CN106318099A - Modified epoxy-grafted acrylic resin coating - Google Patents

Modified epoxy-grafted acrylic resin coating Download PDF

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Publication number
CN106318099A
CN106318099A CN201610693474.8A CN201610693474A CN106318099A CN 106318099 A CN106318099 A CN 106318099A CN 201610693474 A CN201610693474 A CN 201610693474A CN 106318099 A CN106318099 A CN 106318099A
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China
Prior art keywords
epoxy
modified
acrylic acid
resin
coating
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Pending
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CN201610693474.8A
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Chinese (zh)
Inventor
胡浩东
刘薇薇
苏献兰
柳昀
徐庆
李金伟
贾飞虎
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HAOLISEN COATING (SHANGHAI) Co Ltd
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HAOLISEN COATING (SHANGHAI) Co Ltd
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Priority to CN201610693474.8A priority Critical patent/CN106318099A/en
Publication of CN106318099A publication Critical patent/CN106318099A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • 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
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4028—Isocyanates; Thioisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Abstract

The invention relates to a modified epoxy-grafted acrylic resin coating that is a bicomponent coating prepared from: a, high-weatherable acrylic modified emulsion made by mixing well epoxy-modified acrylic resin and a closed aliphatic isocyanate curing agent, neutralizing with an added neutralizer and adding deionized water; b, high-salt fog weatherable color paste made by mixing epoxy-modified acrylic resin, a functional aid, a pigment, a functional filler and deionized water and grinding a mixture to a fineness of </= 15 Mum at a ratio of 6:1. The epoxy-modified acrylic resin is made by grafting epoxy resin with toughening modifying structure to semi-terminated polyisocyanate curing agent, grafting acrylic acid to obtain epoxy-modified resin, and subjecting the resin to quaternization. The modified epoxy-grafted acrylic resin coating is convenient to apply and is environment-friendly and safe to use; a planar surface is flat and glossy, good decoration effect is provided, bath solution stability is good, a coating layer has excellent mechanical properties, acid resistance and alkali resistance, and the coating layer also has excellent weatherability.

Description

Modified epoxy graft acrylic acid cold coating
[technical field]
The present invention relates to acrylic resin paint, particularly relate to a kind of modified epoxy graft acrylic acid cold coating.
[background technology]
Cathode electrophoresis dope through decades development auto industry and building materials, five metals, household electrical appliances, furniture etc. other Coated metal field is widely applied.Epoxy resin cathode electrophoresis dope has adhesive force and the anticorrosive property of excellence Can, but owing to epoxy resin weatherability is poor, it is impossible to as finish paint, and acrylate class cathode electrophoresis dope has good Protect color, gloss retention, good weatherability and plentiful coating film gloss, it is possible to adapt to monolayer application, the requirement of reduction construction cost.Mesh Before the most also have some bottom surfaces unification series electrophoretic coating, due to Stability of Bath Solution, the problem such as paint film appearance and patience, do not have It is used widely.Cathode electrophoresis dope typically uses bi-component, i.e. mill base and emulsion, presently relevant research focus on breast The improvement of liquid, is optimized emulsion formulations by the way of the cold spelling of epoxy and acrylic acid or epoxy grafted acrylate.Lack one The arranging in pairs or groups with emulsion of applicable different colours system planting high durable and high salt fog resistance uses the compatibility preferable, the color of stable circulation Slurry.Grind resin used by this mill base can provide good levelling outward appearance, and mill base stores the more stable property of process.
So being grafted acrylic acid grind resin and containing this resin mill base after being badly in need of developing a kind of modified epoxy, meet The market demand to bottom surface unification series cathode electrophoresis dope.
[summary of the invention]
It is an object of the invention to provide the sum of a kind of applicable different colours system with high durable and high salt fog resistance The modified epoxy graft acrylic acid cold coating that emulsion collocation uses.
To achieve these goals, it is provided that a kind of modified epoxy graft acrylic acid cold coating, this modified epoxy grafting third Olefin(e) acid cold coating is dual-component coating, by the high weather resistant acrylic acid modified emulsion of formula as below and the weather-proof mill base of high salt fog according to The proportional arrangement of 6:1 forms,
A. high weather resistant acrylic acid modified emulsion, is solidified by epoxy modified acrylic resin and enclosed type aliphatic isocyanates After agent mix homogeneously, add in nertralizer and after, add deionized water and prepare,
The weather-proof mill base of the highest salt fog, by epoxy modified acrylic resin, function additive, pigment, functional stuffing, deionized water Fineness≤15 μm it is ground to after mixing,
In a and b, epoxy modified acrylic resin is many by the epoxy resin graft containing toughening modifying structure half end-blocking After isocyanate curing agent, graft acrylic acid forms epoxy modified resin, and last quaternization is formed.
The cathode electrophoresis dope of the present invention provides the benefit that: this coating is aqueous double-component electrophoretic coating, and application is convenient, Use environmental protection, safety；Plate face smooth, decorative effect are good, and Stability of Bath Solution is good, and coating has the mechanical performance and resistance to of excellence Acid, alkali resistance, coating also has the most excellent weather resistance, through 800 hours QUV degradations, gloss loss≤10%, Δ E ≤ 2, and preferably decay resistance.
This coating also has a following optimization of C/C composites:
The preparation method of the polyisocyanate curing agent of described half end-blocking is as follows: stir at band, condensing tube and Dropping funnel Flask in, add isophorone diisocyanate, methyl iso-butyl ketone (MIBK) by formula ratio, logical nitrogen, be warmed up to 75 DEG C, drip different Capryl alcohol, drips off for 1 hour, cools to less than 45 DEG C acquisitions after being incubated 2 hours.
The described epoxy resin containing Reinforced structure is to control reaction vessel temperature to add matrix epoxy below 60 DEG C Resin, polycaprolactone diols, PPG-400, add bisphenol-A, methyl iso-butyl ketone (MIBK), be warming up to 100 DEG C, adds dimethylbenzyl Amine, 125 DEG C of reactions prepare for 1.5 hours.
Described enclosed type aliphatic isocyanates firming agent is by 20-30 weight portion methyl iso-butyl ketone (MIBK), 38-42 weight portion Hexamethylene diisocyanate, 32-38 part by weight of n-butanol prepares.
Described nertralizer is any one in lactic acid or sulfamic acid nertralizer.
In the described weather-proof mill base of high salt fog: the pigment of white slurry: 3.5-4.5, black wash and the pigment of color slurry: 1-2.5, ash The pigment of slurry: 3-4.Pigment i.e. color stuffing (pigment+filler) and the mass ratio of matrix resin, matrix resin in the present invention For epoxy modified acrylic resin.
The program gives the surface color and polish that coating is abundant, has preferable exterior decorative effect, can recall as requested Satisfied color, uses phosphomolybdic acid aluminum to improve anti-corrosive properties, uses rare-earth oxide ceria to improve the ageing-resistant of paint film Property, make paste formula performance be promoted further.
Titanium white, white carbon black, Kaolin, Pulvis Talci, the red R254 of phthalein cyanogen green G36, DPP, pucherite, oxygen is used in described pigment Change ferrum, phosphomolybdic acid aluminum, aluminium triphosphate.
The weather-proof mill base of high salt fog is also added with in ceria, Dineodymium trioxide one or both.
Product of the present invention is double-component system, is adapted to colour, white, gray systems, has and joins groove good stability, construction Convenient, after an electrophoretic painting, appearance of coat smooth, there is good decorative effect, yellowing resistance, excellent machinery Performance and acidproof, alkali resistance, coating also has the most excellent weather resistance and salt fog resistance, weather resistance and salt fog resistance Can, through 800 hours QUV degradations, gloss loss≤10%, Δ E≤2, the NSS salt spray test of 600 hours, salt fog is drawn at fork single To Erosion Width≤2mm, draw at fork and edge is all without foaming phenomena.
[detailed description of the invention]
Principle and feature to the present invention are described below, and example is served only for explaining the present invention, is not intended to limit Determine the scope of the present invention.
The polyisocyanates of preparation embodiment 1 preparation half end-blocking
22.2 part isophorone diisocyanate
3.9 parts of methyl iso-butyl ketone (MIBK)s
13.1 part isooctanol
Stir at band, in the flask of condensing tube and Dropping funnel, add isophorone diisocyanate, methyl by formula ratio Isobutyl ketone, leads to nitrogen, is warmed up to 75 DEG C, drip isooctanol, within 1 hour, drip off, after being incubated 2 hours, and detection NCO (108 ± 5), 45 DEG C are cooled to bottom discharge, it is thus achieved that the polyisocyanates (solid part is 90%) of half described end-blocking after qualified.
Preparation embodiment 2 prepares epoxy-modified acrylic acid grind resin
74.1 parts of bisphenol A epoxide resins (epoxide equivalent 188)
10 parts of polycaprolactone diolss (Mn=1000, hydroxyl value 112mgKOH.g-1)
6 parts of PPG-400
0.02 part of dibutyl tin laurate
20.4 part bisphenol-A
14.5 part methylisobutylketone
0.1 part of dimethyl benzylamine
The polyisocyanates of 43 part of half end-blocking
8 parts of methyl methacrylates
10 parts of n-butyl acrylates
4 parts of styrene
1 part of azodiisobutyronitrile
1.5 parts of benzoyl peroxides
12.5 parts of propylene glycol monobutyl ethers,
14.3 part dimethylethanolamine
8 parts of lactic acid
3.5 parts of deionized waters
Stir at band, in the flask of condensing tube and Dropping funnel, add the bisphenol-A epoxy of epoxide equivalent 188 by formula ratio Resin, polycaprolactone diols, PPG-400, dibutyl tin laurate, bisphenol-A, methyl iso-butyl ketone (MIBK), it is warming up to 100 DEG C, Adding dimethyl benzylamine, be continuously heating to 135 DEG C and stir 1.5 hours, until epoxide equivalent is 1000 ± 100,130-140 DEG C drips Add the polyisocyanates of half end-blocking, half an hour complete dropping after continue stirring 1 hour after be cooled to 115 DEG C dropping mixed liquors (methyl methacrylate, n-butyl acrylate, styrene, azodiisobutyronitrile, benzoyl peroxide), drips for 3 hours Add propylene glycol monobutyl ether after becoming insulation half an hour, be cooled to less than 80 DEG C, add dimethylethanolamine, lactic acid, deionization Water reacts at a temperature of 70-80 DEG C, until acid number ＜ 1, product deionized water is diluted to solid part is 30%, obtains modification Grind resin.
Substrate ring epoxy resins, through isocyanate-modified, improves the reactivity with cross-linking agent and impact strength, improves paint The pliability of film and thermostability；The polyisocyanates of side chain graft half end-blocking, forms dressing structure, improves the stable merit to pigment Energy；Graft acrylic acid, improves pliability and the weatherability of paint film；Ionizing forms quaternary ammonium salt, and grind resin viscosity stabilization, to face Filler has excellently wetting and dispersing effect, prevents color stuffing from reuniting, it is provided that preferably levelling effect, improves the stability of mill base The compatibility with ring the third modified emulsion is preferable.
Preparation embodiment 3 prepares enclosed type aliphatic isocyanates firming agent:
25 parts of methyl iso-butyl ketone (MIBK)s
40 parts of hexamethylene diisocyanates
35 parts of n-butyl alcohol
By formula ratio methyl iso-butyl ketone (MIBK) and hexamethylene diisocyanate added with agitator and condensing tube anti- Answer in container, lead to nitrogen, be warmed up to 75 DEG C, drip n-butyl alcohol, within 1 hour, drip off, after being incubated 2 hours, cool to less than 45 DEG C and go out Material, it is thus achieved that described enclosed type aliphatic isocyanates firming agent.
Preparation embodiment 4 prepares high weather resistant acrylic acid modified emulsion
36 parts of acrylic acid modified resins (60% solid part)
12 parts of enclosed type aliphatic isocyanates firming agent
0.6 part of lactic acid
0.3 part of sulfamic acid
10 parts of deionized waters
41 parts of deionized waters
Acrylic acid modified resin and enclosed type aliphatic isocyanates firming agent addition reaction vessel will be stirred by formula ratio Mixing 1 hour mix homogeneously, next step adds nertralizer (lactic acid and sulfamic acid are in advance with deionized water dissolving) and stirs 1 hour, Then deionized water disposably adding reaction vessel high speed stir 2 hours, whole preparation process reaction vessel temperature controls Below 45 DEG C, it is thus achieved that described high weather resistant acrylic acid modified emulsion.
Example 1 bottom surface unification redness slurry
55 parts of embodiments 2 prepare grind resin
5 parts of deionized waters
14 parts of R-254 red powder
5 parts of R-960 titanium whites
3 parts of Kaolin
2 parts of phosphomolybdic acid aluminum
0.5 part of ceria
By formula ratio, the modified abrasive resin made, deionized water are added and disperse in grinding pot 20 minutes to ensure stirring Uniformly, adding R-254 red powder, R-960 titanium white, Kaolin, phosphomolybdic acid aluminum, ceria under stirring, powder adds Rear raising rotating speed continues dispersion 30 minutes, and dispersion adds zirconium pearl (dispersion liquid: zirconium pearl=1 part: 1-2 after terminating in grinding pot Part), logical condensed water high speed sand milling 1 hour, to fineness≤15 μm, prepare required mill base.
Example 2 bottom surface unification military green mill base
55 parts of embodiments 2 prepare grind resin
5 parts of deionized waters
7 parts of phthalocyanine green G 36 powders
2 parts of pucherites
5 parts of Y-139 are deep yellow
4 parts of R-960 titanium whites
3 parts of phosphomolybdic acid aluminum
0.5 part of ceria
Carry out disperseing sand milling by the same way of example 1, be a difference in that used by mill base, color pigment changes, to reach To different colours effect.
Example 3 bottom surface unification black slurry
51 parts of embodiments 2 prepare grind resin
5 parts of deionized waters
5 parts of white carbon blacks (Rhizoma Sparganii MA-7)
15 parts of Kaolin
3 parts of phosphomolybdic acid aluminum
0.5 part of ferrum oxide
1 part of ceria
Carry out disperseing sand milling by the same way of example 1, be a difference in that color pigment used by mill base and functional stuffing are used Amount changes, and adjusts pigment, to reach different colours effect and weather-proof salt spray resistance.
Example 4 bottom surface unification ash mill base
30 parts of embodiments 2 prepare grind resin
0.2 part of silane coupler (DOW CORNING KH-550)
5 parts of deionized waters
2 parts of white carbon blacks (Rhizoma Sparganii MA-7)
16 parts of titanium whites (Du Pont R-960)
8 parts of Kaolin
3 parts of phosphomolybdic acid aluminum
0.5 part of ferrum oxide
1 part of ceria
Carry out disperseing sand milling by the same way of example 1, be a difference in that color pigment used by mill base and functional stuffing are used Amount changes, and adjusts pigment, introduces silane coupler and improves the stabilization function to pigment.
Examples detailed above 1-4 is prepared high weather resistant acrylic acid modified emulsion that bottom surface unification mill base prepared with embodiment 4 according to 1:6, is made into the electrophoresis groove liquid that solid part is 12%, ripening 24h in electrophoresis tank, at electrophoretic voltage 160V, and tank liquor temperature 30 DEG C, Electrophoresis time is to prepare model (galvanized sheet does ground, controls thickness between 20-25um) under conditions of 30s, and solidification temperature is 180℃/20min。
Thus the bottom surface unification cathode electrophoresis dope of the high durable for preparing of the present invention and high salt fog performance is adapted to colour, black Color, gray systems, have appearance of coat smooth, have good decorative effect, yellowing resistance, excellent mechanical performance and Acidproof, alkali resistance, coating also has the advantages such as the most excellent weather resistance, corrosion resistance.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.

Claims (8)

1. a modified epoxy graft acrylic acid cold coating, it is characterised in that this modified epoxy graft acrylic acid cold coating is Dual-component coating, by the high weather resistant acrylic acid modified emulsion of formula as below and the weather-proof mill base of high salt fog according to the proportional arrangement of 6:1 Form,
A. high weather resistant acrylic acid modified emulsion, is mixed by epoxy modified acrylic resin and enclosed type aliphatic isocyanates firming agent After closing uniformly, add in nertralizer and after, add deionized water and prepare,
The weather-proof mill base of the highest salt fog, comprises white slurry, black wash, mortar, color slurry, by epoxy modified acrylic resin, function additive, face It is ground to fineness≤15 μm after the mixing of material, functional stuffing, deionized water,
In a and b, epoxy modified acrylic resin is by many isocyanides of the epoxy resin graft containing toughening modifying structure half end-blocking After acid esters firming agent, graft acrylic acid forms epoxy modified resin, and last quaternization is formed.
2. modified epoxy graft acrylic acid cold coating as claimed in claim 1, it is characterised in that the polyisocyanate of described half end-blocking The preparation method of cyanate firming agent is as follows: stir at band, in the flask of condensing tube and Dropping funnel, adds different Buddhist by formula ratio That ketone diisocyanate, methyl iso-butyl ketone (MIBK), lead to nitrogen, be warmed up to 75 DEG C, drip isooctanol, within 1 hour, drip off, be incubated 2 hours After cool to less than 45 DEG C acquisitions.
3. modified epoxy graft acrylic acid cold coating as claimed in claim 1, it is characterised in that described containing toughness reinforcing knot The epoxy resin of structure is to control reaction vessel temperature to add substrate ring epoxy resins, polycaprolactone diols, PPG-below 60 DEG C 400, add bisphenol-A, methyl iso-butyl ketone (MIBK), be warming up to 100 DEG C, add dimethyl benzylamine, 125 DEG C of reactions are prepared into for 1.5 hours Arrive.
4. modified epoxy graft acrylic acid cold coating as claimed in claim 1, it is characterised in that described enclosed type aliphatic Isocyanate curing agent is by 20-30 weight portion methyl iso-butyl ketone (MIBK), 38-42 weight portion hexamethylene diisocyanate, 32-38 Part by weight of n-butanol prepares.
5. modified epoxy graft acrylic acid cold coating as claimed in claim 1, it is characterised in that described nertralizer is lactic acid Or any one in sulfamic acid nertralizer.
6. modified epoxy graft acrylic acid cold coating as claimed in claim 1, it is characterised in that the described weather-proof color of high salt fog In slurry: the pigment of white slurry: 3.5-4.5, black wash and the pigment of color slurry: 1-2.5, the pigment of mortar: 3-4.
7. modified epoxy graft acrylic acid cold coating as claimed in claim 6, it is characterised in that described pigment uses titanium In vain, white carbon black, Kaolin, Pulvis Talci, the red R254 of phthalein cyanogen green G36, DPP, pucherite, ferrum oxide, phosphomolybdic acid aluminum, aluminium triphosphate.
8. modified epoxy graft acrylic acid cold coating as claimed in claim 1, it is characterised in that in the weather-proof mill base of high salt fog Be also added with in ceria, Dineodymium trioxide one or both.
CN201610693474.8A 2016-08-19 2016-08-19 Modified epoxy-grafted acrylic resin coating Pending CN106318099A (en)

Priority Applications (1)

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CN110437391A (en) * 2019-09-17 2019-11-12 浩力森化学科技（江苏）有限公司 Epoxy acrylic resin, lotion and water paint with sound deadening
CN112251126A (en) * 2020-10-29 2021-01-22 浩力森化学科技（江苏）有限公司 Water-based environment-friendly high-performance low-temperature coating and preparation method thereof
CN112266687A (en) * 2020-10-29 2021-01-26 浩力森化学科技（江苏）有限公司 Preparation method of quaternary ammonium salt type grinding resin and grinding-free cationic color electrophoresis paste
CN113072683A (en) * 2021-04-12 2021-07-06 杭州安誉科技有限公司 Composite material heating plate for real-time fluorescent quantitative PCR instrument
CN113072683B (en) * 2021-04-12 2022-04-12 杭州安誉科技有限公司 Composite material heating plate for real-time fluorescent quantitative PCR instrument
CN113444435A (en) * 2021-09-01 2021-09-28 浩力森化学科技（江苏）有限公司 Wear-resistant electrophoretic paint
CN113930147A (en) * 2021-11-12 2022-01-14 上海三棵树防水技术有限公司 Silane modified aliphatic epoxy resin waterproof coating and preparation method thereof
CN114276735A (en) * 2022-01-05 2022-04-05 浩力森化学科技（江苏）有限公司 Aqueous environment-friendly low-temperature matte coating

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