CN106519133B - A kind of sulfonic acid type water-based polyurethane-acrylate is from matting resin and its preparation method and application - Google Patents
A kind of sulfonic acid type water-based polyurethane-acrylate is from matting resin and its preparation method and application Download PDFInfo
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- CN106519133B CN106519133B CN201610988120.6A CN201610988120A CN106519133B CN 106519133 B CN106519133 B CN 106519133B CN 201610988120 A CN201610988120 A CN 201610988120A CN 106519133 B CN106519133 B CN 106519133B
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- 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
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- 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
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- 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
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- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
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- 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
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- 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
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- 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
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- C08G18/4833—Polyethers containing oxyethylene units
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- 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
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- 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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- 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
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- 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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Abstract
The invention discloses a kind of sulfonic acid type water-based polyurethane-acrylate from matting resin, it is obtained including following component reaction: (A) diisocyanate terminated prepolymer, (B) component of the diisocyanate terminated prepolymer of dissolved dilution, (C) small molecule amine chain extender, (D) radical initiator.Resin of the present invention combines the excellent performance of polyurethane and acrylic acid, excellent adhesive attraction can be realized on the substrates such as ABS, PC, PVC, PET, and good resistance to hand perspiration performance, pass through rear addition crosslinking agent, the performances such as excellent resistance to alcohol wiping, solvent resistant can be achieved, can be applied to the fields such as leather finish, woodenware plastics, paper printing, cloth printing ink, printing coating, packaging coating, delustring nail polish.
Description
Technical field
The present invention relates to a kind of sulfonic acid type water-based polyurethane-acrylate from matting resin and its preparation method and application,
Belong to acrylic ester modified water-soluble polyurethane resin art.
Background technique
With the development of economy with the raising of people's aesthetic standards, incrustation product, which does not require nothing more than, to be had excellent performance, and is more needed
Have good appearance and sense of touch.Incrustation product is towards two extreme developments at present, first is that the poly- ammonia of the bloom high grade of transparency
Ester resin coating surface decorative product, mainly by most of the reflecting of their light of directive；Second is that with delustring polyurethane resin
The incrustation product of the natural in color of covering with paint, mainly by directive, their light carries out refraction absorption, repellel small part,
It can produce less image deflects in this way, so that this low glass coating usually aesthetically more makes us feeling pleasant.
Traditional delustring water-base polyurethane material is that delustering agent is added in dispersions of polyurethanes, keeps delustering agent dry in film
Film coated surface is floated in dry process and generates the microcosmic out-of-flatness of film coated surface, thus achieve the effect that delustring, it is this with object
The delustering agent that reason mode is added mainly includes high filler material, micro- wax powder, inorganic silicon dioxide etc. in nature, although by outer
The mode of addition delustering agent can achieve the purpose that delustring, but its disadvantage is also apparent: delustering agent 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 phenomena such as frost, seriously affect incrustation product
Presentation quality；Delustering agent higher cost is largely used simultaneously；Coating brittleness increases, easily broken to fall off；The precipitating of delustering agent is led
The inhomogenous mixing before spreading is caused, to keep the gloss of entire coating variant；Under resistance to rubbing, bending and rub resistance
Drop.
In order to avoid some defects brought by outer addition delustering agent, provided in Chinese publication CN104974324A
It is a kind of to react from extinction type waterborne polyurethane resin and preparation method thereof, belong to sulfonic acid type-carboxylic acid type aqueous polyurethane, prepared
Without introducing acrylic ester monomer in journey, structure is single, and the performances such as alkaline-resisting, solvent resistant, wear-resisting cannot be met the requirements.
CN103626930A describes a kind of preparation of Aqueous acrylic urethane's matting resin with phase separation structure
Method, it is necessary first to prepare anionic and non-ionic two kinds of polyurethane, then by acrylate mixture in two kinds of polyurethane
Middle progress seeded emulsion polymerization obtains, when preparing anion-type water-thinned polyurethane using triethylamine carry out in and, using
Cheng Zhonghui brings the hydrolysis of the presence of biggish smell and higher VOC and this weak acid meeting acceleration molecular chain, while the cream
Liquid polymerization procedure is cumbersome, it is difficult to industrialization flow line production be its shortcoming.
CN104193946A discloses a kind of preparation method from delustring polyurethane resin, including using absorbable light
Acrylic acid-grafted substance sealing end, since molecule chain end is double bond sealing end, be not it is isocyanate-terminated, cannot be further with water
Chain extension-crosslinking, molecular weight is smaller, and patience is poor.
Therefore, it is necessary to develop a kind of new formula, to solve existing to exist in use from delustring polyurethane resin
The various drawbacks such as patience difference.
Summary of the invention
The primary purpose of the present invention is that providing 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 dry
Value is less than 1 degree.
Another object of the present invention is to provide the sulfonic acid type water-based polyurethane-acrylate from the preparation of matting resin
Method.
A further object of the present invention is to provide sulfonic acid type water-based polyurethane-acrylate answering from matting resin
With.
In order to realize that the above goal of the invention, the present invention are achieved through the following technical solutions:
A kind of sulfonic acid type water-based polyurethane-acrylate is prepared from matting resin, including following component:
(A) diisocyanate terminated prepolymer, including the preparation of following component:
S1, at least one diisocyanate, additional amount account for 18-32.5wt%, preferably 20.5-29wt%；
S2, at least one polyether Glycols and/or polyester diol, have the average molecular weight in 500-3000g/mol,
It is preferred that 1500-2000g/mol, additional amount accounts for 48-72wt%, preferably 54-67wt%；The molar 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 dihydric alcohol of polyoxyethylene segments, have
The molecular weight of 500-3000g/mol, additional amount account for 0.5-2wt%, preferably 1-2wt%；
S4, at least one dihydric alcohol small molecule chain extender containing active hydrogen have the molecular weight in 60-400g/mol,
Its additional amount accounts for 0.8-4.5wt%, preferably 1.3-4.3wt%；
S5, at least one containing the active groups that can react with isocyanates of two or more and contain at least one olefinic not
The compound of saturated group, additional amount account for 2.9-10wt%, preferably 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 additional amount account for 0.2-
1.2 times, low boiling point organic solvent additional amount 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, additional amount account for 0.7-2.2wt%, preferably 0.9-
1.6wt%；
S8, at least one diamine small molecule chain extender containing active hydrogen have the molecular weight in 59-200g/mol,
Its additional amount accounts for 0.6-4.9wt%, preferably 2-4wt%；
(D) radical initiator, including following component:
S9, at least one oxidant are combined with the radical initiator that at least one reducing agent forms, and additional amount accounts for
(B) 0.1-0.6% of acrylate monomer component described in, preferably 0.15-0.5%；
Wherein, in S1, S2, S3, S4, S5, S6, S7, S8 the additional amount of each component be based on S1, S2, S3, S4, S5, S7 and
The weight and calculating of S8.
Diisocyanate described in component S1, including but not limited to toluene di-isocyanate(TDI), two isocyanide of diphenyl methane
Acid esters, isophorone diisocyanate, one kind or more of hexamethylene diisocyanate and dicyclohexyl methyl hydride diisocyanate
Kind is, it is preferable to use in isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl methyl hydride diisocyanate
It is one or more.
Polyether Glycols described in component S2 or polyester diol, including but not limited to polyethylene glycol, are gathered polypropylene glycol
Ethylene glycol and 1,2-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diols, polycarbonate glycol, polyethylene glycol adipate
Dihydric alcohol, polyadipate 1,4- butanediol ester dihydric alcohol, polyneopentyl glycol adipate dihydric alcohol, polyadipate 1,6-HD
Ester dihydric alcohol and polyneopentyl glycol adipate 1, one of 6- hexylene glycol ester dihydric alcohol or a variety of, it is preferable to use polyadipate
1,4- butanediol ester dihydric alcohol and/or polyneopentyl glycol adipate 1,6-HD ester dihydric alcohol.
Main chain described in component S3 and/or side chain contain the monohydric alcohol and/or dihydric alcohol of polyoxyethylene segments, described to contain
There is the ethylene oxide in the polymerized unit of polyoxyethylene segments containing 90-100wt%, the S3 is preferably Tego Chemie
CompanyThe Ymer of D-3403, Perstrop companyTMOne in N120 and the MPEG1200 of South Korea's Lotte Company
Kind or a variety of, the more preferably YmerTM N120 of Perstrop company and/or the MPEG1200 of South Korea's Lotte Company.
Dihydric alcohol small molecule chain extender described in component S4 containing active hydrogen, including but not limited to 1,3-PD, 1,
One of 4- butanediol, diglycol, neopentyl glycol, 1,6- hexylene glycol and 1,4-CHDM are a variety of, excellent
Choosing uses one of 1,4- butanediol, 1,6-HD and neopentyl glycol or a variety of.
The active group that can react with isocyanates described in component S5 containing two or more and contain at least one
The compound of a ethylenically unsaturated group, can be molecular weight ranges is 62-400, and hydroxy functionality contains an alkene for 2 simultaneously
Belong to the compound of unsaturated group, preferably trimethyolol propane monoallyl ether (TMPME)；Structure are as follows:
More preferably use the trimethylolpropane monoallyl of Sweden Perstorp company
Ether (TMPME)；
Or also may be preferred that epoxy functionalities are 2 or 3, preferably 2 epoxy resin and (methyl) acrylate open loop
Compound obtained from reaction；The compound more preferably obtained using epoxy resin E51 and acrylic acid (molar ratio 1:2) open loop
Epoxy acrylateSpecific 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, ethyl methacrylate, hydroxyethyl methacrylate, methacrylic acid fourth
One of ester, styrene, methyl styrene, isobornyl acrylate and Isooctyl acrylate monomer are a variety of, the acrylate
It is preferable to use methyl methacrylate and/or butyl acrylates for monomer；The low boiling point organic solvent, including but not limited to third
Ketone and/or butanone are, it is preferable to use acetone.
Contain the sulfonic acid type hydrophilic chain extender of active hydrogen, including 2- (2- amino-ethyl) tarine described in component S7
In sodium, 2- (2- amino-ethyl) aminopropanesulfonic acid sodium, 1,4- butanediol -2- sodium sulfonate and 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium
It is one or more, it is preferable to use 2- (2- amino-ethyl) tarine sodium.
Diamine small molecule chain extender described in component S8 containing active hydrogen, including but not limited to ethylenediamine, six methylenes
In base diamines, five methylene diamine, diethylenetriamines, isophorone diamine, 4,4- diphenylmethanediamiand and diethanol amine
It is one or more, it is preferable to use ethylenediamine and/or isophorone diamine.
Oxidant described in component S9 includes in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate and tert-butyl hydroperoxide
One or more, reducing agent includes sodium hydrosulfite (sodium dithionite), sodium formaldehyde sulfoxylate, sodium hydrogensulfite and arabo-ascorbic acid (IAA)
One of or it is a variety of, it is preferable to use mass ratio be 1:1 tert-butyl hydroperoxide/sodium hydrosulfite.
The preparation method of sulfonic acid type water-based polyurethane-acrylate of the present invention, comprising 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) dissolved dilution is carried out to B component S6 is added in step (1), it is diisocyanate terminated pre- after being diluted
Polymers；
(3) it is added into step (2) and carries out chain extending reaction, shearing dispersion with the aqueous solution of deionized water diluted S7 and S8
Obtain aqueous polyurethane-acrylate mixed emulsion；
(4) S9 is added into step (3) and causes polymerization, obtain the thick lotion of aqueous polyurethane-acrylate；
(5) sulfonic acid type water-based polyurethane-acrylate product is obtained to the lotion 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 75-85 DEG C of reaction, and reaction to NCO reaches 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), water consumption are 3-5 times of S7 and S8 mass sum, 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, when polymerization
Between 2-3h；
Removing solvent (acetone) condition described in step (5) is vacuum distillation.
Sulfonic acid type water-based polyurethane-acrylate the solid content is obtained by above-mentioned preparation method preferably to exist
35-55%, more preferably in 40-50%.
Sulfonic acid type water-based polyurethane-acrylate average particle size is preferably in 500-4000nm range
It is interior, more preferably within the scope of 800-2500nm.
Sulfonic acid type water-based polyurethane-acrylate of the present invention can be used as coatings with low gloss finish and be applied, can
Applied to fields such as leather finish, woodenware plastics, paper printing, cloth printing ink, printing coating, packaging coating, delustring nail polish.
The beneficial effects are mainly reflected as follows the following aspects:
(1) extinction effect of the present invention is generated by resin itself, does not need to add any delustering agent, in the synthesis process controllably
The particle of certain grain size distribution processed causes surface microroughness to increase in dried coating film dehydration after-contraction, and glossiness reduces；
(2) aqueous polyurethane-acrylate resin provided by the invention, hydrophily is realized by sulfamic acid sodium salt, is not necessarily to
It neutralizes, avoids the low boiling points such as triethylamine neutralizer bring smell and VOC, while sulfamic acid sodium salt belongs to strong acid and strong base
Salt, not facile hydrolysis, so that product has better water resistance；
(3) aqueous polyurethane-acrylate resin provided by the invention is from matting resin, in polyurethane, that is, diisocyanate
The prepolymer composite part of sealing end introduces double bond, while introducing propylene diluting diisocyanate terminated pre-polymer fraction
Acid ester monomer carries out free radical polymerization between monomer and monomer and monomer and double bond, so just with polyurethane molecular interchain shape
At the mutual biography network structure of chemical crosslinking, the performances such as alkaline-resisting, solvent resistant, wear-resisting are greatly improved.
(4) simple production process of the present invention, it is safe and non-toxic convenient for operation.
Specific embodiment
Admittedly containing test method: taking appropriate lotion in container made of masking foil, weigh the weight before and after 150 degree of 20min
Variation, calculates its solid content.
Partial size test method: Malvern particle instrument is used.
PH test method: pH meter is used.
Viscosity determining procedure: using BROOKFIELD viscosity apparatus, and No. 3 rotor/30rpm are tested.
Appearance test method: eye sight is judged.
Feel test method: PVC leather at 20um bar table, 100 degree of drying about 1min grab by hand and touch progress feel
Judgement.
Blackness test method: black PVC is removed from office at 20um bar table, 100 degree of drying about 1min, observes blackness and thoroughly degree effect
Fruit.
Resistance to room temperature complications test method: black PVC is removed from office at 20um bar table, and 100 degree of drying about 1min are cut into 4*7cm sample
Item, each 3 through broadwise, room temperature complications instrument is tested.
Resistance to alcohol test method: taking slurry, add 2% isocyanate crosslinking (268), at 20um bar table
Black matrixes PVC leather, 100 degree of drying about 1min are placed 1 day, take 95% industrial alcohol, and dry and wet is wiped color fastness instrument and tested 20 times,
Whether observation coating surface has the bad phenomenons such as fall off or brighten, (1-5 grades, 5 grades best).
Perspiration resistance test method: taking slurry, add 2% isocyanate crosslinking (268), 20um bar table
Locate black matrixes PVC leather, 100 degree of drying about 1min are placed 1 day, take synthetic perspiration, and dry and wet is wiped color fastness instrument and tested 20 times, are seen
Examine whether coating surface there are the bad phenomenons such as fall off or brighten, (1-5 grades, 5 grades best).
Adhesion test method: 100um bar blade coating PET base material, ABS substrate and PC substrate, 60 degree of drying about 30min,
Using GB/T9286-1998 national standard: (PET base material, 0-5 grades, 0 grade best)；(ABS substrate, 0-5 grades, 0 grade best)；(PC base
Material, 0-5,0 grade of grade best)
Resistance to heat-blocking: PVC leather at 20um bar table, 100 degree of drying about 1min are cut into 5*5cm, to patch, 80 DEG C/3kg/
For 24 hours, opening adhesion is resistance to heat-blocking.
Black and white plate glossiness test method: take slurry on black and white paper jam, 150um applicator carries out extension painting, 100 degree of drying
About 3min records the gloss value of 60 degree of incidence angles with vancometer.
Stability test method: taking at 1 kilogram of table agent slurry in 1 kilogram of plastic bottle, sealing, room 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
Limited liability company)；
(isophorone diisocyanate, NCO content are about 37.8% to IPDI, ten thousand magnificent chemical groups shares
Co., Ltd)；
(1, hexamethylene-diisocyanate, NCO content is about 50% to HDI, the ten thousand limited public affairs of magnificent chemical groups share
Department)；
CMA-654 (polyadipate neopentyl glycol hexylene glycol esterdiol, hydroxyl value 74.8mgKOH/g, number-average molecular weight ≈
1500, degree of functionality 2, Yantai Hua Da chemistry)；
PBA-2000 (polyadipate 1,4-butanediol esterdiol, 56 mgKOH/g of hydroxyl value, number-average molecular weight=2000, official
Energy degree is 2, Yantai Hua Da chemistry)；
MPEG1200 (poly glycol monomethyl ether, 46.75 mgKOH/g of hydroxyl value, number-average molecular weight=1200, degree of functionality 1,
South Korea is carefree)；
YmerTMN120 (polyethylene oxide ether glycol, hydroxyl value 110mgKOH/g, number-average molecular weight ≈ 1000, Sweden
Perstorp company)；
NPG (neopentyl glycol, Wanhua Chemical Group Co., Ltd.)；
HDO (1,6- hexylene glycol, BASF Corp. of Germany)；
BDO (1,4-butanediol, BASF Corp. of Germany)；
A95 (N- (2- amino-ethyl) -2-aminoethanesulfonic acid sodium salt, 51 ± 2% aqueous solution of solid content, amine
260 ± 20mgKOH/g of value, German EVONIK company)；
EDA (ethylenediamine, BASF Corp. of Germany)；
IPDA (isophorone diamine, Wanhua Chemical Group Co., Ltd.)；
E51 (epoxy resin, epoxide number 0.48-0.54eq/100g, Guangzhou Li Hou trade Co., Ltd)；
TMPME (trimethyolol propane monoallyl ether, Perstorp company of Sweden)；
Acrylic acid (Wan Hua chemical group limited liability company) MMA (methyl methacrylate, Qilu Petrochemical)；
BA (butyl acrylate, Wan Hua chemical group limited liability company)；
268 (isocyanate curing agent, Wanhua Chemical Group Co., Ltd.)；
Tego245 (substrate wetting agents, Bick)；
Defom W-0506 (defoaming agent, 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
300g epoxy resin E51,1.65g catalyst triphenyl phosphorus are added in three-necked flask, 0.205g polymerization inhibitor is to first
Oxygroup phenol MEHQ, 2.47g yellowing additive triphenyl phosphite TPP, temperature are increased to 90-95 degree, then add dropwise in 1 hour
Enter acrylic acid 110.2g, until acid value is reduced to 0.5mgKOH/g hereinafter, compound epoxy acrylate required for obtaining.
Embodiment 2
40g is added to being equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI、
26gHDI, 240gCMA-654,23.8g according to epoxy acrylate obtained in embodiment 1,4gMPEG1200,
3g neopentyl glycol, 80 degree are reacted, and sampling monitoring NCO in experimentation is cooled to 60 degree until NCO reaches theoretical value 1.81%
445g acetone is added in left and right and 171g methyl methacrylate stirs 5min, by 2.2g ethylenediamine and 3.5gA95
It is diluted with 23g deionized water, stirring 25min is added under the conditions of 45 degree, 487g water is added in the case where shearing dispersion condition, obtains aqueous
Polyurethane-acrylate mixed emulsion.System is warming up to 45 degree, 0.26g tert-butyl hydroperoxide and 0.26g sodium hydrosulfite is added
(sodium dithionite) causes polymerization, stirs polyase 13 h at this temperature, which is evaporated under reduced pressure and removes acetone, obtains solid content
White sulfonic acid type water-based polyurethane-acrylic acid ester emulsion of 50wt%, partial size 1730nm.
Embodiment 3
74g is added to being equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI、
47.5gHDI, 190gCMA-654,37g according to epoxy acrylate obtained in embodiment 1,
5.2gMPEG1200,16.5g neopentyl glycol, 80 degree are reacted, sampling monitoring NCO in experimentation, until NCO reaches theoretical value
4.73%, 60 degree or so addition 306g acetone and 382g methyl methacrylate stirring 5min are cooled to, by 8g ethylenediamine and 4gA95 is diluted with 48g deionized water, and stirring 25min is added under the conditions of 45 degree, adds in the case where shearing dispersion condition
Enter 712g water, obtains aqueous polyurethane-acrylate mixed emulsion.System is warming up to 45 degree, 0.76g tert-butyl hydroperoxide is added
Hydrogen and 0.76g sodium hydrosulfite (sodium dithionite) cause polymerization, stir polyase 13 h at this temperature, and lotion vacuum distillation is removed
Acetone is removed, solid content 50wt%, white sulfonic acid type water-based polyurethane-acrylic acid ester emulsion of partial size 1350nm are obtained.
Embodiment 4
74g is added to being equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI、
47.5gHDI, 240gPBA-2000,37g according to epoxy acrylate obtained in embodiment 1,
5.2gMPEG1200,16.5g neopentyl glycol, 80 degree are reacted, sampling monitoring NCO in experimentation, until NCO reaches theoretical value
4.30%, 60 degree or so addition 347g acetone and 433g methyl methacrylate stirring 5min are cooled to, by 9g ethylenediamine and 4gA95 is diluted with 52g deionized water, and stirring 25min is added under the conditions of 45 degree, adds in the case where shearing dispersion condition
Enter 810g water, obtains aqueous polyurethane-acrylate mixed emulsion.System is warming up to 45 degree, 0.87g tert-butyl hydroperoxide is added
Hydrogen and 0.87g sodium hydrosulfite (sodium dithionite) cause polymerization, stir polyase 13 h at this temperature, and lotion vacuum distillation is removed
Acetone is removed, solid content 50wt%, white sulfonic acid type water-based polyurethane-acrylic acid ester emulsion of partial size 2430nm are obtained.
Embodiment 5
47g is added to being equipped in 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 are reacted, sampling monitoring NCO in experimentation, until NCO reaches theoretical value 3.66%, are cooled to 60 degree of left sides
Right addition 485g acetone, 112g methyl methacrylate stir 5min, by 18g isophorone diamine and 3gA95
It is diluted with 84g deionized water, stirring 25min is added under the conditions of 45 degree, 398g water is added in the case where shearing dispersion condition, obtains aqueous
Polyurethane-acrylate mixed emulsion.System is warming up to 45 degree, 0.34g tert-butyl hydroperoxide and 0.34g sodium hydrosulfite is added
(sodium dithionite) causes polymerization, stirs polyase 13 h at this temperature, which is evaporated under reduced pressure and removes acetone, obtains solid content
White sulfonic acid type water-based polyurethane-acrylic acid ester emulsion of 50wt%, partial size 2030nm.
Embodiment 6
48g is added to being equipped in 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 glycol, 80 degree are reacted, and sampling monitoring NCO in experimentation is cooled to 60 degree or so until NCO reaches theoretical value 3.47%
284g acetone, 284g methyl methacrylate, 71g butyl acrylate is added and stirs 5min, by the different Buddhist diketone diamines of 14g and 7.2gA95 is diluted with 85g deionized water, and stirring 25min is added under the conditions of 45 degree, adds in the case where shearing dispersion condition
Enter 774g water, obtains aqueous polyurethane-acrylate mixed emulsion.System is warming up to 45 degree, 1.77g tert-butyl hydroperoxide is added
Hydrogen and 1.77g sodium hydrosulfite (sodium dithionite) cause polymerization, stir polyase 13 h at this temperature, and lotion vacuum distillation is removed
Acetone is removed, solid content 45wt%, white sulfonic acid type water-based polyurethane-acrylic acid ester emulsion of partial size 1680nm are obtained.
Embodiment 7
45g is added to being equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskIPDI、
34gHDI、245gPBA-2000、7gYmerTMN120,19g trimethyolol propane monoallyl ether, 7g 1,4-
Butanediol, 80 degree are reacted, and sampling monitoring NCO in experimentation is cooled to 60 degree or so until NCO reaches theoretical value 2.28%
296g acetone, 296g methyl methacrylate, 74g butyl acrylate is added and stirs 5min, by the different Buddhist diketone diamines of 8g and 5.6gA95 is diluted with 54g deionized water, and stirring 25min is added under the conditions of 45 degree, adds in the case where shearing dispersion condition
Enter 681g water, obtains aqueous polyurethane-acrylate mixed emulsion.System is warming up to 45 degree, 1.85g tert-butyl hydroperoxide is added
Hydrogen and 1.85g sodium hydrosulfite (sodium dithionite) cause polymerization, stir polyase 13 h at this temperature, and lotion vacuum distillation is removed
Acetone is removed, solid content 45wt%, white sulfonic acid type water-based polyurethane-acrylic acid ester emulsion of partial size 2270nm are obtained.
Comparative example 1
47g is added to being equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskIPDI、
36gHDI、245gCMA-654、4g YmerTMN120,12.5g1,6 hexylene glycols, 80 degree are reacted, in experimentation
Sampling monitoring NCO is cooled to 60 degree or so addition 476g acetone and 110g metering system until NCO reaches theoretical value 3.72%
Sour methyl esters stirs 5min, by 17g isophorone diamine and 5gA95 is diluted with 88g deionized water, and flask is added,
45 degree of reaction 25min are added the shearing dispersion of 383g water, obtain aqueous polyurethane-acrylate mixed emulsion.System is warming up to 45
Degree, is added 0.22g tert-butyl hydroperoxide and 0.22g sodium hydrosulfite (sodium dithionite) causes polymerization, stirs at this temperature
The lotion is evaporated under reduced pressure and removes acetone, obtains solid content 50wt%, the aqueous poly- ammonia of the white sulfonic acid type of partial size 1930nm by polyase 13 h
Ester-acrylic acid ester emulsion.
Comparative example 2
47g is added to being equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskIPDI、36gHDI、245gCMA-654、4gYmerTMN120,12.5g 1,6- hexylene glycol, 80 degree are reacted, and are taken in experimentation
Sample monitors NCO, until NCO reaches theoretical value 3.72%, 60 degree or so 586 acetone of addition stirring 5min is cooled to, by the different Buddhist of 17g
That ketone diamines and 5gA95 is diluted with 88g deionized water, and flask is added, and 274g water is added in 45 degree of reaction 25min
Shearing dispersion, obtains aqueous polyurethane dispersion lotion.The lotion is evaporated under reduced pressure and removes acetone, obtains solid content 50wt%, partial size
The white sulfonic acid type water-based emulsion of 1030nm.
Comparative example 3
47g is added to being equipped in reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskIPDI、
36gHDI, 245gCMA-654,11.2g trimethyolol propane monoallyl ether, 4g YmerTM N120、6g1,6
Hexylene glycol, 80 degree are reacted, and sampling monitoring NCO in experimentation is cooled to 60 degree or so until NCO reaches theoretical value 3.57%
485g acetone is added and 112g methyl methacrylate stirs 5min, by 14g isophorone diamine and 9.5g
A95 is diluted with 94g deionized water, and flask is added, and 45 degree of reaction 25min are added the shearing dispersion of 488g water, obtain aqueous polyurethane-
Crylic acid ester mixture lotion.System is warming up to 45 degree, 0.22g tert-butyl hydroperoxide and 0.22g sodium hydrosulfite (Lian Erya is added
Sodium sulphate) cause polymerization, polyase 13 h is stirred at this temperature, which is evaporated under reduced pressure and removes acetone, obtains solid content 45wt%,
White sulfonic acid type water-based polyurethane-acrylic acid ester emulsion of partial size 380nm.
Take 9 groups of implementations 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, is diluted to 30% solid content, rear to add 0.2%Defom W-0506,0.5%Tego245,1%Acrysol RM-8W and
1%Acrysol RM-12W is configured to slurry of the viscosity between 400cps-1000cps.
It is obtained to be shown in Table 1 from the performance indicator 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
Same goth black dumb light, stabilizing effect can only be obtained, also there is preferable resistance to alcohol to wipe, resistance to heat-blocking and ABS,
Excellent adhesive force is realized on PC, PET plastic substrate, and there is biggish actual use value.
The foregoing is merely presently preferred embodiments of the present invention, practical range not for the purpose of limiting the invention；If do not taken off
It from the spirit and scope of the present invention, modifies or equivalently replaces the present invention, should all cover in the claims in the present invention
In protection scope.
Claims (34)
1. a kind of sulfonic acid type water-based polyurethane-acrylate is prepared from matting resin, including following component:
(A) diisocyanate terminated prepolymer, including the preparation of following component:
S1, at least one diisocyanate, additional amount account for 18-32.5wt%；
S2, at least one polyether Glycols and/or at least one polyester diol, have the average mark in 500-3000g/mol
Son amount, additional amount account for 48-72wt%；The molar ratio of the S1 and S2 is 1.8:1-4.8:1；
S3, main chain and/or side chain contain at least one of monohydric alcohol of polyoxyethylene segments, have in 500-3000g/
The molecular weight of mol, additional amount account for 0.5-2wt%；
S4, at least one dihydric alcohol small molecule chain extender containing active hydrogen have the molecular weight in 60-400g/mol, add
Enter amount and accounts for 0.8-4.5wt%；
S5, at least one containing the active groups that can react with isocyanates of two or more and contain at least one olefinic unsaturation
The compound of group, additional amount account for 2.9-10wt%；
(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, the acrylate monomer include acrylic acid first
Ester, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid
One of butyl ester, styrene, methyl styrene, isobornyl acrylate and Isooctyl acrylate monomer are a variety of；Acrylate list
Body additional amount accounts for 0.2-1.2 times,
Low boiling point organic solvent additional amount 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, additional amount account for 0.7-2.2wt%；
S8, at least one diamine small molecule chain extender containing active hydrogen have the molecular weight in 59-200g/mol, add
Enter amount and accounts for 0.6-4.9wt%；
(D) radical initiator, including following component:
S9, at least one oxidant are combined with the radical initiator that at least one reducing agent forms, and additional amount accounts for propylene
The 0.1-0.6% of acid ester monomer component；
Wherein, the additional amount of each component is based on S1, S2, S3, S4, S5, S7 and S8 in S1, S2, S3, S4, S5, S6, S7, S8
Weight and.
2. resin according to claim 1, which is characterized in that the S1 additional amount accounts for 20.5-29wt%.
3. resin according to claim 1, which is characterized in that the S2 has the mean molecule in 1500-2000g/mol
Amount.
4. resin according to claim 1, which is characterized in that the S2 additional amount accounts for 54-67wt%.
5. resin according to claim 1, which is characterized in that the molar ratio of the S1 and S2 is 2.5:1-4.5:1.
6. resin according to claim 1, which is characterized in that the S3 additional amount accounts for 1-2wt%.
7. resin according to claim 1, which is characterized in that the S4 additional amount accounts for 1.3-4.3wt%.
8. resin according to claim 1, which is characterized in that the S5 additional amount accounts for 3-8.6wt%.
9. resin according to claim 1, which is characterized in that the S7 additional amount accounts for 0.9-1.6wt%.
10. resin according to claim 1, which is characterized in that the S8 additional amount accounts for 2-4wt%.
11. resin according to claim 1, which is characterized in that the S9 additional amount accounts for acrylate monomer component
0.15-0.5%.
12. resin according to claim 1, which is characterized in that the S5 is that molecular weight ranges are 62-400, hydroxyl-functional
Degree is 2 compound simultaneously containing an ethylenically unsaturated group.
13. resin according to claim 12, which is characterized in that the S5 is trimethyolol propane monoallyl ether, knot
Structure are as follows:
14. resin according to claim 12, which is characterized in that the S5 is the epoxy resin that epoxy functionalities are 2 or 3
With compound obtained from (methyl) acrylic acid ring-opening reaction.
15. resin according to claim 14, which is characterized in that the S5 be epoxy functionalities be 2 epoxy resin with
Compound obtained from (methyl) acrylic acid ring-opening reaction.
16. resin according to claim 12, which is characterized in that the S5 is
17. resin according to claim 1, which is characterized in that contain the polymerization of polyoxyethylene segments described in component S3
Contain the ethylene oxide of 90-100wt% in unit.
18. resin according to claim 17, which is characterized in that the S3 is Tego Chemie company
The Ymer of D-3403, Perstrop companyTMOne of N120 and the MPEG1200 of South Korea's Lotte Company or a variety of.
19. resin according to claim 18, which is characterized in that the S3 is the Ymer of Perstrop companyTM N120
And/or the MPEG1200 of South Korea's Lotte Company.
20. resin according to claim 1, which is characterized in that component S7 includes 2- (2- amino-ethyl) tarine
In sodium, 2- (2- amino-ethyl) aminopropanesulfonic acid sodium, 1,4- butanediol -2- sodium sulfonate and 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium
It is one or more.
21. resin according to claim 20, which is characterized in that component S7 is 2- (2- amino-ethyl) tarine
Sodium.
22. resin according to claim 1, which is characterized in that diisocyanate described in component S1 includes that toluene two is different
Cyanate, methyl diphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl first
Alkane diisocyanate it is one or more；Component S2 includes polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, poly- tetrahydro furan
It mutters ether glycol, polycaprolactone diols, polycarbonate glycol, polyethylene glycol adipate dihydric alcohol, polyadipate 1,4- fourth
Diol ester dihydric alcohol, polyneopentyl glycol adipate dihydric alcohol, polyadipate 1,6-HD ester dihydric alcohol and polyadipate are new
One of pentadiol ester 1,6-HD ester dihydric alcohol is a variety of.
23. resin according to claim 22, which is characterized in that diisocyanate described in component S1 is isophorone two
One of isocyanates, hexamethylene diisocyanate and dicyclohexyl methyl hydride diisocyanate are a variety of.
24. resin according to claim 22, which is characterized in that component S2 is polyadipate 1,4-butanediol ester dihydric alcohol
And/or polyneopentyl glycol adipate 1,6-HD ester dihydric alcohol.
25. resin according to claim 1, it is characterised in that: low boiling point organic solvent described in component S6 includes acetone
And/or butanone.
26. resin according to claim 1, it is characterised in that: acrylate monomer described in component S6 is metering system
Sour methyl esters and/or butyl acrylate.
27. resin according to claim 25, it is characterised in that: the low boiling point organic solvent is acetone.
28. resin according to claim 1, it is characterised in that: component S4 includes 1,3-PD, 1,4-butanediol, one
One of diglycol ethylene, neopentyl glycol, 1,6-HD, 1,4 cyclohexane dimethanol are a variety of；Component S8 includes second two
In amine, hexamethylene diamine, five methylene diamine, diethylenetriamines, isophorone diamine and 4,4- diphenylmethanediamiand
It is one or more；Oxidant in component S9 includes in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate and tert-butyl hydroperoxide
It is one or more, reducing agent includes one of sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium hydrogensulfite and arabo-ascorbic acid or a variety of.
29. resin according to claim 28, it is characterised in that: component S4 is 1,4-butanediol, 1,6- hexylene glycol and new
One of pentanediol is a variety of.
30. resin according to claim 28, it is characterised in that: component S8 is one in ethylenediamine and isophorone diamine
Kind or two kinds.
31. resin according to claim 28, it is characterised in that: component S9 is the group of tert-butyl hydroperoxide and sodium hydrosulfite
It closes.
32. the preparation method of resin described in any one of claim 1-31, which is characterized in that comprise the steps of:
(1) S1, S2, S3, S4 and S5 hybrid reaction will be entered, generate diisocyanate terminated prepolymer；
(2) B component S6 is added into step (1) and carries out dissolved dilution, the diisocyanate terminated prepolymer after being diluted；
(3) it is added into step (2) and carries out chain extending reaction with the aqueous solution of deionized water diluted S7 and S8, shearing dispersion obtains
Aqueous polyurethane-acrylate mixed emulsion；
(4) S9 is added into step (3) and causes polymerization, obtain the thick lotion of aqueous polyurethane-acrylate；
(5) sulfonic acid type water-based polyurethane-acrylate product is obtained to the lotion desolventizing of step (4).
33. according to the method for claim 32, it is characterised in that:
Reaction condition described in step (1) is 75-85 DEG C of reaction, and reaction to NCO reaches 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), water consumption are 3-5 times of S7 and S8 mass sum, reaction temperature 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；
Removing solvent condition described in step (5) is vacuum distillation.
34. application of the resin as coatings with low gloss finish described in any one of claim 1-31 is applied to leather finish, woodenware
Plastics, paper printing, cloth printing ink, printing coating, packaging coating, delustring nail polish field.
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| CN106883370B (en) * | 2017-04-20 | 2020-02-28 | 广州百思创科技有限公司 | Self-extinction waterborne polyurethane resin with ultralow glossiness and preparation method and application thereof |
| CN107446108A (en) * | 2017-07-27 | 2017-12-08 | 滁州金桥德克新材料有限公司 | A kind of aqueous polyurethane acrylate emulsion and preparation method thereof |
| CN111406081A (en) * | 2017-12-01 | 2020-07-10 | 爱克发有限公司 | Radiation curable polyurethane resins for inkjet inks |
| CN108546323B (en) * | 2018-04-18 | 2020-08-28 | 万华化学集团股份有限公司 | Cation self-extinction resin and preparation method and application thereof |
| CN109160980B (en) * | 2018-06-01 | 2020-09-08 | 万华化学集团股份有限公司 | Preparation method of waterborne polyurethane-acrylate resin and application of waterborne polyurethane-acrylate resin in printing adhesive |
| CN109679543B (en) * | 2018-09-03 | 2021-01-29 | 万华化学集团股份有限公司 | Quick-drying water-based adhesive and preparation method and application thereof |
| 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 |
| CN111253577A (en) * | 2020-01-22 | 2020-06-09 | 黎明化工研究设计院有限责任公司 | Method for preparing modified epoxy acrylate |
| CN111793188B (en) * | 2020-08-10 | 2021-03-12 | 上海思盛聚合物材料有限公司 | Hydroxyl-containing self-extinction waterborne polyurethane and self-extinction coating composed of same |
| CN113549392B (en) * | 2021-07-23 | 2022-09-23 | 江门市制漆厂有限公司 | Polyurethane dispersion, method for the production thereof and use thereof |
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