CN100503746C - Water soluble oil painting stick composition, water soluble oil painting stick and its preparing method - Google Patents
Water soluble oil painting stick composition, water soluble oil painting stick and its preparing method Download PDFInfo
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- CN100503746C CN100503746C CNB2006100290527A CN200610029052A CN100503746C CN 100503746 C CN100503746 C CN 100503746C CN B2006100290527 A CNB2006100290527 A CN B2006100290527A CN 200610029052 A CN200610029052 A CN 200610029052A CN 100503746 C CN100503746 C CN 100503746C
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Abstract
The present invention discloses a kind of water soluble oil painting stick composition, which consists of stearic cid 5-35 wt%, polyethylene glycol 4-15 wt%, peregal 4-15 wt%, stuffing of talc, kaolin and/or calcium carbonate 50-80 wt%, pigment 2-10 wt% and wax 2-8 wt%. The present invention also discloses the making process of the water soluble oil painting stick. The water soluble oil painting stick may be used as oil painting stick directly and as water color, and has bright color, excellent drawing performance and relatively high breaking strength.
Description
Technical field
The present invention relates to a kind of be used to the make composition of water-soluble oil painting rod, a kind of water-soluble oil painting rod and manufacture method thereof.
Background technology
Modal in the market drawing product mainly is artistic oil painting stick and wax crayon, though this series products can satisfy general drawing requirement, but because the used starting material of product are oiliness, therefore belong to petroleum hydrocarbon raw material mostly, can produce wax crayon (artistic oil painting stick) and sign in or be stained with on clothes or the skin not easy cleaning and wax crayon (artistic oil painting stick) has heavier problems such as petroleum hydrocarbon raw material smell.In addition, also there is inhomogeneous, the bright-coloured bright and beautiful inadequately and more single problem of available drawing means of colouring in this class wax crayon (artistic oil painting stick).
Though also begun to research and develop water-soluble oil painting rod in this area, but water-soluble oil painting rod of the prior art all has much room for improvement aspect performance and the fracture resistence force drawing, draw performance not ideal enough be in particular in repeat to be coated with when retouching inadequately evenly, level of coverage is not enough, shading can occur; The dissolving and the dispersion effect of water-soluble oil painting rod powder are general when water dipping is painted, and cause the homogeneity of color lump relatively poor.
Summary of the invention
An object of the present invention is to provide a kind of composition that is used to make water-soluble oil painting rod, the water-soluble oil painting rod that is made by said composition not only can be used as artistic oil painting stick but also can be used as the watercolors use, and bright in colour bright and beautiful, draw excellent property, and fracture resistence force is stronger.
Another object of the present invention provides a kind of water-soluble oil painting rod, and it not only can be used as artistic oil painting stick but also can be used as the watercolors use, and bright in colour bright and beautiful, draw excellent property, and fracture resistence force is stronger.
A further object of the invention provides a kind of manufacture method of water-soluble oil painting rod.
A first aspect of the present invention provides a kind of composition that is used to make water-soluble oil painting rod, and said composition comprises following component: 5-35 weight % stearic acid, 4-15 weight % polyoxyethylene glycol, 4-15 weight % peregal, 50-80 weight % are selected from one or more fillers, 2-10 weight % pigment and the 2-8 weight % wax of talcum, kaolin or lime carbonate.
Be more preferably, the content of said components is as follows respectively: 10-32 weight % stearic acid, 4-10 weight % polyoxyethylene glycol, 4-10 weight % peregal, 50-75 weight % are selected from one or more fillers, 2-10 weight % pigment and the 2-8 weight % wax of talcum, kaolin or lime carbonate.
Preferably, described filler be selected from talcum or kaolinic one or both.Especially preferably, described filler is selected from talcum.Preferably, described wax is to be selected from one or both of paraffin or Fei Xier indoles synthetic wax.
A second aspect of the present invention provides a kind of water-soluble oil painting rod, and it is made by the composition that comprises following component and content: 5-35 weight % stearic acid, 4-15 weight % polyoxyethylene glycol, 4-15 weight % peregal, 50-80 weight % are selected from one or more fillers, 2-10 weight % pigment and the 2-8 weight % wax of talcum, kaolin or lime carbonate.
Preferably, the included component concentration of described composition is distinguished as follows: 10-32 weight % stearic acid, 4-10 weight % polyoxyethylene glycol, 4-10 weight % peregal, 50-75 weight % are selected from one or more fillers, 2-10 weight % pigment and the 2-8 weight % wax of talcum, kaolin or lime carbonate.
Preferably, described filler be selected from talcum or kaolinic one or both.Especially preferably, described filler is selected from talcum.Preferably, described wax is to be selected from one or both of paraffin or Fei Xier indoles synthetic wax.
In a third aspect of the present invention, a kind of manufacture method of above-mentioned water-soluble oil painting rod is provided, this method may further comprise the steps:
(a) stearic acid, polyoxyethylene glycol, peregal and wax are carried out mixed melting;
(b) in the melt that step (a) obtains, add pigment and described filler, carry out uniform mixing;
(c) uniform mixture that step (b) is obtained is processed into fine granular semi-solid state thing;
(d) the semi-solid state thing mixed melting that step (c) is obtained forms paste;
(e) paste that step (d) is obtained forms water-soluble oil painting rod by injection moulding.
In aforesaid method, the mixed melting temperature of preferably described step (a) is 50-90 ℃; The mixing temperature of described step (b) is 50-90 ℃; The mixed melting temperature of described step (d) is 50-90 ℃; The cooling temperature of injection moulding is 10-25 ℃ in the described step (e).
In aforesaid method, preferably, in the step (c), uniform mixture is processed into fine granular semi-solid state thing by three-roll grinder, the granularity of described semi-solid state thing is at the 20-50 micron.
Be more preferably, the mixed melting temperature of described step (a) is 55-75 ℃, and the mixing temperature of described step (b) is 55-75 ℃, and the mixed melting temperature of described step (d) is 55-75 ℃, and the cooling temperature of injection moulding is 14-20 ℃ in the described step (e).
The reaction times of above-mentioned steps (a) is as the criterion to finish mixed melting, preferably 60-120 minute.The reaction times of above-mentioned steps (b) is as the criterion to realize mixing, and preferably 20-30 minute, preferably can adopt stirring method to realize mixing.Be preferably 3-15 second the cooling time of injection moulding in the above-mentioned steps (e), more preferably 7-10 second.
Make in the method for water-soluble oil painting rod in the present invention, more preferably, after injection moulding forms water-soluble oil painting rod, artistic oil painting stick is placed for some time, preferably more than 3 days, be more preferably 3-4 days, carry out roll packaging with automatic paper winder then.
Embodiment
Be used for making the composition of water-soluble oil painting rod in the present invention, polyoxyethylene glycol and peregal play emulsification, level dyeing, wetting and dispersive effect.Polyoxyethylene glycol also is used to regulate the viscosity and the fusing point of other component, and plays lubrication.Stearic acid, wax mainly carry out emulsification and dispersion under the effect of peregal, polyoxyethylene glycol and peregal acting in conjunction fully disperse filler and pigment.
There is no particular restriction for the used polyoxyethylene glycol of the present invention, only otherwise can have a negative impact to purpose of the present invention and get final product, more preferably is the polyoxyethylene glycol of PEG200-10000 series.
There is no particular restriction for the used peregal of the present invention, only otherwise can have a negative impact to purpose of the present invention and get final product.Peregal is a class fatty alcohol-polyoxyethylene ether, and it can use chemical formula RO-(CH
2CH
2O)
n-H represents (R represents alkyl, and n represents positive integer, for example 3,8,9,10,15,20,25,30,35).Particularly preferably be paregal O-10, paregal O-15, paregal O-20, paregal O-25.
There is no particular restriction for the used pigment of the present invention, only otherwise can have a negative impact to purpose of the present invention and get final product.Those skilled in the art can easily select suitable pigment according to required water-soluble oil painting rod.For example, can be carbon black, acetylene black, ivory black, nigrosine, iron black etc. as black pigment.As yellow ultramarine can be such as but not limited to organic yellow, permanent yellow, iron oxide yellow, zinc yellow, cadmium yellow, nickel titanium yellow, Naples yellow, naphthol yellow S, hansa yellow G, organic yellow 10G, benzidine yellow G, benzidine yellow G R, quinoline yellow, Tartrazol yellow etc.As orange pigments can be such as but not limited to molybdate orange, cadmium orange, chrome vermilion, permanent orange GTR, Benzidine orange G etc.As red pigment can be such as but not limited to red iron oxide, madder lake, crimson lake, permanent bordeaux, lithol red, pyrazolone red, C lake red CAN'T D, eosine lake, rhodamine color lake B, alizarine lake etc.As brown pigments such as but not limited to umber, loess, burnt ochre, burnt sienna etc.As violet pigment can be such as but not limited to manganese violet, cobalt violet, iron oxide purple, methyl violet color lake etc.As blue pigments can be such as but not limited to Prussian blue, ultramarine, cobalt blue, alkali blue lake, victoria blue color lake, phthalocyanine blue, indanthrene blue BC etc.As veridian can be such as but not limited to chrome green, pigment green B, Victoria Green WPB color lake, phthalocyanine green, naphthol green etc.As white pigment can be such as but not limited to zinc white, titanium dioxide, stibium trioxide, zinc sulfate etc.Above-mentioned pigment can use separately, also can two or more be used in combination.
There is no particular restriction for wax of the present invention, only otherwise can have a negative impact to purpose of the present invention and get final product.Suitable wax is such as but not limited to paraffin, Microcrystalline Wax, Japan tallow, carnauba wax, gama wax, montanin wax, Fei Xier indoles synthetic wax.Wherein, particularly preferably be paraffin and Fei Xier indoles synthetic wax.Above-mentioned wax can use separately, also can two or more be used in combination.
The method that the present invention makes water-soluble oil painting rod may further comprise the steps: (a) stearic acid, polyoxyethylene glycol, peregal and wax are carried out mixed melting; (b) in the melt that step (a) obtains, add pigment and described filler, carry out uniform mixing; (c) uniform mixture that step (b) is obtained is processed into fine granular semi-solid state thing; (d) the semi-solid state thing mixed melting that step (c) is obtained forms paste; (e) paste that step (d) is obtained forms water-soluble oil painting rod by injection moulding.
In aforesaid method, the mixed melting temperature of preferably described step (a) is 50-90 ℃; The mixing temperature of described step (b) is 50-90 ℃; The mixed melting temperature of described step (d) is 50-90 ℃; The cooling temperature of injection moulding is 10-25 ℃ in the described step (e).Preferably, in the step (c), by three-roll grinder uniform mixture is processed into fine granular semi-solid state thing, the granularity of described semi-solid state thing is at the 20-50 micron.
Be more preferably, the mixed melting temperature of described step (a) is 55-75 ℃, and the mixing temperature of described step (b) is 55-75 ℃, and the mixed melting temperature of described step (d) is 55-75 ℃, and the cooling temperature of injection moulding is 14-20 ℃ in the described step (e).
The reaction times of above-mentioned steps (a) is as the criterion to finish mixed melting, preferably 60-120 minute.The reaction times of above-mentioned steps (b) is as the criterion to realize mixing, and preferably 20-30 minute, preferably can adopt stirring method to realize mixing.Be preferably 3-15 second the cooling time of injection moulding in the above-mentioned steps (e), more preferably 7-10 second.
Make in the method for water-soluble oil painting rod in the present invention, more preferably, after injection moulding forms water-soluble oil painting rod, artistic oil painting stick is placed for some time, preferably more than 3 days, be more preferably 3-4 days, carry out roll packaging with automatic paper winder then.
Major advantage of the present invention is as follows:
(1) water-soluble oil painting rod of the present invention had both had the characteristics easy to use, beautiful in colour of artistic oil painting stick, have simultaneously the toning and the water-soluble function of watercolors again, and spot evenly, is not stayed in colouring, both can directly on paper, paint, also can on picture, be in harmonious proportion performance watercolor effect behind the drawing with the writing brush that dips in water.
(2) the not dirty hand of water-soluble oil painting rod of the present invention also is easy to cleaning even if be stained with on the clothes.
(3) water-soluble oil painting rod of the present invention is except directly painting on paper, also can adopt multiple other drawing means.For example, barred body can be whittled into powdery, paint after dip in writing brush the back that is dissolved in water, several color powder can be put together like this, re-use after mixing colours.And for example, can also dip in water, behind dab on the barred body, paint with writing brush with writing brush.
(4) water-soluble oil painting rod of the present invention preferably adopts three roller grinding techniques in manufacturing processed, and pigment reaches the micron order fineness.
(5) the national light industry stationery sports goods quality surveillance of water-soluble oil painting rod process of the present invention inspection center is detected, and meets EN71, ASTM and national toy safety standard and artistic oil painting stick and forces standard-required.Wherein, antimony, arsenic, barium, chromium, cadmium, lead, mercury, selenium content have only 3.52-4.58mg/kg, 3.22-3.78mg/kg, 52.01-76.48mg/kg, 0.98-1.77mg/kg, 0.28-0.48mg/kg, 8.71-10.01mg/kg, 0.10-0.17mg/kg and 8.19-10.11mg/kg respectively, well below above-mentioned standard.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, or carries out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage.
Embodiment 1
Make 1000 water-soluble oil painting rods, wherein every 7.5 restrains, and the raw material gross weight is 7500 grams.
The prescription of raw material is as follows: 22 weight % stearic acid, 4 weight % polyoxyethylene glycol (PEG6000), 15 weight % peregals (O-20), 50 weight % talcums, 7 weight % permanent yellows and 2 weight % paraffin.
Stearic acid, polyoxyethylene glycol, peregal and paraffin are put into agitation vat mix the stirring fusing, temperature is 85 ℃, and churning time is 60 minutes.Add permanent yellow and talcum powder in mixture after being mixed, after stirring, controlled temperature is stirred to 20 minutes at 75 ℃.With stir mixture grind into fine opaque semi-solid state thing through three-roll grinder, the agitation vat of again semi-solid mixtures being put into shaper fuses into paste, temperature is 70 ℃.Then, above-mentioned plaster material is injected in the die forming machine, cools off, cooling temperature is 14 ℃, and be 7 seconds cooling time, makes the water-soluble oil painting rod of moulding thus.
Embodiment 2
Make 1000 water-soluble oil painting rods, wherein every 7.5 restrains, and the raw material gross weight is 7500 grams.
The prescription of raw material is as follows: 10 weight % stearic acid, 7 weight % polyoxyethylene glycol (PEG-4000), 4 weight % peregals (O-10), 55 weight % talcums, 20 weight % kaolin, 2 weight % phthalocyanine greens and 2 weight % Fei Xier indoles synthetic waxs.
Stearic acid, polyoxyethylene glycol, peregal and Fei Xier indoles synthetic wax are put into agitation vat mix the stirring fusing, temperature is 55 ℃, and churning time is 120 minutes.Add phthalocyanine green, talcum and kaolin in mixture after being mixed, after stirring, controlled temperature is stirred to 30 minutes at 55 ℃.With stir mixture grind into fine opaque semi-solid state thing through three-roll grinder, the agitation vat of again semi-solid mixtures being put into shaper fuses into paste, temperature is 55 ℃.Then, above-mentioned plaster material is injected in the die forming machine, cools off, cooling temperature is 10 ℃, and be 13 seconds cooling time, makes the water-soluble oil painting rod of moulding thus.
Embodiment 3
Make 1000 water-soluble oil painting rods, wherein every 7.5 restrains, and the raw material gross weight is 7500 grams.
The prescription of raw material is as follows: 10 weight % stearic acid, 15 weight % polyoxyethylene glycol (PEG-6000), 10 weight % peregals (O-25), 60 weight % talcums, 2 weight % phthalocyanine blues and 3 weight % paraffin.
Stearic acid, polyoxyethylene glycol, peregal and paraffin are put into agitation vat mix the stirring fusing, temperature is 70 ℃, and churning time is 100 minutes.Add phthalocyanine blue and talcum powder in mixture after being mixed, after stirring, controlled temperature is stirred to 25 minutes at 70 ℃.With stir mixture grind into fine opaque semi-solid state thing through three-roll grinder, the agitation vat of again semi-solid mixtures being put into shaper fuses into paste, temperature is 85 ℃.Then, above-mentioned plaster material is injected in the die forming machine, cools off, cooling temperature is 20 ℃, and be 8 seconds cooling time, makes the water-soluble oil painting rod of moulding thus.The water-soluble oil painting rod of moulding was left standstill 3 days in room temperature, and roll packaging is made finished product then.
Embodiment 4
Press 1000 water-soluble oil painting rods of embodiment 3 described making, wherein every 7.5 restrains, and the raw material gross weight is 7500 grams.The prescription of different is raw material is as follows: 32 weight % stearic acid, 4 weight % polyoxyethylene glycol (PEG-6000), 4 weight % peregals (O-25), 50 weight % talcums, 2 weight % phthalocyanine blues and 8 weight % paraffin.
Embodiment 5
Press 1000 water-soluble oil painting rods of embodiment 3 described making, wherein every 7.5 restrains, and the raw material gross weight is 7500 grams.The prescription of different is raw material is as follows: 15 weight % stearic acid, 10 weight % polyoxyethylene glycol (PEG-6000), 6 weight % peregals (O-25), 55 weight % talcums, 10 weight % phthalocyanine blues and 4 weight % paraffin.
Comparative example
The trade mark that refined inspiring confidence in (Guangzhou) stationery Industrial Co., Ltd is produced be " graceful board ", model be DO-100-124 water-soluble oil painting rod as a comparison case, with the water-soluble oil painting rod of the embodiment of the invention 3 compare test as follows.
Draw performance
Draw on plumbous drawing paper with above-mentioned two kinds of artistic oil painting sticks, found that, both all easily adhere papers and can repeat to tint.Yet when repeating to tint, the level of coverage of the color that detects by an unaided eye finds that the level of coverage of embodiment 3 samples is good, and color lump is even, no shading; And the level of coverage of comparative example is not enough, shows as color lump not too evenly and shading arranged.
Two kinds of artistic oil painting sticks are dipped in that water is wet to be scribbled performance and compare, dipping in suitable water with writing brush is in harmonious proportion on the color lump coating on the paper at artistic oil painting stick and draws, observe both mediations and draw the result, the color lump coating of finding embodiment 3 samples can be dissolved in water soon and the dispersion effect drawn fine, do not have insolubles or sharp trace, present watercolor effect preferably; And the dissolving of the color lump coating of comparative example and dispersive effect are general, and the color that shows as after dipping in water and drawing is even inadequately, and shading is arranged.
Fracture resistence force
Place 37 ± 2 ℃ thermostat container to take out after interior 1 hour artistic oil painting stick to be measured, stride immediately and be placed on two fulcrums of 4 centimetres,, place the force part with ergometer at two fulcrums central authorities applied loads, plus load power during the measure sample fracture is as fracture resistence force.
Comparative example and embodiment 3 samples are respectively taken a sample 10, calculate fracture resistence force mean value then.The fracture resistence force of comparative example is 18.5N; The fracture resistence force of embodiment 3 samples is 24N, has improved 30% than comparative example.
Solvency power
This test is following to be carried out: getting about artistic oil painting stick to be measured 1 gram and put into mortar, grind to form powdery, claim sample 0.5 gram and add water 1 gram with watch-glass, is Glass rod grinding about 8mm with diameter, observes and writes down sample and all be dissolved in the water the required time.
The consoluet time of comparative example is 2.0 minutes; The consoluet time of embodiment 3 samples is 1.5 minutes, has accelerated 25% than Comparative Examples.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. composition that is used to make water-soluble oil painting rod, said composition is composed of the following components: 5-35 weight % stearic acid, 4-15 weight % polyoxyethylene glycol, 4-15 weight % peregal, 50-80 weight % are selected from one or more fillers, 2-10 weight % pigment and the 2-8 weight % wax of talcum, kaolin or lime carbonate.
2. composition as claimed in claim 1, it is characterized in that described components contents is as follows respectively: 10-32 weight % stearic acid, 4-10 weight % polyoxyethylene glycol, 4-10 weight % peregal, 50-75 weight % are selected from one or more fillers, 2-10 weight % pigment and the 2-8 weight % wax of talcum, kaolin or lime carbonate.
3. composition as claimed in claim 1 or 2 is characterized in that, described filler be selected from talcum or kaolinic one or both.
4. composition as claimed in claim 1 or 2 is characterized in that, described wax is to be selected from one or both of paraffin or Fei Xier indoles synthetic wax.
5. water-soluble oil painting rod, it is made by the composition of following component and content: 5-35 weight % stearic acid, 4-15 weight % polyoxyethylene glycol, 4-15 weight % peregal, 50-80 weight % are selected from one or more fillers, 2-10 weight % pigment and the 2-8 weight % wax of talcum, kaolin or lime carbonate.
6. water-soluble oil painting rod as claimed in claim 5, it is characterized in that the composition of described composition is as follows respectively: 10-32 weight % stearic acid, 4-10 weight % polyoxyethylene glycol, 4-10 weight % peregal, 50-75 weight % are selected from one or more fillers, 2-10 weight % pigment and the 2-8 weight % wax of talcum, kaolin or lime carbonate.
7. water-soluble oil painting rod as claimed in claim 5 is characterized in that, described filler be selected from talcum or kaolinic one or both; And/or described wax is to be selected from one or both of paraffin or Fei Xier indoles synthetic wax.
8. the manufacture method of each described water-soluble oil painting rod among the claim 5-7, this method may further comprise the steps:
(a) stearic acid, polyoxyethylene glycol, peregal and wax are carried out mixed melting;
(b) in the melt that step (a) obtains, add pigment and described filler, carry out uniform mixing;
(c) uniform mixture that step (b) is obtained is processed into fine granular semi-solid state thing;
(d) the semi-solid state thing mixed melting that step (c) is obtained forms paste;
(e) paste that step (d) is obtained forms water-soluble oil painting rod by injection moulding.
9. method as claimed in claim 8 is characterized in that, the mixed melting temperature of described step (a) is 50-90 ℃; The mixing temperature of described step (b) is 50-90 ℃; The mixed melting temperature of described step (d) is 50-90 ℃; The cooling temperature of injection moulding is 10-25 ℃ in the described step (e).
10. method as claimed in claim 8 is characterized in that, in the step (c), by three-roll grinder uniform mixture is processed into fine granular semi-solid state thing, and the granularity of described semi-solid state thing is at the 20-50 micron.
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| CNB2006100290527A CN100503746C (en) | 2006-07-18 | 2006-07-18 | Water soluble oil painting stick composition, water soluble oil painting stick and its preparing method |
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| CNB2006100290527A CN100503746C (en) | 2006-07-18 | 2006-07-18 | Water soluble oil painting stick composition, water soluble oil painting stick and its preparing method |
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| CN100503746C true CN100503746C (en) | 2009-06-24 |
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| CN101831210B (en) * | 2010-03-23 | 2011-06-15 | 贝碧欧美术颜料(昆山)有限公司 | Solid watercolor and preparation method thereof |
| CN103160151A (en) * | 2011-12-14 | 2013-06-19 | 吴江市冰心文教用品有限公司 | Oil painting pigment |
| CN102618122B (en) * | 2012-02-06 | 2013-12-25 | 栗永伟 | Water-soluble grease pen |
| CN105176202B (en) * | 2015-10-21 | 2018-02-09 | 上海晨光文具股份有限公司 | Artistic oil painting stick and preparation method thereof |
| CN105623387A (en) * | 2016-03-28 | 2016-06-01 | 上海晨光文具股份有限公司 | Colored pencil lead and preparation method thereof |
| CN106009932A (en) * | 2016-07-15 | 2016-10-12 | 宁波易威教育用品有限公司 | Solid marking pen and preparation method thereof |
| CN107033677A (en) * | 2016-11-18 | 2017-08-11 | 江南大学 | A kind of washable three-in-one wax crayon and its manufacture method |
| CN107351600A (en) * | 2017-08-09 | 2017-11-17 | 新乡学院 | A kind of water-soluble artistic oil painting stick composition and its preparation method |
| CN107805419A (en) * | 2017-11-26 | 2018-03-16 | 山西大学 | One kind flash of light artistic oil painting stick and preparation method thereof |
| CN109868009A (en) * | 2019-03-20 | 2019-06-11 | 张一田 | A kind of water-soluble lipid wax crayon artistic oil painting stick and preparation method thereof |
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| CN1554718A (en) * | 2003-12-29 | 2004-12-15 | 黄智仕 | Recipe of water oil painting stick and its producing method |
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| CN1900182A (en) | 2007-01-24 |
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