CN114149548A - Flame-retardant acrylic resin and solvent-type thermal foaming inkjet ink prepared from same - Google Patents

Flame-retardant acrylic resin and solvent-type thermal foaming inkjet ink prepared from same Download PDF

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CN114149548A
CN114149548A CN202111538931.3A CN202111538931A CN114149548A CN 114149548 A CN114149548 A CN 114149548A CN 202111538931 A CN202111538931 A CN 202111538931A CN 114149548 A CN114149548 A CN 114149548A
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acrylic resin
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卓德康
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Fujian Greenda New Material Technology Co ltd
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Xiamen Gelintai New Material Science & Technology Co ltd
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    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks

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  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

The invention provides flame-retardant acrylic resin and solvent-type thermal foaming inkjet ink prepared from the same. The technical scheme firstly synthesizes the modified epoxy acrylic resin, which comprises the following steps: 15 to 20 percent of monomer, 5 to 10 percent of functional monomer, 50 to 80 percent of epoxy resin, 0.2 to 2 percent of polymerization inhibitor and 0.1 to 1 percent of alkaline catalyst; wherein the monomer is selected from acrylic acid or methyl acrylate; the functional monomer is selected from hydroxyethyl acrylate or glycidyl methacrylate; the modified epoxy acrylic resin is prepared by ring-opening esterification of epoxy resin, insufficient acrylic acid and functional monomer under the action of a catalyst. On the basis, the ink is mixed with a dye colorant, an organic solvent, a humectant and an auxiliary agent in a specific proportion to obtain the solvent type thermal foaming ink-jet ink with excellent performance. The ink has good adhesion on plastic base materials such as OPP, nylon and the like, and has remarkable technical advantages of remarkably improved flame retardance.

Description

Flame-retardant acrylic resin and solvent-type thermal foaming inkjet ink prepared from same
Technical Field
The invention relates to the technical field of inkjet ink, in particular to flame-retardant acrylic resin and solvent-type thermal foaming inkjet ink prepared from the same.
Background
1. Thermal foaming inkjet
The drop-on-demand techniques are mainly classified into thermal, piezoelectric and electrostatic types. Thermal transfer ink jet printing technology, the formation of droplets is due to the rapid heating of resistive elements in ink containing cartridges. The temperature of the resistance element rises to 350-400 ℃, so that the ink film above the heater is evaporated, bubbles are rapidly generated by evaporation, and air pressure pulses are generated to push liquid drops to pass through the nozzle. After the droplet is ejected, a cavity is formed in the cartridge and then filled with liquid, waiting for the next droplet to be formed.
The jet printing mechanism of thermal bubble jet ink: the process of ink drop ejection from a Thermal Ink Jet (TIJ) printhead starts with an electrical pulse applied across a resistor. Within about 2 to 5us, the resistor surface reaches a temperature of 200 to 300 ℃, and the ink near the resistor surface boils, creating a high pressure bubble (about 100 atmospheres) that pushes the ink through the nozzle. The pressure chamber is then refilled with ink from the reservoir due to capillary action.
2. Flame retardancy of solvent-based thermal foaming jet printing ink
The solvent type thermal foaming ink-jet ink has a serious defect and is inflammable, so that potential safety hazards are brought to life of people. With the development of society, the safety awareness of people is improved, and a new requirement for flame retardance is provided for the application of the ink-jet ink.
The adhesive adopted by the thermal foaming ink-jet ink is multipurpose acrylic resin, and the acrylic ester belongs to organic substances, is inflammable when meeting fire after film forming, generates thick smoke and generates a large amount of harmful substances, so that the application range of the thermal foaming ink-jet ink is influenced, and the thermal foaming ink-jet ink is very necessary to be modified in flame retardance.
In order to improve the flame retardant property of the ink, flame retardant additives are often added to the ink or flame retardant elements are often introduced into the polymer chain. The addition of small-molecule flame retardant in the ink can obtain a good flame retardant effect, but the flame retardant has mobility and influences the performance of the coating. The flame retardant property of the halogen flame retardant can be improved by introducing halogen and phosphorus elements into a high molecular chain, but the halogen flame retardant generates toxic hydrogen halide gas during combustion and is corrosive. The phosphate flame retardant forms a coke layer during combustion, prevents heat and flame from spreading, has a good flame retardant effect, and has the advantages of small migration, good durability, low toxicity and the like. Therefore, if phosphorus is introduced into the acrylic resin structure, an ink having flame retardancy can be prepared.
Unsaturated acrylate groups and phosphate groups are introduced into the skeleton of the epoxy resin, so that the epoxy resin has flame retardance.
And the phosphate is a common adhesion promoter, is suitable for various substrates such as copper, iron, aluminum, wood, plastics and the like, and particularly has an obvious promoting effect on the adhesion of metal substrates such as copper, iron, aluminum and the like because strong polarity of phosphate groups generates strong chemical bonding action with the substrates, but the phosphate has a high acid value, and the water resistance of a coating is influenced by excessive addition amount which is not excessive.
The phosphate modified acrylic resin effectively improves the flame retardant and smoke suppression performance of the flame retardant polymer material, and can improve the thermal stability of the material. In the combustion process of the phosphate modified acrylic resin, the formation of a compact expanded carbon layer is promoted, the transfer of oxygen and heat is reduced, the thermal stability of the material is improved, the thermal cracking rate of the acrylic resin is reduced, the generation and release of smoke are reduced, the high-temperature carbon residue rate is improved, the conversion of the carbon layer to similar graphitization is promoted, the flame retardant property is improved, the peak value of the heat release rate, the total heat release rate, the peak value of the smoke release rate and the total smoke generation amount of the composite material are reduced, and the acrylic resin is endowed with excellent flame retardant property.
3. Other Performance parameters of thermally foamable inkjet inks
Viscosity
Viscosity refers to a property of preventing liquid flow, which is a measure of the ability of molecules of a fluid to move relative to each other due to interaction between the molecules, i.e., resistance to fluid flow, also referred to as internal friction.
Surface tension
Surface tension is characterized by the force of mutual traction within a unit length between two adjacent portions of a liquid surface, which is a manifestation of molecular forces. Digital proofing inks must have a suitable surface tension which also has a significant impact on the ink drop formation during the ink jet process and the quality of the ink jet printing.
(iii) adhesive force
Adhesion is characterized by the ability of the film layer to adhere to the surface of the substrate to which it is attached by physical and chemical interactions. The adhesion mechanism of the film layer is as follows: chemical attachment and mechanical attachment. Chemical adhesion refers to the mutual attraction of the film molecules and the substrate molecules in the interface between the film layer and the substrate, which is determined by the physical and chemical properties of the film layer and the substrate. Cohesive forces of chemical attachment include van der waals attractive forces, electrostatic forces, chemical affinity forces, and forces of hydrogen bonding. The mechanical adhesion depends on the roughness, porosity, etc. of the substrate and the strength of the formed film.
Disclosure of Invention
The invention aims to provide a flame-retardant acrylic resin and a solvent-type thermal foaming inkjet ink prepared from the flame-retardant acrylic resin aiming at the technical defects of the prior art, so as to solve the technical problems that the adhesion and the flame retardance of the conventional inkjet ink need to be improved.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the flame-retardant acrylic resin comprises the following components in percentage by mass: 15 to 20 percent of monomer, 5 to 10 percent of functional monomer, 50 to 80 percent of epoxy resin, 0.2 to 2 percent of polymerization inhibitor and 0.1 to 1 percent of alkaline catalyst; wherein the monomer is selected from one or more of the following components: acrylic acid, methyl acrylate; the functional monomer is selected from one or more of the following components: hydroxyethyl acrylate, glycidyl methacrylate.
Preferably, the epoxy resin is selected from one or several of the following components: epoxy resin E51 type, epoxy resin E44 type.
Preferably, the polymerization inhibitor is p-hydroxyanisole.
Preferably, the basic catalyst is triethanolamine.
On the basis of the technical scheme, the invention further provides phosphoric acid modified epoxy acrylic resin prepared from the flame-retardant acrylic resin, which comprises the following components in percentage by mass: 50-80% of flame-retardant acrylic resin, 5-30% of dibutyl phosphate and 20-50% of butanone.
On the basis of the technical scheme, the invention further provides a solvent type thermal foaming inkjet ink prepared from the phosphoric acid modified epoxy acrylic resin, which comprises the following components in percentage by mass: 5 to 10 percent of dye colorant, 80 to 95 percent of organic solvent, 1 to 5 percent of humectant, 2 to 5 percent of adhesive and 0.1 to 2 percent of auxiliary agent; wherein the adhesive is the phosphoric acid modified epoxy acrylic resin.
Preferably, the organic solvent is selected from one or several of the following components: short-chain alcohols, short-chain esters, short-chain ketones, short-chain ethers.
Preferably, the humectant is selected from one or several of the following components: ethylene glycol ether, propylene glycol ether, cyclohexanone.
Preferably, the auxiliary agent is selected from one or several of the following components: leveling agent, wetting agent, defoaming agent and surfactant.
The invention provides flame-retardant acrylic resin and solvent-type thermal foaming inkjet ink prepared from the same. The technical scheme firstly synthesizes a modified epoxy acrylic resin, and the modified epoxy acrylic resin is prepared by ring-opening esterification of epoxy resin, insufficient acrylic acid and functional monomers under the action of a catalyst. On the basis, the ink is mixed with a dye colorant, an organic solvent, a humectant and an auxiliary agent in a specific proportion to obtain the solvent type thermal foaming ink-jet ink with excellent performance. The ink has good adhesion on plastic base materials such as OPP, nylon and the like, and has remarkable technical advantages of remarkably improved flame retardance.
Drawings
FIG. 1 is a graph showing the results of a test using a nylon plastic film as a substrate in accordance with an embodiment of the present invention.
FIG. 2 is a graph showing the results of the test using an OPP plastic film as a substrate in the embodiment of the present invention.
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in detail. Well-known structures or functions may not be described in detail in the following embodiments in order to avoid unnecessarily obscuring the details. Approximating language, as used herein in the following examples, may be applied to identify quantitative representations that could permissibly vary in number without resulting in a change in the basic function. Unless defined otherwise, technical and scientific terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Synthesis of flame-retardant phosphoric acid modified epoxy acrylic resin
Synthetic steps of phosphoric acid modified epoxy acrylic resin
The synthesis of the phosphoric acid modified epoxy acrylic resin is completed by the following two steps:
1. synthesizing modified epoxy acrylic resin;
2. synthesis of phosphoric acid modified epoxy acrylic resin
(II) Synthesis of modified epoxy acrylate
The synthesis of modified epoxy acrylic resin is mainly characterized by that under the action of catalyst the epoxy resin and insufficient acrylic acid and functional monomer are undergone the processes of ring-opening esterification so as to obtain the invented product.
1. The synthesis of the modified epoxy acrylic resin is mainly prepared from the following raw materials:
(1) functional monomer: hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl ester, acrylamide
Functional acrylic acid and ester monomers: acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl acrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, alpha-nitrile acrylate (methyl or ethyl ester), trifluoroethyl methacrylate
(2) Epoxy resin: e51 type or E44 type epoxy resin.
(3) And polymerization inhibitor: one or more of p-hydroxyanisole, hydroquinone, p-tert-butyl catechol or copper naphthenate
(4) And a basic catalyst: one or more of triphenylphosphine, triethylamine, triethanolamine, N-dimethylbenzylamine or tetraethylammonium bromide. The function is to catalyze the addition reaction of epoxy groups.
2. Proportioning and process steps
Figure BDA0003411532740000051
The process comprises the following steps:
mixing epoxy resin and a polymerization inhibitor, heating to 80-100 ℃, uniformly stirring in the heating process, then carrying out heat preservation and dropwise adding a monomer mixed solution dissolved with an alkaline catalyst, carrying out heat preservation for 4-8 hours after dropwise adding is completed within 2 hours, reacting until the acid value is 3-5 mgKOH/g, and cooling.
3. Principle of reaction
The hydroxypropyl methacrylate is copolymerized with other acrylic monomers to prepare the acrylic resin containing active hydroxyl. Then, the acrylic resin and the acrylic acid esterification epoxy resin are insufficient, and the prepared epoxy acrylic resin contains active hydroxyl and unreacted epoxy groups.
(III) phosphoric acid modified epoxy acrylic resin
1. The main raw materials of the phosphoric acid modified epoxy acrylic resin are as follows:
(1) modified epoxy acrylic resin
(2) Dibutyl phosphate
(3) And a solvent: butanone
2. Proportioning and process steps
Figure BDA0003411532740000061
The process comprises the following steps: dissolving the epoxy acrylate in a solvent, adding the epoxy acrylate into a four-neck flask provided with a stirrer, a condenser tube and a thermometer, stirring, heating to 40 ℃, dissolving dibutyl phosphate in the solvent, slowly adding the dibutyl phosphate into a reaction bottle within 3 hours, continuously stirring, and keeping the temperature at 40 ℃. And when the dibutyl phosphate is added, reacting for about 5 hours, heating to 60 ℃, and volatilizing the solvent.
3. Principle of reaction
And (3) carrying out phosphorylation esterification on epoxy groups in the modified epoxy acrylic resin to obtain the phosphoric acid modified epoxy acrylic resin. Preparation of solvent type thermal foaming ink-jet ink
Raw materials of the solvent-based thermal foaming inkjet ink: 1. a dye colorant; 2. an organic solvent; 3. a humectant; 4. a resin binder; 5. various assistants
1. Dye colorant:
the colorant may include one dye or a plurality of dyes. The colorant includes alcohol-soluble dyes and ketone-soluble dyes. Multiple dyes can achieve brighter or more vibrant colors than a single dye. Multiple dyes can better tune secondary properties such as gloss in printing inks.
Examples of suitable dyes include those obtainable from:
dyes from BASF, such as: blue 670, c.i. solvent Blue 35; black X60; and Orange 220.
Oil palm 102 from Passaic Color & Chemical Company; oil Red 234 from Passaic Color & Chemical Company;
the series of dyes from BASF, including Black X55 and Orange 247, and the series of dyes;
valifast Black 3808, c.i. solvent Black 29 from Oriental Chemical Company, Ltd.
The black solvent dye may include c.i. solvent blacks 5, 7, 27, 28, 29, 34, 35, 45, 46, and 48.
The blue solvent dye may include c.i. solvent blue 4, 5, 6, 35, 38, 48, 59, 67, 70, 104, and 136.
The violet solvent dyes may include c.i. solvent violet 8, 9, 11, 14 and 38.
The brown solvent dye may include c.i. solvent brown 1, 3, 5, 20, 42, 43, 44, 48, and 52.
The orange solvent dye may include c.i. solvent orange 3, 11, 20, 25, 54, 60, 62, 63, 86, 99, and 105.
The red solvent dye may include c.i. solvent reds 1, 23, 29, 49, 119, 122, 125, 127, 130, 132, 135, 149, 160, 164, 168, 169, 172, and 233.
The yellow solvent dye may include c.i. solvent yellows 10, 13, 14, 19, 25, 28, 33, 88, 89, 114, 146, and 163.
2. Organic solvent
One of the most important factors in the choice of organic solvent is the trade-off between the need to ensure drying of the base ink and resistance to jet lag and head clogging. It is more reliable to use a solvent that dries at a very slow rate because it minimizes drying of the ink in the head and thus prevents clogging. However, drying a slow solvent requires more energy and time to separate the solvent.
The solvent mixture is chosen to be well soluble in the resin and dye, and the rate of evaporation of the solvent is noted.
Short-chain alcohols, short-chain esters, short-chain ketones, short-chain ethers;
short-chain alcohols: methanol, ethanol, propanol, isopropanol, butanol, etc
Short-chain esters: methyl acetate, ethyl acetate, butyl acetate and the like
Short-chain ketones: acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, etc
Short-chain ethers: ethyl ether, ethylene glycol ethyl ether, and the like
The vehicle for solvent-based inks has a very low vapor pressure at room temperature. Such inks are generally referred to as solvent-based inks where the carrier solvent evaporates or is removed after printing. The solvent in the ink generally serves to transport the functional material to the substrate surface. Such solvents may be removed by passive drying or active drying mechanisms.
The drying time of the ink and the ability of the polymer to release the solvent mixture are also important. Solvent mixtures are often used to ensure the solubility of certain key components, maintaining a good balance of ink properties.
3. Moisture-retaining agent
Humectant (one or a mixture of several kinds): ethylene glycol ethers, propylene glycol ethers, cyclohexanone, etc
4. Resin binder
Resin binder: mixtures of one or more acrylic resins
Resin binder: the resin binder for thermal foaming type ink-jet ink is a film-forming substance of an ink system, and the performance of the resin binder plays an important role in the properties of an ink film, such as flexibility, adhesion, hardness and the like. The resin is chosen as desired if good adhesion of the ink to glass is desired, and the ink is required to be free of relatively odorous solvents such as MEK. We also consider the relationship between resin properties and printer function. For example, if the relative molecular mass of the polymer is too low, then it may be necessary to add a large amount of polymer to ensure a certain viscosity. Too much polymer may result in extended ink drying times. The use of polymers of high relative molecular mass or high viscosity can have a negative effect on droplet breakup, often resulting in the undesirable formation of a tail accompanying the droplet, affecting print quality and printer performance.
5. Various assistants
Various auxiliaries (levelling agent, wetting agent, defoaming agent, etc.)
Leveling agent: dow corning DC57, DC29, DC204 SL; BYK3500, BYK3510, BYK 3520; height of the Digao: TEGO 410, TEGO 435, etc.
Wetting agent: dow corning DC27, DC 67; digao TEGO 270, and the like.
Defoaming agent: digao 6800, etc.
Surfactant (b): thermal bubble jet ink has a close relationship between the spread of the ejected ink droplets on the substrate and the print quality. Spreading of the ink droplets depends on many factors in the ink droplets, including surface tension, viscosity, evaporation rate of the solvent, interaction with the substrate, and the like. Print quality on a particular print substrate can be improved by fine tuning of the optimum droplet spread, a common tuning method being to add surfactants to the formulation. The chemical nature of the surfactant determines the spreading of the ink droplets. There are hundreds of surfactants, including anionic, cationic, and nonionic surfactants.
The process comprises the following steps:
(1) mixing the dye, the organic solvent, the humectant, the resin binder and various auxiliaries in proportion according to the formula of the ink for later use; (2) placing the prepared raw materials on a JJ-1 type mechanical stirrer, stirring for 20-30 minutes, and uniformly stirring to obtain the prepared ink-jet ink; (3) and filtering the ink, injecting the ink into a Hewlett packager ink box for packaging, installing the Hewlett packager ink box on an ink-jet printer, editing the pattern to be jet-printed on the ink-jet printer, jet-printing the pattern on a specified substrate, and testing after the handwriting is dried.
Figure BDA0003411532740000091
Third, solvent type thermal foaming ink-jet ink performance
The solvent type thermal hairstyle inkjet ink has the following performance advantages that the adhesive adopts phosphoric acid modified epoxy acrylic resin:
1. better adhesion on plastic base materials such as OPP, nylon and the like;
2. the flame retardance is good.
The adhesive force of the resin is tested according to the mixture ratios A and B.
Firstly, the adhesive is well adhered on plastic base materials such as OPP, nylon and the like
1. 3M tape peel test method
Proportioning A, wherein phosphoric acid modified epoxy acrylic resin is adopted as resin; and B, adopting hydroxyl acrylic resin as the resin.
Figure BDA0003411532740000101
Injecting two solvent type thermal foaming ink-jet inks into an ink box, installing the ink box on an ink-jet printer, editing patterns needing to be sprayed and printed on the ink-jet printer, then spraying and printing the patterns on film substrates such as OPP, nylon and the like, standing and drying for 5M, and testing the stripping resistance of the ink-jet printer by adopting a 3M adhesive tape stripping test method.
The 3M adhesive tape stripping test method refers to part of operations of national standard GB/T2792-. The specific contents are as follows: and respectively sticking the silk screen printing area to three areas (a character area, a mark area and a code spraying area) by using a 3M600 special adhesive tape, wherein the sticking area is required to cover the silk screen printing content as much as possible, and the adhesive tape cannot have bubbles, folds and inclination. Then, rolling the adhesive tapes in the three areas back and forth for 30 times at a constant speed (300mm/min) by using a 2KG roller; and then lifting one end of the adhesive tape, quickly pulling the adhesive tape in a direction of 90 degrees with the surface to be tested in the opposite direction, testing for 5 times by the same method, replacing a new 3M adhesive tape each time, and testing at the same position each time.
After the 3M adhesive tape is tested, the image is rated according to the GB/T9286-88 standard and is divided into 6 grades (0-5), the best grade 0 and the worst grade 5.
The adhesion on the nylon substrate is tested by a 3M adhesive tape stripping test method for the ratio A and the ratio B:
Figure BDA0003411532740000111
the results of the experiment are shown in FIG. 1.
The adhesion on the OPP plastic film substrate is tested by a 3M adhesive tape stripping test method for the mixture A and the mixture B:
Figure BDA0003411532740000112
the results of the experiment are shown in FIG. 2.
Secondly, good flame retardance
Flame retardant principle of phosphoric acid modified epoxy acrylic resin
The phosphoric acid modified epoxy acrylic resin can improve the flame retardant and smoke suppression performance of the flame retardant polymer material and can improve the thermal stability of the material. In the combustion process, the formation of a compact expanded carbon layer is promoted, the transfer of oxygen and heat is reduced, the thermal stability of the material is improved, the thermal cracking rate of the acrylic resin is reduced, the generation and the release of smoke are reduced, the flame retardant property is improved, the peak value of the heat release rate, the total heat release, the peak value of the smoke release rate and the total smoke generation amount of the composite material are reduced, and therefore the acrylic resin is endowed with excellent flame retardant property.
(II) flame-retardant testing method
The peak heat release rate of the resin was measured using a cone calorimeter of the cone type, test Standard GB/T16172-2007.
The smoke density grade of the resin is tested by adopting a JCY-3 type building material smoke density tester, and the test standard is GB/T8627-2007.
(III) test results
Testing the peak values of the heat release rates of the hydroxyl acrylic resin and the phosphoric acid modified acrylic resin by using a cone type cone calorimeter, and respectively taking three samples for testing according to a test standard GB/T16172-;
the smoke density grades of the hydroxyl acrylic resin and the phosphoric acid modified acrylic resin are tested by adopting a JCY-3 type building material smoke density tester, the test standard is GB/T8627-containing 2007, and three samples are respectively taken for testing.
Figure BDA0003411532740000121
The peak value of the heat release rate of the phosphoric acid modified acrylic resin is obviously smaller than that of the hydroxyl acrylic resin; the smoke density rating is significantly less than that of the hydroxyacrylic resin.
And (4) conclusion: the phosphoric acid modified acrylic resin is applied to the solvent type thermal foaming inkjet ink, and has good adhesive force and flame retardance.
The embodiments of the present invention have been described in detail, but the description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. Any modification, equivalent replacement, and improvement made within the scope of the application of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. The flame-retardant acrylic resin is characterized by comprising the following components in percentage by mass: 15 to 20 percent of monomer, 5 to 10 percent of functional monomer, 50 to 80 percent of epoxy resin, 0.2 to 2 percent of polymerization inhibitor and 0.1 to 1 percent of alkaline catalyst; wherein the monomer is selected from one or more of the following components: acrylic acid, methyl acrylate; the functional monomer is selected from one or more of the following components: hydroxyethyl acrylate, glycidyl methacrylate.
2. The flame-retardant acrylic resin as claimed in claim 1, wherein the epoxy resin is selected from one or more of the following components: epoxy resin E51 type, epoxy resin E44 type.
3. The flame-retardant acrylic resin as claimed in claim 1, wherein the polymerization inhibitor is p-hydroxyanisole.
4. The flame retardant acrylic resin as claimed in claim 1, wherein said basic catalyst is triethanolamine.
5. A phosphoric acid modified epoxy acrylic resin prepared from the flame-retardant acrylic resin as claimed in any one of claims 1 to 4 is characterized by comprising the following components in percentage by mass: 50-80% of flame-retardant acrylic resin, 5-30% of dibutyl phosphate and 20-50% of butanone.
6. A solvent-based thermal foaming inkjet ink prepared from the phosphoric acid modified epoxy acrylic resin of claim 5 is characterized by comprising the following components in percentage by mass: 5 to 10 percent of dye colorant, 80 to 95 percent of organic solvent, 1 to 5 percent of humectant, 2 to 5 percent of adhesive and 0.1 to 2 percent of auxiliary agent; wherein the adhesive is the phosphoric acid modified epoxy acrylic resin.
7. The solvent-based thermal foaming inkjet ink according to claim 6, wherein the organic solvent is selected from one or more of the following components: short-chain alcohols, short-chain esters, short-chain ketones, short-chain ethers.
8. The solvent-based thermal foaming inkjet ink according to claim 6, wherein the humectant is selected from one or more of the following components: ethylene glycol ether, propylene glycol ether, cyclohexanone.
9. The solvent-based thermal foaming inkjet ink according to claim 6, wherein the auxiliary agent is selected from one or more of the following components: leveling agent, wetting agent, defoaming agent and surfactant.
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Cited By (1)

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CN114890814A (en) * 2022-03-31 2022-08-12 共享智能装备有限公司 Inorganic resin for thermal foaming process and preparation method thereof

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