CN112239599A - Active energy ray-curable resin composition, aqueous resin composition, coating agent composition, cured film, and film - Google Patents

Active energy ray-curable resin composition, aqueous resin composition, coating agent composition, cured film, and film Download PDF

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CN112239599A
CN112239599A CN202010673277.6A CN202010673277A CN112239599A CN 112239599 A CN112239599 A CN 112239599A CN 202010673277 A CN202010673277 A CN 202010673277A CN 112239599 A CN112239599 A CN 112239599A
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meth
acrylate
resin composition
active energy
energy ray
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CN112239599B (en
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木村和毅
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Arakawa Chemical Industries Ltd
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Arakawa Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • 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
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • 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

Abstract

The subject is as follows: provided is an active energy ray-curable resin composition which can be easily dispersed in water without using a special dispersing device and which can form a cured film having excellent hardness and abrasion resistance. The solution is as follows: an active energy ray-curable resin composition comprising a polyurethane (meth) acrylate (A) which is a reaction product of a hydroxyl group-containing (meth) acrylate (a1), a polyisocyanate (a2) and a hydroxyl group-containing polyalkylene glycol (a3), and a polyfunctional (meth) acrylate (B) having a hydroxyl value of 80 to 300 mgKOH/g.

Description

Active energy ray-curable resin composition, aqueous resin composition, coating agent composition, cured film, and film
Technical Field
The present invention relates to an active energy ray-curable resin composition, an active energy ray-curable aqueous resin composition, a coating agent composition, a cured film, and a film.
Background
The active energy ray-curable resin composition generally contains a reactive oligomer and a reactive diluent, and is excellent in safety because it does not contain a solvent, and is also generally considered to be a characteristic substance from the viewpoint of productivity and energy saving because it is excellent in curability.
The active energy ray-curable resin composition may need to have a low viscosity depending on the application, and in this case, a method of using a large amount of a reactive diluent or using an organic solvent in combination is employed. However, when a large amount of the reactive diluent is used, curability is reduced, and it is difficult to obtain sufficient physical properties of the coating film; in addition, when an organic solvent is used in combination, the risk of air pollution or fire is increased. Although reactive diluents having high dilution performance have been developed, there is a limit to the reduction in viscosity of active energy ray-curable resin compositions. Therefore, when the active energy ray-curable resin composition is used in applications requiring a low viscosity, such as a film hard coat coating material, an inkjet ink, and a spray coating material, which are applied to a gravure coater, a spin coater, and the like, the resin composition is often diluted with an organic solvent and used.
In recent years, there has been an increasing demand for an aqueous active energy ray-curable resin composition from the viewpoints of handling and safety. For example, patent documents 1 and 2 propose active energy ray-curable resin compositions that are reduced in viscosity by being dissolved or dispersed in water (see patent documents 1 and 2).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 6-136015
Patent document 2: japanese laid-open patent publication No. 6-287260
Disclosure of Invention
Technical problem to be solved by the invention
However, the active energy ray-curable resin compositions of patent documents 1 and 2 are not suitable for applications such as hard coatings because the hardness and abrasion resistance of the resulting cured films are insufficient. In addition, in the active energy ray-curable resin composition, there are cases where the viscosity rises sharply upon water dispersion, and in such cases, it is necessary to disperse water using a special dispersing device, and thus it is difficult to make the active energy ray-curable resin composition aqueous.
The present invention addresses the problem of obtaining an active energy ray-curable resin composition that can be easily dispersed in water without using a special dispersing device and that can form a cured film having excellent hardness and abrasion resistance.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by an active energy ray-curable resin composition comprising a polyurethane (meth) acrylate which is a reaction product of a predetermined hydroxyl group-containing (meth) acrylate, a polyisocyanate and a hydroxyl group-containing polyalkylene glycol, and a specific polyfunctional (meth) acrylate having a high hydroxyl value, and have completed the present invention.
Specifically, the present inventors have found that an active energy ray-curable resin composition which can be easily dispersed in water without using a special dispersing device, can be reduced in viscosity, and can form a cured film excellent in hardness and abrasion resistance can be obtained by using the polyurethane (meth) acrylate and the polyfunctional (meth) acrylate in combination. Namely, the present invention relates to the following active energy ray-curable resin composition.
1. An active energy ray-curable resin composition comprising:
a polyurethane (meth) acrylate (a) which is a reaction product of reaction components containing a hydroxyl group-containing (meth) acrylate (a1), a polyisocyanate (a2) and a hydroxyl group-containing polyalkylene glycol (a 3); and
a polyfunctional (meth) acrylate (B) having a hydroxyl value of 80 to 300 mgKOH/g.
2. The active energy ray-curable resin composition according to claim 1, wherein the component (a1) is a hydroxyl group-containing (meth) acrylate having at least 3 (meth) acryloyl groups in the molecule.
3. The active energy ray-curable resin composition according to item 1 or 2, wherein the component (a2) is a polyisocyanate having at least 3 isocyanate groups in the molecule.
4. The active energy ray-curable resin composition according to any one of the above items 1 to 3, wherein the component (a3) is a compound represented by the following general formula (1):
(formula 2)
H-(OCH2CH2)n-OR (1)
Wherein R represents any one of an alkyl group, an allyl group, a (meth) acryloyl group and an acyl group, and n represents an integer of 3 to 25.
5. The active energy ray-curable resin composition according to any one of the above items 1 to 4, wherein the component (B) is pentaerythritol poly (meth) acrylate and/or glycerol poly (meth) acrylate having a hydroxyl value of 80 to 300 mgKOH/g.
6. The active energy ray-curable resin composition according to any one of the above items 1 to 5, wherein the hydroxyl value of the component (B) is 200 to 300 mgKOH/g.
7. The active energy ray-curable resin composition according to any one of items 1 to 6, wherein the content of the component (B) is 10 to 70 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B) in terms of solid content.
8. An active energy ray-curable aqueous resin composition comprising the active energy ray-curable resin composition according to any one of the above items 1 to 7 and water.
9. A coating agent composition comprising the active energy ray-curable aqueous resin composition described in the above item 8.
10. A cured film formed from the coating agent composition as described in the above item 9.
11. A film comprising the cured film as described in item 10 above.
Advantageous effects
The active energy ray-curable resin composition of the present invention can be dispersed with only water, and therefore, in applications where a low viscosity is required, the handling safety is high as compared with the case where an organic solvent is used. In addition, since the resin composition suppresses a change in viscosity in water dispersion, water dispersion can be easily performed without using a special dispersing device. In addition, the resin composition can form a cured film having excellent hardness and abrasion resistance, and is therefore useful as a coating agent for a hard coating layer or the like.
Detailed Description
[ active energy ray-curable resin composition ]
The active energy ray-curable resin composition of the present invention comprises a specific polyurethane (meth) acrylate (A) (hereinafter referred to as component (A)) and a polyfunctional (meth) acrylate (B) (hereinafter referred to as component (B)) having a hydroxyl value of 80 to 300 mgKOH/g.
In the present specification, "(meth) acrylic acid" ("(メタ) アクリル") means "at least one selected from the group consisting of acrylic acid and methacrylic acid". Likewise, "(meth) acrylate" means "at least one selected from the group consisting of acrylate and methacrylate", and "(meth) acryl" means "at least one selected from the group consisting of acryl and methacryl".
< polyurethane (meth) acrylate (A) >
The component (a) is not particularly limited as long as it is a reaction product of a reaction component (hereinafter also simply referred to as a reaction component) containing a hydroxyl group-containing (meth) acrylate (a1) (hereinafter referred to as a component (a1)), a polyisocyanate (a2) (hereinafter referred to as a component (a2)), and a hydroxyl group-containing polyalkylene glycol (a3) (hereinafter referred to as a component (a 3)).
(hydroxyl group-containing (meth) acrylate (a1))
Any known compound having at least 1 hydroxyl group and at least 1 (meth) acryloyl group in the molecule can be used as the component (a1), without any particular limitation. (a1) One of the components may be used alone, or two or more of the components may be used in combination. The component (a1) may be the same as the component (B) described later.
From the viewpoint of excellent hardness and abrasion resistance of the obtained cured film, the larger the number of (meth) acryloyl groups in the molecule in the component (a1), the better. The number of (meth) acryloyl groups in the molecule of component (a1) is usually about 1 to 5 from the viewpoint of easy availability.
(a1) Examples of the component (A) include hydroxyl group-containing glycerol poly (meth) acrylate, hydroxyl group-containing polyglycerol poly (meth) acrylate, hydroxyl group-containing pentaerythritol poly (meth) acrylate, hydroxyl group-containing polypentaerythritol poly (meth) acrylate, hydroxyl group-containing trimethylolpropane poly (meth) acrylate, hydroxyl group-containing mono (meth) acrylate and the like.
Examples of the hydroxyl group-containing glycerol poly (meth) acrylate include glycerol di (meth) acrylate; and a mixture of at least two selected from the group consisting of glycerol mono (meth) acrylate, glycerol di (meth) acrylate, and glycerol tri (meth) acrylate, and the like.
Examples of the above-mentioned hydroxyl group-containing polyglycerol poly (meth) acrylate include diglycerol di (meth) acrylate, diglycerol tri (meth) acrylate, triglycerol di (meth) acrylate, triglycerol tri (meth) acrylate, triglycerol tetra (meth) acrylate, and the like.
Examples of the hydroxyl group-containing pentaerythritol poly (meth) acrylate include pentaerythritol di (meth) acrylate and pentaerythritol tri (meth) acrylate; and a mixture of at least two selected from the group consisting of pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate, and the like.
Examples of the hydroxyl group-containing polypentaerythritol poly (meth) acrylate include dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol di (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and mixtures of at least two kinds selected from these (meth) acrylates; mixtures of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and the like.
Examples of the above-mentioned hydroxyl group-containing trimethylolpropane poly (meth) acrylate include trimethylolpropane di (meth) acrylate and the like.
Examples of the above-mentioned hydroxyl group-containing polytrimethylolpropane poly (meth) acrylate include ditrimethylolpropane di (meth) acrylate and ditrimethylolpropane tri (meth) acrylate.
Examples of the hydroxyl group-containing mono (meth) acrylate include hydroxyl group-containing linear alkyl (meth) acrylate, hydroxyl group-containing linear alkyl (meth) acrylate caprolactone adduct, hydroxyl group-containing branched alkyl (meth) acrylate caprolactone adduct, hydroxyl group-containing cycloalkyl (meth) acrylate caprolactone adduct, polyalkylene glycol mono (meth) acrylate caprolactone adduct, glycerin mono (meth) acrylate, and the like.
Examples of the hydroxyl group-containing linear alkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the hydroxyl group-containing linear alkyl (meth) acrylate caprolactone adduct include a 3-hydroxypropyl (meth) acrylate caprolactone adduct, a 2-hydroxyethyl (meth) acrylate caprolactone adduct, and a 4-hydroxybutyl (meth) acrylate caprolactone adduct.
Examples of the branched alkyl (meth) acrylate containing a hydroxyl group include 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) acrylate.
Examples of the hydroxyl group-containing branched alkyl (meth) acrylate caprolactone adduct include a 2-hydroxypropyl (meth) acrylate caprolactone adduct, a 2-hydroxybutyl (meth) acrylate caprolactone adduct, and a 3-hydroxybutyl (meth) acrylate caprolactone adduct.
Examples of the above-mentioned cycloalkyl (meth) acrylate containing a hydroxyl group include hydroxycyclohexyl (meth) acrylate and the like.
Examples of the above-mentioned cycloalkyl (meth) acrylate caprolactone adduct containing a hydroxyl group include hydroxycyclohexyl (meth) acrylate caprolactone adduct and the like.
Examples of the polyalkylene glycol mono (meth) acrylate caprolactone adduct include polyethylene glycol mono (meth) acrylate caprolactone adduct and polypropylene glycol mono (meth) acrylate caprolactone adduct.
The component (a1) is preferably a hydroxyl group-containing (meth) acrylate having at least 3 (meth) acryloyl groups in the molecule, more preferably a hydroxyl group-containing (meth) acrylate having 1 hydroxyl group and at least 3 (meth) acryloyl groups in the molecule, from the viewpoint of excellent curability and solvent resistance of the cured film. The hydroxyl group-containing (meth) acrylate is preferably pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, a mixture of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate, or a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
The content of the component (a1) in the reaction components is not particularly limited, and is preferably about 20 to 80 mass%, and more preferably about 30 to 70 mass% in terms of solid content relative to 100 mass% of the reaction components, from the viewpoint of an excellent balance between hardness and abrasion resistance of the cured film.
(polyisocyanate (a2))
Any known compound can be used as the component (a2) without any particular limitation as long as it has at least 2 isocyanate groups in the molecule. The polyisocyanate may be used alone or in combination of two or more.
(a2) Examples of the component (A) include linear aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, biuret forms, isocyanurate forms, allophanate forms, and adduct forms of these diisocyanates; and a complex obtained by reacting two or more selected from the group consisting of a biuret form, an isocyanurate form, an allophanate form and an adduct form.
Examples of the linear aliphatic diisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate.
Examples of the branched aliphatic diisocyanate include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.
Examples of the alicyclic diisocyanate include hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, tricyclodecylene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and bicyclodecylene diisocyanate.
Examples of the aromatic diisocyanate include dialkyl diphenylmethane diisocyanates such as 4, 4' -diphenyldimethylmethane diisocyanate; tetraalkyldiphenylmethane diisocyanates such as 4, 4' -diphenyltetramethylmethane diisocyanate; 4,4 '-diphenylmethane diisocyanate, 4' -dibenzyl diisocyanate, 1, 3-phenylene diisocyanate (1, 3- フェニレンジイソシアネート), 1, 4-phenylene diisocyanate, toluene diisocyanate (トリレンジイソシアネート), xylene diisocyanate (キシリレンジイソシアネート), m-tetramethylxylene diisocyanate, 1, 5-naphthylene diisocyanate (1, 5- ナフチレンジイソシアネート), and the like.
The biuret form of the diisocyanate includes compounds represented by the following structural formula:
[ solution 1]
Figure BDA0002583124080000081
{ formula (II) wherein nbIs an integer of 1 or more; rbA～RbEEach independently is any one of a straight-chain aliphatic diisocyanate residue, a branched-chain aliphatic diisocyanate residue, an alicyclic diisocyanate residue and an aromatic diisocyanate residue; rbα～RbβEach independently is an isocyanate group or
[ solution 2]
Figure BDA0002583124080000082
(nb1Is an integer of 0 or more; rb1～Rb5And RbA～RbEThe same; rb’～Rb"are each independently an isocyanate group or Rbα～RbβA group of itself. For each structural unit, Rb4～Rb5、RbThe "groups may also be different. )
For each structural unit, RbD～RbE、RbβThe groups of (a) may also be different. }.
Specifically, examples of the biuret form of the diisocyanate include Duranate (デュラネ - ト)24A-100 and Duranate 22A-75P, Duranate 21S-75E (manufactured by Asahi Kasei corporation, supra); desmodur (デスモジュール) N3200A (biuret form of hexamethylene diisocyanate) (manufactured by Sumitomo バイエルウレタン, Inc.) and the like.
The isocyanurate form of the diisocyanate includes a compound represented by the following structural formula:
[ solution 3]
Figure BDA0002583124080000091
{ formula (II) wherein niIs an integer of 0 or more; riA～RiEEach independently is any one of a straight-chain aliphatic diisocyanate residue, a branched-chain aliphatic diisocyanate residue, an alicyclic diisocyanate residue and an aromatic diisocyanate residue; riα～RiβEach independently is an isocyanate group or
[ solution 4]
Figure BDA0002583124080000092
(ni1Is an integer of 0 or more; ri1～Ri5And RiA～RiEThe same; ri’～Ri"are each independently an isocyanate group or Riα～RiβA group of itself. For each structural unit, Ri4～Ri5、RiThe "groups may also be different. )
For each structural unit, RiD～RiE、RiβThe groups of (a) may also be different. }.
Specifically, the isocyanurate form of the diisocyanate includes Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, and Duranate MHG-80B (manufactured by Asahi Kasei corporation); coronate (コロネート) HXR, Coronate HX (above in the form of the isocyanurate of hexamethylene diisocyanate) (above manufactured by imperial ソー strain); takenate (タケネート) D-127N (the isocyanurate form of hydrogenated xylene diisocyanate) (manufactured by Mitsui Chemicals, Inc.) was used; VESTANAT T1890/100 (isocyanurate form of isophorone diisocyanate) (manufactured by Evonik Japan (エボニック. ジャパン, Inc.) and the like.
The allophanate form of the diisocyanate includes a compound represented by the following structural formula:
[ solution 5]
Figure BDA0002583124080000101
{ formula (II) wherein naIs an integer of 0 or more; raAIs an alkyl group, an aryl group, a polyether group, a polyester group or a polycarbonate group; raB～RaGEach independently is any one of a straight-chain aliphatic diisocyanate residue, a branched-chain aliphatic diisocyanate residue, an alicyclic diisocyanate residue and an aromatic diisocyanate residue; raα～RaγEach independently is an isocyanate group or
[ solution 6]
Figure BDA0002583124080000102
(na1Is an integer of 0 or more; ra1～Ra6And RaB～RaGThe same; ra’～Ra"' are each independently an isocyanate group or Raα～RaγA group of itself. For each structural unit, Ra1～Ra4、Ra’～RaThe "groups may also be different. )
For each structural unit, RaB～RaE、Raα～RaβThe groups of (a) may also be different. }.
Specifically, examples of the allophanate form of the diisocyanate include Coronate 2793 (manufactured by Egyptian ソー Co., Ltd.), Takenate D-178N (manufactured by Mitsui chemical Co., Ltd.), and the like.
The above adduct form of the above diisocyanate is exemplified by an adduct form of trimethylolpropane and diisocyanate represented by the following structural formula:
[ solution 7]
Figure BDA0002583124080000111
{ formula (II) wherein nadIs an integer of 0 or more; radA～RadEIndependently of each other, a straight-chain aliphatic diisocyanate residue, a branched-chain aliphatic diisocyanate residue, an alicyclic diisocyanateAny one of an acid ester residue and an aromatic diisocyanate residue; rad1～Rad2Each independently is
[ solution 8]
Figure BDA0002583124080000112
(in the formula, nad’Is an integer of 0 or more; rad’～RadAnd RadA～RadEThe same; rad”’Is Rad1～Rad2A group of itself; for each structural unit, Rad’～Rad”’The groups of (a) may also be different. ) For each structural unit, RadD～RadE、Rad2The groups of (a) may also be different. };
an adduct form of glycerol and a diisocyanate represented by the following structural formula:
[ solution 9]
Figure BDA0002583124080000113
{ formula (II) wherein nad1Is an integer of 0 or more; radα～RadεEach independently is any one of a straight-chain aliphatic diisocyanate residue, a branched-chain aliphatic diisocyanate residue, an alicyclic diisocyanate residue and an aromatic diisocyanate residue; radA～RadBEach independently is
[ solution 10]
Figure BDA0002583124080000121
(in the formula, nad1’Is an integer of 0 or more; radδ’～Radε’And Radα～RadεThe same; radB’Is RadA～RadBA group of itself; for each structural unit, Radδ’～Radε’、RadB’The groups of (a) may also be different. ) For each structural unit, Radδ～Radε、RadBThe groups of (a) may also be different. And so on.
Specifically, the adduct form of the diisocyanate is Duranate P301-75E (manufactured by Asahi Kasei corporation, supra); takenate D-110N and Takenate D-160N (manufactured by Mitsui Chemicals, Inc.); coronate L and Coronate HL (manufactured by imperial ソー, imperial arts).
In the above formulae, the expression "straight-chain aliphatic diisocyanate residue, branched-chain aliphatic diisocyanate residue, alicyclic diisocyanate residue and aromatic diisocyanate residue" means the remaining groups of the straight-chain aliphatic diisocyanate, the branched-chain aliphatic diisocyanate, the alicyclic diisocyanate and the aromatic diisocyanate except the isocyanate group.
The component (a2) is preferably a polyisocyanate having at least 3 isocyanate groups in the molecule, from the viewpoint of an excellent balance between hardness and abrasion resistance of the cured film. The polyisocyanate having at least 3 isocyanate groups in the molecule is preferably the biuret form, the isocyanurate form, the allophanate form, or the adduct form.
(a2) The content of the isocyanate group (NCO%) in the component (a) is not particularly limited, but is preferably about 10 to 30% from the viewpoint of excellent balance between hardness and abrasion resistance of the cured film.
(a2) The molar ratio (NCO/OH) of the isocyanate group contained in component (a1) to the hydroxyl group contained in component (a1) is not particularly limited, but is preferably about 1.2 to 6.0, more preferably about 1.5 to 3.0, from the viewpoint of excellent balance between hardness and abrasion resistance of the cured film.
The content of the component (a2) in the reaction components is not particularly limited, but is preferably about 15 to 75 mass%, more preferably about 15 to 60 mass% in terms of solid content, relative to 100 mass% of the reaction components, from the viewpoint of an excellent balance between hardness and abrasion resistance of the cured film.
(hydroxyl-containing polyalkylene glycols (a3))
The component (a3) is not particularly limited and various known components can be used as long as they are polyalkylene glycols having at least 1 hydroxyl group in the molecule. (a3) One of the components may be used alone, or two or more of the components may be used in combination.
(a3) Examples of the component (A) include polyalkylene glycol, polyalkylene glycol monoalkyl ether, polyalkylene glycol mono (meth) acrylate, polyalkylene glycol monoallyl ether, and polyalkylene glycol monoacid ester (ポリアルキレングリコールモノアシレート).
Examples of the polyalkylene glycol include polyether glycol having at least one structure of polyethylene glycol, polypropylene glycol, polybutylene glycol, ethylene oxide/propylene oxide/butylene oxide block or random copolymer, polyoxytetramethylene glycol (ポリオキシテトラメチレングリコール), polyethylene glycol polypropylene glycol polyethylene glycol (block copolymer), polypropylene glycol polyethylene glycol polypropylene glycol (block copolymer), polyethylene glycol polypropylene glycol (random copolymer), polyoxytetramethylene glycol polyethylene glycol polyoxytetramethylene glycol (block copolymer), polyethylene glycol polyoxytetramethylene glycol polyethylene glycol (random copolymer), polypropylene glycol polyoxytetramethylene glycol polypropylene glycol (block copolymer), polyoxytetramethylene glycol polypropylene glycol polyoxytetramethylene glycol (block copolymer), Polypropylene glycol polyoxytetramethylene glycol (random copolymer), and the like.
Examples of the polyalkylene glycol monoalkyl ether include polyethylene glycol derivatives such as polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monobutyl ether, polyethylene glycol monopentyl ether, polyethylene glycol monohexyl ether, polyethylene glycol monoheptyl ether, polyethylene glycol monooctyl ether, polyethylene glycol lauryl ether, polyethylene glycol cetyl ether, polyethylene glycol stearyl ether, polyethylene glycol nonylphenyl ether, polyethylene glycol tridecyl ether, polyethylene glycol oleyl ether, polyethylene glycol octylphenyl ether, and polyoxyethylene oleyl cetyl ether (ポリオキシエチレンオレイルセチルエーテル); polypropylene glycol derivatives such as polypropylene glycol monomethyl ether.
Examples of the polyalkylene glycol mono (meth) acrylate include polyethylene glycol derivatives such as polyethylene glycol mono (meth) acrylate; polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate; polyethylene glycol polypropylene glycol mono (meth) acrylate, poly (ethylene glycol tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol tetramethylene glycol) mono (meth) acrylate, and the like.
Examples of the polyalkylene glycol monoallyl ether include polyethylene glycol derivatives such as polyethylene glycol monoallyl ether; polypropylene glycol derivatives such as polypropylene glycol monoallyl ether; polyethylene glycol polypropylene glycol monoallyl ether, and the like.
Examples of the polyalkylene glycol monoacid ester include polyethylene glycol derivatives such as polyethylene glycol monolaurate, polyethylene glycol monostearate, and polyethylene glycol monooleate.
The component (a3) is preferably a compound represented by the following general formula (1) from the viewpoint of excellent water dispersibility.
(chemical formula 13)
H-(OCH2CH2)n-OR (1)
Wherein R represents any one of an alkyl group, an allyl group, a (meth) acryloyl group and an acyl group, and n represents an integer of 3 to 25.
From the viewpoint of excellent water dispersibility, polyethylene glycol monomethyl ether and polyethylene glycol mono (meth) acrylate are particularly preferable as the component (a 3).
(a3) Examples of commercially available products of the component (A) include PEG #200T, PEG #200, PEG #300, PEG #400, PEG #600, PEG #1000, PEG #1500, PEG #1540, PEG #2000, PEG #4000P, PEG #6000, PEG #6000P, PEG #11000, PEG #20000, Uniox (ユニオックス) M-400, Uniox M-550, Uniox M-1000, Uniox M-2000, Uniox M-2500, Uniox M-3000, Uniox M-4000, Blemmer (ブレンマー) PE-90, Blemmer PE-200, Blemmer PE-300, Blemmer AE-90, Blemmer AE-200, and Blemmer AE-400 (manufactured by Nizhi oil Co., Ltd.).
(a3) The physical properties of the components are not particularly limited. The hydroxyl value (JIS K0070; the same shall apply hereinafter to the hydroxyl value) of the component (a3) is preferably about 10 to 300mgKOH/g, and from the same viewpoint, more preferably about 30 to 140mgKOH/g, from the viewpoint of excellent water dispersibility.
The number average molecular weight of the component (a3) is preferably about 200 to 3,000, more preferably about 400 to 2,000, from the viewpoint of excellent balance between water dispersibility and hardness and abrasion resistance of the cured film. The number average molecular weight is a polystyrene equivalent value in gel permeation chromatography, but the measurement method is not particularly limited, and various known methods may be used, or a commercially available measuring instrument may be used.
The amount of the component (a3) in the reaction components is not particularly limited, but is preferably about 5 to 50 mass%, more preferably about 10 to 30 mass%, in terms of solid content, relative to 100 mass% of the reaction components, from the viewpoint of excellent water dispersibility. When the amount of the component (a3) used is 5% by mass or more, the aqueous resin composition is more excellent in water dispersibility, and the composition can be inhibited from separating with time, which is preferable. Further, if the amount of the component (a3) used is 50% by mass or less, the crosslinking density is high, the curability is more sufficient, and the water resistance of the resulting cured film is high, which is preferable.
The molar ratio of the hydroxyl group of the component (a1), the isocyanate group of the component (a2), and the hydroxyl group of the component (a3) in the component (a) is not particularly limited, but is preferably (0.1 to 0.9):1 (0.1 to 0.9), and more preferably (0.4 to 0.8):1 (0.1 to 0.6), from the viewpoint of excellent balance between water dispersibility and hardness and abrasion resistance of the cured film.
(A) The reaction component among the components may contain another component (hereinafter referred to as "other component") which does not belong to any of the components (a1), (a2) and (a 3). The other component is not particularly limited as long as it is a compound having at least 1 functional group capable of reacting with an isocyanate group in the molecule. Examples of the functional group capable of reacting with an isocyanate group include a hydroxyl group and an amino group.
< physical Properties and production method of polyurethane (meth) acrylate (A) >
(A) The physical properties of the components are not particularly limited. The weight average molecular weight of the component (A) is preferably about 1,000 to 10,000 from the viewpoint of curability. The weight average molecular weight is a polystyrene equivalent value in gel permeation chromatography, but the measurement method is not particularly limited, and various known methods may be used, or a commercially available measuring machine may be used.
The component (a) is preferably a compound having at least 2 (meth) acryloyl groups in the molecule, from the viewpoint of excellent curability.
The method for producing the component (a) is not particularly limited as long as it is a method for reacting the component (a1), the component (a2) and the component (a3), and various known production methods are exemplified. Specifically, for example, a method in which the component (a2) and the component (a3) are reacted in the presence of a catalyst at an appropriate reaction temperature (for example, 60 to 90 ℃), and then the component (a1) is added to the reaction mixture, and the reaction mixture is reacted in the presence of a catalyst at an appropriate reaction temperature (for example, 60 to 90 ℃). The order of reacting the component (a1), the component (a2), and the component (a3) is not particularly limited, and examples thereof include a method of optionally mixing and reacting the components, a method of mixing all the components together and reacting the components, and the like.
Examples of the above catalyst include organic tin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate; organic acid tin catalysts such as tin octylate; organic titanium catalysts such as titanium ethylacetoacetate; organic zirconium catalysts such as zirconium tetraacetylacetonate; organic iron catalysts such as iron acetylacetonate, and the like. The above-mentioned catalyst may be used singly or in combination of two or more kinds.
< polyfunctional (meth) acrylate (B) >
(B) The component (A) is a polyfunctional (meth) acrylate having a hydroxyl value of 80 to 300 mgKOH/g. The component (B) is not particularly limited and various known compounds can be used as long as the compound has a hydroxyl value of 80 to 300mgKOH/g and at least 2 (meth) acryloyl groups in the molecule. (B) One of the components may be used alone, or two or more of the components may be used in combination.
(B) The present inventors have found that an active energy ray-curable resin composition comprising a combination of a specific component (a) of a polyurethane (meth) acrylate and a component (B) having a high hydroxyl value has good water dispersibility and is suppressed in viscosity change when dispersed in water. Thus, the active energy ray-curable resin composition can be easily dispersed in water without using a special dispersing device. Further, it has been found that the active energy ray-curable resin composition can form a cured film excellent in hardness and abrasion resistance.
The larger the number of (meth) acryloyl groups in the molecule in the component (B), the better, from the viewpoint of excellent hardness and abrasion resistance of the resulting cured film. The number of (meth) acryloyl groups in the molecule of component (B) is usually about 2 to 5 from the viewpoint of easy availability.
(B) Component (a1) is a compound having a hydroxyl value of 80 to 300mgKOH/g and at least 2 (meth) acryloyl groups in the molecule.
The component (B) is preferably pentaerythritol poly (meth) acrylate and/or glycerol poly (meth) acrylate having a hydroxyl value of 80 to 300mgKOH/g in the component (a1) from the viewpoint of excellent water dispersibility.
Examples of the pentaerythritol poly (meth) acrylate include pentaerythritol di (meth) acrylate and pentaerythritol tri (meth) acrylate; and a mixture having a hydroxyl value of 80 to 300mgKOH/g, which is composed of at least two selected from the group consisting of pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate.
Examples of the above glycerin poly (meth) acrylate include glycerin di (meth) acrylate; and a mixture having a hydroxyl value of 80 to 300mgKOH/g, which is composed of at least two selected from the group consisting of glycerol mono (meth) acrylate, glycerol di (meth) acrylate and glycerol tri (meth) acrylate.
Examples of commercially available products of the pentaerythritol poly (meth) acrylate include Aronix (アロニックス) MT-3548, Aronix M-306, and Aronix M-305 (manufactured by Toyo Seisaku-sho Co., Ltd.). Examples of commercially available products of the above-mentioned glycerol poly (meth) acrylate include Aronix MT-3560 (manufactured by Toyo Seisaku-sho Co., Ltd.).
The hydroxyl value of the component (B) is preferably about 200 to 300mgKOH/g, more preferably about 250 to 300mgKOH/g, from the viewpoint of excellent water dispersibility.
The content of the component (a) in the active energy ray-curable resin composition is not particularly limited, and is preferably about 25 to 90 parts by mass in terms of solid content with respect to 100 parts by mass of the active energy ray-curable resin composition, from the viewpoint of an excellent balance between hardness and abrasion resistance of the cured film.
The content of the component (B) in the active energy ray-curable resin composition is not particularly limited, and is preferably about 10 to 75 parts by mass in terms of solid content with respect to 100 parts by mass of the active energy ray-curable resin composition, from the viewpoint of an excellent balance between hardness and abrasion resistance of the cured film.
The content of the component (B) in the active energy ray-curable resin composition is not particularly limited, but is preferably about 10 to 70 parts by mass, more preferably about 25 to 60 parts by mass in terms of solid content, relative to 100 parts by mass of the total amount of the components (a) and (B), from the viewpoint of an excellent balance between hardness and abrasion resistance of the cured film.
[ active energy ray-curable aqueous resin composition ]
The active energy ray-curable aqueous resin composition (hereinafter also referred to as an aqueous resin composition) of the present invention contains the active energy ray-curable resin composition, water, and, if necessary, (meth) acrylate, a photopolymerization initiator, and a solvent.
The content of the active energy ray-curable resin composition in the aqueous resin composition is not particularly limited, and is preferably about 0.5 to 50 parts by mass in terms of solid content with respect to 100 parts by mass of the aqueous resin composition from the viewpoint of coatability.
< Water >
The water is not particularly limited, and examples thereof include distilled water, ion-exchanged water, and ion-exchanged distilled water. From the viewpoint of coatability, the water content in the aqueous resin composition is preferably such that the solid content concentration of the active energy ray-curable aqueous resin composition is in the range of about 5 to 50% by mass.
[ meth (acrylic acid ester ]
The aqueous resin composition may contain a (meth) acrylate. Any known compound (meth) acrylate may be used without particular limitation as long as the compound has at least 1 (meth) acryloyl group in the molecule. One kind of the (meth) acrylate may be used alone, or two or more kinds may be used in combination.
Examples of the (meth) acrylate include a mono (meth) acrylate having 1 (meth) acryloyl group in the molecule, a di (meth) acrylate having 2 (meth) acryloyl groups in the molecule, and a poly (meth) acrylate having at least 3 (meth) acryloyl groups in the molecule.
Examples of the mono (meth) acrylate include a compound having 1 (meth) acryloyl group in a molecule in the component (a1), and a mono (meth) acrylate having no hydroxyl group.
Examples of the di (meth) acrylate include a compound having 2 (meth) acryloyl groups in a molecule in the component (a1), and a di (meth) acrylate having no hydroxyl group. Examples of the di (meth) acrylate having no hydroxyl group include 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentadiene di (meth) acrylate, bisphenol A ethylene oxide-modified di (meth) acrylate, propylene oxide-modified bisphenol A type di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, propylene glycol di (meth), Phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) acrylate, and the like.
Examples of the poly (meth) acrylate include poly (meth) acrylates having at least 3 (meth) acryloyl groups in a molecule in the component (a 1); trimethylolpropane tri (meth) acrylate esters such as trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, and epichlorohydrin-modified trimethylolpropane tri (meth) acrylate; glycerol tri (meth) acrylates such as glycerol tri (meth) acrylate, ethylene oxide-modified glycerol tri (meth) acrylate, and propylene oxide-modified glycerol tri (meth) acrylate; pentaerythritol tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate, ethylene oxide-modified pentaerythritol tetra (meth) acrylate, and propylene oxide-modified pentaerythritol tetra (meth) acrylate; dipentaerythritol hexa (meth) acrylates such as dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate; (poly) glycerol poly (meth) acrylates such as diglycerol tetra (meth) acrylate and triglycerol penta (meth) acrylate; (poly) pentaerythritol poly (meth) acrylates such as tripentaerythritol octa (meth) acrylate and tetrapentaerythritol deca (meth) acrylate; (poly) trimethylolpropane poly (meth) acrylates such as ditrimethylolpropane tetra (meth) acrylate; polyester (meth) acrylates, urethane (meth) acrylates, epoxy (meth) acrylates, polyether (meth) acrylates, polyol (meth) acrylates, polyacrylic (meth) acrylates, and the like.
Examples of the urethane (meth) acrylate include a reaction product of a hydroxyl group-containing (meth) acrylate and a polyisocyanate; hydroxyl group-containing (meth) acrylates, reactants of polyols and polyisocyanates, and the like. The urethane (meth) acrylate is different from the component (A).
Examples of the hydroxyl group-containing (meth) acrylate include those similar to the component (a 1). Examples of the polyisocyanate include those similar to the component (a 2).
Examples of the polyhydric alcohol include aliphatic diols such as alkylene glycol; alicyclic diols such as 1, 4-cyclohexanedimethanol; glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, polyolefin polyols, and the like.
Examples of the polyacrylic acid (meth) acrylate include a reaction product of an acrylic copolymer obtained by polymerizing an epoxy group-containing mono (meth) acrylate and, if necessary, a mono (meth) acrylate, and (meth) acrylic acid.
Examples of the epoxy group-containing mono (meth) acrylate include glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, and vinylcyclohexene monoxide (ビニルシクロヘキセンモノオキサイド) (i.e., 1, 2-epoxy-4-vinylcyclohexane).
The multi (meth) acrylate is preferably pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, or tripentaerythritol octa (meth) acrylate, from the viewpoint of excellent curability and solvent resistance.
The physical properties of the above poly (meth) acrylate are not particularly limited. The poly (meth) acrylate preferably has a molecular weight of about 300 to 10,000, more preferably about 300 to 5,000, from the viewpoint of excellent curability and solvent resistance of the cured film.
In the present specification, the term "molecular weight" refers to the following meanings. That is, in the case where the structure of the compound can be expressed uniquely by a specific chemical formula, such as pentaerythritol tetra (meth) acrylate, the molecular weight means the formula weight. On the other hand, in the case where the structure of the compound cannot be expressed uniquely by a specific chemical formula like the polymer poly (meth) acrylate, the above molecular weight means the weight average molecular weight.
The content of the (meth) acrylic acid ester in the aqueous resin composition is not particularly limited, and is preferably about 0 to 300% by mass in terms of solid content with respect to 100% by mass of the aqueous resin composition.
< photopolymerization initiator >
The aqueous resin composition may contain a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more. Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl ketone, 2-dimethoxy-1, 2-diphenylethan-1-one, 1-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, and the like. The photopolymerization initiator is used when ultraviolet curing is performed, but is not necessarily required when electron beam curing is performed.
The content of the photopolymerization initiator in the aqueous resin composition is not particularly limited. From the viewpoint of the progress of the reaction of the (meth) acryloyl group, the content of the photopolymerization initiator is preferably about 0.5 to 15 parts by mass in terms of solid content with respect to 100 parts by mass of the composition.
< additives >
The aqueous resin composition may contain, as an additive, a reagent other than water, the (meth) acrylate, a photopolymerization initiator, and a solvent, as long as the effects of the present invention are not impaired. One kind of the additive may be used alone, or two or more kinds may be used in combination. Examples of the additives include a binder, a curing agent, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antifoaming agent, a surface conditioner, an antifouling agent, an antiseptic agent, a rust inhibitor, a pH adjuster, a lubricant, a leveling agent, an anti-blocking agent (ブロッキング inhibitor), a conductive agent, a pigment, a dye, a metal oxide fine particle dispersion, an organic fine particle dispersion, and the like.
The active energy ray-curable resin composition of the present invention is easily mixed with additives such as a photopolymerization initiator and an antistatic agent, and therefore, the aqueous resin composition containing the resin composition and the coating agent composition described later have a characteristic of excellent stability even when various additives are contained. In particular, although the photopolymerization initiator is usually poor in water dispersibility because it is often insoluble or poorly soluble in water, the aqueous resin composition and coating agent of the present invention are excellent in stability even when the photopolymerization initiator is contained.
The content of the above-mentioned additive in the above-mentioned aqueous resin composition is not particularly limited. The content of the additive is preferably about 0 to 50 parts by mass with respect to 100 parts by mass of the aqueous resin composition.
< solvent >
The aqueous resin composition may be used with a solvent as long as the effects of the present invention are not impaired. Examples of the solvent include methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, diacetone alcohol, acetone, acetylacetone, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isopropyl ether, methyl cellosolve, ethyl cellosolve, 1, 4-dioxane, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. The above solvents may be used alone or in combination of two or more. When water is used in combination, the solvents mixed with water, such as ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, diacetone alcohol, acetone, methyl cellosolve, ethyl cellosolve, 1, 4-dioxane, and propylene glycol monomethyl ether, are preferred.
The content of the solvent in the above aqueous resin composition is not particularly limited. From the viewpoint of coatability, the content of the solvent is preferably about 0 to 200 parts by mass with respect to 100 parts by mass of the aqueous resin composition. From the viewpoint of coatability, the content of water and the solvent is preferably contained in such a range that the solid content concentration of the aqueous resin composition is about 5% by mass to 50% by mass.
[ physical Properties and production method of active energy ray-curable aqueous resin composition ]
The physical properties of the above aqueous resin composition are not particularly limited. The solid content concentration of the aqueous resin composition is preferably about 5 to 50% by mass from the viewpoint of coatability. From the viewpoint of coatability, the viscosity of the aqueous resin composition at 25 ℃ is preferably about 0.5 to 1000 mPas, more preferably about 1 to 100 mPas.
In the aqueous resin composition, the average primary particle diameter by the light scattering method is preferably about 1 to 1000nm, more preferably about 1 to 100 nm.
The aqueous resin composition can be obtained by mixing the component (a) and the component (B) with water, the (meth) acrylate, if necessary, the photopolymerization initiator, and a solvent, and then emulsifying (or dispersing) them. The emulsification method is not particularly limited, and various known methods such as inverse emulsification and mechanical emulsification may be used. In addition, various known emulsifiers and dispersants may be used as necessary within the range not impairing the effects of the present invention. The emulsification conditions are not particularly limited, and the temperature is usually about 5 to 70 ℃ and preferably about 10 to 50 ℃. The time is usually about 1 to 24 hours, preferably about 1 to 12 hours. Alternatively, a mixture of the component (a) and the component (B) may be pre-emulsified before emulsification.
The device used for the emulsification is not particularly limited, and examples thereof include a propeller mixer (プロペラミキサー), a turbine mixer, a homomixer, a dispersion mixer, a super mixer (ウルトラミキサー), a colloid mill, a high-pressure homogenizer, and an ultrasonic wave, and a single device may be used or a plurality of devices may be used in combination as appropriate.
The aqueous resin composition can be used as an active ingredient of various coating agents for various plastic films, various coating agents such as woodwork coating materials and printing inks, adhesives, photoresists, and the like.
[ coating agent composition ]
The coating agent composition (hereinafter also referred to as a coating agent) of the present invention contains the above aqueous resin composition.
The coating agent may contain various additives as long as the effects of the present invention are not impaired. One kind of the additive may be used alone, or two or more kinds may be used in combination. Examples of the additives include the above additives.
The content of the additive in the coating agent is not particularly limited. The content of the additive is preferably about 0 to 50 parts by mass with respect to 100 parts by mass of the coating agent.
The coating agent can be used as a coating agent for various plastic films, particularly a coating agent for preventing scratching (hard coating agent). Further, the composition can be used as various coating agents for woodwork paints, printing inks, and the like.
[ cured film ]
The cured film of the present invention is obtained from the coating agent. Specifically, for example, the mass of the composition after drying is 0.05 to 30g/m2About, preferably 0.1 to 20g/m2The coating agent is applied to the right and left sides, dried, and then cured by irradiation with active energy rays such as ultraviolet rays, electron beams, and radioactive rays. The cured film is formed by applying a coating agent for preventing scratches on a plastic substrate and curing the coating agent.
Examples of the plastic substrate include polycarbonate, polymethyl methacrylate, polystyrene, polyethylene terephthalate (PET), polyimide, polyolefin, nylon, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, and norbornene resin. Examples of the form of the plastic substrate include a film form and a molded body.
The cured film can be produced by various known methods. Specifically, for example, a method of applying the coating agent to the plastic substrate, drying the coating agent as needed, and then irradiating the dried coating agent with active energy rays such as ultraviolet rays, electron beams, and radiation to cure the coating agent is exemplified. Further, there is a method of applying the coating agent to a release film, irradiating the release film with an active energy ray to cure the coating agent, providing an adhesive layer or the like on the release film, bonding the plastic substrate to the adhesive layer, releasing the release film, and transferring the cured film to the plastic substrate.
Examples of the active energy ray used for the curing reaction include ultraviolet rays and electron beams. As the light source of the ultraviolet ray, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp can be used. The amount of light, the arrangement of light sources, the transport speed, and the like may be adjusted as needed, and for example, in the case of using a high-pressure mercury lamp, curing is preferably performed at a transport speed of about 5 to 50 m/min for a lamp having a lamp output of about 80 to 160W/cm. On the other hand, in the case of an electron beam, it is preferable to cure the resin composition at a transport speed of about 5 to 50 m/min by using an electron beam accelerator having an acceleration voltage of about 10 to 300 kV.
Examples of the coating method include bar coater coating, wire bar coating, meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and spray coating.
The coating agent is suitable for plastics that are easily deformed by heat because it can form a cured film by curing with an active energy ray.
[ film ]
The film of the present invention comprises the above-described cured film. The film is an article comprising the cured film and various base films as components.
Examples of the substrate film include plastic films, and various known films can be used. Examples of the plastic film include a polycarbonate film, a polyester film, a polyolefin film, a polystyrene film, an epoxy resin film, a melamine resin film, a triacetyl cellulose film, an ABS resin film, an AS resin film, an acrylic resin film, and an alicyclic polyolefin resin film. From the viewpoint of transparency and adhesion to a cured film, the plastic film is preferably 1 film selected from the group consisting of a polycarbonate film, a triacetyl cellulose film, an acrylic resin film, and an alicyclic polyolefin-based resin film. The average thickness of the base film is not particularly limited, but is usually about 20 to 1000 μm, and preferably 20 to 200 μm.
The above-mentioned film can be produced by various known methods. Specifically, for example, a method of applying the coating agent to the substrate film, drying the coating agent as needed, and then irradiating the coating agent with the active energy ray to cure the coating agent is exemplified. Alternatively, a laminated film may be produced by applying the resin composition of the present invention to the non-coating surface of the obtained substrate film, laminating another substrate film thereon, and then irradiating with an active energy ray.
Examples of the coating method include the above-mentioned methods.
The coating amount is not particularly limited, and the mass after drying is preferably 0.1 to 30g/m2About, preferably 1 to 20g/m2. The average thickness of the cured film formed on the substrate film is usually about 0.05 to 30 μm, preferably about 0.1 to 20 μm.
Examples
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In each example, parts and% are on a mass basis unless otherwise indicated.
< Synthesis of polyurethane (meth) acrylate (A) >
Production example 1
42.9 parts of isocyanurate modified hexamethylene diisocyanate (manufactured by imperial ソー, trade name "Coronate HXR"), 50.7 parts of polyethylene glycol monomethyl ether (manufactured by Nichigan oil, trade name "Uniox M-1000"), 66.3 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Toyo Synthesis, trade name "Aronix M-305"), 0.04 parts of tin octylate, and 0.09 parts of 4-methoxyphenol were put in a reaction vessel equipped with a stirring device and a cooling tube, and then the temperature in the system was increased to 70 ℃ over about 15 minutes. Then, the reaction system was kept at the same temperature for 1.5 hours, and then cooled to 60 ℃. Subsequently, 28.8 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name "Aronix M-305" manufactured by east asia corporation) and 0.08 part of tin octylate were added, and the temperature in the system was raised to 75 ℃ over about 15 minutes. Subsequently, the reaction system was kept at the same temperature for 1 hour, and then 0.09 part of 4-methoxyphenol was added thereto, followed by cooling, whereby a polyurethane (meth) acrylate 1 having a solid content of 100% was obtained.
Production example 2
To a reaction vessel equipped with a stirring device and a cooling tube, 47.9 parts of isocyanurate modified hexamethylene diisocyanate (manufactured by imperial ソー, trade name "Coronate HXR"), 84.0 parts of polyethylene glycol monomethyl ether (manufactured by Nichikura oil, trade name "Uniox M-1000"), 117.6 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Toyo Synthesis, trade name "Aronix M-403"), 0.06 parts of tin octylate, and 0.15 parts of 4-methoxyphenol were added, and then the temperature in the system was raised to 70 ℃ over about 15 minutes. Then, the reaction system was kept at the same temperature for 1.5 hours, and then cooled to 60 ℃. Subsequently, 50.4 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name "Aronix M-403" manufactured by east asia corporation) and 0.12 part of tin octylate were added, and the temperature in the system was raised to 75 ℃ over about 15 minutes. Subsequently, the reaction system was kept at the same temperature for 1 hour, and then 0.15 part of 4-methoxyphenol was added thereto, followed by cooling, whereby a polyurethane (meth) acrylate 2 having a solid content of 100% was obtained.
< preparation of active energy ray-curable resin composition >
Example 1
An active energy ray-curable resin composition was obtained by mixing 50 parts of the above-mentioned polyurethane (meth) acrylate 1 and 50 parts of pentaerythritol multi (meth) acrylate having a hydroxyl value of 275mgKOH/g (product name "Aronix MT-3548" manufactured by Tokya corporation, solid content: 100%).
Example 2
An active energy ray-curable resin composition was obtained by blending 50 parts of the above polyurethane (meth) acrylate 1 and 50 parts of glycerol poly (meth) acrylate having a hydroxyl value of 240mgKOH/g (product name "Aronix MT-3560" manufactured by Tokya corporation, solid content 100%).
Example 3
An active energy ray-curable resin composition was obtained by mixing 50 parts of the above polyurethane (meth) acrylate 1, 10 parts of glycerol poly (meth) acrylate having a hydroxyl value of 240mgKOH/g (product name "Aronix MT-3560" manufactured by Tokya corporation, solid content 100%) and 40 parts of dipentaerythritol poly (meth) acrylate having a hydroxyl value of 90mgKOH/g (product name "Aronix M-403" manufactured by Tokya corporation, solid content 100%).
Example 4
An active energy ray-curable resin composition was obtained by mixing 50 parts of the above polyurethane (meth) acrylate 1, 10 parts of pentaerythritol multi (meth) acrylate having a hydroxyl value of 275mgKOH/g (product name "Aronix MT-3548" manufactured by Tokya corporation, solid content 100%) and 40 parts of pentaerythritol multi (meth) acrylate having a hydroxyl value of 160mgKOH/g (product name "Aronix M-306" manufactured by Tokya corporation, solid content 100%).
Example 5
An active energy ray-curable resin composition was obtained by blending 70 parts of the above polyurethane (meth) acrylate 1 and 30 parts of pentaerythritol multi (meth) acrylate having a hydroxyl value of 275mgKOH/g (product name "Aronix MT-3548" manufactured by Tokya corporation, solid content 100%).
Example 6
An active energy ray-curable resin composition was obtained by blending 70 parts of the above polyurethane (meth) acrylate 1 and 30 parts of glycerol poly (meth) acrylate having a hydroxyl value of 240mgKOH/g (product name "Aronix MT-3560" manufactured by Tokya corporation, solid content 100%).
Example 7
An active energy ray-curable resin composition was obtained by mixing 70 parts of the above polyurethane (meth) acrylate 1 and 30 parts of pentaerythritol multi (meth) acrylate having a hydroxyl value of 160mgKOH/g (product name "Aronix M-306" manufactured by Tokya corporation, solid content 100%).
Example 8
An active energy ray-curable resin composition was obtained by mixing 70 parts of the above polyurethane (meth) acrylate 1 and 30 parts of dipentaerythritol poly (meth) acrylate having a hydroxyl value of 90mgKOH/g (product name "Aronix M-403" manufactured by Tokya corporation, solid content: 100%).
Example 9
An active energy ray-curable resin composition was obtained by blending 90 parts of the above polyurethane (meth) acrylate 1 and 10 parts of pentaerythritol multi (meth) acrylate having a hydroxyl value of 275mgKOH/g (product name "Aronix MT-3548" manufactured by Tokya corporation, solid content 100%).
Example 10
An active energy ray-curable resin composition was obtained by blending 90 parts of the above polyurethane (meth) acrylate 1 and 10 parts of glycerol poly (meth) acrylate having a hydroxyl value of 240mgKOH/g (product name "Aronix MT-3560" manufactured by Tokya corporation, solid content 100%).
Example 11
An active energy ray-curable resin composition was obtained by blending 50 parts of the above polyurethane (meth) acrylate 2 and 50 parts of pentaerythritol multi (meth) acrylate having a hydroxyl value of 275mgKOH/g (product name "Aronix MT-3548" manufactured by Tokya corporation, solid content 100%).
Example 12
An active energy ray-curable resin composition was obtained by blending 50 parts of the above polyurethane (meth) acrylate 2 and 50 parts of glycerol poly (meth) acrylate having a hydroxyl value of 240mgKOH/g (product name "Aronix MT-3560" manufactured by Tokya corporation, solid content 100%).
Example 13
An active energy ray-curable resin composition was obtained by blending 70 parts of the above polyurethane (meth) acrylate 2 and 30 parts of pentaerythritol multi (meth) acrylate having a hydroxyl value of 275mgKOH/g (product name "Aronix MT-3548" manufactured by Tokya corporation, solid content: 100%).
Example 14
An active energy ray-curable resin composition was obtained by blending 70 parts of the above polyurethane (meth) acrylate 2 and 30 parts of glycerol poly (meth) acrylate having a hydroxyl value of 240mgKOH/g (product name "Aronix MT-3560" manufactured by Tokya corporation, solid content 100%).
Example 15
An active energy ray-curable resin composition was obtained by blending 90 parts of the above polyurethane (meth) acrylate 2 and 10 parts of pentaerythritol multi (meth) acrylate having a hydroxyl value of 275mgKOH/g (product name "Aronix MT-3548" manufactured by Tokya corporation, solid content 100%).
Example 16
An active energy ray-curable resin composition was obtained by blending 90 parts of the above polyurethane (meth) acrylate 2 and 10 parts of glycerol poly (meth) acrylate having a hydroxyl value of 240mgKOH/g (product name "Aronix MT-3560" manufactured by Tokya corporation, solid content 100%).
Comparative example 1
An active energy ray-curable resin composition was obtained by mixing 50 parts of the above-mentioned polyurethane (meth) acrylate 1 and 50 parts of glycerol poly (meth) acrylate having a hydroxyl value of 30mgKOH/g (product name "Aronix MT-3547", 100% solid content, manufactured by Tokya synthesis Co., Ltd.).
Comparative example 2
An active energy ray-curable resin composition was obtained by mixing 50 parts of the above polyurethane (meth) acrylate 1 and 50 parts of pentaerythritol multi (meth) acrylate having a hydroxyl value of 0mgKOH/g (product name "Beamset (ビームセット) 710" manufactured by Ishikawa chemical Co., Ltd., solid content 100%).
Comparative example 3
An active energy ray-curable resin composition was obtained by blending 50 parts of the above polyurethane (meth) acrylate 1 and 50 parts of trimethylolpropane EO-modified triacrylate (product name "MIRAMER M3150" manufactured by MIWON Co., Ltd., solid content 100%) having a hydroxyl value of 0 mgKOH/g.
Comparative example 4
An active energy ray-curable resin composition was obtained by mixing 70 parts of the above polyurethane (meth) acrylate 1 and 30 parts of dipentaerythritol poly (meth) acrylate having a hydroxyl value of 35mgKOH/g (product name "Aronix M-402" manufactured by Toyo Seisaku Co., Ltd., solid content: 100%).
Comparative example 5
The urethane (meth) acrylate 1 is used as it is as an active energy ray-curable resin composition.
Comparative example 6
An active energy ray-curable resin composition was obtained by blending 50 parts of the above polyurethane (meth) acrylate 2 and 50 parts of glycerol poly (meth) acrylate having a hydroxyl value of 30mgKOH/g (product name "Aronix MT-3547", solid content 100%) manufactured by Tokya synthesis Co., Ltd.).
Comparative example 7
An active energy ray-curable resin composition was obtained by mixing 50 parts of the above polyurethane (meth) acrylate 2 and 50 parts of pentaerythritol multi (meth) acrylate having a hydroxyl value of 0mgKOH/g (product of Ishikawa chemical Co., Ltd., "Beamset 710", solid content: 100%).
Comparative example 8
An active energy ray-curable resin composition was obtained by blending 50 parts of the above polyurethane (meth) acrylate 2 and 50 parts of trimethylolpropane EO-modified triacrylate (product name "MIRAMER M3150" manufactured by MIWON Co., Ltd., solid content 100%) having a hydroxyl value of 0 mgKOH/g.
Comparative example 9
An active energy ray-curable resin composition was obtained by blending 70 parts of the above polyurethane (meth) acrylate 2 and 30 parts of dipentaerythritol poly (meth) acrylate having a hydroxyl value of 35mgKOH/g (product name "Aronix M-402" manufactured by Tokya corporation, solid content: 100%).
Comparative example 10
The urethane (meth) acrylate 2 is used as it is as the active energy ray-curable resin composition.
Comparative example 11
As the active energy ray-curable resin composition, pentaerythritol multi (meth) acrylate having a hydroxyl value of 275mgKOH/g (product name "Aronix MT-3548", solid content 100%) was used as it is.
(Water dispersibility of active energy ray-curable resin composition)
25 parts of the active energy ray-curable resin compositions of examples 1 to 16 and comparative examples 1 to 11 and 75 parts of water were put in a spiral tube and shaken at an oscillation speed of 250r/min using a powerful shaker (manufactured by Tietech (タイテック, Ltd., trade name: SR-2 DS)). After shaking for 10 minutes, 30 minutes and 90 minutes, the state of the obtained aqueous dispersion was visually confirmed, and evaluated according to the following criteria. The results are shown in Table 1. The shorter the time taken for the aqueous dispersion to become uniform means that the active energy ray-curable resin composition can be easily dispersed in water.
Very good: after shaking for 10 minutes the aqueous dispersion became homogeneous and its appearance was cloudy or translucent.
O: after shaking for 30 minutes the aqueous dispersion became homogeneous and its appearance was cloudy or translucent.
And (delta): after shaking for 90 minutes the aqueous dispersion became homogeneous and its appearance was cloudy or translucent.
X: the aqueous dispersion was also not homogeneous after shaking for 90 minutes and the appearance was that the resin separated from the water.
(stability of aqueous Dispersion of active energy ray-curable resin composition)
The aqueous dispersion obtained above was allowed to stand at room temperature, and the appearance after 24 hours was visually observed, and evaluated according to the following criteria. The results are shown in Table 1.
O: no separation of the aqueous dispersion was observed.
X: separation of the aqueous dispersion takes place.
[ Table 1]
Figure BDA0002583124080000311
The blending amount in table 1 is a value converted into parts by mass of the solid component. Abbreviations in table 1 are as follows.
(abbreviations and details of Compounds)
MT-3548: pentaerythritol Poly (meth) acrylate having a hydroxyl value of 275mgKOH/g (trade name "Aronix MT-3548", solid content 100%), manufactured by Toyo Seiya Kabushiki Kaisha
MT-3560: glycerol poly (meth) acrylate having a hydroxyl value of 240mgKOH/g (trade name "Aronix MT-3560", solid content 100%), manufactured by Toyo Seiya Kabushiki Kaisha
M-306: pentaerythritol Poly (meth) acrylate having a hydroxyl value of 160mgKOH/g (trade name "Aronix M-306", solid content 100%), manufactured by Toyo Seiya Kabushiki Kaisha
M-403: dipentaerythritol poly (meth) acrylate having a hydroxyl value of 90mgKOH/g (trade name "Aronix M-403", solid content 100%), manufactured by Toyo Seiya Kabushiki Kaisha
MT-3547: glycerol poly (meth) acrylate having a hydroxyl value of 30mgKOH/g (trade name "Aronix M-3547", solid content 100%), manufactured by Toyo Seiya Kabushiki Kaisha
B-710: pentaerythritol Poly (meth) acrylate having a hydroxyl value of 0mgKOH/g (trade name "Beamset 710", solid content 100%), manufactured by Ishikawa chemical industry Co., Ltd
M-402: dipentaerythritol poly (meth) acrylate having a hydroxyl value of 35mgKOH/g (trade name "Aronix M-402", solid content 100%), manufactured by Toyo Seiya Kabushiki Kaisha
M-M3150: trimethylolpropane EO-modified triacrylate (trade name: MIRAMER M3150; solid content 100%) having a hydroxyl value of 0mgKOH/g, manufactured by MIWON
< preparation of active energy ray-curable aqueous resin composition (coating agent composition) >
Example 17
To 100 parts of the active energy ray-curable resin composition of example 1,5 parts of 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (trade name "OMNIRAD 2959" and solid content 100%) as a photopolymerization initiator and 0.5 parts of a fluorine-based surfactant (trade name "Ftergent (フタージェント) 212M" and solid content 100%) as a surface conditioner were mixed, and after dissolving, 315 parts of water were mixed and placed in a spiral tube, the resultant was shaken with a high power shaker (trade name "SR-2 DS", manufactured by Tietech corporation) at a shaking speed of 250r/min for 30 minutes to obtain an active energy ray-curable aqueous resin composition. The obtained active energy ray-curable aqueous resin composition was used as it is as a coating agent composition (hereinafter referred to as a coating agent).
Example 18
To 100 parts of the active energy ray-curable resin composition of example 2, 5 parts of 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (trade name "OMNIRAD 2959" and solid content 100%) as a photopolymerization initiator and 0.5 part of a fluorine-based surfactant (trade name "Ftergent 212M" and solid content 100%) as a surface conditioner were mixed, and after dissolution, 315 parts of water were mixed, the mixture was placed in a spiral tube, and shaken at an oscillation speed of 250r/min by a strong shaker (trade name "SR-2 DS" and manufactured by Tietech corporation) to obtain an active energy ray-curable aqueous resin composition. The obtained active energy ray-curable aqueous resin composition was used as it is as a coating agent composition (hereinafter referred to as a coating agent).
Example 19
To 100 parts of the active energy ray-curable resin composition of example 4, 5 parts of 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (trade name "OMNIRAD 2959" and solid content 100%) as a photopolymerization initiator and 0.5 part of a fluorine-based surfactant (trade name "Ftergent 212M" and solid content 100%) as a surface conditioner were mixed, and after dissolution, 315 parts of water were mixed, the mixture was placed in a spiral tube, and shaken by a strong shaker (trade name "SR-2 DS" and manufactured by Tietech) at a shaking speed of 250r/min for 30 minutes to obtain an active energy ray-curable aqueous resin composition. The obtained active energy ray-curable aqueous resin composition was used as it is as a coating agent composition (hereinafter referred to as a coating agent).
Example 20
To 100 parts of the active energy ray-curable resin composition of example 8, 5 parts of 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (trade name "OMNIRAD 2959" and solid content 100%) as a photopolymerization initiator and 0.5 part of a fluorine-based surfactant (trade name "Ftergent 212M" and solid content 100%) as a surface conditioner were mixed and dissolved, and then 315 parts of water were mixed and placed in a spiral tube and shaken by a strong shaker (trade name "SR-2 DS" and manufactured by Tietech) at an oscillation speed of 250r/min for 30 minutes to obtain an active energy ray-curable aqueous resin composition. The obtained active energy ray-curable aqueous resin composition was used as it is as a coating agent composition (hereinafter referred to as a coating agent).
Example 21
To 100 parts of the active energy ray-curable resin composition of example 11, 5 parts of 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (trade name "OMNIRAD 2959" and solid content 100%) as a photopolymerization initiator and 0.5 part of a fluorine-based surfactant (trade name "Ftergent 212M" and solid content 100%) as a surface conditioner were mixed, and after dissolution, 315 parts of water were mixed, the mixture was placed in a spiral tube, and shaken by a strong shaker (trade name "SR-2 DS" and manufactured by Tietech) at a shaking speed of 250r/min for 30 minutes to obtain an active energy ray-curable aqueous resin composition. The obtained active energy ray-curable aqueous resin composition was used as it is as a coating agent composition (hereinafter referred to as a coating agent).
Example 22
To 100 parts of the active energy ray-curable resin composition of example 12, 5 parts of 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (trade name "OMNIRAD 2959" and solid content 100%) as a photopolymerization initiator and 0.5 part of a fluorine-based surfactant (trade name "Ftergent 212M" and solid content 100%) as a surface conditioner were mixed, and after dissolution, 315 parts of water were mixed, the mixture was placed in a spiral tube, and shaken by a strong shaker (trade name "SR-2 DS" and manufactured by Tietech) at a shaking speed of 250r/min for 30 minutes to obtain an active energy ray-curable aqueous resin composition. The obtained active energy ray-curable aqueous resin composition was used as it is as a coating agent composition (hereinafter referred to as a coating agent).
Comparative example 12
To 100 parts of the active energy ray-curable resin composition of comparative example 3, 5 parts of 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (trade name "OMNIRAD 2959" and solid content 100%) as a photopolymerization initiator and 0.5 part of a fluorine-based surfactant (trade name "Ftergent 212M" and solid content 100%) as a surface conditioner were mixed, and after dissolution, 315 parts of water were mixed, the mixture was placed in a spiral tube, and shaken at an oscillation speed of 250r/min by a strong shaker (trade name "SR-2 DS" and manufactured by Tietech corporation) to obtain an active energy ray-curable aqueous resin composition. The obtained active energy ray-curable aqueous resin composition was used as it is as a coating agent composition (hereinafter referred to as a coating agent).
Comparative example 13
To 100 parts of the active energy ray-curable resin composition of comparative example 5, 5 parts of 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (trade name "OMNIRAD 2959" and solid content 100%) as a photopolymerization initiator and 0.5 part of a fluorine-based surfactant (trade name "Ftergent 212M" and solid content 100%) as a surface conditioner were mixed, and after dissolution, 315 parts of water were mixed, the mixture was placed in a spiral tube, and shaken at an oscillation speed of 250r/min by a strong shaker (trade name "SR-2 DS" and manufactured by Tietech corporation) to obtain an active energy ray-curable aqueous resin composition. The obtained active energy ray-curable aqueous resin composition was used as it is as a coating agent composition (hereinafter referred to as a coating agent).
Comparative example 14
To 100 parts of the active energy ray-curable resin composition of comparative example 8, 5 parts of 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (trade name "OMNIRAD 2959" and solid content 100%) as a photopolymerization initiator and 0.5 parts of a fluorine-based surfactant (trade name "Ftergent 212M" and solid content 100%) as a surface conditioner were mixed and dissolved, and then 315 parts of water were mixed and placed in a spiral tube and shaken at an oscillation speed of 250r/min by a strong shaker (trade name "SR-2 DS" and manufactured by Tietech corporation) to obtain an active energy ray-curable aqueous resin composition. The obtained active energy ray-curable aqueous resin composition was used as it is as a coating agent composition (hereinafter referred to as a coating agent).
Comparative example 15
To 100 parts of the active energy ray-curable resin composition of comparative example 10, 5 parts of 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (trade name "OMNIRAD 2959" and solid content 100%) as a photopolymerization initiator and 0.5 parts of a fluorine-based surfactant (trade name "Ftergent 212M" and solid content 100%) as a surface conditioner were mixed, and after dissolution, 315 parts of water were mixed, the mixture was placed in a spiral tube, and shaken at an oscillation speed of 250r/min by a strong shaker (trade name "SR-2 DS" and manufactured by Tietech corporation) to obtain an active energy ray-curable aqueous resin composition. The obtained active energy ray-curable aqueous resin composition was used as it is as a coating agent composition (hereinafter referred to as a coating agent).
< preparation of cured film >
The coating agent of example 17 was applied to a 50 μm-thick polyethylene terephthalate film (trade name "Cosmoshine (コスモシャイン) a 4100", manufactured by tokyo corporation) using a #12 bar coater so that the film thickness of the cured coating film (coating film) was 3 μm, and the cured coating film was dried at 80 ℃ for 2 minutes to prepare a film. Then, the sheet was passed 3 times (3 パス) under conditions of a high pressure mercury lamp of 120W/cm (1 lamp), an irradiation distance of 10cm and a belt speed of 10 m/min to give a cumulative irradiation amount of 300mJ/cm2A film with a cured film was obtained. Cured film-attached films were obtained in the same manner for the coating agents of examples 18 to 22 and comparative examples 12 to 15.
(Pencil hardness)
The pencil hardness of the cured film of the above-mentioned film with a cured film described in example 17 was measured by a pencil hardness tester in accordance with JIS K5600-5-4. The results are shown in Table 2. The cured film-attached films described in examples 18 to 22 and comparative examples 12 to 15 were measured in the same manner.
(scratch resistance)
The cured film of the above film with a cured film described in example 17 was applied at 300g/cm2The loaded steel wool was reciprocated 10 times at a width of 5cm, and the presence or absence of a flaw was observed, and the scratch resistance was evaluated according to the following criteria. The results are shown in Table 2. The cured film-attached films described in examples 18 to 22 and comparative examples 12 to 15 were also evaluated in the same manner.
O: completely free from scar
And (delta): more than 1 and less than 5 scars
X: more than 5 scars
(stability of active energy ray-curable aqueous resin composition (coating agent))
The coating agent of example 17 was left to stand at room temperature, and the appearance after 24 hours was visually observed, and evaluated according to the following criteria. The results are shown in Table 2. The coating agents of examples 18 to 22 were also evaluated in the same manner.
O: no separation of the aqueous dispersion was observed.
X: separation of the aqueous dispersion takes place.
[ Table 2]
Figure BDA0002583124080000361
The blending amount in table 2 is a value converted into parts by mass of the solid component. Abbreviations in table 2 are as follows.
(abbreviations and details of Compounds)
MT-3548: pentaerythritol Poly (meth) acrylate having a hydroxyl value of 275mgKOH/g (trade name "Aronix MT-3548", solid content 100%), manufactured by Toyo Seiya Kabushiki Kaisha
MT-3560: glycerol poly (meth) acrylate having a hydroxyl value of 240mgKOH/g (trade name "Aronix MT-3560", solid content 100%), manufactured by Toyo Seiya Kabushiki Kaisha
M-306: pentaerythritol Poly (meth) acrylate having a hydroxyl value of 160mgKOH/g (trade name "Aronix M-306", solid content 100%), manufactured by Toyo Seiya Kabushiki Kaisha
M-403: dipentaerythritol poly (meth) acrylate having a hydroxyl value of 90mgKOH/g (trade name "Aronix M-403", solid content 100%), manufactured by Toyo Seiya Kabushiki Kaisha
M-M3150: trimethylolpropane EO-modified triacrylate (trade name "MIRAMER M3150", solid content 100%), manufactured by MIWON
OMNI 2959: 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (trade name "OMNIRAD 2959", solid content 100%), manufactured by IGM Resins B.V
F-212M: fluorine-based surfactant (trade name "Ftergent 212M", solid content 100%), (strain) NEOS

Claims (11)

1. An active energy ray-curable resin composition comprising:
a polyurethane (meth) acrylate (a) which is a reaction product of reaction components containing a hydroxyl group-containing (meth) acrylate (a1), a polyisocyanate (a2) and a hydroxyl group-containing polyalkylene glycol (a 3); and
a polyfunctional (meth) acrylate (B) having a hydroxyl value of 80 to 300 mgKOH/g.
2. The active energy ray-curable resin composition according to claim 1, wherein the component (a1) is a hydroxyl group-containing (meth) acrylate having at least 3 (meth) acryloyl groups in the molecule.
3. The active energy ray-curable resin composition according to claim 1 or 2, wherein the component (a2) is a polyisocyanate having at least 3 isocyanate groups in the molecule.
4. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the component (a3) is a compound represented by the following general formula (1):
(formula 1)
H-(OCH2CH2)n-OR (1)
Wherein R represents any one of an alkyl group, an allyl group, a (meth) acryloyl group and an acyl group, and n represents an integer of 3 to 25.
5. The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the component (B) is pentaerythritol poly (meth) acrylate and/or glycerol poly (meth) acrylate having a hydroxyl value of 80 to 300 mgKOH/g.
6. The active energy ray-curable resin composition according to any one of claims 1 to 5, wherein the hydroxyl value of the component (B) is 200 to 300 mgKOH/g.
7. The active energy ray-curable resin composition according to any one of claims 1 to 6, wherein the content of the component (B) is 10 to 70 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B) in terms of solid content.
8. An active energy ray-curable aqueous resin composition comprising the active energy ray-curable resin composition according to any one of claims 1 to 7 and water.
9. A coating agent composition comprising the active energy ray-curable aqueous resin composition according to claim 8.
10. A cured film formed from the coating agent composition according to claim 9.
11. A film comprising the cured film of claim 10.
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