CN113881264B - Pigment composition and preparation method and application thereof - Google Patents

Pigment composition and preparation method and application thereof Download PDF

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Publication number
CN113881264B
CN113881264B CN202111294682.8A CN202111294682A CN113881264B CN 113881264 B CN113881264 B CN 113881264B CN 202111294682 A CN202111294682 A CN 202111294682A CN 113881264 B CN113881264 B CN 113881264B
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pigment composition
parts
composition according
pigment
weight
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CN113881264A (en
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莫振宇
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Shanghai Marley Painting Materials Co ltd
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Shanghai Marley Painting Materials Co ltd
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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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/06—Artists' paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Plant Pathology (AREA)
  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention provides a pigment composition, a preparation method and application thereof. The pigment composition comprises 20 to 60 parts by weight of binder, 5 to 30 parts by weight of colorant and 0.25 to 1.8 parts by weight of sterilization and mildew inhibitor; the sterilization mildewcide comprises an inorganic sterilization mildewcide and/or an organic sterilization mildewcide; the inorganic sterilization mildewcide comprises the combination of lithium carbonate and zinc oxide; the organic sterilization and mildew-proof agent comprises A and B; said A includes 1, 2-benzisothiazolin-3-one and 2-butyl-1, 2-benzisothiazolin-3-one; the B comprises 2, 2-dibromo-3-nitrilopropionamide or phenoxyethanol. According to the invention, the specific combination of the sterilization and mildew preventive is adopted, so that the pigment composition not only has excellent mildew and corrosion resistance, but also has low sensitization.

Description

Pigment composition and preparation method and application thereof
Technical Field
The invention belongs to the technical field of art painting pigments, and particularly relates to a pigment composition, and a preparation method and application thereof.
Background
Painting is a way of human interest activity, and as people's living standard improves, more and more people have an interest in painting. The painting pigment is a fast-disappearing product, and in order to prolong the storage time of the painting pigment, a sterilization mildew-proof agent needs to be added into the components.
For example, CN102796420A discloses an aqueous ink color pigment composition with halation effect on rice paper, comprising the following components: 30 to 60 parts of binder, 10 to 30 parts of colorant, 20 to 50 parts of system pigment, 0.1 to 3 parts of wetting dispersant and 0.2 to 1 part of mildew preventive; the composition adopts pure natural vegetable gum, belongs to an environment-friendly binder, pigment toner is easy to disperse in the binder, flocculation separation phenomenon cannot occur, when the composition is used on rice paper, the color is extended along with the mixture of the binder, water and ink, fine particle precipitation phenomenon cannot occur, and the composition has good stability and strong halation property. However, the aqueous ink color pigment has a small sterilization range, and the mildew-proof effect needs to be further improved.
With the increase of health consciousness of people, european countries have listed a plurality of bactericides as possible sensitizers and require to identify the bactericides, and common bactericidal mildewcides are generally in the table of possible sensitizers. CN113122037A discloses an anti-cracking and anti-curl water-based painting pigment composition, and a preparation method and application thereof. The aqueous painting pigment composition comprises the following components in parts by weight: 40 to 70 parts of binder, 10 to 30 parts of colorant, 10 to 40 parts of filler, 0.1 to 3 parts of wetting dispersant and 0.2 to 1 part of mildew preventive. The water-based painting pigment composition can adopt natural plant glue or synthetic modified glue, uses heavy calcium carbonate and montmorillonite as composite fillers, and combines a novel dispersing auxiliary agent, so that each component is easy to disperse in a binder, flocculation separation phenomenon can not occur, dry-wet change is small, the water-based painting pigment composition has good stability, and the phenomenon of roll paper cracking can not occur in normal use on gouache paper. However, the aqueous painting pigments may have high sensitization and low mildewproof effect.
Therefore, the problem to be solved in the art is to develop a hypoallergenic water-based painting pigment under the condition of ensuring the mildew-proof effect and the storage life of the pigment.
Disclosure of Invention
In order to solve the technical problems, the invention provides a pigment composition and a preparation method and application thereof. The specific combination of the bactericidal and mildewproof agent in the pigment composition enables the pigment composition to have excellent mildewproof and antiseptic properties and to be less prone to allergy.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a pigment composition. The pigment composition comprises 20 to 60 parts by weight of binder, 5 to 30 parts by weight of colorant and 0.25 to 1.8 parts by weight of sterilization and mildew inhibitor; the sterilization mildewcide comprises an inorganic sterilization mildewcide and/or an organic sterilization mildewcide; the inorganic sterilization mildewcide comprises a combination of lithium carbonate and zinc oxide; the organic sterilization and mildew-proof agent comprises A and B; said A includes 1, 2-benzisothiazolin-3-one (BIT-20) and 2-butyl-1, 2-benzisothiazolin-3-one (BBIT); the B comprises 2, 2-dibromo-3-nitrilopropionamide or phenoxyethanol.
According to the pigment composition provided by the invention, the inorganic sterilization mildew preventive adopts the combination of lithium carbonate and zinc oxide, so that bacteria and mould can be effectively killed, and the pigment composition has long storage time and stable property; 2, 2-dibromo-3-nitrilopropionamide (DBNPA) or phenoxyethanol in the organic sterilization mildew preventive is used for eliminating initial strains in materials, and the combination of BIT-20 and BBIT is used, so that the pigment composition is more excellent in mildew resistance and corrosion resistance, low in sensitization performance and suitable for manufacturing drawing pigments.
In the present invention, the pigment composition comprises 20 to 60 parts by weight of the binder, for example, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, etc.
The pigment composition includes 5 to 30 parts by weight of a colorant, and may be, for example, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, and the like.
In the present invention, the colorant may be used in any combination of a plurality of colors to obtain a mixed color. There are no particular requirements regarding the amount of colorant used, depending primarily on the color requirements. The color intensity of the painting color depends on the concentration of the colorant, and the weight parts of the colorants of different colors in the formula are different.
The pigment composition comprises 0.25-1.8 parts of sterilization and mildew-proof agent by weight, and can be 0.25 part, 0.3 part, 0.4 part, 0.5 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.2 part, 1.4 part, 1.6 part, 1.8 part and the like.
In a preferred embodiment of the present invention, the bactericidal and antifungal agent further comprises one or a combination of at least two of bronopol, iodopropynyl n-butyl carbamate, sodium pyrithione, zinc pyrithione, potassium sorbate, sodium benzoate, and formaldehyde release-controlling agents.
Preferably, the inorganic sterilization and mildew-proof agent is contained in the pigment composition in an amount of 0.05 to 0.06% by mass, and may be, for example, 0.05%, 0.052%, 0.054%, 0.056%, 0.058%, 0.06%, or the like.
Preferably, the pigment composition contains 0.002 to 0.005 mass% of pure 1, 2-benzisothiazolin-3-one (BIT-20), such as 0.002%, 0.0025%, 0.003%, 0.0035%, 0.004%, 0.0045%, 0.005% and the like.
Preferably, the pigment composition has a pure 2-butyl-1, 2-benzisothiazolin-3-one (BBIT) content of 0.04 to 0.1% by mass, for example, 0.04%, 0.045%, 0.05%, 0.055%, 0.06%, 0.065%, 0.07%, 0.075%, 0.08%, 0.085%, 0.09%, 0.095%, 0.1% or the like.
In the invention, the mass percentage of pure BIT-20 in the pigment composition is more than 0.005 percent, so that the sensitization probability of the pigment composition can be increased, and easy sensitization needs to be marked; the mass percentage of pure BBIT in the pigment composition is less than 0.04 percent, and the mildew-proof and anti-corrosion effects of the pigment composition do not meet the requirements; and the mass percentage of pure BBIT in the pigment composition is more than 0.1 percent, which does not accord with the use regulation of BBIT and increases the sensitization probability of the pigment composition. The combination effect of BBIT and BIT-20 is the best, and when only BBIT is selected as the organic sterilization and mildew-proof agent, the needed BBIT content is too high, the cost is increased, and the risk of sensitization is increased.
Preferably, the mass percentage of the pure 2, 2-dibromo-3-nitrilopropionamide in the pigment composition is 0.01 to 0.04%, and may be, for example, 0.01%, 0.015%, 0.02%, 0.025%, 0.03%, 0.035%, 0.04%, or the like.
The pure phenoxyethanol content in the pigment composition is preferably 0.2 to 0.4% by mass, and may be, for example, 0.2%, 0.22%, 0.24%, 0.26%, 0.28%, 0.3%, 0.32%, 0.34%, 0.36%, 0.38%, 0.4%, or the like.
In the invention, the mass percent of the pure 2, 2-dibromo-3-nitrilopropionamide in the pigment composition is less than 0.01 percent or the mass percent of the pure phenoxyethanol is less than 0.2 percent, and the bactericidal effect of the pigment composition cannot meet the requirement; the mass percent of the pure 2, 2-dibromo-3-nitrilopropionamide in the pigment composition is more than 0.04 percent or the mass percent of the pure phenoxyethanol is more than 0.4 percent, which influences the color and the smell of the pigment composition.
Preferably, the binder comprises a natural binder and/or a synthetic binder.
Preferably, the natural binder comprises any one of arabinose, galactose, glucuronic acid, modified starch, starch gum, dextrin gum, maltose or a vegetable resin or a combination of at least two thereof.
In the present invention, the arabinose, galactose and glucuronic acid belong to gum arabic.
Preferably, the synthetic binder comprises a polyacrylic acid emulsion.
Preferably, the binder has a solids content of 20 to 50%, for example, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, etc., and more preferably 35% to 42%.
Preferably, the pigment composition further comprises 1 to 40 parts by weight of extender pigment, for example, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts and the like.
Preferably, the extender pigment comprises any one of or a combination of at least two of silicates, oxides of silicon, barium sulphate or carbonates.
Preferably, the silicate comprises any one of, or a combination of at least two of, aluminum silicate, magnesium silicate, bentonite, china clay or attapulgite.
Preferably, the oxide of silicon comprises precipitated silica or fumed silica.
Preferably, the carbonate comprises calcium carbonate and/or magnesium carbonate.
Preferably, the pigment composition further comprises 0.1 to 3 parts by weight of wetting and dispersing agent, for example, 0.1 part, 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1.0 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2.0 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3.0 parts and the like.
Preferably, the wetting and dispersing agent comprises any one or a combination of at least two of polyacrylate, alkyl polyoxyethylene ether or acrylic acid copolymer.
Preferably, the pigment composition further comprises 0.05 to 1 part by weight of a defoaming agent, and may be, for example, 0.05 part, 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, 0.5 part, 0.55 part, 0.6 part, 0.65 part, 0.7 part, 0.75 part, 0.8 part, 0.85 part, 0.9 part, 0.95 part, 1.0 part, etc.
Preferably, the defoamer comprises any one of a mineral oil defoamer, a polyether modified silicone defoamer or an alkynol defoamer or a combination of at least two thereof.
The fineness of the pigment composition is preferably 25 to 40 μm, and may be, for example, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, 36 μm, 37 μm, 38 μm, 39 μm, 40 μm, or the like.
Preferably, the pigment composition has a fluidity of 2.6 to 3.4cm, and may be, for example, 2.6cm, 2.7cm, 2.8cm, 2.9cm, 3.0cm, 3.1cm, 3.2cm, 3.3cm, 3.4cm or the like.
In a second aspect, the present invention provides a process for preparing a pigment composition according to the first aspect, comprising the steps of:
and mixing and dispersing the binder, the colorant and the sterilization and mildew-proof agent according to the formula amount to obtain the pigment composition.
As a preferable technical scheme of the invention, the mixed material also comprises any one or a combination of at least two of extender pigment, defoaming agent or wetting dispersant.
Preferably, the method of dispersion is mill dispersion.
Preferably, the grinding dispersion apparatus is a three-roll mill.
Preferably, the rotation speed of the grinding dispersion is 100 to 300r/min, for example, 100r/min, 120r/min, 140r/min, 160r/min, 180r/min, 200r/min, 220r/min, 240r/min, 260r/min, 280r/min, 300r/min, etc.
Preferably, the time for the grinding dispersion is 20 to 40min, for example, 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, 40min, etc.
In a third aspect, the present invention provides the use of a pigment composition according to the first aspect in a paint pigment.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a pigment composition, which is characterized in that a specific combination of sterilization and mildew preventive is added, wherein an inorganic sterilization and mildew preventive adopts the combination of lithium carbonate and zinc oxide, and an organic sterilization and mildew preventive adopts the synergistic use of BIT-20, BBIT and DBNPA or phenoxyethanol, so that the pigment composition has a good in-tank storage effect, is not easy to mildew or deteriorate and is not easy to be allergic;
(2) The pigment composition has good stability, is not easy to generate flocculation separation phenomenon, and has small dry-wet change.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
The following examples and comparative examples do not indicate any particular technique or condition, and are carried out according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or apparatus used are conventional products commercially available from normal sources, not indicated by the manufacturer.
Example 1
This example provides a pigment composition comprising, in parts by weight, 40 parts binder (gum arabic, 40% solids, available from dell glue ltd.), 30 parts titanium dioxide, 0.312 parts germicidal and mildewcide agent, 25 parts extender pigment (20 parts ground calcium carbonate and 5 parts fumed silica), 0.5 parts wetting and dispersing agent (Dispers 752W, digao), and 0.5 parts defoamer (sanopuco NXY defoamer). The sterilization and mildew-proof agent comprises, by weight, 0.05 parts of DBNPA (mass fraction of 20%), 0.012 parts of BIT-20 (mass fraction of 20%) and 0.25 parts of BBIT (mass fraction of 20%).
The embodiment also provides a preparation method of the pigment composition, which comprises the following specific steps:
the materials are mixed according to the formula amount, and a three-roll grinder is adopted to grind and disperse for 30min at the rotating speed of 200r/min, so that the pigment composition is obtained.
Example 2
This example provides a pigment composition comprising, in parts by weight, 60 parts binder (gum arabic, 35% solids, available from gelfoam, inc.), 25 parts titanium dioxide, 0.67 parts germicidal and mold-proof agent, 10 parts extender pigment (5 parts ground calcium carbonate and 5 parts fumed silica), 1.5 parts wetting and dispersing agent (BYK 190 of bike) and 0.2 parts defoamer (sanopusco NXY defoamer). The sterilization and mildew-proof agent comprises, by weight, 0.18 parts of DBNPA (mass fraction of 20%), 0.01 parts of BIT-20 (mass fraction of 20%) and 0.48 parts of BBIT (mass fraction of 20%).
The embodiment also provides a preparation method of the pigment composition, which comprises the following specific steps:
the materials are mixed according to the formula amount, and a three-roll grinder is adopted to grind and disperse for 20min at the rotating speed of 300r/min, so that the pigment composition is obtained.
Example 3
This example provides a pigment composition comprising, in parts by weight, 25 parts binder (gum arabic, 25% solids, available from dell corporation), 8 parts titanium dioxide, 1.18 parts germicidal and mildewcide agent, 40 parts extender pigment (30 parts ground calcium carbonate and 10 parts fumed silica), 3 parts wetting and dispersing agent (Dispers 752W digao) and 1 part defoamer (NXY defoamer of sannopraceae); the sterilization and mildew-proof agent comprises, by weight, 0.91 parts of phenoxyethanol (mass fraction is 20%), 0.02 parts of BIT-20 (mass fraction is 20%), and 0.25 parts of BBIT (mass fraction is 20%).
This example also provides a method for preparing a pigment composition, comprising the following steps:
the materials are mixed according to the formula amount, and a three-roll grinder is adopted to grind and disperse for 40min at the rotating speed of 100r/min, so that the pigment composition is obtained.
Example 4
This example provides a pigment composition comprising, in parts by weight, 25 parts binder (gum arabic, 45% solids, available from delrin glue, inc.), 8 parts titanium dioxide, 1.68 parts germicidal and anti-mold agent, 40 parts extender pigment (30 parts ground calcium carbonate and 10 parts fumed silica), 3 parts wetting and dispersing agent (Dispers 752W dike) and 1 part defoamer (NXY defoamer of sanopuco); the sterilization mildew preventive comprises, by weight, 1.4 parts of phenoxyethanol (mass fraction is 20%), 0.02 part of BIT-20 (mass fraction is 20%), and 0.26 part of BBIT (mass fraction is 20%).
The embodiment also provides a preparation method of the pigment composition, which comprises the following specific steps:
the materials are mixed according to the formula amount, and a three-roll grinder is adopted to grind and disperse for 40min at the rotating speed of 100r/min, so that the pigment composition is obtained.
Example 5
This example provides a pigment composition that differs from example 1 only in that the germicidal mildewcide includes a mixture of 0.05 parts by weight DBNPA and 0.262 parts by weight lithium carbonate plus zinc oxide (Omyasmart zero, available from Europe, shanghai).
This example provides a method for preparing a pigment composition, which comprises the same steps as in example 1.
Example 6
This example provides a pigment composition that differs from example 1 only in that the fungicidal and fungicidal agent includes 0.05 parts by weight of DBNPA (mass fraction of 20%), 0.012 parts by weight of BIT-20 (mass fraction of 20%), 0.22 parts by weight of BBIT (mass fraction of 20%), and 0.03 parts by weight of iodopropynyl n-butyl carbamate (IPBC, mass fraction of 20%).
This example also provides a method for preparing a pigment composition, which comprises the same steps as in example 1.
Example 7
This example provides a pigment composition that differs from example 1 only in that the fungicidal and fungicidal agent includes, in parts by weight, 0.142 parts of DBNPA (mass fraction of 20%), 0.02 parts of BIT-20 (mass fraction of 20%), and 0.15 parts of BBIT (mass fraction of 20%).
This example also provides a method for preparing a pigment composition, which comprises the same steps as in example 1.
Example 8
This example provides a pigment composition that differs from example 1 only in that the fungicidal and fungicidal agent includes, in parts by weight, 0.03 parts of DBNPA (20% by mass), 0.022 parts of BIT-20 (20% by mass), and 0.26 parts of BBIT (20% by mass).
This example also provides a method for preparing a pigment composition, which comprises the same steps as in example 1.
Example 9
This example provides a pigment composition which differs from example 2 only in that the fungicidal and mildewproof agent comprises, in parts by weight, 0.25 parts of DBNPA (mass fraction of 20%), 0.01 parts of BIT-20 (mass fraction of 20%), and 0.41 parts of BBIT (mass fraction of 20%).
This example also provides a method for preparing a pigment composition, which comprises the same steps as in example 2.
Comparative example 1
This comparative example provides a pigment composition which differs from example 1 only in that DBNPA is not present in the fungicidal mildewcide; the sterilization and mildew-proof agent comprises, by weight, 0.012 parts of BIT-20 (mass fraction is 20%) and 0.3 parts of BBIT (mass fraction is 20%).
The comparative example also provides a preparation method of the pigment composition, and the specific steps are the same as those of the example 1.
Comparative example 2
This comparative example provides a pigment composition which differs from example 1 only in that BIT-20 is not present in the fungicidal mildewcide; the sterilization and mildew-proof agent comprises 0.05 part of DBNPA (20 mass percent) and 0.262 part of BBIT (20 mass percent).
The comparative example also provides a preparation method of the pigment composition, and the specific steps are the same as those of the example 1.
Comparative example 3
The present comparative example provides a pigment composition which differs from example 1 only in that no BBIT is present in the fungicidal agent; the sterilization and mildew-proof agent comprises, by weight, 0.05 parts of DBNPA (mass fraction of 20%) and 0.262 parts of BIT-20 (mass fraction of 20%).
The comparative example also provides a preparation method of the pigment composition, and the specific steps are the same as those of the example 1.
Comparative example 4
This comparative example provides a pigment composition which differs from example 1 only in that the fungicidal agent comprises, in parts by weight, 0.05 parts of DBNPA and 0.262 parts of Bronopol (Bronopol, 20% by mass).
This comparative example provides a process for preparing a pigment composition, the specific procedure being the same as in example 1.
Comparative example 5
This comparative example provides a pigment composition which is different from example 1 only in that the fungicidal agent comprises 0.05 parts by weight of DBNPA and 0.262 parts by weight of IPBC (mass fraction 20%).
This comparative example provides a process for preparing a pigment composition, the specific procedure being the same as in example 1.
Comparative example 6
This comparative example provides a pigment composition which differs from example 3 only in that the fungicidal agent comprises, in parts by weight, 0.91 part of phenoxyethanol and 0.27 part of zinc pyrithione (mass fraction: 20%).
This comparative example provides a process for the preparation of a pigment composition, the procedure being the same as in example 3.
Comparative example 7
This comparative example provides a pigment composition which differs from example 3 only in that the bactericidal and fungicidal agent includes 0.91 part by weight of phenoxyethanol and 0.27 part by weight of potassium sorbate (mass fraction: 20%).
This comparative example provides a process for preparing a pigment composition, the specific procedure being the same as in example 3.
Comparative example 8
This comparative example provides a pigment composition which is different from example 1 only in that the fungicidal agent comprises, in parts by weight, 0.05 parts of DBNPA, 0.012 parts of BIT-20 and 0.25 parts of IPBC (mass fraction 20%).
This comparative example provides a process for preparing a pigment composition, the specific procedure being the same as in example 1.
Comparative example 9
This comparative example provides a pigment composition which is different from example 1 only in that the fungicidal agent comprises 0.05 parts by weight of DBNPA, 0.012 parts by weight of BIT-20 and 0.25 parts by weight of methylisothiazolinone (MIT, mass fraction 20%).
This comparative example provides a process for the preparation of a pigment composition, the specific procedure being the same as in example 1.
Comparative example 10
This comparative example provides a pigment composition which differs from example 1 only in that the fungicidal agent comprises, in parts by weight, 0.05 parts of DBNPA, 0.012 parts of BIT-20 and 0.25 parts of formaldehyde slow-release agent preservative (imidazolidinyl urea, mass fraction 20%).
This comparative example provides a process for the preparation of a pigment composition, the specific procedure being the same as in example 1.
Performance testing
The following performance tests were carried out on the pigment compositions prepared in the above examples and comparative examples:
(1) In-tank mildew-proof effect testing method
Tested according to ASTM D4783-2001, standard test method for resistance of adhesive preparations infected with bacteria in containers. Storing at 45 deg.C, testing the mould content in the tank once a week for 4 weeks;
adding mould: a mixed spore suspension of Aspergillus niger, aspergillus flavus, chaetomium globosum, penicillium citrinum, paecilomyces variotii, trichoderma, aspergillus versicolor and Rhizopus cereus;
weekly added mould content: in the first week: 5.8X 10 7 cfu/mL; in the second week: 5X 10 7 cfu/mL; in the third week: 4.6X 10 7 cfu/mL; and fourthly: 4.2X 10 7 cfu/mL；
Mold content (cfu/mL): excellent results were found at < 10, pass at 10-100 and fail at > 100.
(2) Method for testing in-tank corrosion prevention effect
The resistance of the adhesive preparation to bacterial infestation in a container was tested according to ASTM D4783-2001. Storing at 45 deg.C, testing the bacteria content in the tank once a week for 4 weeks;
adding bacteria: mixed spore suspension of escherichia coli, staphylococcus aureus, pseudomonas fluorescens, pseudomonas aeruginosa, common proteus and enterobacter aerogenes;
weekly added bacterial content: in the first week: 4.5X 10 7 cfu/mL; in the second week: 3.8X 10 7 cfu/mL; in the third week: 3.5X 10 7 cfu/mL; fourth, the following steps: 3 x 10 7 cfu/mL；
Bacterial content (cfu/mL): excellent values are found when < 10, pass values of 10 to 100 and fail values when > 100.
(3) Method for testing mildew-proof effect of dry film
Tested according to the GB/T1741-2020 paint film resistance assay. Storing at 45 deg.C, and testing mould content after 1 week;
adding mould: a mixed spore suspension of Aspergillus niger, aspergillus flavus, penicillium citrinum, paecilomyces variotii, trichoderma viride, brevibacterium sp, rhizopus cerealis and Alternaria alternata;
wherein, the mildew-proof effect of the dry films is good at 0-1 level and 1 level; the mildew-proof effect of the dry film above grade 1 is poor.
(4) Color testing method
Observing the color change of the pigment composition by visual means after four weeks; the pigment composition has stable property if the color does not change; the pigment composition is unstable in its properties if a color change occurs.
The specific test results are shown in table 1:
TABLE 1
Figure BDA0003336102730000131
Figure BDA0003336102730000141
Figure BDA0003336102730000151
As can be seen from the above table, in the pigment composition provided by the invention, the bactericidal mildewcide adopts a mixture of lithium carbonate and zinc oxide or a combination of BIT-20+ BBIT and DBNPA and/or phenoxyethanol, so that the pigment composition has excellent mildewproof and anticorrosive performances, and as can be seen from examples 1 to 5, the mildewproof effect grade of a dry film of the pigment composition is less than or equal to 1 grade; after four weeks, the content of bacteria in the tank is less than 10cfu/mL; the mold content is less than 10cfu/mL, the property is stable, and the color can not change after four weeks. Meanwhile, the mixture of lithium carbonate and zinc oxide, BIT-20 and BBIT have low sensitization, so that the pigment composition has low sensitization rate and is suitable for the field of drawing pigments.
As can be seen from a comparison of example 1 and example 6, when IPBC was added to the pigment composition, the pigment composition changed color after four weeks and was unstable in properties; as is clear from comparison between example 1 and examples 7 to 9, when the contents of BBIT, BIT-20 and DBNPA are too large or too small, the effect of in-can preservation or color is affected to some extent; as can be seen from comparison between example 1 and comparative example 1, when DBNPA is not contained in the organic sterilization and mildew-proof agent, the in-can corrosion prevention and dry film mildew prevention effects are extremely poor; as can be seen from comparison between example 1 and comparative example 2, when BIT-20 is not present in the organic sterilization and mold proofing agent, the in-can preservation effect is deteriorated; as can be seen from comparison between example 1 and comparative example 3, the organic sterilization and mildew-proof agent adopts the combination of DBNPA and BIT-20, although the mildew-proof and corrosion-proof effects meet the requirements, the dosage of BIT-20 exceeds the standard; as can be seen from the comparison between example 1 and comparative examples 4 to 10, the pigment composition has poor in-can preservation, dry film mold-proof effect or stability after BBIT or BIT-20 is replaced in the organic bactericidal and mildewproof agent.
In conclusion, the pigment composition provided by the invention selects a mixture of lithium carbonate and zinc oxide or a combination of BIT-20 and BBIT, and under the assistance of DBNPA and/or phenoxyethanol, the pigment composition has excellent mildew-proof and corrosion-proof properties, is not easy to sensitize, has a small dosage of the bactericidal mildew-proof agent, is low in cost, and meets the performance requirements of the painting pigment field on the pigment composition.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and should not be construed as limiting the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (25)

1. The pigment composition is characterized by comprising 20 to 60 parts by weight of a binder, 5 to 30 parts by weight of a colorant and 0.25 to 1.8 parts by weight of a bactericidal and mildewproof agent;
the sterilization and mildew-proof agent comprises A and B;
said A comprises 1, 2-benzisothiazolin-3-one and 2-butyl-1, 2-benzisothiazolin-3-one;
the B comprises 2, 2-dibromo-3-nitrilopropionamide or phenoxyethanol;
the mass percentage content of the 1, 2-benzisothiazolin-3-one in the pigment composition is 0.002 to 0.005 percent;
the mass percentage content of the 2-butyl-1, 2-benzisothiazolin-3-one in the pigment composition is 0.04 to 0.1 percent;
the mass percentage content of the 2, 2-dibromo-3-nitrilopropionamide in the pigment composition is 0.01 to 0.04 percent;
the mass percentage of the phenoxyethanol in the pigment composition is 0.2 to 0.4 percent;
or, the sterilization mildewcide comprises the combination of lithium carbonate, zinc oxide and 2, 2-dibromo-3-nitrilopropionamide;
the mass percentage content of the inorganic sterilization mildew inhibitor in the pigment composition is 0.05 to 0.06 percent.
2. The pigment composition according to claim 1, wherein the bactericidal and fungicidal agent further comprises any one or a combination of at least two of bronopol, iodopropynyl n-butyl carbamate, sodium pyrithione, zinc pyrithione, potassium sorbate, sodium benzoate, or formaldehyde release-retarding agents.
3. Pigment composition according to claim 1, wherein the binder comprises a natural binder and/or a synthetic binder.
4. A pigment composition according to claim 3, wherein the natural binder comprises any one of or a combination of at least two of arabinose, galactose, glucuronic acid, modified starch, starch gum, dextrin gum, maltose or a vegetable resin.
5. The pigment composition according to claim 3, wherein the synthetic binder comprises a polyacrylic emulsion.
6. The pigment composition according to claim 1, wherein the binder has a solids content of 20% to 50%.
7. The pigment composition according to claim 6, wherein the binder has a solids content of 35% to 42%.
8. The pigment composition according to claim 1, further comprising 1 to 40 parts by weight of an extender pigment.
9. The pigment composition according to claim 8, wherein the extender pigment comprises any one of or a combination of at least two of silicates, oxides of silicon, barium sulfate or carbonates.
10. A pigment composition according to claim 9, wherein the silicate comprises any one of, or a combination of at least two of, aluminium silicate, magnesium silicate, bentonite, china clay or attapulgite.
11. Pigment composition according to claim 9, characterized in that the silicon oxide comprises precipitated silica and/or fumed silica.
12. Pigment composition according to claim 9, characterized in that the carbonate comprises calcium carbonate and/or magnesium carbonate.
13. The pigment composition according to claim 1, further comprising 0.1 to 3 parts by weight of a wetting and dispersing agent.
14. The pigment composition according to claim 13, wherein the wetting and dispersing agent comprises any one of polyacrylates, alkyl polyoxyethylene ethers or acrylic copolymers or a combination of at least two of the polyacrylates.
15. The pigment composition according to claim 1, further comprising 0.05 to 1 part by weight of an antifoaming agent.
16. The pigment composition according to claim 15, wherein the defoamer comprises any one of or a combination of at least two of a mineral oil defoamer, a polyether modified silicone defoamer or an alkynol defoamer.
17. The pigment composition according to claim 1, wherein the fineness of the pigment composition is 25 to 40 μm.
18. The pigment composition according to claim 1, wherein the pigment composition has a fluidity of 2.6 to 3.4 cm.
19. A process for the preparation of a pigment composition according to any one of claims 1 to 18, characterized in that it comprises the following steps:
and mixing and dispersing the binder, the colorant and the sterilization and mildew-proof agent according to the formula amount to obtain the pigment composition.
20. The method of claim 19, wherein the mixed material further comprises any one or a combination of at least two of an extender pigment, an antifoaming agent, or a wetting dispersant.
21. The method of claim 19, wherein the dispersing is by milling.
22. The method of claim 21, wherein the grinding and dispersing device is a three-roll mill.
23. The method for preparing the polyurethane foam material according to claim 21, wherein the rotation speed of the grinding dispersion is 100 to 300 r/min.
24. The method for preparing a polyurethane foam material according to claim 21, wherein the grinding dispersion time is 20 to 40 min.
25. An aqueous painting pigment, characterized in that it comprises a pigment composition according to any one of claims 1 to 18.
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