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CN106519133A - Sulfonic acid type waterborne polyurethane-acrylate self extinction resin and preparation method and application thereof - Google Patents

Sulfonic acid type waterborne polyurethane-acrylate self extinction resin and preparation method and application thereof Download PDF

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Publication number
CN106519133A
CN106519133A CN201610988120.6A CN201610988120A CN106519133A CN 106519133 A CN106519133 A CN 106519133A CN 201610988120 A CN201610988120 A CN 201610988120A CN 106519133 A CN106519133 A CN 106519133A
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Prior art keywords
acrylate
component
resin
preferred
diisocyanate
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CN201610988120.6A
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CN106519133B (en
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王萃萃
张洁
赵炳炎
胡海东
高强
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/58—Epoxy resins
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

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  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a sulfonic acid type waterborne polyurethane-acrylate self extinction resin, the resin is prepared through the reaction of the components of A, prepolymer of diisocyanate sealing side, B, a component of the prepolymer dissolving and diluting the diisocyanate sealing side, C, small molecule amine chain extender, and D, radical initiator. The resin combines the excellent properties of polyurethane and acrylic acid, can achieve excellent adhesion force on the base materials of ABS, PC, PVC, PET and the like, and can achieve excellent hand sweat resistant property, and through adding a cross-linking agent the resin can achieve the excellent properties of alcohol rub resistance, and solvent resistance and the like, the resin can be applied in the fields of leather finish, wood plastic, paper printing, printing ink, printing coating, packaging coating, and matt nail polish and the like.

Description

A kind of sulfonic acid type water-based polyurethane-acrylate is from matting resin and preparation method thereof And application
Technical field
The present invention relates to a kind of sulfonic acid type water-based polyurethane-acrylate is from matting resin and its preparation method and application, Belong to acrylic ester modified water-soluble polyurethane resin art.
Background technology
With expanding economy and the raising of people's aesthetic standards, incrustation product does not require nothing more than excellent performance, more needs Possess good outward appearance and sense of touch.Towards two extreme developments, one is the poly- ammonia of the bloom high grade of transparency to incrustation product at present Ester resin coating surface decorative product, mainly by most of reflection of their light of directive；Two is to use delustring polyurethane resin The incrustation product of the natural in color of covering with paint, mainly by directive, their light carries out refraction absorption, a repellel small part, Less image deflects can be so produced, so that this low glass coating usually aesthetically more makes us feeling pleasure.
Traditional delustring water-base polyurethane material is that delustering agent is added in dispersions of polyurethanes, makes delustering agent dry in film Film coated surface is floated in dry process and produce the microcosmic out-of-flatness of film coated surface, it is so as to reach the effect of delustring, this with thing The delustering agent that reason mode is added is mainly including the high inserts in nature, micro- wax powder, inorganic silicon dioxide etc., although by outer The mode of addition delustering agent can reach the purpose of delustring, but its shortcoming is also apparent from：Delustering agent Jing is often normal with resin used Often occur that matching is poor, cause the surface covered with paint, lacquer, colour wash, etc. occur whiting, it is gloomy, hang the phenomenons such as frost, have a strong impact on incrustation product Presentation quality；It is simultaneously relatively costly using delustering agent in a large number；Coating fragility increases, broken to come off；The precipitation of delustering agent is led The heterogeneity mixing before spreading is caused, so that the gloss of whole coating is variant；It is resistance to rub, bend and rub resistance under Drop.
In order to avoid some defects that outer addition delustering agent is brought, provide in Chinese publication CN104974324A A kind of reaction belongs to sulfonic acid type-carboxylic acid type aqueous polyurethane, prepared from extinction type waterborne polyurethane resin and preparation method thereof Acrylic ester monomer is not introduced in journey, structure is single, the performance such as its alkaline-resisting, solvent resistant, wear-resisting can not meet requirement.
CN103626930A describes a kind of preparation of the Aqueous acrylic urethane's matting resin with phase separation structure Method, it is necessary first to prepare two kinds of polyurethane of anionic and nonionic, then by acrylate mixture in two kinds of polyurethane In carry out seeded emulsion polymerization and obtain, be neutralized using triethylamine when anion-type water-thinned polyurethane is prepared, used Cheng Zhonghui brings larger smell and higher VOC, and the hydrolysis of the presence meeting acceleration molecular chain of this weak acid, while the breast Liquid polymerization procedure is loaded down with trivial details, it is difficult to industrialization production line balance be its weak point.
CN104193946A discloses a kind of preparation method from delustring polyurethane resin, including using absorbable light Acrylic acid-grafted class material end-blocking, as molecule chain end is double bond end-blocking, is not isocyanate-terminated, it is impossible to further with water Chain extension-crosslinking, molecular weight, patience are poor.
Accordingly, it would be desirable to develop a kind of new formula, to solve existing to exist from delustring polyurethane resin in use The various drawbacks such as patience difference.
The content of the invention
The primary and foremost purpose of the present invention is to provide a kind of sulfonic acid type water-based polyurethane-acrylate from matting resin.The sulphur Acid type aqueous polyurethane-acrylate does not use any additional extinction material from matting resin, 60 ° of blank glossiness when being dried Value is less than 1 degree.
Another object of the present invention is to provide preparation of the sulfonic acid type water-based polyurethane-acrylate from matting resin Method.
It is still another object of the present invention to provide sulfonic acid type water-based polyurethane-the acrylate answering from matting resin With.
In order to realize above goal of the invention, the present invention is achieved through the following technical solutions：
A kind of sulfonic acid type water-based polyurethane-acrylate is from matting resin, including following component is prepared：
(A) diisocyanate terminated prepolymer, including the preparation of following component：
S1, at least one diisocyanate, its addition account for 18-32.5wt%, preferred 20.5-29wt%；
S2, at least one polyether Glycols and/or polyester diol, with the mean molecule quantity in 500-3000g/mol, It is preferred that 1500-2000g/mol, its addition accounts for 48-72wt%, preferred 54-67wt%；The mol ratio of the S1 and S2 is 1.8: 1-4.8:1, preferably 2.5:1-4.5:1；
S3, at least one main chain and/or side chain contain the monohydric alcohol and/or dihydroxylic alcohols of polyoxyethylene segments, with The molecular weight of 500-3000g/mol, its addition account for 0.5-2wt%, preferred 1-2wt%；
S4, at least one dihydroxylic alcohols small molecule chain extender containing active hydrogen, with the molecular weight in 60-400g/mol, Its addition accounts for 0.8-4.5wt%, preferred 1.3-4.3wt%；
S5, it is at least one containing two or more can with isocyanates reaction active group and containing at least one olefinic not The compound of saturated group, its addition account for 2.9-10wt%, preferred 3-8.6wt%；
(B) component of the diisocyanate terminated prepolymer of dissolved dilution, including following component：
S6, at least one acrylate monomer and a kind of low boiling point organic solvent, acrylate monomer addition account for 0.2- 1.2 times, low boiling point organic solvent addition accounts for 1.8-0.8 times；
(C) small molecule amine chain extender, including following component：
S7, at least one sulfonic acid type hydrophilic chain extender containing active hydrogen, addition account for 0.7-2.2wt%, preferred 0.9- 1.6wt%；
S8, at least one diamine small molecule chain extender containing active hydrogen, with the molecular weight in 59-200g/mol, Its addition accounts for 0.6-4.9wt%, preferred 2-4wt%；
(D) radical initiator, including following component：
The radical initiator that S9, at least one oxidant are constituted with least one reducing agent is combined, and its addition is accounted for (B) 0.1-0.6% of acrylate monomer component described in, preferred 0.15-0.5%；
Wherein, in S1, S2, S3, S4, S5, S6, S7, S8 the addition of each component be based on S1, S2, S3, S4, S5, S7 and The weight of S8 and calculating.
Diisocyanate described in component S1, including but not limited to toluene di-isocyanate(TDI), two isocyanide of diphenyl methane One kind of acid esters, IPDI, hexamethylene diisocyanate and dicyclohexyl methyl hydride diisocyanate is more Kind, preferably use in IPDI, hexamethylene diisocyanate and dicyclohexyl methyl hydride diisocyanate One or more.
It is polyether Glycols or polyester diol described in component S2, including but not limited to polyethylene glycol, polypropylene glycol, poly- Ethylene glycol and 1,2-propylene glycol, PTMG, polycaprolactone diols, PCDL, polyethylene glycol adipate Dihydroxylic alcohols, polyadipate 1,4- butanediol ester dihydroxylic alcohols, polyneopentyl glycol adipate dihydroxylic alcohols, polyadipate 1,6-HD Ester dihydroxylic alcohols and polyneopentyl glycol adipate 1, one or more in 6- hexylene glycol ester dihydroxylic alcohols, preferably use polyadipate 1,4- butanediol esters dihydroxylic alcohols and/or polyneopentyl glycol adipate 1,6-HD ester dihydroxylic alcohols.
Main chain and/or side chain described in component S3 contains the monohydric alcohol and/or dihydroxylic alcohols of polyoxyethylene segments, described to contain There is the oxirane containing 90-100wt% in the polymerized unit of polyoxyethylene segments, the S3 is preferably Tego Chemie CompanyThe Ymer of D-3403, Perstrop companyTMIn the MPEG1200 of N120 and RAKUTEN of Korea one Plant or various, the more preferably MPEG1200 of the YmerTM N120 of Perstrop companies and/or RAKUTEN of Korea.
The dihydroxylic alcohols small molecule chain extender containing active hydrogen described in component S4, including but not limited to 1,3-PD, 1, One or more in 4- butanediols, diglycol, neopentyl glycol, 1,6- hexylene glycols and 1,4-CHDM, it is excellent Choosing is using one or more in 1,4- butanediols, 1,6-HD and neopentyl glycol.
Described in component S5 containing two or more can with isocyanates reaction active group and contain at least one The compound of individual ethylenically unsaturated group, can be that molecular weight ranges are 62-400, and hydroxy functionality is 2 simultaneously containing an alkene The compound of category unsaturated group, preferred trimethyolol propane monoallyl ether (TMPME)；Structure is：
More preferably using the trimethylolpropane monoallyl of Perstorp companies of Sweden Ether (TMPME)；
Or epoxy functionalities can also be preferably for 2 or 3, preferably 2 epoxy resin and (methyl) acrylate open loop Compound obtained from reaction；More preferably using epoxy resin E51, (mol ratio is 1 with acrylic acid:2) compound that open loop is obtained Epoxy acrylateConcrete reaction equation is as follows：
Acrylic monomers described in component S6, including methyl acrylate, ethyl acrylate, hydroxypropyl acrylate, propylene Propyl propionate, butyl acrylate, methyl methacrylate, EMA, hydroxyethyl methacrylate, methacrylic acid fourth One or more in ester, styrene, methyl styrene, isobornyl acrylate and Isooctyl acrylate monomer, the acrylate Monomer preferably uses methyl methacrylate and/or butyl acrylate；Described low boiling point organic solvent, including but not limited to third Ketone and/or butanone, preferably use acetone.
The sulfonic acid type hydrophilic chain extender containing active hydrogen described in component S7, including 2- (2- amino-ethyls) tarine In sodium, 2- (2- amino-ethyls) aminopropanesulfonic acid sodium, 1,4- butanediol -2- sodium sulfonates and 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium One or more, preferably use 2- (2- amino-ethyls) tarine sodium.
The diamine small molecule chain extender containing active hydrogen described in component S8, including but not limited to ethylenediamine, six methylenes In base diamines, five methylene diamine, diethylenetriamines, IPD, 4,4- diphenylmethanediamiands and diethanol amine One or more, preferably use ethylenediamine and/or IPD.
During oxidant described in component S9 includes ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate and TBHP One or more, reducing agent includes sodium hydrosulfite (sodium dithionite), sodium formaldehyde sulfoxylate, sodium hydrogensulfite and arabo-ascorbic acid (IAA) In one or more, preferably use mass ratio for 1:1 TBHP/sodium hydrosulfite.
The preparation method of sulfonic acid type water-based polyurethane-acrylate of the present invention, comprises the following steps：
(1) to equipped with addition S1, S2, S3, S4 and S5 in reflux condensing tube, thermometer and churned mechanically four-hole boiling flask Hybrid reaction, generates diisocyanate terminated prepolymer；
(2) it is to adding in step (1) B component S6 to carry out dissolved dilution, diisocyanate terminated pre- after being diluted Polymers；
(3) in step (2), add the aqueous solution of the S7 and S8 of deionized water dilution to carry out chain extending reaction, shearing dispersion Obtain aqueous polyurethane-acrylate mixed emulsion；
(4) in step (3) add S9 to cause polymerization, obtain the thick emulsion of aqueous polyurethane-acrylate；
(5) sulfonic acid type water-based polyurethane-acrylate product is obtained to the emulsion desolventizing (acetone) of step (4).
In the present invention, sulfonic acid type water-based polyurethane-acrylate is prepared,
Reaction condition described in step (1) is reacted for 75-85 DEG C, is reacted to NCO and is reached theoretical value；
Dissolved dilution condition described in step (2) is 50-60 DEG C, reaction time 5-10min；
The aqueous solution of S7 and S8 described in step (3), its water consumption are 3-5 times of S7 and S8 mass sums, and reaction temperature is 45-50 DEG C, reaction time 20-30min；
Addition radical initiator initiation temperature described in step (4) is 35-45 DEG C, and polymerization temperature is 45 DEG C, during polymerization Between 2-3h；
Desolvation (acetone) condition described in step (5) is vacuum distillation.
Described sulfonic acid type water-based polyurethane-acrylate solid content is obtained by above-mentioned preparation method preferably to exist 35-55%, more preferably in 40-50%.
The average particle size of described sulfonic acid type water-based polyurethane-acrylate is preferably in 500-4000nm scopes It is interior, more preferably in the range of 800-2500nm.
Sulfonic acid type water-based polyurethane-acrylate of the present invention can be applied as coatings with low gloss finish, can It is applied to the fields such as leather finish, woodenware plastics, paper printing, cloth printing ink, printing coating, packaging coating, delustring nail polish.
The beneficial effects are mainly as follows the following aspects：
(1) extinction effect of the present invention is produced by resin itself, it is not necessary to add any delustering agent, controllable in building-up process The particle of certain grain size distribution processed, in dried coating film dehydration after-contraction, causes surface microroughness to increase, and glossiness is reduced；
(2) aqueous polyurethane-acrylate resin that the present invention is provided, hydrophily, need not by the realization of sulfamic acid sodium salt Neutralization, it is to avoid smell and VOC that the low boiling nertralizer such as triethylamine brings, while sulfamic acid sodium salt belongs to strong acid and strong base Salt, not facile hydrolysis so that product has more preferable resistance to water；
(3) aqueous polyurethane-acrylate resin that the present invention is provided, from matting resin, is diisocyanate in polyurethane The prepolymer composite part of end-blocking introduces double bond, while introducing propylene diisocyanate terminated pre-polymer fraction is diluted Acid ester monomer, carries out radical polymerization between monomer and monomer and monomer and double bond, so just with polyurethane molecular interchain shape Into the mutual biography network structure of chemical crosslinking, the performance such as alkaline-resisting, solvent resistant, wear-resisting is greatly improved.
(4) simple production process of the present invention, is easy to operation, safety non-toxic.
Specific embodiment
Admittedly contain method of testing：Appropriate emulsion is taken in container made by masking foil, the weight before and after 150 degree of 20min is weighed Change, calculates its solids content.
Particle diameter method of testing：Using Malvern particle instrument.
PH method of testings：Using pH meter.
Viscosity determining procedure：Using BROOKFIELD viscosity apparatus, No. 3 rotor/30rpm are tested.
Outward appearance method of testing：Observe and judged.
Feel method of testing：PVC leather at 20um bar tables, 100 degree of drying about 1min, being grabbed by hand and being touched carries out feel Judge.
Blackness method of testing：Black PVC leather at 20um bar tables, 100 degree of drying about 1min, thoroughly observation blackness and degree effect Really.
Resistance to normal temperature complications method of testing：Black PVC leather at 20um bar tables, 100 degree of drying about 1min, is cut into 4*7cm samples Bar, longitude and latitude to each 3, tested by normal temperature complications instrument.
Resistance to alcohol method of testing：Slurry is taken, the isocyanate crosslinking of plus 2% (268), at 20um bars table Black matrixes PVC leather, 100 degree of drying about 1min, places 1 day, takes 95% industrial alcohol, and dry and wet is wiped color fastness instrument and tested 20 times, Whether observation coating surface has the bad phenomenon such as come off or brighten, (1-5 levels, 5 grades best).
Perspiration resistance method of testing：Slurry is taken, the isocyanate crosslinking of plus 2% (268), 20um bars table Place's black matrixes PVC leather, 100 degree of drying about 1min, places 1 day, takes synthetic perspiration, and dry and wet is wiped color fastness instrument and tested 20 times, sees Examine whether coating surface has the bad phenomenon such as come off or brighten, (1-5 levels, 5 grades best).
Adhesion test method：100um bars blade coating PET base material, ABS substrate and PC base materials, 60 degree of drying about 30min, Using GB/T9286-1998 GBs：(0 grade best for PET base material, 0-5 levels)；(0 grade best for ABS substrate, 0-5 levels)；(PC bases Material, 0-5,0 grade of level are best)
Resistance to heat-blocking：PVC leather at 20um bar tables, 100 degree of drying about 1min, is cut into 5*5cm, to pasting, 80 DEG C/3kg/ 24h, opens adhesion for resistance to heat-blocking.
Black and white plate glossiness method of testing：Slurry is taken in black and white paperboard, 150um applicators carry out extension painting, 100 degree of drying About 3min, records the gloss value of 60 degree of incidence angles with vancometer.
Stability test method：Agent slurry is taken at 1 kilogram of table in 1 kilogram of plastic bottle, sealing, normal temperature stand 6 months and 1 month is stood in 50 degree of baking ovens, whether observation bottom has sedimentation and performance whether stable.
Product used in embodiment：
(dicyclohexyl methyl hydride diisocyanate, NCO content are about 32.0% to HMDI, ten thousand magnificent chemical groups stocks Part Co., Ltd)；
(IPDI, NCO content are about 37.8% to IPDI, and ten thousand magnificent chemical groups shares have Limit company)；
(1, hexamethylene-diisocyanate, NCO content are about 50% to HDI, the limited public affairs of ten thousand China's chemical groups shares Department)；
CMA-654 (polyadipate neopentyl glycol hexylene glycol esterdiol, hydroxyl value 74.8mgKOH/g, number-average molecular weight ≈ 1500, degree of functionality is 2, Yantai Hua Da chemistry)；
PBA-2000 (polyadipate BDO esterdiol, hydroxyl value 56mgKOH/g, number-average molecular weight=2000, sense Spend for 2, Yantai Hua Da chemistry)；
MPEG1200 (number-average molecular weight=1200, degree of functionality are 1 for poly glycol monomethyl ether, hydroxyl value 46.75mgKOH/g, Korea is carefree)；
YmerTMN120 (PEO ether glycol, hydroxyl value 110mgKOH/g, number-average molecular weight ≈ 1000, Sweden Perstorp companies)；
NPG (neopentyl glycol, Wanhua Chemical Group Co., Ltd.)；
HDO (1,6- hexylene glycol, BASF Corp. of Germany)；
BDO (BDO, BASF Corp. of Germany)；
A95 (N- (2- amino-ethyls)-Tau sodium salt, 51 ± 2% aqueous solution of solid content, amine 260 ± 20mgKOH/g of value, German EVONIK companies)；
EDA (ethylenediamine, BASF Corp. of Germany)；
IPDA (IPD, Wanhua Chemical Group Co., Ltd.)；
E51 (epoxy resin, epoxide number 0.48-0.54eq/100g, Guangzhou Li Hou trade Co., Ltds)；
TMPME (trimethyolol propane monoallyl ether, Perstorp companies of Sweden)；
Acrylic acid (Wan Hua chemical groups limited company) MMA (methyl methacrylate, Qilu Petrochemical)；
BA (butyl acrylate, Wan Hua chemical groups limited company)；
268 (isocyanate curing agent, Wanhua Chemical Group Co., Ltd.)；
Tego245 (substrate wetting agents, Bick)；
Defom W-0506 (defoamer, moral are modest)；
Acrysol RM-8W (solvent-free non-ionic polyurethanes association thickener, DOW Chemical)；
Acrysol RM-12W (solvent-free non-ionic polyurethanes association thickener, DOW Chemical).
Embodiment 1
Addition 300g epoxy resin E51,1.65g catalyst triphenyl phosphorus in there-necked flask, 0.205g polymerization inhibitors are to first Epoxide phenol MEHQ, 2.47g yellowing additive triphenyl phosphite TPP, temperature are increased to 90-95 degree, then dropwise add in 1 hour Enter acrylic acid 110.2g, the compound epoxy acrylate until acid number is reduced to below 0.5mgKOH/g, required for obtaining.
Embodiment 2
40g is added to being equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI、26g, according to the epoxy acrylate obtained in embodiment 1,4gMPEG1200,3g are new for HDI, 240gCMA-654,23.8g Pentanediol, 80 degree of reactions, sampling monitoring NCO in experimentation, until NCO reaches theoretical value 1.81%, are cooled to 60 degree or so 445g acetone and 171g methyl methacrylates stirring 5min are added, by 2.2g ethylenediamines and 3.5gA95 is used 23g deionized waters dilute, and stirring 25min is added under the conditions of 45 degree, under shearing dispersion condition add 487g water, obtain aqueous poly- Urethane-crylic acid ester mixture emulsion.System is warming up to into 45 degree, 0.26g TBHPs and 0.26g sodium hydrosulfites is added (sodium dithionite) causes polymerization, stirs polyase 13 h at this temperature, the emulsion vacuum distillation is removed acetone, solid content is obtained White sulfonic acid type water-based polyurethane-the acrylic acid ester emulsion of 50wt%, particle diameter 1730nm.
Embodiment 3
74g is added to being equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI、 47.5gHDI, 190gCMA-654,37g according to the epoxy acrylate obtained in embodiment 1, 5.2gMPEG1200,16.5g neopentyl glycol, 80 degree of reactions, sampling monitoring NCO in experimentation, until NCO reaches theoretical value 4.73%, it is cooled to 60 degree or so and adds 306g acetone and 382g methyl methacrylates stirring 5min, by 8g ethylenediamines and 4gA95 is diluted with 48g deionized waters, and stirring 25min is added under the conditions of 45 degree, is added under shearing dispersion condition Enter 712g water, obtain aqueous polyurethane-acrylate mixed emulsion.System is warming up to into 45 degree, 0.76g tert-butyl hydroperoxides are added Hydrogen and 0.76g sodium hydrosulfites (sodium dithionite) cause polymerization, stir polyase 13 h at this temperature, the emulsion vacuum distillation is removed Acetone is removed, solid content 50wt%, the white sulfonic acid type water-based polyurethane-acrylic acid ester emulsion of particle diameter 1350nm is obtained.
Embodiment 4
74g is added to being equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI、 47.5gHDI, 240gPBA-2000,37g according to the epoxy acrylate obtained in embodiment 1, 5.2gMPEG1200,16.5g neopentyl glycol, 80 degree of reactions, sampling monitoring NCO in experimentation, until NCO reaches theoretical value 4.30%, it is cooled to 60 degree or so and adds 347g acetone and 433g methyl methacrylates stirring 5min, by 9g ethylenediamines and 4gA95 is diluted with 52g deionized waters, and stirring 25min is added under the conditions of 45 degree, is added under shearing dispersion condition Enter 810g water, obtain aqueous polyurethane-acrylate mixed emulsion.System is warming up to into 45 degree, 0.87g tert-butyl hydroperoxides are added Hydrogen and 0.87g sodium hydrosulfites (sodium dithionite) cause polymerization, stir polyase 13 h at this temperature, the emulsion vacuum distillation is removed Acetone is removed, solid content 50wt%, the white sulfonic acid type water-based polyurethane-acrylic acid ester emulsion of particle diameter 2430nm is obtained.
Embodiment 5
47g is added to being equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskIPDI、36gHDI、245gCMA-654、7.5gYmerTMN120,11.2g trimethyolol propane monoallyl ether, 5g 1,6- Hexylene glycol, 80 degree of reactions, sampling monitoring NCO in experimentation, until NCO reaches theoretical value 3.66%, are cooled to 60 degree or so 485g acetone, 112g methyl methacrylates stirring 5min are added, by 18g IPDs and 3gA95 is used 84g deionized waters dilute, and stirring 25min is added under the conditions of 45 degree, under shearing dispersion condition add 398g water, obtain aqueous poly- Urethane-crylic acid ester mixture emulsion.System is warming up to into 45 degree, 0.34g TBHPs and 0.34g sodium hydrosulfites is added (sodium dithionite) causes polymerization, stirs polyase 13 h at this temperature, the emulsion vacuum distillation is removed acetone, solid content is obtained White sulfonic acid type water-based polyurethane-the acrylic acid ester emulsion of 50wt%, particle diameter 2030nm.
Embodiment 6
48g is added to being equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskIPDI、 37gHDI、220gPBA-2000、2gYmerTMN120,11.2g trimethyolol propane monoallyl ether, 15g 1, 6- hexylene glycols, 80 degree reaction, sampling monitoring NCO in experimentation, until NCO reach theoretical value 3.47%, be cooled to 60 degree it is left Right addition 284g acetone, 284g methyl methacrylates, 71g butyl acrylates stirring 5min, by 14g different Buddhist diketone diamines and 7.2gA95 is diluted with 85g deionized waters, and stirring 25min is added under the conditions of 45 degree, in shearing dispersion condition Lower addition 774g water, obtains aqueous polyurethane-acrylate mixed emulsion.System is warming up to into 45 degree, 1.77g tert-butyl group mistakes are added Hydrogen oxide and 1.77g sodium hydrosulfites (sodium dithionite) cause polymerization, stir polyase 13 h at this temperature, and the emulsion decompression is steamed Acetone is removed in distillation, obtains solid content 45wt%, the white sulfonic acid type water-based polyurethane-acrylic acid ester emulsion of particle diameter 1680nm.
Embodiment 7
45g is added to being equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskIPDI、34gHDI、245gPBA-2000、7gYmerTMN120,19g trimethyolol propane monoallyl ether, 7g 1,4- fourths two Alcohol, 80 degree of reactions, sampling monitoring NCO in experimentation, until NCO reaches theoretical value 2.28%, are cooled to 60 degree or so additions 296g acetone, 296g methyl methacrylates, 74g butyl acrylates stirring 5min, by 8g different Buddhist diketone diamines and 5.6gA95 is diluted with 54g deionized waters, and stirring 25min is added under the conditions of 45 degree, is added under shearing dispersion condition Enter 681g water, obtain aqueous polyurethane-acrylate mixed emulsion.System is warming up to into 45 degree, 1.85g tert-butyl hydroperoxides are added Hydrogen and 1.85g sodium hydrosulfites (sodium dithionite) cause polymerization, stir polyase 13 h at this temperature, the emulsion vacuum distillation is removed Acetone is removed, solid content 45wt%, the white sulfonic acid type water-based polyurethane-acrylic acid ester emulsion of particle diameter 2270nm is obtained.
Comparative example 1
47g is added to being equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskIPDI、36gHDI、245gCMA-654、4g YmerTMN120,12.5g1,6 hexylene glycols, 80 degree of reactions are taken in experimentation Sample monitors NCO, until NCO reaches theoretical value 3.72%, is cooled to 60 degree or so and adds 476g acetone and 110g methacrylic acids Methyl esters stirs 5min, by 17g IPDs and 5gA95 is diluted with 88g deionized waters, addition flask, and 45 Degree reaction 25min, adds the shearing dispersion of 383g water, obtains aqueous polyurethane-acrylate mixed emulsion.System is warming up to into 45 Degree, adds 0.22g TBHPs and 0.22g sodium hydrosulfites (sodium dithionite) to cause polymerization, stirs at this temperature The emulsion vacuum distillation is removed acetone, obtains solid content 50wt%, the aqueous poly- ammonia of white sulfonic acid type of particle diameter 1930nm by polyase 13 h Ester-acrylic acid ester emulsion.
Comparative example 2
47g is added to being equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskIPDI、36gHDI、245gCMA-654、4gYmerTMN120,12.5g 1,6- hexylene glycol, 80 degree of reactions, takes in experimentation Sample monitors NCO, until NCO reaches theoretical value 3.72%, is cooled to 60 degree or so and adds 586 acetone stirring 5min, by 17g different Buddhist That ketone diamines and 5gA95 is diluted with 88g deionized waters, adds flask, 45 degree of reaction 25min to add 274g water Shearing dispersion, obtains aqueous pu dispersions emulsion.The emulsion vacuum distillation is removed into acetone, solid content 50wt%, particle diameter is obtained The white sulfonic acid type water-based emulsion of 1030nm.
Comparative example 3
47g is added to being equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskIPDI、36gHDI, 245gCMA-654,11.2g trimethyolol propane monoallyl ether, 4g YmerTMN120,6g1,6 oneself two Alcohol, 80 degree of reactions, sampling monitoring NCO in experimentation, until NCO reaches theoretical value 3.57%, are cooled to 60 degree or so additions 485g acetone and 112g methyl methacrylates stirring 5min, by 14g IPDs and 9.5gA95 is used 94g deionized waters dilute, and add flask, 45 degree of reaction 25min to add the shearing dispersion of 488g water, obtain water-borne polyurethane-acrylate Ester mixed emulsion.System is warming up to into 45 degree, 0.22g TBHPs and 0.22g sodium hydrosulfite (hydrosulfurous acids is added Sodium) cause polymerization, polyase 13 h is stirred at this temperature, and the emulsion vacuum distillation is removed into acetone, solid content 45wt%, particle diameter is obtained White sulfonic acid type water-based polyurethane-the acrylic acid ester emulsion of 380nm.
Take 9 groups of enforcements from embodiment 2, example 3, example 4, example 5, example 6, example 7 and comparative example 1, comparative example 2 and comparative example 3 Example sample, be diluted to 30% solid content, afterwards add 0.2%Defom W-0506,0.5%Tego245,1%Acrysol RM-8W and 1%Acrysol RM-12W, are configured to slurry of the viscosity between 400cps-1000cps.
Resulting is shown in Table 1 from the performance indications of antiglossing pigment.
1 performance data table of table
From the results, it was seen that sulfonic acid type water-based polyurethane-acrylate of the present invention from the preparation method of matting resin not Equal goth black dumb light, stabilizing effect can only be obtained, also wipe with preferably resistance to alcohol, resistance to heat-blocking and ABS, Excellent adhesive force is realized on PC, PET base material, with larger actually used value.
The foregoing is only presently preferred embodiments of the present invention, not for limit the present invention practical range；If do not taken off From the spirit and scope of the present invention, the present invention is modified or equivalent, all should be covered in the claims in the present invention In the middle of protection domain.

Claims (10)

1. a kind of sulfonic acid type water-based polyurethane-acrylate is from matting resin, including following component is prepared：
(A) diisocyanate terminated prepolymer, including the preparation of following component：
S1, at least one diisocyanate, its addition account for 18-32.5wt%, preferred 20.5-29wt%；
S2, at least one polyether Glycols and/or polyester diol, with the mean molecule quantity in 500-3000g/mol, preferably The mean molecule quantity of 1500-2000g/mol, its addition account for 48-72wt%, preferred 54-67wt%；The S1 and S2 mole Than for 1.8:1-4.8:1, preferably 2.5:1-4.5:1；
S3, at least one main chain and/or side chain contain the monohydric alcohol and/or dihydroxylic alcohols of polyoxyethylene segments, with 500- The molecular weight of 3000g/mol, its addition account for 0.5-2wt%, preferred 1-2wt%；
S4, at least one dihydroxylic alcohols small molecule chain extender containing active hydrogen, with the molecular weight in 60-400g/mol, which adds Enter amount and account for 0.8-4.5wt%, preferred 1.3-4.3wt%；
S5, it is at least one can be with the active group of isocyanates reaction and unsaturated containing at least one olefinic containing two or more The compound of group, its addition account for 2.9-10wt%, preferred 3-8.6wt%；
(B) component of the diisocyanate terminated prepolymer of dissolved dilution, including following component：
S6, at least one acrylate monomer and a kind of low boiling point organic solvent, acrylate monomer addition account for 0.2-1.2 Times,
Low boiling point organic solvent addition accounts for 1.8-0.8 times；
(C) small molecule amine chain extender, including following component：
S7, at least one sulfonic acid type hydrophilic chain extender containing active hydrogen, addition account for 0.7-2.2wt%, preferred 0.9- 1.6wt%；
S8, at least one diamine small molecule chain extender containing active hydrogen, with the molecular weight in 59-200g/mol, which adds Enter amount and account for 0.6-4.9wt%, preferred 2-4wt%；
(D) radical initiator, including following component：
The radical initiator that S9, at least one oxidant are constituted with least one reducing agent is combined, and its addition accounts for propylene The 0.1-0.6% of acid ester monomer component, preferred 0.15-0.5%；
Wherein, in S1, S2, S3, S4, S5, S6, S7, S8, the addition of each component is based on S1, S2, S3, S4, S5, S7 and S8 Weight and.
2. resin according to claim 1, it is characterised in that the S5 is that molecular weight ranges are 62-400, hydroxyl-functional Spend for 2 while the compound containing an ethylenically unsaturated group；Preferably, the S5 is trimethylolpropane monoallyl Ether, structure is：
Or preferably, the S5 is that epoxy functionalities are 2 or 3, and preferably 2 epoxy resin is anti-with (methyl) acrylate open loop Compound obtained from answering；Preferred S5 components are
3. resin according to claim 1 and 2, it is characterised in that poly- containing polyoxyethylene segments described in component S3 The oxirane containing 90-100wt% in unit is closed, the S3 is preferably Tego Chemie companiesD- 3403rd, the Ymer of Perstrop companiesTMOne or more in the MPEG1200 of N120 and RAKUTEN of Korea, more preferably S3 components include the Ymer of Perstrop companiesTMThe N120 and/or MPEG1200 of RAKUTEN of Korea.
4. the resin according to any one of claim 1-3, it is characterised in that component S7 includes 2- (2- amino-ethyls) ammonia Base ethyl sulfonic acid sodium, 2- (2- amino-ethyls) aminopropanesulfonic acid sodium, 1,4- butanediol -2- sodium sulfonates and 1,2- dihydroxy the third sulphurs of -3- One or more in sour sodium, preferred 2- (2- amino-ethyls) tarine sodium.
5. the resin according to any one of claim 1-4, it is characterised in that the diisocyanate described in component S1 includes Toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, IPDI, hexamethylene diisocyanate and two One or more of diphenylmethane diisocyanate, preferably uses IPDI, two isocyanic acid of hexa-methylene One or more in ester and dicyclohexyl methyl hydride diisocyanate；Component S2 includes polyethylene glycol, polypropylene glycol, poly- second two Alcohol-propane diols, PTMG, polycaprolactone diols, PCDL, polyethylene glycol adipate binary Alcohol, polyadipate 1,4- butanediol ester dihydroxylic alcohols, polyneopentyl glycol adipate dihydroxylic alcohols, polyadipate 1,6-HD ester two First alcohol and polyneopentyl glycol adipate 1, one or more in 6- hexylene glycol ester dihydroxylic alcohols, preferred polyadipate Isosorbide-5-Nitrae-fourth two Alcohol ester dihydroxylic alcohols and/or polyneopentyl glycol adipate 1,6-HD ester dihydroxylic alcohols.
6. the resin according to any one of claim 1-5, it is characterised in that：Acrylate monomer bag described in component S6 Include methyl acrylate, ethyl acrylate, hydroxypropyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, first Base ethyl acrylate, hydroxyethyl methacrylate, butyl methacrylate, styrene, methyl styrene, isobornyl acrylate With one or more in Isooctyl acrylate monomer, preferred methyl methacrylate and/or butyl acrylate；Described low boiling has Machine solvent includes acetone and/or butanone, preferred acetone.
7. the resin according to any one of claim 1-6, it is characterised in that：Component S4 includes 1,3- propane diols, 1,4- One or more in butanediol, diglycol, neopentyl glycol, 1,6- hexylene glycols, 1,4-CHDM, preferably 1, One or more in 4- butanediols, 1,6-HD and neopentyl glycol；Component S8 include ethylenediamine, hexamethylene diamine, five One kind or many in methylene diamine, diethylenetriamines, IPD, 4,4- diphenylmethanediamiands and diethanol amine Kind, one or two in preferred ethylenediamine and IPD；Oxidant in component S9 includes ammonium persulfate, persulfuric acid One or more in sodium, potassium peroxydisulfate and TBHP, reducing agent include sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium hydrogensulfite With one or more in arabo-ascorbic acid, the combination of component S9 preferably TBHP and sodium hydrosulfite.
8. the preparation method of the resin any one of claim 1-7, it is characterised in that comprise the steps of：
(1) S1, S2, S3, S4 and S5 hybrid reaction will be entered, diisocyanate terminated prepolymer will be generated；
(2) in step (1) B component S6 is added to carry out dissolved dilution, the diisocyanate terminated prepolymer after being diluted；
(3) in step (2), the aqueous solution of the S7 and S8 of deionized water dilution is added to carry out chain extending reaction, shearing dispersion is obtained Aqueous polyurethane-acrylate mixed emulsion；
(4) in step (3) add S9 to cause polymerization, obtain the thick emulsion of aqueous polyurethane-acrylate；
(5) sulfonic acid type water-based polyurethane-acrylate product is obtained to the emulsion desolventizing of step (4).
9. method according to claim 8, it is characterised in that：
Reaction condition described in step (1) is reacted for 75-85 DEG C, is reacted to NCO and is reached theoretical value；
Dissolved dilution condition described in step (2) is 50-60 DEG C, reaction time 5-10min；
The aqueous solution of S7 and S8 described in step (3), 3-5 times for S7 and S8 mass sums of its water consumption, reaction temperature is 45-50 DEG C, reaction time 20-30min；
Addition radical initiator initiation temperature described in step (4) is 35-45 DEG C, and polymerization temperature is 45 DEG C, polymerization time 2- 3h；
Desolvation condition described in step (5) is vacuum distillation.
10. resin any one of claim 1-7 or the resin that prepared by claim 8 or 9 methods describeds are used as low The application of gloss paint, is preferably applied to leather finish, woodenware plastics, paper printing, cloth printing ink, printing coating, packaging painting Layer, delustring nail polish field.
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CN110204740A (en) * 2019-05-22 2019-09-06 上海思盛聚合物材料有限公司 From delustring polyurethane aqueous dispersion body
CN111454608A (en) * 2019-08-02 2020-07-28 东莞市浩彩油墨科技有限公司 Water-based ink for ABS and PVC edge banding strips of furniture boards and preparation method thereof
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