CN103703038B - Aqueous polyurethane resin dispersion and application thereof - Google Patents
Aqueous polyurethane resin dispersion and application thereof Download PDFInfo
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- CN103703038B CN103703038B CN201280035864.6A CN201280035864A CN103703038B CN 103703038 B CN103703038 B CN 103703038B CN 201280035864 A CN201280035864 A CN 201280035864A CN 103703038 B CN103703038 B CN 103703038B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
Abstract
The invention provides a kind of aqueous polyurethane resin dispersion, its manufacturing time is short, package stability is excellent, and the film after using active energy beam (such as ultraviolet) to irradiate and solidifying has high rigidity and has high adhesion relative to base material.The feature of aqueous polyurethane resin dispersion of the present invention is, it is the urethane resin (A) at least making to have polymerizability unsaturated link(age), with the aqueous polyurethane resin dispersion composition that the compound (B) with polymerizability unsaturated link(age) disperses in water-medium, wherein, the urethane resin (A) with polymerizability unsaturated link(age) at least makes polyvalent alcohol (a), containing the polyvalent alcohol (b) of acidic-group, polymeric polyisocyanate (c) and the urethane resin obtained containing (methyl) acrylate (d) reaction of primary hydroxyl, containing (methyl) acrylate (d) of primary hydroxyl and the total amount of compound (B) with polymerizability unsaturated link(age) be resin solid content overall 60 ~ 80 % by weight, the present invention also provides the Photocurable composition containing this aqueous polyurethane resin dispersion, coating composition and Liniment composition.
Description
Technical field
The present invention relates to that to utilize take ultraviolet as the aqueous polyurethane resin dispersion that is cured of the active energy beam of representative and application thereof.
Background technology
Polycarbonate polyol is as the useful compound of the raw material of urethane resin, by the reaction with isocyanate compound, the urethane resin used in rigid foam, flexible foam, coating, caking agent, synthetic leather, black liquid binding agent etc. can be manufactured on.In addition, photostabilization, weathering resistance, thermotolerance, hydrolytic resistance, the oil-proofness excellence (with reference to patent documentation 1) of known coating film that polycarbonate polyol is obtained as the aqueous polyurethane resin dispersion of raw material.
Wherein, known to employing the aqueous polyurethane resin dispersion coating of aliphatic polycarbonate polybasic alcohol and the film that obtain, adaptation, the resistance to blocking of itself and base material are improved, and therefore can be used as silane coupling agent (reference patent documentation 2).But, when only aliphatic polycarbonate polybasic alcohol being used as raw material, there is following problems, that is, by the hardness, insufficient in the paint field, Liniment field of the synthetic resin forming bodies such as earth material such as built-in material, Cell phone housing, household appliances housing, notebook computer casing, decorating film, blooming, floor of such as automobile with the adaptation of base material of the film of aqueous polyurethane resin dispersion gained.
In order to improve hardness, the weather resistance of film, also proposed the aqueous polyurethane resin dispersion (with reference to patent documentation 3,4 and 5) employing the polycarbonate polyol with alicyclic structure.But, when use there is the polycarbonate polyol of alicyclic structure, have that urethane resin is deteriorated to the dispersiveness in water-medium, the disposal of aqueous polyurethane resin dispersion and a such problem of bad stability.And, such as, for the aqueous polyurethane resin dispersion of patent documentation 3, indefinite on the impact of adaptation, and also can not meet its requirement for for the dispersiveness in water-medium.
About hardness of film, when hard painting purposes, film generally needs the pencil hardness of more than 2H.Therefore, in order to improve hardness of film, be investigated the situation using carbamate (methyl) acrylate, propose the water-based radiation-curing composition (with reference to patent documentation 6) such as comprising (methyl) acrylated urethanes prepolymer and ethene unsaturated compound and the water-based irradiation solidification compound (with reference to patent documentation 7) comprising high molecular weight ethylene unsaturated polyurethanes and low-molecular-weight ethylenic unsaturated polyurethanes.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 10-120757 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2005-281544 publication
Patent documentation 3: Japanese Unexamined Patent Publication 6-248046 publication
Patent documentation 4: International Publication No. 2009/145242 publication
Patent documentation 5: International Publication No. 2009/004951 publication
Patent documentation 6: Japanese Unexamined Patent Application Publication 2009-533504 publication
Patent documentation 7: International Publication No. 2009/147092 publication
Summary of the invention
Invent problem to be solved
But, for disclosed composition concrete in patent documentation 6, in the manufacture of (methyl) acrylated urethanes prepolymer, use (methyl) acrylate of 2 officials' energy with secondary hydroxyl, or marginally employ the DPHA of hydroxyl value less than 80mgKOH/g.Therefore known, when manufacturing prepolymer, need to make the reaction times under heating elongated, even if thus use do not have aromatic nucleus without xanthochromia type isocyanic ester, also can produce the problem of xanthochromia.In addition we know, if make the reaction times shorten, and use hydroxyl value less than the DPHA of 80mgKOH/g in large quantities, or do not use (methyl) acrylate of 2 officials' energy with secondary hydroxyl, then can produce following problem: the package stability deterioration of water-based Radioactive composition, or hardness is not enough, or when the film of composition is formed on plexiglass (PMMA resin), adaptation is not enough.
In addition we know, for the disclosed composition particularly of institute in patent documentation 7, exist and do not have closely sealed as transparent material completely for multi-purpose (methyl) acrylic resin, and pencil hardness also too low such problem.
Problem of the present invention is, provides that a kind of manufacturing time is short, package stability is excellent and uses active energy beam (such as ultraviolet) to irradiate and film after solidification has the aqueous polyurethane resin dispersion of high rigidity.In addition, problem of the present invention is, provide use active energy beam (such as ultraviolet) irradiate and solidification after film for base material, especially, (methyl) acrylic resin (such as plexiglass (PMMA resin)) and acrylic nitrile-butadiene-alkene-styrene resin (ABS resin) have the aqueous polyurethane resin dispersion of high adhesion.
For solving the means of problem
The present inventor etc. are in order to solve above-mentioned problem in the past and carry out various research, result obtains the opinion that can be solved described problem by following aqueous polyurethane resin dispersion, thus complete the present invention, described aqueous polyurethane resin dispersion be make following have the urethane resin (A) of polymerizability unsaturated link(age) with there is the compound (B) of polymerizability unsaturated link(age), with the described compound (B) with polymerizability unsaturated link(age) and the total amount of (methyl) acrylate (d) containing primary hydroxyl reach resin solid content overall 60 ~ 80 % by weight the mode of amount carry out combining and the aqueous polyurethane resin dispersion that obtains, wherein, the described urethane resin (A) with polymerizability unsaturated link(age) at least makes polyvalent alcohol (a), containing the polyvalent alcohol (b) of acidic-group, polymeric polyisocyanate (c) and the urethane resin obtained containing (methyl) acrylate (d) reaction of primary hydroxyl.At this, resin solid content refers to, urethane resin (A) and have the total of compound (B) of polymerizability unsaturated link(age).But resin solid content does not comprise for the neutralizing agent by the alkali of the acidic-group of the polyvalent alcohol (b) containing acidic-group neutralization or alkalescence etc.
The present invention (1) relates to a kind of aqueous polyurethane resin dispersion, it is characterized in that, it is the aqueous polyurethane resin dispersion composition that the urethane resin (A) at least making to have polymerizability unsaturated link(age) and the compound (B) with polymerizability unsaturated link(age) are dispersed in water-medium, wherein
The urethane resin (A) with polymerizability unsaturated link(age) is the resin at least making polyvalent alcohol (a), polyvalent alcohol (b) containing acidic-group, polymeric polyisocyanate (c) and obtain containing (methyl) acrylate (d) reaction of primary hydroxyl,
Containing (methyl) acrylate (d) of primary hydroxyl and the total amount of compound (B) with polymerizability unsaturated link(age) be resin solid content overall 60 ~ 80 % by weight.
The present invention (2) relates to the aqueous polyurethane resin dispersion of the present invention (1), and wherein, polyvalent alcohol (a) is polycarbonate diol.
The present invention (3) relates to the aqueous polyurethane resin dispersion of the present invention (1) or (2), wherein, containing (methyl) acrylate (d) and the total amount of compound (B) with polymerizability unsaturated link(age) of primary hydroxyl be resin solid content overall 65 ~ 75 % by weight.
The present invention (4) relates to the aqueous polyurethane resin dispersion any one of the present invention (1) ~ (3), and wherein, the compound (B) with polymerizability unsaturated link(age) is the compound in 1 molecule with more than 3 (methyl) acryls more than 3.
The present invention (5) relates to the aqueous polyurethane resin dispersion any one of the present invention (1) ~ (3), wherein, there is the compound (B) of polymerizability unsaturated link(age) for being selected from more than a kind in oxirane modification tetramethylolmethane four (methyl) acrylate, oxirane modification trimethylolpropane tris (methyl) acrylate, oxirane modification ethylene glycol bisthioglycolate (methyl) acrylate.
The present invention (6) relates to the aqueous polyurethane resin dispersion any one of the present invention (1) ~ (5), and wherein, the compound (B) with polymerizability unsaturated link(age) is oxirane modification tetramethylolmethane four (methyl) acrylate.
The present invention (7) relates to the aqueous polyurethane resin dispersion any one of the present invention (1) ~ (6), wherein, containing (methyl) acrylate (d) of primary hydroxyl with the form of its mixture with inactive relative to isocyanate base (methyl) acrylate, and be imparted in the reaction for obtaining urethane resin (A).
The present invention (8) relates to the aqueous polyurethane resin dispersion any one of the present invention (1) ~ (7), wherein, (methyl) acrylate (d) containing primary hydroxyl is more than 80mgKOH/g and the form of the mixture of Dipentaerythritol six (methyl) acrylate of below 120mgKOH/g and Dipentaerythritol five (methyl) acrylate with hydroxyl value, and is imparted in the reaction for obtaining urethane resin (A).
The present invention (9) relates to the aqueous polyurethane resin dispersion any one of the present invention (1) ~ (7), wherein, (methyl) acrylate (d) containing primary hydroxyl is more than 100mgKOH/g and the form of the mixture of tetramethylolmethane four (methyl) acrylate of below 280mgKOH/g and tetramethylolmethane three (methyl) acrylate with hydroxyl value, and is imparted in the reaction for obtaining urethane resin (A).
The present invention (10) relates to the Photocurable composition any one of the present invention (1) ~ (9), and it contains Photoepolymerizationinitiater initiater.
The present invention (11) relates to a kind of coating composition, and it contains the aqueous polyurethane resin dispersion any one of the present invention (1) ~ (9).
The present invention (12) relates to the coating composition of the present invention (11), and it is for (methyl) acrylic resin or acrylic nitrile-butadiene-alkene-styrene resin.
The present invention (13) relates to a kind of Liniment composition, and it contains the aqueous polyurethane resin dispersion any one of the present invention (1) ~ (9).
The present invention (14) relates to the Liniment composition of the present invention (13), and it is for (methyl) acrylic resin or acrylic nitrile-butadiene-alkene-styrene resin.
Invention effect
According to the present invention, can provide that manufacturing time is short, package stability is excellent and use active energy beam (such as ultraviolet) to irradiate and film after solidification has the aqueous polyurethane resin dispersion of high rigidity.In addition, according to the present invention, also provide use active energy beam (such as ultraviolet) to irradiate and film after solidification for base material, especially there is (methyl) acrylic resin and acrylic nitrile-butadiene-alkene-styrene resin (ABS resin) aqueous polyurethane resin dispersion of high adhesion.
Embodiment
The present invention relates to a kind of aqueous polyurethane resin dispersion, it is the aqueous polyurethane resin dispersion that the urethane resin (A) at least making to have polymerizability unsaturated link(age) and the compound (B) with polymerizability unsaturated link(age) are disperseed in water-medium, wherein
The urethane resin (A) with polymerizability unsaturated link(age) is the urethane resin at least making polyvalent alcohol (a), polyvalent alcohol (b) containing acidic-group, polymeric polyisocyanate (c) and obtain containing (methyl) acrylate (d) reaction of primary hydroxyl.
< has urethane resin (A) > of polymerizability unsaturated link(age)
< < polyvalent alcohol (a) > >
As polyvalent alcohol (a), such as high molecular weight polyols, low molecular weight polyols can be used.From the easiness manufacturing aqueous polyurethane resin dispersion, preferably use high molecular weight diol, low molecular weight diols.
High molecular weight diol is not particularly limited, but preferred number average molecular weight is 400 ~ 8000.If number-average molecular weight is in this scope, then easily obtain the viscosity of appropriateness and good disposal.Easily guarantee the performance as soft chain segment, and when use comprise the urethane resin of gained aqueous polyurethane resin dispersion to form film, be easy to the generation suppressing crackle, and abundant with the reactivity of polymeric polyisocyanate (c), the manufacture of urethane resin (A) can be carried out efficiently.The number-average molecular weight of polyvalent alcohol (a) is more preferably 400 ~ 4000.
In present specification, number-average molecular weight is set to the number-average molecular weight calculated based on the hydroxyl value recorded according to JISK1577.Specifically, measure hydroxyl value, by terminal group quantitative method, calculate with (56.1 × 1000 × valence mumber)/hydroxyl value [mgKOH/g].In previously described formula, valence mumber is the hydroxyl value in 1 molecule.
As high molecular weight diol, such as polycarbonate diol, polyester glycol, polyether glycol etc. can be enumerated.From the aspect of the photostabilization of the aqueous polyurethane resin dispersion of urethane resin and the film that utilizes this dispersion and obtain that comprise gained, weathering resistance, thermotolerance, hydrolytic resistance, oil-proofness, be preferably polycarbonate diol.
In polycarbonate diol, diol component is preferably aliphatic diol and/or alicyclic diol, low from the viscosity of the urethane resin of gained, dispose easily and the aspect of favorable dispersity in water-medium, diol component is more preferably the aliphatic diol without alicyclic structure.
Polycarbonate polyol is by making the monomeric polyol of more than a kind, with carbonic ether or react with carbonyl chloride and obtain.From aspect easy to manufacture and there is no the secondary raw muriatic aspect of end, preferably make the monomeric polyol of more than a kind and carbonate reaction and the polycarbonate polyol that obtains.
Monomeric polyol is not particularly limited, and can enumerate such as aliphatic polybasic alcohol monomer, the monomeric polyol with alicyclic structure, aromatic polyvalent alcohol monomer, polyester polyols alcohol monomer, polyether polyols alcohol monomer etc.
As aliphatic polybasic alcohol monomer, be not particularly limited, but the straight-chain aliphatic diols such as such as 1,3-PD, BDO, 1,5-PD, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol can be enumerated; 2-methyl isophthalic acid, ammediol, 2-methyl isophthalic acid, 5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl isophthalic acid, the branched aliphatic diols such as 9-nonanediol; TriMethylolPropane(TMP), tetramethylolmethane etc. 3 official can above polyvalent alcohol etc.
As the monomeric polyol with alicyclic structure, be not particularly limited, but such as 1,4 cyclohexane dimethanol, 1 can be enumerated, 3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-ring pentanediol, Isosorbide-5-Nitrae-ring heptanediol, 2, two (hydroxymethyl)-1 of 5-, 4-diox, 2,7-norbornane glycol, tetrahydrofurandimethanol, Isosorbide-5-Nitrae-bis-(hydroxyl-oxethyl) hexanaphthene etc. have the glycol etc. of ester ring type structure at main chain.
As aromatic polyvalent alcohol monomer, be not particularly limited, but such as Isosorbide-5-Nitrae-xylyl alcohol, 1,3-xylyl alcohol, 1,2-xylyl alcohol, 4 can be enumerated, 4 '-naphthalene dimethanol, 3,4 '-naphthalene dimethanol etc.
As polyester polyols alcohol monomer, be not particularly limited, but the polyester polyol etc. of the dicarboxylic acid such as the polyester polyol of the polyester polyol of the hydroxycarboxylic acids such as the polyester polyol of such as 6 hydroxycaproic acid and hexylene glycol and glycol, hexanodioic acid and hexylene glycol and glycol can be enumerated.
As polyether polyols alcohol monomer, be not particularly limited, but the polyalkylene glycols etc. such as such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol can be enumerated.
As carbonic ether, be not particularly limited, but the such as aliphatic acid ester carbonate such as methylcarbonate, diethyl carbonate can be enumerated, the aromatic carbonates such as diphenyl carbonate, the cyclic carbonates etc. such as ethylene carbonate ester.In addition, the carbonyl chloride etc. that can generate polycarbonate polyol can also be used.Wherein, from the easiness manufacturing polycarbonate polyol, be preferably aliphatic acid ester carbonate, be particularly preferably methylcarbonate.
As the method being manufactured polycarbonate polyol by monomeric polyol and carbonic ether, example method described as follows can be enumerated, namely, add in the reactor carbonic ether and relative to this carbonic ether mole number the polyvalent alcohol of excessive mole number, make their reactions 5 ~ 6 hours at temperature 160 ~ 200 DEG C, pressure about 50mmHg, then under the pressure of several below mmHg, at 200 ~ 220 DEG C, make their stoichiometric numbers hour further.In above-mentioned reaction, the system that is preferably drawn into by the alcohol that pair is raw is outward while reaction.Now, when by making the alcohol generation azeotropic of carbonic ether and pair life extract outside system, the carbonic ether of excess quantity can be added.In addition, in above-mentioned reaction, the catalyzer such as four titanium butoxide can be used.
As polyester glycol, be not particularly limited, such as polyethylene glycol adipate glycol can be enumerated, polybutylene glyool adipate, poly-adipate glycol butanediol ester glycol, poly-m-phthalic acid hexanodioic acid hexylene glycol esterdiol (Port リ へ キ サ メ チ レ Application イ ソ Off タ レ ー ト ア ジ ペ ー ト ジ オ ー Le), polyethylene glycol succinate glycol, poly butylene succinate glycol, polyethylene glycol sebacate glycol, polydiethylene glycol sebacate glycol, poly-6-caprolactone glycol, poly-(3-methyl isophthalic acid, 5-hexanodioic acid pentadiol ester) glycol, 1, the polycondensate etc. of 6-hexylene glycol and dimeracid.
As polyether glycol, be not particularly limited, the random copolymers or segmented copolymer etc. of such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, oxyethane and propylene oxide, oxyethane and butylene oxide ring can be enumerated.And, the polyether polyester polyvalent alcohol etc. with ehter bond and ester bond can be used.
As low molecular weight diols, be not particularly limited, but such as number-average molecular weight can be enumerated be more than 60 and glycol less than 400.Such as ethylene glycol, 1 can be enumerated, ammediol, 2-methyl isophthalic acid, ammediol, 2,2-dimethyl-1, ammediol, 2-butyl-2-ethyl-1, ammediol, BDO, 1,5-PD, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, 1,9-nonanediol, 2-methyl isophthalic acid, the aliphatic diol of the carbon numbers 2 ~ 9 such as 8-ethohexadiol, glycol ether, triglycol, Tetraglycol 99; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1, two (hydroxyethyl) hexanaphthene, 2 of 4-, the glycol etc. with ester ring type structure of the carbon numbers 6 ~ 12 such as 7-norbornane glycol, tetrahydrofurandimethanol, 2,5-two (hydroxymethyl)-Isosorbide-5-Nitrae-dioxs.And, as aforementioned low molecular weight polyols, the low molecular weight polyols such as TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder can be used.
Polyvalent alcohol (a) can be used alone, and also can be used together multiple.
< < is containing polyvalent alcohol (b) the > > of acidic-group
Polyvalent alcohol (b) containing acidic-group is the polyvalent alcohol containing the hydroxyl of more than 2 and the acidic-group of more than 1 in 1 molecule.As acidic-group, carboxyl, sulfonic group, phosphate, phenolic hydroxyl group etc. can be enumerated.As the polyvalent alcohol (b) containing acidic-group, preferably there is in 1 molecule the compound of 2 hydroxyls and 1 carboxyl.Polyvalent alcohol (b) containing acidic-group can be used alone, and also can be used together multiple.
As the polyvalent alcohol (b) containing acidic-group, specifically, can 2 be enumerated, the dimethylolalkanoic acids such as 2-dimethylol propionic acid, 2,2-dimethylolpropionic acids, N, N-two hydroxyethyl glycine, N, N-two hydroxyethyl L-Ala, 3,4-dihydroxyl butane sulfonic acid, 3,6-dihydroxyl-2-toluenesulphonic acidss etc.Wherein, from the view point of the easiness of starting with, the carbon number preferably comprising 2 methylols is the dimethylolalkanoic acids of 4 ~ 12, in dimethylolalkanoic acids, is more preferably 2,2-dimethylol propionic acid.
In the present invention, polyvalent alcohol (a) is preferably 120 ~ 600 with the hydroxyl equivalent number of the total of the polyvalent alcohol (b) containing acidic-group.If hydroxyl equivalent number is in this scope, be then easy to obtain following film, that is, comprise the easy to manufacture of the aqueous polyurethane resin dispersion of the urethane resin of gained and in hardness the film of excellence.From the view point of the package stability of the aqueous polyurethane resin dispersion of gained and the hardness of film carrying out being coated with and obtain, hydroxyl equivalent number is preferably 130 ~ 600, is more preferably 150 ~ 500, is particularly preferably 170 ~ 400.
Hydroxyl equivalent number can be calculated by following formula (1) and formula (2).
The quantity (1) of the hydroxyl of molecular weight/each polyvalent alcohol of hydroxyl equivalent number=each polyvalent alcohol of each polyvalent alcohol
The total mole number (2) of total hydroxyl equivalent number=M/ polyvalent alcohol of polyvalent alcohol
When for urethane resin (A), in formula (2), M represents [(mole number of the hydroxyl equivalent number × polyvalent alcohol (a) of polyvalent alcohol (a))+(the hydroxyl equivalent number × containing the mole number of the polyvalent alcohol (b) of acidic-group containing the polyvalent alcohol (b) of acidic-group)].
< < polymeric polyisocyanate (c) > >
As polymeric polyisocyanate (c), be not particularly limited, such as aromatic poly-isocyanate, aliphatic polymeric isocyanate, ester ring type polymeric polyisocyanate etc. can be enumerated.
As aromatic poly-isocyanate, specifically, can 1 be enumerated, 3-phenylene vulcabond, 1, 4-phenylene vulcabond, 2, 4-tolylene diisocyanate (TDI), 2, 6-tolylene diisocyanate, 4, 4 '-diphenylmethanediisocyanate (MDI), 2, 4-diphenylmethanediisocyanate, 4, 4 '-two isocyanato-biphenyl, 3, 3 '-dimethyl-4, 4 '-two isocyanato-biphenyl, 3, 3 '-dimethyl-4, 4 '-two isocyanato-ditan, 1, 5-naphthalene diisocyanate, 4, 4 ', 4 ' '-triphenylmethane triisocyanate, between isocyanatophenyi sulfonylisocyanates, to isocyanatophenyi sulfonylisocyanates etc.
As aliphatic polymeric isocyanate, specifically, ethylidene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), ten dimethylene diisocyanates, 1 can be enumerated, 6,11-undecane triisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, lysinediisocyanate, 2,6-bis-isocyanatomethyl capronate, two (2-isocyanatoethyl) fumarate, two (2-isocyanatoethyl) carbonic ether, 2-isocyanatoethyl-2,6-bis-isocyanato-capronate etc.
As ester ring type polymeric polyisocyanate, specifically, isophorone diisocyanate (IPDI), 4 can be enumerated, 4 '-dicyclohexyl methane diisocyanate (hydrogenation MDI), tetrahydrobenzene vulcabond, tetrahydrotoluene vulcabond (hydrogenation TDI), two (2-isocyanatoethyl)-4-tetrahydrobenzene-1,2-dicarboxylic ester, 2,5-norbornene alkyl diisocyanate, 2,6-norbornene alkyl diisocyanates etc.
Isocyanate base in every 1 molecule of polymeric polyisocyanate is generally 2, but the urethane resin in the present invention, occurring in the scope of gelation, also can use the polymeric polyisocyanate with the isocyanate base of more than 3 that triphenylmethane triisocyanate is this kind of.
In polymeric polyisocyanate, hardness after being cured from the view point of using active energy beam (such as ultraviolet) uprises such, preferably there is the ester ring type polymeric polyisocyanate of alicyclic structure, from the view point of the control being easy to carry out reacting, be particularly preferably isophorone diisocyanate (IPDI), HMDI (hydrogenation MDI).
Polymeric polyisocyanate can be used alone, and also can be used together multiple.
< < is containing (methyl) acrylate (d) > > of primary hydroxyl
Containing (methyl) of primary hydroxyl if acrylate is for having methyl (acrylate) compound of primary hydroxyl, be then not particularly limited." primary hydroxyl " in present specification refers to, the Sauerstoffatom of hydroxyl and the hydroxyl of methylene radical bonding.In addition; " (methyl) acryl compound ", " (methyl) acrylic compound " in present specification, " (methyl) acrylate " are all the concepts comprising the compound with acryl and the compound with methacryloyl, also can have both acryl and methacryloyl.
As (methyl) acrylate (d) containing primary hydroxyl, 2-hydroxyethyl (methyl) acrylate can be enumerated, 3-hydroxypropyl (methyl) acrylate, 4-hydroxybutyl (methyl) acrylate, glycerol two (methyl) acrylate, two glycerol three (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Sorbitol Powder five (methyl) acrylate, glycerol list (methyl) acrylate, two glycerol list (methyl) acrylate, tetramethylolmethane list (methyl) acrylate, Sorbitol Powder list (methyl) acrylate, two glycerol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, Dipentaerythritol two (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Sorbitol Powder two (methyl) acrylate, Sorbitol Powder three (methyl) acrylate, Sorbitol Powder four (methyl) acrylate etc.
Wherein, the hardness after being cured from the view point of using active energy beam (such as ultraviolet) uprises, and the quantity of (methyl) acryl in 1 molecule is preferably more than 3.As such (methyl) acrylate, two glycerol three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Sorbitol Powder five (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Sorbitol Powder three (methyl) acrylate, Sorbitol Powder four (methyl) acrylate etc. can be enumerated.
The quantity of (methyl) acryl in 1 molecule be more than 3 containing in (methyl) acrylate of primary hydroxyl; from the view point of the manufacturing time of urethane resin (A) can be made to shorten, more preferably only there is (methyl) acrylic compound of primary hydroxyl.As such (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate can be enumerated.From the view point of hardness and the manufacturing time of film, be particularly preferably Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate.
(methyl) acrylate (d) containing primary hydroxyl can be used alone, and also can be used together multiple.
As (methyl) acrylate containing primary hydroxyl, can directly use commercially available product.
By (methyl) acrylate containing primary hydroxyl with the form of its mixture with inactive relative to isocyanate base (methyl) acrylate, and can be imparted in the reaction for obtaining urethane resin (A).Inactive relative to unreacted isocyanate base (methyl) acrylate can form the compound (B) with polymerizability unsaturated link(age).
As mixture, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate can be enumerated: the mixture etc. of commercially available Dipentaerythritol four (methyl) acrylate and the mixture of Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate.Dipentaerythritol six (methyl) acrylate is equivalent to isocyanate base inactive (methyl) acrylate.
The hydroxyl value of the mixture of Dipentaerythritol four (methyl) acrylate and Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate or the mixture of Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate is preferably more than 80mgKOH/g.If hydroxyl value is within the scope of this, then can easily avoid expending time in the manufacture of urethane resin (A) and the painted such problem of resin generation.From suppressing viscosity to rise when manufacturing urethane resin (A) and avoiding the aspect of gelation, hydroxyl value is preferably 80 ~ 130mgKOH/g.Hydroxyl value is 85 ~ 120mgKOH/g.Be Dipentaerythritol six (methyl) acrylate of more than 80mgKOH/g and the mixture of Dipentaerythritol five (methyl) acrylate as hydroxyl value, such as East Asia Synesis Company AronixM403 etc. can be enumerated.
In addition, as mixture, the mixture of pentaerythritol triacrylate and tetramethylol methane tetraacrylate also can be used.Tetramethylol methane tetraacrylate is equivalent to not containing (methyl) acrylate of primary hydroxyl.In this case, hydroxyl value is preferably 100 ~ 280mgKOH/g.If hydroxyl value is within the scope of this, then can easily avoid expending time in the manufacture of urethane resin (A) and the painted such problem of resin generation.From the view point of suppressing viscosity rise and avoid gelation when manufacturing urethane resin (A), hydroxyl value is preferably 120 ~ 250mgKOH/g.And then preferred hydroxyl value is 140 ~ 220mgKOH/g.Be the pentaerythritol triacrylate of 100 ~ 280mgKOH/g and the mixture of tetramethylol methane tetraacrylate as hydroxyl value, AronixM305, M306 etc. of such as East Asia Synesis Company can be enumerated.
The hydroxyl value of above-mentioned mixture can the method according to JISK0070 measure.
Amount containing (methyl) acrylate (d) of primary hydroxyl preferably has 25 ~ 70 % by weight in the weight of the urethane resin (A) of polymerizability unsaturated link(age).If within the scope of this, then can make containing (methyl) acrylate (d) of primary hydroxyl and the reaction times of isocyanate base is reasonable time, the hardness of the film after active energy beam (such as ultraviolet) can be made to solidify is suitable scope, and can keep the package stability of the aqueous polyurethane resin dispersion comprising gained urethane resin well.(methyl) acrylate (d) containing primary hydroxyl is more preferably 30 ~ 70 % by weight.
By (methyl) acrylate (d) containing primary hydroxyl with its mixture with inactive relative to isocyanate base (methyl) acrylate (specifically, there is the mixture of Dipentaerythritol four (methyl) acrylate and Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate, the mixture of Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate, the mixture etc. of pentaerythritol triacrylate and tetramethylol methane tetraacrylate) form and for reacting when, the amount of mixture preferably has in the weight of the urethane resin (A) of polymerizability unsaturated link(age) 50 ~ 80 % by weight, be more preferably 60 ~ 80 % by weight.
< has urethane resin (A) > of polymerizability unsaturated link(age)
The urethane resin (A) (below also referred to as " urethane resin (A) ") with polymerizability unsaturated link(age) is the urethane resin at least making polyvalent alcohol (a), polyvalent alcohol (b) containing acidic-group, polymeric polyisocyanate (c) and obtain containing (methyl) acrylate (d) reaction of primary hydroxyl.Polymerizability unsaturated link(age) can be the polymerizability unsaturated link(age) in (methyl) acryl source of (methyl) acrylate (d) containing primary hydroxyl.
The mole number of the isocyanate base of polymeric polyisocyanate (c), is preferably 0.1 ~ 0.9 relative to the ratio of the mole number of whole hydroxyls of polyvalent alcohol (a), the polyvalent alcohol (b) containing acidic-group and (methyl) acrylate (d) containing primary hydroxyl.
If within the scope of this, then be easy to avoid the mole number because of hydroxyl very few and the problem causing the reaction times elongated, on the other hand, also can be easy to avoid the mole number because of hydroxyl too much to cause unreacted polyvalent alcohol (a), the polyvalent alcohol (b) containing acidic-group and (methyl) acrylate (d) containing primary hydroxyl remaining in large quantities, and make package stability reduce such problem.The mole number of the isocyanate base of polymeric polyisocyanate (c) is preferably 0.15 ~ 0.8 relative to the ratio of the mole number of whole hydroxyl, is particularly preferably 0.2 ~ 0.7.
For the reaction of polyvalent alcohol (a), polyvalent alcohol (b) containing acidic-group, polymeric polyisocyanate (c) and (methyl) acrylate (d) containing primary hydroxyl, (a) and (b) can be made, (d) react with (c) with different orders, also multiple mixing can be reacted with (c) again.(methyl) acrylate (d) containing primary hydroxyl can be imparted in reaction with the form of its mixture with inactive relative to isocyanate base (methyl) acrylate.
When making polyvalent alcohol (a), the polyvalent alcohol (b) containing acidic-group, (methyl) acrylate (d) containing primary hydroxyl and polymeric polyisocyanate (c) react, also catalyzer can be used.
Catalyzer is not particularly limited, but can enumerate such as Sn(tin) salt of the metal such as series catalysts (tin trimethyl laurate, dibutyltin dilaurate etc.), plumbous series catalysts (lead octoate 36 etc.) and organic acid and mineral acid and Organometallic derivatives, amine series catalysts (triethylamine, N-ethylmorpholine, triethylenediamine etc.), diazabicyclo undecylene (diazabicycloundecene) series catalysts etc.Wherein, from reactive viewpoint, be preferably dibutyltin dilaurate, dioctyl tin dilaurate.
Temperature of reaction when reacting is not particularly limited, but is preferably 40 ~ 120 DEG C.If be this scope; then the solvability of raw material is also good; the viscosity of the urethane resin (A) of gained is suitable, can stir fully, (methyl) acryl not easily occurs and causes polyreaction and the undesirable condition that gelation or isocyanate base cause side reaction such occurs.Temperature of reaction more preferably 60 ~ 100 DEG C.
When making to react with polymeric polyisocyanate (c) containing (methyl) acrylate (d) of primary hydroxyl, in order to avoid the unnecessary consumption of (methyl) acryl of (methyl) acrylate (d) containing primary hydroxyl, and preferably carry out in the presence of oxygen.
In addition, in order to avoid the unnecessary consumption of (methyl) acryl of (methyl) acrylate (d) containing primary hydroxyl, also stopper can be added in advance in reaction system.
As stopper, can enumerate: the quinone system stopper such as quinhydrones, Hydroquinone monomethylether, benzoquinones, TBHQ, p-tert-butyl catechol, 2,5-two (1,1,3,3-tetramethyl butyl) quinhydrones, 2,5-two (1,1-dimethylbutyl) quinhydrones; Two (1,1-the dimethyl ethyl)-4-methylphenol, 2 of 2,6-, 6-DI-tert-butylphenol compounds, 2,4-DTBP, the 2-tertiary butyl-4,6-xylenol, 2, the alkylphenol system stoppers such as 6-di-tert-butyl-4-methy phenol, 2,4,6-tri-butyl-phenols; The aromatic amine system stoppers such as thiodiphenylamine; Alkylated diphenylamine, N, N '-diphenyl-p-phenylenediamine, thiodiphenylamine, 4-hydroxyl-2,2,6,6-tetramethyl piperidine, 4-benzoyloxy-2,2,6,6-tetramethyl piperidine, Isosorbide-5-Nitrae-dihydroxyl-2,2,6,6-tetramethyl piperidine, 1-hydroxyl-4-benzoyloxy-2,2,6,6-tetramethyl piperidine, two para-fluoroaniline, 2, the amine system stoppers such as 2,6,6-tetramethyl piperidine-1-oxyradical (TEMPO); 2,2-diphenylpicrylhydrazine (DPPH), three p-nitrophenyl ylmethyls, N-(3N-oxygen base anilino-1,3-dimethylbutylene)-the aliquat such as aniline oxide compound, benzyltrimethylammon.um muriate; The organic acids such as diethylhydroxylamine, cyclic amide, nitrile compound, substituted urea, benzothiazole, two-(1,2,2,6,6 pentamethyl--4-piperidyl) sebate, lactic acid, oxalic acid, citric acid, tartrate, phenylformic acid; Organic phosphine, phosphite etc.They can be used alone, and also can be used together multiple.Especially by by quinone system stopper and alkylphenol system stopper and use, thus the consumption caused because of the polymerization of (methyl) acryl can be made further to tail off.
As the amount of stopper, preferably be set to 0.001 ~ 1 weight part relative to total 100 weight part of polyvalent alcohol (a), the polyvalent alcohol (b) containing acidic-group, (methyl) acrylate (d) containing primary hydroxyl and polymeric polyisocyanate (c), be preferably 0.01 ~ 0.5 weight part.
The reaction of polyvalent alcohol (a), the polyvalent alcohol (b) containing acidic-group, (methyl) acrylate (d) containing primary hydroxyl and polymeric polyisocyanate (c) can be carried out under solvent free conditions, also can carry out in presence of organic solvent.As organic solvent, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), tetrahydrofuran (THF), diox, dimethyl formamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, N-ethyl pyrrolidone, vinyl acetic monomer etc. can be enumerated.Wherein, acetone, methyl ethyl ketone, vinyl acetic monomer because can make urethane resin (A) be dispersed in water after by heat decompression be removed, thus preferably.In addition, N-Methyl pyrrolidone, N-ethyl pyrrolidone use comprise gained urethane resin aqueous polyurethane resin dispersion to make film time play a role as membrane producing promoter, thus preferably.
The amount of organic solvent is preferably 0 ~ 2.0 times relative to the total amount of polyvalent alcohol (a), the polyvalent alcohol (b) containing acidic-group, (methyl) acrylate (d) containing primary hydroxyl and polymeric polyisocyanate (c) with weight basis, is more preferably 0.05 ~ 0.7 times.If be this scope, then can avoid expending time in such problem in the operation of removing organic solvent, the dispersiveness of urethane resin in water of gained is also good, can also avoid in addition using remaining organic solvent in the film made by aqueous polyurethane resin dispersion and cause Physical properties of coating film to reduce such problem.
< has compound (B) > of polymerizability unsaturated link(age)
Aqueous polyurethane resin dispersion of the present invention comprises the compound (B) with polymerizability unsaturated link(age).The compound (B) with polymerizability unsaturated link(age) is preferably free-radical polymerised compound.As long as free-radical polymerised compound is under the coexisting of optical free radical propellant or carries out the free-radical polymerised compound that is polymerized under the coexisting of hot radical propellant, be just not particularly limited, but be preferably (methyl) acrylic compound.
As free-radical polymerised compound, (methyl) acrylic compound of monomer class, urethane (methyl) acrylic compound, polyester (methyl) acrylate based compound, polyalkylene (methyl) acrylate based compound etc. can be enumerated.
As (methyl) acrylic compound of monomer class, poly-(methyl) acrylate such as list (methyl) acrylate, two (methyl) acrylate, three (methyl) acrylate, four (methyl) acrylate, five (methyl) acrylate, six (methyl) acrylate can be enumerated.
As list (methyl) acrylate, such as acryloyl morpholine can be enumerated, (methyl) 2-EHA, vinylbenzene, (methyl) methyl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) dodecylacrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid dicyclopentenyl ester, dicyclopentenyl oxygen base ethyl (methyl) acrylate, Phenoxyethyl (methyl) acrylate, (methyl) isobornyl acrylate, NVP, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polyethylene glycol-propylene glycol list (methyl) acrylate, poly-(ethylene glycol-tetramethylene glycol) single (methyl) acrylate, poly-(Bing bis-Chun ー tetramethylene glycol) single (methyl) acrylate, methoxy poly (ethylene glycol) list (methyl) acrylate, octyloxy polyethylene glycol-propylene glycol list (methyl) acrylate, bay oxygen base polyethyleneglycol (methyl) acrylate, stearic oxygen base polyethyleneglycol (methyl) acrylate, Nonylphenoxy polyethyleneglycol (methyl) acrylate, Nonylphenoxy polypropylene glycol polyethyleneglycol (methyl) acrylate etc.
As two (methyl) acrylate, such as ethylene glycol bisthioglycolate (methyl) acrylate can be enumerated, propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polyethylene glycol-propylene glycol two (methyl) acrylate, poly-(ethylene glycol-tetramethylene glycol) two (methyl) acrylate, poly-(propylene glycol-tetramethylene glycol) two (methyl) acrylate, methoxy poly (ethylene glycol) two (methyl) acrylate, octyloxy polyethylene glycol-propylene glycol two (methyl) acrylate, bay oxygen base polyoxyethylene glycol two (methyl) acrylate, stearic oxygen base polyoxyethylene glycol two (methyl) acrylate, Nonylphenoxy polyoxyethylene glycol two (methyl) acrylate, Nonylphenoxy polypropylene glycol polyoxyethylene glycol two (methyl) acrylate, the reaction product (such as Nagasechemtex Inc. " DA-212 ") of (methyl) vinylformic acid of 2 molecules and 1,6-hexanediol diglycidyl ether of 1 molecule, the reaction product of epoxy (methyl) vinylformic acid of 2 molecules and the neopentylglycol diglycidyl ether of 1 molecule, the reaction product (such as Nagasechemtex Inc. " DA-250 ") of (methyl) vinylformic acid of 2 molecules and the bisphenol A diglycidyl ether of 1 molecule, the reaction product of the 2-glycidyl body of (methyl) vinylformic acid of 2 molecules and the propylene oxide adduct of dihydroxyphenyl propane, reaction product (the such as Nagasechemtex Inc. " DA-721 " of (methyl) vinylformic acid of 2 molecules and the o-phthalic acid diglycidyl ester of 1 molecule, reaction product (the such as Nagasechemtex Inc. " DM-811 " of (methyl) vinylformic acid of 2 molecules and the polyethyleneglycol diglycidylether of 1 molecule, " DM-832 ", " DM-851 "), the reaction product of (methyl) vinylformic acid such as the reaction product of (methyl) vinylformic acid of 2 molecules and the polypropylene glycol diglycidyl ether of 1 molecule and polyvalent alcohol diglycidylether, (methyl) glycidyl acrylate and (methyl) acrylic acid affixture etc.
As three (methyl) acrylate, such as trimethylolpropane tris (methyl) acrylate can be enumerated, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, oxyethane (6 moles) modification trimethylolpropane tris (methyl) acrylate (BASF AG Laromer(registered trademark) LR8863) etc. oxirane modification trimethylolpropane tris (methyl) acrylate (BASF AG Laromer(registered trademark) PO33F) etc.
As four (methyl) acrylate, such as oxirane modification tetramethylolmethane four (methyl) acrylate etc. such as tetramethylolmethane four (methyl) acrylate, oxyethane (4 moles) modification tetramethylolmethane four (methyl) acrylate (Daicel-Cytec company, Ebecryl40) can be enumerated.
As five (methyl) acrylate, such as Dipentaerythritol five (methyl) acrylate etc. can be enumerated.
As six (methyl) acrylate, such as Dipentaerythritol six (methyl) acrylate etc. can be enumerated.
As (methyl) acrylic compound of polymer class, known material can be used.As (methyl) acrylic compound of polymer class, except list (methyl) acrylate, also can enumerate poly-(methyl) acrylate such as two (methyl) acrylate, three (methyl) acrylate, four (methyl) acrylate.
In these free-radical polymerised compounds, from the aspect of the hardness of the film of gained, be preferably poly-(methyl) acrylate that three (methyl) acrylate, four (methyl) acrylate, five (methyl) acrylate, six (methyl) acrylate are such.
In these free-radical polymerised compounds, from the aspect of the adaptation of the film of gained, be preferably oxirane modification tetramethylolmethane four (methyl) acrylate, oxirane modification trimethylolpropane tris (methyl) acrylate, oxirane modification ethylene glycol bisthioglycolate (methyl) acrylate.From the aspect taking into account adaptation and hardness, more preferably oxirane modification tetramethylolmethane four (methyl) acrylate, from the easiness of starting with, is particularly preferably ethylene-oxide-modified tetramethylolmethane four (methyl) acrylate.
In order to obtain urethane resin (A), when being imparted in reaction with the form of its mixture with inactive relative to isocyanate base (methyl) acrylate by (methyl) acrylate (d) containing primary hydroxyl, inactive relative to isocyanate base (methyl) acrylate contained by reaction system can form the compound (B) with polymerizability unsaturated link(age).
(methyl) acrylate (d) and the total amount of compound (B) with polymerizability unsaturated link(age) containing primary hydroxyl with the urethane resin (A) of polymerizability unsaturated link(age) be resin solid content overall 60 ~ 80 % by weight.When less than 60 % by weight, the situation that the hardness that there is the film used made by aqueous polyurethane resin dispersion reduces, when being greater than 85 % by weight, the situation that the package stability that there is aqueous polyurethane resin dispersion reduces.Total amount is more preferably 60 ~ 80 % by weight, and more preferably 65 ~ 75 % by weight.
In addition, when (methyl) acrylate (d) containing primary hydroxyl is set to 100 % by weight with the total amount of the compound (B) with polymerizability unsaturated link(age), the compound (B) with polymerizability unsaturated link(age) is preferably 30 ~ 50 % by weight.If be this scope, use the adaptation of the film made by aqueous polyurethane resin dispersion and PMMA resin good, and be easy to obtain the high film of hardness, in addition, the package stability of aqueous polyurethane resin dispersion is also good.
Aqueous polyurethane resin dispersion of the present invention is dispersed in water-medium urethane resin (A) and the compound (B) with polymerizability unsaturated link(age).As water-medium, the mixed solvent etc. of water, water and hydrophilic organic solvent can be enumerated.
As water, such as tap water, ion exchanged water, distilled water, ultrapure water etc. can be enumerated.Wherein, consider the situation etc. obtaining easiness, cause particle instability because of the impact of salt, preferably use ion exchanged water.
As hydrophilic organic solvent, can enumerate such as: rudimentary 1 yuan of alcohol such as methyl alcohol, ethanol, propyl alcohol; The polyvalent alcohol such as ethylene glycol, glycerol; The hydrophilic organic solvent etc. of the aprotic such as N-methylmorpholine, dimethyl sulfoxide (DMSO), dimethyl formamide, N-Methyl pyrrolidone.As the amount of the hydrophilic organic solvent in water-medium, be preferably 0 ~ 20 % by weight.
In the present invention, the acid number of aqueous polyurethane resin dispersion is preferably 10 ~ 80mgKOH/g.If be this scope, be then easy to guarantee the good dispersiveness in water-medium and the water tolerance of film.Acid number can be derived according to following formula (3) specifically.
(acid number of aqueous urethane resin composition)=(mole number containing the acidic-group of the polyvalent alcohol (b) of acidic-group) × 56.11/ (urethane resin (A) and there is the gross weight of compound (B) of polymerizability unsaturated link(age)) (3)
Acid number is more preferably 12 ~ 70mgKOH/g, more preferably 14 ~ 60mgKOH/g.
In the present invention, when the solids component of water dispersion of polyurethane resin is set to 100 weight part, preferably be 2 ~ 50 weight parts with the ratio of polyvalent alcohol (a), be the amount of 1 ~ 15 weight part containing the ratio of the polyvalent alcohol (b) of acidic-group, prepare urethane resin (A).
If the ratio of polyvalent alcohol (a) is in above-mentioned scope, then urethane resin (A) favorable dispersity in water-medium, aqueous polyurethane resin dispersion also can obtain good masking, if contain the ratio of the polyvalent alcohol (b) of acidic-group in above-mentioned scope, then the water tolerance of film is good, and the dispersiveness of urethane resin (A) in water-medium can be made also good.
The ratio of polyvalent alcohol (a) is more preferably 3 ~ 40 weight parts, is particularly preferably 5 ~ 30 weight parts, and the ratio containing the polyvalent alcohol (b) of acidic-group is more preferably 2 ~ 10 weight parts, is particularly preferably 3 ~ 7 weight parts.
The manufacture method > of < aqueous polyurethane resin dispersion
Next, the manufacture method of aqueous polyurethane resin dispersion is described.
The manufacture method of aqueous polyurethane resin dispersion of the present invention can comprise:
At least make polyvalent alcohol (a), polyvalent alcohol (b) containing acidic-group, polymeric polyisocyanate (c) and obtain the operation (α) of urethane resin (A) containing (methyl) acrylate (d) reaction of primary hydroxyl,
To the operation (β) that the acidic-group of aforementioned urethane resin (A) neutralizes, and
The compound (B) making aforementioned urethane resin (A) and have a polymerizability unsaturated link(age) is dispersed in the operation (γ) in water-medium.
In order to avoid unnecessary the expending of polymerizability unsaturated link(age), the operation (α) obtaining urethane resin (A) is preferably carried out in the presence of oxygen.In addition, preferably in reaction system, stopper is added as required.
In order to avoid the unnecessary polymerization of polymerizability unsaturated link(age), preferably carry out under the temperature of the operation (α) obtaining urethane resin (A) is the condition of 0 ~ 120 DEG C.Be preferably 0 ~ 100 DEG C.
As the acidic-group neutralizing agent that can use in the operation (β) neutralized the acidic-group of urethane resin (A), can enumerate: the organic amines such as Trimethylamine 99, triethylamine, tri-isopropyl amine, Tributylamine, trolamine, N methyldiethanol amine, N-phenyldiethanol-amine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine, pyridine; The inorganic base such as sodium hydroxide, potassium hydroxide, ammonia etc.Wherein, preferably can use organic amine, more preferably can use tertiary amine, most preferably can use triethylamine.At this, the acidic-group of urethane resin (A) refers to carboxyl, sulfonic group, phosphate, phenolic hydroxyl group etc.
The usage quantity of acidic-group neutralizing agent is preferably the amount reaching 0.8 ~ 1.5 acidic-group relative to urethane resin (A) with molar basis.If within the scope of this, the situation of the package stability reduction of the situation that the dispersiveness being then easy to avoid urethane resin (A) in water reduces or waterborne polyurethane resin water dispersion, is also easy to avoid the situation that the stink grow of waterborne polyurethane resin water dispersion is such.
Be dispersed in the operation (γ) in water-medium at the compound (B) making urethane resin (A) and have a polymerizability unsaturated link(age), as long as (A) and (B) can be made to disperse in water-medium, then its method and working order etc. are just not particularly limited.The method be such as redispersed in after mixing (B) in (A) in water-medium can be enumerated, the method in water-medium is redispersed in after mixing (A) in (B), (A) is made to be dispersed in after in water-medium the method making (B) blending dispersion again, (B) is made to be dispersed in after in water-medium the method making (A) blending dispersion again, (A) and (B) is dispersed in respectively carry out after in water-medium the method mixed, the method etc. mixing (B) when manufacturing (A) and then be dispersed in water-medium.
In the manufacture of urethane resin (A), when (methyl) acrylate (d) containing primary hydroxyl is imparted in reaction with the form of its mixture with inactive relative to isocyanate base (methyl) acrylate, inactive relative to isocyanate base (methyl) acrylate is included in the reaction product of operation (α) together with urethane resin (A), and be imparted into operation (β) and operation (γ), in final aqueous polyurethane resin dispersion, form the compound (B) with polymerizability unsaturated link(age).In this case, acidic-group neutralizing agent can be added in the reaction product of operation (α), then make it be dispersed in water system dispersion medium together with the compound (B) with polymerizability unsaturated link(age).Before interpolation has the compound (B) of polymerizability unsaturated link(age), according to circumstances can add water-medium.
For aforementioned mixing, stirring, dispersion, the known whipping appts such as mixer for well-distribution, homogenizer can be used.In addition, at urethane resin (A), have in the compound (B) of polymerizability unsaturated link(age), in order to adjust viscosity, improve workability, improve dispersed, also can add hydrophilic organic solvent, water etc. in advance before combination.
In order to avoid the unnecessary consumption of polymerizability unsaturated link(age), the operation (γ) that urethane resin (A) and the compound (B) with polymerizability unsaturated link(age) mix preferably is carried out in the presence of oxygen.In addition, stopper can be added as required.In order to avoid the unnecessary consumption of polymerizability unsaturated link(age), temperature preferably when urethane resin (A) and the compound (B) with polymerizability unsaturated link(age) being mixed is carried out under being the condition of 0 ~ 100 DEG C, more preferably be carry out under the condition of 0 ~ 90 DEG C in temperature, preferred is further carry out under the condition of 0 ~ 80 DEG C in temperature, is carry out under the condition of 50 ~ 70 DEG C particularly preferably in temperature.
In manufacture method of the present invention, the operation (β) that the acidic-group of urethane resin (A) is neutralized, to be dispersed in water-medium operation (γ) with the compound (B) making urethane resin (A) and there is polymerizability unsaturated link(age) in arbitrary operation can formerly carry out, also can two operations carry out simultaneously.In this case, by (A), (B), water-medium and the disposable mixing of acidic-group neutralizing agent, also acidic-group neutralizing agent can be mixed with water-medium, (B) in advance, then they are mixed with (A).
The ratio of the urethane resin (A) in aqueous polyurethane resin dispersion is preferably 5 ~ 60 % by weight, is more preferably 15 ~ 50 % by weight.More preferably 25 ~ 40 % by weight.In addition, number-average molecular weight is preferably 1, and 000 ~ 1,000,000.
In aqueous polyurethane resin dispersion of the present invention, the additives such as thickening material, photosensitizer, curing catalysts, UV light absorber, photostabilizer, defoamer, softening agent, surface conditioner, antisettling agent can also be added as required.Additive can be used alone, and also can be used together multiple.The hardness of aqueous polyurethane resin dispersion of the present invention from the film of gained, the aspect of reagent resistance, preferably in fact not containing protective colloid, emulsifying agent, tensio-active agent.
< Photocurable composition >
The invention still further relates to the Photocurable composition comprising above-mentioned aqueous polyurethane resin dispersion and Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater, known material can be used, such as, can use: cracking is easily occurred by uviolizing and the initiator of the optical cleavage type of 2 free radicals, the initiator of dehydrogenation type can be produced.Can be used together above-mentioned initiator.As these compounds, such as methyl phenyl ketone can be enumerated, 2, 2-diethoxy acetophenone, to dimethylamino benzoylformaldoxime, benzophenone, 2-chlorobenzophenone, p, p '-bis-diethylamino benzophenone, benzoin ethyl ether, bitter almond oil camphor n-propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, bitter almond oil camphor n-butyl ether, bitter almond oil camphor dimethyl ketone acetal, thioxanthone, p-sec.-propyl-Alpha-hydroxy isobutyl-benzophenone, 2, 2-dimethoxy-2-phenyl acetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2, 4, 6,-tri-methyl benzophenone, 4-methyl benzophenone, 2, 2-dimethoxy-1, 2-phenylbenzyl ketone etc.Preferably hydroxycyclohexylphenylketone can be enumerated.
When adding Photoepolymerizationinitiater initiater, add preferably be dispersed in the operation (γ) in water-medium at the compound (B) making urethane resin (A) and there is polymerizability unsaturated link(age) after.As the amount of Photoepolymerizationinitiater initiater, be preferably 0.5 ~ 5 % by weight relative to all solids composition (comprising the compound (B) with polymerizability unsaturated link(age)) of aqueous polyurethane resin dispersion.
< coating composition and Liniment composition >
The invention still further relates to the coating composition and Liniment composition that comprise above-mentioned aqueous polyurethane resin dispersion.
In coating composition of the present invention and Liniment composition, except above-mentioned aqueous polyurethane resin dispersion, also can add other resin.As other resin, vibrin, acrylic resin, polyether resin, polycarbonate resin, urethane resin, epoxy resin, Synolac, polyolefin resin etc. can be enumerated.They can be used alone, and also can be used together multiple.Other resin preferably has the hydrophilic radical of more than a kind.As hydrophilic radical, hydroxyl, carboxyl, sulfonic group, polyethylene glycol groups etc. can be enumerated.
As other resin, be preferably selected from least a kind in vibrin, acrylic resin, polyolefin resin.
Vibrin manufactures by the esterification of sour composition and alcohol composition or transesterification reaction usually.As sour composition, the compound being typically used as sour composition when manufacturing vibrin can be used in.As sour composition, such as, can use aliphatic polybasic acids, alicyclic polyprotonic acid, aromatic polyvalent acid etc.
The hydroxyl value of vibrin is preferably about 10 ~ 300mgKOH/g, is more preferably about 50 ~ 250mgKOH/g, more preferably about 80 ~ 180mgKOH/g.The acid number of previous polyesters resin is preferably about 1 ~ 200mgKOH/g, is more preferably about 15 ~ 100mgKOH/g, more preferably about 25 ~ 60mgKOH/g.
The weight-average molecular weight of vibrin is preferably 500 ~ 500, and 000, be more preferably 1,000 ~ 300,000, more preferably 1,500 ~ 200,000.
As acrylic resin, be preferably the acrylic resin of hydroxyl.The acrylic resin of hydroxyl by the known method such as such as solution polymerization process in organic solvent, emulsion polymerization in water, can make the polymerizability unsaturated monomer of hydroxyl and can manufacture with other polymerizability unsaturated monomer copolymerization of the polymerizability unsaturated monomer copolymerization of this hydroxyl.
The polymerizability unsaturated monomer of hydroxyl can be in 1 molecule, have hydroxyl and the polymerizability unsaturated link(age) compound of more than 1 respectively.Such as can enumerate: the monoesters compound of 2 yuan of alcohol of (methyl) vinylformic acid such as (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxy-propyl ester, (methyl) vinylformic acid 3-hydroxy-propyl ester, (methyl) vinylformic acid 4-hydroxybutyl ester and carbon number 2 ~ 8; The 6-caprolactone modification body of these monoesters compounds; N-hydroxymethyl (methyl) acrylamide; Allyl alcohol; Molecular end is (methyl) acrylate etc. with polyoxyethylene chain of hydroxyl.
The acrylic resin of hydroxyl preferably has the resin of anionic property functional group.About the acrylic resin of hydroxyl with anionic property functional group, such as, by using the polymerizability unsaturated monomer with anionic property functional groups such as carboxylic acid group, sulfonic group, phosphates to be manufactured as a kind of polymerizability unsaturated monomer.
The hydroxyl value of the acrylic resin of hydroxyl, from viewpoints such as the water tolerance of the film of the package stability of composition, gained, is preferably about 1 ~ 200mgKOH/g, is more preferably about 2 ~ 100mgKOH/g, more preferably about 3 ~ 60mgKOH/g.
In addition, when the acrylic resin of hydroxyl has the acidic-groups such as carboxyl, the acid number of the acrylic resin of this hydroxyl is from viewpoints such as the water tolerance of the film of gained, be preferably about 1 ~ 200mgKOH/g, be more preferably about 2 ~ 150mgKOH/g, more preferably about 5 ~ 100mgKOH/g.
The weight-average molecular weight of the acrylic resin of hydroxyl is preferably 1, and 000 ~ 200,000, be more preferably 2,000 ~ 100,000, more preferably 3,000 ~ 50, in the scope of 000.
As polyether resin, the polymkeric substance or multipolymer with ehter bond can be enumerated, such as, can enumerate the polyethers etc. that polyoxyethylene system polyethers, polyoxypropylene system polyethers, polybutylene system polyethers, dihydroxyphenyl propane or Bisphenol F etc. are derived by aromatic series poly hydroxyl compound.
As polycarbonate resin, the polymkeric substance manufactured by bisphenol cpd can be enumerated, such as, can enumerate bisphenol-a polycarbonate etc.
As urethane resin, the reaction by the various polyhydroxy reactant such as vinylformic acid, polyester, polyethers, polycarbonate and polymeric polyisocyanate can be enumerated and the resin with amino-formate bond obtained.
As epoxy resin, the reaction by bisphenol cpd and Epicholorohydrin can be enumerated and the resin etc. obtained.As bis-phenol, such as dihydroxyphenyl propane, Bisphenol F can be enumerated.
As Synolac, polyprotonic acid and polyvalent alcohols such as making phthalic acid, terephthalic acid, succsinic acid can be enumerated, react and the Synolac obtained with properties-correcting agent such as grease oil fatty acid (soybean oil, linseed oil, Oleum Cocois, stearic acid etc.), natural resins (rosin, amber etc.) further.
As polyolefin resin, the resin obtained as follows can be enumerated: according to common polymerization by olefinic monomers and other suitable monomer polymerizations or copolymerization, use emulsifying agent to carry out water-dispersion the polyolefin resin obtained thus; Or olefinic monomers is carried out letex polymerization together with other suitable monomers, obtains resin thus.In addition, according to circumstances, the so-called chlorinatedpolyolefins modified resin above-mentioned polyolefin resin chlorination obtained can also be used.
As olefinic monomers, the alpha-olefins such as such as ethene, propylene, 1-butylene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 1-heptene, 1-hexene, 1-decene, 1-laurylene can be enumerated, divinyl, ethylidene norbornene, Dicyclopentadiene (DCPD), 1,5-hexadiene, styrenic, equiconjugate diene or non-conjugated diene etc., these monomers can be used alone, and also can be used together multiple.
As can with other monomers of olefinic monomers copolymerization, such as, can enumerate vinyl acetate, vinyl alcohol, toxilic acid, citraconic acid, methylene-succinic acid, maleic anhydride, citraconic anhydride, itaconic anhydride etc., these monomers can be used alone, and also can be used together multiple.
Coating composition of the present invention and Liniment composition can contain solidifying agent, thus, can improve and use coating composition or Liniment composition and the water tolerance etc. of the film that obtains or multilayer film, coated film.
As solidifying agent, such as aminoresin, polymeric polyisocyanate, blocked polymeric polyisocyanate, melmac, carbodiimide etc. can be used.Solidifying agent can be used alone, and also can be used together multiple.
As aminoresin, the reaction by amino component and aldehyde composition can be enumerated and the partially or completely methylolation aminoresin obtained.As above-mentioned amino component, such as melamine, urea, benzoguanamine, acetylguanamine, steroid guanamines (ス テ ロ グ ア Na ミ Application), spiral shell guanamines, Dyhard RU 100 etc. can be enumerated.As aldehyde composition, such as formaldehyde, paraformaldehyde, acetaldehyde, phenyl aldehyde etc. can be enumerated.
As polymeric polyisocyanate, the compound of the isocyanate base such as in 1 molecule with more than 2 can be enumerated, such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate etc. can be enumerated.
As blocked polymeric polyisocyanate, addition block agent in the polyisocyanate foundation of aforesaid polymeric polyisocyanate can be enumerated and the material obtained, as block agent, phenol can be enumerated, the phenol systems such as cresols, methyl alcohol, the fatty alcohol systems such as ethanol, dimethyl malonate, methyl ethyl diketone isoreactivity methylene base system, butanethiol, the mercaptan systems such as lauryl mercaptan, Acetanilide, the sour acid amides system such as amide, ε-caprolactam, the lactan systems such as δ-Valerolactim, bromosuccinimide, the sour imide series such as toxilic acid imide, ethylidenehydroxylamine, acetoxime, the oxime systems such as methyl ethyl ketone oxime, phenylbenzene aniline, aniline, the block agents such as amine system such as ethyleneimine.
As melmac, the such as methylol melamine such as dihydroxymethyl melamine, trishydroxymethyl melamine can be enumerated; The alkyl oxide compound of these methylol melamines or condenses; The condenses etc. of the alkyl oxide compound of methylol melamine.
Tinting pigment, pigment extender, bright pigment can be added in coating composition of the present invention and Liniment composition.
As tinting pigment, such as titanium oxide, zinc white, carbon black, chrome vermillion, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, intellectual circle's series pigments, perylene dye etc. can be enumerated.They can be used alone also can be multiple and use.As tinting pigment, particularly preferably use titanium oxide and/or carbon black.
As pigment extender, such as clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talcum, silicon-dioxide, white lake etc. can be enumerated.They can be used alone, and can be used together multiple.Especially, as pigment extender, preferably use barium sulfate and/or talcum, more preferably use barium sulfate.
The mica etc. that aluminum oxide, oxidized titanium or ferric oxide that bright pigment can use such as aluminium, copper, zinc, brass, nickel, aluminum oxide, mica, oxidized titanium or ferric oxide to cover cover.
In coating composition of the present invention and Liniment composition, the common additive for coatings such as thickening material, curing catalysts, UV light absorber, photostabilizer, defoamer, softening agent, surface conditioner, antisettling agent can be contained as required.They can be used alone, and also can be used together multiple.
The manufacture method of coating composition of the present invention and Liniment composition is not particularly limited, and can use known manufacture method.In general, for coating composition and Liniment composition, by by above-mentioned aqueous polyurethane resin dispersion and the mixing of above-mentioned various additive, add water-medium, be adjusted to the viscosity that adapts with coating process and manufactured.
As the coated material being coated material or Liniment composition of coating composition, metal, plastics, inorganics, timber etc. can be enumerated.
The adaptation of coating composition of the present invention and Liniment composition and plastics is high, particularly high to the adaptation of poly-(methyl) acrylic resin, ABS resin.Therefore, as being coated material and coated material, preferably poly-(methyl) acrylate resin and/or ABS resin.
As the coating process of coating composition or the coating method of Liniment composition, can enumerate and revolve a glass application, spraying, roller coat, showering, dipping coating etc.
For coating composition of the present invention and Liniment composition, preferably after application or coating, under heating or under not heating, making the evaporation at least partially of aqueous medium, being then cured by irradiating active energy beam.As active energy beam, be preferably ultraviolet.
Ultraviolet light source can use xenon lamp, low pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, carbon arc lamp, tungsten lamp etc.Irradiation time can according to having the kind of compound of polymerizability unsaturated link(age), the condition such as kind, coating thickness, ultraviolet source of Photoepolymerizationinitiater initiater is suitably changed.From the aspect of workability, preferably irradiate 1 ~ 60 second.The object completed for making curing reaction further, also can carry out heat treated after uv irradiation.
The ultraviolet irradiation amount used when solidifying as making composition of the present invention, from the view point of rapidly-curable, workability, is preferably 300 ~ 3,000mJ/cm
2.
As active energy beam, also electron beam etc. can be used.When being cured by electron beam, can Photoepolymerizationinitiater initiater be added, preferably using the electron beam booster machinery with the energy of 100 ~ 500eV.
The thickness of the film after solidification is not particularly limited, but is preferably the thickness of 1 ~ 100 μm.More preferably the film of the thickness of 3 ~ 50 μm is formed.
Embodiment
Next, enumerate embodiment and comparative example is described in further detail to the present invention, but the present invention is by their restriction.
[embodiment 1]
In the reaction unit possessing stirrer and well heater, by ETERNACOLL(registered trademark) PH100(space portion is emerging produces; Number-average molecular weight 1054; Hydroxyl value 106mgKOH/g; Polyhydroxy reactant is for making 1,5-pentanediol: 1, the polyol blends of the mol ratio of 6-hexylene glycol=1:1 and carbonate reaction and the polycarbonate diol, the 41.0g that obtain), 2,2-dimethylol propionic acid (DMPA, 14.4g) and isophorone diisocyanate (IPDI, 56.7g), in N-ethyl pyrrolidone (45.9g), under the existence of dibutyltin dilaurate (0.2g), in a nitrogen atmosphere, heat 3 hours at 80-90 DEG C.Add 2,6 di tert butyl 4 methyl phenol (0.4g) and 4-methoxyphenol (0.4g), make atmosphere be air.Then, put into the mixture (DPHA, hydroxyl value 95mgKOH/g, 181g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, heat 7 hours at 90 DEG C.NCO base content at the end of urethane reaction is 0.23 % by weight.Extract 55.7g be cooled to 70 DEG C in the reactive mixture, add the mixture (DPHA, hydroxyl value 41mgKOH/g, 5.4g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate and triethylamine (2.9g) and mix.Reaction mixture is cooled to 45 DEG C, stirs, add water (96.3g) lentamente on one side, obtain aqueous polyurethane resin dispersion.
[embodiment 2]
In the reaction unit possessing stirrer and well heater, by ETERNACOLL(registered trademark) PH100(space portion is emerging produces; Number-average molecular weight 1054; Hydroxyl value 106mgKOH/g; Polyhydroxy reactant is for making 1,5-pentanediol: 1, the polyol blends of the mol ratio of 6-hexylene glycol=1:1 and carbonate reaction and the polycarbonate diol, the 41.0g that obtain), 2,2-dimethylol propionic acid (DMPA, 14.4g) and isophorone diisocyanate (IPDI, 56.7g), in N-ethyl pyrrolidone (45.9g), under the existence of dibutyltin dilaurate (0.2g), in a nitrogen atmosphere, heat 3 hours at 80-90 DEG C.Add 2,6 di tert butyl 4 methyl phenol (0.4g) and 4-methoxyphenol (0.4g), make atmosphere be air.Then, put into the mixture (DPHA, hydroxyl value 95mgKOH/g, 181g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, heat 7 hours at 90 DEG C.NCO base content at the end of urethane reaction is 0.23 % by weight.Extract 57.9g be cooled to 70 DEG C in the reactive mixture, add the mixture (DPHA, hydroxyl value 41mgKOH/g, 12.9g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate and triethylamine (2.8g) and mix.Reaction mixture is cooled to 45 DEG C, carries out stirring and add water (136g) lentamente, obtain aqueous polyurethane resin dispersion.
[embodiment 3]
In the reaction unit possessing stirrer and well heater, by ETERNACOLL(registered trademark) PH100(space portion is emerging produces; Number-average molecular weight 1054; Hydroxyl value 106mgKOH/g; Polyhydroxy reactant is for making 1,5-pentanediol: 1, the polyol blends of the mol ratio of 6-hexylene glycol=1:1 and carbonate reaction and the polycarbonate diol, the 41.0g that obtain), 2,2-dimethylol propionic acid (DMPA, 14.4g) and isophorone diisocyanate (IPDI, 56.7g), in N-ethyl pyrrolidone (45.9g), under the existence of dibutyltin dilaurate (0.2g), in a nitrogen atmosphere, heat 3 hours at 80-90 DEG C.Add 2,6 di tert butyl 4 methyl phenol (0.4g) and 4-methoxyphenol (0.4g), make atmosphere be air.Then, put into the mixture (DPHA, hydroxyl value 95mgKOH/g, 181g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, heat 7 hours at 90 DEG C.NCO base content at the end of urethane reaction is 0.23 % by weight.Extract 57.9g be cooled to 70 DEG C in the reactive mixture, add tetramethylol methane tetraacrylate (PETA(4), 12.0g) and triethylamine (2.7g) mixing.Reaction mixture is cooled to 45 DEG C, carries out stirring and add water (130g) lentamente, obtain aqueous polyurethane resin dispersion.
[embodiment 4]
In the reaction unit possessing stirrer and well heater, by ETERNACOLL(registered trademark) PH100(space portion is emerging produces; Number-average molecular weight 1054; Hydroxyl value 106mgKOH/g; Polyhydroxy reactant is for making 1,5-pentanediol: 1, the polyol blends of the mol ratio of 6-hexylene glycol=1:1 and carbonate reaction and the polycarbonate diol, the 41.0g that obtain), 2,2-dimethylol propionic acid (DMPA, 14.4g) and isophorone diisocyanate (IPDI, 56.7g), in N-ethyl pyrrolidone (45.9g), under the existence of dibutyltin dilaurate (0.2g), in a nitrogen atmosphere, heat 3 hours at 80-90 DEG C.Add 2,6 di tert butyl 4 methyl phenol (0.4g) and 4-methoxyphenol (0.4g), make atmosphere be air.Then, put into the mixture (DPHA, hydroxyl value 95mgKOH/g, 181g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, heat 7 hours at 90 DEG C.NCO base content at the end of urethane reaction is 0.23 % by weight.Extract 63.8g be cooled to 70 DEG C in the reactive mixture, add pentaerythritol triacrylate (PETA(3), 13.8g) and triethylamine (3.2g) mixing.Reaction mixture is cooled to 45 DEG C, stirs, add water (147g) lentamente on one side, obtain aqueous polyurethane resin dispersion.
[embodiment 5]
In the reaction unit possessing stirrer and well heater, by ETERNACOLL(registered trademark) PH100(space portion is emerging produces; Number-average molecular weight 1054; Hydroxyl value 106mgKOH/g; Polyhydroxy reactant is for making 1,5-pentanediol: 1, the polyol blends of the mol ratio of 6-hexylene glycol=1:1 and carbonate reaction and the polycarbonate diol, the 41.0g that obtain), 2,2-dimethylol propionic acid (DMPA, 14.4g) and isophorone diisocyanate (IPDI, 56.7g), in N-ethyl pyrrolidone (45.9g), under the existence of dibutyltin dilaurate (0.2g), in a nitrogen atmosphere, heat 3 hours at 80-90 DEG C.Add 2,6 di tert butyl 4 methyl phenol (0.4g) and 4-methoxyphenol (0.4g), make atmosphere be air.Then, add the mixture (DPHA, hydroxyl value 95mgKOH/g, 181g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, heat 7 hours at 90 DEG C.NCO base content at the end of urethane reaction is 0.23 % by weight.Extract 45.1g be cooled to 70 DEG C in the reactive mixture, add two (TriMethylolPropane(TMP)) tetraacrylate (DTTA, 10.0g) and triethylamine (2.2g) and mix.Reaction mixture is cooled to 45 DEG C, carries out stirring and add water (100g) lentamente, obtain aqueous polyurethane resin dispersion.
[embodiment 6]
In the reaction unit possessing stirrer and well heater, by ETERNACOLL(registered trademark) PH100(space portion is emerging produces; Number-average molecular weight 1054; Hydroxyl value 106mgKOH/g; Polyhydroxy reactant is for making 1,5-pentanediol: 1, the polyol blends of the mol ratio of 6-hexylene glycol=1:1 and carbonate reaction and the polycarbonate diol, the 89.8g that obtain), 2,2-dimethylol propionic acid (DMPA, 31.4g) and isophorone diisocyanate (IPDI, 124g), in N-ethyl pyrrolidone (103g), under the existence of dibutyltin dilaurate (0.4g), in a nitrogen atmosphere, heat 3 hours at 80-90 DEG C.Add 2,6 di tert butyl 4 methyl phenol (0.8g) and 4-methoxyphenol (0.8g), make atmosphere be air.Then, put into the mixture (DPHA, hydroxyl value 95mgKOH/g, 397g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, heat 7 hours at 90 DEG C.NCO base content at the end of urethane reaction is 0.24 % by weight.Extract 130g in the reactive mixture and be cooled to 70 DEG C, add Viscoat 295 (TMPTA, 14.0g), tripropylene glycol diacrylate (TPGDA, 14.0g) and triethylamine (5.2g) and mix.Reaction mixture is cooled to 45 DEG C, carries out stirring and add water (304g) lentamente, obtain aqueous polyurethane resin dispersion.
[embodiment 7]
In the reaction unit possessing stirrer and well heater, by ETERNACOLL(registered trademark) PH100(space portion is emerging produces; Number-average molecular weight 1054; Hydroxyl value 106mgKOH/g; Polyhydroxy reactant is for making 1,5-pentanediol: 1, the polyol blends of the mol ratio of 6-hexylene glycol=1:1 and carbonate reaction and the polycarbonate diol, the 41.0g that obtain), 2,2-dimethylol propionic acid (DMPA, 14.4g) and isophorone diisocyanate (IPDI, 56.7g), in N-ethyl pyrrolidone (45.9g), under the existence of dibutyltin dilaurate (0.2g), in a nitrogen atmosphere, heat 3 hours at 80-90 DEG C.Add 2,6 di tert butyl 4 methyl phenol (0.4g) and 4-methoxyphenol (0.4g), make atmosphere be air.Then, put into the mixture (DPHA, hydroxyl value 95mgKOH/g, 181g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, heat 7 hours at 90 DEG C.NCO base content at the end of urethane reaction is 0.23 % by weight.Extract 48.3g be cooled to 70 DEG C in the reactive mixture, add ethylene-oxide-modified tetramethylolmethane five acrylate (tetraacrylate, 10.8g that EOPETA, the alcohol obtained by making tetramethylolmethane 1 moles of added ethylene oxide 4 moles derive) and triethylamine (2.3g) and mix.Reaction mixture is cooled to 45 DEG C, carries out stirring and add water (107g) lentamente, obtain aqueous polyurethane resin dispersion.
[embodiment 8]
In the reaction unit possessing stirrer and well heater, by ETERNACOLL(registered trademark) PH100(space portion is emerging produces; Number-average molecular weight 1054; Hydroxyl value 106mgKOH/g; Polyhydroxy reactant is for making 1,5-pentanediol: 1, the polyol blends of the mol ratio of 6-hexylene glycol=1:1 and carbonate reaction and the polycarbonate diol, the 41.0g that obtain), 2,2-dimethylol propionic acid (DMPA, 14.4g) and isophorone diisocyanate (IPDI, 56.7g), in N-ethyl pyrrolidone (45.9g), under the existence of dibutyltin dilaurate (0.2g), in a nitrogen atmosphere, heat 3 hours at 80-90 DEG C.Add 2,6 di tert butyl 4 methyl phenol (0.4g) and 4-methoxyphenol (0.4g), make atmosphere be air.Then, add the mixture (DPHA, hydroxyl value 95mgKOH/g, 181g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, heat 7 hours at 90 DEG C.NCO base content at the end of urethane reaction is 0.23 % by weight.Extract 32.4g be cooled to 70 DEG C in the reactive mixture, add polyethyleneglycol diacrylate (number-average molecular weight at PEGDA, polyoxyethylene glycol position be 400,7.0g) and triethylamine (1.7g) and mix.Reaction mixture is cooled to 45 DEG C, carries out stirring and add water (75.5g) lentamente, obtain aqueous polyurethane resin dispersion.
[embodiment 9]
In the reaction unit possessing stirrer and well heater, by ETERNACOLL(registered trademark) PH100(space portion is emerging produces; Number-average molecular weight 1054; Hydroxyl value 106mgKOH/g; Polyhydroxy reactant is for making 1,5-pentanediol: 1, the polyol blends of the mol ratio of 6-hexylene glycol=1:1 and carbonate reaction and the polycarbonate diol, the 41.0g that obtain), 2,2-dimethylol propionic acid (DMPA, 14.4g) and isophorone diisocyanate (IPDI, 56.7g), in N-ethyl pyrrolidone (45.9g), under the existence of dibutyltin dilaurate (0.2g), in a nitrogen atmosphere, heat 3 hours at 80-90 DEG C.Add 2,6 di tert butyl 4 methyl phenol (0.4g) and 4-methoxyphenol (0.4g), make atmosphere be air.Then, put into the mixture (PETA, hydroxyl value 188mgKOH/g, 181g) of tetramethylol methane tetraacrylate and pentaerythritol triacrylate, heat 7 hours at 90 DEG C.NCO base content at the end of urethane reaction is 0.23 % by weight.Extract 55.7g be cooled to 70 DEG C in the reactive mixture, add the mixture (DPHA, hydroxyl value 41mgKOH/g, 5.4g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate and triethylamine (2.9g) and mix.Reaction mixture is cooled to 45 DEG C, carries out stirring and add water (96.3g) lentamente, obtain aqueous polyurethane resin dispersion.
[comparative example 1]
In the reaction unit possessing stirrer and well heater, by ETERNACOLL(registered trademark) PH100(space portion is emerging produces; Number-average molecular weight 1054; Hydroxyl value 106mgKOH/g; Polyhydroxy reactant is for making 1,5-pentanediol: 1, the polyol blends of the mol ratio of 6-hexylene glycol=1:1 and carbonate reaction and the polycarbonate diol, the 41.0g that obtain), 2,2-dimethylol propionic acid (DMPA, 14.4g) and isophorone diisocyanate (IPDI, 56.7g), in N-ethyl pyrrolidone (45.9g), under the existence of dibutyltin dilaurate (0.2g), in a nitrogen atmosphere, heat 3 hours at 80-90 DEG C.Add 2,6 di tert butyl 4 methyl phenol (0.4g) and 4-methoxyphenol (0.4g), make atmosphere be air.Then, put into the mixture (DPHA, hydroxyl value 95mgKOH/g, 181g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, heat 7 hours at 90 DEG C.NCO base content at the end of urethane reaction is 0.23 % by weight.Extract 60.4g in the reactive mixture and be cooled to 70 DEG C, add triethylamine (2.9g) and mix.Reaction mixture is cooled to 45 DEG C, carries out stirring and add water (111g) lentamente, obtain aqueous polyurethane resin dispersion.
[comparative example 2]
In the reaction unit possessing stirrer and well heater, by ETERNACOLL(registered trademark) PH100(space portion is emerging produces; Number-average molecular weight 1054; Hydroxyl value 106mgKOH/g; Polyhydroxy reactant is for making 1,5-pentanediol: 1, the polyol blends of the mol ratio of 6-hexylene glycol=1:1 and carbonate reaction and the polycarbonate diol, the 89.9g that obtain), 2,2-dimethylol propionic acid (DMPA, 31.3g) and isophorone diisocyanate (IPDI, 124g), in N-ethyl pyrrolidone (101g), under the existence of dibutyltin dilaurate (0.3g), in a nitrogen atmosphere, heat 3 hours at 80-90 DEG C.Add 2,6 di tert butyl 4 methyl phenol (0.8g) and 4-methoxyphenol (0.8g), make atmosphere be air.Then, put into the mixture (DPHA, hydroxyl value 58mgKOH/g, 399g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, heat 7 hours at 90 DEG C.Measure NCO base content, result is 1.89 % by weight, remains the NCO base of 21%.
[comparative example 3]
In the reaction unit possessing stirrer and well heater, by ETERNACOLL(registered trademark) PH100(space portion is emerging produces; Number-average molecular weight 1054; Hydroxyl value 106mgKOH/g; Polyhydroxy reactant is for making 1,5-pentanediol: 1, the polyol blends of the mol ratio of 6-hexylene glycol=1:1 and carbonate reaction and the polycarbonate diol, the 24.1g that obtain), 2,2-dimethylol propionic acid (DMPA, 8.4g) and isophorone diisocyanate (IPDI, 33.6g), in N-ethyl pyrrolidone (25.1g), under the existence of dibutyltin dilaurate (0.1g), in a nitrogen atmosphere, heat 3 hours at 80-90 DEG C.Add 2,6 di tert butyl 4 methyl phenol (0.2g) and 4-methoxyphenol (0.2g), make atmosphere be air.Then, put into the mixture (DPHA, hydroxyl value 58mgKOH/g, 169g) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, heat 7 hours at 90 DEG C.Measure NCO base content, result is 0.21 % by weight.Extract 60.4g in the reactive mixture and be cooled to 70 DEG C, add triethylamine (1.8g) and mix.Reaction mixture is cooled to 45 DEG C, carries out stirring and add water (119g) lentamente, obtain aqueous polyurethane resin dispersion.
[comparative example 4]
In the reaction unit possessing stirrer and well heater, by ETERNACOLL(registered trademark) PH100(space portion is emerging produces; Number-average molecular weight 1054; Hydroxyl value 106mgKOH/g; Polyhydroxy reactant is for making 1,5-pentanediol: 1, the polyol blends of the mol ratio of 6-hexylene glycol=1:1 and carbonate reaction and the polycarbonate diol, the 41.0g that obtain), 2,2-dimethylol propionic acid (DMPA, 14.4g) and isophorone diisocyanate (IPDI, 56.7g), in N-ethyl pyrrolidone (45.9g), under the existence of dibutyltin dilaurate (0.2g), in a nitrogen atmosphere, heat 3 hours at 80-90 DEG C.Add 2,6 di tert butyl 4 methyl phenol (0.4g) and 4-methoxyphenol (0.4g), make atmosphere be air.Then, put into the mixture (DPHA, hydroxyl value 188mgKOH/g, 181g) of tetramethylol methane tetraacrylate and pentaerythritol triacrylate, heat 7 hours at 90 DEG C.NCO base content at the end of urethane reaction is 0.23 % by weight.Extract 60.4g in the reactive mixture and be cooled to 70 DEG C, add triethylamine (2.9g) and mix.Reaction mixture is cooled to 45 DEG C, carries out stirring and add water (111g) lentamente, obtain aqueous polyurethane resin dispersion.
[sample production of pencil hardness and adaptation]
In each aqueous polyurethane resin dispersion of previous embodiment 1 ~ 9, comparative example 1 ~ 4, add polymerization starter (IRGACURE500, CibaSpecialtyChemicals Inc.) 3 % by weight/solids components, carry out fully stirring and obtaining Liniment.Respectively it is coated on equably on ABS resin, PMMA resin to make dried thickness reach about 20 μm.Then, by drying at 60 DEG C 30 minutes, film (before uviolizing) is obtained.The film of gained is passed through under high voltage mercury lamp (irradiate 1 time, ultraviolet irradiation amount 1000mJ/cm
2).The urethane resin film of gained is used for the evaluation of determination of pencil hardness and adaptation.
(evaluation of hardness)
Evaluated by the pencil hardness measuring urethane resin film.
[mensuration of pencil hardness]
For the urethane resin film on the PMMA resin of aforementioned middle gained, utilize method according to JISK5600-5-4 to measure the pencil hardness of resin coating film.
(evaluation of adaptation)
For the ABS resin of aforementioned middle gained, the urethane resin film of PMMA resin, evaluated by grid stripping method.That is, utilize cutting device on test film, make 25 4mm
2grid (instructor order), utilize cellulose film adhesive tape to investigate separability.
(evaluation of package stability)
After fabrication after 3 days, the outward appearance of each aqueous polyurethane resin dispersion of observation embodiment 1 ~ 9, comparative example 1 ~ 4, confirms package stability.Metewand is as described below.
Zero: do not see condensation product.
×: see condensation product.
Weight part in table represents the weight part of each compound when becoming to be divided into 100 weight part by all solids in resin.
For the pencil hardness in table, such as the pencil of " H " expression H can not cause the situation of damage completely.The pencil of " 2H-3H " expression 3H can cause maybe can not cause damage and pencil with 2H time can not cause the situation of damage completely.
Adaptation in table represents the result of stripping test." 25/25 " represents that 25 grid are closely sealed in 25 grid after test.
Utilizability in industry
Aqueous polyurethane resin dispersion of the present invention can be widely used as the raw material etc. of coating, Liniment.
Claims (16)
1. an aqueous polyurethane resin dispersion, it is characterized in that, it is the aqueous polyurethane resin dispersion composition that the urethane resin (A) at least making to have polymerizability unsaturated link(age) and the compound (B) with polymerizability unsaturated link(age) are dispersed in water-medium, wherein
The urethane resin (A) with polymerizability unsaturated link(age) is the resin at least making polyvalent alcohol (a), polyvalent alcohol (b) containing acidic-group, polymeric polyisocyanate (c) and obtain containing (methyl) acrylate (d) reaction of primary hydroxyl
Containing (methyl) acrylate (d) of primary hydroxyl and the total amount of compound (B) with polymerizability unsaturated link(age) be resin solid content overall 60 ~ 80 % by weight,
Containing (methyl) acrylate (d) of primary hydroxyl, with the form containing (methyl) acrylate (d) of primary hydroxyl and the mixture of inactive relative to isocyanate base (methyl) acrylate, and be imparted in the reaction for obtaining urethane resin (A).
2. aqueous polyurethane resin dispersion according to claim 1, wherein, polyvalent alcohol (a) is polycarbonate diol.
3. aqueous polyurethane resin dispersion according to claim 1 and 2, wherein, containing (methyl) acrylate (d) of primary hydroxyl and the total amount of compound (B) with polymerizability unsaturated link(age) be resin solid content overall 65 ~ 75 % by weight.
4. aqueous polyurethane resin dispersion according to claim 1 and 2, wherein, the compound (B) with polymerizability unsaturated link(age) has (methyl) acryl of more than 3 in 1 molecule.
5. aqueous polyurethane resin dispersion according to claim 1 and 2, wherein, there is the compound (B) of polymerizability unsaturated link(age) for being selected from more than a kind in oxirane modification tetramethylolmethane four (methyl) acrylate, oxirane modification trimethylolpropane tris (methyl) acrylate, oxirane modification ethylene glycol bisthioglycolate (methyl) acrylate.
6. aqueous polyurethane resin dispersion according to claim 1 and 2, wherein, has the compound (B) of polymerizability unsaturated link(age) for oxirane modification tetramethylolmethane four (methyl) acrylate.
7. aqueous polyurethane resin dispersion according to claim 1 and 2, wherein, be the form of Dipentaerythritol six (methyl) acrylate of 80 ~ more than 120mgKOH/g and the mixture of Dipentaerythritol five (methyl) acrylate with hydroxyl value containing (methyl) acrylate (d) of primary hydroxyl, and be imparted in the reaction for obtaining urethane resin (A).
8. aqueous polyurethane resin dispersion according to claim 1 and 2, wherein, being the form of tetramethylolmethane four (methyl) acrylate of 100 ~ 280mgKOH/g and the mixture of tetramethylolmethane three (methyl) acrylate with hydroxyl value by (methyl) acrylate (d) containing primary hydroxyl, being imparted in the reaction for obtaining urethane resin (A).
9. aqueous polyurethane resin dispersion according to claim 1 and 2, wherein, containing acidic-group polyvalent alcohol (b) for the carbon number comprising 2 methylols be the dimethylolalkanoic acids of 4 ~ 12.
10. aqueous polyurethane resin dispersion according to claim 1 and 2, wherein, polymeric polyisocyanate (c) is for having the ester ring type polymeric polyisocyanate of alicyclic structure.
The manufacture method of the aqueous polyurethane resin dispersion according to any one of 11. claims 1 ~ 10, it comprises:
At least make polyvalent alcohol (a), polyvalent alcohol (b) containing acidic-group, polymeric polyisocyanate (c) and obtain the operation (α) of urethane resin (A) containing (methyl) acrylate (d) reaction of primary hydroxyl;
Neutralize the operation (β) of the acidic-group of described urethane resin (A); With
The compound (B) making described urethane resin (A) and have a polymerizability unsaturated link(age) is dispersed in the operation (γ) in water-medium.
12. 1 kinds of Photocurable compositions, it contains the aqueous polyurethane resin dispersion according to any one of Photoepolymerizationinitiater initiater and claim 1 ~ 10.
13. 1 kinds of coating compositions, it contains the aqueous polyurethane resin dispersion according to any one of claim 1 ~ 10.
14. coating compositions according to claim 13, it is for (methyl) acrylic resin or acrylic nitrile-butadiene-alkene-styrene resin.
15. 1 kinds of Liniment compositions, it contains the aqueous polyurethane resin dispersion according to any one of claim 1 ~ 10.
16. Liniment compositions according to claim 15, it is for (methyl) acrylic resin or acrylic nitrile-butadiene-alkene-styrene resin.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-158646 | 2011-07-20 | ||
| JP2011158646 | 2011-07-20 | ||
| PCT/JP2012/068307 WO2013012031A1 (en) | 2011-07-20 | 2012-07-19 | Aqueous polyurethane resin dispersion and use thereof |
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| CN103703038A CN103703038A (en) | 2014-04-02 |
| CN103703038B true CN103703038B (en) | 2016-03-09 |
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| JP (2) | JP6112012B2 (en) |
| KR (1) | KR20140048281A (en) |
| CN (1) | CN103703038B (en) |
| TW (1) | TWI546335B (en) |
| WO (1) | WO2013012031A1 (en) |
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| JP2013082863A (en) * | 2011-09-26 | 2013-05-09 | Asahi Kasei Chemicals Corp | Water-dispersible urethane (meth)acrylate and coating composition |
| JP6246686B2 (en) * | 2014-09-16 | 2017-12-13 | 富士フイルム株式会社 | Inkjet recording method |
| JP6388116B2 (en) * | 2014-09-17 | 2018-09-12 | 東亞合成株式会社 | Curable composition |
| US20160090504A1 (en) * | 2014-09-30 | 2016-03-31 | Fujifilm Corporation | Undercoat composition, composition set, inkjet recording method, and printed material |
| JP2017115028A (en) * | 2015-12-24 | 2017-06-29 | 日本合成化学工業株式会社 | Active energy ray-curable resin composition and coating agent containing the same |
| CN105694565A (en) * | 2016-04-27 | 2016-06-22 | 柳州申通汽车科技有限公司 | Waterborne automobile nano paint and preparation method thereof |
| CN107418410B (en) * | 2017-08-24 | 2021-02-12 | Ppg涂料(天津)有限公司 | Low VOC aqueous UV-curable single layer coating composition, method of coating and substrates coated therewith |
| US20210276143A1 (en) * | 2018-05-11 | 2021-09-09 | Kuraray Co., Ltd. | Modification method of polyurethane, polyurethane, polishing pad, and modification method of polishing pad |
| CN110819224B (en) * | 2018-08-09 | 2021-06-25 | 江苏百赛飞生物科技有限公司 | Coating composition, protective coating based on coating composition and coated product |
| KR102173182B1 (en) * | 2018-11-06 | 2020-11-02 | (주)이녹스첨단소재 | flexible photo imageable coverlay film and manufacturing method thereof |
| CN110003837A (en) * | 2019-04-17 | 2019-07-12 | 李智远 | Polyurethane binder and its preparation process |
| KR102123279B1 (en) * | 2020-03-02 | 2020-06-16 | 표상현 | Method for separating partial (meth)acrylated polyols and urethane-based materials functionalized with (meth)acrylate produced by the partial (meth)acrylated polyols |
| CN115449290A (en) * | 2022-10-18 | 2022-12-09 | 上海展辰涂料有限公司 | High-adhesion water-based UV resin for woodware bottom color wiping and preparation method thereof |
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| CN103703038A (en) | 2014-04-02 |
| JP2017133016A (en) | 2017-08-03 |
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| TWI546335B (en) | 2016-08-21 |
| WO2013012031A1 (en) | 2013-01-24 |
| JPWO2013012031A1 (en) | 2015-02-23 |
| JP6332498B2 (en) | 2018-05-30 |
| TW201315771A (en) | 2013-04-16 |
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