CN113150693B - Glazing oil and preparation method and application thereof - Google Patents
Glazing oil and preparation method and application thereof Download PDFInfo
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- CN113150693B CN113150693B CN202110474036.3A CN202110474036A CN113150693B CN 113150693 B CN113150693 B CN 113150693B CN 202110474036 A CN202110474036 A CN 202110474036A CN 113150693 B CN113150693 B CN 113150693B
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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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention provides glazing oil and a preparation method and application thereof, wherein the glazing oil comprises the following raw materials in parts by weight: 25-40 parts of hydrocarbon resin; 15-35 parts of polyethylene vinyl alcohol copolymer resin; 0.2-2 parts of an antioxidant; 2-5 parts of nano inorganic silicon powder; 30-50 parts of a hydrocarbon solvent. The finishing oil has the characteristics of excellent weather resistance, oxidation resistance and oxygen penetration resistance, can be used for finishing the artistic oil painting, can realize the excellent protection effect on the artistic oil painting, and can be used for long-time display of outdoor artworks; and the transparent color film has excellent transparency and color representation, and does not influence the expressive force of original works.
Description
Technical Field
The invention belongs to the technical field of oil painting artware painting, relates to finishing varnish and a preparation method and application thereof, and particularly relates to art oil painting finishing varnish and a preparation method and application thereof.
Background
As an important artwork, the artistic oil painting plays an important role in the fields of art collection and decoration. The artistic oil painting is mainly characterized in that artists use artistic oil painting pigments to display contents and emotions to be expressed on canvas through different expression forms, and the canvas comprises various artistic themes such as landscapes, people, buildings, flowers and the like.
The artistic oil painting is made up by using slow-drying vegetable oil, such as linseed oil, poppy oil and walnut oil, etc. to blend different colours of pigments and making them on canvas (linen), paper board or wood board. The diluent used in drawing comprises volatile oleum Terebinthinae and dry oleum Lini. The paint attached to the picture has strong hardness, and can keep luster for a long time after the picture is dried. The painting object is fully expressed by virtue of the covering power and the transparency of the pigment, and the painting object is rich in color and strong in three-dimensional texture.
As the art pigment used for oil painting mostly uses vegetable oil containing double bonds as film forming substances, the vegetable oil containing double bonds can generate oxidative crosslinking in the air, thereby establishing better hardness and stacking effect. However, these vegetable oils contain relatively many double bonds, and therefore tend to generate more cross-links oxidized by oxygen in the air at a later stage, which leads to brittleness and pigment falling off; moreover, the color of the oxidized vegetable oil can be changed, and usually obvious yellowing can occur, which can greatly affect the overall color of the oil painting, and sometimes can change the color and artistic expression theme of the whole work, which is a problem caused by the general weather resistance. Therefore, the maintenance of the artistic oil paintings is required frequently, but the maintenance is carried out by professional personnel, and the maintenance cannot be carried out comprehensively for most works. If the weather resistance of the oil painting can be improved in a simpler mode, the color and the expressive force of the original work can be kept.
The maintenance of the works of art collected in the art museum and museum is carried out by very professional artists and maintainers, and the collection conditions of the art museum and museum are very favorable for the durability of the works of art. Such professional maintenance is difficult for the average people to use for decoration and general collection. When the oil painting is used outdoors and places where sunlight is seen, discoloration and fading are more likely to occur, and particularly when the degree of irradiation of the oil painting by sunlight at different places is different, the phenomenon is more likely to occur. Based on the problems, the mode of using the glazing oil can effectively relieve, and the glazing oil is coated on the surface of the oil painting to play a certain role in protecting the sunlight.
CN103965709A discloses a fluorocarbon finishing varnish and a preparation method thereof, which is composed of 28-30% of PVDF fluorocarbon resin, 30-32% of thermoplastic acrylic resin with the content of 40%, 0.5-1% of leveling auxiliary agent, and other solvents containing xylene, ethylene glycol monobutyl ether and butyl acetate. The fluorocarbon resin used in the invention can obviously improve the weather resistance, but has poor solubility, and needs to use toxic xylene as a solvent, thereby not only causing inconvenience in transportation and storage, but also causing harm to the body; and the hardness of the fluorocarbon resin is generally low, the adhesion is poor, and the fluorocarbon resin is easy to fall off on the base material of the oil painting.
CN104371513A discloses a gloss oil and metal print, a preparation method and application thereof, comprising 40-50% of polyester resin, 1-8% of aliphatic diamine as a curing agent and 1-8% of tetramethylbenzene as a solvent. The resin used in the invention is polyester resin, the weather resistance of the polyester resin is not greatly different from that of drying oil, so that the improvement of the weather resistance is not facilitated, and the curing agent used is aliphatic diamine, so that amines are easy to oxidize and discolor under the condition of illumination, and if the curing agent is used as finish gloss oil of oil paintings, the weather resistance is also reduced.
CN104910706A discloses an anti-aging water-based varnish and a preparation method thereof, wherein the varnish is prepared from the following raw materials in parts by weight: 60-80 parts of modified styrene-acrylic emulsion, 0.05-0.1 part of magnesium ascorbyl phosphate, 0.3-0.5 part of inositol hexaphosphate, 3-5 parts of polyethylene wax emulsion, 3-5 parts of white mineral oil, 1-2 parts of peanut protein, 0.1-0.2 part of sodium benzoate, 0.2-0.4 part of diacetyl tartaric acid monoglyceride and diglyceride, 0.01-0.02 part of propyl gallate and 10-15 parts of water. The invention realizes the water-based environment protection, and although the styrene-acrylic emulsion is used and has better weather resistance than dry vegetable oil, the styrene-acrylic emulsion contains styrene, so the styrene-acrylic emulsion has the tendency of oxidation yellowing for a long time in the air and cannot achieve excellent protection effect.
Although the gloss oil has a certain protection effect, as the artistic oil painting, the works expressed by slight differences such as light and shade of colors, different colors and the like, the effect of the works is influenced by slight color changes, and the painting is difficult to be used for outdoor display for a long time. The analysis of the influencing factors causing the defects has two more key factors, one is that the oxygen in the air oxidizes the film-forming substances of the resin and the gloss oil resin in the oil painting pigment to cause yellowing and degradation; the other is that oxygen in the air penetrates the resin, and the effect on the resin-coated pigment causes a change in the color of the pigment itself.
If the oil painting is protected by means of the gloss oil, the gloss oil is required to have very excellent weather resistance and oxidation resistance and relatively low oxygen transmittance, so that the effect of simultaneously protecting the pigment and preventing the resin from being oxidized is achieved; it is also desirable to have a high degree of transparency without affecting the color of the original work.
Therefore, there is a need in the art to develop a gloss oil that combines high transparency, excellent weatherability, oxidation resistance, and resistance to oxygen penetration.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide finishing oil and a preparation method and application thereof, and particularly provides artistic oil painting finishing oil and a preparation method and application thereof. The finishing oil has the characteristics of excellent weather resistance, oxidation resistance and oxygen penetration resistance, can be used for finishing the artistic oil painting, can realize the excellent protection effect on the artistic oil painting, and can be used for long-time display of outdoor artworks; and the transparent color film has excellent transparency and color representation, and the expressive force of the original works is not influenced.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides glazing oil, which comprises the following raw materials in parts by weight:
the structure of the hydrocarbon resin does not contain polar groups, so that the weather resistance and the oxidation resistance are excellent, the hydrocarbon resin is used as a main film forming substance, the weakening of the oxidation resistance caused by the influence of other groups on a polymer chain is avoided, and the oxidation resistance and the weather resistance of the finishing varnish are effectively improved; although the hydrocarbon resin is not easy to discolor and oxidize, the hydrocarbon resin is poor in oxygen penetration resistance and cannot prevent oxygen from penetrating into an oil painting raw material layer to damage oil painting pigments, so that on the basis, the polyethylene vinyl alcohol copolymer resin with good oxygen penetration resistance is added, an excellent oxygen blocking effect can be provided, the penetration effect of oxygen on gloss oil is effectively reduced, and a more excellent protection effect on the resin and the pigments of oil painting works is achieved; the nano inorganic silicon powder can generate a synergistic effect with the polyvinyl alcohol copolymer resin, and further increase the oxygen-resistant penetrability of the finishing varnish. Therefore, the prepared finishing oil has excellent weather resistance, oxygen penetrability resistance and long-acting oxidation and degradation resistance.
In the invention, the amount of the hydrocarbon resin used in the raw material for preparing the finishing oil can be 25 parts, 28 parts, 30 parts, 33 parts, 35 parts, 38 parts or 40 parts.
In the present invention, the amount of the polyvinyl alcohol copolymer resin used in the raw material for preparing the overprint varnish may be 15 parts, 18 parts, 20 parts, 23 parts, 25 parts, 28 parts, 30 parts, 33 parts, 35 parts, or the like.
If the amount of the polyvinyl alcohol copolymer resin is less than 15 parts, the oxygen barrier effect is drastically reduced, and if the amount of the polyvinyl alcohol copolymer resin is more than 35 parts, the solubility is reduced, thereby reducing the transparency of the overprint varnish.
In the invention, the antioxidant can be used in an amount of 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts or 2 parts in the raw materials for preparing the finishing oil.
In the invention, in the raw material for preparing the overprint varnish, the nano inorganic silicon powder can be used in an amount of 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts.
When the amount of the nano inorganic silicon powder is 2-5 parts, the oxygen blocking effect can be effectively improved, and when the amount of the nano inorganic silicon powder exceeds 5 parts, the transparency of the glazing oil is reduced.
In the invention, the amount of the hydrocarbon solvent in the raw materials for preparing the finishing oil can be 30 parts, 33 parts, 35 parts, 38 parts, 40 parts, 43 parts, 45 parts, 48 parts or 50 parts.
The hydrocarbon resin is resin consisting of two elements of hydrocarbon and does not contain other electron-withdrawing groups which influence the weather resistance.
Preferably, the hydrocarbon resin is a branched hydrocarbon resin.
Preferably, the weight average molecular weight of the hydrocarbon resin is 2000-15000, such as 2000, 4000, 6000, 8000, 10000, 12000, 14000 or 15000, etc., preferably 2000-8000.
If the weight average molecular weight of the hydrocarbon resin is higher than 15000, the solubility thereof is lowered, thereby resulting in a decrease in transparency of the overprint varnish; if the weight average molecular weight of the hydrocarbon resin is less than 2000, the adhesion of the overprint varnish may be reduced.
The polyethylene vinyl alcohol copolymer resin of the present invention is a linear polymer containing ethylene and vinyl alcohol in the main polymer chain, wherein the mass content of vinyl group is 30-60%, such as 30%, 35%, 40%, 45%, 50%, 55% or 60%.
Preferably, the antioxidant comprises a phosphorus-containing antioxidant and/or a hindered phenol antioxidant, preferably a combination of a phosphorus-containing antioxidant and a hindered phenol antioxidant.
Preferably, the weight part ratio of the phosphorus-containing antioxidant to the hindered phenol antioxidant is (0.8-1.2):1, such as 0.8:1, 0.9:1, 1:1, 1.1:1 or 1.2:1, and the like, preferably 1: 1.
In the preferred technical scheme of the invention, the phosphorus-containing antioxidant and the hindered phenol antioxidant are compounded for use, so that a longer-lasting antioxidant degradation protection effect is provided for the finishing oil. When the phosphorus-containing antioxidant and the hindered phenol antioxidant are used in a matching way according to the weight ratio of (0.8-1.2) to 1, the antioxidant degradation protection effect is better, wherein the effect is best when the ratio is 1: 1.
Preferably, the phosphorus-containing antioxidant is a phosphite antioxidant.
Preferably, the phosphite antioxidant comprises any one of Irgafos TNPP, Irgafos 168, Irgafos 38, Ultranox 626 or Ultranox 641 or a combination of at least two thereof.
Preferably, the phosphite antioxidant comprises Irgafos 168 and/or Ultranox 626.
Preferably, the hindered phenolic antioxidant comprises any one of or a combination of at least two of Irganox E201, BHT, Irganox 1076, Irganox 1010, Irganox 1098, Irganox 2246, Irganox 1035, Irganox 1222, or Irganox 245.
Preferably, the hindered phenolic antioxidant comprises any one of or a combination of at least two of Irganox 1035, BHT, Irganox 1076, or Irganox 245.
Preferably, the nano inorganic silicon powder is inorganic nano silica powder with an untreated surface.
Preferably, the average particle size of the nano inorganic silicon powder is 10-80nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm or 80 nm.
Preferably, the hydrocarbon solvent includes an aliphatic hydrocarbon solvent, preferably any one of odorless kerosene D60, odorless kerosene D80, odorless kerosene D90, isohexadecane hydrocarbon or isooctadecane hydrocarbon.
Preferably, the hydrocarbon solvent has a boiling point higher than 350 ℃.
The hydrocarbon solvent used in the preferred technical scheme of the invention is high-boiling-point aliphatic hydrocarbon solvent which has lower odor and higher flash point, has lower odor in the processes of production, transportation, storage and use and is more environment-friendly.
In the preferred technical scheme of the invention, the hydrocarbon resin and the polyethylene vinyl alcohol copolymer resin have good solubility in high boiling point aliphatic hydrocarbon, and the environment-friendly high boiling point aliphatic hydrocarbon is used as a solvent, so that the invention has the effects of low odor and environment protection.
Preferably, the preparation raw materials of the finishing varnish comprise the following components in parts by weight:
the second purpose of the invention is to provide a preparation method of the glazing oil, which comprises the following steps:
(1) Mixing hydrocarbon resin, polyvinyl alcohol copolymer resin and hydrocarbon solvent, stirring and heating until the mixture is completely dissolved and transparent;
(2) adding nano inorganic silicon powder into the solution obtained in the step (1), and stirring until the solution is completely transparent;
(3) and (3) cooling, adding an antioxidant into the solution obtained in the step (2), and stirring to obtain the finishing oil.
Preferably, the rotation speed of the stirring in the step (1) is 280-320rpm, such as 280rpm, 290rpm, 300rpm, 310rpm or 320rpm, and the like, and the stirring time is 20-40min, such as 20min, 25min, 30min, 35min or 40min, and the like.
Preferably, the heating in step (1) is to 60-80 ℃, such as 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, etc.
Preferably, the rotation speed of the stirring in the step (2) is 1000-2000rpm, such as 1000rpm, 1200rpm, 1400rpm, 1600rpm, 1800rpm or 2000rpm, and the like, and the stirring time is 25-35min, such as 25min, 28min, 30min, 32min, 34min or 35min, and the like.
Preferably, the temperature reduction in step (3) is to be 35-45 ℃, such as 35 ℃, 37 ℃, 40 ℃, 42 ℃, 44 ℃ or 45 ℃ and the like.
Preferably, the rotation speed of the stirring in step (3) is 200-500rpm, such as 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm or 500rpm, etc., and the stirring time is 25-35min, such as 25min, 27min, 30min, 31min, 33min or 35min, etc.
The third purpose of the invention is to provide the application of the finishing oil in painting, preferably in painting artistic oil paintings.
Compared with the prior art, the invention at least has the following beneficial effects:
the addition of the hydrocarbon resin in the invention ensures that the prepared finishing varnish has excellent weather resistance (yellowing delta b: 0.98-1.85) and oxidation resistance; the synergistic use of the polyvinyl alcohol copolymer resin and the nano inorganic silicon powder ensures that the prepared finishing gloss oil has excellent oxygen penetration resistance (oxygen permeability: standing at normal temperature for 48 h: 10-28 cc/(m)224 h.mpa); the climate box is placed for 1500 h: 13-45 cc/(m)224h.mpa)) can effectively prevent the oxidative degradation and color change of the artistic oil painting pigment caused by oxygen in the air. Therefore, the finishing varnish has the characteristics of excellent weather resistance, oxidation resistance and oxygen penetration resistance, can be used for finishing the artistic oil painting, can realize the excellent protection effect on the artistic oil painting, and can be used for long-time display of outdoor artworks; in addition, the transparent color film has excellent transparency and color representation, and does not influence the expressive force of original works.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. 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 limitations of the present invention.
Example 1
The preparation raw materials of the finishing oil comprise the following components in parts by weight:
wherein the hydrocarbon resin is branched hydrocarbon resin, and the weight average molecular weight is 2500; the mass content of vinyl in the polyvinyl alcohol copolymer resin is 33%; the average grain diameter of the nano inorganic silicon powder is 20 nm; the hydrocarbon solvent is odorless kerosene D90.
The preparation method comprises the following steps:
(1) sequentially adding a hydrocarbon solvent, hydrocarbon resin and polyvinyl alcohol copolymer resin into a high-speed stirring dispersion kettle, heating to 65 ℃, and stirring at the rotating speed of 280rpm for 20min until the hydrocarbon solvent, the hydrocarbon resin and the polyvinyl alcohol copolymer resin are completely dissolved;
(2) adding nano inorganic silicon powder into the solution obtained in the step (1), and stirring at the rotating speed of 1200rpm for 25min until the solution is transparent;
(3) and (3) cooling to 35 ℃, adding a phosphorus antioxidant Irgafos 168 and a hindered phenol antioxidant Irganox 245 into the solution obtained in the step (2), stirring at the rotating speed of 200rpm for 25min until the phosphorus antioxidant Irgafos and the hindered phenol antioxidant Irganox 245 are completely dissolved, and filtering by using a 200-mesh filter screen to obtain the finishing varnish.
Example 2
The preparation raw materials of the finishing oil comprise the following components in parts by weight:
wherein the hydrocarbon resin is branched hydrocarbon resin, and the weight average molecular weight is 2000; the mass content of vinyl in the polyvinyl alcohol copolymer resin is 33%; the average grain diameter of the nano inorganic silicon powder is 20 nm; the hydrocarbon solvent is odorless kerosene D80.
The preparation method comprises the following steps:
(1) sequentially adding a hydrocarbon solvent, hydrocarbon resin and polyvinyl alcohol copolymer resin into a high-speed stirring dispersion kettle, heating to 65 ℃, and stirring at 290rpm for 20min until the hydrocarbon solvent, the hydrocarbon resin and the polyvinyl alcohol copolymer resin are completely dissolved;
(2) adding nano inorganic silicon powder into the solution obtained in the step (1), and stirring at the rotating speed of 1200rpm for 26min until the solution is transparent;
(3) and (3) cooling to 35 ℃, adding a phosphorus antioxidant Irgafos 168 and a hindered phenol antioxidant Irganox 245 into the solution obtained in the step (2), stirring at the rotating speed of 300rpm for 25min until the phosphorus antioxidant Irgafos and the hindered phenol antioxidant Irganox 245 are completely dissolved, and filtering by using a 200-mesh filter screen to obtain the finishing varnish.
Example 3
The preparation raw materials of the finishing oil comprise the following components in parts by weight:
wherein the hydrocarbon resin is branched hydrocarbon resin, and the weight average molecular weight is 5000; the mass content of vinyl in the polyvinyl alcohol copolymer resin is 42%; the average grain diameter of the nano inorganic silicon powder is 20 nm; the hydrocarbon solvent is odorless kerosene D90.
The preparation method comprises the following steps:
(1) adding a hydrocarbon solvent, hydrocarbon resin and polyethylene vinyl alcohol copolymer resin into a high-speed stirring dispersion kettle in sequence, heating to 75 ℃, and stirring at the rotating speed of 300rpm for 30min until the components are completely dissolved;
(2) Adding nano inorganic silicon powder into the solution obtained in the step (1), and stirring at the rotating speed of 1500rpm for 27min until the solution is transparent;
(3) and (3) cooling to 40 ℃, adding a phosphorus antioxidant Ultranox 626 and a hindered phenol antioxidant Irganox 1076 into the solution obtained in the step (2), stirring at the rotating speed of 400rpm for 28min until the phosphorus antioxidant Ultranox and the hindered phenol antioxidant Irganox 1076 are completely dissolved, and filtering by using a 200-mesh filter screen to obtain the finishing oil.
Example 4
In this embodiment, a finishing oil is provided, and a raw material for preparing the finishing oil comprises the following components in parts by weight:
wherein the hydrocarbon resin is branched hydrocarbon resin, and has a weight average molecular weight of 10000; the mass content of vinyl in the polyvinyl alcohol copolymer resin is 50 percent; the average grain diameter of the nano inorganic silicon powder is 20 nm; the hydrocarbon solvent is odorless kerosene D90.
The preparation method comprises the following steps:
(1) sequentially adding a hydrocarbon solvent, hydrocarbon resin and polyvinyl alcohol copolymer resin into a high-speed stirring dispersion kettle, heating to 75 ℃, and stirring at the rotating speed of 310rpm for 30min until the hydrocarbon solvent, the hydrocarbon resin and the polyvinyl alcohol copolymer resin are completely dissolved;
(2) adding nano inorganic silicon powder into the solution obtained in the step (1), and stirring at the rotating speed of 1500rpm for 28min until the solution is transparent;
(3) and (3) cooling to 40 ℃, then adding a phosphorus-containing antioxidant Ultranox 626 and a hindered phenol antioxidant Irganox 1076 into the solution obtained in the step (2), stirring at the rotating speed of 500rpm for 28min until the phosphorus-containing antioxidant Ultranox and the hindered phenol antioxidant Irganox 1076 are completely dissolved, and filtering by using a 200-mesh filter screen to obtain the finishing oil.
Example 5
In this embodiment, a finishing oil is provided, and a raw material for preparing the finishing oil comprises the following components in parts by weight:
wherein the hydrocarbon resin is branched hydrocarbon resin, and the weight average molecular weight is 8000; the mass content of vinyl in the polyethylene vinyl alcohol copolymer resin is 30 percent; the average grain diameter of the nano inorganic silicon powder is 10 nm; the hydrocarbon solvent is isohexadecane.
The preparation method comprises the following steps:
(1) sequentially adding a hydrocarbon solvent, hydrocarbon resin and polyvinyl alcohol copolymer resin into a high-speed stirring dispersion kettle, heating to 60 ℃, and stirring at the rotating speed of 320rpm for 40min until the hydrocarbon solvent, the hydrocarbon resin and the polyvinyl alcohol copolymer resin are completely dissolved;
(2) adding nano inorganic silicon powder into the solution obtained in the step (1), and stirring at the rotating speed of 1000rpm for 30min until the solution is transparent;
(3) and (3) cooling to 45 ℃, adding a phosphorus antioxidant Irgafos TNPP and a hindered phenol antioxidant Irganox 1035 into the solution obtained in the step (2), stirring at the rotating speed of 250rpm for 30min until the phosphorus antioxidant Irgafos TNPP and the hindered phenol antioxidant Irganox 1035 are completely dissolved, and filtering by using a 200-mesh filter screen to obtain the finishing oil.
Example 6
The preparation raw materials of the finishing oil comprise the following components in parts by weight:
Wherein the hydrocarbon resin is branched hydrocarbon resin, and the weight average molecular weight is 15000; the mass content of vinyl in the polyethylene vinyl alcohol copolymer resin is 60 percent; the average grain diameter of the nano inorganic silicon powder is 80 nm; the hydrocarbon solvent is an isostearyl hydrocarbon.
The preparation method comprises the following steps:
(1) sequentially adding a hydrocarbon solvent, hydrocarbon resin and polyvinyl alcohol copolymer resin into a high-speed stirring dispersion kettle, heating to 80 ℃, and stirring at the rotation speed of 285rpm for 40min until the hydrocarbon solvent, the hydrocarbon resin and the polyvinyl alcohol copolymer resin are completely dissolved;
(2) adding nano inorganic silicon powder into the solution obtained in the step (1), and stirring at 2000rpm for 32min until the solution is transparent;
(3) and (3) cooling to 45 ℃, adding a phosphorus antioxidant Irgafos 38 and a hindered phenol antioxidant Irganox 1035 into the solution obtained in the step (2), stirring at the rotating speed of 300rpm for 30min until the phosphorus antioxidant Irgafos and the hindered phenol antioxidant Irganox 1035 are completely dissolved, and filtering by using a 200-mesh filter screen to obtain the finishing oil.
Example 7
The preparation raw materials of the finishing oil comprise the following components in parts by weight:
wherein the hydrocarbon resin is branched hydrocarbon resin, and the weight average molecular weight is 12000; the mass content of vinyl in the polyvinyl alcohol copolymer resin is 40 percent; the average grain diameter of the nano inorganic silicon powder is 50 nm; the hydrocarbon solvent is isohexadecane.
The preparation method comprises the following steps:
(1) sequentially adding a hydrocarbon solvent, hydrocarbon resin and polyvinyl alcohol copolymer resin into a high-speed stirring dispersion kettle, heating to 70 ℃, and stirring at the rotating speed of 295rpm for 25min until the hydrocarbon solvent, the hydrocarbon resin and the polyvinyl alcohol copolymer resin are completely dissolved;
(2) adding nano inorganic silicon powder into the solution obtained in the step (1), and stirring at the rotation speed of 1800rpm for 33min until the solution is transparent;
(3) and (3) cooling to 38 ℃, adding a phosphorus antioxidant Irgafos TNPP and a hindered phenol antioxidant Irganox 1010 into the solution obtained in the step (2), stirring at the rotating speed of 350rpm for 35min until the phosphorus antioxidant Irgafos and the hindered phenol antioxidant Irganox 1010 are completely dissolved, and filtering by using a 200-mesh filter screen to obtain the finishing oil.
Example 8
The preparation raw materials of the finishing oil comprise the following components in parts by weight:
wherein the hydrocarbon resin is branched hydrocarbon resin, and the weight average molecular weight is 6000; the mass content of vinyl in the polyvinyl alcohol copolymer resin is 45%; the average grain diameter of the nano inorganic silicon powder is 60 nm; the hydrocarbon solvent is an isostearyl hydrocarbon.
The preparation method comprises the following steps:
(1) sequentially adding a hydrocarbon solvent, hydrocarbon resin and polyvinyl alcohol copolymer resin into a high-speed stirring dispersion kettle, heating to 70 ℃, and stirring at the rotating speed of 305rpm for 35min until the hydrocarbon solvent, the hydrocarbon resin and the polyvinyl alcohol copolymer resin are completely dissolved;
(2) Adding nano inorganic silicon powder into the solution obtained in the step (1), and stirring at the rotating speed of 1500rpm for 35min until the solution is transparent;
(3) and (3) cooling to 42 ℃, adding a phosphorus antioxidant Ultranox 641 and a hindered phenol antioxidant Irganox 1098 into the solution obtained in the step (2), stirring at the rotating speed of 450rpm for 33min until the phosphorus antioxidant Ultranox 641 and the hindered phenol antioxidant are completely dissolved, and filtering by using a 200-mesh filter screen to obtain the finishing oil.
Comparative example 1
This comparative example is different from example 1 only in that the polyvinyl alcohol copolymer resin was not included in the preparation raw materials, and the weight part of the hydrocarbon resin was 60 parts.
Comparative example 2
The comparative example is different from example 1 only in that the nano inorganic silicon powder is not included in the preparation raw material, and the weight part of the hydrocarbon solvent is 39.5 parts.
Comparative example 3
The comparative example is different from example 1 only in that the phosphorus antioxidant Irgafos168 and the hindered phenol antioxidant Irganox 245 are not included in the preparation raw materials, and the weight part of the hydrocarbon solvent is 38 parts.
Comparative example 4
The preparation method of patent CN103965709A is adopted to prepare the finishing oil, and the preparation raw materials comprise the following components in parts by weight:
wherein the weight average molecular weight of the PVDF fluorocarbon resin is 28000.
Comparative example 5
This comparative example differs from example 1 only in that the hydrocarbon resin and the polyethylene vinyl alcohol copolymer resin were replaced with a thermoplastic acrylic resin, the thermoplastic acrylic resin being 60 parts by weight.
The overprint varnish prepared in examples 1 to 8 and comparative examples 1 to 5 were subjected to transparency test, weather resistance test (color difference, yellowing, flaking), oxygen penetration resistance test and solar irradiation and real climate comparison test as follows:
(1) and (3) testing the transparency: brushing the finishing oil on the surface of the same oil painting, drying for 24 hours, and observing whether the transparency of the oil painting is affected, wherein if the phenomena of fogging and color change do not occur, the transparency of the finishing oil is considered to be good;
(2) and (3) weather resistance testing: brushing the finishing varnish on linen cloth uniformly coated with oil painting pigments of red, yellow, blue, green, white and the like for finishing, then putting the linen cloth into an aging box, controlling the humidity at 50 percent and the temperature at 30 ℃, irradiating the linen cloth for 3000 hours by using a 313nm wave band xenon lamp, observing the adhesive force of the finishing varnish on the surface of the linen cloth, and testing the color change of the pigments by using a color difference meter (Konika CR-20);
(3) oxygen penetration resistance test: the gloss oil was coated on the surface of the PET film using a mini coater, the dry film coating thickness was controlled to 2 μm, and after standing at room temperature for 48 hours, an oxygen permeation resistance test was performed on an oxygen permeameter (Mocon OX-TRAN/50) by an isobaric method. Meanwhile, placing the film in a climatic chamber for 1500 hours, and carrying out oxygen permeability test again;
(4) Sunlight irradiation resistance test: and (3) brushing the finishing oil on the surface of the same oil painting, drying for 24 hours, placing the oil painting coated with the finishing oil in an uncovered outdoor environment, observing the color change of the oil painting and the cracking and falling states of the finishing oil, recording the time, and observing and testing for 4 months.
The results of the performance tests are shown in table 1.
TABLE 1
As can be seen from Table 1, the overprint varnishes prepared in examples 1 to 8 were glossyGood brightness, no cracking or chalking after weather resistance test, no yellowing by naked eye observation, small yellowing delta b value (0.98-1.85) tested by a color difference meter, and excellent oxygen penetration resistance (oxygen permeability: standing at normal temperature for 48 h: 10-28 cc/(m)224 h.mpa); the climate box is placed for 1500 h: 13-45 cc/(m)224h.mpa)), the paint has better sunlight irradiation resistance, and the oil painting coated with the overprint varnish is placed in the open air without covering, and the color change still does not occur after 4 months.
The finishing gloss oil prepared in the comparative examples 1 to 5 has the advantages that the protective effect on the colors of the artistic oil paintings is obviously weakened under the condition of higher oxygen permeability, and the protective requirements under the outdoor illumination condition cannot be met.
The applicant states that the invention is illustrated by the above examples to the gloss oil of the invention and the preparation method and application thereof, but the invention is not limited to the above examples, i.e. it does not mean that the invention must be implemented by means of the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (16)
1. The art oil painting finishing varnish with high transparency, weather resistance, oxidation resistance and oxygen penetration resistance is characterized in that the finishing varnish is prepared from the following raw materials in parts by weight:
25-40 parts of hydrocarbon resin;
15-35 parts of polyethylene vinyl alcohol copolymer resin;
0.2-2 parts of antioxidant;
2-5 parts of nano inorganic silicon powder;
30-50 parts of a hydrocarbon solvent;
the hydrocarbon resin is resin consisting of two elements of hydrocarbon and does not contain other electron-withdrawing groups which influence weather resistance;
the hydrocarbon resin is branched hydrocarbon resin;
the weight average molecular weight of the hydrocarbon resin is 2000-15000;
the mass content of vinyl in the polyvinyl alcohol copolymer resin is 30-60%;
the antioxidant comprises a combination of a phosphorus-containing antioxidant and a hindered phenol antioxidant, and the weight part ratio of the phosphorus-containing antioxidant to the hindered phenol antioxidant is 1: 1;
the phosphorus-containing antioxidant is a phosphite antioxidant, and the phosphite antioxidant comprises any one or the combination of at least two of Irgafos TNPP, Irgafos 168, Irgafos 38, Ultranox 626 and Ultranox 641;
The hindered phenol antioxidant comprises any one or a combination of at least two of Irganox E201, BHT, Irganox 1076, Irganox 1010, Irganox 1098, Irganox 2246, Irganox 1035, Irganox 1222 or Irganox 245;
the nano inorganic silicon powder is inorganic nano silicon dioxide powder with untreated surface, and the average particle size of the nano inorganic silicon powder is 10-80 nm.
2. The overprint varnish of claim 1, wherein the weight average molecular weight of the hydrocarbon resin is 2000-8000.
3. The overprint varnish of claim 1, wherein the phosphite antioxidant comprises Irgafos 168 and/or Ultranox 626.
4. The overprint varnish of claim 1, wherein the hindered phenolic antioxidant comprises any one or a combination of at least two of Irganox 1035, BHT, Irganox 1076, or Irganox 245.
5. The overprint varnish of claim 1, wherein the hydrocarbon solvent comprises an aliphatic hydrocarbon solvent.
6. The overprint varnish of claim 5, wherein the hydrocarbon solvent comprises any one of odorless kerosene D60, odorless kerosene D80, odorless kerosene D90, isohexadecane or isooctadecane.
7. The overprint varnish of claim 1, wherein the hydrocarbon solvent has a boiling point above 350 ℃.
8. The finishing oil as claimed in claim 1, wherein the raw materials for preparing the finishing oil comprise the following components in parts by weight:
25-35 parts of hydrocarbon resin;
20-35 parts of polyethylene vinyl alcohol copolymer resin;
0.4-1 part of antioxidant;
3-5 parts of nano inorganic silicon powder;
30-50 parts of a hydrocarbon solvent.
9. A method of preparing an overprint varnish according to any of claims 1 to 8, characterized in that the method comprises the steps of:
(1) mixing hydrocarbon resin, polyvinyl alcohol copolymer resin and hydrocarbon solvent, stirring and heating;
(2) adding nano inorganic silicon powder into the solution obtained in the step (1), and stirring;
(3) and (3) cooling, adding an antioxidant into the solution obtained in the step (2), and stirring to obtain the finishing oil.
10. The method as claimed in claim 9, wherein the rotation speed of the stirring in step (1) is 280-320 rpm, and the stirring time is 20-40 min.
11. The method according to claim 9, wherein the heating in the step (1) is heating to 60 to 80 ℃.
12. The preparation method according to claim 9, wherein the stirring speed in step (2) is 1000-2000 rpm, and the stirring time is 25-35 min.
13. The preparation method of claim 9, wherein the temperature reduction in the step (3) is to be reduced to 35-45 ℃.
14. The method as claimed in claim 9, wherein the stirring speed in step (3) is 200-500 rpm, and the stirring time is 25-35 min.
15. Use of a overprint varnish according to any one of claims 1 to 8 in painting.
16. Use according to claim 15, wherein the use is the use of a overprint varnish for drawing artistic paintings.
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| CN106750841A (en) * | 2016-04-16 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | The good polyethylene composition of puncture resistance |
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| EP1305374A1 (en) * | 2000-07-31 | 2003-05-02 | PPG Industries Ohio, Inc. | Dual cure coating compositions having improved scratch resistance, coated substrates and methods related thereto |
| CN102757544B (en) * | 2012-07-16 | 2014-06-11 | 兰州石化职业技术学院 | High-hydroxy phenolic resin prepared by using phenols residues as raw material, and application of high-hydroxy phenolic resin to production of high-temperature-resistant paint |
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| CN106497303A (en) * | 2016-11-02 | 2017-03-15 | 美国三和（香港）化工科技集团有限公司 | Spray paint and preparation method thereof |
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