CN107227042A - A kind of formaldehydeless fluorescent pigment powder of thermosetting and preparation method thereof - Google Patents
A kind of formaldehydeless fluorescent pigment powder of thermosetting and preparation method thereof Download PDFInfo
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- CN107227042A CN107227042A CN201710274182.5A CN201710274182A CN107227042A CN 107227042 A CN107227042 A CN 107227042A CN 201710274182 A CN201710274182 A CN 201710274182A CN 107227042 A CN107227042 A CN 107227042A
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- Prior art keywords
- fluorescent pigment
- thermosetting
- formaldehydeless
- pigment powder
- powder
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Classifications
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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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0004—Coated particulate pigments or dyes
- C09B67/0008—Coated particulate pigments or dyes with organic coatings
- C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
- C08F212/10—Styrene with nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
Abstract
The present invention relates to formaldehydeless fluorescent pigment powder of a kind of thermosetting and preparation method thereof, belong to organic pigment field, the formaldehydeless fluorescent pigment powder of the thermosetting is as obtained from monomer and the alkaline fluorescent dye press filtration after suspension polymerization in a kettle., the dispersion emulsifier used is polyvinyl alcohol 1750 and neopelex, in addition to initiator ammonium persulfate, colouring agent and deionized water.Gained fluorescent pigment is evenly distributed in microsphere powder, and powder diameter, regular shape, with excellent high temperature resistant and solvent resistance, available for plastics plastic cement, textile printing, building coating and printing packaging, 300 DEG C of Shooting Techniques of five minutes can be subjected to, pigment nondiscolouring is colour-fast, does not migrate.
Description
Technical field
The invention belongs to organic pigment, plastics and textile printing mill base field, it is related to a kind of environment-friendly type, formaldehydeless and resistance to height
Temperature（Heatproof is higher than 300 DEG C）Fluorescent pigment powder and preparation method.
Technical background
The preparation of current fluorescent pigment powder mainly wraps up fluorescent dye using resin, first prepares pigmentary resin, then
Again size-reduced and ultra-fine grinding and obtain fluorescent pigment.Resin for wrapping up fluorescent dye is usually melamine resin, polyamide
Resin, polyester resin, polyesteramide resin and polyacrylate type resin etc., for example：US3922232 describes a kind of polyester
Resin parcel fluorescent dye prepares pigmented polyester resin, the method that then crushing prepares fluorescent pigment；US5236621 describes one
Kind using polyamide wrap up fluorescent dye prepare should pigment method；Patent CN201410848331.0 describes one kind
The method that polyester resin prepares fluorescent pigment, and three (2- ethoxys) chlorinated isocyanurates of addition in resin polymerization single polymerization monomer（Match
Gram）As modifying agent to improve the heat resistance of fluorescent pigment；Patent CN201410839745.7 describes one kind and can be used for
The organic fluorescent pigment and preparation method of EVA foaming, its preparation method are that unsaturated binary of fatty acids is introduced in preparation process
Monomer；Chinese patent CN201310285551.2 describes a kind of fluorescent pigment with good heat resistance；Patent
CN201210469697.8 describes a kind of Production method of strong-solvent-resisthermosetting thermosetting organic fluorescent pigment, and it is mainly with to first
Benzamide, melamine, formaldehyde and auxiliary agent prepare melamine resin and fluorescent dye are wrapped up and the pigment is prepared；
A kind of preparation method of polyurethane resin-based fluorescent pigment is described in US3741907；US4975220 describes a kind of polyester acyl
The preparation method of polyimide resin base fluorescent pigment.One kind is described in patent CN201310487242.3 and utilizes cationic polymerization list
The method that body pi-allyl trimethyl ammonium chloride prepares fluorescent pigment latex as functional monomer and acid fluorescent dye；Patent
201310685454.2 it is initiator using azo-bis-isobutyl cyanide to describe a kind of, fluorescent pigment breast is prepared by emulsion polymerization
The method of liquid.Above-mentioned block resin crushing method prepares fluorescence and also there are shortcomings.Such as：Process is more, and technique is coarse, consumption energy consumption
Electricity, easily produces dust；The granules of pigments that block resin is prepared after crushed is larger, and in irregular shape, and influence prepares fluorescence
Storage stability during pigment emulsion.Meanwhile, face is prepared as carrier using melamine resin, polyester, polyamide and polyesteramide
During material, its heat resistance is poor, use of the influence pigment in fields such as plastic cement, plastics.
Lee you preferably describe it is a kind of prepare the method for styrene-divinylbenzene microballoon, and have studied dispersion stabilizer to production
The influence of moral character energy（Chemistry circular, 1981 (12):26-27）；Li Hong et al. reports a kind of suspension polymerization synthesis nano
The method of Monodispersed cross linking polystyrene microsphers（Petrochemical industry, 2004,33 (6):560-562）.Patent CN102898572A is situated between
Continued a kind of preparation method of the poly- divinylbenzene microspheres of highly cross-linked single dispersing；Patent CN102382226A describes a kind of poly- N-
The preparation method of vinylpyrrolidone-divinylbenzene microspheres；Patent CN101612543A describes a kind of polystyrene-diethyl
The preparation method of alkene benzene microballoon, and use it for field of blood purification；Patent CN102335597B describes one kind and utilizes diethyl
Alkene benzene prepares the method for limiting and silica gel chromatographic column filling material being coated into type poly- (styrene-co- divinylbenzenes).Qin Lu utilizes porous membrane emulsiilcation
Homogeneous PST-DVB porous microspheres are prepared with suspension polymerisation combined techniques（Process engineering journal, 2007,7 (3):526-530）；Wang Jing
Polydivinylbenezene microballoon has been prepared using suspension polymerization, and has been applied in small molecule and polypeptide reversed phase chromatography separation
（Process engineering journal, 2009,9 (4):763-769）；Li Lu has prepared stryrene divinyl using seed swelling polymerization method
Benzene stephanoporate crosslinked microsphere（Fine chemistry industry, 20063,2（6）：527-532）；Li Yi etc. have studied monodisperse polystyrene microsphere
Preparation method and its influence factor（Beijing University of Chemical Technology's journal, 2004,31（5）：53-55）.
The content of the invention
Complicated for prior art fluorescent pigment powder process, dust is larger in production process, and product particle is not advised
Then with the deficiency of heat resistance difference, it is an object of the invention to provide a kind of formaldehydeless fluorescent pigment powder of thermosetting, particle diameter distribution
Uniform rule, heat resistance are good, are amenable to 300 DEG C of Shooting Techniques of five minutes, pigment nondiscolouring is colour-fast, does not migrate.Not only
Available for textile printing, building coating and printing packaging.
It is another object of the present invention to provide a kind of preparation method of the formaldehydeless fluorescent pigment powder of thermosetting, use
Press filtration is obtained after suspension polymerization, and being dispersed through polymerization by monomer wraps up alkaline fluorescent dye, dust in production process
It is small.
The present invention is adopted the following technical scheme that：
A kind of formaldehydeless fluorescent pigment powder of thermosetting, including polymerized monomer, and account for the following of polymerized monomer percetage by weight
Component：Polyvinyl alcohol（PVA1750）0.5%~2%, lauryl sodium sulfate 1%~4%, initiator 0.01%~3%, colouring agent
0.001%~5% and deionized water 50~500%.
Described polyvinyl alcohol 1750（PVA1750）It is dispersion emulsifier, and polyvinyl alcohol with neopelex
Mass ratio with lauryl sodium sulfate quality is 1:2；
Described initiator is ammonium persulfate（APS）；
Described colouring agent is fluorescent dye；Described fluorescent dye is basic yellow 24, basic yellow 40, alkali red 1:1:1st, alkalescence is red
2nd, Basic Red 13, alkali red 1:1 4, alkalescence red 27, alkaline purple 7, alkaline purple 10, Basic Violet16, alkali violet 11:1:Any one of 1.
Described polymerized monomer is methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, styrene, third
Alkene nitrile, 2- acrylamide-2-methylpro panesulfonic acids（AMPS）And divinylbenzene（DVB）Mixture, and each component accounts for monomer
The percetage by weight of total amount is as follows：Methyl acrylate 1%~30%, methyl methacrylate 1%~30%, acrylic acid 0~10%, first
Base acrylic acid 0~10%, styrene 30%~50%, acrylonitrile 2~15%, 2- acrylamide-2-methylpro panesulfonic acids（AMPS）0.5
~1.5%, divinylbenzene 1~5%.
The preparation method of the above-mentioned formaldehydeless fluorescent pigment powder of thermosetting, comprises the following steps：
（1）It is prepared by dispersion：Water is first added in the reactor, is added anionic emulsifier lauryl sodium sulfate, is divided
Powder polyvinyl alcohol 1750, colouring agent, polymerized monomer, high-speed stirred form uniform dispersion；
（2）Heating triggers：Warming while stirring adds the initiator ammonium persulfate of total initiator amount 2/3 to 80 DEG C, keeps
80-90 DEG C of reaction；
（3）Polymeric precipitation：After 80-90 DEG C is reacted 3-4 hours, there is substantial amounts of fluorescent pigment particle Precipitation in reaction system,
Continue to stir, add the initiator of residue 1/3, keep reaction 2-3 hours；
（4）It is cooled to room temperature, filtering, washing, press filtration and dries to obtain thermosetting fluorescent pigment microballoon.
The formaldehydeless fluorescent pigment powder of thermosetting that the present invention is obtained, is a kind of thermosetting powders, different from polyester,
The Thermoplastic fluorescent pigment powder such as polyamide and polyurethane-base；And prepare pigment powder different from traditional block resin crushing method
End, the present invention is that monomer is carried out into suspension polymerisation acquisition.
Term explanation：Soften when thermoplastic is heating so that flowing, cooling is hardened, this process be it is reversible, can
To be repeated.Molecular resin chain is all without chemical bond production between line style or branched structure, strand in thermoplastic
Raw, the process that softening flowing, cooling are hardened during heating is physical change.
And thermosetting plastics can soften flowing when being and heating for the first time, certain temperature is heated to, produce and chemically react one
Interlinkage solidifies and is hardened, and this change is irreversible, hereafter, when heating again, can not become soft flow again.Exactly by
This characteristic carries out processing and forming, and plasticizing when being heated using first time is flowed, and under stress full of die cavity, and then is solidified into
The product of shape and size is determined, this material is referred to as thermosetting plastics.It is line style or band before the resin solidification of thermosetting plastics
Side chain, chemical bond is formed after solidification between strand, as three degree of network structure, not only can not again melt and touch, in a solvent
It can not dissolve.
The present invention introduces functional form monomer divinylbenzene in suspension polymerisation monomer（DVB）(such as formula（Ⅰ）It is shown), it contains
Two carbon-carbon double bonds（C=C）Functional group, can be crosslinked in the course of the polymerization process so that styrene-acrylonitrile-acrylate is common
Poly resin turns into a kind of thermosetting resin, to improve the heat resistance and application performance of fluorescent pigment.
Formula（Ⅰ）
Relative to prior art, the beneficial effects of the invention are as follows：(1) suspension polymerisation and press filtration are used, a step obtains fluorescent pigment
Microsphere powder, and powder diameter is evenly distributed, regular shape.（2）Monomer divinylbenzene is introduced, fluorescent pigment microballoon is improved
Hot property（The fluorescent pigment microballoon of divinylbenzene is thermoplastic resin, and general 100 DEG C or so of Tg is heated to 90 DEG C or 100
DEG C resin starts to soften, and continues to raise temperature, resin initially enters elastomeric state and viscous state；Patent of the present invention, adds crosslinking
Monomer, obtained resin microsphere is thermosetting resin, is heated to any temperature all without softening and flows, only can directly decompose；
（3）Prepared fluorescent pigment powder can be subjected to 300 DEG C of injection nondiscolourings in five minutes colour-fast when for plastic plastics.
Brief description of the drawings
Fig. 1 is the electron microscope of the gained thermosetting fluorescent pigment microballoon of embodiment 3（Scale 500nm is total length in figure, each
Individual scale is 50nm）, it is seen that gained fluorescent pigment powder external form is microballoon；（2）Particle diameter distribution is uniform, regular shape.
Embodiment
Following examples are that the present invention is further illustrated, but the invention is not limited in this.
Embodiment 1-8 prepares the raw material of the formaldehydeless fluorescent pigment powder of thermosetting as shown in table 1, and monomer component is shown in Table 2
It is shown：
Each stock blend and synthesis technologic parameter of the formaldehydeless fluorescent pigment powder of the thermosetting of table 1
Particle obtained by embodiment 1-8 is in microballoon, and the uniform rule of particle diameter distribution, heat resistance are good,
300 DEG C of Shooting Techniques of five minutes are amenable to, pigment nondiscolouring is colour-fast, does not migrate.
The polymerized monomer proportioning of the formaldehydeless fluorescent pigment powder of the thermosetting of table 2（Unit：Kg）
Embodiment 1-8 preparation process is as follows：
In the reactor that water, polyvinyl alcohol, lauryl sodium sulfate are charged first to 2000 liters, warming while stirring to 80 DEG C,
After polyvinyl alcohol is completely dissolved, room temperature is cooled to.Continue to stir, sequentially add drawing for polymerized monomer, colouring agent and 2/3 consumption
Send out agent ammonium persulfate.After monomer is added, side is drastically stirred, while being warming up to 80 DEG C, reacts 3-4 hours, has in reaction system
Fluorescent pigment microballoon is separated out.Continue insulated and stirred, add the initiator of residue 1/3, then react after 2-3 hours, be cooled to room temperature,
Filtering, fluorescent pigment powder is obtained after washing, then press filtration, drying.
Gained organic fluorescent pigment powder has excellent fluorescence and dispersiveness.Gained fluorescent pigment powder is at 300 DEG C
Under the conditions of be used for PP materials coloring, through pigment heat-resistant stability method of testing（DIN53772）With pigment resistance to migration method of testing
（DIN 53775）Detection is all qualified.
The above-mentioned embodiment technical scheme that the invention is not limited in any way, every use equivalent substitution or is waited
The technical scheme that the mode of effect conversion is obtained all falls within protection scope of the present invention.
Claims (5)
1. a kind of formaldehydeless fluorescent pigment powder of thermosetting, it is characterised in that including polymerized monomer, and account for polymerized monomer weight
The following component of percentage：Polyvinyl alcohol 0.5%~2%, lauryl sodium sulfate 1%~4%, initiator 0.01%~3%, colouring agent
0.001%~5% and deionized water 50~500%；Described polymerized monomer is methyl acrylate, methyl methacrylate, propylene
Acid, methacrylic acid, styrene, acrylonitrile, the mixture of 2- acrylamide-2-methylpro panesulfonic acids and divinylbenzene.
2. the formaldehydeless fluorescent pigment powder of thermosetting according to claim 1, it is characterised in that described polyvinyl alcohol with
The mass ratio of lauryl sodium sulfate quality is 1:2；Described initiator is ammonium persulfate；Described colouring agent is fluorescence dye
Material.
3. the formaldehydeless fluorescent pigment powder of thermosetting according to claim 1, it is characterised in that in polymerized monomer, each component
The percetage by weight for accounting for monomer total amount is as follows：Methyl acrylate 1%~30%, methyl methacrylate 1%~30%, acrylic acid 0~
10%th, methacrylic acid 0~10%, styrene 30%~50%, acrylonitrile 2~15%, 2- acrylamide-2-methylpro panesulfonic acids 0.5
~1.5%, divinylbenzene 1~5%.
4. the formaldehydeless fluorescent pigment powder of thermosetting according to claim 2, it is characterised in that described fluorescent dye is
Basic yellow 24, alkali red 1:1:1st, alkali red 1:1, alkaline purple 10, Basic Violet16, alkali violet 11:1:1 any one or mixture.
5. the preparation method of the formaldehydeless fluorescent pigment powder of thermosetting described in claim 1, it is characterised in that including following step
Suddenly：（1）The preparation of dispersion：Water is first added in the reactor, adds lauryl sodium sulfate, polyvinyl alcohol, colouring agent,
Polymerized monomer, high-speed stirred forms uniform dispersion；（2）Heating triggers：Warming while stirring adds total trigger to 80 DEG C
The initiator of agent consumption 2/3, keeps 80-90 DEG C of reaction；（3）Polymeric precipitation：After 80-90 DEG C is reacted 3-4 hours, in reaction system
There is substantial amounts of fluorescent pigment particle Precipitation, continue to stir, add the initiator of residue 1/3, keep reaction 2-3 hours；（4）
It is cooled to room temperature, filtering, washing, press filtration and dries to obtain thermosetting fluorescent pigment microballoon.
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| CN201710274182.5A CN107227042A (en) | 2017-04-25 | 2017-04-25 | A kind of formaldehydeless fluorescent pigment powder of thermosetting and preparation method thereof |
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| CN201710274182.5A CN107227042A (en) | 2017-04-25 | 2017-04-25 | A kind of formaldehydeless fluorescent pigment powder of thermosetting and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1067963A (en) * | 1996-08-28 | 1998-03-10 | Pentel Kk | Water base fluorescent pigment composition |
| JP2007224142A (en) * | 2006-02-23 | 2007-09-06 | Dainichiseika Color & Chem Mfg Co Ltd | Fluorescent colorant and its use |
| CN101098939A (en) * | 2004-04-28 | 2008-01-02 | 科莱恩产品（德国）有限公司 | Method for production of polymer-encapsulated pigments |
| CN103709298A (en) * | 2013-12-16 | 2014-04-09 | 丽王化工(南通)有限公司 | Non-formaldehyde fluorescent paint emulsion and preparation method thereof |
| CN105017462A (en) * | 2014-04-23 | 2015-11-04 | 南京工业大学 | Sunlight-resistant fluorescent coating emulsion and preparation method thereof |
| CN105482019A (en) * | 2015-12-29 | 2016-04-13 | 江苏丽王科技股份有限公司 | High-temperature-resistant formaldehyde-free fluorescent pigment emulsion and preparation method thereof |
-
2017
- 2017-04-25 CN CN201710274182.5A patent/CN107227042A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1067963A (en) * | 1996-08-28 | 1998-03-10 | Pentel Kk | Water base fluorescent pigment composition |
| CN101098939A (en) * | 2004-04-28 | 2008-01-02 | 科莱恩产品（德国）有限公司 | Method for production of polymer-encapsulated pigments |
| JP2007224142A (en) * | 2006-02-23 | 2007-09-06 | Dainichiseika Color & Chem Mfg Co Ltd | Fluorescent colorant and its use |
| CN103709298A (en) * | 2013-12-16 | 2014-04-09 | 丽王化工(南通)有限公司 | Non-formaldehyde fluorescent paint emulsion and preparation method thereof |
| CN105017462A (en) * | 2014-04-23 | 2015-11-04 | 南京工业大学 | Sunlight-resistant fluorescent coating emulsion and preparation method thereof |
| CN105482019A (en) * | 2015-12-29 | 2016-04-13 | 江苏丽王科技股份有限公司 | High-temperature-resistant formaldehyde-free fluorescent pigment emulsion and preparation method thereof |
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