CN110093056B - Water-based formaldehyde-free painting pigment and preparation method thereof - Google Patents

Abstract

The invention relates to an aqueous formaldehyde-free painting pigment and a preparation method thereof, wherein the aqueous formaldehyde-free painting pigment comprises the following components: 10-15 parts of toner, 60-65 parts of vegetable gum, 3.5-5.5 parts of surfactant, 1-5 parts of inorganic thickener, 0.05-0.1 part of antibacterial agent and 0.05-0.15 part of inorganic electrolyte. According to the invention, the inorganic thickener combination with a special composition is used, and the inorganic thickener exists in a system in a melting state in the technical scheme, so that air cannot be adsorbed on the surface, the environmental condition which is not beneficial to bacterial breeding is provided, and the phenomenon that the traditional filler exists in a product system in a granular state and is easy to adsorb air to cause bacterial breeding is effectively avoided. The product can achieve better antibacterial property only by adding a small amount of antibacterial agent, the addition of the inorganic thickening agent can also achieve low color difference and crack resistance equivalent to those of the filler, and the production cost of the product can be reduced.

Description

Water-based formaldehyde-free painting pigment and preparation method thereof

Technical Field

The invention relates to the field of pigments, in particular to a water-based formaldehyde-free painting pigment and a preparation method thereof.

Background

The aqueous painting pigment is a painting pigment which can be dissolved or diluted by water, and generally comprises watercolor painting pigment, gouache painting pigment, acrylic painting pigment, finger painting pigment, Chinese painting pigment and the like.

In order to make the water-based painting pigment have better service performance, such as no cracking, low color difference and the like, and lower manufacturing cost, fillers, such as calcium carbonate, talcum powder and the like, are generally added into the painting pigment, but the fillers exist in the form of granular particles in products, have larger specific surface area, adsorb a large amount of air, and easily cause bacterial breeding, and in order to overcome the defect, a large amount of antibacterial agents are often needed to effectively sterilize. In the prior art, in order to prevent the breeding of bacteria, formaldehyde, BCM and chlorothalonil are generally added into the pigment, or a metal material with bacteriostatic efficacy, such as metal silver, is added. But formaldehyde has great harm to human body, mainly has sensitization stimulation effect, and is a genotoxic substance, and free formaldehyde is released in the using process of the product, so that respiratory tract infection or carcinogenesis is caused by human body inhalation; BCM and chlorothalonil germicides have stimulation effect on human skin and eyes, can cause dermatitis, have extremely high toxicity on aquatic organisms and have long-term adverse effect on water environment; the metallic silver is expensive, which makes the manufacturing cost of the pigment higher.

Disclosure of Invention

The invention aims to provide an aqueous formaldehyde-free painting pigment which has the effects of preventing bacteria from breeding, preventing moisture absorption and softening, preventing cracking and having good glossiness.

The invention also aims to provide a preparation method of the water-based formaldehyde-free painting pigment.

In order to achieve the above object, the present invention provides an aqueous formaldehyde-free painting pigment comprising the following components: 10-15 parts of toner, 60-65 parts of vegetable gum, 3.5-5.5 parts of surfactant, 1-5 parts of inorganic thickener, 0.05-0.1 part of antibacterial agent and 0.05-0.15 part of inorganic electrolyte.

Preferably, the inorganic thickener is one or more of bentonite, attapulgite and aluminum silicate.

Preferably, the inorganic thickener is a mixture of 1: 1.2-1.5: 2-3 of a mixture of bentonite, attapulgite and aluminum silicate.

Preferably, the surfactant is a cationic surfactant.

Preferably, the inorganic electrolyte is one or more of sodium chloride, potassium chloride, sodium sulfate and potassium sulfate.

Preferably, the vegetable gum is one or more of pectin, maltitol, carrageenan, peach gum and acacia gum.

Preferably, at least one of the vegetable gums is gum arabic.

Preferably, the antibacterial agent is chlorphenesin and/or paraben.

In order to achieve the above object, the present invention also provides a method for preparing the aqueous formaldehyde-free painting pigment, comprising the following steps:

s1, mixing the toner, the vegetable gum and the surfactant, and grinding to prepare color paste;

s2, adding inorganic electrolyte and inorganic thickener into the color paste, stirring, then sterilizing at 120-130 ℃, and dispersing and activating under the conditions of vacuum pressure of 0.7-0.9 KPa and rotation speed of 400-500 r/min after sterilization; and

and S3, after the dispersion and activation are finished, reducing the temperature to be below 40 ℃, adding the antibacterial agent, and uniformly stirring to obtain a finished product.

The invention has the beneficial effects that:

compared with the traditional mode of adding the filler in the formula of the drawing pigment, the invention uses the inorganic thickener combination with special composition, and in the technical scheme, the inorganic thickener exists in a system in a melting state, so that the surface can not adsorb air, the environmental condition which is not beneficial to bacterial breeding is provided, and the phenomenon that the traditional filler exists in a product system in a granular state, so that the air is easily adsorbed, and the bacterial breeding is caused is effectively avoided. The product can achieve better antibacterial property only by adding a small amount of antibacterial agent, the addition of the inorganic thickening agent can also achieve low color difference and crack resistance equivalent to those of the filler, and the production cost of the product can be reduced.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more apparent, the present invention is further described in detail below 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.

An aqueous formaldehyde-free drawing pigment comprising the following components: 10-15 parts of toner, 60-65 parts of vegetable gum, 3.5-5.5 parts of surfactant, 1-5 parts of inorganic thickener, 005-0.1 part of antibacterial agent and 0.05-0.15 part of inorganic electrolyte.

The inorganic thickener is one or more of bentonite, attapulgite and aluminum silicate. The invention adopts inorganic thickener to thicken the system, and the thickener has special structure, such as: the layered structure, expanded lattice structure, the existing metal ions diffuse out from the platelets in aqueous solution, the metal ions swell due to hydration, and finally are completely separated from the platelets to form a colloidal suspension. At this time, the surface of the platelet separated from the metal ions has negative charges, and the edges of the platelet have small positive charges due to the occurrence of the fracture surfaces of the crystal lattice. In dilute solution, the negative charge on the surface is larger than the positive charge on the corners, the particles can not be thickened due to the electric repulsion action, in order to reduce the negative charge on the surfaces of the platelets, the interaction force of the particles is changed from the original mutual repulsion between the platelets into the mutual attraction of the negative charge on the surfaces of the platelets and the positive charge on the corners, the inorganic electrolyte is added into the system, so that the platelets are arranged in parallel due to the existence of the repulsive force originally and are changed into the mutual attraction of the positive charge and the negative charge, the platelets are vertically arranged, swelling is realized, and the purpose of thickening is achieved. And the swelling principle enables the thickening agent to exist in a system in a molten state, so that fillers existing in the system in a granular particle form are well replaced, the adsorption of air on the surfaces of particles is avoided, and the breeding of bacteria is effectively avoided under the environmental condition. Furthermore, the use performance of the pigment, such as low color difference and cracking resistance, cannot be influenced because the traditional filler such as calcium carbonate or talcum powder is not added in the formula.

The particle size of the inorganic thickener is 5-20 microns, if the particle size is smaller than 5 microns, the viscosity of a system is insufficient, the use of the pigment is influenced, and if the particle size is larger than 20 microns, the surface roughness of the dried pigment during drawing is overlarge.

The inorganic thickener is prepared from the following components in a mass ratio of 1: 1.2-1.5: 2-3, in the compounding ratio range, the system viscosity is appropriate, the swelling effect is better, the bacterial breeding is more effectively prevented, and the painting pigment formed by using the bentonite, the attapulgite and the aluminum silicate together with other components in the formula has good glossiness and is not easy to crack.

The surfactant is a cationic surfactant, can promote the thickening effect of the inorganic thickener, and can enable the pigment to have better leveling property.

The inorganic electrolyte is one or more of sodium chloride, potassium chloride, sodium sulfate and potassium sulfate.

The vegetable gum is one or more of pectin, maltitol, carrageenan, peach gum and Arabic gum, and preferably, at least one of the vegetable gums is the Arabic gum. The gum arabic is a high molecular weight electrolyte, contributes to swelling of the inorganic thickener, and can make the pigment not easily absorb moisture, hydrolyze and soften, and not adhere when in contact with the inorganic thickener.

In the present invention, it is preferable that the surfactant is used in combination with a vegetable gum, and when the vegetable gum contains peach gum or maltitol, a quaternary ammonium salt type cationic surfactant is used.

The antibacterial agent can be formaldehyde, BCM, chlorothalonil and other common antibacterial components in the field, but is preferably chlorphenesin and/or p-hydroxybenzoate ester, chlorphenesin and p-hydroxybenzoate ester, and has inhibiting and killing effects on bacteria such as escherichia coli and staphylococcus aureus and fungi such as aspergillus brazilian, aspergillus niger and aspergillus niger. Meanwhile, the antibacterial agent can be applied to cosmetics and has no stimulation and harm to human bodies. The sterilization principle is that the structure of microbial cell membranes is destroyed, or the synthesis of cell walls is interfered, or the permeability of the cell membranes is changed, so that substances in the microbial bodies escape out of the cells, or respiratory chain electron transfer systems related to the membranes are influenced, and the normal physiological balance of the microbes is destroyed and inactivated; simultaneously acts on an enzyme system in a microorganism body, inhibits the activity of the enzyme and interferes the normal metabolism of the enzyme. Such as the action of preservatives with the thiol groups of enzymes, disrupt the activity of various sulfur-containing proteases and interfere with the normal metabolism of microorganisms, thereby affecting their survival and reproduction. Can also act on genetic material or genetic particle structure, and further influence the replication, transcription, protein translation and the like of the genetic material; the antibacterial agent does not generate stimulation and harm to human body and environment, such as formaldehyde, BCM, chlorothalonil and other antibacterial agents, so that the product is free of formaldehyde and stimulation.

In the invention, the toner plays a role in coloring, and only a commercial product is selected.

A preparation method of the water-based formaldehyde-free painting pigment comprises the following steps:

s1, mixing the toner, the vegetable gum and the surfactant, and grinding to prepare color paste;

s2, adding inorganic electrolyte and inorganic thickener into the color paste, stirring, then sterilizing at 120-130 ℃, and dispersing and activating under the conditions of vacuum pressure of 0.7-0.9 KPa and rotation speed of 400-500 r/min after sterilization; and

and S3, after the dispersion and activation are finished, reducing the temperature to be below 40 ℃, adding the antibacterial agent, and uniformly stirring to obtain a finished product.

The grinding is to grind the specified fineness by a three-roller grinder through mutual extrusion of the surfaces of three horizontal rollers and friction at different speeds to prepare color paste, and the fineness of the color paste is less than 10 mu m.

The method adopts an ultrahigh-temperature instantaneous sterilizer to perform instantaneous ultrahigh-temperature sterilization, hydrogen bonds in inner sphere protein molecules of bacteria are destroyed at high temperature, and the protein is subjected to irreversible change, so that enzymes are inactivated, the cell structure of a living body is irreversibly damaged, and the life function of the bacteria is lost; meanwhile, the high temperature can change the volume of the intracellular fluid, thereby breaking the cells; but also genetic material DNA is decomposed at high temperature, causing bacterial death. The bacteria in the product system are killed by an instant ultra-high temperature sterilization process, the utilization rate of the preservative added into the product is effectively improved, the temperature is controlled to be very important in the process, the later swelling effect of the inorganic thickener is influenced if the temperature is too high, the sterilization effect is not ideal if the temperature is too low, and the preferable temperature is 120-130 ℃.

The dispersion activation is carried out in a vacuum high-speed dispersing agent, the dispersion activation lasts for 25-30 minutes, the stirring speed and the dispersion activation time are strictly controlled in the process, if the stirring speed is too high and the stirring time is too long, the viscosity of the color paste is reduced, and if the rotating speed is too low and the time is too short, the components cannot be uniformly mixed.

After activation, the temperature is reduced to below 40 ℃, the antibacterial agent is added under the vacuum condition, the mixture is uniformly stirred in vacuum, the vacuum pressure is controlled to be 0.7-0.9 KPa, the mixture is stirred for about 15 minutes, the temperature is ensured not to be higher than 40 ℃ in the step, otherwise, the antibacterial agent is easy to lose efficacy.

The adding amount of the antibacterial agent in the product is reduced by adding the antibacterial agent later, and the utilization rate of the antibacterial agent is effectively improved; the cosmetic grade antibacterial agent without formaldehyde and stimulation is adopted for corrosion prevention, the harm of the product to human bodies and the environment is avoided, and the product is free of formaldehyde and stimulation.

Example 1

Mixing 10 parts by mass of toner, 60 parts by mass of vegetable gum (a mixture of gum arabic, peach gum and pectin in a mass ratio of 1:1.2: 1.5) and 3.5 parts by mass of surfactant (cetyltrimethylammonium chloride), and grinding to obtain color paste with a fineness of 10 microns;

adding 0.05 part by mass of inorganic electrolyte sodium chloride and 1 part by mass of inorganic thickening agent (bentonite, attapulgite and aluminum silicate in a mass ratio of 1:1.2: 2) into the color paste, uniformly stirring, sterilizing at 120 ℃, and performing dispersion activation for 25 minutes under the conditions of vacuum pressure of 0.7KPa and rotation speed of 400r/min after sterilization;

and after the dispersion and activation are finished, reducing the temperature to 40 ℃, adding 0.05 part by mass of the antibacterial agent chlorphenesin, and uniformly stirring to obtain a finished product.

Example 2

Mixing 15 parts by mass of toner, 65 parts by mass of vegetable gum (a mixture of gum arabic and carrageenan in a mass ratio of 1: 1) and 5.5 parts by mass of surfactant (octadecyl amine acetate), and grinding to obtain color paste with fineness of 5 microns;

adding 0.15 part by mass of inorganic electrolyte potassium chloride and 1 part by mass of inorganic thickening agent (bentonite, attapulgite and aluminum silicate in a mass ratio of 1: 1.5: 3) into the color paste, uniformly stirring, sterilizing at 130 ℃, and dispersing and activating for 30 minutes under the conditions of vacuum pressure of 0.9KPa and rotation speed of 500r/min after the sterilization is finished;

after the dispersion activation is finished, the temperature is reduced to 30 ℃, 0.1 part by mass of the antibacterial agent p-hydroxybenzoate is added, and the mixture is uniformly stirred to obtain a finished product.

Example 3

13 parts by mass of toner, 62 parts by mass of vegetable gum (a mixture of gum arabic and maltitol in a mass ratio of 1: 0.5) and 4.5 parts by mass of surfactant (octadecyl trimethyl ammonium chloride) are mixed and ground to prepare color paste with the fineness of 8 microns;

adding 0.1 part by mass of inorganic electrolyte sodium sulfate and 3 parts by mass of inorganic thickening agent (bentonite, attapulgite and aluminum silicate in a mass ratio of 1: 1.5: 2.5) into the color paste, stirring uniformly, sterilizing at 120 ℃, and performing dispersion activation under the conditions of vacuum pressure of 0.8KPa and rotation speed of 450r/min after sterilization;

after the dispersion activation is finished, the temperature is reduced to below 20 ℃, 0.75 part by mass of an anti-microbial agent (a mixture of chlorphenesin and p-hydroxybenzoate in a mass ratio of 1: 1) is added, and the mixture is uniformly stirred to obtain a finished product.

Example 4

Mixing 10 parts by mass of toner, 60 parts by mass of vegetable gum (a mixture of gum arabic, peach gum and pectin in a mass ratio of 1:1.2: 1.5) and 3.5 parts by mass of surfactant (cetyltrimethylammonium chloride), and grinding to obtain color paste with a fineness of 10 microns;

adding 0.05 part by mass of inorganic electrolyte sodium chloride and 1 part by mass of inorganic thickening agent (bentonite, attapulgite and aluminum silicate in a mass ratio of 2: 1.2: 1) into the color paste, uniformly stirring, sterilizing at 120 ℃, and performing dispersion activation for 25 minutes under the conditions of vacuum pressure of 0.7KPa and rotation speed of 400r/min after sterilization;

and after the dispersion and activation are finished, reducing the temperature to 40 ℃, adding 0.05 part by mass of the antibacterial agent chlorphenesin, and uniformly stirring to obtain a finished product.

Comparative example 1

Mixing 10 parts by mass of toner, 60 parts by mass of vegetable gum (a mixture of gum arabic, peach gum and pectin in a mass ratio of 1:1.2: 1.5) and 3.5 parts by mass of surfactant (cetyltrimethylammonium chloride), and grinding to obtain color paste with a fineness of 10 microns;

adding 0.05 part by mass of inorganic electrolyte sodium chloride into the color paste, uniformly stirring, then sterilizing at 120 ℃, and dispersing and activating for 25 minutes under the conditions of vacuum pressure of 0.7KPa and rotating speed of 400r/min after the sterilization is finished;

and after the dispersion and activation are finished, reducing the temperature to 40 ℃, adding 0.05 part by mass of the antibacterial agent chlorphenesin, and uniformly stirring to obtain a finished product.

Comparative example 2

Mixing 10 parts by mass of toner, 60 parts by mass of vegetable gum (a mixture of gum arabic, peach gum and pectin in a mass ratio of 1:1.2: 1.5) and 3.5 parts by mass of surfactant (cetyltrimethylammonium chloride), and grinding to obtain color paste with a fineness of 10 microns;

adding 0.05 part by mass of inorganic electrolyte sodium chloride and 1 part by mass of filling material calcium carbonate into the color paste, uniformly stirring, then sterilizing at 120 ℃, and dispersing and activating for 25 minutes under the conditions of vacuum pressure of 0.7KPa and rotating speed of 400r/min after the sterilization is finished;

and after the dispersion and activation are finished, reducing the temperature to 40 ℃, adding 0.05 part by mass of the antibacterial agent chlorphenesin, and uniformly stirring to obtain a finished product.

The products prepared in examples 1-4 and comparative examples 1-2 were subjected to performance tests under the same conditions, including antibacterial property, color difference, cracking resistance, and moisture absorption resistance, and specific comparison results are shown in table 1.

TABLE 1

The above 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, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (3)

1. The water-based formaldehyde-free drawing pigment is characterized by comprising the following components: the toner comprises, by mass, 10-15 parts of toner, 60-65 parts of vegetable gum, 3.5-5.5 parts of surfactant, 1-5 parts of inorganic thickener, 0.05-0.1 part of antibacterial agent and 0.05-0.15 part of inorganic electrolyte, wherein the inorganic thickener is a mixture of, by mass, 1: 1.2-1.5: 2-3 of a mixture of bentonite, attapulgite and aluminum silicate, wherein the surfactant is a cationic surfactant, the vegetable gum is selected from pectin, maltitol, carrageenan, peach gum and gum arabic, and at least one of the vegetable gums is gum arabic; the preparation method of the water-based formaldehyde-free painting pigment comprises the following steps:

s1, mixing the toner, the vegetable gum and the surfactant, and grinding to prepare color paste;

s2, adding inorganic electrolyte and inorganic thickener into the color paste, stirring, then sterilizing at 120-130 ℃, and dispersing and activating under the conditions of vacuum pressure of 0.7-0.9 KPa and rotation speed of 400-500 r/min after sterilization; and

and S3, after the dispersion and activation are finished, reducing the temperature to be below 40 ℃, adding the antibacterial agent, and uniformly stirring to obtain a finished product.

2. The aqueous formaldehyde-free graphic pigment according to claim 1, wherein the inorganic electrolyte is one or more of sodium chloride, potassium chloride, sodium sulfate and potassium sulfate.

3. The aqueous formaldehyde-free graphic paint of claim 1, wherein the anti-microbial agent is chlorphenesin and/or parabens.