CN1099398A - Preparation of micro colored resin coated on acrylic resin - Google Patents
Preparation of micro colored resin coated on acrylic resin Download PDFInfo
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- CN1099398A CN1099398A CN 93109755 CN93109755A CN1099398A CN 1099398 A CN1099398 A CN 1099398A CN 93109755 CN93109755 CN 93109755 CN 93109755 A CN93109755 A CN 93109755A CN 1099398 A CN1099398 A CN 1099398A
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- resin
- reaction product
- microparticle
- dyestuff
- benzo guanamine
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Abstract
Said resin possesses excellent dispersity in hydrophilic and hydrophobic system. In this invention, benzo cyanuro-diamide or mixture of benzo cyanuro-diamide and cyanuramine is subjected to a condensation coplymerization with formaldehyde or polyformaldehyde in optional optimum ratio. Said reacted product is coloured with solution of dyestuff; at same time, protective colloid is added in order to emulsify the reacted product. After emulsification and during solidification, two or more ethylene monomers mixed with dyestuff and catalyst are added to reacted product to form a stable coating, so microparticle colouring resin with define size is produced.
Description
The present invention relates to a kind of microparticle pigmentary resin, this resin has very large-scale consistency and dispersiveness, and the microparticle pigmentary resin that obtains is carried out not needing process of lapping when painted as the heavy colour material with immobilized particles size.
In addition, non-aggegation resin formation one masked film that this microparticle is painted, this film has splendid thermotolerance, water tolerance, chemical resistant properties and ageing resistance.Up to the present, in order to make the particle grade resins have surface property, the post-treating method of synthetic resins is used, wherein have the emulsification of benzo guanamine resin (is illustrated referring to Japanese Patent: 51-27679) with preparation microparticle pigmentary resin, acrylic resin emulsification with preparation microparticle pigmentary resin (referring to Japanese Patent explanation 51-46214), and is pulverized the melamine resin with preparation microparticle pigmentary resin (referring to Japanese Patent explanation 51-46124) with ball milling.
But the resin that carries out aftertreatment with oiliness or tackifying resin has binding property and cohesion, and needs to be used for a kind of technology the processing and the storage of this resin.
Because use various tinting materials, use range Da Yi causes consistency poor, therefore, only wetting ability and hydrophobic tinting material are used in restriction.
As everyone knows, the dispersion agent of liquid is usually used in ink and the paint, and similarly, owing to consider the processing and the storage problem of liquid colourant, liquid colourant also is limited to use.Yet liquid colourant is distributed in the matrix than particulate form tinting material is easier.; from economic benefit and stable angle, found the resin of micronizing, NAG resin, the resin of dry coloring is easy to disperse on a large scale in matrix; can use effectively in various pigment field, can keep film performance when using as tinting material simultaneously.
The present invention relates to a kind of solid-state microparticle pigmentary resin, this resin is easy to be dispersed in wetting ability and the hydrophobic tinting material, wherein the purpose of the composition of microparticle pigmentary resin stability that should be had with aforesaid microparticle pigmentary resin and non-compendency is consistent, compare with liquid coloring agent, the composition of solid-state microparticle pigmentary resin has better weather resistance, photostabilization, thermotolerance and have splendid chemical resistant properties, water tolerance, and this resin (for example: thermoset and thermoplastic resin can obtain splendid dispersiveness in hydrophilic and hydrophobic colorant system, printer's varnish China ink and dye system).
Similarly, use this solid-state microparticle pigmentary resin, its course of processing can be omitted curing, grinding and the ball milling step after painted, replaces the filtration, the washing step that carry out after painted.
The mixture of the trimeric cyanamide of benzo guanamine according to aforesaid method, 100p.b.w.(parts by weight) or the benzo guanamine of 50～100p.b.w. and 5～50p.b.w. and formaldehyde or Paraformaldehyde 96 react that (benzo guanamine or its mixture with the ratio of formaldehyde or Paraformaldehyde 96 are: 1.3～3.5mol) with the formation reaction product.Then, this reaction product is carried out painted with dyestuff, again a protective colloid solution is added successively in this reaction product to form the emulsification product.
After emulsifying effect, under emulsified state, when solidifying or in the whole solidification process, (consumption of vinyl monomer and the weight ratio of above-mentioned reaction product are 0.5～100: 100) add in the reaction product with the vinyl monomer more than 2 kinds and dye mixture, obtain having the microparticle resin of fixed measure, this resin does not need to grind as coating the time.
After filtration, the microparticle pigmentary resin contrast liquid colourant that obtains after washing and the drying has better weather resistance, photostabilization and thermotolerance, this microparticle pigmentary resin can stably be used as the heavy colour material and apply.
In the present invention, the pH value scope of benzo guanamine, trimeric cyanamide and protective colloid solution is bigger, and pH is 3.5～10.The reaction of producing the microparticle pigmentary resin is to carry out under temperature is 30～98 ℃ condition.
In addition, making the painted dyestuff of reaction product is not to be added in reaction product and the protective colloid solution, is added into exactly in the emulsification product.And, when under emulsified state, being cured, also can use acid curing catalysts.
Below in conjunction with embodiment the present invention is described in further detail.
The mixture of benzo guanamine or benzo guanamine and trimeric cyanamide is added in the formaldehyde solution, the pH value is adjusted to 3.5～10.Then, under 40～100 ℃ of temperature, react.Simultaneously, under uniform liquid condition, carry out described reaction to make hydrophobic reaction product.Then; at reaction end; directly add a suitable dyestuff in the reaction product; perhaps reaction product is joined in the dye solution that has prepared and dye, (ratio of weight and number of protective colloid solution and reaction product is 1-40: 100) to produce emulsifying effect then to add suitable protective colloid solution.
Add a suitable catalyzer then, (ratio of weight and number of catalyzer and reaction product is 0.01～5: 100) to carry out the emulsion polymerization reaction under 40-100 ℃.
Before curing reaction terminal point or terminal point, temperature be add under 50～98 ℃ of conditions vinyl monomer (ratio of weight and number of vinyl monomer and reaction product is 1-100: 100) and initiators for polymerization, to obtain the emulsification product of a coated with resins.
Similarly, also dyestuff, emulsifying agent and tensio-active agent can be joined in the protective colloid solution to produce emulsifying effect.And, under emulsified state, when solidifying or in the whole curing polymerization process, add vinyl monomer and catalyzer to obtain the emulsification of a microparticle pigmentary resin, by centrifugation it is separated then, and it is filtered, washs and dry fully to obtain final microparticle pigmentary resin product.
The particle size range of the microparticle pigmentary resin that obtains with the method for foregoing description is 0.1～20 μ, and has splendid thermotolerance, water tolerance, chemical resistant properties and ageing resistance, can be used as in pigment, printing ink, paint vehicle and the dye field.
According to the method described above, prepare the microparticle pigmentary resin, make least easy Industrial processes obtain very big improvement by carrying out micronizing.
The main raw material(s) that uses among the present invention has benzo guanamine, trimeric cyanamide, formaldehyde, Paraformaldehyde 96, trioxal and grioxal; Dyestuff used in the present invention has: duranol is bright orange-the 8G dyestuff, and rhodamine B basic dye, azosol be bright orange-6FF dyestuff, champac-5G dyestuff, champac-G dyestuff, diaresin orange dye, positively charged ion lucidin 10GFF dyestuff, rhodamine 6G CP dyestuff, rhodamine F5G dyestuff, the acid rhodamine FB of acid red XB dye well dyestuff.
Except above-mentioned dyestuff, dispersed dyestuff, matching stain, basic dyestuff, chemically-reactive dyes, a spot of organic or inorganic pigment and other well-known dyestuff 1 or 2 types also can be used as above-mentioned dyestuff and use.
An amount of dyestuff and reaction product and monomeric ratio of weight and number are 1-10: 100.
Employed tensio-active agent is an anion surfactant, have: the sulfonate of the carboxylic ester salt of soap, divalence, liquid aliphatic oil, sulphonate salt, binary fatty acid ester, fatty acid amide sulfonate, alkylallyl sulfonate and formalin condensation naphthalene sulfonate.
Described non-cationic surfactant has: Voranol EP 2001, polyxyethylated alkylphenol, the tensio-active agent that Sorbitol Powder alkyl ester and polyoxyethylene sorbitol alkyl ester use as the best.
The parts by weight ratio of an amount of dosage of surfactant and benzo guanamine and vinyl monomer is preferably 0.1-5.0.
When vinyl monomer partly occurs at the emulsive benzo guanamine that is used as coating,, under suitable temperature, can carry out polyreaction along with adding initiators for polymerization.
Employed initiators for polymerization has: hydrogen peroxide, cumene hydroperoxide (cumen hydroperoxide), benzoyl peroxide, Diisopropyl azodicarboxylate, hydrophosphate, dimethyl etc. are well-known initiator.
The preferred temperature of suggestion polyreaction is 50～98 ℃.
Employed vinyl monomer has: vinylchlorid, vinylidene chloride, vinyl acetate between to for plastic, vinylbenzene, vinyl cyanide, methacrylic acid, ethylacrylic acid, propyl group vinylformic acid, butylacrylic acid, octyl group vinylformic acid, dodecyl vinylformic acid, basic vinylformic acid, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, methacrylic acid time butyl ester, tert-butyl methacrylate, allyl methacrylate, the methacrylic acid phenylester, the methacrylic acid benzyl ester, basic ester of methacrylic acid and methacrylic acid Lauryl Ester.
The weight ratio of the consumption of vinyl monomer and benzo guanamine is 1-100: 100.
Employed protective colloid has: polyvinyl alcohol, gum Arabic, carboxymethyl cellulose, polyacrylic acid an alkali metal salt.
The consumption of protective colloid and the ratio of weight and number of reaction product are 1-40: 100.
Employed curing catalysts has: the strong acid of similar spirit of salt, similar benzoic carboxylic acid, the ammonium salt of similar ammonium chloride, the sulfonic acid of similar Phenylsulfonic acid and the spendable catalyzer of other potential.
The ratio of weight and number of the consumption of curing catalysts and trimeric cyanamide and benzo guanamine is 0.01～5: 100.
The present invention can further describe by following embodiment.
Embodiment 1
Be equipped with in 4 elongated necks flasks of agitator, reflux exchanger and thermometer 150g(0.8mol be housed respectively) the benzo guanamine, 80% Paraformaldehyde 96 60.06g(1.6mol) and the yellow soda ash of 0.4g10%.
Under 94～95 ℃ of temperature, stir and reacted in 3 hours.After the reaction, champac-5G of the rhodamine B-alkali of 5.1p.b.w. and 6p.b.w. is joined carry out in the reaction product of flask painted.
Dissolve in formation one aqueous solution in the 600g water by polyvinyl alcohol and a spot of emulsifying agent, this aqueous solution is carried out high-speed stirring obtain the emulsification product 5g.
After 1 hour, under the emulsified particle state, in greater than 1 hour time, add 10g methyl methacrylate, the styrene monomer of 20g and the benzoyl peroxide of 0.2g in reaction under 65 ℃.And, keep reaction to carry out down 2 hours at 70～80 ℃, obtain microparticle color solidification particle respectively; This microparticle pigmentary resin is termination reaction with the insoluble point of acetone or by nearly insoluble some the time, and with the product filtration, the washing, dry to obtain the microparticle pigmentary resin that generate.
Embodiment 2
Replace the 150g benzo guanamine among the embodiment 1 with 75g benzo guanamine, 75g trimeric cyanamide, and with the Paraformaldehyde 96 (80%) of 97.22g, 0.4g 10% sodium carbonate solution pack into together in the flask, 94～95 ℃ of reactions 2 hours and obtain reaction product down.Except that above-mentioned reaction, repeat to implement 1 reaction and obtain the microparticle pigmentary resin.
Embodiment 3
The methyl methacrylate monomer that replaces embodiment 1, methyl methacrylate and methacrylic acid are to be aggregated with coated at 1: 1 with weight ratio.Except that above-mentioned reaction, the reaction that repeats embodiment 1 is to obtain the microparticle pigmentary resin.
Comparative example 1
In embodiment 1, acrylic resin is not aggregated and applies.In addition, the reaction of repetition embodiment 1 obtains the microparticle pigmentary resin.
Comparative example 2
In embodiment 2, acrylic resin is not aggregated and applies.In addition, carry out same step and obtain the microparticle pigmentary resin.
The microparticle pigmentary resin that obtains by this way uses the same method and carries out weather resisteant, thermotolerance, dispersiveness, color transparency and water tolerance comparison test.
Test-results is as shown in table 1:
Table 1
The dispersed color transparency of weather resisteant thermotolerance water tolerance
Implement
Example 133333
Implement
Example 233333
Implement
Example 322333
Relatively
Example 111222
Relatively
Example 222122
* 1. differ from 2. 3. fabulous
Claims (5)
1, a kind of preparation method who is coated in the microparticle pigmentary resin on the acrylic resin; it is characterized in that: described step is for passing through adding formaldehyde or Paraformaldehyde 96 in the mixture of benzo guanamine or benzo guanamine and trimeric cyanamide; by carrying out painted to reaction product with dyestuff; by with the described reaction product of a protective colloid emulsifying soln, and with 1 or 2 kind of vinyl monomer add back in the described reaction product and prepare the microparticle pigmentary resin by the step that applies and solidify described reaction product.
2, the method for claim 1 is characterized in that: the mixture of described benzo guanamine or benzo guanamine and trimeric cyanamide and the reaction ratio between formaldehyde or the Paraformaldehyde 96 are 1.2～3.5mol.
3, the method for claim 1 is characterized in that: described dyestuff usage quantity and described reaction product and monomeric weight ratio are 1-10: 100.
4, the method for claim 1 is characterized in that: the consumption of described protective colloid solution and the weight ratio of described reaction product are 1-40: 100.
5, the method for claim 1 is characterized in that: the weight ratio of described vinyl monomer consumption and described reaction product is 1-100: 100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93109755 CN1099398A (en) | 1993-08-26 | 1993-08-26 | Preparation of micro colored resin coated on acrylic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93109755 CN1099398A (en) | 1993-08-26 | 1993-08-26 | Preparation of micro colored resin coated on acrylic resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1099398A true CN1099398A (en) | 1995-03-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93109755 Pending CN1099398A (en) | 1993-08-26 | 1993-08-26 | Preparation of micro colored resin coated on acrylic resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163929A (en) * | 2017-05-17 | 2017-09-15 | 浙江精通科技股份有限公司 | A kind of high weather-resistant fluorescent colored particles preparation method |
-
1993
- 1993-08-26 CN CN 93109755 patent/CN1099398A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163929A (en) * | 2017-05-17 | 2017-09-15 | 浙江精通科技股份有限公司 | A kind of high weather-resistant fluorescent colored particles preparation method |
| CN107163929B (en) * | 2017-05-17 | 2019-06-28 | 浙江精通科技股份有限公司 | A kind of high weather-resistant fluorescent colored particles preparation method |
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