CN113214758B - Stone adhesive toning paste and preparation method and application thereof - Google Patents
Stone adhesive toning paste and preparation method and application thereof Download PDFInfo
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- CN113214758B CN113214758B CN202110559511.7A CN202110559511A CN113214758B CN 113214758 B CN113214758 B CN 113214758B CN 202110559511 A CN202110559511 A CN 202110559511A CN 113214758 B CN113214758 B CN 113214758B
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Abstract
The invention discloses a stone adhesive color mixing paste and a preparation method and application thereof, wherein the stone adhesive color mixing paste comprises, by weight, 100 parts of a blender, 60-120 parts of an inorganic pigment, 4-6 parts of a dispersant, 5-10 parts of an anti-settling agent, 2-6 parts of an oil absorbent and 4-10 parts of a defoaming agent; in the anti-settling agent, the fumed silica accounts for 70-90 wt%, and the polyamide modified hydrogenated castor oil accounts for 10-30 wt%; in the oil absorbent, the styrene-methyl methacrylate copolymer accounts for 20-60 wt%, the polybutylmethacrylate accounts for 20-60 wt%, and the microcrystalline wax accounts for 20-60 wt%. The stone adhesive toning paste has good compatibility and dispersibility with a stone adhesive, does not foam in the stirring process of the stone adhesive, has strong tinting strength, can be stored at the temperature of 25-35 ℃, keeps paste for more than one year without oil bleeding and sedimentation, is convenient to use, has good economical efficiency and low manufacturing cost, is applied to stone repair, keeps the color of a stone repair surface consistent with the whole color of a stone for a long time, and is particularly suitable for the technical field of stone adhesive toning.
Description
Technical Field
The invention belongs to the technical field of stone adhesive color matching, and particularly relates to a stone adhesive color matching paste as well as a preparation method and application thereof.
Background
The stone adhesive is mainly used for bonding natural granite, natural marble and artificial quartz plates and for plane matching, caulking, pointing, hole filling and stone repairing of stones. At present, the commonly used stone adhesive is mainly divided into two major types of stone adhesives which take unsaturated polyester resin and epoxy resin as matrix resin.
In recent years, the kinds of stones are increasing, the colors of the stones are different, and when the stones are subjected to pattern matching, caulking, pointing, hole patching and repairing, in order to achieve the overall aesthetic property, the stone adhesive needs to be subjected to color matching so as to keep the colors of the stone adhesive consistent with the colors of the stones. At present, the color matching of the stone adhesive is generally realized by directly adding the toner and the auxiliary agent into the adhesive, and the method has the defects that the toner is easy to agglomerate and has poor dispersibility.
Disclosure of Invention
Aiming at the problems that the toner is easy to agglomerate and the dispersibility is poor when the toner and the auxiliary agent are directly added into the adhesive in the prior art, the invention provides the stone adhesive toning paste and the preparation method and the application thereof. The stone adhesive toning paste has good compatibility and dispersibility with stone adhesives, good stability, good weather resistance, strong tinting strength and convenient construction.
The technical scheme provided by the invention is as follows:
according to the first aspect, the invention provides a stone adhesive toning paste which comprises, by weight, 100 parts of a blender, 60-120 parts of an inorganic pigment, 4-6 parts of a dispersing agent, 5-10 parts of an anti-settling agent, 2-6 parts of an oil absorbent and 4-10 parts of a defoaming agent; in the anti-settling agent, the fumed silica accounts for 70-90 wt%, and the polyamide modified hydrogenated castor oil accounts for 10-30 wt%; in the oil absorbent, the styrene-methyl methacrylate copolymer accounts for 20-60 wt%, the polybutylmethacrylate accounts for 20-60 wt%, and the microcrystalline wax accounts for 20-60 wt%.
On the basis of the technical scheme, in the anti-settling agent, the fumed silica accounts for 90 wt%, and the polyamide modified hydrogenated castor oil accounts for 10 wt%.
On the basis of the technical scheme, in the oil absorbent, the styrene-methyl methacrylate copolymer accounts for 60 wt%, the polybutylmethacrylate accounts for 20 wt%, and the microcrystalline wax accounts for 20 wt%.
On the basis of the technical scheme, in the blender, the epoxidized soybean oil accounts for 70 wt% -80 wt%, the methyl hydrogen-containing silicone oil accounts for 15 wt% -20 wt%, and the glycerol accounts for 5 wt% -10 wt%.
On the basis of the technical scheme, the inorganic pigment is one or more of iron oxide red, zinc chrome yellow, cobalt blue, zinc barium green, carbon black and titanium dioxide.
On the basis of the technical scheme, the dispersing agent is one or more of ethylene glycol monohexyl ether, triethylene glycol monobutyl ether, diethylene glycol monoethyl ether, 2,6, 8-trimethyl-4-nonanone, N-methyl pyrrolidone and benzyl alcohol.
On the basis of the technical scheme, in the defoaming agent, 40-60 wt% of polyether siloxane defoaming agent Foamex KS 10 and 40-60 wt% of silicone-free defoaming agent Airex 910 are contained.
In a second aspect, the invention provides a method for preparing the stone adhesive color mixing paste, which comprises the following steps:
(1) stirring at high speed under negative pressure of 0.08-0.1MPa and temperature of 55 + -2 deg.C to disperse the blending agent in the molten anti-settling agent to form cream-like paste;
(2) cooling the cream-like paste to room temperature, adding the inorganic pigment, the defoaming agent, the dispersing agent and the oil absorbent, and uniformly mixing;
(3) grinding the mixture to a particle size of 1-2 μm to obtain the stone adhesive toning paste.
In a third aspect, the invention provides a method for using a stone adhesive color mixing paste, which comprises the following steps:
(1) determining the color of a target stone, and selecting stone adhesive color mixing paste consisting of required colors;
(2) preparing the stone adhesive toning paste into a preparation matter which is in accordance with the color of the target stone;
(3) the mixture is mixed with stone adhesive to bond stone.
Preferably, the addition amount of the concoction is 0.1-1 wt% of the stone adhesive.
Preferably, the stone adhesive is an unsaturated polyester resin matrix stone adhesive or an epoxy resin matrix stone adhesive.
The invention adopts fumed silica and polyamide modified hydrogenated castor oil as anti-settling agent; the particle size of the fumed silica is small, the specific surface area is large, the silanol groups on the surface and the adjacent fumed silica particles interact to form hydrogen bonds, the hydrogen bonds can be associated with the hydroxyl groups in the blending agent to form bonding hydrogen bonds, a three-dimensional interpenetrating network-shaped structure is easy to form, the paste body has good physical stability, and the paste body is not easy to settle under the condition of standing for a long time; the polyamide modified hydrogenated castor oil is molten under the condition of heating, can be well dispersed into a system after being stirred, and has the long chains intertwined with each other after being cooled to room temperature, so that the paste has excellent anti-settling performance. Due to the synergistic effect of the fumed silica and the polyamide-modified hydrogenated castor oil, the inorganic pigment with high specific gravity does not settle even when the toner is left for one year.
The invention adopts the copolymer of styrene and methyl methacrylate, polybutylmethacrylate and alkane microcrystalline wax as the oil absorbent, and the styrene and the methyl methacrylate can form a three-dimensional network structure between macromolecules after copolymerization to achieve proper crosslinking degree, thereby greatly improving the oil absorption speed and the oil absorption capacity; the oil absorbent has lipophilic group, so that the adsorption capacity is similar to chemical adsorption, the stability is higher, and the oil retention capacity of the ointment is improved. Under the synergistic effect of the copolymer of styrene and methyl methacrylate, the polybutylmethacrylate and the alkane microcrystalline wax, the toning paste has better oil absorption capacity, oil absorption speed and oil retention capacity, is more stable, and does not generate oil separation even when being placed for one year.
The technical scheme of the invention can obtain the following beneficial effects:
(1) the stone adhesive toning paste provided by the invention adopts the mutual cooperation of different types of dispersing agents, so that the toning paste can be effectively and quickly dispersed in the stone adhesive taking unsaturated polyester resin as matrix resin and epoxy resin as matrix resin; the stone adhesive toning paste provided by the invention is compounded by adopting different types of defoaming agents, has good defoaming effect on the stone adhesives of the two systems, and avoids the physical defect of bubbles on a colloid condensate during toning and stirring; the stone adhesive toning paste provided by the invention adopts inorganic pigment, so that the color of the repaired surface of the stone is lasting and is consistent with the whole color of the stone; the stone adhesive toning paste provided by the invention adopts different types of oil absorbents to be mutually cooperated, so that the toning paste can be kept for a long time without oil bleeding; the settling agent and the blending agent adopted by the stone adhesive color mixing paste provided by the invention form a three-dimensional structure, the appearance of the paste is creamy, the paste has the effect similar to a carrier, and the inorganic pigment with high specific gravity is adsorbed, so that the inorganic pigment cannot settle.
(2) The preparation method of the stone adhesive toning paste provided by the invention adopts a three-step method, the blender and the anti-settling agent are stirred under the conditions of negative pressure, heating and high speed in the step (1) to form a cream-like paste, the negative pressure aims to avoid the generation of tiny and thick-walled bubbles in the high-speed stirring process, the bubbles are difficult to discharge and difficult to eliminate by a defoaming agent, and the appearance of the stone toning paste is rough; in the step (2), the creamy paste and other raw materials are further stirred and dispersed, negative pressure does not need to be pumped due to the addition of the defoaming agent, so that energy waste is avoided, and the adopted defoaming agent can play a defoaming role in the step (2) of preparing the color mixing paste and can also play a defoaming role in the stirring and mixing process of the color mixing paste and the stone adhesive during construction; and (4) grinding the toning paste in the step (3), and fully grinding to eliminate micro particles in the paste, so that the stone toning paste is more homogenized and finer.
(3) The stone adhesive toning paste provided by the invention has good compatibility and dispersibility with a stone adhesive, does not bubble in the process of stirring with the stone adhesive, and has excellent performances of fineness, good cutting property, good stability, good weather resistance, simple preparation process, convenient construction, low manufacturing cost and the like.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is an image of a stone adhesive tinting paste provided in example 1 of the present invention observed under an optical microscope at 200 magnifications;
FIG. 2 is an image of the stone adhesive tinting paste provided in comparative example 10 of the present invention observed under an optical microscope at 200 magnifications;
FIG. 3 is an image of the stone adhesive tinting paste provided in example 1 of the present invention observed under a 1000-magnification optical microscope;
fig. 4 is an image of the stone adhesive tinting paste provided in comparative example 10 of the present invention observed under a 1000-magnification optical microscope.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
According to the first aspect, the invention provides a stone adhesive toning paste which comprises, by weight, 100 parts of a blender, 60-120 parts of an inorganic pigment, 4-6 parts of a dispersing agent, 5-10 parts of an anti-settling agent, 2-6 parts of an oil absorbent and 4-10 parts of a defoaming agent; in the anti-settling agent, the fumed silica accounts for 70-90 wt%, the polyamide modified hydrogenated castor oil accounts for 10-30 wt%, and the sum of the fumed silica and the polyamide modified hydrogenated castor oil is 100 wt%; in the oil absorbent, the styrene-methyl methacrylate copolymer accounts for 20 to 60 weight percent, the polybutylmethacrylate accounts for 20 to 60 weight percent, the microcrystalline wax accounts for 20 to 60 weight percent, and the sum of the styrene-methyl methacrylate copolymer, the polybutylmethacrylate and the microcrystalline wax is 100 weight percent.
On the basis of the technical scheme, in the anti-settling agent, the fumed silica accounts for 90 wt%, and the polyamide modified hydrogenated castor oil accounts for 10 wt%.
On the basis of the technical scheme, in the oil absorbent, the styrene-methyl methacrylate copolymer accounts for 60 wt%, the polybutylmethacrylate accounts for 20 wt%, and the microcrystalline wax accounts for 20 wt%.
On the basis of the technical scheme, in the blender, the epoxidized soybean oil accounts for 70-80 wt%, the methyl hydrogen-containing silicone oil accounts for 15-20 wt%, the glycerol accounts for 5-10 wt%, and the sum of the three is 100 wt%.
On the basis of the technical scheme, the inorganic pigment is one or more of iron oxide red, zinc chrome yellow, cobalt blue, zinc barium green, carbon black and titanium dioxide.
On the basis of the technical scheme, the dispersing agent is one or more of ethylene glycol monohexyl ether, triethylene glycol monobutyl ether, diethylene glycol monoethyl ether, 2,6, 8-trimethyl-4-nonanone, N-methylpyrrolidone and benzyl alcohol.
On the basis of the technical scheme, in the defoaming agent, 40-60 wt% of polyether siloxane defoaming agent Foamex KS 10 and 40-60 wt% of silicone-free defoaming agent Airex 910 are contained, and the sum of the three is 100 wt%.
In a second aspect, the invention provides a method for preparing the stone adhesive color mixing paste, which comprises the following steps:
(1) stirring at high speed under negative pressure of 0.08-0.1MPa and temperature of 55 + -2 deg.C to disperse the blending agent in the molten anti-settling agent to form cream-like paste;
(2) cooling the cream-like paste to room temperature, adding the inorganic pigment, the defoaming agent, the dispersing agent and the oil absorbent, and uniformly mixing;
(3) grinding the mixture to a particle size of 1-2 μm to obtain the stone adhesive toning paste.
In the step (3), in order to further eliminate bubbles generated in the stirring process and some possibly existing larger particles, the paste is made to be more fine by grinding. Grinding for three times to obtain homogeneous and fine paste, wherein the particle size of the inorganic pigment is 1-2 μm.
In a third aspect, the invention provides a method for using a stone adhesive color mixing paste, which comprises the following steps:
(1) determining the color of a target stone, and selecting stone adhesive color mixing paste consisting of required colors;
(2) preparing the stone adhesive toning paste into a preparation matter which is in accordance with the color of the target stone;
(3) the mixture is mixed with stone adhesive to bond stone.
Preferably, the addition amount of the concoction is 0.1-1 wt% of the stone adhesive.
The stone adhesive color mixing paste prepared by the invention can be uniformly mixed with a stone adhesive, and two representative stone adhesives with unsaturated polyester resin matrixes and two representative stone adhesives with epoxy resin matrixes are selected.
The experimental procedures used in the following examples are conventional unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. The gas phase silicon dioxide adopted by the invention is in a nanometer level; the polyamide modified hydrogenated castor oil is purchased from Shanghai Akema chemical Co., Ltd, and is of a Caryvallac MT model; the styrene-methyl methacrylate copolymer was purchased from Nippon Denshoku Kogyo, model number TX-100S; the polybutylmethacrylate is purchased from Wuhan Laanabai pharmaceutical chemical Co., Ltd, and is FD 4543; the microcrystalline wax is purchased from Beijing Germany, Henghong technology, Inc.; the methyl hydrogen-containing silicone oil is purchased from Jinan Langshan New Material Co., Ltd, and has the model of JHF-901-1; epoxidized soybean oil is purchased from soaring chemical company Limited in Jinan, and is AOX 68; the invention adopts two stone adhesives with different matrixes to verify the performance of the color paste, wherein the stone adhesive I: the stone adhesive of the unsaturated polyester resin matrix is made of Hercules transparent marble adhesive with higher market share of Kodak marble nursing materials Limited company in Wuhan; stone adhesive II: the stone adhesive of the epoxy resin matrix is a Dalishi white epoxy dry-hanging structural adhesive with higher market share of the Kodak marble nursing materials Limited company in Wuhan.
Example (b):
the stone adhesive tinting pastes provided in examples 1 to 12 comprise the raw materials in parts by weight shown in table 1.
TABLE 1 examples 1-12 compositions
The ingredients of the formulations of examples 1 to 12 in Table 1 were weighed out accurately, and then the blender and the anti-settling agent were added to a planetary stirring disperser model TXJ to 100, and stirred for 35 minutes under the conditions of negative pressure of 0.1MPa, temperature of 55 + -2 ℃ and rotation speed of 1500r/min, to form a creamy ointment. And after the creamy paste body is cooled to room temperature, adding the inorganic pigment, the defoaming agent, the dispersing agent and the oil absorbent, stirring at the rotating speed of 1500r/min at normal pressure and normal temperature for 35 minutes, and finally grinding for three times by using a glue grinder with the model of JmL-65 to obtain the stone adhesive color mixing paste. The particle size of the pigment particles in the paste is measured to be in the range of 1-2 μm by a laser particle size analyzer with a model number of Euramerican Kerr LS 900.
To demonstrate the excellent effects of the present invention, comparative examples 1 to 10 were also provided to be compared with example 1 described above, and the raw materials of comparative examples 1 to 10 are shown in Table 2 in parts by weight.
TABLE 2 comparative examples 1-10 compositions
Comparative examples 1-10 tinting pastes were prepared as in examples 1-12; the invention also purchases two commercial blue stone adhesive toning pastes with better sales quantity as the toning pastes of a comparative example 11 and a comparative example 12 respectively.
The toner pastes prepared in example 1 and comparative example 10 were observed by high power optical microscope; the toning pastes prepared in the above examples 1 to 12 and comparative examples 1 to 10 and the toning paste purchased in comparative example 11 and comparative example 12 were subjected to visual inspection, high-speed centrifugation test, accelerated heat treatment test and ultraviolet aging discoloration test. The performance of the toning paste can be detected through the experimental means.
High power optical microscope observation: the toner pastes obtained in example 1 and comparative example 10 were applied to a glass slide in an amount of 0.1g each. The paste was observed under an optical microscope of Nikon NCZ-TS2R at high magnification and low magnification, respectively.
Visual inspection: the stone adhesive I and the stone adhesive II are respectively 24 parts, each 100g of the stone adhesive I and the stone adhesive II are respectively added with 1g (actual construction amount) of the toning paste of the examples 1-12 and the comparative examples 1-12, and after the stone adhesive I and the stone adhesive II are uniformly stirred, whether the stone adhesive is uniform and fine, whether the stone adhesive foams or not and the color and luster degree of the stone adhesive are bright and dark are observed by naked eyes in the sun.
High-speed centrifugation experiment: 5g of each of the toner pastes of examples 1 to 12 and comparative examples 1 to 12 was taken and contained in 24 10mL centrifuge tubes. Under the condition of normal temperature, selecting a No. 1 angle rotor, placing each test tube in a high-speed centrifuge (model TG-16G), selecting a rotation speed of 16000r/min to centrifuge for 10min, 20min and 30min respectively, and observing whether phenomena of sedimentation and oil separation exist.
Accelerated heat treatment experiments: 50g of each of the toner pastes of examples 1 to 12 and comparative examples 1 to 12 was filled in 24 125mL wide-mouth reagent bottles. After the preparation, the sample is placed in an oven at 80 ℃ and treated for 30 days, and the conditions of sample sedimentation and oil separation are observed once a day. Whether the color mixing paste still has good stability after being placed for one year can be detected through the two experiments.
Ultraviolet aging discoloration experiment: the stone adhesive I and the stone adhesive II are respectively taken 24 parts, each 100g is added with 0.6g (actual construction amount) of the toning paste of the examples 1-12 and the comparative examples 1-12, and the mixture is stirred uniformly. And adding a curing agent into the adhesive after color matching, fully stirring, uniformly coating the adhesive on a flat stone plate, controlling the thickness to be 1mm, and performing ultraviolet aging cycle test on the cured adhesive after color matching according to a GB/T23987 test method after the adhesive is completely cured.
The test results are shown in tables 3 to 6.
TABLE 3 results of visual examination, high-speed centrifugation experiment, accelerated heat treatment experiment and ultraviolet aging discoloration experiment
TABLE 4 results of visual examination, high-speed centrifugation experiment, accelerated heat treatment experiment and ultraviolet aging discoloration experiment
TABLE 5 results of visual examination, high-speed centrifugation experiment, accelerated heat treatment experiment and ultraviolet aging discoloration experiment
TABLE 6 results of visual examination, high-speed centrifugation experiment, accelerated heat treatment experiment and ultraviolet aging discoloration experiment
As shown in tables 3 and 4, the toner pastes prepared in examples 1 to 12 provided by the present invention were excellent in state, did not settle and did not separate out oil after high speed centrifugation for 30min, and did not settle and did not separate out oil after standing for 30 days in the accelerated heat treatment experiment. The color of the cured adhesive after color matching is not changed after being treated for 6 weeks in an ultraviolet aging color-changing experiment, which is equivalent to that the cured adhesive does not change color after being placed in an outdoor environment for more than one year. The stone adhesive I and the stone adhesive II are uniform, fine and smooth in state, bright in color and free of bubbles after being subjected to color matching in the examples 1-12.
The following conclusions can be drawn from the figures and the test results in tables 3-6:
1. fig. 1 and 2 are images observed under an optical microscope at 200 magnifications of example 1 and comparative example 10, respectively, in the present invention. After comparison, it can be found that the toner paste with the dispersant is more uniform under the low power mirror, and the toner paste without the dispersant is not uniformly dispersed. Fig. 3 and 4 are images observed under an optical microscope of 1000 magnifications of example 1 and comparative example 10 in the present invention. After comparison, inorganic pigment particles are uniformly distributed in the toning paste added with the dispersing agent under a high-power mirror, and the periphery of the inorganic pigment particles is coated by the solvent; in the toning paste without the dispersant, the inorganic pigment particles are not uniformly distributed, the dark color part is the agglomerated particles, and an obvious interface exists.
2. Comparative example 10 is a toner paste without dispersant, and other raw materials and amounts were the same as in example 1. After the color matching paste prepared by the formula is uniformly stirred with the adhesive, the color matching paste can be observed by naked eyes in the sun: the adhesive after color matching is not uniform, agglomeration phenomenon obviously exists, and the color is darker than that of other comparative examples; the adhesive toned by the embodiment 1 and the comparative examples 1 to 9 is uniform, fine, non-foaming and bright in color.
From conclusion 1 and conclusion 2, the inorganic pigment can be better dispersed into the toning paste system by adding the dispersing agent, and the toning paste has good compatibility with the unsaturated polyester resin-based adhesive and the epoxy resin-based adhesive, so that the dispersibility of the toning paste in the adhesive is obviously improved.
3. The toner paste prepared in example 1 provided by the present invention has the best stability. Comparative example 1 is a toning paste without adding an anti-settling agent and an oil absorbent, the rest formula is the same as that of example 1, the toning paste prepared according to the formula of comparative example 1 has the worst physical stability, and the conditions of settling and oil bleeding occur after high-speed centrifugation for 10 min; in the accelerated heat treatment experiment, the phenomena of sedimentation and oil separation appear after the test piece is placed for one day; the cured adhesive after color matching does not change color after being treated for 6 weeks in an ultraviolet aging color-changing experiment.
Therefore, comparing example 1 with comparative example 1, it can be found that the stability of the tinting paste can be effectively improved by adding the anti-settling agent and the oil absorbent, the stone adhesive tinting paste provided by the invention can achieve the excellent performance that the tinting paste can not separate oil and settle after being placed for more than one year, and the cured adhesive after tinting can not be discolored after being placed for a long time.
4. Comparative example 2 is a toning paste without adding an anti-settling agent, the toning paste prepared by the formula settles after being centrifuged at high speed for 10min, slight oil separation occurs after being centrifuged at high speed for 20min, and a larger amount of oil is separated out after being centrifuged at high speed for 30 min; in the accelerated heat treatment experiment, the mixture is placed for one day to generate sedimentation, and is placed for 12 days to generate oil separation; the cured adhesive after color matching does not change color after being treated for 6 weeks in an ultraviolet aging color-changing experiment. Comparative examples 3 and 4 are respectively added with only one of the anti-settling agents adopted by the invention, other raw materials and the using amount are consistent with those of the example 1, and the anti-settling performance of the color mixing paste is improved to a certain extent by adding the single-component anti-settling agent into the comparative examples 3 and 4, but the phenomena of settling and slight oil bleeding still exist, so that the color mixing paste is not as good as the color mixing paste in the example 1 formed by matching two anti-settling agents.
5. Comparative example 5 is a toning paste without adding an oil absorbent, the toning paste prepared by the formula does not settle after being centrifuged at a high speed for 30min, but separates oil after being centrifuged at a high speed for 10min, separates oil after being placed for one day in an accelerated heat treatment experiment, and settles after being placed for 18 days; the cured adhesive after color matching does not change color after being treated for 6 weeks in an ultraviolet aging color-changing experiment. The comparative examples 6, 7 and 8 only add one of the oil absorbents used in the invention, the other raw materials and the use amount are the same as those of the example 1, and the comparative examples 6, 7 and 8 add the single-component oil absorbent, so that the toning paste is improved in oil separation, but the phenomenon of oil separation still exists, which is not the same as that of the example 1 after the three oil absorbents are mixed.
6. Comparative example 9 is a toner paste with the addition of the organic pigment phthalocyanine blue, and the other raw materials and amounts are the same as those in example 1. The toning paste prepared in the comparative example 9 does not settle and does not separate oil after being centrifuged at high speed for 30 min; the product is placed for 30 days in an accelerated heat treatment experiment without sedimentation and oil precipitation; the cured adhesive after color matching is treated for 6 weeks in an ultraviolet aging color-changing experiment and then seriously changes color. Therefore, the inorganic pigment selected by the invention can effectively avoid the color change phenomenon caused by the influence of the external environment, thereby achieving the purpose of keeping the color of the repaired surface of the stone consistent with the whole color of the stone for a long time.
7. Comparative examples 11 and 12 are common commercially available stone adhesive tinting pastes. Both of them have good appearance and use effect. However, in comparative example 11, the adhesive does not settle after being placed for 30 days in the accelerated heat treatment experiment, and the oil is separated after being placed for 23 days, and the color of the adhesive cured material after color mixing slightly changes after being treated for 6 weeks in the ultraviolet aging color change experiment; comparative example 12 does not settle after standing for 18 days in the accelerated heat treatment experiment, oil is separated after standing for 15 days, and the color of the adhesive condensate after color matching is seriously changed after being treated for 6 weeks in the ultraviolet aging color change experiment. Therefore, after comparison, it can be found that the stone adhesive tinting pastes provided by embodiments 1-12 of the invention are superior to the existing stone adhesive tinting pastes on the market in terms of stability, weather resistance and the like.
In summary, the stone adhesive toning paste and the preparation method and application thereof provided by the invention have the advantages that the stone adhesive toning paste is subjected to formula design in a targeted manner by fully combining the characteristics of the toning paste and the comprehensive application requirements, and accordingly, excellent effects are achieved in various aspects such as dispersibility, settling resistance, no oil bleeding, weather resistance and the like, because the addition amount is only 0.1-1 wt%, the addition amount is small, and the performance of the adhesive is not influenced after the addition.
Finally, those skilled in the art should readily appreciate that they can only use the preferred embodiments of the present invention and should not be considered as limiting the invention, and that all changes, equivalents and modifications which come within the spirit and scope of the invention are desired to be protected.
Claims (10)
1. The stone adhesive color mixing paste is characterized in that: the paint comprises, by weight, 100 parts of a blending agent, 60-120 parts of an inorganic pigment, 4-6 parts of a dispersing agent, 5-10 parts of an anti-settling agent, 2-6 parts of an oil absorbent and 4-10 parts of a defoaming agent; in the anti-settling agent, fumed silica accounts for 70-90 wt%, and polyamide modified hydrogenated castor oil accounts for 10-30 wt%; in the oil absorbent, the styrene-methyl methacrylate copolymer accounts for 20-60 wt%, the polybutylmethacrylate accounts for 20-60 wt%, and the microcrystalline wax accounts for 20-60 wt%.
2. The stone adhesive color mixing paste of claim 1, wherein: in the anti-settling agent, the fumed silica accounts for 90 wt%, and the polyamide modified hydrogenated castor oil accounts for 10 wt%.
3. The stone adhesive color mixing paste of claim 1, wherein: in the oil absorbent, the styrene-methyl methacrylate copolymer accounts for 60 wt%, the polybutylmethacrylate accounts for 20 wt%, and the microcrystalline wax accounts for 20 wt%.
4. The stone adhesive color mixing paste of claim 1, wherein: in the blender, the epoxidized soybean oil accounts for 70-80 wt%, the methyl hydrogen-containing silicone oil accounts for 15-20 wt%, and the glycerol accounts for 5-10 wt%.
5. The stone adhesive color mixing paste of claim 1, wherein: the inorganic pigment is one or more of iron oxide red, zinc chrome yellow, cobalt blue, zinc barium green, carbon black and titanium dioxide; the dispersing agent is one or more of ethylene glycol monohexyl ether, triethylene glycol monobutyl ether, diethylene glycol monoethyl ether, 2,6, 8-trimethyl-4-nonanone, N-methyl pyrrolidone and benzyl alcohol.
6. The stone adhesive color mixing paste of claim 1, wherein: in the defoaming agent, 40-60 wt% of a polyether siloxane defoaming agent Foamex KS 10 and 40-60 wt% of a silicone-free defoaming agent Airex 910 are contained.
7. A method for preparing the stone adhesive toning paste of any one of claims 1 to 6, which is characterized by comprising the following steps: the method comprises the following steps:
(1) stirring at high speed under negative pressure of 0.08-0.1MPa and temperature of 55 + -2 deg.C to disperse the blending agent in the molten anti-settling agent to form cream-like paste;
(2) when the cream-like paste is cooled to room temperature, adding the inorganic pigment, the defoaming agent, the dispersing agent and the oil absorbent, and uniformly mixing;
(3) grinding the mixture to a particle size of 1-2 μm to obtain the stone adhesive toning paste.
8. The use method of the stone adhesive color mixing paste as defined in any one of claims 1 to 7, which is characterized in that: the method comprises the following steps:
(1) determining the color of a target stone, and selecting stone adhesive color mixing paste consisting of required colors;
(2) preparing the stone adhesive toning paste into a mixture with the color consistent with the color of the target stone;
(3) the mixture is mixed with stone adhesive to bond stone.
9. The use method of the stone adhesive color mixing paste as claimed in claim 8, wherein: the addition amount of the modifier is 0.1-1 wt% of the stone adhesive.
10. The use method of the stone adhesive color mixing paste according to claim 8 or 9, characterized in that: the stone adhesive is a stone adhesive of an unsaturated polyester resin matrix or a stone adhesive of an epoxy resin matrix.
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Effective date of registration: 20230828 Address after: No. 6 Danjin Road, Industrial Concentration Zone, Baita Town, Jintan District, Changzhou City, Jiangsu Province, 213299 Patentee after: Jiangsu Hercules Marble Care Materials Co.,Ltd. Address before: 430000 No. 26, Jinhai Industrial Park Road, Jinyinhu office, Dongxihu District, Wuhan City, Hubei Province (10) Patentee before: WUHAN KEDA MARBLE PROTECTIVE MATERIALS Co.,Ltd. |
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