Improve lac and the method for modifying thereof of varnish thermotolerance
Technical field
The present invention relates to a kind of lac, particularly relate to a kind of lac and the method for modifying thereof that improve varnish thermotolerance.
Background technology
The feature of environmental protection of coating is a major subjects of wood lacquer industry.The surface protection major requirement material of timber provides good mechanical property, aesthetic property and weather etc.Woodwork coating is mainly used in Furniture manufacture and interior decoration.Wherein, furniture manufacturing industry holds the balance to woodwork coating industry.And in furniture manufacturing industry, outlet furniture is the engine of promotion industry.The market requirement is powerful.Meanwhile, Domestic Environment has the development being beneficial to environment protecting paint for wooden articles.On June 1st, 2010, " in the indoor decorating and refurnishing materials solvent wood coatings limits of harmful substances " national standard being drafted formulation by national coating and Pigments Standardization Technical Committee is formally implemented.Along with the strict enforcement of this standard, the market outlook of environment friendly wood coatings are very wide.
Lac (Shellac, also known as shellac) is by the oozy a kind of natural resin of tachardia lacca, have nontoxic, electrical insulation capability good, binding property and thermoplastic strong; The characteristics such as waterproof, protection against the tide, antirust, corrosion resistant, be widely used in military affairs, electrically, coating, paint, machinery, rubber, plastics, process hides, papermaking, medicine, in the industry such as food.Shellac varnish dissolves brown translucent or light yellow clear liquid in ethanol by shellac, white shellac (popular name shellac) or refined bleached lac.Dry rapidly after brushing, formed and there is excellent hardness and electrical insulating property protective film, and the color and luster of light can be showed through polishing grinding.Be mainly used in brushing woodenware and electrical apparatus insulation material.Shellac varnish uses the history of existing more than one thousand years as a kind of traditional wood lacquer, and its consumption reaches peak in the eighties in last century.Because traditional shellac varnish film quality is more crisp, thermotolerance and weather resistance are also poor compared with synthetic coating, unsuitable external application.Along with the appearance of synthetic coating, the feature of shellac varnish poor heat resistance makes the application of shellac varnish decline by containing to turn.Along with the raising of people's living standard, concern for the environment and own health, uphold nature has become a kind of fashion.Synthetic coating to the hazardness of environmental protection and health progressively be familiar with by people.Lac base wood lacquer except there is excellent use properties, also impart that lac product is natural, environmental protection, healthy excellent attribute.The development of thermotolerance to the application of shellac varnish product and lac base environment protecting paint for wooden articles industry how improving shellac varnish has very important meaning.The present invention utilize dry vegetable oil, glycerine, Gum Rosin, tetramethylolmethane under the molten state of laccol in addition modification promotor with lac, modification is carried out to varnish and the toughness of shellac varnish and thermotolerance is largely increased.Press GBT4893.3-2005 " furniture surface dry heat resistance assay method ", GB/T4893.2-2005 " furniture surface wet-heat resisting assay method " through quality product research institute of Yunnan Province to detect, compared with the varnish that the varnish that the modified shellac utilizing the present invention to produce makes and common lac make, dry heat resistance performance improves 12-25%, and wet-hot aging performance improves 10-28%.
The research and development of lac modification technology are focuses of current lac application technical research.Through having the close patent that existing literature search finds: 1) patent of invention number: CN100415840C, denomination of invention: the method for environment friendly coated layer material is prepared in a kind of lac modification.Object is to provide a kind of method that environment friendly coated layer material is prepared in lac modification, namely form by chemical reaction the physical and mechanical properties that crosslinking structure improves lac, add into sustained release dosage, inorganic salt and the method being prepared by environmentally friendly thinner to environment friendly coated layer material.And make material in construction and use procedure to environment and body harmless.The multiple carboxyl reaction that the Basic Mechanism of this invention is in multi-functional organic amine and lac forms the object that amido linkage reaches crosslinked.The object that the mechanical property that the formation of cross-linked structure improves lac reaches material protection improves simultaneously and stops extraneous factor to the erosional competency of metallic surface; Amido linkage can improve lac and interface cohesive force and to metallic substance resistance to corrosion, add thinner and inorganic salt etc. and the Corrosion Protection of modified shellac had significantly improve further.Aggregation, the aggregation of this invention add inorganic salt face with sustained release dosage or aggregation with sustained release dosage and mix, and obtain the coated material of different components, are applied to timber, copper and the non-ferrous metal surface such as alloy, aluminum magnesium alloy and have good protection preservative effect.This material can solid or solution state store, stable performance.The coating prepared by this material for thinner, belongs to environment friendly coated layer material with non-benzene homologues solvent.But to how not related to by the thermotolerance of adding softening agent and modification promotor raising shellac varnish.2) number of patent application: 200810117661.7 denominations of invention: shellac varnish; The invention provides the shellac varnish that a kind of preparation method is simple, nontoxic pollution-free, result of use are good.For reaching above-mentioned technical requirements, shellac varnish involved in the present invention adopts following technical scheme: main raw material composition of the present invention comprises: shellac, solvent etc.Technology described by this patent is make shellac varnish in ethanol shellac being dissolved in 95%, belongs to typical shellac varnish traditional manufacturing technique, poor heat resistance.3) number of patent application: 00123626.1 denomination of invention: a kind of production method of lacquer, invention relates to a kind of production method of lacquer, natural shellac varnish is milled into 50-200 object powder, dip treating 4-300 hour is carried out under putting into airtight Glass Containers what 10 DEG C of-80 DEG C of temperature after being mixed with hydrogen peroxide liquid by lacquer powder, every 10 grams of lacquer powder mixtures 10 milliliters of-100 milliliters of hydrogen peroxide liquid, dry the lacquer taking-up after dip treating and namely can be made into red lacquer, look lacquer or colourless lacquer.To how but not related to by the thermotolerance of modification technology raising shellac varnish.4) number of patent application: 01112705.8 denomination of invention: printing paint for protecting wooden articles, a kind of printing paint for protecting wooden articles, comprise protective liquid and bottom closing paint, protective liquid is by ethanol, phosphorothionate, dimethyl fumarate, Sorbic Acid, creosote and lac bar mix and blend composition, bottom closing paint is by medium-oil-length Semen Lini oil modified alkyd resin, No. 200 industrial napthas, dimethylbenzene, zinc naphthenate, cobalt naphthenate, copper naphthenate and pyrethroid emulsifiable concentrate mix and blend composition, by protective liquid brushing in wood substrates, protective liquid can play the effect of pest control and anticorrosion, then by bottom closing paint brushing on timber, composition each in protective liquid can be closed in wood by bottom closing paint, keep the effect of pest control and anticorrosion.To how but not related to by the thermotolerance of modification technology raising shellac varnish.5) number of patent application: 201110197401.7 denominations of invention: a kind of aqueous bottom coating for wood products.Invention provides a kind of aqueous bottom coating for wood products, the weight percent of each component of its constitutive material is: potter's clay powder 6.134-7.535%, calcium carbonate 14.45-17.45%, shellac 0.416-0.498%, animal skin glue 4.156-4.956%, pure water 65.391-71.261%, alcohol 1.495-1.695%, sticky rice flour 2.078-2.478%.Aqueous bottom coating for wood products of the present invention has contamination-free, has no irritating odor, nontoxic, the formaldehyde hidden danger avoided in common coating, and flatness is high, and construction easily; adhesivity is strong, and flame retardant resistance is high, and coating hardness height easily forms protective layer; there is quick-drying, the feature of not after-tacking simultaneously.To how but not related to by the thermotolerance of modification technology raising shellac varnish.6) number of patent application: 201110197398.9 denominations of invention: a kind of aqueous surface coating for wood products.Invention provides a kind of aqueous surface coating for wood products, and the weight percent of each component of its constitutive material is: potter's clay powder 24.286-29.286%, shellac 0.813-0.973%, animal skin glue 5.452-6.452%, water 56.524-62.524%, alcohol 1.388-1.588%, starch 4.857-5.857%.Aqueous surface coating for wood products of the present invention has contamination-free, has no irritating odor, nontoxic, the formaldehyde hidden danger avoided in common coating, and flatness is high, and construction easily; adhesivity is strong, and flame retardant resistance is high, and coating hardness height easily forms protective layer; there is quick-drying, the feature of not after-tacking simultaneously.To how but not related to by the thermotolerance of modification technology raising shellac varnish.7) number of patent application: 201110197399.3 denominations of invention: a kind of wood-product aqueous crack coating material.Invention provides a kind of wood-product aqueous crack coating material, and the weight percent of each component of its constitutive material is: flatting silica 7.139-9.439%, shellac 1.910-2.310%, alcohol 79.388-86.388%, sticky rice flour 4.46-5.56%.Wood-product aqueous crack coating material of the present invention has contamination-free, has no irritating odor, nontoxic, the formaldehyde hidden danger avoided in common coating, and plasticity-is high, and construction easily, has quick-drying, environmental protection simultaneously, harmless in construction.To how but not related to by the thermotolerance of modification technology raising shellac varnish.8) number of patent application: 201010039147.3 denominations of invention: modified shellac fruit coating agent of anti-hickie and preparation method thereof.Invention provides modified shellac fruit coating agent of a kind of anti-hickie and preparation method thereof.Be made up of the component of following masses part: modified shellac resin 10 ~ 25 parts, mass concentration is the solvent 75 ~ 90 parts of 8 ~ 13%; Preparation method is: be first mixed in sclerolac by basic group polymkeric substance, then adds in solvent by mixture, and heated and stirred is to dissolving completely; The amount of 0.1 ~ 2 times of fumaric acid siccative oil by sclerolac quality is joined in above-mentioned gained mixture, obtains modified shellac resin; The solvent being 8 ~ 13% by modified shellac resin and mass concentration mixes by above-mentioned mass parts, and adjust ph to 7 ~ 9 obtain the modified shellac fruit coating agent of anti-hickie.This invention adopts the polymkeric substance and the drying oil-modified lac of fumaric acidization that contain basic group, closes lac carboxyl and hydroxyl, makes it to lose chance esterification occurring and produces cross linkage, thus avoids rete to occur hickie under high temperature, high humidity environment.Lac method of modifying and the present invention of this invention have essence different, and to how but not related to by the thermotolerance of modification technology raising shellac varnish.
Summary of the invention
Embodiment of the present invention technical problem to be solved is, provides a kind of lac of improving varnish thermotolerance,
As follows according to the content of weight percent major ingredient: lac 40-50%; Dry vegetable oil 3-7%; Glycerine 5-9%; Gum Rosin 10-20%; Tetramethylolmethane 5-10%; Modification promotor 10-15%.
Wherein, described modification promotor is the one in morpholine, urea, thiocarbamide, borax, dicarboxylic acid or dicarboxylic anhydride.
Described lac is white shellac, refining refined bleached lac, dewaxing lac or hot ethanol insolubles be less than 1% sheet or grain lac in one.
Described Gum Rosin is mainly the one in gum resin, staybelite, modified rosin, nilox resin, polymerized rosin.
Described dry vegetable oil is the one through heating in Viscotrol C, oleum lini or the boiled wood oil boiled.
In order to solve the problems of the technologies described above, embodiments provide a kind of method of modifying improving the lac of varnish thermotolerance, comprising the steps:
(a), lac, Gum Rosin are stirred and are dissolved in thinner, then get modification promotor to add in solution and heating until all dissolve, Heating temperature is 50-80 DEG C;
(b), in above-mentioned mixing solutions, add dry vegetable oil, tetramethylolmethane and glycerine, warming while stirring to 40-82 DEG C, reaction 1-4 hour, obtain the shellac solution of modification;
(c), the shellac solution of modification is made shellac varnish finished product.
Wherein, the method making shellac varnish in described step c is: when modified shellac solution is cooled to 30-56 DEG C, adds obtaining property of the oxalic acid shellac varnish finished product of 0.1-5%.
The method making shellac varnish in described step c is: cold for modified shellac solution distillating recovering solvent is obtained modified shellac solid, obtains modified shellac through compressing tablet or granulation, is diluted to the modified shellac varnish of 6-51% during use with thinner.
The method making shellac varnish in described step c is: the weighting agent and the pigment that modified shellac solution are added solution weight 0.1-10% stir 1-2 hour, make environment-friendly modified lacquer.
Described weighting agent is the one in barium sulfate, calcium carbonate, titanium dioxide or carbon black
Implement the embodiment of the present invention, there is following beneficial effect:
Basic Mechanism of the present invention is multi-functional filmogen dry vegetable oil, rosin, tetramethylolmethane is miscible in laccol solution, hydroxyl generation esterification in carboxyl ethanol in lac obtains carboxylate, adding the properties-correcting agent glycerine that improves lac toughness and modification promotor makes the multiple carboxyl reaction in lac molecule form interaction force between group, modification promotor plays the crosslinked effect impelling chemistry or physics, dry vegetable oil, rosin, the toughness that the plastification of tetramethylolmethane and the formation of cross-linked structure improve lac paint film improves the temperature capacity of lac paint film simultaneously, the dry heat resistance performance of lac paint film and wet-hot aging performance are had significantly improve further.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below will the present invention is described in further detail by embodiment.
example 1. be dissolved in 100 gram of 95% alcohol by 20 grams of lacs, 6 grams of gum resin under stirring, Heating temperature is 50 ~ 80 DEG C, until all dissolve; Add dry vegetable oil tung oil 2 grams, tetramethylolmethane 3 grams, glycerine 3 grams, warming while stirring are to 40 ~ 82 DEG C, get modification promotor morpholine 5 grams and add heating in solution until all dissolve, react 1 ~ 4 hour, obtain modified shellac solution, when being cooled to 30-56 DEG C, add the modified shellac varnish finished product that 0.1 ~ 5% oxalic acid obtains; By this liquid directly by being coated on smooth plank, room temperature places 24 hours, obtains the coating that thickness is 2 microns.Dry heat resistance temperature is 84 DEG C, and wet-heat resisting hot temperature degree is 76 DEG C.The shellac varnish paint film of non-modified on year-on-year basis, dry heat resistance temperature is 75 DEG C, and wet-heat resisting hot temperature degree is 65 DEG C.
example 2. 20 grams of lacs, 6 grams of hydrogenated rosin resin are dissolved in 100 grams of thinner 95% alcohol under stirring, Heating temperature is 50 ~ 80 DEG C, until all dissolve.Add dry vegetable oil oleum lini 3 grams, tetramethylolmethane 3 grams, glycerine 3 grams, warming while stirring are to 40 ~ 82 DEG C, get 5 grams, modification promotor urea and add heating in solution until all dissolve, react 1 ~ 4 hour, obtain modified shellac solution, when being cooled to 30-56 DEG C, add the modified shellac varnish finished product that 0.1 ~ 5% oxalic acid obtains; By this liquid directly by being coated on smooth plank, room temperature places 24 hours, obtains the coating that thickness is 2 microns.Dry heat resistance temperature is 87 DEG C, and wet-heat resisting temperature is 75 DEG C.The shellac varnish paint film of non-modified on year-on-year basis, dry heat resistance temperature is 75 DEG C, and wet-heat resisting hot temperature degree is 65 DEG C.
example 3. 20 grams of lacs, 6 grams of maleic acid modified rosin pentaerythritol resins are dissolved in 100 grams of thinner 95% alcohol under stirring, Heating temperature is 50 ~ 80 DEG C, until all dissolve.Add dry vegetable oil tung oil 2 grams, glycerine 3 grams, warming while stirring is to 40 ~ 82 DEG C, get 5 grams, modification promotor urea and add heating in solution until all dissolve, react 1 ~ 4 hour, obtain modified shellac solution, when being cooled to 30-56 DEG C, add the modified shellac varnish finished product that 0.1 ~ 5% oxalic acid obtains; By this liquid directly by being coated on smooth plank, room temperature places 24 hours, obtains the coating that thickness is 2 microns.Dry heat resistance temperature is 90 DEG C, and wet-heat resisting temperature is 78 DEG C.The shellac varnish paint film of non-modified on year-on-year basis, dry heat resistance temperature is 75 DEG C, and wet-heat resisting hot temperature degree is 65 DEG C.
example 4. be dissolved in 100 gram of 95% alcohol by 20 grams of lacs, 6 grams of maleic acid modified Gum Rosins under stirring, Heating temperature is 50 ~ 80 DEG C, until all dissolve; Add dry vegetable oil tung oil 2 grams, tetramethylolmethane 3 grams, glycerine 3 grams, warming while stirring are to 40 ~ 82 DEG C, get modification promotor morpholine 5 grams and add heating in solution until all dissolve, react 1 ~ 4 hour, obtain modified shellac solution, when being cooled to 30-56 DEG C, add the modified shellac varnish finished product that 0.1 ~ 5% oxalic acid obtains; By this liquid directly by being coated on smooth plank, room temperature places 24 hours, obtains the coating that thickness is 2 microns.Put into 110 DEG C of baking oven bakings 2 hours, dry heat resistance temperature is 92 DEG C, and wet-heat resisting hot temperature degree is 83 DEG C.The shellac varnish paint film of non-modified on year-on-year basis, dry heat resistance temperature is 75 DEG C, and wet-heat resisting hot temperature degree is 65 DEG C.
example 5. 20 grams of lacs, 6 grams of nilox resin resins are dissolved in 100 grams of thinner 95% alcohol under stirring, Heating temperature is 50 ~ 80 DEG C, until all dissolve.Add dry vegetable oil oleum lini 3 grams, tetramethylolmethane 3 grams, glycerine 3 grams, warming while stirring are to 40 ~ 82 DEG C, get 5 grams, modification promotor urea and add heating in solution until all dissolve, react 1 ~ 4 hour, obtain modified shellac solution, when being cooled to 30-56 DEG C, add the modified shellac varnish finished product that 0.1 ~ 5% oxalic acid obtains; By this liquid directly by being coated on smooth plank, room temperature places 24 hours, obtains the coating that thickness is 2 microns.Put into 110 DEG C of baking oven bakings 2 hours, dry heat resistance temperature is 93 DEG C, and wet-heat resisting hot temperature degree is 84 DEG C.The shellac varnish paint film of non-modified on year-on-year basis, dry heat resistance temperature is 75 DEG C, and wet-heat resisting hot temperature degree is 65 DEG C.
example 6. 20 grams of lacs, 6 grams of maleic acid modified rosin pentaerythritol resins are dissolved in 100 grams of thinner 95% alcohol under stirring, Heating temperature is 50 ~ 80 DEG C, until all dissolve.Add dry vegetable oil tung oil 2 grams, glycerine 3 grams, warming while stirring is to 40 ~ 82 DEG C, get 5 grams, modification promotor urea and add heating in solution until all dissolve, react 1 ~ 4 hour, obtain modified shellac solution, when being cooled to 30-56 DEG C, add the modified shellac varnish finished product that 0.1 ~ 5% oxalic acid obtains; By this liquid directly by being coated on smooth plank, room temperature places 24 hours, obtains the coating that thickness is 2 microns.Put into 110 DEG C of baking oven bakings 2 hours, dry heat resistance temperature is 95 DEG C, and wet-heat resisting hot temperature degree is 84 DEG C.The shellac varnish paint film of non-modified on year-on-year basis, dry heat resistance temperature is 75 DEG C, and wet-heat resisting hot temperature degree is 65 DEG C.
example 7. be dissolved in 100 gram of 95% alcohol by 20 grams of lacs, 6 grams of gum resin under stirring, Heating temperature is 50 ~ 80 DEG C, until all dissolve; Add dry vegetable oil tung oil 2 grams, tetramethylolmethane 3 grams, glycerine 3 grams, warming while stirring are to 40 ~ 82 DEG C, get modification promotor thiocarbamide 5 grams and add heating in solution until all dissolve, react 1 ~ 4 hour, when being cooled to 30-56 DEG C, add the modified shellac varnish finished product that 0.1 ~ 5% oxalic acid obtains; By this liquid directly by being coated on smooth plank, room temperature places 24 hours, obtains the coating that thickness is 2 microns.Put into 110 DEG C of baking oven bakings 2 hours, dry heat resistance temperature is 93 DEG C, and wet-heat resisting hot temperature degree is 82 DEG C.The shellac varnish paint film of non-modified on year-on-year basis, dry heat resistance temperature is 75 DEG C, and wet-heat resisting hot temperature degree is 65 DEG C.
example 8.20 grams of lacs, 6 grams of hydrogenated rosin resin are dissolved in 100 grams of thinner 95% alcohol under stirring, Heating temperature is 50 ~ 80 DEG C, until all dissolve.Add dry vegetable oil oleum lini 3 grams, tetramethylolmethane 3 grams, glycerine 3 grams, warming while stirring are to 40 ~ 82 DEG C, get modification promotor morpholine 5 grams and add heating in solution until all dissolve, when being cooled to 30-56 DEG C, add the modified shellac varnish finished product that 0.1 ~ 5% oxalic acid obtains; React 1 ~ 4 hour, obtain modified shellac solution, by this liquid directly by being coated on smooth plank, room temperature places 16 hours, obtains the coating that thickness is 2 microns.Put into 110 DEG C of baking oven bakings 2 hours, dry heat resistance temperature is 95 DEG C, and wet-heat resisting hot temperature degree is 85 DEG C.The shellac varnish paint film of non-modified on year-on-year basis, dry heat resistance temperature is 75 DEG C, and wet-heat resisting hot temperature degree is 65 DEG C.
example 9.20 grams of lacs, 6 grams of hydrogenated rosin resin are dissolved in 100 grams of thinner 95% alcohol under stirring, Heating temperature is 50 ~ 80 DEG C, until all dissolve.Add dry vegetable oil oleum lini 3 grams, tetramethylolmethane 3 grams, glycerine 3 grams, warming while stirring are to 40 ~ 82 DEG C, get modification promotor morpholine 5 grams and add heating in solution until all dissolve, when being cooled to 30-56 DEG C, add the modified shellac solution that 0.1 ~ 5% oxalic acid obtains; Stir and add the weighting agent light calcium carbonate that is equivalent to lac 3% and 2% charcoal blacks stirs 2 hours; Directly use as environment-friendly modified lacquer.Put into 110 DEG C of baking oven bakings 2 hours after paint film natural air drying, dry heat resistance temperature is 91 DEG C, and wet-heat resisting hot temperature degree is 83 DEG C.The shellac varnish paint film of non-modified on year-on-year basis, dry heat resistance temperature is 75 DEG C, and wet-heat resisting hot temperature degree is 65 DEG C.
Above disclosedly be only a kind of preferred embodiment of the present invention, the interest field of the present invention can not be limited with this, therefore according to the equivalent variations that the claims in the present invention are done, still belong to the scope that the present invention is contained.