CN104995224B - aqueous resin dispersion and its use - Google Patents

aqueous resin dispersion and its use Download PDF

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Publication number
CN104995224B
CN104995224B CN201380069563.XA CN201380069563A CN104995224B CN 104995224 B CN104995224 B CN 104995224B CN 201380069563 A CN201380069563 A CN 201380069563A CN 104995224 B CN104995224 B CN 104995224B
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methyl
acrylate
resin dispersion
aqueous resin
hydroxyl
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CN104995224A (en
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山田健史
藤井辉昭
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Ube Corp
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Ube Industries Ltd
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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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/147—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The present invention provides a kind of aqueous resin dispersion, and the aqueous resin dispersion can provide film and fine properties with high transparency in the case of being mixed with high-molecular aqueous polyurethane resin water dispersion, also.The present invention provides a kind of aqueous resin dispersion, with the solidification compound containing the aqueous resin dispersion, coating composition and coating agent composition, the aqueous resin dispersion is characterised by, it is at least to make the polyurethane resin (A) with polymerism unsaturated bond, compound (B) and nertralizer (C) with polymerism unsaturated bond are scattered in the aqueous resin dispersion in water-medium, wherein, polyurethane resin (A) with polymerism unsaturated bond is at least to make polyalcohol (a), polyalcohol (b) containing acidic-group, obtained by (methyl) acrylate (d) reaction of polyisocyanates (c) and hydroxyl, nertralizer (C) is the tertiary amine represented by following formulas (1).Formula (1)：(in formula, R1、R2And R3The alkyl of carbon number 1~10 or the hydroxy alkyl of carbon number 1~10 are separately represented, wherein, R1、R2And R3In at least one be carbon number 1~10 hydroxy alkyl, R1、R2And R3Total carbon number be 5~20.).

Description

Aqueous resin dispersion and its use
Technical field
Disperse the present invention relates to the water-base resin that can be solidified by the active energy beam, the heat that are represented with ultraviolet Body and its use.
Background technology
Polycarbonate polyol is the useful compound of the raw material as polyurethane resin.Polycarbonate polyol passes through With the reaction of isocyanate compound, so as to manufacture rigid foam, flexible foam, coating, bonding agent, synthetic leather, The polyurethane resin used in black liquid adhesive etc..Additionally, it is known that aqueous poly- ammonia of the coating by raw material of polycarbonate polyol The light resistance of film, weatherability, heat resistance, hydrolytic resistance, oil resistivity obtained by ester resin dispersion are excellent (with reference to patent document 1)。
It is known that：It is coated with and regard aliphatic polycarbonate polybasic alcohol as raw material and the aqueous urethane tree that uses Film obtained by fat dispersion is improved to adaptation, the resistance to adhesive of base material, therefore is used as silane coupling agent (with reference to patent document 2).However, only using aliphatic polycarbonate polybasic alcohol as raw material in use, being obtained in the presence of by aqueous polyurethane resin dispersion The hardness of film, chemical reagent resistance is in the interior material of such as automobile, mobile phone framework, family's electrical article framework, individual The paint field of the synthetic resin forming body of the bed such as computer framework, decorating film, optical film, flooring material material (flooring) etc., The problem of insufficient in the field of smears.
In order to improve hardness of film, chemical reagent resistance, it also studied using carbamate (methyl) acrylate, example Such as, it is proposed that the aqueous active energy ray-curable resin combination comprising (methyl) acrylated urethanes is (with reference to patent Document 3) and aqueous active energy ray-curable containing (methyl) acrylated urethanes and alefinically unsaturated compounds Composition (with reference to patent document 4).It is excellent that such aqueous active energy ray-curable composition can provide chemical reagent resistance Good hard coat film, therefore the interior material of such as automobile, mobile phone framework, family's electrical article framework, PC can be used as Coating, smears, priming paint, the bonding agent of the synthetic resin forming body of the bed material such as framework, decorating film, optical film, flooring material etc. Raw material use.
In addition, being used as the method for improving the durability of aqueous active energy ray-curable composition, it is proposed that combination Aqueous active containing low molecule amount olefinic unsaturated polyurethanes and HMW olefinic unsaturated polyurethanes is energy ray curing Property composition (with reference to patent document 5).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 10-120757 publications
Patent document 2：Japanese Unexamined Patent Publication 2005-281544 publications
Patent document 3：Japanese Unexamined Patent Publication 2010-202869 publications
Patent document 4：Japanese Unexamined Patent Application Publication 2009-533504 publications
Patent document 5：No. 2009/147092 publication of International Publication
The content of the invention
The invention problem to be solved
In coatings agent field, it is known that in order to improve film performance, by coatings agent composition and high score The polyurethane mixing of son amount.It is well known, however, that：By the aqueous active energy ray-curable as disclosed in patent document 3,4 When composition is mixed with HMW polyurethane dispersion, the problem of white opacity etc can occur for film.It is known that：(first Base) aqueous active energy ray-curable composition that the content of acrylate compounds is big easily produces the problem.
Used in the common heat cured water composition for not containing the compound with polymerism unsaturated bond In aqueous polyurethane resin dispersion, the problem is not found, the problem is containing the compound with polymerism unsaturated bond Active energy ray-curable aqueous resin dispersion or its composition specific to.
The problem of the present invention is to provide a kind of aqueous resin dispersion, the aqueous resin dispersion even in high score In the case of son amount aqueous polyurethane resin dispersion mixing, the film with high transparency can be also provided, and store stabilization Property is excellent.
The method for solving problem
The problem of the present inventor is in order to overcome above-mentioned and carried out various researchs, as a result obtained following opinion：With poly- The polyurethane resin (A) of conjunction property unsaturated bond is at least to make polyalcohol (a), the polyalcohol (b) containing acidic-group, polyisocyanates (c) and obtained by (methyl) acrylate (d) reaction of hydroxyl, unsaturated by the polyurethane resin (A), with polymerism In the aqueous resin dispersion that the compound (B) and nertralizer (C) of key are combined, neutralization is used as by using specific tertiary amine Agent (C) can solve problem, so as to complete the present invention.
(1) of the invention is related to a kind of aqueous resin dispersion, and it is at least to make the polyurethane with polymerism unsaturated bond Resin (A), the compound (B) with polymerism unsaturated bond and nertralizer (C) are scattered in the aqueous tree in water-medium Fat dispersion, wherein,
Polyurethane resin (A) with polymerism unsaturated bond is at least to make polyalcohol (a), the polyalcohol containing acidic-group (b), obtained by (methyl) acrylate (d) reaction of polyisocyanates (c) and hydroxyl,
Nertralizer (C) is the tertiary amine represented by following formulas (1),
[changing 1]
(in formula, R1、R2And R3The alkyl of carbon number 1~10 or the hydroxy alkyl of carbon number 1~10 are separately represented, its In, R1、R2And R3In at least one be carbon number 1~10 hydroxy alkyl, R1、R2And R3Total carbon number be 5~20.).
(2) of the invention are related to the aqueous resin dispersion described in (1) of the invention, wherein, nertralizer (C) is selected from diethyl More than a kind in monoethanolamine, ethyldiethanolamine, methyl diethanolamine and triethanolamine.
(3) of the invention are related to the aqueous resin dispersion described in (1) or (2) of the invention, wherein, nertralizer (C) is three second Hydramine.
(4) of the invention are related to the aqueous resin dispersion described in wantonly 1 in (1)~(3) of the invention, wherein, nertralizer (C) Molal quantity of the molal quantity relative to the acidic-group in polyurethane resin (A) ratio be 0.65~0.95.
(5) of the invention are related to the aqueous resin dispersion described in wantonly 1 in (1)~(4) of the invention, wherein, with polymerization Property unsaturated bond compound (B) be (methyl) acrylate without polyethylene glycol structures.
(6) of the invention are related to the aqueous resin dispersion described in wantonly 1 in (1)~(5) of the invention, wherein, with polymerization Property unsaturated bond compound (B) be selected from (methyl) acrylate of dipentaerythritol six and dipentaerythritol five (methyl) propylene 1 kind in mixture, (methyl) acrylate of pentaerythrite four and double trimethylolpropane four (methyl) acrylate of acid esters More than.
(7) of the invention are related to the aqueous resin dispersion described in wantonly 1 in (1)~(6) of the invention, wherein, polyalcohol (a) For PCDL.
(8) of the invention are related to the aqueous resin dispersion described in wantonly 1 in (1)~(7) of the invention, wherein, hydroxyl The total amount of (methyl) acrylate (d) and the compound (B) with polymerism unsaturated bond is the tree in aqueous resin dispersion 65~75 overall weight % of fat solid constituent.
(9) of the invention are related to the aqueous resin dispersion described in wantonly 1 in (1)~(8) of the invention, wherein, with polymerization Property unsaturated bond polyurethane resin (A) be by hydroxyl (methyl) acrylate (d) with the compound with relative to isocyanide The form of the mixture of inactive (methyl) acrylate of acid group base, using in the reaction for obtaining polyurethane resin (A) In obtained by.
(10) of the invention are related to the aqueous resin dispersion described in wantonly 1 in (1)~(9) of the invention, wherein, it is described to contain hydroxyl (methyl) acrylate (d) of base is that hydroxyl value is with the mixture relative to inactive (methyl) acrylate of isocyanate base 80~more than 120mgKOH/g (methyl) acrylate of dipentaerythritol five and dipentaerythritol six (methyl) acrylate Mixture.
(11) of the invention are related to the aqueous resin dispersion described in wantonly 1 in (1)~(10) of the invention, and it, which also contains, does not have There is the waterborne polyurethane resin (D) of polymerism unsaturated bond.
(12) of the invention are related to the aqueous resin dispersion described in (11) of the invention, wherein, it is unsaturated without polymerism The weight average molecular weight of the waterborne polyurethane resin (D) of key is 40000~1000000.
(13) of the invention are related to a kind of solidification compound, and it contains aqueous described in wantonly 1 in (1)~(12) of the invention Resin dispersion and polymerization initiator.
(14) of the invention are related to a kind of coating composition, and it contains the aqueous tree described in wantonly 1 in (1)~(12) of the invention Fat dispersion.
(15) of the invention are related to a kind of coating agent composition, and it contains aqueous described in wantonly 1 in (1)~(12) of the invention Resin dispersion.
Invention effect
According to the present invention there is provided a kind of aqueous resin dispersion, the aqueous resin dispersion even in HMW In the case that polyurethane is mixed, the film with high transparency, and fine properties can be also provided.
Embodiment
The present invention relates to the polyurethane resin at least made with polymerism unsaturated bond (A), with polymerism unsaturated bond Compound (B) and nertralizer (C) be scattered in aqueous resin dispersion in water-medium.
＜ has polyurethane resin (A) ＞ of polymerism unsaturated bond
The polyurethane resin (A) with polymerism unsaturated bond of the present invention (below, is also simply referred as " polyurethane tree Fat (A) ") it is at least to make (methyl) of polyalcohol (a), the polyalcohol (b) containing acidic-group, polyisocyanates (c) and hydroxyl Obtained by acrylate (d) reaction.
＜ ＜ polyalcohols (a) ＞ ＞
As polyalcohol (a), for example, high molecular weight polyols, low molecular weight polyols can be used, high score is preferably used Sub- weight polyalcohol, it is further preferably equal using number more preferably using the high molecular weight polyols that number-average molecular weight is 400~8000 Molecular weight is 400~4000 high molecular weight polyols, and particularly preferably number-average molecular weight is more for 400~4000 makrolon First alcohol.From the easness of the manufacture of aqueous resin dispersion, high molecular weight diol, low molecular weight diols are preferably used.
High molecular weight diol is not particularly limited, but the preferably high molecular weight diol of number-average molecular weight 400~8000.If Number-average molecular weight is the scope, then is readily obtained appropriate viscosity and good operability.It is easy to ensure that being used as polyurethane resin In soft chain segment performance, using containing rewarding polyurethane resin aqueous resin dispersion formation film when, easily suppress The generation of crackle.Further, since it is abundant with the reactivity of polyisocyanates (c), therefore, it is possible to effectively carry out polyurethane resin (A) manufacture.The number-average molecular weight of high molecular weight diol is more preferably 400~4000.
In present specification, number-average molecular weight (Mn) is obtained by following formula by hydroxyl value [mgKOH/g].
Mn=(56100 × valence mumber)/hydroxyl value
In above-mentioned formula, valence mumber is the number of the hydroxyl in 1 molecule, B method measure of the hydroxyl value based on JIS K 1557.It is polynary Valence mumber is 2 when alcohol is glycol.
As high molecular weight diol, it can enumerate such as PCDL, polyester-diol, PTMEG.From comprising institute Polyurethane resin aqueous resin dispersion, and utilize the light resistance of film obtained by the dispersion, weatherability, heat-resisting Set out in terms of property, hydrolytic resistance, oil resistivity, preferably PCDL.
In PCDL, preferably diol component is the makrolon of aliphatic diol and/or alicyclic diol Glycol, from the viscosity of the polyurethane resin of gained is low, disposal goes out easily and in terms of favorable dispersibility in water-medium Hair, more preferably diol component are straight for PCDL, the i.e. diol component of the aliphatic diol without alicyclic structure The PCDL of the aliphatic diol of chain or side chain, more preferably diol component are the poly- of the aliphatic diol of straight chain Carbonate diol.
Polycarbonate polyol is by making more than a kind of monomeric polyol, being obtained with carbonic ester and/or phosgene reaction. In terms of easy to manufacture and the accessory substance aspect without generation end chloride, preferably make more than a kind polynary Alcohol monomer and polycarbonate polyol obtained by carbonate reaction.
Described polycarbonate polyol can contain with the number of average carbonic acid ester bond in 1 molecule etc. in the present invention Ehter bond, the ester bond of same or following number.
As the example of monomeric polyol, it is not particularly limited, but such as aliphatic polybasic alcohol monomer can be enumerated, with fat Monomeric polyol, aromatic polyvalent alcohol monomer, polyester polyols alcohol monomer, polyether polyols alcohol monomer of ring structure etc..
As the example of aliphatic polybasic alcohol monomer, it is not particularly limited, but can enumerates for example：1,3-PD, 1, The straight-chains such as 4- butanediols, 1,5-PD, 1,6- hexylene glycols, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols Aliphatic diol；2- methyl isophthalic acids, ammediol, 2- methyl isophthalic acids, 5- pentanediols, 3- methyl isophthalic acids, 5- pentanediols, 2- Methyl isophthalic acid, the branched aliphatic diol such as 9- nonanediols；The polyalcohol more than function of trimethylolpropane, pentaerythrite etc. 3 Deng.
As the example of the monomeric polyol with alicyclic structure, it is not particularly limited, but such as Isosorbide-5-Nitrae-hexamethylene can be enumerated Alkane dimethanol, 1,3-CHDM, Isosorbide-5-Nitrae-cyclohexanediol, 1,3- rings pentanediol, Isosorbide-5-Nitrae-cycloheptyl glycol, 2,5- are double The dioxane of (hydroxymethyl)-Isosorbide-5-Nitrae-, 2,7- norbornanes glycol, tetrahydrofurandimethanol, Isosorbide-5-Nitrae-bis- (hydroxyl-oxethyl) Hexamethylene etc. has glycol of ester ring type structure etc. in main chain.
As the example of aromatic polyvalent alcohol monomer, it is not particularly limited, but can enumerates such as Isosorbide-5-Nitrae-benzene dimethanol, 1, 3- benzene dimethanols, 1,2- benzene dimethanols, 4,4 '-naphthalene dimethanol, 3,4 '-naphthalene dimethanol etc..
As the example of polyester polyols alcohol monomer, it is not particularly limited, but such as 6 hydroxycaproic acid and hexylene glycol can be enumerated The hydroxycarboxylic acid such as PEPA and the PEPA of glycol, adipic acid and hexylene glycol the dicarboxylic acids such as PEPA with PEPA of glycol etc..
As the example of polyether polyols alcohol monomer, be not particularly limited, but can enumerate for example polyethylene glycol, polypropylene glycol, PAGs such as polytetramethylene glycol etc..
As above-mentioned polyalcohol, the hydroxyl value of preferably every 1 molecule is the glycol of 2.In glycol, preferred straight or branched Aliphatic diol, specifically, more preferably 1,6- hexylene glycols or 1,6- hexylene glycol with selected from 1,3-PD, Isosorbide-5-Nitrae- Butanediol, 1,5-PD, 1,7- heptandiols, 1,8- ethohexadiols, the combination of glycol in 1,9- nonanediols.
As the example of carbonic ester, it is not particularly limited, but can enumerates for example：The fat such as dimethyl carbonate, diethyl carbonate Fat race carbonic ester；The aromatic carbonates such as diphenyl carbonate；Cyclic carbonates such as ethylene carbonate etc..In addition, it can also make With phosgene that can generate polycarbonate polyol etc..Wherein, from the easiness of manufacture polycarbonate polyol, preferably Aliphatic acid ester carbonate, particularly preferred dimethyl carbonate.
As the method for manufacturing polycarbonate polyol by above-mentioned polyalcohol and carbonate products, it is not particularly limited, But for example following methods can be enumerated：Carbonate products and polyalcohol are added in the reactor, in 160~200 DEG C of temperature, normal pressure After lower reaction 15~25 hours, further reacted 10~20 hours at 200~220 DEG C under 30mmHg or so pressure.Upper State in reaction, preferably while will be retracted to as the raw alcohol of pair outside system while reacting.Now, by making carbonic ester be given birth to pair Alcohol azeotropic come to outside system extract out in the case of, excessive carbonate products can be added.In addition, in above-mentioned reaction, The catalyst such as four titanium butoxides can be used.
As the example of polyester-diol, it is not particularly limited, but such as polyethylene glycol adipate glycol can be enumerated, gather oneself Succinate adipate glycol, polyadipate ethylene glycol butyl glycol ester diol, poly- M-phthalic acid adipic acid hexamethylene glycol ester Glycol, polyethylene glycol succinate glycol, poly butylene succinate glycol, polyethylene glycol sebacate glycol, poly- decanedioic acid Butyl glycol ester diol, poly- 6-caprolactone glycol, poly- (adipic acid 3- methyl isophthalic acids, 5- pentadiol esters) glycol, 1,6- oneself two Condensation polymer of alcohol and dimeric dibasic acid etc..
As the example of PTMEG, it is not particularly limited, but such as polyethylene glycol, polypropylene glycol, poly- four Asia can be enumerated Random copolymer or block copolymer of methyl glycol, oxirane and expoxy propane, oxirane and epoxy butane etc..This Outside, polyether polyester polyalcohol with ehter bond and ester bond etc. can also be used.
As low molecular weight diols, it is not particularly limited, but it is more than 60 and less than 400 that can enumerate such as number-average molecular weight Glycol.It can enumerate for example：Ethylene glycol, 1,3-PD, 2- methyl isophthalic acids, ammediol, 2,2- dimethyl -1,3- Propane diols, 2- butyl -2- ethyls -1,3-PD, BDO, 1,5-PD, 3- methyl isophthalic acids, 5- penta Glycol, 1,6- hexylene glycols, 1,9- nonanediols, 2- methyl isophthalic acids, 8- ethohexadiols, diethylene glycol, triethylene glycol, tetraethylene glycol Deng the aliphatic diol of carbon number 2~9；1,4-CHDM, 1,3-CHDM, Isosorbide-5-Nitrae-cyclohexanediol, 1, Double (hydroxyethyl) hexamethylenes of 4-, 2,7- norbornanes glycol, tetrahydrofurandimethanol, double (hydroxymethyl) -1 of 2,5-, Glycol with ester ring type structure of the carbon numbers such as 4- dioxanes 6~12 etc.., can be with addition, as above-mentioned low molecular weight polyols Use the low molecular weight polyols such as trimethylolpropane, pentaerythrite, D-sorbite.
Polyalcohol (a) can be used alone, can also and with a variety of.
Polyalcohol (b) ＞ ＞s of the ＜ ＜ containing acidic-group
Polyalcohol (b) containing acidic-group is the acidic-group containing the hydroxyl of more than 2 and more than 1 in 1 molecule Polyalcohol.As acidic-group, carboxyl, sulfonic group, phosphate, phenolic hydroxyl group etc. can be enumerated.As containing many of acidic-group First alcohol (b), the preferably polyalcohol containing the compound in 1 molecule with 2 hydroxyls and 1 carboxyl.Containing acidic-group Polyalcohol (b) can be used alone, can also and with a variety of.
As the example of the polyalcohol (b) containing acidic-group, specifically, it can enumerate：2,2- dihydromethyl propionic acids, 2, The dihydroxymethyl alkanoic acid such as 2- dimethylolpropionic acids；The double hydroxyethyl glycine of N, N-, N, the double hydroxyethyl alanine of N-, 3,4- dihydroxy butane sulfonic acid, 3,6- dihydroxy -2- toluenesulfonic acids etc..Wherein, from the viewpoint of the easiness started with, Preferably comprise the dihydroxymethyl alkanoic acid of the carbon number 4~12 of 2 methylols, in dihydroxymethyl alkanoic acid, more preferably 2,2- bis- Hydroxymethyl propionic acid and/or 2,2- dimethylolpropionic acid.
In the present invention, total hydroxyl equivalent number of polyalcohol (a) and the polyalcohol (b) containing acidic-group is preferably 120 ~600.If hydroxyl equivalent number is within the range, be easily obtained following films, i.e. the polyurethane resin comprising gained it is aqueous The film easy to manufacture and excellent in terms of hardness of resin dispersion.Storage from the aqueous resin dispersion of gained is stable Property and film obtained by being coated hardness from the viewpoint of, hydroxyl equivalent number is preferably 130~600, more preferably 150~ 500th, it is more preferably 170~400.
Hydroxyl equivalent number can be calculated by following formula (1) and formula (2).
The quantity (1) of the hydroxyl of the molecular weight of the hydroxyl equivalent number of each polyalcohol=each polyalcohol/each polyalcohol
The total mole number (2) of total hydroxyl equivalent number=M/ polyalcohols of polyalcohol
When calculating the hydroxyl equivalent number of the polyalcohol (a) of polyurethane resin (A) and the polyalcohol (b) containing acidic-group, In above-mentioned formula (2), M represent [(molal quantity of hydroxyl equivalent number × polyalcohol (a) of the polyalcohol (a) calculated by formula (1))+(by Mole of the hydroxyl equivalent number for the polyalcohol (b) containing acidic-group that formula (1) is calculated × polyalcohol (b) containing acidic-group Number)].
＜ ＜ polyisocyanates (c) ＞ ＞
As polyisocyanates (c), it is not particularly limited, but it is more to enumerate such as aromatic polyisocyanate, aliphatic Isocyanates, ester ring type polyisocyanates etc..
As the example of aromatic polyisocyanate, specifically, can enumerate 1,3- phenylene vulcabonds, Isosorbide-5-Nitrae- Phenylene vulcabond, 2,4- toluene di-isocyanate(TDI)s (TDI), 2,6- toluene di-isocyanate(TDI)s, 4,4 '-diphenylmethyl Alkane diisocyanate (MDI), 2,4- methyl diphenylene diisocyanates, 4,4 '-two isocyanato- biphenyl, 3,3 '-diformazan Base -4,4 '-two isocyanato- biphenyl, 3,3 '-dimethyl -4,4 '-two isocyanato- diphenyl methanes, 1,5- naphthalenes Diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, an isocyanatophenyi sulfonylisocyanates, to different Cyanatophenyl sulfonylisocyanates etc..
As the example of aliphatic polyisocyante, specifically, ethylidene diisocyanate, tetramethylene two can be enumerated Isocyanates, hexamethylene diisocyanate (HDI), ten dimethylene diisocyanates, the isocyanic acid of 1,6,11- hendecane three Ester, 2,2,4- trimethyl hexamethylene diisocyanates, the isocyanatomethyl capronates of 2,6- bis-, double (2- isocyanos Close ethyl) fumarate, double (2- isocyanatoethyls) carbonic esters, the isocyanic acid of 2- isocyanatoethyls -2,6- bis- Root closes capronate etc..
As the example of ester ring type polyisocyanates, specifically, IPDI (IPDI), 4 can be enumerated, 4 '-dicyclohexyl methyl hydride diisocyanate (hydrogenation MDI), cyclohexene diisocyanate, methylcyclohexene diisocyanate (hydrogen Change TDI), double (2- isocyanatoethyls) -4- cyclohexene -1,2- dicarboxylic esters, the isocyanic acid of 2,5- norbornanes two Ester, 2,6- norbornene alkyl diisocyanates etc..
Polyisocyanates is preferably the diisocyanate with 2 isocyanate bases in every 1 molecule, but in the present invention Polyurethane resin will not occur gelation in the range of, can also use triphenylmethane triisocyanate is such to have 3 The polyisocyanates of isocyanate base more than individual.
In polyisocyanates, the hardness after being solidified using active energy beam (such as ultraviolet) is uprised so From the viewpoint of, the ester ring type polyisocyanates preferably with alicyclic structure, from the viewpoint of the control for being easy to be reacted, Particularly preferred IPDI (IPDI) and/or HMDI (H12-MDI).
Polyisocyanates can be used alone, can also and with a variety of.
(methyl) acrylate (d) ＞ ＞ of ＜ ＜ hydroxyls
In the present invention, as (methyl) acrylate (d) of hydroxyl, (methyl) acrylic acid containing primary hydroxyl can be used Ester compounds and (methyl) acrylate compounds containing secondary hydroxyl." primary hydroxyl " in present specification refers to hydroxyl The hydroxyl that oxygen atom is bonded with methylene." secondary hydroxyl " in present specification refers to that the oxygen atom of hydroxyl is bonded with methine Hydroxyl.In addition, " (methyl) acryl compound ", " (methyl) acrylate compounds " in present specification, " (methyl) acrylate " is the concept comprising the compound with acryloyl group and the compound with methylacryloyl, Energy used interchangeably, can also have both acryloyl group and methylacryloyl.From the poly- ammonia with polymerism unsaturated bond The aspect that the manufacturing time of ester resin (A) shortens is set out, (methyl) acrylate compounds preferably containing primary hydroxyl.
As the example of (methyl) acrylate containing primary hydroxyl, can enumerate (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid -3- hydroxy propyl esters, (methyl) acrylic acid -4- hydroxybutyls, glycerine list (methyl) acrylate, 3- Hydroxy propane -1,2- diyls two (methyl) acrylate, two glycerine three (methyl) acrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, D-sorbite five (methyl) acrylate, glycerine list (first Base) acrylate, two glycerine list (methyl) acrylate, pentaerythrite list (methyl) acrylate, D-sorbite list (first Base) acrylate, two glycerine two (methyl) acrylate, pentaerythrite two (methyl) acrylate, (the first of dipentaerythritol two Base) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, D-sorbite two (methyl) acrylate, D-sorbite three (methyl) acrylate, D-sorbite four (methyl) acrylate etc..
As the example of (methyl) acrylate containing secondary hydroxyl, it can enumerate：Glycidyl (methyl) acrylate with The addition product, glycerine list (methyl) acrylate, (methyl) third of 2- hydroxy propanes -1,3- diyl two of (methyl) acrylic acid Olefin(e) acid ester, two glycerine list (methyl) acrylate, D-sorbite list (methyl) acrylate, two glycerine two (methyl) propylene Acid esters, D-sorbite two (methyl) acrylate, D-sorbite three (methyl) acrylate, D-sorbite four (methyl) acrylic acid Reaction product (such as Nagese of 1, the 6- hexanediol diglycidyl ethers of ester, (methyl) acrylic acid of 2 molecules and 1 molecule Chemtex company systems " DA-212 "), epoxy (methyl) acrylic acid and the neopentylglycol diglycidyl ether of 1 molecule of 2 molecules Reaction product, reaction product (such as Nagese of the bisphenol A diglycidyl ether of (methyl) acrylic acid of 2 molecules and 1 molecule Chemtex company systems " DA-250 "), the two of the propylene oxide adduct of (methyl) acrylic acid of 2 molecules and bisphenol-A shrink sweet The reaction product of the o-phthalic acid diglycidyl ester of the reaction product of oily ether body, (methyl) acrylic acid of 2 molecules and 1 molecule (such as Nagese Chemtex company systems " DA-721 "), (methyl) acrylic acid of 2 molecules contract with the polyethylene glycol two of 1 molecule The reaction product (such as Nagese Chemtex company systems " DM-811 ", " DM-832 ", " DM-851 ") of water glycerin ether, 2 points (methyl) acrylic acid and the polyalcohol such as (methyl) acrylic acid of son and the reaction product of polypropylene glycol diglycidyl ether of 1 molecule Reaction product of diglycidyl ether etc..
Wherein, it is excellent from the viewpoint of the hardness after being solidified using active energy beam (such as ultraviolet) is uprised The quantity for electing (methyl) acryloyl group in 1 molecule as is (methyl) acrylate of the hydroxyl of more than 3.It is used as 1 molecule In the quantity of (methyl) acryloyl group be the example of (methyl) acrylate (d) of the hydroxyl of more than 3, dipropyl can be enumerated Triol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, D-sorbite five (methyl) acrylate, two seasons penta Tetrol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, mountain Pears sugar alcohol three (methyl) acrylate, D-sorbite four (methyl) acrylate etc..
The quantity of (methyl) acryloyl group in 1 molecule is (methyl) acrylate (d) of the hydroxyl of more than 3 In, from the viewpoint of the manufacturing time that can shorten polyurethane resin (A), more preferably only contain primary hydroxyl as hydroxyl (methyl) acrylate compounds.As the example of (methyl) acrylate (d) of such hydroxyl, pentaerythrite can be enumerated Three (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, two seasons penta Tetrol five (methyl) acrylate.From the viewpoint of the hardness and manufacturing time of film, (methyl) propylene of hydroxyl is used as Ester compound, particularly preferred (methyl) acrylate of dipentaerythritol four and/or dipentaerythritol five (methyl) acrylate.
(methyl) acrylate (d) of hydroxyl can be used alone, can also and with a variety of.
As (methyl) acrylate (d) of hydroxyl, commercially available product can be used directly.
(methyl) acrylate (d) of hydroxyl, can with its with it is inactive (methyl) third relative to isocyanate base The form of the mixture of olefin(e) acid ester, is used in the reaction for obtaining polyurethane resin (A).With (methyl) third with hydroxyl (methyl) acrylate that the form of the mixture of olefin(e) acid ester (d) is used, inactive relative to isocyanate base, can turn into water The compound (B) with polymerism unsaturated bond in property resin dispersion.(methyl) inactive relative to isocyanate base Acrylate refers to, (methyl) third for the group that can be reacted in the molecule without hydroxyl, amino, carboxylic acid etc. with isocyanate base Olefin(e) acid ester.
It is used as (methyl) acrylate (d) and (methyl) acrylate inactive relative to isocyanate base of hydroxyl Mixture, can enumerate as (methyl) acrylate (d) of hydroxyl (methyl) acrylate of dipentaerythritol four and/or Dipentaerythritol five (methyl) acrylate, be used as two seasons relative to inactive (methyl) acrylate of isocyanate base The mixture of penta tetrol six (methyl) acrylate.As such mixture, it can enumerate：Commercially available (the first of dipentaerythritol four Base) acrylate and (methyl) acrylate of dipentaerythritol five and dipentaerythritol six (methyl) acrylate mixture； Mixture of (methyl) acrylate of dipentaerythritol five and dipentaerythritol six (methyl) acrylate etc..Dipentaerythritol six (methyl) acrylate meets (methyl) acrylate inactive relative to isocyanate base.
(methyl) acrylate of dipentaerythritol four and (methyl) acrylate of dipentaerythritol five and dipentaerythritol six The mixture or (methyl) acrylate of dipentaerythritol five of (methyl) acrylate and dipentaerythritol six (methyl) propylene The hydroxyl value of the mixture of acid esters is preferably more than 80mgKOH/g.If hydroxyl value is within the range, can easily it avoid in poly- ammonia The problem of time and resin generation coloring etc are expended in the manufacture of ester resin (A).It is viscous from suppression when manufacturing polyurethane resin (A) Degree rises and avoids setting out in terms of gelation, and the hydroxyl value of mixture is preferably 80~130mgKOH/g, more preferably 80~ 120mgKOH/g, more preferably 85~120mgKOH/g.It is used as the dipentaerythritol six that hydroxyl value is more than 80mgKOH/g The example of (methyl) acrylate and the mixture of dipentaerythritol five (methyl) acrylate, can enumerate such as East Asia synthesis public Department Aronix M403 processed etc..
In addition, being used as (methyl) acrylate (d) and (methyl) third inactive relative to isocyanate base of hydroxyl The mixture of olefin(e) acid ester, it is also possible to use the mixture of pentaerythritol triacrylate and tetramethylol methane tetraacrylate.Now, on The hydroxyl value for stating mixture is preferably 100~280mgKOH/g.If hydroxyl value is within the range, can easily it avoid in poly- ammonia The problem of time and resin generation coloring etc are expended in the manufacture of ester resin (A).Suppress from when manufacturing polyurethane resin (A) From the viewpoint of viscosity rises and avoids gelation, the hydroxyl value of said mixture is preferably 120~250mgKOH/g.More preferably 140~220mgKOH/g.It is used as pentaerythritol triacrylate and pentaerythrite tetrapropylene of the hydroxyl value for 100~280mgKOH/g The mixture of acid esters, can be enumerated such as Aronix M305, M306 of East Asia Synesis Company.
The hydroxyl value of above-mentioned mixture can be determined based on the method described in JIS K0070.
The amount of (methyl) acrylate (d) of hydroxyl is preferably the polyurethane resin (A) with polymerism unsaturated bond Weight in 25~70 weight %.If the scope, then it can make (methyl) acrylate (d) and isocyanate base of hydroxyl Reaction time in reasonable time, can make active energy beam (such as ultraviolet) solidify after the hardness of film be appropriate Scope, and can keep well comprising gained polyurethane resin aqueous polyurethane resin dispersion bin stability. The amount of (methyl) acrylate (d) of hydroxyl is more preferably 30~70 weight % in polyurethane resin (A) weight.
By (methyl) acrylate (d) of hydroxyl with its with relative to inactive (methyl) propylene of isocyanate base The mixture of acid esters (specifically, has (methyl) acrylate of dipentaerythritol four and dipentaerythritol five (methyl) acrylic acid Mixture, (methyl) acrylate of dipentaerythritol five and the dipentaerythritol of ester and dipentaerythritol six (methyl) acrylate Mixture of the mixture of six (methyl) acrylate, pentaerythritol triacrylate and tetramethylol methane tetraacrylate etc.) Form is used in the case of reacting, and the addition of mixture is preferably the polyurethane resin (A) with polymerism unsaturated bond 50~80 weight % in weight, more preferably 60~80 weight %.
The molal quantity of the isocyanate base of polyisocyanates (c) is relative to polyalcohol (a) and the polyalcohol containing acidic-group And the ratio between the molal quantity of whole hydroxyls of (methyl) acrylate (d) of hydroxyl is preferably 0.1~0.9 (b).
If the scope, then be easy to avoid because the molal quantity of hydroxyl is very few cause the reaction time elongated the problem of, it is another Aspect, is also easy to avoid to cause unreacted polyalcohol (a), the polyalcohol containing acidic-group because the molal quantity of hydroxyl is excessive (b) remained in large quantities with (methyl) acrylate (d) of hydroxyl, the problem of bin stability reduction etc.Polyisocyanates (c) molal quantity of isocyanate base is preferably 0.15~0.8 relative to the ratio between molal quantity of whole hydroxyls, particularly preferably 0.2~0.7.
(methyl) propylene of polyalcohol (b), polyisocyanates (c) and hydroxyl for polyalcohol (a), containing acidic-group For the reaction of acid esters (d), (a), (b), (d) can be made to be reacted in a different order with (c), can also by (a), (b), (d) a variety of mixing are reacted with (c) again.Can by (methyl) acrylate (d) of hydroxyl with its with relative to isocyanide The form of the mixture of inactive (methyl) acrylate of acid group base is supplied and the reaction for obtaining polyurethane resin (A).
Make polyalcohol (a), the polyalcohol (b) containing acidic-group, (methyl) acrylate (d) of hydroxyl and many isocyanides When acid esters (c) reacts, catalyst it is also possible to use.
As the example of catalyst, it is not particularly limited, but such as Sn (tin) series catalysts (laurate trimethyl can be enumerated Tin, dibutyl tin laurate etc.), salt, the Yi Jiyou of the metal such as lead series catalysts (lead octoate etc.) and organic acid and inorganic acid Machine metal derivative, amine system catalyst (triethylamine, N-ethylmorpholine, triethylenediamine etc.), diazabicyclo endecatylene system urge Agent etc..Wherein, from the viewpoint of reactivity, preferably dibutyl tin laurate, tin dilaurate dioctyl tin.
Reaction temperature when being reacted is not particularly limited, but preferably 40~120 DEG C.If the scope, then raw material Dissolubility it is also good, the viscosity of the polyurethane resin (A) of gained is appropriate, can be sufficiently carried out stirring.In addition, being not susceptible to (methyl) acryloyl group causes polymerisation and occurs gelation or isocyanate base causes the bad shape of side reaction etc Condition.Reaction temperature is more preferably 60~100 DEG C.
When making (methyl) acrylate (d) of hydroxyl with polyisocyanates (c) reaction, in order to avoid hydroxyl The unnecessary consumption of (methyl) acryloyl group of (methyl) acrylate (d), is preferably carried out in the presence of oxygen.
In addition, the unnecessary consumption of (methyl) acryloyl group in order to avoid (methyl) acrylate (d) of hydroxyl, Also polymerization inhibitor can be added in reaction system in advance.
As the example of polymerization inhibitor, it can enumerate：Quinhydrones, Hydroquinone monomethylether, benzoquinones, TBHQ, to the tert-butyl group The quinone system resistances such as double (1,1,3, the 3- tetramethyl butyl) quinhydrones of catechol, 2,5-, double (1, the 1- dimethylbutyl) quinhydrones of 2,5- Poly- agent；2,6- double (1,1- dimethyl ethyl) -4- methylphenols, 2,6- DI-tert-butylphenol compounds, 2,4- di-tert-butyls Phenol, 2- tert-butyl groups -4,6- xylenol, 2,6- di-tert-butyl-4-methy phenols, 2,4,6- tri-butyl-phenols Deng alkylphenol system polymerization inhibitor；The aromatic series amine system polymerization inhibitor such as phenthazine；Alkylated diphenylamine, N, N '-diphenyl is to benzene two Amine, phenthazine, 4- hydroxyls -2,2,6,6- tetramethyl piperidines, 4- benzoyloxys -2,2,6,6- tetramethyl piperidines, 1, 4- dihydroxy -2,2,6,6- tetramethyl piperidines, 1- hydroxyl -4- benzoyloxys -2,2,6,6- tetramethyl piperidines, two Para-fluoroaniline, 2, the amine system polymerization inhibitor such as 2,6,6- tetramethyl piperidine -1- epoxides (TEMPO)；2,2- diphenylpicrylhydrazines (DPPH), three p-nitrophenyl ylmethyls, N- (3N- epoxide anilino- -1,3- dimethyl butane)-aniline oxide, benzyl The aliquats such as base trimethylammonium chloride；Diethylhydroxylamine, cyclic amide, nitrile compound, substituted urea, benzothiazole, Double-(1,2,2,6,6- pentamethyl -4- piperidyls) sebacate, lactic acid, oxalic acid, citric acid, tartaric acid, benzoic acid etc. has Machine acid；Organic phosphine, phosphite etc..They can be used alone, can also and with a variety of.Especially by by quinone system polymerization inhibitor It is used in combination with alkylphenol system polymerization inhibitor, thus, it is possible to further make the consumption caused by the polymerization of (methyl) acryloyl group become more It is few.
It is used as the amount of the polymerization inhibitor, (first of polyalcohol (b), hydroxyl preferably with respect to polyalcohol (a), containing acidic-group Base) total 100 parts by weight of acrylate (d) and polyisocyanates (c) are set to 0.001~1 parts by weight, preferably 0.01~ 0.5 parts by weight.
Polyalcohol (a), the polyalcohol (b) containing acidic-group, (methyl) acrylate (d) and polyisocyanates of hydroxyl (c) reaction can be carried out in the absence of a solvent, can also be carried out in presence of organic solvent.It is used as organic solvent Example, can enumerate acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), tetrahydrofuran, dioxanes, dimethylformamide, dimethyl sub- Sulfone, 1-METHYLPYRROLIDONE, N- ethyl pyrrolidones, ethyl acetate etc..Wherein, acetone, methyl ethyl ketone, ethyl acetate because Can to be removed under reduced pressure after polyurethane resin (A) is dispersed in water by heating, thus preferably.In addition, N- methylpyrroles The conduct when using the aqueous resin dispersion comprising gained polyurethane resin to make film of alkanone, N- ethyl pyrrolidones Membrane producing promoter plays a role, thus preferably.
Polyalcohol (b), (methyl) propylene of hydroxyl of the amount of organic solvent relative to polyalcohol (a), containing acidic-group The total amount of acid esters (d) and polyisocyanates (c) is preferably 0~2.0 times with weight basis, more preferably 0.05~0.7 times.If For the scope, then time-consuming situation in the process for removing organic solvent is not occurred at, the polyurethane resin of gained is in water In dispersiveness it is also good.In addition it is possible to avoid remaining in using the film made by aqueous resin dispersion organic molten Agent and cause Physical properties of coating film reduce etc the problem of.
＜ has compound (B) ＞ of polymerism unsaturated bond
The aqueous resin dispersion of the present invention includes the compound (B) with polymerism unsaturated bond.With polymerism not The compound (B) of saturated bond is the compound beyond the polyurethane resin (A) with polymerism unsaturated bond.With polymerism not The compound (B) of saturated bond is preferably free-radical polymerised compound.As free-radical polymerised compound, if for light from The free-radical polymerised compound being polymerize under the coexisting of base initiator or under the coexisting of thermal free radical initiator, does not just have There is special limitation, it is preferred that being (methyl) acrylate compounds.
As the example of free-radical polymerised compound, (methyl) acrylate compounds, the poly- ammonia of monomer class can be enumerated Ester (methyl) acrylate compounds, polyester (methyl) acrylate based compound, polyalkylene (methyl) acrylic ester Compound etc..
As the example of (methyl) acrylate compounds of monomer class, it can enumerate：Single (methyl) acrylate, two (first Base) acrylate, three (methyl) acrylate, four (methyl) acrylate, five (methyl) acrylate, six (methyl) acrylic acid Poly- (methyl) acrylate such as ester.
As the example of list (methyl) acrylate, it can enumerate for example：Acryloyl morpholine, (methyl) acrylic acid 2- second The own ester of base, styrene, (methyl) methyl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) dodecylacrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid dicyclopentenyl base ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, (methyl) phenoxy ethyl acrylate, (methyl) isobornyl acrylate, NVP, polyethylene glycol Single (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polyethylene glycol propane diols list (methyl) acrylate, Poly- (ethylene glycol-tetramethylene glycol) single (methyl) acrylate, poly- (propane diols-tetramethylene glycol) single (methyl) propylene Acid esters, methoxy poly (ethylene glycol) list (methyl) acrylate, octyloxy polyethylene glycol propane diols list (methyl) acrylate, Bay epoxide polyethyleneglycol (methyl) acrylate, stearic epoxide polyethyleneglycol (methyl) acrylate, Nonylphenoxy Polyethyleneglycol (methyl) acrylate, Nonylphenoxy polypropylene glycol polyethyleneglycol (methyl) acrylate etc..
As the example of two (methyl) acrylate, it can enumerate for example：Ethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,6- hexylene glycols two (methyl) acrylate, the three ring last of the ten Heavenly stems It is alkane dimethanol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, poly- It is ethylene glycol-polypropylene glycol two (methyl) acrylate, poly- (ethylene glycol-tetramethylene glycol) two (methyl) acrylate, poly- (propane diols-tetramethylene glycol) two (methyl) acrylate, methoxy poly (ethylene glycol) two (methyl) acrylate, octyloxy Polyethylene glycol propane diols two (methyl) acrylate, bay epoxide polyethylene glycol two (methyl) acrylate, stearic epoxide Polyethylene glycol two (methyl) acrylate, Nonylphenoxy polyethylene glycol two (methyl) acrylate, Nonylphenoxy poly- the third two 1, the 6- hexylene glycol 2-glycidyls of alcohol polyethylene glycol two (methyl) acrylate, (methyl) acrylic acid of 2 molecules and 1 molecule The reaction product (such as Nagese Chemtex company systems " DA-212 ") of ether, epoxy (methyl) acrylic acid of 2 molecules and 1 point The reaction product of neopentylglycol diglycidyl ether of son, the bisphenol-A two of (methyl) acrylic acid of 2 molecules and 1 molecule shrink sweet The reaction product (such as Nagese Chemtex company systems " DA-250 ") of oily ether, (methyl) acrylic acid and bisphenol-A of 2 molecules The reaction product of diglycidyl ether body of propylene oxide adduct, the adjacent benzene two of (methyl) acrylic acid of 2 molecules and 1 molecule The reaction product (such as Nagese Chemtex company systems " DA-721 ") of formic acid 2-glycidyl ester, (methyl) third of 2 molecules Reaction product (such as Nagese Chemtex company systems " DM- of the polyethyleneglycol diglycidylether of olefin(e) acid and 1 molecule 811 ", " DM-832 ", " DM-851 "), the polypropylene glycol diglycidyl ether of (methyl) acrylic acid of 2 molecules and 1 molecule The reaction product of (methyl) acrylic acid such as reaction product and polyalcohol diglycidyl ether, (methyl) glycidyl acrylate With the addition product of (methyl) acrylic acid etc..
As the example of three (methyl) acrylate, it can enumerate for example：Trimethylolpropane tris (methyl) acrylate, ring Oxidative ethane is modified trimethylolpropane tris (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylic acid Ester, pentaerythrite three (methyl) acrylate, (6 moles) modified trimethylolpropane tris (methyl) acrylate of oxirane Alkylene oxides such as (BASF AG Laromer (registration mark) LR8863) is modified trimethylolpropane tris (methyl) acrylate (BASF AG Laromer (registration mark) PO33F) etc..
As the example of four (methyl) acrylate, it can enumerate for example：Pentaerythrite four (methyl) acrylate, double three hydroxyls Modified (methyl) acrylate of the pentaerythrite four (Daicel- of methylpropane four (methyl) acrylate, (4 moles) of oxirane Allnex companies, Ebecryl 40) etc. alkylene oxide be modified pentaerythrite four (methyl) acrylate etc..
As the example of five (methyl) acrylate, it can enumerate such as dipentaerythritol five (methyl) acrylate.
As the example of six (methyl) acrylate, it can enumerate such as dipentaerythritol six (methyl) acrylate.
As (methyl) acrylate compounds of polymerization species, known material can be used.It is used as (the first of polymerization species Base) acrylate compounds example, list (methyl) acrylate, two (methyl) acrylate, three (methyl) propylene can be enumerated Poly- (methyl) acrylate such as acid esters, four (methyl) acrylate.
In these free-radical polymerised compounds, from the transparent aspect of obtained film, ring is not preferably carried out Oxidative ethane is modified, i.e., (methyl) acrylate without polyethylene glycol structures.More preferably pentaerythrite four (methyl) acrylic acid Ester, double trimethylolpropane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, (first of dipentaerythritol six Base) acrylate and their mixture.
In these free-radical polymerised compounds, from the base material adaptation aspect of obtained film, preferably two seasons Mixture, the pentaerythrite four (methyl) third of (methyl) acrylate of penta tetrol six and dipentaerythritol five (methyl) acrylate Olefin(e) acid ester, double trimethylolpropane four (methyl) acrylate.More preferably double trimethylolpropane four (methyl) acrylate.
There is the compound (B) of polymerism unsaturated bond can be used only a kind for these, it is possible to use a variety of.
In order to obtain polyurethane resin (A), by (methyl) acrylate (d) of hydroxyl and relative to isocyanate base The mixture of inactive (methyl) acrylate supply with reaction in the case of, contained by reaction system relative to isocyanate base Inactive (methyl) acrylate can turn into the compound (B) with polymerism unsaturated bond in aqueous resin dispersion.
(methyl) acrylate (d) of the hydroxyl of polyurethane resin (A) with polymerism unsaturated bond is poly- with having The total amount of the compound (B) of conjunction property unsaturated bond is preferably 60~85 weights of the resin solid content totality of aqueous resin dispersion Measure %.Than 60 weight % hours, there is a situation where to reduce using the hardness of the film made by aqueous resin dispersion, big When 85 weight %, there is a situation where the bin stability reduction of aqueous resin dispersion.The hydroxyl of polyurethane resin (A) (methyl) acrylate (d) is more preferably 60~80 weight % with compound (B) total amount with polymerism unsaturated bond, enters one Step is preferably 65~75 weight %.
In addition, by (methyl) acrylate (d) of hydroxyl with polymerism unsaturated bond compound (B) it is total When amount is set to 100 weight %, the amount of the compound (B) with polymerism unsaturated bond is preferably 30~50 weight %.
(water-medium)
The aqueous resin dispersion of the present invention is by polyurethane resin (A) and the compound with polymerism unsaturated bond (B) it is dispersed in nertralizer (C) in water-medium.As water-medium, water, water and hydrophilic organic solvent can be enumerated Mixed solvent etc..
As water, it can enumerate such as running water, ion exchange water, distilled water, ultra-pure water.Wherein, it is contemplated that obtain and hold Yi Xing, because of the influence of salt cause particle to become unstable situation etc., preferably use ion exchange water.
As hydrophilic organic solvent, it can enumerate for example：Rudimentary 1 yuan of alcohol such as methanol, ethanol, propyl alcohol；Ethylene glycol, glycerine Deng polyalcohol；The aprotics such as N-methylmorpholine, dimethyl sulfoxide (DMSO), dimethylformamide, 1-METHYLPYRROLIDONE it is hydrophilic Property organic solvent etc..It is used as the amount of the hydrophilic organic solvent in water-medium, preferably 0~20 weight %.
(aqueous resin dispersion)
In the present invention, the acid number of aqueous resin dispersion preferably 10~80mgKOH/g.If the scope, then it is easy to true Protect the water resistance of the good dispersed and film in water-medium.Acid number can specifically be exported according to following formula (3).
(acid number (mgKOH/g) of aqueous resin dispersion)=(milli of the acidic-group of the polyalcohol (b) containing acidic-group Rub number) × 56.1/ (polyurethane resin (A) and the gross weight of the compound (B) with polymerism unsaturated bond) (3)
The acid number of aqueous resin dispersion is more preferably 12~70mgKOH/g, more preferably 14~60mgKOH/g.
In the present invention, when the solid constituent of water dispersion of polyurethane resin is set into 100 parts by weight, preferably with polynary The amount mode that the ratio of alcohol (a) is 2~50 parts by weight, the ratio of polyalcohol (b) containing acidic-group is 1~15 parts by weight, comes Prepare polyurethane resin (A).
If the ratio of polyalcohol (a) is in above range, polyurethane resin (A) is dispersed good in water-medium Good, aqueous resin dispersion can also obtain good Film making properties.If the ratio of the polyalcohol (b) containing acidic-group is in above-mentioned model Enclose, then the water resistance of film is good, and dispersiveness of the polyurethane resin (A) in water-medium can be made also good.
The ratio of polyalcohol (a) is more preferably 3~40 parts by weight, more preferably 5~30 parts by weight.Containing acidic-group The ratio of polyalcohol (b) be more preferably 2~10 parts by weight, more preferably 3~7 parts by weight.
＜ nertralizers (C) ＞
The aqueous resin dispersion of the present invention contains nertralizer (C).Nertralizer (C) is by polyurethane resin (A) acidic groups Group neutralizes.As nertralizer (C), as long as the tertiary amine represented by following formulas (1), is just not particularly limited.
[changing 2]
(in formula, R1、R2And R3The alkyl of carbon number 1~10 or the hydroxy alkyl of carbon number 1~10 are separately represented, its In, R1、R2And R3In at least one be carbon number 1~10 hydroxy alkyl, R1、R2And R3Total carbon number be 5~20.)
In formula (1), R1、R2And R3It is preferably separately the alkyl of carbon number 1~6 or the hydroxyl alkane of carbon number 1~6 Base.If R1、R2And R3Carbon number become it is too much, then exist polyurethane resin (A) dispersiveness reduction, it is impossible to obtain water-base resin Dispersion, or the stability of obtained aqueous resin dispersion are reduced, the situation of water-base resin sedimentation.
In addition, in formula (1), R1、R2And R3Total carbon number be preferably 5~15.If R1、R2And R3Total carbon number become It is too much, then there is the dispersiveness reduction of polyurethane resin (A), it is impossible to obtain aqueous resin dispersion, or obtain it is aqueous The stability reduction of resin dispersion, the situation of water-base resin sedimentation.
As the example of the tertiary amine of above-mentioned formula (1), such as triethanolamine, N methyldiethanol amine, N- second can be enumerated Base diethanol amine, diethyl ethylene diamine.Herein, the acidic-group of polyurethane resin (A) refers to carboxyl, sulfonic group, phosphate, phenol Property hydroxyl etc..
These nertralizers (C) can be used alone, can also and with a variety of.In addition, not damaging the effect of the present invention In the range of, can also and with the amine beyond the tertiary amine represented by formula (1).
But, from the mist degree step-down aspect of the film obtained using aqueous resin dispersion, preferably using only logical Tertiary amine represented by formula (1) is used as nertralizer.
In these nertralizers (C), from by the high score beyond the aqueous resin dispersion and polyurethane resin (A) of the present invention The transparent aspect for the film that the composition that the aqueous urethane resin dispersion of son amount is mixed is obtained is set out, excellent Select triethanolamine, N methyldiethanol amine, N- ethyldiethanolamines, diethyl ethylene diamine.
In these nertralizers (C), beyond using the aqueous resin dispersion and polyurethane resin (A) by the present invention The painting that the aqueous urethane resin dispersion mixing of HMW and the aqueous resin dispersion after 40 DEG C of preservations are obtained The transparency aspect of film is set out, preferably triethanolamine.
That is, by using triethanolamine as nertralizer (C), it is possible to preserve water-base resin for a long time at normal temperatures and disperses Body.
The molal quantity of nertralizer (C) is relative to the acidic-group of the polyurethane resin (A) in water-base resin aqueous dispersion The ratio of molal quantity is 0.5~1.7.If the scope, then following situation can be avoided：Degree of neutralization is low, bin stability reduction Situation, or, utilize by the present invention aqueous resin dispersion and polyurethane resin (A) beyond HMW it is aqueous The transparency drop for the film that carbamate resins aqueous dispersion is mixed and the aqueous resin dispersion after 40 DEG C of preservations is obtained Low situation.The molal quantity of nertralizer (C) is more preferably relative to the ratio of the molal quantity of the acidic-group of polyurethane resin (A) 0.65~1.05, more preferably 0.65~0.95.
It should be noted that the molal quantity of the acidic-group of polyurethane resin (A) is substantially in polyurethane resin (A) The molal quantity of the polyalcohol (b) containing acidic-group used in synthesis.In addition, the molal quantity of nertralizer (C) be make an addition to it is aqueous The molal quantity of the nertralizer of resin dispersion.
When compound (B) with polymerism unsaturated bond has acidic-group, the acidic-group of (B) is also with polyurethane tree The form calculus of the acidic-group of fat (A).
＜ aqueous resin dispersions ＞
In the aqueous resin dispersion of the present invention, its solid constituent is preferably overall 1~70 of aqueous resin dispersion Weight %, more preferably 5~50 weight %.
In the present invention, the solid constituent of aqueous resin dispersion refers to, aqueous resin dispersion is coated on into base material and made It is dried, and makes the composition that it is remained after being crosslinked as film by light irradiation or/and heating.It is situated between in solid constituent without water system Matter, nertralizer.
In addition, curability group can also be made without polymerization initiator described later in the aqueous resin dispersion of the present invention Compound.
The manufacture method ＞ of ＜ aqueous resin dispersions
Next, the manufacture method to aqueous resin dispersion is illustrated.
The manufacture method of the aqueous resin dispersion of the present invention may include：
At least make (methyl) of polyalcohol (a), the polyalcohol (b) containing acidic-group, polyisocyanates (c) and hydroxyl Acrylate (d) reacts and obtained polyurethane resin (A) process (α)；
Above-mentioned polyurethane resin (A) and nertralizer (C) are mixed and the acidic-group of above-mentioned polyurethane resin (A) is neutralized Process (β)；And
Above-mentioned polyurethane resin (A) and the compound (B) with polymerism unsaturated bond is set to be dispersed in water-medium Process (γ).
In order to avoid the unnecessary consuming of polymerism unsaturated bond, the process (α) for obtaining polyurethane resin (A) preferably exists Carried out in the presence of oxygen.Additionally, it is preferred that adding polymerization inhibitor in reaction system as needed.
In order to avoid the unnecessary polymerization of polymerism unsaturated bond, the process (α) of polyurethane resin (A) can obtained Temperature be 0~120 DEG C under conditions of carry out.Preferably 0~100 DEG C.
For the process (β) for neutralizing the acidic-group of polyurethane resin (A), as long as polyurethane resin can be neutralized (A) acidic-group, then its method and operation order etc. are just not particularly limited.It can enumerate for example：Produced in the reaction of process (α) The method that nertralizer (C) is added in thing；The method that (A), (B), water-medium and nertralizer (C) are disposably mixed；It will neutralize Agent (C) is pre-mixed in water-medium, (B), then by them with (A) method mixed etc..
The work in water-medium is dispersed in making polyurethane resin (A) and compound (B) with polymerism unsaturated bond In sequence (γ), as long as (A) and (B) can be made to disperse in water-medium, then its method and operation order etc. are not just limited especially System.It can enumerate for example：The method in water-medium is redispersed in after mixing (B) in (A)；(A) redisperse afterwards is mixed in (B) Method in water-medium；(A) is set to make the scattered method of (B) mixing after being dispersed in water-medium again；(B) is set to be dispersed in water Be in medium after make the scattered method of (A) mixing again；The side for making (A) and (B) to be mixed after being dispersed in respectively in water-medium Method；(B) and then the method being redispersed in water-medium etc. are mixed when manufacturing (A).
In polyurethane resin (A) process (α) is obtained, by (methyl) acrylate (d) of hydroxyl with itself and phase For the form of the mixture of inactive (methyl) acrylate of isocyanate base, for for obtaining polyurethane resin (A) Reaction in the case of, (methyl) acrylate inactive relative to isocyanate base is wrapped together with polyurethane resin (A) In the reaction product for being contained in process (α), and supplied with process (β) and process (γ), the structure in final aqueous resin dispersion Into the compound (B) with polymerism unsaturated bond.In this case, nertralizer can be added in process (α) reaction product (C), further it is dispersed in together with the compound (B) with polymerism unsaturated bond in water system decentralized medium.Further Before compound (B) of the addition with polymerism unsaturated bond, water-medium can be according to circumstances added.
In above-mentioned mixing, stirring, disperseing, agitating device known to mixer for well-distribution, homogenizer etc. can be used.In addition, In polyurethane resin (A), the compound (B) with polymerism unsaturated bond, in order to adjust viscosity, improve operability, raising Dispersiveness, hydrophilic organic solvent, water etc. can be also previously added before combination.
In order to avoid the unnecessary consumption of polymerism unsaturated bond, by polyurethane resin (A) and with polymerism insatiable hunger The process (γ) mixed with the compound (B) of key is preferably carried out in the presence of oxygen.Furthermore it is possible to be added as needed on polymerization inhibitor. In order to avoid the unnecessary consumption of polymerism unsaturated bond, preferably by polyurethane resin (A) and unsaturated with polymerism Temperature during compound (B) mixing of key is progress under conditions of 0~100 DEG C, more preferably under conditions of temperature is 0~90 DEG C Carry out, further preferably carried out under conditions of temperature is 0~80 DEG C, particularly preferably entered under conditions of temperature is 50~70 DEG C OK.
In the manufacture method of the present invention, for by the process (β) of the acidic-group of polyurethane resin (A) neutralization and Polyurethane resin (A) and the compound (B) with polymerism unsaturated bond is set to be dispersed in for the process in water-medium (γ), Either of which process can be carried out first, can also two processes carry out simultaneously.At this point it is possible to by (A), (B), water-medium Disposably mix, nertralizer (C) can also be pre-mixed in water-medium, (B) with nertralizer (C), then by they and (A) Mixing.
The ratio of polyurethane resin (A) in aqueous resin dispersion is preferably 5~60 weight %, more preferably 15~50 Weight %.More preferably 25~40 weight %.In addition, the number-average molecular weight of polyurethane resin (A) be preferably 1000~ 1000000。
In the aqueous resin dispersion of the present invention, thickener, photosensitizer, solidification catalysis can also be added as needed on The additives such as agent, ultra-violet absorber, light stabilizer, defoamer, plasticizer, surface conditioner, antisettling agent.Additive can be with Be used alone, can also and with a variety of.Hardness of the aqueous resin dispersion from the film of gained of the present invention, chemical reagent resistance Aspect set out, be preferably substantially free of protecting colloid, emulsifying agent, surfactant.
The aqueous resin dispersion of the present invention can mix to increase volume with vinyl chloride-based resin emulsion.It can pass through Method known to emulsion polymerization, phase conversion emulsifying, emulsion dispersion method etc. obtains vinyl chloride-based resin emulsion, wherein, preferably lead to Cross the vinyl chloride-based resin emulsion that emulsion polymerization is obtained.Because, by using emulsion dispersion method, can make HMW, The vinyl chloride-based resin of low acid number is emulsified with higher-solid.As the concrete example of vinyl chloride-based resin emulsion, day letter can be enumerated Chemical company vinyblan 271, vinyblan 278, vinyblan 603, vinyblan 690, vinyblan 900, Vinyblan 902, vinyblan 985, Dow Chemical company system UCAR AW-875.It is preferred that in aqueous resin dispersion In contain 0.1~40 weight % vinyl chloride-based resin emulsions, further preferably 3.0~30 weight % vinyl chloride-based resin emulsions.
Vinyl chloride-based resin emulsion can be formed by the way that vinyl chloride is polymerized alone, can also be by by vinyl chloride-acetic acid The copolymerization such as vinyl acetate or vinyl chloride and acrylic monomer are formed., can be by methyl acrylate, third as acrylic monomer Olefin(e) acid ethyl ester, n-butyl acrylate, isobutyl acrylate, acrylic acid-2-ethyl caproite, n-octyl, acrylic acid are different The alkyl acrylate system such as nonyl ester, lauryl acrylate, stearyl acrylate base ester monomer, methyl methacrylate, metering system The methacrylic acids such as acetoacetic ester, n-BMA, 2-Ethylhexyl Methacrylate, stearyl methacrylate Alkyl ester monomer etc. is used alone or two or more is applied in combination.In addition, can be by styrene, α-methylstyrene, second The aromatic vinyl base system monomer such as alkenyl toluene, vinyl xylene, ethyl vinyl benzene；The saturated fatty acids such as propionate, vinyl neodecanoate Vinyl esters system monomer；The vinyl cyanide base system monomer such as acrylonitrile, methacrylonitrile；The olefinic monomers such as propylene, butadiene；Horse Carry out the ethene system metal carboxylates such as the monoalkyl ester and their ammonium salt or alkali metal salt of the ethene system dicarboxylic acids such as sour mono-n-butylester；Third The carboxyl acylamide of the ethene such as acrylamide, Methacrylamide, diacetone acrylamide system carboxylic acid；Methacrylic acid 2- hydroxyl second The hydroxy alkyl esters of the ethene system carboxylic acids such as ester, acrylic acid 2- hydroxy propyl esters, methacrylic acid 2- hydroxy esters；Methacrylic acid The ethene such as dimethylamino ethyl ester, diethyl aminoethyl methacrylate system's carboxylic acid and the esters of alcohol with amino etc. are independent Using or two or more be applied in combination.
The more big then film patience of the molecular weight of vinyl chloride-based resin, film draftability are better, therefore preferably.
In addition, the average grain diameter of the particle in vinyl chloride-based resin emulsion is preferably 30~500nm, more preferably 50 ~400nm.If average grain diameter is more than 500nm, the viscosity of emulsion in itself is uprised sometimes.
In addition, the acid number of vinyl chloride-based resin is preferably 1~100mgKOH/g, more preferably 1~50mgKOH/g enters one Step is preferably 1~10mgKOH/g.If acid number is more than 1mgKOH/g, can emulsify and through when it is stable, if 100mgKOH/g with Under then the rub resistance of film, water resistance, chemical reagent resistance improve.
When the aqueous resin dispersion of the present invention contains vinyl chloride-based resin emulsion, by coordinating the plant containing unsaturated group Thing oil, can suppress the discoloration of vinyl chloride-based resin emulsion.Vegetable oil containing unsaturated group be containing palmitoleic acid, oleic acid, The unrighted acids such as linoleic acid, leukotrienes, eicosenoic acid, erucic acid specifically may be used as the vegetable oil for constituting aliphatic acid Enumerate linseed oil, safflower oil, sunflower oil, soybean oil, corn oil, peanut oil, cottonseed oil, sesame oil, rapeseed oil, olive oil, palm fibre Palmitic acid oil, palm-kernel oil, coconut oil, castor oil etc..
Solid constituent 100 parts by weight of the use level of vegetable oil containing unsaturated group relative to vinyl chloride-based resin emulsion It is preferably set to 1~10 parts by weight.By being set to more than 1 parts by weight, the inhibition that changes colour significantly is shown, by being set to 10 weights Measure below part, the influence to other physical property such as anti-flammabilitys can be suppressed.
＜ solidification compounds ＞
The aqueous resin dispersion and polymerization initiator of the present invention can be mixed, solidification compound is made.As upper Polymerization initiator is stated, Photoepolymerizationinitiater initiater, thermal polymerization etc. can be enumerated.They can be used only a kind, also can and with a variety of. In addition, can also add chain-transferring agent.
＜ Photoepolymerizationinitiater initiaters ＞
In the aqueous resin dispersion of the present invention, Photoepolymerizationinitiater initiater can also be added and photocurable compositions are made Thing.As Photoepolymerizationinitiater initiater, known material can be used, for example, can be used：Irradiated and easily cracked by ultraviolet And the initiator of the optical cleavage type of 2 free radicals, the initiator of dehydrogenation type can be produced.Above-mentioned initiator can be used together.It is used as this The example of a little Photoepolymerizationinitiater initiaters, can be enumerated for example：Acetophenone, 2,2- diethoxy acetophenones, to dimethylamino benzene second Ketone, benzophenone, 2- chlorobenzophenones, p, p '-bis- diethylaminos benzophenone, benzoin ethyl ether, benzoin positive third It is base ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal, thioxanthones, right Isopropyl-Alpha-hydroxy isobutyrophenone, 2,2- dimethoxy -2- phenyl acetophenones, 1- hydroxycyclohexylphenylketones, 2- Methyl isophthalic acid-[4- (methyl mercapto) phenyl] -2- morpholino propane -1- ketone, 2- hydroxy-2-methyl -1- phenyl third Alkane -1- ketone, 2,4,6- tri-methyl benzophenones, 4- methyl benzophenones, 2,2- dimethoxy -1,2- benzyl phenyl ketones Deng.They can be used only a kind, can also and with a variety of.Preferably enumerate hydroxycyclohexylphenylketone.
In the case where adding Photoepolymerizationinitiater initiater, preferably make polyurethane resin (A) and with polymerism unsaturated bond The process (γ) that is dispersed in water-medium of compound (B) after be added.It is used as the amount of Photoepolymerizationinitiater initiater, preferably phase All solids composition (including compound (B) with polymerism unsaturated bond) for aqueous resin dispersion is 0.5~5 weight Measure %.
＜ thermal polymerizations ＞
Thermal polymerization can also be added in the aqueous resin dispersion of the present invention and heat-curable composition is made. As thermal polymerization, material known to organic peroxide etc. can be used.As the example of these thermal polymerizations, It can enumerate for example：Azo；Diacyl peroxide based compound；Peroxy esters based compound；Hydrogen peroxide system chemical combination Thing；Dialkyl peroxide based compound；Ketone peroxide based compound；Ketal peroxide based compound；Alkyl ester Based compound；Peroxycarbonates based compound etc..As these compounds, it can enumerate for example：Azonitrile compound [2,2 '- Azo double (2,4- methyl pentane nitrile), 2,2 '-azo double (isobutyronitrile), 2,2 '-azo double (2- methylbutyronitriles), 2,2 '- Azo double (4- methoxyl groups -2,4- methyl pentane nitrile) etc.], azo amide compound 2,2 '-azo it is double 2- methyl - N- [1,1- double (hydroxymethyl) -2- hydroxyethyls] propionamide } etc., azo amidine compound { 2, double (the 2- amidines of 2 '-azo Base propane) dihydrochloride, 2, double [2- (2- imidazoline -2- bases) propane] dihydrochlorides of 2 '-azo etc., azo it is alkylating Compound [2,2 '-azo double (2,4,4- trimethylpentane), 4,4 '-azo double (4- cyanopentanoic acids) etc.], 2,2 '-azo Azos such as double (2- methyl propanamides oximes)；Dialkanoyl peroxide (lauryl peroxide etc.), two aroyls Peroxide (benzoyl peroxide, benzoyl toluyl groups peroxide, toluyl groups peroxide etc.) etc. Diacyl peroxide based compound；Peroxy esters based compound；Hydrogen peroxide based compound；It is di-tert-butyl peroxide, two withered The dialkyl peroxide based compound such as base peroxide；Ketone peroxide based compound；Ketal peroxide based compound；Cross second The alkyl peroxy ester based compound such as tert-butyl acrylate, the peroxidation acid tert-butyl ester, peroxidized t-butyl perbenzoate；Peroxycarbonates Based compound etc..They can be used only a kind, can also and with a variety of.
When adding thermal polymerization, preferably make polyurethane resin (A) and compound with polymerism unsaturated bond (B) it is added after the process (γ) being scattered in water-medium.As the amount of thermal polymerization, relative to water-base resin point The total solid content (including compound (B) with polymerism unsaturated bond) of granular media is preferably 0.05~5 weight %.
＜ does not have waterborne polyurethane resin (D) ＞ of polymerism unsaturated bond
In the aqueous resin dispersion of the present invention, the aqueous polyurethane tree without polymerism unsaturated bond can be added Fat (D).Waterborne polyurethane resin refers to the polyurethane resin that can be dispersed in water-medium.In addition, water-medium not only includes Pure water, in addition to there is the organic solvent of intermiscibility and the mixed solvent of water to water.
The above-mentioned waterborne polyurethane resin (D) without polymerism unsaturated bond can also aqueous polyurethane resin dispersion State, with the present invention aqueous resin dispersion mix.
In addition, the nothing of the film before being solidified obtained by coating aqueous resin dispersion by active energy beam is glued Property good aspect set out, the weight average molecular weight of the waterborne polyurethane resin (D) without polymerism unsaturated bond is preferably 40000 ~1000000.
The above-mentioned waterborne polyurethane resin (D) without polymerism unsaturated bond can use commercially available aqueous polyurethane tree Fat (D), in above-mentioned polyurethane resin (A) manufacture method, can also without hydroxyl (methyl) acrylate (d) and Polyurethane resin is manufactured, the waterborne polyurethane resin (D) without polymerism unsaturated bond is thus obtained.
＜ coating compositions and coating agent composition ＞
The invention further relates to the coating composition containing above-mentioned aqueous polyurethane resin dispersion and coating agent composition.
In the coating composition and coating agent composition of the present invention, in addition to above-mentioned aqueous polyurethane resin dispersion Other resins can also be added.As other resins, polyester resin, acrylic resin, polyether resin, poly- carbonic acid can be enumerated Ester resin, polyurethane resin, epoxy resin, alkyd resin, vistanex etc..They can be used alone, and can also be used in combination It is a variety of.Other resins preferably have more than a kind of hydrophilic radical.As hydrophilic radical, hydroxyl, carboxyl, sulphur can be enumerated Acidic group, polyethylene glycol groups etc..
As other resins, it is preferably selected from least one kind of in polyester resin, acrylic resin, vistanex.
Polyester resin can generally be manufactured by sour composition with the esterification or ester exchange reaction of alcohol composition.As acid into Point, the compound of sour composition is typically used as when maying be used at manufacture polyester resin.As sour composition, it can be used such as aliphatic many Sour, the alicyclic polyacid of member, aromatic polyvalent acid etc..
The hydroxyl value of polyester resin preferably 10~300mgKOH/g or so, more preferably 50~250mgKOH/g or so, enter one Step is preferably 80~180mgKOH/g or so.The acid number of above-mentioned polyester resin is preferably 1~200mgKOH/g or so, more preferably 15~100mgKOH/g or so, more preferably 25~60mgKOH/g or so.
The weight average molecular weight of polyester resin is preferably 500~500000, and more preferably 1000~300000, further preferably For 1500~200000.
It is used as the acrylic resin of acrylic resin, preferably hydroxyl.The acrylic resin of hydroxyl can be with Method known to emulsion polymerization for example, by solution polymerization process in organic solvent, in water etc., makes the poly- of hydroxyl Conjunction property unsaturated monomer and other polymerism unsaturated monomers that can be with the polymerism unsaturated monomer copolymerization of the hydroxyl Copolymerization is manufactured.
The polymerism unsaturated monomer of hydroxyl can be respectively with the hydroxyl and polymerism of more than 1 in 1 molecule Unsaturated bond compound.It can enumerate for example：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (first Base) (methyl) acrylic acid such as acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls and carbon number 2~8 2 yuan of alcohol Monoesters compound；The 6-caprolactone modified body of these monoesters compounds；N- hydroxymethyls (methyl) acrylamide；Allyl alcohol；Point Sub- end is (methyl) acrylate with polyoxyethylene chain of hydroxyl etc..
The acrylic resin of hydroxyl is preferably the resin with anionic property functional group.On with anionic property official Can group hydroxyl acrylic resin, such as can by using with carboxylic acid group, sulfonic group, phosphate anionic property official The polymerism unsaturated monomer that can be rolled into a ball is manufactured as a kind of polymerism unsaturated monomer.
The hydroxyl value of the acrylic resin of hydroxyl is seen from bin stability, water resistance of the film of gained of composition etc. Point sets out, preferably 1~200mgKOH/g or so, more preferably 2~100mgKOH/g or so, more preferably 3~ 60mgKOH/g or so.
In addition, in the case where the acrylic resin of hydroxyl has the acidic-groups such as carboxyl, the propylene of the hydroxyl The acid number of acid system resin is from the viewpoints such as the water resistance of the film of gained, preferably 1~200mgKOH/g or so, more preferably 2~150mgKOH/g or so, more preferably 5~100mgKOH/g or so.
The weight average molecular weight of the acrylic resin of hydroxyl is preferably 1000~200000, more preferably 2000~ In the range of 100000, more preferably 3000~50000.
As polyether resin, polymer or copolymer with ehter bond can be enumerated, can enumerate such as polyoxyethylene system polyethers, The polyethers that polyoxypropylene system polyethers, polybutylene system polyethers, bisphenol-A or Bisphenol F etc. are derived by aromatic series poly hydroxyl compound Deng.
As polycarbonate resin, the polymer manufactured by bisphenol compound can be enumerated, such as polymer with bis phenol A carbon can be enumerated Acid esters etc..
As polyurethane resin, can enumerate by the various polyol components such as acrylic acid, polyester, polyethers, makrolon with There is the resin of amino-formate bond obtained by the reaction of polyisocyanates.
As epoxy resin, it can enumerate by resin etc. obtained by the reaction of bisphenol compound and epichlorohydrin.As bis-phenol, Such as bisphenol-A, Bisphenol F can be enumerated.
As alkyd resin, can enumerate makes the polyacids such as phthalic acid, terephthalic acid (TPA), butanedioic acid and polyalcohol enter one Step changes with grease oil fatty acid (soybean oil, linseed oil, coconut oil, stearic acid etc.), natural resin (rosin, amber etc.) etc. Property agent reaction obtained by alkyd resin.
As vistanex, the resin obtained as follows can be enumerated：According to common polymerization by olefinic monomers with fitting Suitable other monomers polymerization or copolymerization, by thus obtained vistanex carried out using emulsifying agent moisture dissipate obtained by set Fat；Or olefinic monomers are subjected to emulsion polymerization, thus obtained resin together with suitable other monomers.In addition, according to Situation, can also be used so-called chloridized polyolefin modified resin obtained by above-mentioned vistanex chlorination.
As olefinic monomers, it can enumerate for example：Ethene, propylene, 1- butylene, 3-methyl-1-butene, 4- first The alpha-olefins such as base -1- amylenes, 3- Methyl-1-pentenes, 1- heptene, 1- hexenes, 1- decene, 1- laurylenes；Fourth two Alkene, ethylidene norbornene, bicyclopentadiene, 1,5- hexadienes, phenylethylene equiconjugate diene or non-conjugated diene etc., this A little monomers can be used alone, can also and with a variety of.
As other monomers that can be with olefinic monomers copolymerization, such as vinyl acetate, vinyl alcohol, Malaysia can be enumerated Acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride etc., these monomers can be used alone, and can also be used in combination It is a variety of.
The coating composition and coating agent composition of the present invention can contain curing agent, thus, can improve and use coating group Film obtained by compound or coating agent composition or multilayer film, the water resistance of coated film etc..
As curing agent, such as amino resins, polyisocyanates, blocked polyisocyanates, melamine resin, carbon can be used Diimine etc..Curing agent can be used alone, can also and with a variety of.
As amino resins, it can enumerate for example by partially or completely hydroxyl first obtained by the reaction of amino component and aldehyde composition Base amino resins.As above-mentioned amino component, such as melamine, urea, benzoguanamine, acetylguanamine, steroid guanamines can be enumerated (ス テ ロ グ ア Na ミ Application), spiral shell guanamines, dicyandiamide etc..As aldehyde composition, such as formaldehyde, paraformaldehyde, acetaldehyde, benzene can be enumerated Formaldehyde etc..
As polyisocyanates, the isocyanation esterification of the isocyanate base for example in 1 molecule with more than 2 can be enumerated Compound, can be enumerated such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate.
As blocked polyisocyanates, the addition on the isocyanate base of above-mentioned polyisocyanates can be enumerated blocked Material obtained by agent, as block agent, can be enumerated：The phenol systems such as phenol, cresols；The aliphatic alcohol such as methanol, ethanol system；The third two Dimethyl phthalate, acetylacetone,2,4-pentanedione isoreactivity methylene base system；The mercaptan such as butanethiol, lauryl mercaptan system；Acetanil, acetyl The carboxylic acid amides such as amine system；The lactams systems such as epsilon-caprolactams, δ-valerolactam；The carboxylics such as bromosuccinimide, Malaysia acid imide Imide series；The oxime such as acetaldoxime, acetoxime, methyl ethyl ketone oxime system；The amine systems such as diphenyl aniline, aniline, Ethylenimine etc. are embedding Section agent.
As melamine resin, it can enumerate for example：The methylol melamines such as dihydroxymethyl melamine, trihydroxy methyl melamine；These hydroxyls The alkyl ether compound or condensation product of methyl melamine；Condensation product of alkyl ether compound of methylol melamine etc..
Coloring pigment, extender pigment, bright property can be added in the coating composition and coating agent composition of the present invention Pigment.
As coloring pigment, can enumerate for example titanium oxide, zinc white, carbon black, chrome vermillion, Prussian blue, cobalt blue, AZOpigments, Phthalocyanine color, quinacridone pigment, isoindoline pigment, intellectual circle's series pigments, perylene dyes etc..They can be used alone can also It is a variety of to be used in combination.As coloring pigment, titanium oxide and/or carbon black are particularly preferably used.
As extender pigment, such as clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talcum, titanium dioxide can be enumerated Silicon, alumina white etc..They can be used alone, can also and with a variety of.As extender pigment, particularly preferably using barium sulfate And/or talcum, more preferably using barium sulfate.
Bright pigment can use such as aluminium, copper, zinc, brass, nickel, aluminum oxide, mica, oxidized titanium or iron oxide to cover Mica of the aluminum oxide of lid, oxidized titanium or iron oxide covering etc..
In the coating composition and coating agent composition of the present invention, thickener, curing catalysts, purple can be contained as needed The common additive for coatings such as ultraviolet absorbers, light stabilizer, defoamer, plasticizer, surface conditioner, antisettling agent.It Can be used alone, can also and with a variety of.
The coating composition of the present invention and the manufacture method of coating agent composition are not particularly limited, and known make can be used Make method.Generally, for coating composition and coating agent composition, can by by above-mentioned aqueous resin dispersion with it is above-mentioned Various additives mix, add water-medium, be adjusted to coating process be adapted viscosity and manufacture.
As coating composition be coated material or coating agent composition be applied material, can enumerate metal, plastics, Inorganic matter, timber etc..
The coating composition of the present invention and the adaptation of coating agent composition and plastics are high, particularly to poly- (methyl) propylene The adaptation height of acid system resin, ABS resin.Therefore, as being coated material and be applied material, preferably poly- (methyl) acrylic acid Ester resin and/or ABS resin.
As the coating process or the coating method of coating agent composition of coating composition, can enumerate rotation cup application, spraying, Roller coat, showering, dipping coating etc..
For the present invention coating composition and coating agent composition, preferably after application or coating, under heating or not Under heating, at least a portion of aqueous medium is evaporated, is then solidified by irradiating active energy beam.It is used as activity Energy-ray, preferably ultraviolet.
Xenon lamp, low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, carbon arc can be used in the light source of ultraviolet Lamp, tungsten lamp etc..Irradiation time can according to the species of the compound with polymerism unsaturated bond, the species of Photoepolymerizationinitiater initiater, The conditions such as coating thickness, ultraviolet source suitably change.From the aspect of operability, preferably irradiate 1~60 second.For entering one Step makes the purpose that curing reaction is completed, and can also be heated after uv irradiation.
As used ultraviolet irradiation amount during the composition solidification for making the present invention, from rapidly-curable, operability From the viewpoint of, preferably 300~3000mJ/cm2。
As active energy beam, electron beam etc. it is also possible to use., can be without light when being solidified by electron beam Polymerization initiator, preferably uses the electron beam accelerator of the energy with 100~500eV.
The thickness of film after solidification is not particularly limited, but preferably 1~100 μm of thickness.More preferably form 3~50 μm Thickness film.
Embodiment
Next, enumerate embodiment and comparative example to illustrate the present invention in further detail, but the present invention is not Limited by them.
[synthesis example 1]
Possessing during essence stays tower, mixer, thermometer, the 1000ml of nitrogen ingress pipe glass system round-bottomed flask, adding carbon Dimethyl phthalate 372.0g (4.13mol), 1,6- hexylene glycols 195.6g (1.66mol), 1,5-PD 186.8g (1.79mol), four titanium butoxide 0.05g, while under normal pressure, stirring, distillation for removing methanol and dimethyl carbonate in nitrogen stream Mixture, side carry out 10 hours ester exchange reactions.Now, reaction temperature is made slowly to be warming up to 200 DEG C from 95 DEG C, by distillate Composition be adjusted to the azeotropic of methanol and dimethyl carbonate composition or its near.
Afterwards, 30mmHg is decompressed at leisure, under agitation, the mixture of side distillation for removing methanol and dimethyl carbonate, While further carrying out 10 hours ester exchange reactions at 180 DEG C.(distillation for removing methanol and dimethyl carbonate terminate after reaction terminates Afterwards), reaction solution is cooled to room temperature, obtains PCDL 439.20g.
The number-average molecular weight (Mn) of obtained PCDL is 991, and acid number is 0.05mgKOH/g, weight average molecular weight (Mw) it is 2900, decentralization (Mw/Mn) is 2.2.
[embodiment 1]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.0g, addition, hybrid epoxidized oxide-modified tetramethylol methane tetraacrylate (EO modifications are extracted out PETA, the tetraacrylate that the alcohol as obtained by 4 moles of 1 moles of added ethylene oxide of pentaerythrite is derived；daicel- Allnex company systems " Ebecryl 40 ", 2.58g) and diethyl ethylene diamine (0.56g, pKa=11.5) after, add water (27.9g), carries out strong mixing, thus obtains aqueous resin dispersion.
[embodiment 2]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.0g, addition, hybrid epoxidized oxide-modified tetramethylol methane tetraacrylate (EO modifications are extracted out PETA, the tetraacrylate that the alcohol as obtained by 4 moles of 1 moles of added ethylene oxide of pentaerythrite is derived；daicel- Allnex company systems " Ebecryl 40 ", 2.58g) and ethyldiethanolamine (0.63g, pKa=10.9) after, add water (27.8g), carries out strong mixing, thus obtains aqueous resin dispersion.
[embodiment 3]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.0g, addition, hybrid epoxidized oxide-modified tetramethylol methane tetraacrylate (EO modifications are extracted out PETA, the tetraacrylate that the alcohol as obtained by 4 moles of 1 moles of added ethylene oxide of pentaerythrite is derived；daicel- Allnex company systems " Ebecryl 40 ", 2.59g) and methyl diethanolamine (0.57g, pKa=10.8) after, add water (27.9g), carries out strong mixing, thus obtains aqueous resin dispersion.
[embodiment 4]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.0g, addition, hybrid epoxidized oxide-modified tetramethylol methane tetraacrylate (EO modifications are extracted out PETA, the tetraacrylate that the alcohol as obtained by 4 moles of 1 moles of added ethylene oxide of pentaerythrite is derived；daicel- Allnex company systems " Ebecryl 40 ", 2.60g) and triethanolamine (0.71g, pKa=7.8) after, add water (27.8g), enter Row strong mixing, thus obtains aqueous resin dispersion.
[embodiment 5]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.0g, addition, mixing trimethylolpropane trimethacrylate (TMPTA, 1.3g), three are extracted out Propylene glycol diacrylate (TPGDA, 1.3g) and diethyl ethylene diamine (0.56g, pKa=11.5).Reactant mixture is cooled down To 45 DEG C, water (28.0g) is slowly added into while stirring, aqueous resin dispersion is thus obtained.
[embodiment 6]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.0g, addition, mixing trimethylolpropane trimethacrylate (TMPTA, 1.3g), three are extracted out Propylene glycol diacrylate (TPGDA, 1.3g) and methyl diethanolamine (0.57g, pKa=10.8).In the reactive mixture plus Enter water (27.9g), obtain aqueous resin dispersion.
[embodiment 7]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 15.3g, addition, mixing trimethylolpropane trimethacrylate (TMPTA, 1.7g), three are extracted out Propylene glycol diacrylate (TPGDA, 1.7g) and triethanolamine (0.90g, pKa=7.8).Water is added in the reactive mixture (34.1g), obtains aqueous resin dispersion.
[embodiment 8]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.1g, addition, mixing trimethylolpropane trimethacrylate (TMPTA, 1.3g), three are extracted out Propylene glycol diacrylate (TPGDA, 1.3g) and triethanolamine (0.85g, pKa=7.8).Reactant mixture is cooled to 45 DEG C, water (26.9g) is slowly added into while stirring, obtains aqueous resin dispersion.
[embodiment 9]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.3g, addition, mixing trimethylolpropane trimethacrylate (TMPTA, 1.32g), three are extracted out Propylene glycol diacrylate (TPGDA, 1.32g) and triethanolamine (0.63g, pKa=7.8).Reactant mixture is cooled to 45 DEG C, water (27.4g) is slowly added into while stirring, obtains aqueous resin dispersion.
[embodiment 10]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.1g, addition, mixing trimethylolpropane trimethacrylate (TMPTA, 1.3g), three are extracted out Propylene glycol diacrylate (TPGDA, 1.3g) and triethanolamine (0.57g, pKa=7.8).Reactant mixture is cooled to 45 DEG C, water (27.8g) is slowly added into while stirring, obtains aqueous resin dispersion.
[embodiment 11]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.2g, addition, mixing trimethylolpropane trimethacrylate (TMPTA, 1.3g), three are extracted out Propylene glycol diacrylate (TPGDA, 1.3g) and triethanolamine (0.52g, pKa=7.8).Reactant mixture is cooled to 45 DEG C, water (28.5g) is slowly added into while stirring, obtains aqueous resin dispersion.
[embodiment 12]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.0g, addition, mixing trimethylolpropane trimethacrylate (TMPTA, 1.3g), three are extracted out Propylene glycol diacrylate (TPGDA, 1.3g) and triethanolamine (0.46g, pKa=7.8).Reactant mixture is cooled to 45 DEG C, water (28.2g) is slowly added into while stirring, obtains aqueous resin dispersion.
[embodiment 13]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.1g, addition, mixing trimethylolpropane trimethacrylate (TMPTA, 1.3g), three are extracted out Propylene glycol diacrylate (TPGDA, 1.3g) and triethanolamine (0.40g, pKa=7.8).Reactant mixture is cooled to 45 DEG C, water (28.6g) is slowly added into while stirring, obtains aqueous resin dispersion.
[embodiment 14]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.1g, addition, mixing trimethylolpropane trimethacrylate (TMPTA, 1.3g), three are extracted out Propylene glycol diacrylate (TPGDA, 1.3g) and triethanolamine (0.35g, pKa=7.8).Reactant mixture is cooled to 45 DEG C, water (28.5g) is slowly added into while stirring, obtains aqueous resin dispersion.
[embodiment 15]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.1g, addition, mixing dipentaerythritol acrylate and the propylene of dipentaerythritol five are extracted out The mixture (DPHA, hydroxyl value 95mgKOH/g, 2.6g) and triethanolamine (0.57g, pKa=7.8) of acid esters.By reactant mixture 45 DEG C are cooled to, water (27.8g) is slowly added into while stirring, aqueous resin dispersion is obtained.
[embodiment 16]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.0g, addition, mixing dipentaerythritol acrylate and the propylene of dipentaerythritol five are extracted out The mixture (DPHA, hydroxyl value 42mgKOH/g, 2.6g) and triethanolamine (0.57g, pKa=7.8) of acid esters.By reactant mixture 45 DEG C are cooled to, water (27.7g) is slowly added into while stirring, aqueous resin dispersion is obtained.
[embodiment 17]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.1g, addition, mixing tetramethylol methane tetraacrylate (PETA, 2.6g) and three ethanol are extracted out Amine (0.57g, pKa=7.8).Reactant mixture is cooled to 45 DEG C, water (27.8g) is slowly added into while stirring, obtains aqueous Resin dispersion.
[embodiment 18]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, extract out 12.1g, addition, mixing double trimethylolpropane tetraacrylate (DTMPTA, 2.6g), With triethanolamine (0.57g, pKa=7.8).Reactant mixture is cooled to 45 DEG C, water (27.8g) is slowly added into while stirring, Obtain aqueous resin dispersion.
[comparative example 1]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.0g, addition, hybrid epoxidized oxide-modified tetramethylol methane tetraacrylate (EO modifications are extracted out PETA, the tetraacrylate that the alcohol as obtained by 4 moles of 1 moles of added ethylene oxide of pentaerythrite is derived；daicel- Allnex company systems " Ebecryl 40 ", 2.59g) and triethylamine (0.48g, pKa=10.9) after, add water (28.0g), enter Row strong mixing, thus obtains aqueous resin dispersion.
[comparative example 2]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.0g, addition, hybrid epoxidized oxide-modified tetramethylol methane tetraacrylate (EO modifications are extracted out PETA, the tetraacrylate that the alcohol as obtained by 4 moles of 1 moles of added ethylene oxide of pentaerythrite is derived；daicel- Allnex company systems " Ebecryl 40 ", 2.58g) and dimethylethanolamine (0.42g, pKa=9.3) after, add water (28.0g), carries out strong mixing, thus obtains aqueous resin dispersion.
[comparative example 3]
In possessing the reaction unit of mixer and heater, by the PCDL obtained by synthesis example 1 (PCD, 41.0g), 2,2- dihydromethyl propionic acids (DMPA, 14.4g) and IPDI (IPDI, 56.7g) are in N- ethyls In pyrrolidones (45.9g), in the presence of dibutyl tin laurate (0.2g), under nitrogen atmosphere, 3 are heated at 80~90 DEG C Hour.2,6- di-tert-butyl-4-methy phenols (0.4g) and 4- metoxyphenols (0.4g) are added, atmosphere is set to sky Gas.Further add mixture (DPHA, hydroxyl value of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate 95mgKOH/g, 181g), heated 7 hours at 90 DEG C.NCO bases content at the end of urethane reacts is 0.23 weight Measure %.In the reactive mixture, 12.0g, addition, hybrid epoxidized oxide-modified tetramethylol methane tetraacrylate (EO modifications are extracted out PETA, the tetraacrylate that the alcohol as obtained by 4 moles of 1 moles of added ethylene oxide of pentaerythrite is derived；daicel- Allnex company systems " Ebecryl 40 ", 2.59g) and N-methylmorpholine (0.48g, pKa=7.4) after, add water (28.0g), carries out strong mixing, thus obtains aqueous resin dispersion.
[evaluation of the transparency of film]
Aqueous resin dispersion (the aqueous ultraviolet cure type amino obtained in embodiment 1~18 and comparative example 1~3 Formic acid esters dispersion composite) in (7.0g), add emerging production UW-5034E processed in space portion (weight average molecular weight more than 100,000, without gathering Conjunction property unsaturated bond, 3.0g) as high-molecular aqueous carbamate resins aqueous dispersion, it is sufficiently stirred for.Further addition The weight % of polymerization initiator (IRGACURE500, BASF AG's system) 3/solid constituent, is sufficiently stirred for and obtains smears.With most Telolemma thickness is for 20 microns of mode by obtained coating agent in polycarbonate resin panel.Afterwards, by 60 DEG C of heating Dry 30 minutes, obtain dry coating.
On the sample on makrolon obtained above, mist degree is determined by the method based on JIS K7136.Need Illustrate, when only determining the makrolon used in base material, the mist degree of base material is 0.2%.Result is shown in 1~table of table 7. In table, "-" refers to that mist degree can not be determined.
[evaluation of the film transparency after keeping for a long time]
In aqueous resin dispersion (the aqueous ultraviolet cure type amino obtained by embodiment 1~18 and comparative example 1~3 Formic acid esters dispersion composite) the emerging production UW-5034E processed (weight average molecular weight more than 100,000, without poly- in (7.0g) middle addition space portion Conjunction property unsaturated bond, 3.0g) as high-molecular aqueous carbamate resins aqueous dispersion, it is sufficiently stirred for.By obtained water Property resin combination after 40 DEG C of keepings 1 month, addition polymerization initiator (IRGACURE500, BASF AG's system) 3 weight %/ Solid constituent, obtains smears.By final thickness in the way of 20 microns by obtained coating agent in polycarbonate resin Panel.Afterwards, by 60 DEG C of heat dryings 30 minutes, obtaining dry coating.
On the sample on makrolon obtained above, mist degree is determined by the method based on JIS K7136.Need Illustrate, when only determining the makrolon used in base material, the mist degree of base material is 0.1%.Result is shown in 1~table of table 7. In table, "-" refers to that mist degree can not be determined.
(evaluation of bin stability)
Each aqueous resin dispersion of embodiment 1~18 and comparative example 1~3 is observed after firm manufacture and after manufacturing 1 week Outward appearance, it is thus identified that bin stability.Metewand is as follows.Result is shown in 1~table of table 7.
○：Condensation product is not observed.
×：It was observed that condensation product.
(evaluation of adaptation)
In the aqueous resin dispersion (aqueous ultraviolet obtained by embodiment 10, embodiment 15~18 and comparative example 1~3 Curing type carbamate dispersion composite) add in (7.0g) the emerging production UW-5034E processed in space portion (weight average molecular weight 100,000 with On, 3.0g) as high-molecular aqueous carbamate resins aqueous dispersion, it is sufficiently stirred for.By the combination of obtained water-base resin Thing adds polymerization initiator (IRGACURE500, BASF AG's system) 5 weight %/solid constituent, obtained after 40 DEG C of keepings 1 month To smears.By final thickness in the way of 20 microns by obtained coating agent in various resin panels.Afterwards, by 60 DEG C of heat dryings 30 minutes, obtain dry coating.Using high-pressure sodium lamp, using accumulated light as 1000mJ/cm2Mode to dry Dry film irradiation ultraviolet radiation.
On the sample on resin obtained above, adaptation have rated by gridiron pattern stripping method.I.e. with cutting knife in examination Test 25 4mm of making on piece2Grid, fissility have studied by adhesive tape.10 disbonded tests have been repeated.
○：Stripping is not observed even if 10 experiments are repeated yet.
△：In the 2-10 times experimental observation to stripping.
×：Just observe and peel off in the 1st experiment.
[table 1]
Embodiment 1 Embodiment 2 Embodiment 3
Tertiary amine Diethyl ethylene diamine Ethyldiethanolamine Methyl diethanolamine
NR3/COOH 1.25 1.25 1.25
Polyfunctional acrylic ester EO modified PETs A EO modified PETs A EO modified PETs A
Dispersion liquid bin stability (room temperature, after 1 day) ○ ○ ○
Dispersion liquid bin stability (room temperature, after 1 week) ○ ○ ○
Film mist degree (just manufacture after, %) 2.4 1.6 1.9
Film mist degree (after 40 DEG C, 1 month, %) 60 45 58
[table 2]
[table 3]
[table 4]
[table 5]
Embodiment 13 Embodiment 14
Tertiary amine Triethanolamine Triethanolamine
NR3/COOH 0.7 0.6
Polyfunctional acrylic ester TPGDA/TMPTA TPGDA/TMPTA
Dispersion liquid bin stability (room temperature, after 1 day) ○ ○
Dispersion liquid bin stability (room temperature, after 1 week) ○ ×
Film mist degree (just manufacture after, %) 0.7 1.5
Film mist degree (after 40 DEG C, 1 month, %) 1.5 -
[table 6]
Comparative example 1 Comparative example 2 Comparative example 3
Tertiary amine Triethylamine Dimethylethanolamine N-methylmorpholine
NR3/COOH 1.25 1.25 1.25
Polyfunctional acrylic ester EO modified PETs A EO modified PETs A EO modified PETs A
Dispersion liquid bin stability (room temperature, after 1 day) ○ × ○
Dispersion liquid bin stability (room temperature, after 1 week) ○ × ○
Film mist degree (just manufacture after, %) 11 - 65
Film mist degree (after 40 DEG C, 1 month, %) 52 - -
[table 7]
NR in table 1~73/ COOH represents NR3Molal quantity of the molal quantity of (nertralizer) relative to COOH (acidic-group) Ratio.As the molal quantity of acidic-group, by rubbing for the polyalcohol containing acidic-group used in the synthesis of polyurethane resin That number uses the molal quantity of the nertralizer added in aqueous resin dispersion to calculate as the molal quantity of nertralizer.
In table 7, ABS represents acrylonitrile-butadiene-styrene resin, and PMMA represents plexiglass, PC represents polycarbonate resin, and pet sheet shows pet resin.
Compared with the tertiary amine with hydroxyl, no matter pKa is still used using N-methylmorpholine (pKa=7.4) low pKa High triethylamine (pKa=10.9), the mist degree of film all becomes big, it is seen that the degree of effect is not determined by the pKa of tertiary amine.
Industrial applicability
The aqueous resin dispersion of the present invention can be sharp extensively as coating, smears, priming paint, raw material of bonding agent etc. With.Suitably utilized especially as plastics (film) smears and its raw material etc..

Claims (14)

1. a kind of aqueous resin dispersion, it is characterised in that it is at least to make the polyurethane resin with polymerism unsaturated bond (A) compound (B) and nertralizer (C), with polymerism unsaturated bond are scattered in the water-base resin point in water-medium Granular media, wherein,
Polyurethane resin (A) with polymerism unsaturated bond be at least make polyalcohol (a), the polyalcohol (b) containing acidic-group, Obtained by (methyl) acrylate (d) reaction of polyisocyanates (c) and hydroxyl,
Compound (B) with polymerism unsaturated bond is the change beyond the polyurethane resin (A) with polymerism unsaturated bond Compound, and be (methyl) acrylate without polyethylene glycol structures,
Nertralizer (C) is the tertiary amine represented by following formulas (1),
In formula, R1、R2And R3The alkyl of carbon number 1~10 or the hydroxy alkyl of carbon number 1~10 are separately represented, wherein, R1、R2 And R3In at least one be carbon number 1~10 hydroxy alkyl, R1、R2And R3Total carbon number be 5~20.
2. aqueous resin dispersion according to claim 1, wherein, nertralizer (C) is selected from diethyl ethylene diamine, ethyl More than a kind in diethanol amine, methyl diethanolamine and triethanolamine.
3. aqueous resin dispersion according to claim 1 or 2, wherein, nertralizer (C) is triethanolamine.
4. aqueous resin dispersion according to claim 1 or 2, wherein, the molal quantity of nertralizer (C) is relative to polyurethane The ratio of the molal quantity of acidic-group in resin (A) is 0.65~0.95.
5. aqueous resin dispersion according to claim 1 or 2, wherein, the compound (B) with polymerism unsaturated bond For mixture, pentaerythrite selected from (methyl) acrylate of dipentaerythritol six Yu dipentaerythritol five (methyl) acrylate More than a kind in four (methyl) acrylate and double trimethylolpropane four (methyl) acrylate.
6. aqueous resin dispersion according to claim 1 or 2, wherein, polyalcohol (a) is PCDL.
7. aqueous resin dispersion according to claim 1 or 2, wherein, (methyl) acrylate (d) and the tool of hydroxyl The total amount for having the compound (B) of polymerism unsaturated bond is 65~75 overall weights of the resin solid content of aqueous resin dispersion Measure %.
8. aqueous resin dispersion according to claim 1 or 2, wherein, the polyurethane tree with polymerism unsaturated bond Fat (A) is with the compound and (methyl) inactive relative to isocyanate base by hydroxyl (methyl) acrylate (d) The form of the mixture of acrylate, obtained by the reaction for obtaining polyurethane resin (A).
9. aqueous resin dispersion according to claim 8, wherein, (methyl) acrylate (d) of the hydroxyl with The mixture of (methyl) acrylate inactive relative to isocyanate base is two that hydroxyl value is 80~more than 120mgKOH/g The mixture of (methyl) acrylate of pentaerythrite five and dipentaerythritol six (methyl) acrylate.
10. aqueous resin dispersion according to claim 1 or 2, it also contains the water without polymerism unsaturated bond Property polyurethane resin (D).
11. aqueous resin dispersion according to claim 10, wherein, the aqueous poly- ammonia without polymerism unsaturated bond The weight average molecular weight of ester resin (D) is 40000~1000000.
12. a kind of solidification compound, it contains the aqueous resin dispersion and polymerization in claim 1~11 described in wantonly 1 Initiator.
13. a kind of coating composition, it contains the aqueous resin dispersion described in wantonly 1 in claim 1~11.
14. a kind of coating agent composition, it contains the aqueous resin dispersion described in wantonly 1 in claim 1~11.
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