CN103739800B - Phenolic resin coating film forming matter and preparation method thereof - Google Patents
Phenolic resin coating film forming matter and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of phenolic resin coating film forming matter, its raw material is by following mass percent, comprise the vinylbenzene of 4.0 ~ 6.0%, the butyl acrylate of 3.0 ~ 5.0%, the glycidyl methacrylate of 8.0 ~ 10.0%, the vinylformic acid hexafluoro butyl ester of 3.0 ~ 5.0%, the initiator of 0.04 ~ 0.06%, the n-dodecyl mercaptan of 0.02 ~ 0.05%, the rosin of 9.0 ~ 12.0%, the phenol of 6.0 ~ 8.0%, the paraformaldehyde of 2.0 ~ 3.0%, the H promotor of 0.03 ~ 0.05%, the linolenic acid of 8.0 ~ 10.0%, the behenic acid of 10.0 ~ 12.0% and surplus No. 100-2 solvents.Phenolic resin coating film forming matter of the present invention has that dryness is fast, and water tolerance, chemical proofing, contamination resistance, weather resisteant are good, hardness is high, and speed of response and reaction end controlled, the feature that cost is low.
Description
Technical field
The present invention relates to a kind of phenolic resin coating film forming matter and preparation method thereof, belong to phenolic resin paint technical field.
Background technology
Phenolic resin coating is one of kind that in coatings industry, production history is the longest, the polymkeric substance that it mainly obtains through refining with resol or modified phenolic resins and dry vegetable oil (tung oil, flax wet goods), for film forming matter, coordinates the modulation such as various face, filler, metallic soap drier, solvent to form.In today, although various synthetic resin paint is widely used, but phenolic resin paint is still with features such as higher cost performance and fabulous application properties, in occupation of larger Coating Market share, add up according to relevant authoritative department, the phenolic resin paint output of the above paint manufacturing concern of China's scale in 2012 production reaches more than 300,000 tons, the output value surpasses 3,000,000,000, be one of maximum at present paint kind, built, traffic, machinery, hardware & tools, the industry such as wood furniture adopt in a large number.
At present, along with the fast development of the various high-performance synthetic resin paints such as epoxy coating, polyurethane coating, acrylic coating, phenolic resin coating will obtain synchronized development, just must improve the quality and performance of its product, especially in rate of drying, water-fast, resistant to chemical media, hardness etc., be improved raising; Improve the quality and performance of phenolic resin coating, the crucial performance improving film-forming resin.Relevant resol and the coating such as Chinese patent CN101899136A, CN101712739A, CN102372983A at present, great majority are the performances being improved coating by the performance of raising film forming matter.And domestic paint manufacturers is when producing phenolic resin coating film forming matter, generally adopt the production technique of heat refining method, under 280 ~ 310 DEG C of conditions, refining is carried out by resol or rosin modified phenolic resin and dry vegetable oil etc., make a series of very complicated chemical reaction occurs between each component, as reactions such as polymerization, oxygenolysis, transesterify, saponification, generate the high molecular polymer be cross-linked with each other together.But this is tempered technique and there is more drawback, the period being mainly manifested in reaction end is extremely short, usually at 2-10 minute, and the control of terminal is maked decision in the short period of time by rule of thumb by tempering operator, the quality of film forming matter is very large by the impact of human factor, react with regard to premature termination as being less than reaction end, then can contain the insufficient rosin modified phenolic resin of more reaction in film forming matter, plant wet goods composition, film forming matter inside is made to there is heterogeneous phenomenon, show as film forming matter outward appearance poor definition, therefore will produce paint film with its phenolic resin coating prepared to be clamminess, water tolerance, dryness, the quality problems such as difference of hardness.Do not have timely termination reaction as arrived reaction end, film forming matter viscosity will be caused too high, and painting need add solvent, and the paint storage bad stability made, gelling will occur time serious, and cause product rejection.
Summary of the invention
The object of this invention is to provide one, to have dryness fast, and water tolerance, chemical proofing, contamination resistance, weather resisteant are good, hardness is high, and speed of response and reaction end controlled, phenolic resin coating film forming matter that cost is low and preparation method thereof.
The present invention is the technical scheme achieved the above object: a kind of phenolic resin coating film forming matter, is characterized in that: its raw material is made up of the component of following mass percent, comprises
Wherein: described glycidyl methacrylate is the acrylate monomer containing epoxy-functional.
Wherein: described initiator is peroxide initiator.
The polymerization degree n of described paraformaldehyde is 8 ~ 12.
The preparation method of phenolic resin coating film forming matter of the present invention, is characterized in that: carry out according to the following steps, its raw material all by mass percentage,
1., the vinylbenzene of 4.0 ~ 6.0%, the butyl acrylate of 3.0 ~ 5.0%, the glycidyl methacrylate of 8.0 ~ 10.0% and the vinylformic acid hexafluoro butyl ester of 3.0 ~ 5.0% and the initiator of 0.02 ~ 0.03% are added the high-order dropwise adding tank of band stirrer, throw after finishing and start stirrer, by even, stand-by for abundant for the prepolymer in high-order dropwise adding tank dispersed with stirring;
2., get and add reactor with the 100#-2 solvent of prepolymer equal mass, start stirrer on reactor to 100#-2 stirring solvent and be heated to 90 ± 2 DEG C time, be incubated, drop in reactor by the prepolymer average rate in header tank, time for adding controls at 2 ± 0.05 hours, dropping terminates rear insulation reaction 1 ± 0.05 hour, add in reactor by disposable after the 100#-2 dissolution with solvents of remaining initiator by its quality 5 times, continue insulation reaction 2 ± 0.05 hours, when again feed liquid being heated to 115 ± 2 DEG C, insulation reaction 2 ± 0.05 hours, thereafter at interval of 15 ± 0.2 minutes, viscosity measurements is carried out to the feed liquid in reactor, when the viscosity of sludge in reactor reaches 500 ~ 1000mPas/25 DEG C of scope, the n-dodecyl mercaptan of 0.02 ~ 0.05% is added in reactor, be incubated cooling after 30 ± 5 minutes and terminate reaction, obtained fluorine-containing styrene-acrylate polymer,
3., the rosin of 9.0 ~ 12.0% is added in another reactor, and when being heated to 130 ~ 150 DEG C, insulation is all melted to rosin by solid is liquid, start stirrer to carry out being stirred to evenly, add 6.0 ~ 8.0% phenol and after stirring temperature be down to 80 ~ 90 DEG C, add the paraformaldehyde of 2.0 ~ 3.0% and the H promotor of 0.03 ~ 0.05%, insulation reaction 4 ~ 6 hours post-heating heat up, and steam except moisture content in reactor gradually by the heat-up rate of 10 DEG C/h, be incubated when being again warming up to 130 ± 2 DEG C, and sampling detects intermediate fusing point, when intermediate fusing point reaches 60 ~ 80 DEG C of scopes, be cooled to less than 80 DEG C, the behenic acid of the linolenic acid of 8.0 ~ 10.0% and 10.0 ~ 12.0% is added in reactor with obtained fluorine-containing styrene-acrylate polymer, when being heated to 150 ± 2 DEG C while stirring, slowly heat up with 5 DEG C ± 0.5/h, steadily carry out fat polymerization reaction, and regularly remove esterification water, wherein the temperature of material in reactor is the highest must not more than 190 DEG C, fat polymerization reaction carries out 4 ± 0.05 hours, sampling detects the outward appearance of resin, acid number and viscosity, when resin outward appearance presents transparent limpid, acid number≤8 and viscosity are when 1500 ~ 3000mPas/25 DEG C of scope, termination reaction, resin is cooled to less than 150 DEG C and with remaining 100#-2 solvent latting drown, after filtration, discharging obtains phenolic resin coating film forming matter.
Phenolic resin coating film forming matter of the present invention adopts distinctive formula system, due to the acrylate functional monomer that glycidyl methacrylate is containing epoxy-functional, with epoxide group, there is higher reactive behavior, can with containing carboxyl, amido, the chemical substance of the functional groups such as isocyanato carries out polyreaction, when glycidyl methacrylate and vinylbenzene, butyl acrylate and the polymerization of vinylformic acid hexafluoro butyl ester form fluorine-containing styrene-acrylate polymer, film forming matter is made to have good hardness, strengthen water-fast and chemical proofing and snappiness and resistance to tanning by the sun property preferably, and hexafluoro butyl ester group contained by fluorine-containing styrene-acrylate polymer side chain, give the surface energy that polymkeric substance is lower, have and improve the water-fast of film forming matter, anti-stain characteristic, the effects such as weather resisteant effect.The present invention plays the effect of Molecular regulator amount by n-dodecyl mercaptan in acroleic acid polymerization, speed of response and reaction end controlled, the molecular weight that effectively can control polymkeric substance increases, and controls the molecular size range of polymkeric substance, can improve phenolic resin coating film forming matter yield rate.
Phenolic resin coating film forming matter of the present invention with fluorine-containing styrene acrylic polymer for main chain, with rosin modified phenolic resin, behenic acid, linolenic acid is side chain, form complete high molecular polymer, there is speed of response and reaction end is controlled, polymer molecular structure is regular, narrow molecular weight distribution, because side chain contains the fluorin radical of some amount, the feature that surface energy is lower, efficiently solve the rosin modified phenolic resin containing more not fully reaction in original phenolic resin coating film forming matter, plant wet goods composition and inner occur heterogeneous disadvantage, improving the dryness of phenolic resin coating, water tolerance, chemical proofing, weather resisteant, contamination resistance, in the performance basis such as hardness, effectively can avoid tempering some mass defects that phenolic resin coating film forming matter brings because terminal point control is improper.
Phenolic resin coating film forming matter of the present invention is in whole preparation process, owing to there is not double-bond polymerization reaction, so there is no consume the unsaturated double-bond in vegetable oil acid, solving former heat refining method has double bond copolyreaction to occur in preparation process, the problem of the unsaturated double-bond of some amount need be consumed, therefore, although adopt linolenic acid and behenic acid to combine in formula system of the present invention, but the dryness of film forming matter is still fine, comparatively adopts pure oleum lini phenolic resin coating film forming matter to have certain cost advantage.
Embodiment
Phenolic resin coating film forming matter of the present invention, its raw material is made up of the component of following mass percent, comprises the vinylbenzene of 4.0 ~ 6.0%, the butyl acrylate of 3.0 ~ 5.0%, the glycidyl methacrylate of 8.0 ~ 10.0%, the vinylformic acid hexafluoro butyl ester of 3.0 ~ 5.0%, the initiator of 0.04 ~ 0.06%, the n-dodecyl mercaptan of 0.02 ~ 0.05%, the rosin of 9.0 ~ 12.0%, the phenol of 6.0 ~ 8.0%, the paraformaldehyde of 2.0 ~ 3.0%, the H promotor of 0.03 ~ 0.05%, the linolenic acid of 8.0 ~ 10.0%, the behenic acid of 10.0 ~ 12.0% and the 100#-2 solvent of surplus, wherein, glycidyl methacrylate of the present invention is the acrylate monomer containing epoxy-functional, this acrylate monomer with epoxide group, there is higher reactive behavior, therefore can with containing carboxyl, the chemical substance of the functional group such as amido and isocyanato carries out polyreaction, and the present invention adopts Hubei Longma Chemical Company to manufacture the technical grade methyl glycidyl acrylate produced.
The present invention is played by vinylbenzene and improves film forming matter hardness, strengthens the effects such as water-fast, chemical proofing, as the general industry level vinylbenzene adopting changzhou Xin Chemical Co., Ltd. to produce in phenolic resin coating film forming matter.
The present invention is played by butyl acrylate and improves film forming matter snappiness and resistance to effect of tanning by the sun, the general industry level butyl acrylate produced as adopted Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing in phenolic resin coating film forming matter.
The present invention selects vinylformic acid hexafluoro butyl ester; because its Oil repellent is high; and hexafluoro butyl ester group contained by side chain in phenolic resin coating film forming matter; " shielding protection " effect can be had to high polymer main chain and inside; give polymkeric substance lower surface energy, improve water-fast, the anti-stain characteristic of phenolic resin coating film forming matter, weather resisteant effect.The general industry level vinylformic acid hexafluoro butyl ester that the present invention can adopt Harbin Xue Jiafu chemistry of silicones company limited to manufacture.
Initiator of the present invention is peroxide initiator, is applicable to the synthesis of high solid low viscosity propylene acid resin, Trigonox42 or Trigonox42S that Tianjin Akzo Nobel's superoxide company limited can be adopted to provide or Trigonox21S etc.
The present invention plays the effect of Molecular regulator amount by n-dodecyl mercaptan in acroleic acid polymerization reaction, and the molecular weight that therefore effectively can control polymkeric substance increases, and namely reaches the object of the molecular size range controlling polymkeric substance, the steady quality of film forming matter.The general industry level n-dodecyl mercaptan that the present invention can select Guangzhou He Shi wall chemical materials company limited to manufacture
Its acid number >=166mgHOH/g of the rosin that the present invention selects, due to rosin be a kind of unsaturated acid, containing conjugated double bond, therefore 1 can be occurred with phenol formaldehyde resin of the present invention, 4 addition reactions, therefore oil soluble, the hardness of phenolic resin coating film forming matter can be improved, the general industry level rosin that the present invention can adopt Youxi County, Fujian Province Heng Yuan Chemical Co., Ltd. to manufacture.
The present invention has hyperergy, polyfunctionality feature by phenol, and as the chief component of resol of the present invention, as the general industry level phenol adopting Beijing Yanshan Petrochemical company limited to manufacture.
Its polymerization degree n of paraformaldehyde of the present invention is 8 ~ 12, the present invention utilizes paraformaldehyde have hyperergy feature and phenol polycondensation and form resol, and both can reduce the energy consumption of dehydration in the mill, can wastewater treatment capacity be greatly reduced again, there is good manufacturability.The general industry level paraformaldehyde that the present invention can adopt Shanghai solvent factory to manufacture.
H promotor of the present invention can promote the condensation reaction of phenol and formaldehyde, generates the resol that molecular chain two ends exist methylol.The general industry level H promotor that Jinan Kang Sheng Chemical Co., Ltd. manufactures can be adopted.
The linolenic acid that the present invention selects belongs to dryness oleic acid, therefore containing more unsaturated double-bond, has normal temperature Quick Oxidation film forming properties in atmosphere, therefore can give phenolic resin coating film forming matter and have the fast feature of dryness.The general industry level linolenic acid that Anhui Rui Fen get grease deep processing company limited manufactures can be adopted.
The behenic acid that the present invention selects belongs to semi-drying oleic acid, and it contains the unsaturated double-bond of some amount, has normal temperature oxidation film forming properties in atmosphere, can adopt the general industry level behenic acid that the born grease company limited in Nanjing manufactures.
The 100#-2 solvent that the present invention selects is industrial raw material, has good solvency power, moderate rate of volatilization, is the good solvent manufacturing natural oil lipid paint, as the 100#-2 solvent adopting Hua Lun chemical plant, Yangzhou, Jiangsu to manufacture.
Its concrete raw material of phenolic resin coating film forming matter of the present invention by mass percentage, in table 1,
Table 1
The preparation method of phenolic resin coating film forming matter of the present invention, carries out according to the following steps, its raw material all by shown in table 1,
1., the initiator of vinylbenzene, butyl acrylate, glycidyl methacrylate and vinylformic acid hexafluoro butyl ester and 0.02 ~ 0.03% is added the high-order dropwise adding tank being with stirrer, throw after finishing and start stirrer, by even, stand-by for abundant for the prepolymer in high-order dropwise adding tank dispersed with stirring;
2., get and add reactor with the 100#-2 solvent of prepolymer equal mass, start stirrer on reactor to 100#-2 stirring solvent and be heated to 90 ± 2 DEG C time, be incubated, drop in reactor by the prepolymer average rate in header tank, time for adding controls at 2 ± 0.05 hours, dropping terminates rear insulation reaction 1 ± 0.05 hour, add in reactor by disposable after the 100#-2 dissolution with solvents of remaining initiator by its quality 5 times, continue insulation reaction 2 ± 0.05 hours, when again feed liquid being heated to 115 ± 2 DEG C, insulation reaction 2 ± 0.05 hours, thereafter at interval of 15 ± 0.2 minutes, viscosity measurements is carried out to the feed liquid in reactor, when the viscosity of sludge in reactor reaches 500 ~ 1000mPas/25 DEG C of scope, n-dodecyl mercaptan is added in reactor, be incubated cooling after 30 ± 5 minutes and terminate reaction, obtained fluorine-containing styrene-acrylate polymer,
3., rosin is added in another reactor, and when being heated to 130 ~ 150 DEG C, insulation is all melted to rosin by solid is liquid, start stirrer to carry out being stirred to evenly, add phenol and temperature is down to 80 ~ 90 DEG C after stirring, add paraformaldehyde and H promotor, insulation reaction 4 ~ 6 hours post-heating heat up, and steam except moisture content in reactor gradually by the speed of 10 DEG C/h, be incubated when being again warming up to 130 ± 2 DEG C, and sampling detects intermediate fusing point, when intermediate fusing point reaches 60 ~ 80 DEG C of scopes, be cooled to less than 80 DEG C, linolenic acid and behenic acid are added in reactor with obtained fluorine-containing styrene-acrylate polymer, when being heated to 150 ± 2 DEG C while stirring, slowly heat up with 5 DEG C ± 0.5/h, steadily carry out fat polymerization reaction, and regularly remove esterification water, wherein the temperature of material in reactor is the highest must not more than 190 DEG C, fat polymerization reaction carries out 4 ± 0.05 hours, sampling detects the outward appearance of resin, acid number and viscosity, when resin outward appearance presents transparent limpid, acid number≤8 and viscosity are when 1500 ~ 3000mPas/25 DEG C of scope, termination reaction, resin is cooled to less than 150 DEG C and with remaining 100#-2 solvent latting drown, after filtration, discharging obtains phenolic resin coating film forming matter.
Adopt urea formaldehyde paint film forming matter of the present invention to prepare F01-1 phenolic varnish, carry out Performance Detection by GB/T25253-2010 " phenolic resin paint " standard.Be shown in Table 2, its over-all properties has had very large lifting, meets or exceeds the technical requirements of GB/T25253-2010 " phenolic resin paint " standard completely.
Table 2
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| State in a reservoir | In uniform state | In uniform state | In uniform state | In uniform state | In uniform state | In uniform state | In uniform state |
| Former paint color/number | 12 | 11 | 12 | 11 | 11 | 12 | 11 |
| Elution time (ISO6 cup)/s | 68 | 63 | 72 | 75 | 71 | 65 | 68 |
| Non-volatile content/% | 46.8 | 47.2 | 46.8 | 48.0 | 47.0 | 46.5 | 47.5 |
| Skinning (48h) | Not skinning | Not skinning | Not skinning | Not skinning | Not skinning | Not skinning | Not skinning |
| Application property | Brush accessible | Brush accessible | Brush accessible | Brush accessible | Brush accessible | Brush accessible | Brush accessible |
| Paint film appearance | Smooth | Smooth | Smooth | Smooth | Smooth | Smooth | Smooth |
| Surface drying/hour | 4.0 | 3.5 | 4.0 | 4.5 | 3.5 | 4.0 | 3.5 |
| Do solid work/hour | 13.0 | 15 | 14.5 | 14.5 | 13.5 | 14.0 | 14.5 |
| Hardness | 0.41 | 0.38 | 0.36 | 0.39 | 0.39 | 0.40 | 0.37 |
| Sticking power/level | 1 | 2 | 1 | 1 | 2 | 1 | 1 |
| Snappiness/mm | 2 | 2 | 1 | 2 | 2 | 2 | 1 |
| Gloss (60 °)/unit value | 87 | 86 | 88 | 86 | 87 | 85 | 87 |
| Water tolerance/8h | Without exception | Without exception | Without exception | Without exception | Without exception | Without exception | Without exception |
Claims (4)
1. a phenolic resin coating film forming matter, is characterized in that: its raw material is made up of the component of following mass percent, comprises
Wherein: described glycidyl methacrylate is the acrylate monomer containing epoxy-functional.
2. phenolic resin coating film forming matter according to claim 1, is characterized in that: described initiator is peroxide initiator.
3. phenolic resin coating film forming matter according to claim 1, is characterized in that: the polymerization degree n of described paraformaldehyde is 8 ~ 12.
4. according to the preparation method of the phenolic resin coating film forming matter described in claim 1, it is characterized in that: carry out according to the following steps, its raw material all by mass percentage,
1., the vinylbenzene of 4.0 ~ 6.0%, the butyl acrylate of 3.0 ~ 5.0%, the glycidyl methacrylate of 8.0 ~ 10.0% and the vinylformic acid hexafluoro butyl ester of 3.0 ~ 5.0% and the initiator of 0.02 ~ 0.03% are added the high-order dropwise adding tank of band stirrer, throw after finishing and start stirrer, by even, stand-by for abundant for the prepolymer in high-order dropwise adding tank dispersed with stirring;
2., get and add reactor with the 100#-2 solvent of prepolymer equal mass, start stirrer on reactor to 100#-2 stirring solvent and be heated to 90 ± 2 DEG C time, be incubated, drop in reactor by the prepolymer average rate in header tank, time for adding controls at 2 ± 0.05 hours, dropping terminates rear insulation reaction 1 ± 0.05 hour, add in reactor by disposable after the 100#-2 dissolution with solvents of remaining initiator by its quality 5 times, continue insulation reaction 2 ± 0.05 hours, when again feed liquid being heated to 115 ± 2 DEG C, insulation reaction 2 ± 0.05 hours, thereafter at interval of 15 ± 0.2 minutes, viscosity measurements is carried out to the feed liquid in reactor, when the viscosity of sludge in reactor reaches 500 ~ 1000mPas/25 DEG C of scope, the n-dodecyl mercaptan of 0.02 ~ 0.05% is added in reactor, be incubated cooling after 30 ± 5 minutes and terminate reaction, obtained fluorine-containing styrene-acrylate polymer,
3., the rosin of 9.0 ~ 12.0% is added in another reactor, and when being heated to 130 ~ 150 DEG C, insulation is all melted to rosin by solid is liquid, start stirrer to carry out being stirred to evenly, add 6.0 ~ 8.0% phenol and after stirring temperature be down to 80 ~ 90 DEG C, add the paraformaldehyde of 2.0 ~ 3.0% and the H promotor of 0.03 ~ 0.05%, insulation reaction 4 ~ 6 hours post-heating heat up, and steam except moisture content in reactor gradually by the heat-up rate of 10 DEG C/h, be incubated when being again warming up to 130 ± 2 DEG C, and sampling detects intermediate fusing point, when intermediate fusing point reaches 60 ~ 80 DEG C of scopes, be cooled to less than 80 DEG C, the behenic acid of the linolenic acid of 8.0 ~ 10.0% and 10.0 ~ 12.0% is added in reactor with obtained fluorine-containing styrene-acrylate polymer, when being heated to 150 ± 2 DEG C while stirring, slowly heat up with 5 DEG C ± 0.5/h, steadily carry out fat polymerization reaction, and regularly remove esterification water, wherein material in reactor temperature is the highest must not more than 190 DEG C, fat polymerization reaction carries out 4 ± 0.05 hours, sampling detects the outward appearance of resin, acid number and viscosity, when resin outward appearance presents transparent limpid, acid number≤8 and viscosity are when 1500 ~ 3000mPas/25 DEG C of scope, termination reaction, resin is cooled to less than 150 DEG C and with remaining 100#-2 solvent latting drown, after filtration, discharging obtains phenolic resin coating film forming matter.
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| CN102358815A (en) * | 2011-07-25 | 2012-02-22 | 上海电动工具研究所 | One-component self-drying acrylic acid grafted epoxy ester aqueous dispersion coating and its preparation method |
| CN103102446A (en) * | 2013-03-01 | 2013-05-15 | 湖北乾兴化工有限公司 | Hydroxylated acrylic resin for automobile refinishing varnish and preparation method of hydroxylated acrylic resin |
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| KR102019726B1 (en) * | 2011-12-21 | 2019-09-09 | 아크조노벨코팅스인터내셔널비.브이. | Solvent-based coating compositions |
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| CN102358815A (en) * | 2011-07-25 | 2012-02-22 | 上海电动工具研究所 | One-component self-drying acrylic acid grafted epoxy ester aqueous dispersion coating and its preparation method |
| CN103102446A (en) * | 2013-03-01 | 2013-05-15 | 湖北乾兴化工有限公司 | Hydroxylated acrylic resin for automobile refinishing varnish and preparation method of hydroxylated acrylic resin |
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Address after: 678 Yulong North Road, Xinbei District, Changzhou City, Jiangsu Province Patentee after: CHANGZHOU GUANGHUI CHEMICAL Co.,Ltd. Patentee after: JIANGSU ZHONGTU PAINT DETECTION CENTER Co.,Ltd. Address before: 213016, 505, three Fort Street, bell tower, Jiangsu, Changzhou Patentee before: CHANGZHOU GUANGHUI CHEMICAL Co.,Ltd. Patentee before: JIANGSU ZHONGTU PAINT DETECTION CENTER Co.,Ltd. |