction product, wherein the wavelength of 2200 to 2300cm is not observed from the isocyanate residue-1The absorption of (B) can be judged by the reaction of substantially all isocyanate groups in the component (B) with the component (a) or the component (C).
[ neutralization of urethane (meth) acrylate ]
The neutralized product according to an embodiment of the present invention (hereinafter, also referred to as "present neutralized product") is obtained by neutralizing a tertiary amino group based on the component (a) in the present urethane (meth) acrylate with a carboxylic acid. Water solubility is exhibited by neutralization of the tertiary amino group with a carboxylic acid.
In the present neutralized product, the tertiary amino groups may be completely or partially neutralized. From the viewpoint of water solubility, the proportion of the tertiary amino groups neutralized with the carboxylic acid is preferably 80 mol% or more, more preferably 95 mol% or more, and may be 100 mol% based on 100 mol% of all the tertiary amino groups in the present neutralized product. The higher the proportion of tertiary amino groups neutralized with a carboxylic acid, the more excellent the water solubility tends to be.
All the tertiary amino groups in the neutralized product are the total of tertiary amino groups neutralized with a carboxylic acid and tertiary amino groups not neutralized with a carboxylic acid.
The carboxylic acid may be any carboxylic acid having a carboxyl group and capable of neutralizing a tertiary amino group, and examples thereof include: acetic acid, acrylic acid. These carboxylic acids may be used alone in 1 kind, or may be used in combination with 2 or more kinds. The carboxylic acid is preferably acetic acid or acrylic acid from the viewpoint of solubility in water.
The present neutralized product can be produced, for example, by contacting the present urethane (meth) acrylate with an aqueous carboxylic acid solution.
The temperature during the contact is, for example, 20 to 70 ℃. The contact time is, for example, 10 to 60 minutes.
Instead of the present urethane (meth) acrylate, a mixture of the present urethane (meth) acrylate and dph (m) a may also be used. In this case, a mixture of the present neutralized product with dph (m) a can be obtained.
[ Photocurable resin composition ]
A photocurable resin composition according to an embodiment of the present invention (hereinafter, also referred to as "the present resin composition") includes the present neutralized product and a photopolymerization initiator.
The resin composition preferably further contains a monomer having a polymerizable unsaturated bond. The resin composition may further contain other components as required.
When light is irradiated to the present resin composition, intramolecular cleavage or hydrogen migration of the photopolymerization initiator generates active species (radical or cation) which act on the present urethane (meth) acrylate or monomer to cause polymerization or crosslinking reaction, so that the present resin composition is cured.
< photopolymerization initiator >
As the photopolymerization initiator, known photopolymerization initiators can be used, and examples thereof include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, alpha-hydroxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholinyl (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2,4, 6-trimethylbenzoylphenylethoxyphosphine oxide, benzophenone, methyl o-benzoylbenzoate, hydroxybenzophenone, 2-isopropylthioxanthone, methyl o-benzoate, methyl o-benzoylbenzoate, methyl o-benzophenone, methyl ether, ethyl ether, 2-1-2-1-morpholinophenyl-2-1-2-morpholinophenyl-methyl-1-methyl-morpholinophenyl-2-1-2-methyl-morpholinophenyl-1-methyl-1-2-methyl-2-methyl-2-morpholinophenyl-2-methyl-2-methyl-2-methyl-2-morpholinophenyl-methyl-2-methyl-2-, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 2,4, 6-tris (trichloromethyl) -S-triazine, 2-methyl-4, 6-bis (trichloro) -S-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -S-triazine, iron-allene complexes, titanocene compounds. These photopolymerization initiators may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
< monomer >
The monomer may be a monofunctional monomer having 1 polymerizable unsaturated bond, or may be a polyfunctional monomer having 2 or more polymerizable unsaturated bonds. It is also possible to use monofunctional monomers in combination with polyfunctional monomers.
The monomer may be a water-soluble monomer or a water-insoluble monomer. Water-soluble monomers and water-insoluble monomers may also be used in combination. The term "water-soluble monomer" means a monomer which becomes a homogeneous solution when mixed with water.
Examples of monofunctional monomers include: hydroxyl group-containing monofunctional (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate, acryloylmorpholine, dimethylacrylamide, and isobornyl acrylate.
Examples of the polyfunctional monomer include: hydroxyl group-containing polyfunctional (meth) acrylates such as pentaerythritol di-or tri (meth) acrylate, dipentaerythritol di-, tri-, tetra-or penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, DPH (M) A, tripropylene glycol diacrylate and trimethylolpropane triacrylate.
These monomers may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
The monomer preferably contains a polyfunctional monomer from the viewpoint of forming a cured film excellent in surface hardness. The polyfunctional monomer is preferably a monomer having 3 or more polymerizable unsaturated bonds, and particularly preferably dph (m) a from the viewpoint of hardness.
< other ingredients >
As other components, there may be mentioned: additives such as thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial agents, fungicides, antifoaming agents, leveling agents, fillers, tackifiers, adhesion imparting agents, thixotropy imparting agents, luminescent materials, and the like.
< content of each component >
The total content of the urethane (meth) acrylate and the monomer is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, based on the total mass of the resin composition.
The proportion of the present urethane (meth) acrylate to the total content of the present urethane (meth) acrylate and the monomer is preferably 1 to 30% by mass, and more preferably 1 to 20% by mass. When the ratio of the present urethane (meth) acrylate is not less than the lower limit, the present resin composition easily exhibits water solubility even when a water-insoluble monomer (e.g., dph (m) a) is contained as a monomer.
In the case where the monomer comprises dph (m) a, the content of dph (m) a is preferably such an amount that the hydroxyl value of the mixture of the present urethane (meth) acrylate-forming compound (C1) and dph (m) a in the present resin composition becomes 80mgKOH/g or more. The higher the hydroxyl number of the mixture, the lower the proportion of DPH (M) A. DPH (M) A alone is not water-soluble, but if the hydroxyl value of the mixture of the compound (C1) and DPH (M) A is 80mgKOH/g or more, the resin composition easily shows water solubility.
The upper limit of the hydroxyl value of the mixture of the compound (C1) and DPH (M) A is not particularly limited, and is, for example, 130 mgKOH/g.
The content of the photopolymerization initiator is preferably 0.5 to 7.0% by mass, more preferably 1 to 5% by mass, based on the total mass of the resin composition. When the content of the photopolymerization initiator is not less than the lower limit, the photocurable property of the resin composition is more excellent, and when the content is not more than the upper limit, the storage stability of the resin composition is more excellent.
The resin composition can be produced by mixing the urethane (meth) acrylate, the photopolymerization initiator, and, if necessary, the monomer and other components. The mixing order of the components is not particularly limited. When the monomer includes dph (m) a, the resin composition may be produced using a mixture of the present urethane (meth) acrylate and dph (m) a.
The resin composition can be cured by irradiation with light to produce a cured product.
As the light, there can be mentioned: visible light, ultraviolet light, plasma, infrared, ionizing radiation, and the like. Among these lights, ultraviolet rays are preferable from the viewpoint of wide spread of irradiation devices.
The irradiation conditions of light can be appropriately selected according to the light source used. When ultraviolet rays are irradiated, the cumulative light amount is, for example, 50 to 1000mJ/cm2。
[ liquid composition ]
The liquid composition according to one embodiment of the present invention (hereinafter, also referred to as "the present liquid composition") includes the present resin composition and water. Typically, the present liquid composition is in the form of an aqueous solution.
The content of the present resin composition in the present liquid composition is, for example, 10 to 60% by mass based on the total mass of the present liquid composition.
The present liquid composition may optionally further contain a non-reactive diluent other than water. The non-reactive diluent is a compound which has no polymerizable unsaturated bond and is liquid at ordinary temperature. As the other non-reactive diluent, a diluent compatible with water is preferable, and for example, there can be mentioned: methanol, ethanol, isopropanol, propylene glycol monomethyl ether.
In consideration of the concept of aqueous property, the content of the other non-reactive diluent in 100% by mass of the present liquid composition is preferably 15% by mass or less, and particularly preferably 0% by mass.
The present liquid composition can be used, for example, for forming a coating film made of a cured product of the present resin composition. The present liquid composition is applied to the surface of an arbitrary substrate, dried to form a coating film composed of the present resin composition, and the coating film is irradiated with light to be cured, thereby obtaining a coating film (cured coating film) composed of a cured product of the present resin composition.
Examples of the substrate include: resin, film, sheet, and molded article. Examples of the resin include: polyesters such as polyethylene terephthalate (PET), polycarbonate resins, and ABS resins.
As the coating method, a known coating method can be suitably used, and examples thereof include: spray coating, spin coating, gravure coating.
The drying conditions may be any conditions as long as the non-reactive diluent such as water can be removed, and examples thereof include conditions of 0.5 to 10 minutes at 60 to 110 ℃.
The irradiation conditions of light are as described above.
The thickness of the coating film (after drying) can be, for example, 1 to 10 μm.
Examples
The present invention will be specifically described below with reference to examples.
Hereinafter, "part" means "part by mass" and "%" means "% by mass".
"dipentaerythritol acrylate mixture" is a mixture of a plurality of dipentaerythritol acrylates having different numbers of acryloyl groups, and a mixture containing dipentaerythritol polyacrylate having a hydroxyl group and dipentaerythritol hexaacrylate (DPHA) and having a hydroxyl value of 80mgKOH/g is used.
The ratio of urethane acrylate to DPHA in the mixture containing urethane acrylate and DPHA is the area ratio of GPC (gel permeation chromatography).
Production example 1
640 parts of dipentaerythritol acrylate mixture, 42 parts of 2- (dimethylamino) ethanol, 0.2 parts of dibutyltin dilaurate, 0.8 parts of 2, 6-di-tert-butyl-p-cresol, and 136 parts of hexamethylene diisocyanate were put into a four-necked flask equipped with a thermometer, a cooling tube, and a stirring device, and after sufficient stirring, the temperature was raised to 70 ℃ and the mixture was stirred and heated for about 24 hours to effect a reaction. After the reaction, it was confirmed by infrared absorption spectroscopy that the isocyanate residue was not observed gradually. A mixture containing urethane acrylate and DPHA (hereinafter, also referred to as "a mixture containing urethane acrylate and DPHA") was thus obtained. The ratio of urethane acrylate to DPHA in the mixture containing urethane acrylate, DPHA, i.e. urethane acrylate: DPHA is 55: 45.
production example 2 and comparative production examples 1 to 4
A mixture containing urethane acrylate and DPHA was obtained in the same manner as in production example 1, except that the kind and amount of the materials charged into the four-necked flask were changed to the compositions shown in table 1. In comparative production examples 2 to 3, the mixture obtained did not contain DPHA because the comparative product was used instead of the component (C). Table 1 shows the ratio of urethane acrylate to DPHA in the mixture containing urethane acrylate and DPHA in each production example.
[ example 1]
Into a flask equipped with a stirrer, 35 parts of the urethane acrylate-and DPHA-containing mixture obtained in production example 1, 1.1 parts of a photopolymerization initiator (2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, product name "Omnirad 2959" manufactured by IGM Resins b.v., inc. (hereinafter, simply referred to as "Omnirad 2959"), 1.8 parts of 80% acetic acid, and 66 parts of water were charged, and stirred for about 1 hour to obtain a liquid composition. The stirred liquid composition was transparent and pale yellow.
The obtained liquid composition was coated on a film-like easy-to-adhere PET having a thickness of 100 μm so that the film thickness after drying was 5 μm, and dried at 100 ℃ to form a coating film. Thereafter, the coating film was irradiated with a cumulative light amount of 500mJ/cm2Thereby obtaining a cured coating film.
[ examples 2 to 3]
Liquid compositions were obtained in the same manner as in example 1, except that the kinds and amounts of the materials charged into the flasks were changed to the compositions shown in table 2. In Table 2, "ACMO" represents acryloylmorpholine. The stirred liquid composition was transparent and pale yellow.
The obtained liquid composition was coated on a film-like easy-to-adhere PET having a thickness of 100 μm so that the film thickness after drying was 5 μm, and dried at 100 ℃ to form a coating film. Thereafter, the coating film was irradiated with a cumulative light amount of 500mJ/cm2Thereby obtaining a cured coating film.
[ comparative examples 1 to 4]
Liquid compositions were obtained in the same manner as in example 1, except that the kinds and amounts of the materials charged into the flasks were changed to the compositions shown in table 2. The liquid composition still caused phase separation after stirring and did not become transparent.
[ evaluation ]
The following evaluations were made for the liquid compositions and cured coatings of the examples. The results are shown in table 2. In addition, comparative examples 1 to 4 in which the water solubility was evaluated as B were not evaluated except for the water solubility.
< Water solubility >
The water solubility of the photocurable resin composition (the remaining part of the liquid composition of each example after water removal) was evaluated according to the following criteria.
A: the liquid composition became transparent after stirring for about 1 hour, and did not separate after standing for 7 days.
B: the liquid composition did not become transparent after stirring for about 1 hour.
< curability >
The curability of the photocurable resin composition was evaluated according to the following criteria.
A: cumulative light quantity for irradiation 500mJ/cm2The ultraviolet ray of (3) is followed by curing of the coating film.
B: cumulative light quantity for irradiation 500mJ/cm2The coating film was not cured after the UV irradiation.
Here, the occurrence of curing of the coating film was confirmed by the loss of the tacky feel.
Hardness of pencil
The pencil hardness of the surface of the cured coating film was measured in accordance with JIS K5600-5-4.
< leveling >
The leveling property of the liquid composition was evaluated according to the following criteria.
A: when the liquid composition is coated on an easily bondable PET, a cured coating film having a smooth surface can be obtained without causing shrinkage or the like.
B: when the liquid composition is applied to an easily bondable PET, shrinkage or the like occurs, and a cured coating film having a smooth surface cannot be obtained.
[ Table 1]
Figure BDA0003359640180000161
[ Table 2]
Figure BDA0003359640180000162
In examples 1 to 3 using the urethane acrylate-and DPHA-containing mixture obtained in production examples 1 to 2, the photocurable resin composition showed water solubility. The photocurable resin composition is excellent in curability, surface hardness of a cured coating film, and leveling property of a liquid composition.
In comparative examples 1 to 4 using the mixture containing urethane acrylate and DPHA obtained in comparative production examples 1 to 4, the photocurable resin composition did not show water solubility.
[ industrial applicability ]
The urethane (meth) acrylate of the present invention exhibits water solubility when neutralized, and can be solubilized in water. By the aqueous solution, the leveling property is improved as compared with the case of an aqueous dispersion, and the surface smoothness of the coating film and the physical properties (such as surface hardness) of the coating film after curing can be expected to be improved.
The urethane (meth) acrylate of the present invention can be used as a hard coating agent, a crosslinking agent, and the like.

Claims (10)

1. A urethane (meth) acrylate which is a reaction product of an aminoalcohol component (A) having 1 hydroxyl group and 1 or more tertiary amino groups, a diisocyanate component (B), and a (meth) acrylate component (C) having 1 or more hydroxyl groups,
the (meth) acrylate component (C) comprises dipentaerythritol poly (meth) acrylate (C1) having 1 or more hydroxyl groups,
the urethane (meth) acrylate has a weight average molecular weight of 1000 or more.
2. The urethane (meth) acrylate according to claim 1, wherein the amino alcohol component (a) is at least 1 selected from the group consisting of 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, and 2- (dibutylamino) ethanol.
3. The urethane (meth) acrylate according to claim 1 or 2, wherein the diisocyanate component (B) is at least 1 selected from the group consisting of an alicyclic diisocyanate compound and an aliphatic diisocyanate compound.
4. The urethane (meth) acrylate according to claim 1 or 2, wherein the diisocyanate component (B) is at least 1 selected from the group consisting of isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.
5. A neutralized product obtained by neutralizing a tertiary amino group based on the aminoalcohol component (A) in the urethane (meth) acrylate according to any one of claims 1 to 4 with a carboxylic acid.
6. A photocurable resin composition comprising the neutralized product according to claim 5 and a photopolymerization initiator.
7. The photocurable resin composition according to claim 6, further comprising a monomer having a polymerizable unsaturated bond.
8. The photocurable resin composition according to claim 7, wherein the monomer comprises dipentaerythritol hexa (meth) acrylate.
9. The photocurable resin composition according to claim 8, wherein a hydroxyl value of a mixture of the dipentaerythritol poly (meth) acrylate (C1) and the dipentaerythritol hexa (meth) acrylate is 80mgKOH/g or more.
10. A liquid composition comprising the photocurable resin composition according to any one of claims 6-9 and water.
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* Cited by examiner, † Cited by third party
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JP2010202777A (en) * 2009-03-04 2010-09-16 Toyo Ink Mfg Co Ltd Active energy line curable composition
CN103387655A (en) * 2012-05-08 2013-11-13 长春市三化实业有限责任公司 Aqueous ultraviolet-curable automotive varnish and preparation method thereof
WO2014106939A1 (en) * 2013-01-07 2014-07-10 宇部興産株式会社 Aqueous resin dispersion and use of same
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