CN105602418A - High-thermal-conductivity and high-wear-resistance organosilicon non-stick coating - Google Patents
High-thermal-conductivity and high-wear-resistance organosilicon non-stick coating Download PDFInfo
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- CN105602418A CN105602418A CN201610035117.2A CN201610035117A CN105602418A CN 105602418 A CN105602418 A CN 105602418A CN 201610035117 A CN201610035117 A CN 201610035117A CN 105602418 A CN105602418 A CN 105602418A
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Engineering & Computer Science (AREA)
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Abstract
The invention relates to the technical field of non-stick coatings, aims to solve the problems that a non-stick pan using a stainless steel pan or an iron pan as base material is poor in heat distribution and easy to generate heat accumulation points, coating fracture is caused, food gets burnt, and the service life of the coating is shortened greatly, and provides a high-thermal-conductivity and high-wear-resistance organosilicon non-stick coating. The non-stick coating comprises, by weight, 20-60 parts of organosilicon-modified polyester resin, 20-60 parts of ceramic resin, 5-30 parts of high-temperature-resistant pigment and filler, 1-20 parts of heat-conduction auxiliary and 10-40 parts of solvent. The coating has excellent mechanical strength, high thermal conductivity, and the like after film formation.
Description
Technical field
The present invention relates to non-viscous paint technical field, be specifically related to the non-viscous paint of a kind of high heat conduction, high abrasion.
Background technology
Non-viscous paint, due to the low-down surface tension of its tool, is difficult in surface attachment other material, by itThe non-stick pan of manufacturing has had since coming out lives and brings great convenience to people. Non-stick pan is divided into according to base materialAluminum pot, stainless-steel pan, iron pan. The characteristic of aluminum pot is that heat distribution is good, and heat-transfer effect is 16 of stainless-steel panTimes, and pot body is lighter. But aluminum pot not easy cleaning, with oily many times oil smoke large. The characteristic of stainless-steel pan is heat distributionBad, easily produce heat build-up point and burning foods. Stainless-steel pan pot body weight, non-easy cleaning, easily smolder when many with oily.The heat distribution of Iron-enamel pot is bad, is easily burned at the end. This class pot not easy cleaning, surface is easily damaged, causes iron-based materialGet rusty. Iron pan heat distribution is bad, easily produces heat build-up point and burning foods, its pot of body weight, non-easy cleaning, Yi ShengRust, and with oily many times oil smoke large. Therefore, current coating non-stick pan adopts aluminium or aluminium alloy to be used as a pot base,This is because the good heat conductivity of this metalloid. But how many direct contacting foodstuffs of aluminum products, can affect healthy.But due to poor as the heat distribution of the non-stick pan of base material using stainless-steel pan and iron pan, easily cause heat build-up point,Be coated with film rupture and burning foods thereby cause, greatly reduce the service life of coating.
Summary of the invention
Poor as the heat distribution of the non-stick pan of base material using stainless-steel pan and iron pan for solving, easily cause heat build-upPoint, is coated with film rupture and burning foods thereby cause, and greatly reduces the problem in the service life of coating, the present inventionPropose a kind of high heat conduction high abrasion organosilicon non-viscous paint, after this coating film forming, there is excellent mechanical strength,The features such as higher thermal conductivity.
The present invention is achieved by the following technical solutions: a kind of high heat conduction high abrasion organosilicon non-viscous paint by withLower composition is made, and the weight portion of each component is:
Described ceramic resin is made by following preparation method: after Ludox, water are mixed, regulating pH is 3～5,Add silane, stir 1～5h at 25 DEG C～65 DEG C, obtain ceramic resin.
As preferably, the mass ratio of Ludox and water is 1: 1～3, and the mass ratio of Ludox and silane is 1: 1～10.Ludox can be selected from the hydrosol or alcosol, and described acid is selected from strong acid or weak acid. Described silane have asOne or more in lower structural formula:
Wherein R is organic group, is selected from one in methyl, phenyl, R1For reactive functionality, be selected from chlorine, methoxyA kind of in base, ethyoxyl, hydroxyl.
Described heat conduction auxiliary agent is selected from one in Graphene, CNT, diamond, graphite, aluminium powder, silver powderKind or several. Described Graphene, CNT, graphite can be powders, can be to be also scattered in solventSlurry. Described Graphene or CNT also comprise the various functional group modification Graphenes of modification or carbon nanometerPipe, as: one or more in hydroxyl, carboxyl, carbonyl, amino.
Described solvent be selected from divalent ester mixture, ethylene glycol ether acetate, diethylene glycol monobutyl ether acetate,One or more in isobutyl isobutyrate, propionic acid-3-ether ethyl ester and methyl isoamyl ketone.
Described silicone modified polyester resin is made by following steps: by binary acid, trihydroxylic alcohol, crosslinked catalysisAgent, dimethylbenzene are warming up to 170～210 DEG C after mixing, and after insulation 1～8h, are cooled to 80-90 DEG C again, obtain polyesterResin; Then add organic solvent and silicone oligomer; Be warming up to 110～130 DEG C, insulation 1～3h after againBe cooled to 80-90 DEG C, finally adding organic solvent to make solid content is 51～60wt%, obtains organic-silicon-modified poly-Ester resin.
As preferably, the mol ratio of binary acid and trihydroxylic alcohol is 1: 1～2, binary acid and crosslinking catalyst weightThan being 1: 0.02～0.1, the weight ratio of binary acid and dimethylbenzene is 1: 0.06～0.1, and binary acid and organosilicon are lowThe weight ratio of polymers is 1: 1.0～1.5, and organic solvent use amount is the amount that solute is dissolved.
As preferably, described binary acid is selected from one or both in M-phthalic acid, terephthalic acid (TPA), instituteThe trihydroxylic alcohol of stating is selected from one or both in trimethylolethane, trimethylolpropane, described crosslinked catalysisAgent be selected from a kind of in butyl titanate, tetrabutyl titanate, dioctyl tin oxide, diisooctyl tin oxide orSeveral, described organic solvent be selected from dipropylene glycol methyl ether, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate,One or more in butanols, isobutanol, 1-Methoxy-2-propyl acetate and DPG monobutyl ether acetate, described inThe weight average molecular weight of silicone oligomer be 700～2200, and contain in methoxyl group, ethyoxyl, hydroxyl oneKind, a kind of in methoxyl group, ethyoxyl, hydroxyl is 3～22% of silicone oligomer percentage by weight.
As preferably, described silicone oligomer can be by methltriethoxysilone, dimethyl diethoxyThe condensation reaction that is hydrolyzed of the siloxanes such as base silane and a phenyl triethoxy obtains, also can be by monomethyl front threeThe condensation reaction that is hydrolyzed of the siloxanes such as TMOS, dimethyldimethoxysil,ne and a phenyl trimethoxy obtainsArrive. Wherein, the condensation reaction that is hydrolyzed of described siloxanes adopts the contracting that is hydrolyzed of this area conventional siloxanesClose reaction, its technique and reaction condition adopt routine techniques. As preferably, described silicone oligomer also canTo be selected from the IC836 of Wa Ke company, 233 of Dow Corning Corporation, 249 of Dow Corning Corporation, Dow Corning CorporationZ-6108,3074 of Dow Corning Corporation, the organic siliconresin KR150 of SHIN-ETSU HANTOTAI, the KR211 of company of SHIN-ETSU HANTOTAI,The KR212 of company of SHIN-ETSU HANTOTAI, the KR214 of company of SHIN-ETSU HANTOTAI, the KR216 of company of SHIN-ETSU HANTOTAI, the KR213 of company of SHIN-ETSU HANTOTAIIn one or more.
High temperature resistant color stuffing is made up of than mixing arbitrarily with high temperature resistant filler high-temperature resisting pigment, and described pigment is thisThe high-temperature resisting pigment that field is conventional, can be the inorganic high-temperature resistant such as carbon black, iron oxide red pigment, can be also phthalocyanine blueDeng organic high temperature-resistant pigment. Described filler is the conventional high temperature resistant filler in this area, can be silica,Aluminium oxide.
Described coating can also contain auxiliary agent. Auxiliary agent is the conventional organosilicon auxiliary agent in this area, play levelling,The effects such as froth breaking, pigment wetting, viscosity adjusting. Those skilled in the art can be according to requiring to determine auxiliary agentKind and consumption. Auxiliary agent of the present invention can have silicone oil, organic silicon modified by polyether auxiliary agent, KH-550,KH-560 etc. Organic silicon modified by polyether auxiliary agent of the present invention is the conventional organic silicon modified by polyether in this areaAuxiliary agent, CoatOSil series organic silicon modified by polyether auxiliary agent that can Shi Maitu new high-tech material Co., Ltd. HelpThe percentage by weight of agent is 1～5%.
The preparation method of described coating is for to be mixed to get each component.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail, in embodiment raw materials used all commercially available orObtain by conventional method. The weight average molecular weight of the silicone oligomer described in embodiment is 700～2200, andContain one in methoxyl group, ethyoxyl, hydroxyl, the one in methoxyl group, ethyoxyl, hydroxyl is that organosilicon is low3～22% of polymers percentage by weight.
Embodiment 1:
(1) preparation of ceramic resin
Ludox 100g, water 150g are mixed, and using vinegar acid for adjusting pH is 3, adds 600g phenylTrimethoxy silane stirs 4h under the environment of 40 DEG C, obtains ceramic resin 1.
(2) silicone modified polyester resin
By binary acid (M-phthalic acid) 107.9g (0.65mol), trihydroxylic alcohol (trimethylolpropane) 134g(1mo1), crosslinking catalyst (tetra-n-butyl titanate) 2.3g; , dimethylbenzene 6.7g mix after be warming up to 210DEG C, after insulation 1h, be cooled to again 90 DEG C, obtain mylar; Then add organic solvent (propylene glycol monomethyl etherAcetate) 50g and silicone oligomer (KR212 of company of SHIN-ETSU HANTOTAI) 108g; Be warming up to 130 DEG C, protectAfter temperature 1h, be cooled to 90 DEG C, finally adding organic solvent 1-Methoxy-2-propyl acetate to make solid content is 60wt% again,Obtain silicone modified polyester resin 1.
(3) preparation of organosilicon non-viscous paint
Ceramic resin 40g prepared by step (1), organosilicon modified polyester 20g, charcoal prepared by step (2)Black 5g, aluminium oxide 5g, aluminium powder 10g, silver powder 10g, divalent ester mixture (DBE) 10g mixAfter be ground to required particle diameter, filter to obtain high heat conduction high abrasion organosilicon non-viscous paint 1.
Embodiment 2:
(1) preparation of ceramic resin
Ludox 100g, water 100g are mixed, and using vinegar acid for adjusting pH is 4, adds 100g methylTrimethoxy silane stirs 5h under the environment of 30 DEG C, obtains ceramic resin 2.
(2) silicone modified polyester resin
By binary acid (terephthalic acid (TPA)) 107.9g (0.65mol), trihydroxylic alcohol (trimethylolethane) 78g(0.65mol), crosslinking catalyst (tetrabutyl titanate) 5g; , dimethylbenzene 8g mix after be warming up to 170 DEG C,After insulation 8h, be cooled to again 80 DEG C, obtain mylar; Then add organic solvent (dipropylene glycol methyl ether)50g and silicone oligomer (Dow Corning Corporation 233) 161g; Be warming up to 110 DEG C, after insulation 3h, fall againTemperature is to 80 DEG C, and finally adding organic solvent dipropylene glycol methyl ether to make solid content is 51wt%, obtains organosilicon and changesProperty mylar 2.
(3) preparation of organosilicon non-viscous paint
Ceramic resin 20g prepared by step (1), organosilicon modified polyester 30g, charcoal prepared by step (2)Black 10g, aluminium oxide 20g, Graphene 1g, ethylene glycol ether acetate 29g are ground to required after mixingParticle diameter, filters to obtain high heat conduction high abrasion organosilicon non-viscous paint 2.
Embodiment 3:
(1) preparation of ceramic resin
Ludox 100g, water 300g are mixed, and using vinegar acid for adjusting pH is 5, adds 300g phenylTrimethoxy silane, 700g MTMS stirs 2h under the environment of 50 DEG C, obtains ceramic treeFat 3.
(2) silicone modified polyester resin
By binary acid (M-phthalic acid) 77.9g (0.47mol), (terephthalic acid (TPA)) 30g (0.18mol),Trihydroxylic alcohol (trimethylolpropane) 174.2g (1.3mol), crosslinking catalyst (dioctyl tin oxide) 7.5g; ,Dimethylbenzene 9g is warming up to 180 DEG C after mixing, and after insulation 6h, lowers the temperature 85 DEG C again, obtains mylar; Then addEnter organic solvent (propylene glycol monomethyl ether) 50g and silicone oligomer (IC836 of Wa Ke company) 120g; RiseTemperature, to 120 DEG C, is cooled to 85 DEG C after insulation 2h again, finally adds organic solvent propylene glycol monomethyl ether to make solid contentFor 55wt%, obtain silicone modified polyester resin 3.
(3) preparation of organosilicon non-viscous paint
Ceramic resin 30g prepared by step (1), organosilicon modified polyester 60g prepared by step (2),Silica 5g, CNT 5g, diethylene glycol monobutyl ether acetate 20g are ground to required grain after mixingFootpath, filters to obtain high heat conduction high abrasion organosilicon non-viscous paint 3.
Embodiment 4:
(1) preparation of ceramic resin
Ludox 100g, water 200g are mixed, and using vinegar acid for adjusting pH is 3, adds 600g phenylTrichlorosilane, 150g methyl trichlorosilane stirs 3h under the environment of 25 DEG C, obtains ceramic resin 4.
(2) silicone modified polyester resin
By binary acid (terephthalic acid (TPA)) 107.9g (0.65mol), trihydroxylic alcohol (trimethylolethane) 87.1g(0.65mol), trihydroxylic alcohol (trimethylolpropane) 78g (0.65mol) crosslinking catalyst (diisooctyl oxygenChange tin) 9g; , dimethylbenzene 10g is warming up to 190 DEG C after mixing, insulation is cooled to 90 DEG C after 4h again, is gatheredEster resin; Then add organic solvent (isobutanol) 50g and silicone oligomer (SHIN-ETSU HANTOTAI's organic siliconresinKR150) 140g; Be warming up to 130 DEG C, after insulation 1h, be cooled to again 90 DEG C, finally add organic solvent differentIt is 57wt% that butanols makes solid content, obtains silicone modified polyester resin 4.
(3) preparation of organosilicon non-viscous paint
Ceramic resin 60g prepared by step (1), organosilicon modified polyester 40g prepared by step (2),Silica 1 0g, aluminium oxide 20g, graphite 10g, propionic acid-3-ether ethyl ester 40g mix rear grindingTo required particle diameter, filter to obtain high heat conduction high abrasion organosilicon non-viscous paint 4.
Comparative example:
(1) preparation of silicone modified polyester resin
By binary acid (terephthalic acid (TPA)) 107.9g (0.65mol), trihydroxylic alcohol (trimethylolpropane) 131.3g(0.98mol), crosslinking catalyst (butyl titanate 7.5g, tetrabutyl titanate 2.3g), dimethylbenzene 10.7gAfter mixing, be warming up to 200 DEG C, after insulation 2h, be cooled to again 80 DEG C, obtain mylar; Then add organicSolvent (butanols) 50g and silicone oligomer (KR214 of company of SHIN-ETSU HANTOTAI) 150g; Be warming up to 110 DEG C,After insulation 3h, be cooled to 80 DEG C, finally adding organic solvent methyl isoamyl ketone to make solid content is 60wt% again,Obtain silicone modified polyester resin.
(2) preparation of organosilicon non-viscous paint
By step 1) organosilicon modified polyester 50g, silica 1 0g, aluminium oxide 10g, the carbon black preparedAfter 10g, methyl isoamyl ketone 20g mix, be ground to required particle diameter, filter to obtain organosilicon non-viscous paint.
Test case: high heat conduction high abrasion organosilicon non-viscous paint test performance is as shown in table 1:
Table 1:
| Embodiment | Adhesive force | Hardness (H) | Abrasion resistance | Thermal conductivity (W/mK) |
| Comparative example | 0 grade | 3 | 200 times | 500 |
| Embodiment 1 | 0 grade | 4 | 1200 times | 1050 |
| Embodiment 2 | 1 grade | 3 | 800 times | 1200 |
| Embodiment 3 | 1 grade | 4 | 750 times | 800 |
| Embodiment 4 | 1 grade | 3 | 630 times | 920 |
Claims (9)
1. a high heat conduction high abrasion organosilicon non-viscous paint, is characterized in that, described coating is by making following compositionBecome, the weight portion of each component is:
2. the high heat conduction high abrasion of one according to claim 1 organosilicon non-viscous paint, is characterized in that instituteThe ceramic resin of stating is made by following preparation method: after Ludox, water are mixed, regulating pH is 3～5, addsSilane, stirs 1～5h at 25 DEG C～65 DEG C, obtains ceramic resin.
3. the high heat conduction high abrasion of one according to claim 2 organosilicon non-viscous paint, is characterized in that siliconThe mass ratio of colloidal sol and water is 1: 1～3, and the mass ratio of Ludox and silane is 1: 1～10.
4. according to the high heat conduction high abrasion of the one described in claim 2 or 3 organosilicon non-viscous paint, it is characterized in that,Described silane has one or more in following structural formula:
Wherein R is selected from one in methyl, phenyl, R1Be selected from chlorine, methoxyl group, ethyoxyl, hydroxyl a kind of.
5. the high heat conduction high abrasion of one according to claim 1 organosilicon non-viscous paint, is characterized in that instituteThe heat conduction auxiliary agent of stating is selected from a kind of or several in Graphene, CNT, diamond, graphite, aluminium powder, silver powderKind.
6. the high heat conduction high abrasion of one according to claim 1 organosilicon non-viscous paint, is characterized in that instituteThe solvent of stating is selected from divalent ester mixture, ethylene glycol ether acetate, diethylene glycol monobutyl ether acetate, isobutylOne or more in acid isobutyl ester, propionic acid-3-ether ethyl ester and methyl isoamyl ketone.
7. the high heat conduction high abrasion of one according to claim 1 organosilicon non-viscous paint, is characterized in that instituteThe silicone modified polyester resin of stating is made by following steps: by binary acid, trihydroxylic alcohol, crosslinking catalyst, twoToluene is warming up to 170～210 DEG C after mixing, and after insulation 1～8h, is cooled to 80-90 DEG C again, obtains mylar;Then add organic solvent and silicone oligomer; Be warming up to 110～130 DEG C, after insulation 1～3h, be cooled to again80-90 DEG C, finally adding organic solvent to make solid content is 51～60wt%, obtains silicone modified polyester resin.
8. the high heat conduction high abrasion of one according to claim 7 organosilicon non-viscous paint, is characterized in that twoUnit's acid is 1: 1～2 with the mol ratio of trihydroxylic alcohol, and binary acid and crosslinking catalyst weight ratio are 1: 0.02～0.1,The weight ratio of binary acid and dimethylbenzene is 1: 0.06～0.1, and the weight ratio of binary acid and silicone oligomer is 1:1.0～1.5。
9. according to the high heat conduction high abrasion of the one described in claim 7 or 8 organosilicon non-viscous paint, it is characterized in that,Described binary acid is selected from one or both in M-phthalic acid, terephthalic acid (TPA), and described trihydroxylic alcohol is selected fromOne or both in trimethylolethane, trimethylolpropane, described crosslinking catalyst is selected from metatitanic acid four fourthsOne or more in ester, tetrabutyl titanate, dioctyl tin oxide, diisooctyl tin oxide, described hasMachine solvent be selected from dipropylene glycol methyl ether, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, butanols, isobutanol,One or more in 1-Methoxy-2-propyl acetate and DPG monobutyl ether acetate, described silicone oligomerWeight average molecular weight be 700～2200, and contain in methoxyl group, ethyoxyl, hydroxyl a kind of, methoxyl group, secondA kind of in oxygen base, hydroxyl is 3～22% of silicone oligomer percentage by weight.
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| CN106592189A (en) * | 2016-12-13 | 2017-04-26 | 安徽省煜灿新型材料科技有限公司 | Wear-resistant anti-adhesion iron baseplate and preparation method |
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| CN108178938A (en) * | 2017-12-20 | 2018-06-19 | 广东至诚化学工业有限公司 | A kind of diamond ceramic coating and preparation method and application |
| CN108659586A (en) * | 2018-05-26 | 2018-10-16 | 湖南凯斯利新材料有限公司 | A kind of long-acting automatically cleaning aqueous inorganic ceramic coating and preparation method thereof |
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