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  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
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  • C08F2/00—Processes of polymerisation
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
  • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
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  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
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  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
  • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular

Definitions

• the present invention is a fluorine-containing active energy ray curable type that can be suitably used as a surfactant in an aqueous active energy ray curable resin composition and can contribute to improvement in leveling properties and antifouling properties of the resulting cured coating film.
• the present invention relates to a resin, an active energy ray-curable resin composition containing the resin, and a cured coating film obtained by curing the composition.
• Surfactants are blended in various coating agents because they can impart good leveling and antifouling properties to the cured coating film (cured product).
• a coating agent include a polymer having a polymerizable unsaturated double bond such as acrylic acrylate, a polymer having no unsaturated double bond such as a non-polymerizable acrylic resin, and a polymerizable monomer.
• an active energy ray-curable resin composition organic solvent-type active energy ray-curable resin composition containing an organic solvent as a diluent.
• Examples of the surfactant used in the organic solvent-type active energy ray-curable resin composition include a polymer structure of a radical polymerizable unsaturated monomer, a poly (perfluoroalkylene ether) chain, and a radical polymerizable unsaturated. What has group is disclosed (for example, refer patent document 1).
• the organic solvent type active energy ray-curable resin composition When used as, for example, a paint for spray coating, the organic solvent is contained in the composition in a large amount of 50 to 90% by mass based on the mass of the composition. There is a need. Therefore, when a cured coating film is formed on the surface of a substrate such as plastic using the composition, the organic solvent in the composition is volatilized and the working environment is deteriorated.
• aqueous active energy ray-curable resin composition containing no organic solvent has been developed, and this aqueous composition is becoming mainstream particularly in Europe, the United States and China.
• conventional surfactants do not have good solubility or dispersibility in aqueous active energy ray-curable resin compositions.
• the surfactant disclosed in Patent Document 1 is aqueous active energy ray-curable. Even when added to the mold resin composition, the surfactant cannot be dissolved or dispersed well in the composition, and as a result, it cannot exhibit the role as a surfactant.
• the problem to be solved by the present invention is that it can be suitably used as a surfactant in an aqueous active energy ray-curable resin composition, and can contribute to improvement in leveling properties and antifouling properties of the resulting cured coating film.
• the present inventors have added a resin having a poly (perfluoroalkylene ether) chain, a polymerizable unsaturated group, and a neutralized salt structure of an acid group to an aqueous active energy ray-curable composition.
• a resin having a poly (perfluoroalkylene ether) chain, a polymerizable unsaturated group, and a neutralized salt structure of an acid group to an aqueous active energy ray-curable composition.
• the present invention relates to a polymer structure (a1) of a radically polymerizable unsaturated monomer, a poly (perfluoroalkylene ether) chain (a2), a radically polymerizable unsaturated group (a3), and an acid group.
• the present invention provides a fluorine-containing active energy ray-curable resin characterized by having a neutralized salt structure (a4).
• the present invention also relates to a polymer structure (a1) of a radically polymerizable unsaturated monomer, a poly (perfluoroalkylene ether) chain (a2), a radically polymerizable unsaturated group (a3), and an acid group.
• the present invention provides a surfactant characterized by having a neutralized salt structure (a4).
• the present invention relates to the fluorine-containing active energy ray-curable resin (A) of the present invention, an active energy ray-curable hydrophilic resin (B) other than the fluorine-containing active energy ray-curable resin (A), water,
• An active energy ray-curable resin composition comprising:
• the present invention provides a cured coating film of the active energy ray-curable resin composition.
• the present invention it is possible to provide a fluorine-containing active energy ray-curable resin that can be suitably used as a surfactant in an aqueous active energy ray-curable resin composition.
• the active energy ray-curable resin composition containing the fluorine-containing active energy ray-curable resin of the present invention provides a cured coating film having excellent leveling and antifouling properties even when the medium is mainly water. It can be used as a coating material used for various applications.
• the fluorine-containing active energy ray-curable resin of the present invention comprises a polymer structure (a1) of a radically polymerizable unsaturated monomer, a poly (perfluoroalkylene ether) chain (a2), a radically polymerizable unsaturated group ( a3) and a neutralized salt structure (a4) of an acid group.
• a fluorine-containing active energy ray curable resin for example, a poly (perfluoroalkylene ether) chain (a2) is added to the side chain of the polymer structure (a1) of a radical polymerizable unsaturated monomer, and radical polymerization is performed.
• a resin having a neutral unsaturated group (a3) and a neutral salt structure (a4) of an acid group hereinafter, this may be abbreviated as a fluorine-containing active energy ray-curable resin (A1).
• a plurality of polymer structures (a1) are knotted via a poly (perfluoroalkylene ether) chain (a2), and a radically polymerizable unsaturated group is present on the side chain of the polymer structure (a1).
• Resin having (a3) and acid group neutralized salt structure (a4) [Hereinafter, this may be abbreviated as fluorine-containing active energy ray-curable resin (A2). ] Etc. are mentioned.
• the polymer structure (a1) possessed by the fluorine-containing active energy ray-curable resin of the present invention is a polymer structure of a radically polymerizable unsaturated monomer.
• the radical polymerizable unsaturated monomer include (meth) acrylic monomers, aromatic vinyl monomers, vinyl ester monomers, maleimide monomers, and the like.
• the poly (perfluoroalkylene ether) chain (a2) possessed by the fluorine-containing active energy ray-curable resin of the present invention for example, a divalent fluorocarbon group having 1 to 3 carbon atoms and oxygen atoms are alternately linked.
• the thing which has a structure is mentioned.
• the divalent fluorinated carbon group having 1 to 3 carbon atoms may be one kind or a mixture of plural kinds. Specific examples include those represented by the following structural formula 1. .
• X is the following structural formulas a to d, and all X in the structural formula 1 may have the same structure, or a plurality of structures may be randomly or block-shaped.
• n is a number of 1 or more representing a repeating unit.
• a perfluoromethylene structure having a perfluoromethylene structure represented by the structural formula a is obtained because a cured coating film having particularly excellent antifouling properties due to good wiping of dirt on the surface of the cured coating film is obtained. It is preferable that a methylene ether chain and a perfluoroethylene ether chain having a perfluoroethylene structure represented by the structure b coexist.
• the abundance ratio between the perfluoromethylene structure represented by the structural formula a and the perfluoroethylene structure represented by the structure b is such that the molar ratio (structure a / structure b) is 1/10 to 10 /
• a ratio of 1 is preferable because a cured coating film having excellent antifouling properties can be obtained.
• the value of n in the structural formula 1 is preferably in the range of 3 to 100, more preferably 6 to 70, and still more preferably in the range of 12 to 50.
• the poly (perfluoroalkylene ether) chain (a2) provides a cured coating film having excellent antifouling properties
• the total number of fluorine atoms contained in one poly (perfluoroalkylene ether) chain (a2) is A range of 18 to 200 is preferable, and a range of 25 to 150 is particularly preferable.
• the cured coating film is excellent in compatibility with the later-described active energy ray-curable hydrophilic resin (B) and excellent in antifouling properties. Is preferably 3 to 40% by mass, more preferably 5 to 30% by mass.
• the polymer structure (a1) and the poly (perfluoroalkylene ether) chain (a2) are linked via a structure derived from a styryl group. It is preferable because it becomes a fluorine-containing active energy ray-curable resin from which a cured coating film having excellent water resistance can be obtained.
• radical polymerizable unsaturated group (a3) possessed by the fluorine-containing active energy ray-curable resin of the present invention include those represented by the following structural formulas (U-1) to (U-5).
• a radically polymerizable unsaturated group represented by the above (U-1) can be obtained because a fluorine-containing active energy ray-curable resin can be obtained that provides a cured coating film having excellent curability. Is preferred.
• the content of the radically polymerizable unsaturated group (a3) of the fluorine-containing active energy ray-curable resin of the present invention is such that the poly (perfluoroalkylene ether) chain can be firmly fixed to the cured coating film, and as a result 0.5 to 3.5 mmol / g is preferable and 1.0 to 3.0 mmol / g is more preferable because a cured coating film having excellent soiling properties can be obtained.
• Examples of the acid group of the neutralized salt structure (a4) of the acid group that the fluorine-containing active energy ray-curable resin of the present invention has include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.
• Examples of the neutralized salt structure of the acid group include an amine salt structure of the acid group and an inorganic salt structure of the acid group.
• Examples of the amine salt structure of the acid group include an ammonium salt structure of the acid group, a primary amine salt structure of the acid group, a secondary amine salt structure of the acid group, and a tertiary amine salt structure of the acid group. Is mentioned.
• Examples of the primary amine salt structure include an ethylamine salt structure, an n-propylamine salt structure, a sec-propylamine salt structure, an n-butylamine salt structure, a sec-butylamine salt structure, an i-butylamine salt structure, and a tert-butylamine.
• Salt structure pentylamine salt structure, hexylamine salt structure, heptylamine salt structure, octylamine salt structure, decylamine salt structure, laurylamine salt structure, mistyrylamine salt structure, 1,2-dimethylhexylamine salt structure, 3- Pentylamine salt structure, 2-ethylhexylamine salt structure, allylamine salt structure, aminoethanol salt structure, 1-aminopropanol salt structure, 2-aminopropanol salt structure, aminobutanol salt structure, aminopentanol salt structure, aminohexanol salt structure , 3-Ethoxyp Pyramine salt structure, 3-propoxypropylamine salt structure, 3-isopropoxypropylamine salt structure, 3-butoxypropylamine salt structure, 3-isobutoxypropylamine salt structure, 3- (2-ethylhexyloxy) propylamine salt Structure, aminocyclopentane salt structure, aminocyclohexane salt structure, aminonor
• Ethylenediamine salt structure 1,2-diaminopropane salt structure, 1,3-diaminopropane salt structure, 1,2-diaminobutane salt structure, 1,3-diaminobutane salt structure, 1,4-diaminobutane salt structure, 1 , 5-diaminopentane salt structure, 1,6-diaminohexane salt structure, 1,7-diaminoheptane salt structure, 1,8-diaminooctane salt structure, dimethylaminopropylamine salt structure, diethylaminopropylamine salt structure, bis- (3-aminopropyl) ether salt structure, 1,2-bis- (3-aminopropoxy) ethane salt structure, 1,3-bis- (3-aminopropoxy) -2,2′-dimethylpropane salt structure, amino Ethylethanolamine salt structure, 1,2-bisaminocyclohexane salt structure, 1,3-
• Examples of the secondary amine salt structure include a diethylamine salt structure, a dipropylamine salt structure, a di-n-butylamine salt structure, a di-sec-butylamine salt structure, a diisobutylamine salt structure, and a di-n-pentylamine salt structure.
• Di-3-pentylamine salt structure dihexylamine salt structure, dioctylamine salt structure, di (2-ethylhexyl) amine salt structure, methylhexylamine salt structure, diallylamine salt structure, pyrrolidine salt structure, piperidine salt structure, 2, 4-Lupetidine salt structure, 2,6-Lupetidine salt structure, 3,5-Lupetidine salt structure, Diphenylamine salt structure, N-Methylaniline salt structure, N-Ethylaniline salt structure, Dibenzylamine salt structure, Methylbenzylamine salt Structure, dinaphthylamine salt structure, pyrrole salt structure, indoline salt structure Indole salt structure, secondary monoamine salt structure such as morpholine salt structure;
• tertiary amine salt structure examples include trimethylamine salt structure, triethylamine salt structure, tri-n-propylamine salt structure, tri-iso-propylamine salt structure, tri-1,2-dimethylpropylamine salt structure, -3-methoxypropylamine salt structure, tri-n-butylamine salt structure, tri-iso-butylamine salt structure, tri-sec-butylamine salt structure, tri-pentylamine salt structure, tri-3-pentylamine salt structure, tri -N-hexylamine salt structure, tri-n-octylamine salt structure, tri-2-ethylhexylamine salt structure, tri-dodecylamine salt structure, tri-laurylamine salt structure, dicyclohexylethylamine salt structure, cyclohexyldiethylamine salt structure, Tri-cyclohexylamine salt structure, N, -Dimethylhexylamine salt structure, N-methyldi
• Tetramethylethylenediamine salt structure pyrazine salt structure, N, N′-dimethylpiperazine salt structure, N, N′-bis ((2-hydroxy) propyl) piperazine salt structure, hexamethylenetetramine salt structure, N, N, N ′ , N′-tetramethyl-1,3-butaneamine salt structure, 2-dimethylamino-2-hydroxypropane salt structure, diethylaminoethanol salt structure, N, N, N-tris (3-dimethylaminopropyl) amine salt structure, Examples include tertiary polyamine salt structures such as 2,4,6-tris (N, N-dimethylaminomethyl) phenol salt structure and heptamethylisobiguanide salt structure.
• Examples of the inorganic salt structure of the acid group include a sodium hydroxide (NaOH) salt structure and a potassium hydroxide (KOH) salt structure.
• An amine salt structure of an acid group is preferable because a curable resin is obtained.
• the amine salt structures of acid groups an amine salt structure of a carboxyl group is preferable, and a salt structure of a carboxyl group and a tertiary amine is more preferable.
• N, N-dimethylethanolamine is preferred, and therefore a salt structure of a carboxyl group and N, N-dimethylethanolamine is more preferred.
• a cured coating film having good solubility or dispersibility in the aqueous active energy ray-curable resin composition of the present invention and excellent leveling properties can be obtained.
• Those having an oxyalkylene chain in the side chain are preferred.
• Examples of the oxyalkylene group include an oxyethylene chain, an oxypropylene chain, and an oxybutylene chain.
• an oxyethylene chain is preferred because a fluorine-containing active energy ray-curable resin having good solubility or dispersibility in the aqueous active energy ray-curable resin composition of the present invention can be obtained.
• the fluorine-containing active energy ray-curable resin of the present invention contains an oxyalkylene chain
• the content is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass of the fluorine-containing active energy ray-curable resin. preferable.
• Examples of the method for producing the fluorine-containing active energy ray-curable resin (A1) and the fluorine-containing active energy ray-curable resin (A2), which are examples of the fluorine-containing active energy ray-curable resin of the present invention, will be described later. Examples thereof include methods using monomers (x-1) to (x-6) and a base compound (x-7). Specifically, the fluorine-containing active energy ray-curable resin (A1) can be produced, for example, by the following method.
• Method (A1-1) .Radically polymerizable unsaturated monomer (x-1) having a poly (perfluoroalkylene ether) chain (a2) and one radical polymerizable unsaturated group, and a radical polymerizable unsaturated monomer having an acid group (X-3) is copolymerized to form a polymer structure (a1) of a radically polymerizable unsaturated monomer, a poly (perfluoroalkylene ether) chain (a2) in this side chain and an acid group
• the union (P1-1) is obtained.
• a part of the acid group of the obtained copolymer (P1-1) is reacted with the radically polymerizable unsaturated monomer (x-4) having a functional group reactive with the acid group to react with the polymer.
• Copolymer structure (a1) and a copolymer (P2-1) (containing a poly (perfluoroalkylene ether) chain (a2), a radically polymerizable unsaturated group (a3), and an acid group in its side chain Fluorine active energy ray curable resin) is obtained. Thereafter, the acid group remaining in the copolymer (P2-1) and the base compound (x-7) are reacted to obtain a fluorine-containing active energy ray-curable resin (A1).
• Method (A1-2) .Radically polymerizable unsaturated monomer (x-1) having a poly (perfluoroalkylene ether) chain (a2) and one radical polymerizable unsaturated group, and a radical polymerizable unsaturated monomer having an acid group Polymer (x-3) and a radically polymerizable unsaturated monomer (x-5) having a hydroxyl group, an isocyanate group or a glycidyl group, to give a polymer structure of the radically polymerizable unsaturated monomer ( A copolymer (P1-2) having a1) and a poly (perfluoroalkylene ether) chain (a2) on this side chain, an acid group, and a hydroxyl group, an isocyanate group or a glycidyl group is obtained.
• Fluorine-containing active energy ray-curable resin (A2) can be produced, for example, by the following method.
• Method (A2-1) -Radical polymerizable unsaturated monomer (x-2) having a poly (perfluoroalkylene ether) chain (a2) and radical polymerizable unsaturated groups at both ends thereof, and radical polymerizable unsaturated having an acid group
• the monomer (x-3) is copolymerized, and a plurality of polymer structures (a1) are knotted through poly (perfluoroalkylene ether) chains (a2), and the polymer structure (a1) A copolymer (P1-3) having an acid group in the side chain is obtained.
• a part of the acid group of the obtained copolymer (P1-3) is reacted with a radical polymerizable unsaturated monomer (x-4) having a functional group reactive with the acid group,
• a radical polymerizable unsaturated monomer (x-4) having a functional group reactive with the acid group
• a plurality of polymer structures (a1) are knotted via a poly (perfluoroalkylene ether) chain (a2), and a radically polymerizable unsaturated group (a3) and an acid group are added to the side chain of the polymer structure (a1).
• P2-3) fluorine-containing active energy ray-curable resin
• the acid group remaining in the copolymer (P2-3) is reacted with the base compound (x-7) to obtain a fluorine-containing active energy ray-curable resin (A2).
• Method (A2-2) -Radical polymerizable unsaturated monomer (x-2) having a poly (perfluoroalkylene ether) chain (a2) and radical polymerizable unsaturated groups at both ends thereof, and radical polymerizable unsaturated having an acid group A monomer (x-3) and a radically polymerizable unsaturated monomer (x-5) having a hydroxyl group, an isocyanate group or a glycidyl group are copolymerized to form a plurality of polymer structures (a1) having a poly ( A perfluoroalkylene ether) chain (a2), and a copolymer (P1-4) having an acid group and a hydroxyl group, an isocyanate group or a glycidyl group in the side chain of the polymer structure (a1).
• a plurality of polymer structures (a1) are knotted via a poly (perfluoroalkylene ether) chain (a2), an acid group and a radical polymerizable unsaturated group on the side chain of the polymer structure (a1).
• a copolymer (P2-4) fluorine-containing active energy ray-curable resin) having a group (a3) is obtained. Thereafter, the acid group of the copolymer (P2-4) and the base compound (x-7) are reacted to obtain a fluorine-containing active energy ray-curable resin (A2).
• radical polymerizable unsaturated monomer (x-1) having the poly (perfluoroalkylene ether) chain (a2) and one radical polymerizable unsaturated group include the following structural formula (x-1- 1) to (x-1-13)
• the thing etc. which are represented by are mentioned.
• the radically polymerizable unsaturated monomer (x-1) having a poly (perfluoroalkylene ether) chain (a2) and one radically polymerizable unsaturated group may be used alone or in combination of two or more. You may use together.
• “—PFPE—” represents a poly (perfluoroalkylene ether) chain (a2).
• poly (perfluoroalkylene) Ether a method obtained by dehydrochlorinating (meth) acrylic acid chloride or chloromethylstyrene to a compound having one hydroxyl group at one end of the chain, a method obtained by dehydrating (meth) acrylic acid, 2 -A method obtained by urethanizing (meth) acryloyloxyethyl isocyanate, a method obtained by esterifying itaconic anhydride;
• a method of reacting 2-hydroxyethyl acrylamide, a method of reacting 2-hydroxyethyl acrylate, a reaction of 2-hydroxypropyl acrylate to a compound having one isocyanate group at one end of a poly (perfluoroalkylene ether) chain A method of reacting 4-hydroxybutyl acrylate;
• Examples thereof include a method of reacting a compound having one epoxy group at one end of a poly (perfluoroalkylene ether) chain with (meth) acrylic acid.
• a compound having one hydroxyl group at one end of the poly (perfluoroalkylene ether) chain, a compound having one carboxyl group at one end of the poly (perfluoroalkylene ether) chain, and a poly (perfluoroalkylene ether) chain examples include compounds having the following structures.
• (meth) acrylate refers to one or both of methacrylate and acrylate
• (meth) acryloyl group refers to one or both of methacryloyl group and acryloyl group
• “Acrylic acid” refers to one or both of methacrylic acid and acrylic acid.
• Examples of the radically polymerizable unsaturated monomer (x-2) having a poly (perfluoroalkylene ether) chain (a2) and radically polymerizable unsaturated groups at both ends thereof include the following structural formula (x- (2-1) to (x-2-13)
• the compound represented by (x-2-13) is preferable because it becomes a fluorine-containing active energy ray-curable resin from which a cured coating film having excellent water resistance can be obtained.
• the radically polymerizable unsaturated monomer (x-2) having a poly (perfluoroalkylene ether) chain (a2) and radically polymerizable unsaturated groups at both ends thereof may be used alone, Two or more kinds may be used in combination.
• a radically polymerizable unsaturated monomer (x-2) having a poly (perfluoroalkylene ether) chain (a2) and radically polymerizable unsaturated groups at both ends thereof for example, poly (perfluoroalkylene) (Alkylene ether)
• a method obtained by dehydrochlorinating (meth) acrylic acid chloride or chloromethylstyrene for a compound having one hydroxyl group at both ends of the chain, and a method obtained by dehydrating (meth) acrylic acid A method obtained by urethanization of 2- (meth) acryloyloxyethyl isocyanate, a method obtained by esterification of itaconic anhydride;
• Examples include a method of reacting (meth) acrylic acid with a compound having one epoxy group at each end of a poly (perfluoroalkylene ether) chain.
• a method obtained by dehydrochlorinating (meth) acrylic acid chloride or chloromethylstyrene with respect to a compound having one hydroxyl group at both ends of a poly (perfluoroalkylene ether) chain A method obtained by subjecting (meth) acryloyloxyethyl isocyanate to a urethanization reaction is particularly preferable in terms of easy reaction in production.
• Examples of the compound having one isocyanate group at both ends of the chain and the compound having one epoxy group at both ends of the poly (perfluoroalkylene ether) chain include compounds having the following structures.
• the radical polymerizable unsaturated monomer (x-2) may be used in combination with the radical polymerizable unsaturated monomer (x-1). .
• the radical polymerizable unsaturated monomer (x-1) is used in combination with the radical polymerizable unsaturated monomer (x-2). Also good.
• radical polymerizable unsaturated monomer (x-3) having an acid group examples include a radical polymerizable unsaturated monomer having a carboxyl group, a radical polymerizable unsaturated monomer having a sulfonic acid group, Examples include radically polymerizable unsaturated monomers having a phosphate group.
• radical polymerizable unsaturated monomer having a carboxyl group examples include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, and itaconic acid.
• Carboxylic acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride.
• radical polymerizable unsaturated monomer having a sulfonic acid group examples include acrylamide t-butyl sulfonic acid and styrene sulfonic acid derivatives.
• radical polymerizable unsaturated monomer having a phosphoric acid group examples include acid phosphooxyethyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, and acid phosphooxypolyoxypropylene glycol monomethacrylate.
• the radically polymerizable unsaturated monomer (x-3) having an acid group may be used alone or in combination of two or more.
• radical polymerizable unsaturated monomer (x-4) having a functional group reactive with an acid group examples include a radical polymerizable unsaturated monomer having a glycidyl group and a radical polymerizable having a hydroxyl group. An unsaturated monomer etc. are mentioned.
• examples of the radical polymerizable unsaturated monomer having a glycidyl group include glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether.
• radical polymerizable unsaturated monomer having a hydroxyl group examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth).
• the radically polymerizable unsaturated monomer (x-4) having a functional group reactive with an acid group may be used alone or in combination of two or more.
• radical polymerizable unsaturated monomers (x-5) having a hydroxyl group, an isocyanate group or a glycidyl group a radical polymerizable unsaturated monomer having a hydroxyl group and a radical polymerizable unsaturated monomer having a glycidyl group
• the radical polymerizable unsaturated monomer having a hydroxyl group and the radical polymerizable unsaturated monomer having a glycidyl group mentioned as an example of the radical polymerizable unsaturated monomer (x-4) can be mentioned. it can.
• Examples of the radically polymerizable unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth And acryloyloxymethyl) ethyl isocyanate.
• the radical polymerizable unsaturated monomer (x-5) having a hydroxyl group, an isocyanate group or a glycidyl group may be used alone or in combination of two or more.
• radical polymerizable unsaturated monomers (x-6) having a functional group reactive with a hydroxyl group, an isocyanate group or a glycidyl group a radical polymerizable unsaturated monomer having a functional group reactive with a hydroxyl group.
• the body include a radical polymerizable unsaturated monomer having a carboxyl group and a radical polymerizable unsaturated monomer having an isocyanate group.
• radical polymerizable unsaturated monomer having a functional group reactive with an isocyanate group include the radical polymerizable unsaturated monomer having a hydroxyl group.
• radical polymerizable unsaturated monomer having a functional group having reactivity with a glycidyl group examples include the radical polymerizable unsaturated monomer having a carboxyl group and the radical polymerizable unsaturated monomer having a hydroxyl group. Is mentioned.
• the radical polymerizable unsaturated monomer (x-6) having a functional group reactive with a hydroxyl group, an isocyanate group or a glycidyl group may be used alone or in combination of two or more.
• Examples of the base compound (x-7) include amine compounds and inorganic base compounds.
• Examples of the amine compound include ammonia, primary amine, secondary amine, tertiary amine, and the like.
• Examples of the primary amine include ethylamine, n-propylamine, sec-propylamine, n-butylamine, sec-butylamine, i-butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine.
• Laurylamine mystyrylamine, 1,2-dimethylhexylamine, 3-pentylamine, 2-ethylhexylamine, allylamine, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol , 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3- (2-ethylenealookishirokishi) propylamine, aminocyclopentane, aminocyclohexane, amino norbornene, aminomethyl cyclohexane, aminobenzene, benzylamine, phenethylamine, alpha-phenylethylamine, naphthylamine, primary monoamine such as furfuryl amine;
• Ethylenediamine 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane 1,7-diaminoheptane, 1,8-diaminooctane, dimethylaminopropylamine, diethylaminopropylamine, bis- (3-aminopropyl) ether, 1,2-bis- (3-aminopropoxy) ethane, 1, 3-bis- (3-aminopropoxy) -2,2′-dimethylpropane, aminoethylethanolamine, 1,2-bisaminocyclohexane, 1,3-bisaminocyclohexane, 1,4-bisaminocyclohexane, 1, 3-bisaminomethylcyclohexane
• Examples of the secondary amine include diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine, Di (2-ethylhexyl) amine, methylhexylamine, diallylamine, pyrrolidine, piperidine, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, diphenylamine, N-methylaniline, N-ethylaniline, dibenzyl Secondary monoamines such as amine, methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole, morpholine;
• tertiary amine examples include trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-1,2-dimethylpropylamine, tri-3-methoxypropylamine, and tri-n-butylamine.
• Examples of the inorganic base compound include sodium hydroxide and potassium hydroxide.
• the basic compounds (x-7) fluorine-containing active energy ray curing that provides a cured coating film that has good solubility or dispersibility in the aqueous active energy ray-curable resin composition of the present invention and excellent leveling properties.
• an amine compound is preferred, a tertiary amine is preferred, and N, N-dimethylethanolamine is more preferred.
• the basic compound (x-7) may be used alone or in combination of two or more.
• the copolymer (P1-1), the copolymer (P1-2), the copolymer (P1-3) and the copolymer (P1-4) are, for example, a single unit for obtaining each copolymer. It can be obtained by polymerizing the monomer in an organic solvent using a radical polymerization initiator.
• Examples of the organic solvent include ketones, esters, amides, sulfoxides, ethers, and hydrocarbons. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability.
• radical polymerization initiator examples include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile.
• a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid or the like can be used as necessary.
• the molecular weight of the copolymer (P1-1), copolymer (P1-2), copolymer (P1-3), and copolymer (P1-4) is the fluorine-containing active energy ray-curable type finally obtained. Since the number of polymerizable unsaturated groups in one resin molecule increases, the number average molecular weight (Mn) is preferably 800 to 10,000, more preferably 1,000 to 5,000. Further, the weight average molecular weight (Mw) is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 2,500 to 20,000.
• the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement.
• the measurement conditions for GPC are as follows.
• the amount (acid value) of the acid groups contained in the copolymer (P1-1), the copolymer (P1-2), the copolymer (P1-3) and the copolymer (P1-4) More hydrate salt structure (a4) can be introduced, and a fluorine-containing active energy ray-curable resin excellent in water-solubility or water-dispersibility can be obtained. 50 to 450 mgKOH / g is more preferable.
• -6) may be reacted under the condition that the polymerizable unsaturated group in the radical polymerizable unsaturated monomer is not polymerized.
• the reaction is carried out by adjusting the temperature condition in the range of 30 to 120 ° C. It is preferable to make it.
• This reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor and, if necessary, in the presence of an organic solvent.
• copolymer (P1-2) or copolymer (P1-4) is a copolymer having a hydroxyl group and the functional group having reactivity with the hydroxyl group is an isocyanate group, p- Methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, etc. are used, and dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate, etc.
• a copolymer (P2-2) and a copolymer (P2-4) are used as the urethanization reaction catalyst, It is preferable to obtain a copolymer (P2-2) and a copolymer (P2-4) by a method of reacting at a reaction temperature of 40 to 120 ° C., particularly 60 to 90 ° C., respectively.
• the copolymer (P1-2) or the copolymer (P1-4) is a copolymer having a glycidyl group and the functional group reactive with the glycidyl group is a carboxyl group
• Ammonia, tertiary phosphines such as triphenylphosphine, quaternary phosphoniums such as tetrabutylphosphonium chloride, etc. are used for the copolymerization by a reaction method at a reaction temperature of 80 to 130 ° C., particularly 100 to 120 ° C. P2-2) and a copolymer (P2-4) are preferably obtained.
• the copolymer (P1-2) and the copolymer (P1-4) are copolymers having an isocyanate group, and the functional group reactive with the isocyanate group is a hydroxyl group, a polymerization inhibitor P-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol and the like, and dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate, etc.
• urethanization reaction catalysts It is preferable to obtain a copolymer (P2-2) and a copolymer (P2-4) by a method of using and reacting at a reaction temperature of 40 to 120 ° C., particularly 60 to 90 ° C.
• this method is a reaction product of a copolymer (fluorine-containing active energy ray-curable resin) having an acid value of 10 to 600 mgKOH / g and a base compound,
• the compound used in an amount of 0.5 to 1.0 equivalent to the acid contained in the fluorine-containing active energy ray-curable resin becomes a fluorine-containing active energy ray-curable resin having excellent solubility in water. This is more preferable.
• fluorine-containing active energy ray-curable resins of the present invention those having an oxyalkylene chain in the side chain have good solubility or dispersibility in the aqueous active energy ray-curable resin composition, and the level is low. It is preferable because a cured coating film having excellent ring properties can be obtained.
• the fluorine-containing active energy ray-curable resin having an oxyalkylene chain in the side chain include the copolymer (P1-1), copolymer (P1-2), copolymer (P1-3), and copolymer. (P1-4) can be obtained by using a radically polymerizable unsaturated monomer having an oxyalkylene chain in combination.
• radical polymerizable unsaturated monomer having an oxyalkylene chain examples include polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, and poly (ethylene glycol / propylene).
• Glycol) mono (meth) acrylate polyethylene glycol / polypropylene glycol mono (meth) acrylate, poly (ethylene glycol / tetramethylene glycol) mono (meth) acrylate, polyethylene glycol / polytetramethylene glycol mono (meth) acrylate, poly (propylene) Glycol ⁇ tetramethylene glycol) mono (meth) acrylate, polypropylene glycol ⁇ polytetramethylene glycol mono (Meth) acrylate, poly (propylene glycol / butylene glycol) mono (meth) acrylate, polypropylene glycol / polybutylene glycol mono (meth) acrylate, poly (ethylene glycol / butylene glycol) mono (meth) acrylate, polyethylene glycol / polybutylene glycol Mono (meth) acrylate, poly (ethylene glycol / polybutylene glycol Mono (meth) acrylate, poly (tetraethylene glyco
• Poly (ethylene glycol / propylene glycol) means a random copolymer of ethylene glycol and propylene glycol
• polyethylene glycol / polypropylene glycol means a block copolymer of ethylene glycol and propylene glycol. means. The same applies to other items.
• radical polymerizable unsaturated monomers having an oxyalkylene chain a radical polymerizable unsaturated monomer having an oxyethylene chain is preferable, and polyethylene glycol mono (meth) acrylate is more preferable.
• Examples of commercially available radical polymerizable unsaturated monomers having an oxyalkylene chain include “NK Ester M-20G”, “NK Ester M-40G”, and “NK Ester M” manufactured by Shin-Nakamura Chemical Co., Ltd. -90G “,” NK ester M-230G “,” NK ester AM-90G “,” NK ester AMP-10G “,” NK ester AMP-20G “,” NK ester AMP-60G “, manufactured by NOF Corporation “Blemmer PE-90”, “Blemmer PE-200”, “Blemmer PE-350”, “Blemmer PME-100”, “Blemmer PME-200”, “Blemmer PME-400”, “Blemmer PME-4000”, “ “Blemmer PP-1000”, “Blemmer PP-500”, “Blemmer PP-800", “Blemma 70PEP-350B “,” Blemmer 55PET-800 “,” Blemmer 50POEP-800B “,”
• a radical polymerizable unsaturated monomer other than the above-mentioned radical polymerizable unsaturated monomer is used within a range not impairing the effects of the present invention. Also good.
• Examples of such radically polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, (meth) acrylate-n-butyl, (Meth) acrylic acid isobutyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) (Meth) acrylates such as 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate Aromatic vinyls such as styrene, ⁇ -methylstyrene, p-methylst
• the organic solvent in the reaction system is removed by a method such as reprecipitation and concentration, and water is added to dissolve or disperse in water. You may let them.
• the surfactant of the present invention comprises a polymer structure (a1) of a radically polymerizable unsaturated monomer, a poly (perfluoroalkylene ether) chain (a2), a radically polymerizable unsaturated group (a3), an acid And a neutralized salt structure (a4) of the group.
• the active energy ray-curable resin composition of the present invention is a fluorine-containing active energy ray-curable resin of the present invention (hereinafter, this may be abbreviated as a fluorine-containing active energy ray-curable resin (A)). And an active energy ray-curable hydrophilic resin (B) other than the fluorine-containing active energy ray-curable resin (A), and water, and an active energy ray-curable resin composition. .
• Examples of the active energy ray-curable hydrophilic resin (B) include those having a radical polymerizable group and a hydrophilic functional group.
• Examples of the radical polymerizable group include a (meth) acryloyl group, a vinyl group, and an allyl group. Among these, a (meth) acryloyl group is preferred because it is excellent in photocurability and provides a sufficiently photocured cured coating film.
• hydrophilic functional group examples include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a polyoxyethylene chain.
• the hydrophilic functional group is preferably a carboxyl group or a polyoxyethylene chain because the raw material is easily available, the synthesis is easy, and the active energy ray-curable hydrophilic resin (B) can be easily obtained.
• active energy ray-curable hydrophilic resin (B) examples include, for example, a hydrophilic epoxy resin having a radical polymerizable unsaturated group and a hydrophilic (meth) acrylic resin having a radical polymerizable unsaturated group. Etc.
• the hydrophilic epoxy resin for example, after reacting an epoxy resin with a radical polymerizable unsaturated monomer having a functional group reactive with the epoxy group of the epoxy resin, the epoxy resin is further reacted. It can be obtained by reacting a functional group having reactivity with an epoxy group possessed by a compound having a hydrophilic group.
• epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type An epoxy resin, a biphenyl type epoxy resin, a tetramethyl biphenyl type epoxy resin, etc. are mentioned.
• radical polymerizable unsaturated monomer having a functional group reactive with an epoxy group examples include (meth) acrylic acid, ⁇ -carboxyethyl acrylate, and the like.
• Examples of the compound having a functional group having reactivity with an epoxy group and a hydrophilic group include polyvalent carboxylic acids such as phthalic acid and phthalic anhydride, polyvalent carboxylic acid anhydrides; sulfonic acid, phosphoric acid, and the like. .
• hydrophilic (meth) acrylic resin having a radical polymerizable organic group examples include a reaction product of an acrylic resin having a hydroxyl group, a polyisocyanate compound, and a radical polymerizable unsaturated monomer having a hydroxyl group. .
• the copolymer (b4) includes a radical polymerizable unsaturated monomer (b1) having a polyoxyalkylene group, a radical polymerizable unsaturated monomer (b2) having a hydroxyl group, and the radical polymerizable unsaturated monomer. It is a copolymer using radically polymerizable unsaturated monomer (b3) other than body (b1) and radically polymerizable unsaturated monomer (b2) as an essential raw material.
• the radical polymerizable unsaturated monomer (b1) is, for example, a compound having a polyoxyalkylene group and a (meth) acryloyl group.
• the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, and the like.
• radical polymerizable unsaturated monomer (b1) examples include those represented by the following general formula (b-1).
• R 1 is a hydrogen atom or a methyl group
• X, Y and Z are each independently an alkylene group
• p, q and r are each 0 or an integer of 1 or more
• p, q and are each 0 or an integer of 1 or more
• p, q and The total of r is an integer of 1 or more
• R 2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
• X, Y and Z are alkylene groups.
• alkylene group examples include an ethylene group, a propylene group and a butylene group. These alkylene groups include: Those having a substituent are also included.
• p, q, and r represent the number of repeating units of the oxyalkylene group.
• the dispersibility in water is improved, and the storage stability of the resulting active energy ray-curable resin composition is improved.
• the total is preferably 4 to 100, more preferably 6 to 50, and even more preferably 8 to 25.
• the repeating unit containing X, the repeating unit containing Y, and the repeating unit containing Z may be arrange
• R 2 in the general formula (1) is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
• the radical polymerizable unsaturated monomer (b1) is a mono (meth) acrylic acid ester of polyalkylene glycol such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and R 2 is carbon.
• the end of the alkylene glycol mono (meth) acrylate ester which is not the (meth) acryloyl group is blocked with an alkyl group or phenyl group having 1 to 6 carbon atoms Will be.
• R 2 is preferably an alkyl group having 1 to 3 carbon atoms, R 2 is more preferably a methyl group.
• radical polymerizable unsaturated monomer (b1) examples include polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxypolyethylene glycol (meth) acrylate, and butoxypolyethylene.
• radical polymerizable unsaturated monomers (b1) those having a polyoxyethylene group are preferable because the dispersibility of the acrylic resin (B1) in an aqueous medium is improved.
• the radically polymerizable unsaturated monomer (b1) can be used alone or in combination of two or more.
• the radical polymerizable unsaturated monomer (b2) is a compound other than the radical polymerizable unsaturated monomer (b1) and having a hydroxyl group and a (meth) acryloyl group.
• Specific examples of the radical polymerizable unsaturated monomer (b2) include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2- Hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acryl
• the radical polymerizable unsaturated monomer (b3) is a radical polymerizable unsaturated monomer other than the radical polymerizable unsaturated monomers (b1) and (b2).
• examples of the radical polymerizable unsaturated monomer (b3) include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- Butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodec
• radical polymerizable unsaturated monomers (b3) an aliphatic or alicyclic acrylic monomer is preferable because the storage stability of the obtained active energy ray-curable resin composition is further improved.
• An alicyclic radically polymerizable unsaturated monomer is more preferable.
• the radically polymerizable unsaturated monomer (b3) can be used alone or in combination of two or more.
• radical polymerizable unsaturated monomer (b1) radical polymerizable unsaturated monomer (b2), and radical polymerizable unsaturated monomer (b3) as raw materials for the copolymer (b4)
• Other monomers may be used.
• the other monomers include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, p-methylstyrene, and p-methoxystyrene.
• the amount of the radical polymerizable unsaturated monomer (b1) used is such that the dispersibility in water is improved and the storage stability of the resulting active energy ray-curable resin composition is improved.
• the mass ratio in the monomer component as the raw material of b4) is preferably in the range of 30 to 80% by mass, more preferably in the range of 40 to 70% by mass.
• the amount of the radical polymerizable unsaturated monomer (b2) used is such that the dispersibility in water is improved and the storage stability of the resulting active energy ray-curable resin composition is improved.
• the mass ratio in the monomer component as the raw material of the polymer (b4) is preferably in the range of 2 to 30% by mass, more preferably in the range of 3 to 25% by mass, and still more preferably in the range of 5 to 20% by mass. .
• the usage-amount of the said radically polymerizable unsaturated monomer (b3) and the other monomer used as needed is a total of 100 mass% of the monomer component which is a raw material of the said copolymer (b4). To the remainder obtained by removing the use ratio of the radical polymerizable unsaturated monomer (b1) and the radical polymerizable unsaturated monomer (b2).
• the radically polymerizable unsaturated monomers (b1) to (b3) and other monomers used as required are used in an organic solvent, a polymerization initiator.
• the method of using and copolymerizing is mentioned.
• an alcohol compound, a ketone compound, an ester compound, an ether compound, an amide compound, a sulfoxide compound, and a hydrocarbon compound are preferable, and specifically, methanol, ethanol, propanol, n-butanol, iso -Butanol, tert-butanol, 3-methoxybutanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, diisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol dibutyl ether, propylene glycol mono
• dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and dipropylene glycol dimethyl ether are more preferable because the storage stability of the obtained active energy ray-curable resin composition is improved.
• Examples of the polymerization initiator include ketone peroxide compounds such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2-bis (4,4-di tert-butylperoxycyclohexyl) propane, 2,2-bis (4,4-ditert-amylperoxycyclohexyl) propane, 2,2-bis (4,4-ditert-hexylperoxycyclohexyl) propane, 2 , 2-Bis (4,4-ditert-octyl Peroxyketal compounds such as -oxycyclohexyl) propane and 2,2-bis (4,
• the copolymer (b4) when the copolymer (b4) is produced, chain transfer of lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid or the like is performed as necessary. You may use an agent.
• the hydroxyl value of the copolymer (b4) is preferably in the range of 5 to 130 mgKOH / g because the dispersibility in water is improved and the storage stability of the resulting active energy ray-curable resin composition is improved.
• the range of 10 to 100 mgKOH / g is more preferable, and the range of 15 to 80 mgKOH / g is more preferable.
• the weight average molecular weight (Mw) of the copolymer (b4) is improved in dispersibility in water, and the storage stability of the resulting active energy ray-curable resin composition is improved. In the range of 4,000 to 50,000, more preferably in the range of 5,000 to 30,000.
• polyisocyanate compound (b5) examples include aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, m-phenylenebis (dimethylmethylene) diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, 1, Fats such as 3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate And aliphatic or alicyclic diisocyanate compounds. Among these, an aliphatic or alicyclic diisocyanate compound is preferable because of excellent yellowing resistance.
• polyisocyanate compound (b5) a prepolymer having an isocyanate group obtained by addition reaction of the diisocyanate compound with a polyhydric alcohol; an isocyanurate ring obtained by cyclization and trimerization of the diisocyanate compound.
• the polyisocyanate compound (b5) can be used alone or in combination of two or more.
• the radical polymerizable unsaturated monomer (b6) having a hydroxyl group is a compound having a (meth) acryloyl group as a hydroxyl group and a radical polymerizable unsaturated group.
• examples of the radical polymerizable unsaturated monomer (b6) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) ) (Meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxy
• radical-polymerizable unsaturated monomers (b6) since the viscosity is low, the handling is easy, and the surface hardness of the cured coating film obtained from the obtained active energy ray-curable resin composition can be increased. Erythritol triacrylate is preferred.
• Examples of the reaction method of the copolymer (b4), the polyisocyanate compound (b5), and the radical polymerizable unsaturated monomer (b6) include, for example, the copolymer (b4), the polyisocyanate compound (b5), and a radical.
• a method of reacting the copolymer (b4) and the polyisocyanate compound (b5), and a method of reacting the radical polymerizable unsaturated monomer (b6) may be used. Absent.
• the reaction of the copolymer (b4), the polyisocyanate compound (b5) and the radical polymerizable unsaturated monomer (b6) can be carried out without a catalyst, but in order to accelerate the progress of the reaction, a urethanization catalyst It is preferable to perform in presence of this.
• a urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphine compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, and dibutyltin.
• organotin compounds such as diacetate and tin octylate
• organometallic compounds such as zinc octylate.
• dibutyltin dilaurate is preferable.
• the mass ratio [(b4) / (b6)] of the copolymer (b4) and the radical polymerizable unsaturated monomer (b6) improves the dispersibility in water, and the resulting active energy ray curing
• the range of 0.2 to 8.0 is preferable, the range of 0.3 to 4.5 is more preferable, and the range of 0.5 to 2.5 is more preferable because the storage stability of the mold resin composition is improved. preferable.
• the amount of the copolymer (b4), polyisocyanate compound (b5) and radical polymerizable unsaturated monomer (b6) used is such that the dispersibility in water is improved, and the resulting active energy ray-curable resin is obtained. Since the storage stability of the composition is improved, the hydroxyl group and radical polymerizable unsaturated monomer of the copolymer (b4) with respect to the number of moles of isocyanate group of the polyisocyanate compound (b5) is 1.
• the range in which the total number of moles of hydroxyl groups (b6) has is preferably 0.2 to 1.2, more preferably 0.4 to 1.0.
• the polyisocyanate compound (b5) and the radical polymerizable unsaturated monomer (b6) when an organic solvent is present, it reacts with the polyisocyanate compound (b5). It is preferable to remove the organic solvent.
• the content of the fluorine-containing active energy ray-curable resin (A) in the active energy ray-curable resin composition of the present invention is 0.001 to 10 parts by mass in the composition with respect to 100 parts by mass of the nonvolatile content.
• This is preferably a composition that provides a coating film having excellent compatibility with other resins and excellent antifouling properties, more preferably 0.01 to 3 parts by mass, and still more preferably 0.1 to 1 part by mass.
• the content of the active energy ray-curable hydrophilic resin (B) in the active energy ray-curable resin composition of the present invention is 10 to 50 parts by mass with respect to 100 parts by mass of the non-volatile content, and the viscosity is low. It is preferable because the composition has excellent coating properties, and 20 to 40 parts by mass is more preferable.
• the active energy ray-curable resin composition of the present invention usually contains a polymerization initiator.
• the polymerization initiator include benzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzyl methyl ketal, azobisisobutyronitrile, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- Phenyl-1-one, 1- (4′-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4′-dodecylphenyl) -2-hydroxy-2-methylpropane-1- ON, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4 ′′ -diethylisophthalophene, 2,2-dimethoxy-1,2-diphenylethane-1-one , Benzoin isopropyl ether,
• a photosensitizer such as an amine compound or a phosphorus compound can be added to promote photopolymerization.
• the content of the polymerization initiator in the active energy ray-curable resin composition of the present invention is 100 parts by mass in total of the fluorine-containing active energy ray-curable resin (A) and the active energy ray-curable hydrophilic resin (B).
• the range is preferably from 0.01 to 15 parts by mass, and more preferably from 0.3 to 7 parts by mass.
• the active energy ray-curable resin composition of the present invention includes a filler, a dispersant, a surfactant other than the fluorine-containing active energy ray-curable resin of the present invention, a hydrophilic solvent, and the like within a range not impairing the effects of the present invention. Can also be added.
• hydrophilic solvent examples include tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, methanol, ethanol, propanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, Examples include diethylene glycol monomethyl ether and diethylene glycol dimethyl ether.
• the cured coating film of the present invention is obtained by curing the active energy ray-curable resin composition of the present invention.
• the film thickness of the cured coating film is, for example, 1 to 300 ⁇ m, and may be 10 to 250 ⁇ m or 15 to 200 ⁇ m.
• the method of applying the active energy ray-curable resin composition used in obtaining the cured coating film of the present invention varies depending on the application, for example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, Various methods such as kiss coater, shower coater, wheeler coater, spin coater, dipping, screen printing, spray, applicator, bar coater, air spray, airless spray, roller, ricin gun, universal gun, brush, electrostatic coating, etc. can be used. it can.
• active energy ray-curable resin composition After applying the active energy ray-curable resin composition, it is usually dried.
• the drying method may be either heat drying or room temperature drying.
• active energy rays are irradiated to obtain the cured coating film of the present invention.
• Active energy rays are ionizing radiation such as ultraviolet rays, electron rays, ⁇ rays, ⁇ rays, and ⁇ rays.
• Specific energy sources or curing devices include, for example, germicidal lamps, fluorescent lamps for ultraviolet rays, carbon Examples include arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, ultraviolet rays using natural light as the light source, or electron beams from scanning or curtain type electron beam accelerators. It is done.
• the fluorine-containing active energy ray-curable resin of the present invention can be suitably used as an aqueous active energy ray-curable resin composition as a surfactant.
• the active energy ray-curable resin composition of the present invention can provide a cured coating film excellent in leveling property and antifouling property without containing an organic solvent, and can be used as a coating material for various applications.
• the active energy ray-curable resin composition of the present invention is a protective film for a polarizing plate for a liquid crystal display typified by a TAC film and a hard coat material for a touch panel protective film; a mobile phone, a smartphone, a TV, Hard coating agent for liquid crystal displays and organic EL displays of digital cameras and game machines; Hard coating agent for casings of electrical appliances such as mobile phones, smartphones, personal computers, TVs, refrigerators, washing machines, air conditioners, digital cameras, and game machines Coating agents for optical lenses; black matrix paints and inks used in color filters for liquid crystal displays; black resists; interior materials for various vehicles such as automobiles and railway vehicles; leathers such as artificial leather and synthetic leather; FRP bathtubs FRP products such as, decorative panels, etc.
• Optical fiber cladding materials; various building materials, paints woodworking materials of furniture waveguide; liquid sealant; various optical sealing materials; can be suitably used in optical adhesive or the like.
• methoxypolyethylene glycol acrylate (oxyethylene units per molecule) Number: 13 or less on average, “AM-130G” manufactured by Shin-Nakamura Chemical Co., Ltd.) 325 g, 75 g of 2-hydroxyethyl methacrylate, 241 g of isobornyl acrylate, 2,2′-azobis (2,4-dimethylvaleronitrile) (Nippon Finechem) (ABN-V)) 11 g and methyl ethyl ketone 47 g were added dropwise over 5 hours. After dripping, it reacted at 75 degreeC for 3 hours, and obtained the solution (resin content 65 mass%) containing the polymer (b4) whose weight average molecular weight is 11,500 and whose hydroxyl value is 50.
• Example 1 Fluorine-containing active energy ray-curable resin
• a1 Fluorine-containing active energy ray-curable resin
• PFPE is a perfluoromethylene group and a perfluoroethylene group, and an average of 19 perfluoromethylene groups and an average of 19 perfluoroethylene groups per molecule.
• a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula: 68 g of p-chloromethylstyrene, 0.05 g of p-methoxyphenol, 44 g of a 50% by weight aqueous solution of benzyltriethylammonium chloride and 0.12 g of potassium iodide. Prepared.
• the produced salt was filtered off, the filtrate was allowed to stand, and the supernatant was removed. Further, 500 mL of water was added to the filtrate and washed with water. This water washing was performed 3 times, and after washing with water, 500 mL of methanol was further added to wash the filtrate. Washing of the salt with methanol was performed three times.
• PFPE is a perfluoromethylene group and a perfluoroethylene group, and an average of 19 perfluoromethylene groups and an average of 19 perfluoroethylene groups per molecule.
• a radically polymerizable unsaturated monomer (X1) having a poly (perfluoroalkylene ether) chain represented by the formula (1) and a styryl group at both ends thereof was obtained.
• a glass flask equipped with a stirrer, a thermometer, a condenser, and a dripping device was charged with 100 g of propylene glycol monomethyl ether as a solvent and heated to 105 ° C. while stirring under a nitrogen stream.
• 20 g of radical polymerizable unsaturated monomer (X1), 40 g of polyethylene glycol monoacrylate (ethylene chain repeat number 9) and 40 g of methacrylic acid were dissolved in 150 parts by mass of propylene glycol monomethyl ether, and radical polymerization was started.
• a polymerization initiator solution prepared by dissolving 15 g of t-butylperoxy-2-ethylhexanoate in 50 g of propylene glycol monomethyl ether, were set in separate dripping apparatuses, and the flask was heated to 105 ° C. While maintaining, it was added dropwise over 2 hours. After completion of the dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer (P-1) solution.
• the polymer (P-1) solution obtained above was adjusted to a solid content of 60%, 0.1 g of p-methoxyphenol was added as a polymerization inhibitor, and stirring was started under an air stream.
• the temperature reached 80 ° C.
• 39 g of 4-hydroxybutyl acrylate glycidyl ether and 0.4 g of triphenylphosphine were charged as a catalyst, and the temperature was further raised to 110 ° C., followed by stirring at 110 ° C. for 10 hours.
• a solution of the polymer (P-2) was obtained.
• a part of the solvent was distilled off from the polymer (P-2) solution under reduced pressure to obtain a 90% solution of the polymer (P-2).
• the polymer (P-2) had a weight average molecular weight (Mn) of 6,400 and an acid value of 95 mgKOH / g.
• Mn weight average molecular weight
• 1.5 g (1.0 equivalent) of dimethylethanolamine and 15 g of water were added to 10 g of a 90% solution of the polymer (P-2), stirred for 1 hour at 25 ° C., and further diluted with water.
• An aqueous solution containing 20% of the fluorine-containing active energy ray-curable resin (A1) of the invention was obtained.
• Comparative Example 1 fluorine-containing active energy ray-curable resin for comparison
• a glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 73.1 g of 1,3-bis (trifluoromethyl) benzene as a solvent, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. did.
• Example 2 active energy ray-curable resin composition
• the base of the active energy ray-curable composition is prepared by mixing 100 parts of an aqueous solution (B1) of an active energy curable hydrophilic resin and “Irgacure 500” 1.6 manufactured by Ciba Specialty Chemicals as a photopolymerization initiator. A composition was obtained.
• the fluorine-containing active energy ray-curable resin (1) is added in an amount of 1 part as a resin component and mixed to obtain the active energy ray-curable resin composition (1) of the present invention. It was.
• the active energy ray-curable resin composition (1) was applied to a glass substrate with an applicator so that the film thickness after drying was 20 ⁇ m, and this was placed in a dryer at 25 ° C. for 10 minutes, and then 80 The medium was volatilized for 10 minutes in a dryer at 0 ° C. to obtain a dry coating film.
• the dried coating film was cured by irradiating with ultraviolet rays (UV) with an ultraviolet curing device (in an air atmosphere, a high-pressure mercury lamp, an ultraviolet irradiation amount of 8 kJ / m 2 ) to obtain a cured coating film.
• UV ultraviolet rays
• an ultraviolet curing device in an air atmosphere, a high-pressure mercury lamp, an ultraviolet irradiation amount of 8 kJ / m 2
• ⁇ Evaluation of dirt adhesion prevention> On the surface of the cured coating film, a line was drawn with a felt pen ("Magic Ink Large Blue” manufactured by Teranishi Chemical Industry Co., Ltd.), and the adhesion of the blue ink was visually observed to evaluate the antifouling property. .
• the evaluation criteria are as follows. A: The antifouling property is the best and the ink repels. B: The ink does not repel, but a linear repelling occurs and the line width is less than 50% of the width of the tip of the felt pen. C: Ink repelling occurs and the line width is 50% or more and less than 100% of the width of the tip of the felt pen. D: The ink does not repel at all, and the line can be drawn cleanly on the surface.
• Comparative Example 3 (active energy ray-curable resin composition for comparison) Comparative active energy ray curable resin composition as in Example 1 except that the comparative fluorine containing active energy curable resin (1 ') was used instead of the fluorine containing active energy ray curable resin (1). A product (1 ') was obtained. A cured coating film was prepared using this, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.
• Comparative Example 4 Active energy ray non-curable type for comparison object as in Example 1 except that the fluorine-containing non-active energy curable resin (2 ') for comparison was used instead of the fluorine-containing active energy ray curable resin (1).
• a resin composition (2 ′) was obtained.
• a cured coating film was prepared using this, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.
• Comparative Example 5 Active energy for comparison in the same manner as in Example 1 except that 100 parts of the base composition used in Example 1 was used instead of the active energy ray-curable resin composition (1). A line curable resin composition (3 ′) was obtained. A cured coating film was prepared using this, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.
• Footnote of Table 1 Impossible to measure could not measure because a uniform coating film could not be formed.

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