CN112778496A - PAE polyurea UV resin, synthetic method and coating composition prepared from PAE polyurea UV resin - Google Patents
PAE polyurea UV resin, synthetic method and coating composition prepared from PAE polyurea UV resin Download PDFInfo
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- CN112778496A CN112778496A CN202011627807.XA CN202011627807A CN112778496A CN 112778496 A CN112778496 A CN 112778496A CN 202011627807 A CN202011627807 A CN 202011627807A CN 112778496 A CN112778496 A CN 112778496A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
- C08G18/346—Polycarboxylic acids having at least three carboxylic acid groups having four carboxylic acid groups
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
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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
- 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
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Abstract
The invention discloses PAE polyurea UV resin, a synthesis method and a coating composition prepared by the PAE polyurea UV resin. The product is used for preparing the coating composition of the single-component photocuring polyurea resin, and has the characteristics of strong adhesive force, skid resistance, wear resistance, aging resistance, strong penetration, no foaming, yellowing resistance and the like.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to PAE polyurea UV resin, a synthetic method and a coating composition prepared by the PAE polyurea UV resin.
Background
The polyurea material has excellent elasticity, water resistance, skid resistance, wear resistance and other performances, is an excellent coating and bonding material, but has the defects of easy occurrence of phenomena of shell formation, foaming and the like after being sprayed by two components due to severe polyurea reaction, and limits the use of the material.
Polyaspartic Acid Ester (PAE) is a novel sterically hindered amine structure developed in recent years, and the chemical structural formula of the PAE is shown as a formula I. The polyaspartic acid ester derivatives with different physical properties can be obtained by adopting substituent groups with different structures, and the derivative coating film has excellent yellowing resistance, ultraviolet aging resistance and wear resistance, and is an important polyurea polymer. In the prior art, Polyaspartic Acid Ester (PAE) is used for preparing a floor, and has the advantages of polyurea coating, but beautiful patterns cannot be made by technical means such as silk screen printing, printing and the like due to the limitation of curing time of a two-component coating. The surface and the bottom layer of the paint film are firstly cured under the influence of humidity and moisture in the curing process, and the post-curing in the middle of the paint film is easy to generate curing shrinkage, so that the surface of the paint film has uneven grains, and the phenomena of edge warping, shell rising and the like caused by internal stress shrinkage are easily caused; and the bubbles that can not be discharged below after the surface layer is solidified are sealed, the appearance of the bubbles affects the attractiveness and the service life of the terrace. The PAE polyurea resin is used as a base coat, other coatings on the current market are used as a top coat, so that the interlayer adhesion, the wear resistance and the aging resistance of the coatings can not meet the requirements of the PAE polyurea coatings, and the black or blue coatings can not be deeply cured.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for synthesizing PAE polyurea resin; it is a further object of the present invention to provide PAE polyurea UV resins obtained by the aforementioned process; the invention also aims to provide an ultraviolet curing PAE polyurea coating composition compounded by the PAE polyurea UV resin, which has strong adhesion to the PAE polyurea resin layer, good permeability, skid resistance, wear resistance and aging resistance.
The technical scheme is as follows: in order to achieve the above object, the invention provides a method for synthesizing PAE polyurea UV resin, comprising the following steps:
(1) performing nucleophilic reaction addition on polyaspartic ester and diisocyanate monomer to obtain polyaspartic ester diisocyanate prepolymer;
(2) performing nucleophilic reaction addition on hydroxyl acrylate and diisocyanate monomer to obtain a single-end-capped acrylate diisocyanate prepolymer;
(3) and mixing the polyaspartic ester diisocyanate prepolymer and the single-end-capped acrylate diisocyanate prepolymer for reaction to obtain the polyaspartic ester polyurea UV resin.
The polyaspartic acid ester in the step (1) is shown as a formula (I):
wherein X is selected from polyester, C1-C12 carbon chain containing aromatic hydrocarbon or not containing aromatic hydrocarbon;
y is
Wherein R is1A saturated carbon chain selected from C1-C3;
the amine value of the polyaspartic acid ester is 60-260.
In a preferred embodiment of the present invention, X in the polyaspartic acid ester of formula (I) is selected from a substituted or unsubstituted aliphatic carbon chain of C6-C12, more preferably X is selected from any one of hexyl, methyl or ethyl substituted hexyl, and halogen substituted hexyl.
R1 is selected from C1-C4 straight or branched carbon chain, more preferably, R1 is selected from methyl or ethyl.
The reaction for preparing the polyaspartic ester diisocyanate prepolymer in step (1) of the invention is as follows:
wherein n represents the polymerization degree of the prepolymer of the aspartate diisocyanate, the polymerization degree is generally in the range of 0-5, the molar ratio of the polyaspartate to the diisocyanate is 6: 0-5, the molecular weight is the minimum when the molar ratio is 6:0, the viscosity of the reaction system is the minimum, the molecular weight is larger when the ratio is 6:5, and the viscosity of the reaction system is improved. If the ratio reaches 7:6 or even higher, the viscosity of the system is too high, which is not favorable for the next reaction. In a preferred embodiment of the present invention, the polymerization degree n is 0 to 2. Table 1 shows the graph of polymerization versus viscosity for the aspartate diisocyanate prepolymer:
TABLE 1
| n | 0 | 1 | 2 | 3 | 4 | 5 |
| Viscosity/cps | 215 | 519 | 1500 | 2600 | 6800 | 11000 |
The diisocyanate monomer is dropwise added for 0.5 to 4 hours in the step (1) at the temperature of between 20 and 40 ℃, and then the mixture is stirred for 1 to 3 hours at normal temperature. In the step (1), no reaction catalyst is added, and under the condition, the linear molecules in the step (1) can be ensured to avoid side reaction
Further, the reaction for preparing the mono-blocked acrylate diisocyanate prepolymer in step (2) of the present invention is as follows:
wherein, the acrylic acid hydroxyl ester is selected from any one of but not limited to acrylic acid hydroxyl methyl ester, acrylic acid hydroxyl ethyl ester and acrylic acid hydroxyl propyl ester, wherein, the hydroxyl group is necessarily positioned at the end of a carbon chain; that is, Z in the above formula is a linear alkyl group of C1-C3.
And (3) dropwise adding acrylic hydroxy ester to react for 3 hours at the temperature of 70-90 ℃, and keeping the temperature for 2 hours after dropwise adding, wherein the reaction temperature is preferably 80 ℃. The reaction in the step can be added with an organic tin catalyst, and the adding amount of the organic tin catalyst is 0.01-0.05% of the total mass of the reaction system.
Further, the organic tin catalyst is selected from any one or a combination of two of stannous octoate and dibutyltin dilaurate.
And (3) adding a polymerization inhibitor into the reaction system in the step (2) for protecting the vinyl group of the acrylic ester, wherein the adding amount of the polymerization inhibitor is 0.01-0.1% of the total mass of the reaction system. The polymerization inhibitor is selected from any one or combination of p-hydroxyanisole, hydroquinone, p-benzoquinone and p-tertiary butyl catechol.
As already mentioned above, step (2) according to the invention is "single-blocked" with a polymerization inhibitor, so that the molar ratio NCO: OH in step (2) is 2: 1.
And (2) blocking one side to prevent a byproduct with two closed ends, slowly dripping acrylic hydroxy ester into diisocyanate to increase the reaction temperature, adding a catalyst to improve the NCO activity and increase the contact probability of free NCO and hydroxyl, and particularly, reducing the dripping speed to the minimum in the later dripping stage to minimize the amount of unreacted isocyanate monomer after the reaction.
The diisocyanate monomer used in step (1) and step (2) of the present invention is selected from any one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. In a preferred embodiment of the present invention, the diisocyanate monomer is isophorone diisocyanate. The isocyanate has good weather resistance and yellowing resistance.
The reaction formula of the step (3) is as follows:
and (3) dropwise adding a single-end-capped acrylate diisocyanate prepolymer at the temperature of 20-40 ℃ for reaction for 15-45 minutes, and then preserving heat at the temperature of 50-60 ℃ for 1-3 hours. The determination of the end point of the reaction was that the NCO content was 5mgKOH/g or less.
In the step (3), the molar ratio of the polyaspartic acid ester diisocyanate prepolymer to the single-ended acrylate diisocyanate prepolymer is 1: 1.8-2.0, preferably 1:1.90, and the proportion ensures that the-NH in the system is properly excessive, so that the NCO in the system is completely consumed, and the storage stability of the resin is facilitated.
The invention also provides a poly aspartic ester polyurea UV resin, which is shown as the formula (II):
wherein X is selected from polyester, C1-C12 carbon chain containing aromatic hydrocarbon or not containing aromatic hydrocarbon, more preferably selected from substituted or unsubstituted aliphatic carbon chain of C6-C12, most preferably X is selected from hexyl, methyl or ethyl substituted hexyl, or halogen substituted hexyl.
Y is
Wherein R is1Selected from saturated carbon chains of C1-C3,
z is C1-C3 straight-chain alkyl,
r2 is any one selected from tolyl, 1' -methylenediphenyl, hexamethylene, and 3,5, 5-trimethyl-2-cyclohexen-1-onyl, and n is 0 to 5, preferably 0 to 2.
The polyaspartate polyurea UV resin is amber transparent liquid. The bonding force to glass is more than or equal to 25MPa, and the bonding force to PAE polyurea reaches the damage of a base material; the black and blue coatings with good photosensitivity of the resin can be well cured, and self tertiary amino promotes ultraviolet surface drying and deep curing. The coating is anti-skid, has good wear resistance and is good in pigment dispersibility and uniform in coloring.
The invention provides a coating composition prepared from PAE polyurea UV resin, at least one leveling agent, at least one rheological agent and at least one photoinitiator.
The coating composition comprises the following components in parts by weight:
wherein, the photo-curing monomer comprises but is not limited to any one or combination of TPGDA, HDDA, TMPTA and IBOA.
Wherein, the filler comprises but is not limited to any one or more of rutile type titanium dioxide, silicon micropowder, heavy calcium carbonate, light calcium carbonate, nano glass micropowder and super-hard wear-resistant powder.
Wherein, the leveling agent comprises, but is not limited to, any one or combination of BYK-333 and BYK-354.
Wherein, the rheological agent comprises but is not limited to any one or more of fumed silica and hydroxymethyl cellulose.
Wherein, the photoinitiator includes but is not limited to 1173, 184, 907, TPO, 819, 651, ITX and TPOL.
Has the advantages that: in the early stage of the reaction between the PAE and the diisocyanate, the diisocyanate is added dropwise to control the reaction rate, and the acrylate isocyanate with single end blocked is used for blocking in the later stage of the reaction, so that the linear structure of the whole molecule is improved. The ultraviolet curing PAE polyurea resin prepared by the method has the characteristics of strong adhesion to a PAE polyurea bottom layer, skid resistance, wear resistance, aging resistance, strong permeation, no foaming and the like, is blue and completely cured after being irradiated for 10 seconds based on the standard coating ultraviolet of a terrace coating, has no crust foaming phenomenon, has smooth and line-free surface without bubbles, is resistant to ultraviolet irradiation and yellowing for 4000 hours, and is resistant to 168 hours without bubbles and peeling. The dry friction coefficient reaches more than 0.8.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
A method for synthesizing polyaspartic ester polyurea UV resin comprises the following three steps:
step 1 preparation of polyaspartic acid ester diisocyanate prepolymer
Performing nucleophilic reaction addition on polyaspartic ester and diisocyanate monomer to obtain polyaspartic ester diisocyanate prepolymer;
wherein X is hexyl;
y is
Wherein R is1Is ethyl, n is 2.
The amine value of polyaspartic acid esters is 100-240.
Dripping diisocyanate monomer at 20-40 deg.c for 0.5-4 hr and stirring at normal temperature for 1-3 hr. The step does not add a reaction catalyst, and under the condition, the linear molecules in the step (1) can be ensured to avoid side reaction.
Step 2 preparation of Single-end-capped acrylate diisocyanate prepolymer
The method comprises the steps of carrying out nucleophilic reaction addition on hydroxyl acrylate and diisocyanate monomers to obtain a single-end-capped acrylate diisocyanate prepolymer.
The hydroxyl acrylate is selected from hydroxyethyl acrylate or hydroxypropyl acrylate, stannous octoate or dibutyltin dilaurate is added in the reaction as a catalyst, and the addition amount is 0.01-0.05% of the total mass of the reaction system. Dripping acrylic hydroxy ester at 70-90 deg.C for 3 hr, and holding at 80 deg.C for 2 hr.
A polymerization inhibitor is also added into the reaction system, and the addition amount of the polymerization inhibitor is 0.01-0.1 percent of the total mass of the reaction system. The polymerization inhibitor is selected from any one or combination of p-hydroxyanisole, hydroquinone, p-benzoquinone and p-tertiary butyl catechol.
The diisocyanate monomer used in the above two steps is isophorone diisocyanate.
Step 3, mixing the prepolymer to prepare polyaspartic acid ester polyurea UV resin
And mixing the polyaspartic ester diisocyanate prepolymer and the single-end-capped acrylate diisocyanate prepolymer for reaction to obtain the polyaspartic ester polyurea UV resin.
The mono-end-capped acrylate diisocyanate prepolymer is dripped at the temperature of 25 ℃ for reaction for 30 minutes, and then the temperature is kept at 50-60 ℃ for 1.5 hours. The determination of the end point of the reaction was that the NCO content was 5mgKOH/g or less. The mol ratio of the polyaspartic acid ester diisocyanate prepolymer to the single-end-capped acrylate diisocyanate prepolymer is 1:1.90,
example 2
A PAE polyurea UV resin, represented by formula (II):
wherein X is hexyl selected from substituted or unsubstituted C6-C12 aliphatic carbon chains, most preferably X is hexyl.
Y is
Z is ethyl, R2 is methylene-3, 5, 5-trimethylcyclohexyl, and n is 2.
The polyaspartic ester polyurea UV resin is amber transparent liquid, the bonding force to glass is more than or equal to 25MPa, and the bonding force to PAE polyurea reaches the damage of a base material; the resin has good photosensitivity, and self tertiary amino promotes ultraviolet surface drying and deep curing. The coating is anti-skid, has good wear resistance and is good in pigment dispersibility and uniform in coloring.
Example 3
The single-component PAE polyurea UV resin coating comprises the following components in percentage by mass:
the coating was a blue opaque viscous liquid with a viscosity of 1550cps/25 ℃.
Comparative example 1
The comparative example provides a single-component ultraviolet-curable PAE polyurea resin coating which comprises the following components in percentage by mass:
CN989 is a trifunctional aliphatic polyurethane acrylic oligomer produced by SARTOMER (SARTOMER) and used for UV/EB curing coatings.
Comparative example 2
The comparative example provides a two-component naturally cured PAE polyurea resin coating comprising, by mass percent:
the component A comprises:
and B component:
HDI trimer HI100 curing agent 45.3 Pasvus
Test examples
The screen printing technology is adopted in the embodiment 3, the comparative example 1 and the comparative example 2, the screen printing thickness of the screen printing technology is 20-80um respectively printed on the glass and the PAE polyurea resin surface layer, the comparative example 2 is bi-component natural curing, the curing humidity is 80%, and the temperature is 25 ℃; example 3 and comparative example 1 are single-component uv curable resins with a light source of a 1 kw high pressure mercury lamp, curing humidity 80%, temperature 25 ℃. The coating film appearance, drying time, hardness, tensile strength, wear resistance, skid resistance, adhesion, water resistance, acid resistance, alkali resistance, impact resistance and ultraviolet resistance are tested according to the test requirements according to the GB/T22374-2008 terrace coating standard. The results are shown in table 2:
TABLE 2 floor coating material performance comparison test
Experiments show that the water resistance, acid and alkali resistance, ultraviolet resistance, wear resistance and interlayer adhesion of the light-cured resin are superior to those of the traditional ultraviolet light-cured resin, and the paint film appearance and operability of the resin are superior to those of PAE bi-component polyurea. The practicability and the aesthetic property required by the target are realized.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (13)
1. A method for synthesizing PAE polyurea UV resin is characterized by comprising the following steps:
(1) performing nucleophilic reaction addition on polyaspartic ester and diisocyanate monomer to obtain polyaspartic ester diisocyanate prepolymer;
(2) performing nucleophilic reaction addition on hydroxyl acrylate and diisocyanate monomer to obtain a single-end-capped acrylate diisocyanate prepolymer;
(3) and mixing the polyaspartic ester diisocyanate prepolymer and the single-end-capped acrylate diisocyanate prepolymer for reaction to obtain the polyaspartic ester polyurea UV resin.
2. The method for synthesizing the PAE polyurea UV resin according to claim 1, wherein: the polyaspartic acid ester in the step (1) is shown as a formula (I):
wherein X is selected from organosilicon, C1-C12 carbon chain containing aromatic hydrocarbon or no aromatic hydrocarbon;
y is
Wherein R is1A saturated carbon chain selected from C1-C4;
the amine value of the polyaspartic acid ester is 60-260;
the hydroxyl acrylate is selected from hydroxymethyl acrylate, hydroxyethyl acrylate and hydroxypropyl acrylate, wherein the hydroxyl is positioned at the tail end of a carbon chain.
3. The method for synthesizing the PAE polyurea UV resin according to claim 1 or 2, wherein: the diisocyanate monomer is any one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
4. The method for synthesizing PAE polyurea UV resin according to claim 3, wherein: the organic tin catalyst selected in the step (2) is added in an amount of 0.01-0.05% of the total mass of the reaction system.
5. The method for synthesizing PAE polyurea UV resin according to claim 4, wherein: dripping a diisocyanate monomer at the temperature of 20-40 ℃ for 0.5-4 hours, and then stirring at normal temperature for 1-3 hours; and (3) dropwise adding acrylic hydroxy ester to react for 3 hours at the temperature of 70-90 ℃, and keeping the temperature for 2 hours after dropwise adding.
6. The method for synthesizing PAE polyurea UV resin according to claim 5, wherein: and (3) adding a polymerization inhibitor into the reaction system in the step (2), wherein the adding amount of the polymerization inhibitor is 0.01-0.1% of the total mass of the reaction system.
7. The method for synthesizing PAE polyurea UV resin according to claim 6, wherein: the molar ratio of the polyaspartic acid ester diisocyanate prepolymer to the single-end-capped acrylate diisocyanate prepolymer in the step (3) is 1: 1.6-2.2.
8. The method for synthesizing PAE polyurea UV resin according to claim 7, wherein: and (3) dripping polyaspartic ester diisocyanate prepolymer to react for 15-45 minutes at the temperature of 20-40 ℃, and then preserving heat for 1-3 hours at the temperature of 50-60 ℃.
9. A PAE polyurea UV resin, represented by formula (II):
wherein X is selected from polyester, C1-C12 carbon chain containing aromatic hydrocarbon or not containing aromatic hydrocarbon,
y is
Wherein R is1Selected from saturated carbon chains of C1-C3,
z is C1-C3 straight-chain alkyl,
r2 is selected from any one of tolyl, 1' -methylenediphenyl, hexamethylene and methylene-3, 5, 5-trimethylcyclohexyl, and n is 0-5.
10. The PAE polyurea UV resin according to claim 9, wherein:
the bonding force to glass is more than or equal to 25MPa, and the bonding force of the PAE polyurea coating reaches the substrate damage level; the cured paint film has good flatness and does not bubble, and black blue paint films and the like can be deeply cured.
11. A coating composition of PAE polyurea UV resin characterized by: comprising the PAE polyurea UV resin of claim 9, and
at least one leveling agent,
at least one organic pigment,
at least one rheological agent selected from the group consisting of,
at least one photoinitiator.
12. The PAE polyurea UV resin coating composition according to claim 11, comprising the following components in parts by weight:
13. the coating composition of PAE polyurea UV resin according to claim 11 or 12, characterized in that:
the light-cured monomer comprises any one or combination of TPGDA, HDDA, TMPTA and IBOA;
the filler comprises any one or a combination of more of rutile titanium dioxide, silicon micropowder, heavy calcium, light calcium, nano glass micropowder and superhard wear-resistant powder;
the leveling agent comprises any one or a combination of BYK-333 and BYK-354;
the rheological agent comprises any one or combination of more of fumed silica and hydroxymethyl cellulose;
the photoinitiator comprises any one or the combination of more of 1173, 184, 907, TPO, 819, 651, ITX and TPOL.
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| CN115028802A (en) * | 2021-07-13 | 2022-09-09 | 深圳飞扬兴业科技有限公司 | Polyaspartic acid acrylic resin, preparation method thereof and UV material |
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| US20040110917A1 (en) * | 2002-12-05 | 2004-06-10 | Karsten Danielmeier | In-situ preparation of polyaspartic ester mixutures |
| GB201705163D0 (en) * | 2017-03-30 | 2017-05-17 | Dfs Composites Ltd | Coating |
| CN110396053A (en) * | 2019-07-30 | 2019-11-01 | 深圳市前海博扬研究院有限公司 | Asparagus fern polyureas performed polymer and preparation method and a kind of coating |
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