CN115477721B - Acrylic resin capable of realizing uniform and stable dispersion of carbon black pigment - Google Patents
Acrylic resin capable of realizing uniform and stable dispersion of carbon black pigment Download PDFInfo
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- CN115477721B CN115477721B CN202211243245.8A CN202211243245A CN115477721B CN 115477721 B CN115477721 B CN 115477721B CN 202211243245 A CN202211243245 A CN 202211243245A CN 115477721 B CN115477721 B CN 115477721B
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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
- 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
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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
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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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
- 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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1809—C9-(meth)acrylate
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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
- 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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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- 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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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Abstract
The invention discloses an acrylic resin capable of realizing uniform and stable dispersion of carbon black pigment, which is obtained by carrying out free radical copolymerization reaction on the following comonomers under the action of a free radical initiator and a chain transfer agent, wherein the comonomers comprise the following components: 10-80% of acrylic monomer with aliphatic six-membered ring structure on the side chain; 15% -80% of hard monomer; 0% -10% of soft monomer; 1-10% of polar acrylic monomer; the above percentages refer to the percentage by mass of each constituent monomer to the total mass of the comonomer, and the sum of the percentages of all the constituent monomers is 100%. Experiments show that: the invention not only obtains the acrylic resin product which can realize the uniform and stable dispersion of the carbon black pigment, but also can realize proper viscosity, better blackness and covering power and excellent storage stability of the carbon black ink prepared by adopting the acrylic resin.
Description
Technical Field
The invention relates to acrylic resin, in particular to acrylic resin capable of realizing uniform and stable dispersion of carbon black pigment, and belongs to the technical field of functional materials.
Background
Carbon black (also known as carbon black), which is an amorphous carbon, is a light, loose and extremely fine black powder, has high stability to chemicals, light and heat, is an ideal black pigment, and can be used for manufacturing chinese ink, paint, coating, etc.
Carbon black is a very difficult pigment to disperse, a common practice in the art of coating inks, mainly due to its very large surface area, high surface free energy, very easy agglomeration, and high oil absorption.
The dispersion of carbon black is a physical process, mainly by the steps of breaking, wetting, distribution and stabilization. Because commercial grade carbon black is a carbon black aggregate with larger particle size, the fineness is about 45 microns, and the fineness is far greater than the fineness requirement of downstream application, the coloring performance and other properties of the carbon black can be fully exerted by crushing, and a ball mill, a high-speed stirrer and the like are generally used for crushing the carbon black. The crushed carbon black needs to be wetted by the solvent medium and additives in the formulation before being effectively dispersed in the medium. Wetting, however, is a complex process of surface interaction, and is generally enhanced by the addition of plasticizers or viscosity promoters to the formulation. And then stirring the system under turbulent flow by increasing the processing temperature and reducing the viscosity of the system so as to ensure that the wetted carbon black particles reach better distribution. Because of the inherent attractive force between the carbon black particles, the specific surface area of the carbon black after stirring and dispersing is increased, and the carbon black has higher instability in thermodynamics, so that reagglomeration is easier to occur, therefore, the dispersing agent is required to be added to be adsorbed on the surfaces of the carbon black particles, so that the interaction between the carbon black particles is reduced, and pigment sedimentation is avoided.
Acrylic resins have been used in large amounts in ink formulations because of their excellent gloss, clarity and color development. The acrylic resin used for the ink at present is mainly obtained by copolymerizing common MMA, BMA, MAA and other monomers, and the molecular weight is generally between 1 ten thousand and 10 ten thousand. Although the existing acrylic resin for ink can play a certain auxiliary role in carbon black dispersion, the effect is very limited, and the efficient, uniform and stable dispersion of carbon black is difficult to realize. However, if the carbon black pigment is poorly dispersed in an application system (such as ink, paint and coating), agglomeration or sedimentation occurs, so that a series of properties such as hue, blackness and hiding power of a finished product are significantly affected. Therefore, if an acrylic resin capable of achieving uniform and stable dispersion of carbon black pigment can be developed, it will have great value and significance in improving the performance of ink, paint, coating and other products using carbon black pigment.
Disclosure of Invention
In view of the above-described problems and needs in the prior art, an object of the present invention is to provide an acrylic resin capable of achieving uniform and stable dispersion of carbon black pigment.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an acrylic resin capable of realizing uniform and stable dispersion of carbon black pigment is obtained by carrying out free radical copolymerization reaction on the following comonomers under the action of a free radical initiator and a chain transfer agent, wherein the comonomers comprise the following components:
the above percentages refer to the percentage by mass of each constituent monomer to the total mass of the comonomer, and the sum of the percentages of all the constituent monomers is 100%.
In a preferred embodiment, the composition of the comonomer is as follows:
the above percentages refer to the percentage by mass of each constituent monomer to the total mass of the comonomer, and the sum of the percentages of all the constituent monomers is 100%.
In a preferred scheme, the acrylic monomer with the side chain having an aliphatic six-membered ring structure has the following chemical structural general formula:
and in the general formula: r is-H or-CH 3 ；R 1 、R 2 、R 3 、R 4 、R 5 Each representing two identical or different substituents, each of which is independently selected from-H or C1-C4 alkyl, and R 1 、R 2 、R 3 、R 4 、R 5 The two components are independent or form a bridging structure.
In a further preferred scheme, the acrylic monomer with the side chain having the aliphatic six-membered ring structure is at least one of cyclohexyl acrylate, cyclohexyl methacrylate, 3, 5-trimethyl cyclohexyl acrylate, (3, 5-trimethyl cyclohexyl) methacrylate, isobornyl acrylate and isobornyl methacrylate.
In a preferred scheme, the hard monomer is at least one of methyl methacrylate, tert-butyl methacrylate, isopropyl methacrylate and styrene.
In a preferred embodiment, the soft monomer is at least one selected from ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isooctyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate and lauryl acrylate.
In a preferred embodiment, the polar acrylic monomer is at least one of methacrylic acid, acrylic acid and amino acrylic acid.
In a preferred embodiment, the radical initiator is selected from peroxide radical initiators and azo radical initiators.
In a further preferred scheme, the free radical initiator is at least one selected from benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate and azobisisobutyronitrile.
In a preferred scheme, the free radical initiator is used in an amount of 0.1 to 1.0 percent of the total mass of the comonomer.
In a preferred embodiment, the chain transfer agent is at least one of thiol, mercapto acid and mercapto ester.
In a further preferred scheme, the chain transfer agent is at least one of n-octyl mercaptan, dodecyl mercaptan, mercaptopropionic acid and butyl mercaptopropionate.
In a preferred embodiment, the chain transfer agent is used in an amount of 0.5% to 5.0% of the total mass of the comonomer.
In a preferred embodiment, the radical copolymerization reaction is any one of bulk polymerization, suspension polymerization and solution polymerization.
In a preferred embodiment, the bulk polymerization is performed by a batch bulk polymerization process, namely: firstly adding a comonomer, a free radical initiator and a chain transfer agent into a bulk polymerization bag according to a proportion, then carrying out polymerization reaction for 5-20 hours under the heating of a water bath at 50-80 ℃, then baking for 1-5 hours in a baking oven at 100-130 ℃, and obtaining a final product after crushing and drying the obtained resin.
In a preferred embodiment, the suspension polymerization is carried out by a batch suspension polymerization process, namely: firstly, adding a dispersing agent aqueous solution with the mass fraction of 0.01% -5% into a batch reaction vessel, heating to 40-60 ℃, then adding a mixed solution of a comonomer, a free radical initiator and a chain transfer agent which are mixed uniformly in advance according to the proportion, stirring for 20-40 minutes, heating to 65-90 ℃ for polymerization reaction for 2-6 hours, further heating to 95-99 ℃, continuing stirring for 1-3 hours, ending the reaction, collecting a solid product through standing, settling and filtering, and finally washing and baking for 3-12 hours at 25-95 ℃ to obtain the final product.
In a preferred embodiment, the solution polymerization is performed by a batch solution polymerization process, namely: firstly, adding a polar organic solvent (such as dimethylbenzene and butyl acetate) into a batch reaction container, heating to reflux, then adding a mixed solution obtained by pre-mixing a comonomer, a free radical initiator and a chain transfer agent uniformly in proportion into the reaction container dropwise, keeping stirring and refluxing the solvent, and controlling the mixed solution to be completely dripped within 2-6 hours; after the dripping is finished, continuously reacting for 1-4 hours, transferring the resin solution into a devolatilizer, removing the solvent and the residual monomers under vacuum and at the temperature of 200 ℃ or less, cooling and crushing the obtained resin to obtain the final product.
Preferably, the weight average molecular weight Mw of the acrylic resin is controlled in the range of 2000-20000 Da, and the glass transition temperature Tg of the acrylic resin is controlled in the range of 50-150 ℃.
Compared with the prior art, the invention has the following remarkable beneficial effects:
experiments show that: according to the invention, the acrylic resin is prepared by creatively adopting the acrylic monomer with the aliphatic six-membered ring structure on the side chain in a specific proportion to participate in copolymerization, so that an acrylic resin product capable of realizing uniform and stable dispersion of carbon black pigment is obtained, and the carbon black ink prepared from the acrylic resin provided by the invention has proper viscosity, better blackness and covering power and excellent storage stability, and the acrylic resin can be prepared by adopting the existing preparation process without special equipment, so that large-scale production is easy to realize; thus, the present invention not only represents a significant advance over the prior art, but also produces unexpected technical results.
Detailed Description
The technical scheme of the invention is further and fully described in the following by combining examples.
The measurement methods for the molecular weight in the following examples and comparative examples are as follows:
the molecular weight of the resulting acrylic resin was determined by Gel Permeation Chromatography (GPC), using PS of different molecular weights as a calibrator, tetrahydrofuran as a mobile phase, setting a flow rate of 1mL/min, using an RI detector; the sample was dissolved using tetrahydrofuran.
The measurement methods for the residual monomer ratios in the following examples and comparative examples are as follows:
accurately weighing 15g of a resin sample, dissolving the resin sample in 100-150 ml of dichloromethane, and then adding 1% W/W (relative to the resin sample) of EMA as an internal standard; setting GC conditions to be 200 ℃ of a sample inlet; the column temperature is raised from 100 ℃ to 230 ℃ in 15 minutes and kept for 15 minutes; the detector temperature is 200 ℃; and a filter cotton is arranged at the GC sample inlet to filter out non-volatile components. And testing the ratio of the total peak area of the residual monomers to the peak area of the internal standard, and multiplying the ratio by a percentage number to obtain the monomer residual rate in the resin.
The measurement methods for the glass transition temperature (Tg) in the following examples and comparative examples are as follows:
the Tg of the resulting acrylic resin was measured by a Differential Scanning Calorimeter (DSC), that is: weighing about 0.15 gram of resin sample in a metal crucible, and accurately recording a weighing value; inputting a scanning temperature interval and other necessary parameters into an instrument; after the scan is completed, the midpoint value of the second scan is selected as the Tg value of the sample.
Examples 1 to 3
The acrylic resin capable of realizing uniform and stable dispersion of the carbon black pigment is prepared by adopting a suspension polymerization process:
firstly, adding a dispersing agent aqueous solution with the mass fraction of 0.1% -0.2% into a batch reaction vessel, heating to 40-60 ℃, then adding a mixed solution of a comonomer, a free radical initiator and a chain transfer agent which are mixed uniformly in advance according to the proportion, stirring for 20-40 minutes, heating to 70-85 ℃, carrying out polymerization reaction for 3-6 hours, further heating to 95-99 ℃, continuing stirring for 1-2 hours, ending the reaction, collecting a solid product through standing, settling and filtering, and finally washing and baking for 10-12 hours at 55-65 ℃ to obtain the final product.
The composition information of the comonomer and the radical initiator and the chain transfer agent used in each example, the information of specific process parameters, and the residual monomer, tg value and molecular weight of the obtained acrylic resin are shown in Table 1:
TABLE 1
Examples 4 to 5
The acrylic resin capable of realizing uniform and stable dispersion of the carbon black pigment is prepared by adopting a bulk polymerization process:
firstly adding a comonomer, a free radical initiator and a chain transfer agent into a bulk polymerization bag according to the proportion shown in the table 2, then carrying out polymerization reaction for 10-12 hours under the water bath heating of 60-70 ℃, then baking for 2-3 hours in a baking oven of 110-120 ℃, and obtaining the final product after crushing and drying the obtained resin.
The composition information of the comonomer and the radical initiator and the chain transfer agent used in each example, the information of specific process parameters, and the residual monomer, tg value and molecular weight of the obtained acrylic resin are shown in Table 2:
TABLE 2
Comparative examples 1 to 4
Comparative examples 1 and 2 used the suspension polymerization process described in examples 1 to 3, and comparative examples 3 and 4 used the bulk polymerization process described in examples 4 to 5.
The composition information of the comonomer and the radical initiator and the chain transfer agent used in each comparative example, the information of specific process parameters, and the residual monomer, tg value and molecular weight of the obtained acrylic resin are shown in table 3:
TABLE 3 Table 3
As can be seen from table 3: the comonomer of comparative example 1 has no acrylic monomer with aliphatic six-membered ring structure at the side chain, but the Tg value and the weight average molecular weight of the obtained acrylic resin are both in the control range of the invention; the main difference between comparative example 2 and example 2 is that the amount of chain transfer agent used is different, so that the weight average molecular weight of the acrylic resin obtained in comparative example 2 is far greater than the control range described in the present invention; the main difference between comparative example 3 and examples 4 to 5 is that the amount of soft monomer used is different (up to 35%, much higher than the control range of 0 to 10% according to the present invention), so that the Tg value of the acrylic resin obtained in comparative example 3 is only 30℃and lower than the control range of 50 to 150℃according to the present invention; the amount of the acrylic monomer having an aliphatic six-membered ring structure on the side chain involved in the copolymerization in comparative example 4 was only 5%, which is lower than the lower limit of 10% used in the present invention.
Application performance comparison experiment:
the black ink was prepared by the preparation process of the black ink for gravure printing of PVC shrink films with respect to the acrylic resins prepared in examples 1 to 5 and comparative examples 1 to 4, and then each performance comparison experiment of the obtained ink was performed:
1. preparation of black printing ink for gravure printing of PVC shrink film
Dissolving acrylic resin in propyl acetate at 40% solid content, stirring at normal temperature or under heating to ensure complete dissolution to form a homogeneous solution, and marking the solution as a material 1, namely an acrylic resin solution;
dissolving cellulose acetate butyrate in propyl acetate at 20% solid content, stirring at normal temperature or under heating to ensure complete dissolution to form a homogeneous solution, and recording the solution as a material 2, namely a CAB solution;
the formulation of the black ink for gravure printing of PVC shrink film is shown in table 4.
TABLE 4 Table 4
| Sequence number | Material | Proportion (wt%) | Description of the invention |
| 1 | Acrylic resin solution | 50 | 40% solids propyl acetate solution |
| 2 | CAB solution | 7.5 | 20% solids propyl acetate solution |
| 3 | Dispersing agent | 1.5 | BYK-108 |
| 4 | Carbon black | 10 | CABOT 250R |
| 5 | Acetic acid n-propyl ester | 31 | |
| Totalizing | 100 |
Firstly, mixing the components 1, 2 and 3, and dispersing the components by using a high-speed stirrer for 10 minutes; then the stirring speed is reduced, and the material 4 is slowly added and stirred at the same time; after the material is fed, dispersing at a high speed for 30 minutes; then turning to a sanding process, and grinding until the pigment fineness is less than 10 microns; finally, adding a material 5, and performing performance detection on grinding fineness, blackness, covering power and rotational viscosity after high-speed dispersion for 5 minutes, wherein the performance detection is specifically as follows:
(1) fineness of grind test
The fineness of the pigment in the ink was observed by a particle size method using a blade fineness gauge. The fineness of the pigment after dispersion is less than 10 microns; the fineness of the ink pigment after the stability test is not more than 20 microns, otherwise, the ink pigment is judged to be unqualified.
(2) Testing of blackness
The ink scratch board prepared by the acrylic resin prepared in the comparative example 1 is used as a blackness standard sample, and the rest samples are observed and compared with the standard sample after passing through the scratch board to compare the blackness difference; if the blackness of the ink pigment after the stability test is obviously reduced, the ink pigment is judged to be unqualified.
(3) Testing of hiding power
The ink blade prepared from the acrylic resin prepared in comparative example 1 was used as a hiding power standard sample, and the remaining samples were compared with the standard sample by observation after passing through the blade to compare differences in hiding power; if the hiding power of the ink pigment after the stability test is obviously reduced, the ink pigment is judged to be unqualified.
(4) Rotational viscosity test
Using a rotary viscometer to perform a test, wherein the temperature of a sample is controlled to be 22 ℃ plus or minus 1 ℃; if the rotational viscosity of the ink after the stability test increases by more than 50%, the ink is judged to be unacceptable.
(5) Stability test
And (3) sealing each ink sample in an oven at 50 ℃, taking out and cooling after an accelerated ageing experiment for one week, and testing fineness, blackness, covering power and rotational viscosity again.
The inks prepared using the acrylic resins prepared in examples 1 to 5 are correspondingly described as application examples 1 to 5; the ink formulations using the acrylic resins prepared in comparative examples 1 to 4 were correspondingly recorded as application comparative examples 1 to 4, and the specific test results are shown below:
table 5 fineness of grind test results
| Finished product detection (mum) | Stability post test (μm) | |
| Application example 1 | <10 | 10～15 |
| Application example 2 | <10 | <10 |
| Application example 3 | <10 | <10 |
| Application example 4 | <10 | <15 |
| Application example 5 | <10 | <10 |
| Comparative example 1 was used | <20 | <95; failure to pass |
| Comparative example 2 was used | / | / |
| Comparative example 3 was used | <10 | <15 |
| Comparative example 4 was used | <20 | <40, a step of performing a; does not take qualified product |
The results shown in Table 5 can be seen: the ink prepared by the acrylic resin prepared in the examples 1-5 can ensure that the fineness of the carbon black pigment is below 10 microns, and after stability test, the ink also meets the performance requirement of <20 microns; the ink prepared by the acrylic resin prepared in comparative example 1 (the acrylic monomer with the side chain having the aliphatic six-membered ring structure does not participate in copolymerization, and is an acrylic resin product for the existing ink), the carbon black pigment in the ink is difficult to grind to below 10 microns, the dispersion performance of the resin is poor, the agglomeration condition is serious after the stability test, and the carbon black is obviously settled; the acrylic resin prepared in comparative example 2 has too high viscosity of ink due to too large molecular weight, and is difficult to coat; although the ink prepared from the acrylic resin prepared in comparative example 3 is satisfactory in terms of dispersibility and storage stability of the carbon black pigment, the acrylic resin has a too low Tg value, and the resin is extremely sticky, which makes it difficult to package, transport and store; the ink prepared from the acrylic resin prepared in comparative example 4 has the defects that the grinding fineness is difficult to reach the standard and the storage stability is poor because the using amount of the acrylic monomer with the aliphatic six-membered ring structure in the side chain involved in copolymerization is only 5 percent, which is lower than the lower limit using amount of 10 percent in the invention, so that the carbon black pigment cannot be uniformly dispersed.
Table 6 blackness test results:
the results shown in Table 6 can be seen: the jetness of the inks prepared from the acrylic resins prepared in examples 1 to 5 was better than that of the standard samples, and there was substantially no change after stability testing; the blackness of the standard sample (the existing product, namely the ink of the comparative example 1) is obviously reduced after the stability test, and the standard sample is judged to be unqualified; application comparative example 2 could not be tested because the ink viscosity was too high; in contrast, in comparative example 4, although the initial blackness was slightly better than that of the standard sample, the blackness was decreased after the stability test, and the test was judged to be unacceptable.
Table 7 hiding power test results
| Finished product detection | After stability test | |
| Application of example 1 | Better still | Slightly decline |
| Application example 2 | Better still | Substantially unchanged |
| Application example 3 | Better still | Substantially unchanged |
| Application example 4 | Better still | Slightly decline |
| Application example 5 | Better still | Substantially unchanged |
| Comparative example 1 was used | Standard sample | A significant drop; failure to pass |
| Comparative example 2 was used | / | / |
| Comparative example 3 was used | Better still | Slightly decline |
| Comparative example 4 was used | Slightly better | Descending; failure to pass |
From the results shown in Table 7, it can be seen that: the inks prepared by using the acrylic resins prepared in examples 1 to 5 all have better hiding power than the standard sample (the existing product, i.e., the ink of comparative example 1 is used), and basically have no change after stability test; after stability test, the covering power of the standard sample is obviously reduced; application comparative example 2 could not be tested because the ink viscosity was too high; the finished product of comparative example 4 was slightly better in hiding power than the standard, but after stability testing, the hiding power was significantly reduced, and was judged to be unacceptable.
Table 8 rotational viscosity test
From the results shown in Table 8, it can be seen that: the rotational viscosity of the ink prepared by the acrylic resin prepared in the application examples 1 to 5 is moderate, meets the ink coating requirement, and only slightly rises after the stability test; the viscosity of the standard sample (the existing product, namely the ink of the comparative example 1) rises by more than 50% after the stability test, and the standard sample is judged to be unqualified; the application of the comparative example 2 cannot meet the basic requirements of ink construction coating, pigment dispersion and the like because the viscosity of the ink is too high; after the stability test, the viscosity of comparative example 4 increased by more than 50%, and the test was judged to be unsatisfactory.
The above can be seen in the following: the carbon black ink prepared by the acrylic resin prepared in the examples 1 to 5 has proper viscosity, better blackness and covering power and excellent storage stability; the acrylic resins prepared in comparative examples 1 and 4 (without the acrylic monomer with the aliphatic six-membered ring structure on the side chain of the invention involved in copolymerization or the input amount was too low), the prepared ink could not effectively disperse the carbon black pigment, and had the defects of difficult reaching of the grinding fineness, poor storage stability, easy agglomeration and sedimentation of the carbon black pigment, etc.; the acrylic resin prepared in comparative example 2 has the defects that the rotational viscosity of the prepared ink is too high, and pigments are difficult to coat and disperse due to the large molecular weight; the Tg value of the acrylic resin prepared in comparative example 3 is low, and although the performance parameters of the prepared ink meet the requirements and the stability is good, the Tg value of the acrylic resin is low, and the resin is sticky, so that the problems of difficult operation in the production, packaging, transportation, storage and use links of the resin exist, and the requirements of industrial mass production and use cannot be met. That is, the acrylic resin is prepared by creatively adopting the acrylic monomer with the aliphatic six-membered ring structure on the side chain in a specific proportion to participate in copolymerization, so that not only is the acrylic resin product capable of realizing uniform and stable dispersion of the carbon black pigment obtained, but also the carbon black ink prepared by adopting the acrylic resin provided by the invention has proper viscosity, better blackness and covering power and excellent storage stability, and the acrylic resin can be prepared by adopting the existing preparation process without special equipment, so that large-scale production is easy to realize; thus, the present invention not only represents a significant advance over the prior art, but also produces unexpected technical results.
Finally, it is pointed out here that: the above is only a part of the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adaptations of the present invention based on the foregoing are within the scope of the present invention.
Claims (6)
1. An acrylic resin capable of realizing uniform and stable dispersion of carbon black pigment is obtained by carrying out free radical copolymerization reaction on the following comonomers under the action of a free radical initiator and a chain transfer agent, and is characterized in that the components of the comonomers are as follows:
the percentages refer to the percentages of the mass of each constituent monomer to the total mass of the comonomer, and the sum of the percentages of all the constituent monomers is 100%; wherein, the liquid crystal display device comprises a liquid crystal display device,
the side chain is provided with an acrylic monomer with an aliphatic six-membered ring structure, and the acrylic monomer has the following chemical structural general formula:
and in the general formula: r is-H or-CH 3 ；R 1 、R 2 、R 3 、R 4 、R 5 Each representing two identical or different substituents, each of which is independently selected from-H or C1-C4 alkyl, and R 1 、R 2 、R 3 、R 4 、R 5 The two are independent or form a bridging structure between any two;
the hard monomer is at least one of methyl methacrylate, tert-butyl methacrylate, isopropyl methacrylate and styrene;
the soft monomer is at least one of ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isooctyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate and lauryl acrylate;
the polar acrylic acid monomer is at least one of methacrylic acid, acrylic acid and amino acrylic acid monomer.
2. The acrylic resin capable of achieving uniform and stable dispersion of carbon black pigment according to claim 1, wherein: the free radical initiator is selected from peroxide or azo free radical initiator.
3. The acrylic resin capable of achieving uniform and stable dispersion of carbon black pigment according to claim 1, wherein: the chain transfer agent is at least one of mercaptan, mercapto acid and mercapto ester.
4. The acrylic resin capable of achieving uniform and stable dispersion of carbon black pigment according to claim 1, wherein: the dosage of the free radical initiator is 0.1-1.0% of the total mass of the comonomer, and the dosage of the chain transfer agent is 0.5-5.0% of the total mass of the comonomer.
5. The acrylic resin capable of achieving uniform and stable dispersion of carbon black pigment according to claim 1, wherein: the free radical copolymerization reaction adopts any one of a bulk polymerization method, a suspension polymerization method and a solution polymerization method.
6. The acrylic resin capable of achieving uniform and stable dispersion of carbon black pigment according to any one of claims 1 to 5, characterized in that: the weight average molecular weight Mw of the acrylic resin is controlled to be in the range of 2000-20000 Da, and the glass transition temperature Tg of the acrylic resin is controlled to be in the range of 50-150 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010144122A (en) * | 2008-12-22 | 2010-07-01 | Mitsubishi Pencil Co Ltd | Oil-based correction fluid composition |
| CN102268117A (en) * | 2011-06-27 | 2011-12-07 | 辽宁三环树脂有限公司 | Low molecular weight alcohol-soluble thermoplastic solid acrylic resin |
| CN104311727A (en) * | 2014-11-06 | 2015-01-28 | 任婧 | Acrylic resin for transfer ink |
| CN105038064A (en) * | 2015-08-24 | 2015-11-11 | 栗东林 | Carbon fiber granule methacrylic resin/epoxy resin waterproof membrane composition and method |
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- 2022-10-11 CN CN202211243245.8A patent/CN115477721B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010144122A (en) * | 2008-12-22 | 2010-07-01 | Mitsubishi Pencil Co Ltd | Oil-based correction fluid composition |
| CN102268117A (en) * | 2011-06-27 | 2011-12-07 | 辽宁三环树脂有限公司 | Low molecular weight alcohol-soluble thermoplastic solid acrylic resin |
| CN104311727A (en) * | 2014-11-06 | 2015-01-28 | 任婧 | Acrylic resin for transfer ink |
| CN105038064A (en) * | 2015-08-24 | 2015-11-11 | 栗东林 | Carbon fiber granule methacrylic resin/epoxy resin waterproof membrane composition and method |
Non-Patent Citations (1)
| Title |
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| 丙烯酸树脂基导电油墨正/负升温系数协同效应的研究;李晨光;刘成岑;李万捷;窦涛;;现代化工(S1);全文 * |
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