CN113897127B - Polyurethane bright white finish and preparation method and application thereof - Google Patents
Polyurethane bright white finish and preparation method and application thereof Download PDFInfo
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- CN113897127B CN113897127B CN202111332036.6A CN202111332036A CN113897127B CN 113897127 B CN113897127 B CN 113897127B CN 202111332036 A CN202111332036 A CN 202111332036A CN 113897127 B CN113897127 B CN 113897127B
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
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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
- C09D5/08—Anti-corrosive paints
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Abstract
The invention provides a polyurethane bright white finish and a preparation method and application thereof. The polyurethane bright white finish comprises a component A, a component B and a component C; the component A comprises the following components: synthesizing fatty acid resin, propylene glycol monomethyl ether acetate, titanium dioxide and butyl acetate; the component B comprises the following components: butyl acetate, a dehydrating agent, hexamethylene diisocyanate and toluene diisocyanate trimer; the component C comprises the following components: xylene, butyl acetate, sec-butyl acetate, cyclohexanone and propylene glycol monomethyl ether acetate. The polyurethane bright white finish provided by the invention has good mechanical properties and high fullness, and prickly heat and dark bubbles are not generated in one-time thick coating construction under a high-temperature condition, so that a good coating effect can be achieved.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a polyurethane bright white finish as well as a preparation method and application thereof.
Background
The paint is a continuous solid film which is coated on the surface of an object to be protected or decorated and can form firm adhesion with the object to be coated, also called paint film or coating, and is a viscous liquid which is usually prepared by taking resin or oil or emulsion as a main material, selectively adding pigment, filler and corresponding auxiliary agents and using organic solvent or water. The coatings can be classified into different categories according to different classification methods, wherein the coatings can be classified into: solvent-based coatings, water-based coatings, powder-based coatings, high-solids coatings, metallic coatings, pearlescent coatings, and solventless coatings; the coating can be classified into a matt coating, a flat coating, a matte coating and a high gloss coating (also called a bright coating) according to the brightness of the appearance of the coating film. Along with the improvement of the life quality of people, the requirements of most people on home decoration are higher and higher, the decoration of a toilet and a kitchen is an important part of the home decoration, and in the aspect of coating of a bathroom cabinet, polyurethane white finish is mostly used, so that the research of people on the polyurethane white finish is also more and more.
CN104559597A discloses a super-water-resistant stain-resistant waterborne wood white finish and a preparation method thereof. The white finish paint is prepared from the following components in parts by weight: 54-69 parts of water-based emulsion, 0.1-0.2 part of water-based multifunctional auxiliary agent, 0.2-0.6 part of water-based dispersing agent, 0.2-0.4 part of water-based wetting agent, 16-22 parts of titanium dioxide, 0-6 parts of film-forming auxiliary agent, 0.5-1.5 parts of anti-freezing agent, 0.1-0.3 part of water-based defoaming agent, 0.1-0.2 part of antiseptic bactericide, 0.4-1.2 part of water-based flatting agent, 1-3 parts of hydrophobic agent, 1-3 parts of wax emulsion, 0.6-2 parts of water-based thickening agent and 5-10 parts of water; the water-based dispersant is hydrophobically modified polycarboxylate dispersant. The technical scheme adopts a water repellent agent for an aqueous system, so that the water resistance and the stain resistance of a paint film are greatly improved.
CN102993938A discloses an anti-sagging polyurethane white finish and a main paint thereof. The main paint of the polyurethane white finish comprises the following components in parts by weight: 35-50 parts of short oil alkyd resin, 40-55 parts of 60 mass percent titanium dioxide slurry, 5-8 parts of talcum powder, 0.1-0.5 part of polyether modified silicone oil leveling agent, 0.5-5 parts of fumed silica and 1-2 parts of solvent. According to the technical scheme, through the design of the components of the white finish, the prepared white finish has proper surface tension and is not easy to sag or expose the bottom, and even a paint film can be changed from uneven to flat surface under the action of the surface tension.
CN110229607A discloses an odorless thick-film facade construction white finish and a preparation method thereof. The white finish paint is composed of a polyurethane bright white paint main agent, a curing agent and a diluent, and the white finish paint is prepared from the following components in parts by weight: the polyurethane bright white paint main agent: curing agent: a diluent of 1: 0.8-1: 0.3-0.5; the polyurethane bright white finish main agent comprises the following raw material components in parts by weight: 40-45 parts of isononanoic acid modified alkyd resin, 2-5 parts of propylene glycol methyl ether acetate, 45-50 parts of highlight white slurry, 5-10 parts of vertical anti-sagging slurry, 0.5-1 part of dispersing agent, 0.5-0.5 part of defoaming agent and 0.2-0.5 part of flatting agent. The white finish provided by the technical scheme has no residual smell after film forming, good anti-sagging property on the vertical surface and higher solid content.
However, the existing bright white woodware coating in the market has various defects, such as insufficient fullness, poor hardness, easy miliaria and dark bubbles in the drying process and the like, and the overall coating effect is greatly influenced. Therefore, how to research a woodware coating with high fullness and without miliaria and dark bubbles to solve the problems of the existing bright woodware finish paint is one of the problems to be solved urgently in the industry; meanwhile, with the increasing awareness of the society on environmental protection, how to reduce the emission of VOC is the biggest challenge at present, so that the trend of increasing the solid content of the coating and reducing the emission of VOC is also the current development trend.
Therefore, how to provide a polyurethane white finish with high fullness, no miliaria and dark bubbles in one-time thick coating construction under a high temperature condition and high solid content becomes a technical problem to be solved urgently at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polyurethane bright white finish and a preparation method and application thereof. According to the invention, through the design of the components of the polyurethane gloss white finish and the further use of the synthetic fatty acid resin, the prepared polyurethane gloss white finish has better mechanical property and higher fullness, and miliaria and hidden bubbles are not generated in one-time thick coating construction under a high-temperature condition, so that a better coating effect can be achieved, and the polyurethane gloss white finish is suitable for being used as a woodware coating.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a polyurethane gloss white finish, which comprises a component A, a component B and a component C;
the component A comprises the following components in parts by weight: 65-70 parts of synthetic fatty acid resin, 1-3 parts of propylene glycol monomethyl ether acetate, 25-30 parts of titanium dioxide and 1.5-2.5 parts of butyl acetate;
the component B comprises the following components in parts by weight: 45-60 parts of butyl acetate, 0.3-0.7 part of a dehydrating agent, 25-35 parts of hexamethylene diisocyanate and 15-20 parts of toluene diisocyanate trimer;
The component C comprises the following components in parts by weight: 25-35 parts of dimethylbenzene, 20-30 parts of butyl acetate, 8-12 parts of sec-butyl acetate, 5-8 parts of cyclohexanone and 25-35 parts of propylene glycol monomethyl ether acetate.
According to the invention, through the design of the components of the polyurethane gloss white finish, and further through the use of synthetic fatty acid resin, the prepared polyurethane gloss white finish has better mechanical properties and higher fullness, and miliaria and dark bubbles are not generated in one-step thick coating construction under a high-temperature condition, so that a better coating effect can be achieved, and the polyurethane gloss white finish is suitable for being used as a woodware coating.
Meanwhile, the component B has better storage stability by using the dehydrating agent and further controlling the weight part of the dehydrating agent within a specific range. If the weight part of the dehydrating agent is too small, the storage stability of the prepared polyurethane bright white finish paint is poor; if the weight part of the dehydrating agent is too much, the production cost of the polyurethane glossy surface paint is increased, and the waste of raw materials is caused.
In the present invention, the synthetic fatty acid resin may be 65 parts, 65.5 parts, 66 parts, 66.5 parts, 67 parts, 67.5 parts, 68 parts, 68.5 parts, 69 parts, 69.5 parts, 70 parts, or the like in parts by weight.
The weight portion of the propylene glycol monomethyl ether acetate in the component A can be 1 portion, 1.2 portions, 1.4 portions, 1.6 portions, 1.8 portions, 2 portions, 2.2 portions, 2.4 portions, 2.6 portions, 2.8 portions or 3 portions, etc.
The weight portion of the titanium dioxide can be 25 portions, 25.5 portions, 26 portions, 26.5 portions, 27 portions, 27.5 portions, 28 portions, 28.5 portions, 29 portions, 29.5 portions or 30 portions, etc.
The weight portion of the butyl acetate in the component A can be 1 portion, 1.2 portions, 1.5 portions, 1.8 portions, 2 portions, 2.3 portions, 2.5 portions, 2.7 portions, 3 portions, 3.3 portions, 3.6 portions or 4 portions, etc.
The weight parts of the butyl acetate in the component B can be 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts or 60 parts and the like.
The dehydrating agent may be present in an amount of 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, 0.5 parts, 0.55 parts, 0.6 parts, 0.65 parts, 0.7 parts, etc.
The parts by weight of the hexamethylene diisocyanate may be 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, or the like.
The toluene diisocyanate trimer may be 15 parts, 15.5 parts, 16 parts, 16.5 parts, 17 parts, 17.5 parts, 18 parts, 18.5 parts, 19 parts, 19.5 parts, 20 parts, or the like by weight.
The weight parts of the xylene in the C component can be 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts or 35 parts and the like.
The weight portion of the butyl acetate in the component C can be 20 portions, 21 portions, 22 portions, 23 portions, 24 portions, 25 portions, 26 portions, 27 portions, 28 portions, 29 portions or 30 portions, etc.
The parts by weight of the sec-butyl acetate can be 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts or the like.
The parts by weight of cyclohexanone may be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, or the like.
The parts by weight of the propylene glycol monomethyl ether acetate in the component C can be 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts or 35 parts, etc.
The following are preferred embodiments of the present invention, but not limiting the technical solutions provided by the present invention, and the objects and advantages of the present invention can be better achieved and achieved by the following preferred embodiments.
In a preferred embodiment of the present invention, the mass ratio of the component A, the component B and the component C is 1 (0.8 to 0.9): (0.4 to 0.5), and may be, for example, 1:0.8:0.4, 1:0.8:0.45, 1:0.8:0.5, 1:0.85:0.4, 1:0.85:0.45, 1:0.85:0.5, 1:0.9:0.4, 1:0.9:0.45 or 1:0.9: 0.5.
As a preferred technical scheme of the invention, the preparation raw materials of the synthetic fatty acid resin comprise the following components in parts by weight: 20-25 parts of isooctanoic acid, 2-4 parts of benzoic acid, 6-10 parts of neopentyl glycol, 18-22 parts of pentaerythritol, 20-30 parts of phthalic anhydride, 3-6 parts of a modifier and 3-7 parts of xylene.
Preferably, the modifier comprises the following components in percentage by mass: 25-35% of diethylene glycol, 10% of trimethylolpropane and 55-65% of acrylamide.
According to the invention, through the design of raw materials for preparing the synthetic fatty acid resin, the use of the modifier is further controlled, and the weight part of the modifier is controlled within a specific range, the prepared synthetic fatty acid resin has lower viscosity and better flexibility, so that the prepared polyurethane bright white finish has better gloss, higher hardness, higher fullness and better scratch resistance.
According to the invention, through the design of the modifier, the molecular weight of the synthetic fatty acid resin can be extended and expanded by further using the diethylene glycol, the trimethylolpropane and the acrylamide in a matching manner, so that a space network structure is formed, and the synthetic fatty acid resin has a larger molecular weight, so that the release speed of a solvent in the polyurethane bright white finish paint is improved, and the prepared polyurethane bright white finish paint achieves the coating effect that prickly heat and dark bubbles are not generated in thick coating construction.
In the present invention, the weight part of the isooctanoic acid can be 20 parts, 20.5 parts, 21 parts, 21.5 parts, 22 parts, 22.5 parts, 23 parts, 23.5 parts, 24 parts, 24.5 parts, 25 parts, or the like.
The benzoic acid may be present in an amount of 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.6 parts, 3.8 parts, 4 parts, or the like.
The parts by weight of neopentyl glycol may be 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, or the like.
The pentaerythritol may be in a weight part of 18 parts, 18.5 parts, 19 parts, 19.5 parts, 20 parts, 20.5 parts, 21 parts, 21.5 parts, 22 parts, or the like.
The weight portion of the phthalic anhydride can be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts or 30 parts and the like.
The modifier can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts or 6 parts by weight.
The parts by weight of xylene may be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, or the like.
The diethylene glycol may be present in an amount of 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, or the like, by mass%.
The acrylamide may be present in an amount of 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65% or the like by mass.
In a preferred embodiment of the present invention, the raw material for preparing the synthetic fatty acid resin further comprises 0.1 to 0.5 parts of an antioxidant, which may be, for example, 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, or 0.5 part.
Preferably, the antioxidant is antioxidant M-070.
Preferably, the raw material for preparing the synthetic fatty acid resin further comprises 0.01 to 0.03 part of a catalyst, and for example, 0.01 part, 0.012 part, 0.014 part, 0.016 part, 0.018 part, 0.02 part, 0.022 part, 0.024 part, 0.026 part, 0.028 part, 0.03 part or the like can be used.
Preferably, the catalyst is selected from CaO and/or LiOH.
Preferably, the raw materials for preparing the synthetic fatty acid resin also comprise 4-7 parts of solvent, such as 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts or 7 parts.
Preferably, the solvent is selected from butyl esters and/or xylenes.
As a preferred embodiment of the present invention, the method for preparing the synthetic fatty acid resin comprises the steps of:
(1) mixing isooctanoic acid, benzoic acid, neopentyl glycol, pentaerythritol and an optional catalyst, and carrying out esterification reaction to obtain an esterified substance;
(2) and (2) mixing the esterified substance obtained in the step (1) with phthalic anhydride, xylene, a modifier and an optional antioxidant, carrying out polyester reaction, and adding an optional solvent for dilution to obtain the synthetic fatty acid resin.
As a preferred embodiment of the present invention, the esterification reaction is carried out in the presence of an inert gas.
Preferably, the esterification reaction temperature is 200 ~ 230 ℃, for example can be 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃ or 230 ℃.
Preferably, the polyester reaction is carried out in the presence of an inert gas.
Preferably, the temperature of the polyester reaction is 180 to 220 ℃, for example, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃ or 220 ℃ and the like.
In the present invention, the inert gas is selected from nitrogen and/or carbon dioxide.
As a preferred technical scheme of the invention, the titanium dioxide is rutile titanium dioxide.
Preferably, the component A also comprises 0.3-0.8 part of wetting dispersant, such as 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 or 0.8 part.
Preferably, the wetting dispersant is selected from the dispersants BYK-110 and/or dispersant BYK-103.
Preferably, the component A also comprises 0.2-0.5 part of defoaming agent, such as 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part or 0.5 part.
Preferably, the defoaming agent is selected from Deform 5300 defoaming agent and/or defoaming agent BYK-141.
In a preferred embodiment of the present invention, the component a further comprises 0.2 to 0.5 parts of a leveling agent, which may be, for example, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, or 0.5 part.
Preferably, the leveling agent comprises a combination of a silicone leveling agent and an acrylate leveling agent.
According to the invention, the polyurethane bright white finish prepared by using the organic silicon flatting agent and the acrylate flatting agent together has good flatting property, and does not generate dark bubbles during thick coating construction.
Preferably, the weight part of the organosilicon leveling agent in the component A is 0.1-0.3, such as 0.1, 0.12, 0.14, 0.16, 0.18, 0.2, 0.22, 0.24, 0.26, 0.28 or 0.3.
Preferably, the organosilicon leveling agent is selected from a leveling agent BYK-333 and/or a leveling agent TEGO-450.
Preferably, the weight part of the acrylate leveling agent in the component A is 0.1-0.3, such as 0.1, 0.12, 0.14, 0.16, 0.18, 0.2, 0.22, 0.24, 0.26, 0.28 or 0.3.
Preferably, the acrylate leveling agent is selected from the leveling agents BYK-358N and/or BYK-354.
Preferably, the dehydrating agent is selected from a TI dehydrating agent and/or a BF-5 dehydrating agent.
A second aspect. The invention provides a preparation method of polyurethane glossy white finish paint, which comprises the following steps:
(A) uniformly mixing synthetic fatty acid resin, propylene glycol monomethyl ether acetate, titanium dioxide, butyl acetate and optional wetting dispersant, flatting agent and defoaming agent to obtain a component A;
uniformly mixing butyl acetate, a dehydrating agent, hexamethylene diisocyanate and toluene diisocyanate trimer to obtain a component B;
uniformly mixing xylene, butyl acetate, sec-butyl acetate, cyclohexanone and propylene glycol monomethyl ether acetate to obtain a component C;
(B) and (3) uniformly mixing the component A, the component B and the component C obtained in the step (A) to obtain the polyurethane bright white finish.
In the invention, the adding sequence of the components of the component a is not limited in any way, and in order to facilitate the components to be mixed uniformly, the synthetic fatty acid resin and the optional wetting dispersant are mixed uniformly, then the titanium dioxide is added to the mixture to be mixed uniformly, and finally the propylene glycol monomethyl ether acetate, the butyl acetate, the optional leveling agent and the defoaming agent are added to the mixture to be mixed uniformly to obtain the component a.
In a third aspect, the invention provides an application of the polyurethane white top-coat in wood coatings.
Compared with the prior art, the invention has the following beneficial effects:
the polyurethane gloss white finish prepared by designing the components of the polyurethane gloss white finish, further designing the preparation raw materials of synthetic fatty acid resin and using the modifier has excellent mechanical property, the adhesive force of the polyurethane gloss white finish is 0 grade, the hardness of the polyurethane gloss white finish is 2H, the impact property of the polyurethane gloss white finish is 20-30 cm, the flexibility of the polyurethane gloss white finish is 1-2 mm, the wear resistance of the polyurethane gloss white finish is 0.03-0.034 g, the polyurethane gloss white finish also has good chemical stability, the yellowing resistance of the polyurethane gloss white finish is 2.3-2.6, the water resistance, the alcohol resistance, the alkali resistance and the stain resistance of the polyurethane gloss white finish are good, and the dry heat resistance of the polyurethane gloss white finish is 1-2 grade.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. 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 sources of titanium dioxide in the examples and comparative examples are as follows:
titanium dioxide: U.S. DuPont, rutile titanium dioxide, R-902 +;
dehydrating agent: germany bayer, TI dehydrating agent; bayer, Germany, BF-5 dehydrating agent.
Example 1
The embodiment provides a polyurethane gloss white finish and a preparation method thereof, wherein the polyurethane gloss white finish comprises a component A, a component B and a component C;
the component A comprises the following components in parts by weight: 68 parts of synthetic fatty acid resin, 2 parts of propylene glycol monomethyl ether acetate, 28 parts of titanium dioxide, 3 parts of butyl acetate, 0.3 part of dispersant BYK-1100.5 parts of Deform5300 defoaming agent, 0.3 part of flatting agent BYK-3330.2 parts of flatting agent BYK-358N 0.1 part;
the preparation raw materials of the synthetic fatty acid resin comprise the following components in parts by weight: 23 parts of isooctanoic acid, 3.5 parts of benzoic acid, 8 parts of neopentyl glycol, 21 parts of pentaerythritol, 27 parts of phthalic anhydride, 5 parts of a modifier, 6 parts of xylene, 0.02 part of an antioxidant M-0700.1 part of LiOH and 6 parts of butyl ester;
the modifier comprises the following components in percentage by mass: 30% of diethylene glycol, 10% of trimethylolpropane and 60% of acrylamide;
the preparation method of the synthetic fatty acid resin comprises the following steps:
(1) In the nitrogen atmosphere, mixing isooctanoic acid, benzoic acid, neopentyl glycol, pentaerythritol and LiOH, and then carrying out esterification reaction at 220 ℃ to obtain an esterified substance;
(2) and (2) mixing the esterified product obtained in the step (1) with phthalic anhydride, dimethylbenzene, a modifier and an antioxidant M-070 in a nitrogen atmosphere, carrying out polyester reaction at 200 ℃, and then adding butyl ester for dilution to obtain the synthetic fatty acid resin.
The component B comprises the following components in parts by weight: 50 parts of butyl acetate, 0.5 part of TI dehydrating agent, 30 parts of hexamethylene diisocyanate and 18 parts of toluene diisocyanate trimer;
the component C comprises the following components in parts by weight: 30 parts of dimethylbenzene, 25 parts of butyl acetate, 10 parts of sec-butyl acetate, 7 parts of cyclohexanone and 30 parts of propylene glycol monomethyl ether acetate.
The preparation method of the polyurethane bright white finish comprises the following steps:
(A) uniformly mixing synthetic fatty acid resin, propylene glycol monomethyl ether acetate, titanium dioxide, butyl acetate, a dispersant BYK-110, a flatting agent BYK-333, a flatting agent BYK-358N and a Deform 5300 defoaming agent to obtain a component A;
uniformly mixing butyl acetate, a TI dehydrating agent, hexamethylene diisocyanate and toluene diisocyanate trimer to obtain a component B;
Uniformly mixing xylene, butyl acetate, sec-butyl acetate, cyclohexanone and propylene glycol monomethyl ether acetate to obtain a component C;
(B) and (3) uniformly mixing the component A, the component B and the component C obtained in the step (A) according to the mass ratio of 1:0.8:0.4 to obtain the polyurethane glossy white finish.
Example 2
The embodiment provides a polyurethane gloss white finish and a preparation method thereof, wherein the polyurethane gloss white finish comprises a component A, a component B and a component C;
the component A comprises the following components in parts by weight: 65 parts of synthetic fatty acid resin, 3 parts of propylene glycol monomethyl ether acetate, 25 parts of titanium dioxide, 1 part of butyl acetate, BYK-1030.3 parts of dispersant, BYK-1410.2 parts of defoamer, TEGO-4500.3 parts of flatting agent and BYK-3540.2 parts of flatting agent;
the synthetic fatty acid resin is prepared from the following raw materials in parts by weight: 25 parts of isooctanoic acid, 2 parts of benzoic acid, 6 parts of neopentyl glycol, 22 parts of pentaerythritol, 30 parts of phthalic anhydride, 5 parts of a modifier, 7 parts of xylene, 0.03 part of antioxidant M-0700.3, 0.03 part of CaO and 4 parts of butyl ester;
the modifier comprises the following components in percentage by mass: 35% of diethylene glycol, 10% of trimethylolpropane and 55% of acrylamide;
the preparation method of the synthetic fatty acid resin comprises the following steps:
(1) In the nitrogen atmosphere, mixing isooctanoic acid, benzoic acid, neopentyl glycol, pentaerythritol and CaO, and then carrying out esterification reaction at 200 ℃ to obtain an esterified substance;
(2) and (2) mixing the esterified product obtained in the step (1) with phthalic anhydride, dimethylbenzene, a modifier and an antioxidant M-070 in a nitrogen atmosphere, carrying out polyester reaction at 180 ℃, and then adding butyl ester for dilution to obtain the synthetic fatty acid resin.
The component B comprises the following components in parts by weight: 45 parts of butyl acetate, 0.4 part of BF-5 dehydrating agent, 35 parts of hexamethylene diisocyanate and 20 parts of toluene diisocyanate trimer;
the component C comprises the following components in parts by weight: 25 parts of dimethylbenzene, 30 parts of butyl acetate, 12 parts of sec-butyl acetate, 5 parts of cyclohexanone and 25 parts of propylene glycol monomethyl ether acetate.
The preparation method of the polyurethane glossy white finish is the same as that of example 1.
Example 3
The embodiment provides a polyurethane gloss white finish and a preparation method thereof, wherein the polyurethane gloss white finish comprises a component A, a component B and a component C;
the component A comprises the following components in parts by weight: 70 parts of synthetic fatty acid resin, 1 part of propylene glycol monomethyl ether acetate, 30 parts of titanium dioxide, 4 parts of butyl acetate, 0.5 part of dispersant BYK-1100.8 parts of Deform5300 defoaming agent, 0.1 part of flatting agent BYK-3330.1 parts of flatting agent BYK-358N;
The synthetic fatty acid resin is prepared from the following raw materials in parts by weight: 20 parts of isooctanoic acid, 4 parts of benzoic acid, 10 parts of neopentyl glycol, 18 parts of pentaerythritol, 20 parts of phthalic anhydride, 4 parts of a modifier, 3 parts of xylene, M-0700.5 parts of an antioxidant, 0.01 part of LiOH and 7 parts of butyl ester;
the modifier comprises the following components in percentage by mass: 25% of diethylene glycol, 10% of trimethylolpropane and 65% of acrylamide;
the preparation method of the synthetic fatty acid resin comprises the following steps:
(1) in the nitrogen atmosphere, mixing isooctanoic acid, benzoic acid, neopentyl glycol, pentaerythritol and LiOH, and then carrying out esterification reaction at 230 ℃ to obtain an esterified substance;
(2) and (2) mixing the esterified product obtained in the step (1) with phthalic anhydride, dimethylbenzene, a modifier and an antioxidant M-070 in a nitrogen atmosphere, carrying out polyester reaction at 220 ℃, and then adding butyl ester for dilution to obtain the synthetic fatty acid resin.
The component B comprises the following components in parts by weight: 60 parts of butyl acetate, 0.6 part of TI dehydrating agent, 25 parts of hexamethylene diisocyanate and 15 parts of toluene diisocyanate trimer;
the component C comprises the following components in parts by weight: 35 parts of dimethylbenzene, 20 parts of butyl acetate, 8 parts of sec-butyl acetate, 8 parts of cyclohexanone and 35 parts of propylene glycol monomethyl ether acetate.
The preparation method of the polyurethane glossy white finish is the same as that of example 1.
Example 4
The embodiment provides a polyurethane white top-coat with bright finish and a preparation method thereof, and the difference from the embodiment 1 is that a modifier in a raw material for preparing the synthetic fatty acid resin comprises 14% of trimethylolpropane and 86% of acrylamide in percentage by mass; other conditions were the same as in example 1.
Example 5
The embodiment provides a polyurethane bright white finish and a preparation method thereof, and the difference from the embodiment 1 is that a modifier in a preparation raw material of a synthetic fatty acid resin comprises 33.5% of diethylene glycol and 66.5% of acrylamide in percentage by mass; other conditions were the same as in example 1.
Example 6
The embodiment provides a polyurethane white finish with bright light and a preparation method thereof, and the difference from the embodiment 1 is that a modifier in a raw material for preparing a synthetic fatty acid resin comprises the following components, by mass, 75% of diethylene glycol and 25% of trimethylolpropane; other conditions were the same as in example 1.
Example 7
The embodiment provides a polyurethane glossy white finish and a preparation method thereof, and the polyurethane glossy white finish is different from the embodiment 1 in that the modifier is used in 3 parts by weight in the raw materials for preparing the synthetic fatty acid resin, and other conditions are the same as those in the embodiment 1.
Example 8
The present example provides a polyurethane white top-coat with a bright color and a preparation method thereof, which are different from example 1 in that the weight part of the modifier in the raw materials for preparing the synthetic fatty acid resin is 6 parts, and other conditions are the same as example 1.
Example 9
The embodiment provides a polyurethane glossy white finish and a preparation method thereof, and the polyurethane glossy white finish is different from the embodiment 1 in that the modifier is 1 part by weight in the raw materials for preparing the synthetic fatty acid resin, and other conditions are the same as those in the embodiment 1.
Example 10
The present example provides a polyurethane white top-coat with a bright color and a preparation method thereof, which are different from those in example 1 in that the weight part of the modifier in the raw materials for preparing the synthetic fatty acid resin is 8 parts, and other conditions are the same as those in example 1.
Example 11
This example provides a polyurethane white top-coat with gloss and a preparation method thereof, which are different from example 1 in that the weight part of the dehydrating agent in the component B is 0.3 part, and the other conditions are the same as example 1.
Example 12
This example provides a polyurethane white top-coat with gloss and a preparation method thereof, which are different from example 1 in that the weight part of the dehydrating agent in the component B is 0.7 parts, and the other conditions are the same as example 1.
Comparative example 1
The comparative example provides a polyurethane bright white finish and a preparation method thereof, and is different from the example 1 in that the weight part of the dehydrating agent in the component B is 0.1 part, and other conditions are the same as those in the example 1.
Comparative example 2
The comparative example provides a polyurethane bright white finish and a preparation method thereof, and is different from the example 1 in that the weight part of the dehydrating agent in the component B is 1 part, and other conditions are the same as those in the example 1.
The performance of the polyurethane gloss white finishes provided in the above examples and comparative examples were tested according to the following test methods or test standards:
storage stability: respectively filling 0.5L of component A and component B of polyurethane bright white finish into a well-sealed iron tank, sealing 10% of space in the tank, putting the tank into a (50 +/-2) DEG C constant-temperature drying oven, taking out the tank after 28 days, naturally cooling the tank to room temperature, observing whether the tank is settled, layered or caked, and judging that no abnormity occurs if the tank is not settled, layered or caked.
Coating effect: the polyurethane gloss white finish provided in the above examples and comparative examples was coated on a light-colored faced plywood (made in accordance with GB/T23997-.
Adhesion force: the test was carried out according to the test method of GB/T-9286-1998, and the damage of the paint film was observed: level 0 indicates no breakage; grade 1 indicates a damaged area of less than 5%.
Hardness: the test was performed according to GB/T-6739-2006.
Impact properties: the test was carried out according to GB/T-20624.2-2006, using a 12.7mm spherical punch with a weight of 300 g. And (3) adjusting the falling height of the heavy punch to ensure that the diameter of an impact impression on the surface of the sample plate is within the range of 3.6-4.0 mm, testing two test plates, impacting 5 points on each test plate, and recording the falling height of the heavy punch when at least 3 points on one test plate are coated without falling off or cracking.
Flexibility: paint films were prepared on tinplate according to the specification of GB/T1727-1992, and after curing for 7 days under constant temperature and humidity conditions, the paint films were examined for the extent of the width of the mandrel bar according to the flexibility tester test specified in GB/T1731-1993, and the width of the mandrel bar was recorded.
Wear resistance: the test is carried out according to the specification of GB/T1768-2006, wherein the model of the used rubber grinding wheel is CS-10, and the standard is less than 0.05 g.
Yellowing resistance: according to ISO 11507: 1997, the test was performed.
Water resistance: testing according to the specification of GB/T4893.1, wherein the test solution is distilled water, the middle part of each plate is taken in the test area, the filter paper is kept wet in the test process, a glass cover is covered if necessary, the test paper is taken out after the test for 24h, the test paper is sucked dry and placed for 1h, and the test paper is visually observed under scattered light, so that the condition that the coating film is abnormal if two of three test plates have no foaming, cracking, peeling, obvious color change and obvious gloss change [ the condition of allowing slight color change (the color difference value is not more than 6.0) and slight gloss change (the gloss change rate is not more than 30%) ] is judged to be 'no abnormity'; if the above coating pathological phenomenon occurs, it is described in GB/T1766-2008.
Alcohol resistance: the test solution is 70% (volume percentage) ethanol aqueous solution, the filter paper is taken out after the test time is 8h, the filter paper is washed by water and then is sucked dry, the test solution is observed after being placed for 1h, and the test method and the judgment method are the same as the water resistance test.
Alkali resistance: the test solution is 50g/L Na2CO3The solution is tested for 2h, the filter paper is taken off, washed by water and then dried by suction, and the solution is placed for 1hThe observation, test and evaluation methods are the same as the water resistance test.
Stain resistance: the test solution is vinegar and tea, the filter paper is taken out after the test time is 2 hours, the filter paper is washed with water and then is sucked dry, the test solution is observed after being placed for 1 hour, the vinegar is aromatic vinegar meeting the GB/T18187-.
Dry heat resistance: testing according to the regulation of GB/T4893.3-2000, and observing whether the phenomena of discoloration, tarnish, bubbling and the like occur; grading into 1-5 grades, wherein grade 1 indicates no visible change; a rating of 2 indicates a slightly visible discoloration, gloss or discontinuous impression.
Fullness degree: after the base plate is manufactured according to GB/T23997 plus 2009, fine sand paper (600#) is used for polishing, so that the surface of the base plate has no sand marks, the polyurethane bright white finish paint provided by the above examples and comparative examples is sprayed, after the finish paint is dried, the fullness, texture and sand paper covering effect of a paint film are observed, and the stronger the meat texture, the lighter the sand marks, the better the fullness.
The performance test results of the polyurethane brilliant white finishes provided in the above examples and comparative examples are shown in tables 1 and 2 below:
TABLE 1
| Storage stability | Coating effect | Adhesion/grade | Hardness of | Impact performance | Flexibility of the film | Wear resistance | |
| Example 1 | No abnormality | No abnormality | 0 | 2H | 30cm | 1mm | 0.03g |
| Example 2 | No abnormality | No abnormality | 0 | 2H | 25cm | 2mm | 0.032g |
| Example 3 | No abnormality | No abnormality | 0 | 2H | 25cm | 2mm | 0.034g |
| Example 4 | No abnormality | Has a small amount of miliaria | 1 | 2H | 20cm | 4mm | 0.036g |
| Example 5 | No abnormality | Has a small amount of miliaria | 1 | H | 20cm | 4mm | 0.037g |
| Example 6 | No abnormality | Has a small amount of miliaria | 1 | H | 15cm | 5mm | 0.04g |
| Example 7 | No abnormality | No abnormality | 0 | 2H | 20cm | 2mm | 0.034g |
| Example 8 | No abnormality | No abnormality | 0 | 2H | 30cm | 2mm | 0.03g |
| Example 9 | No abnormality | Has a small amount of miliaria | 1 | H | 15cm | 2mm | 0.043g |
| Example 10 | No abnormality | No abnormality | 1 | 2H | 30cm | 6mm | 0.028g |
| Example 11 | No abnormality | No abnormality | 0 | 2H | 30cm | 1mm | 0.032g |
| Example 12 | No abnormality | No abnormality | 0 | 2H | 30cm | 1mm | 0.033g |
| Comparative example 1 | Agglomeration of | / | / | / | / | / | / |
| Comparative example 2 | No abnormality | No abnormality | 0 | 2H | 30cm | 1mm | 0.03g |
TABLE 2
The contents in tables 1 and 2 show that the polyurethane gloss white finish prepared by the invention through the design of the components of the polyurethane gloss white finish, the design of the synthetic fatty acid resin preparation raw materials and the use of the modifier has excellent mechanical properties, the adhesive force is 0 grade, the hardness is 2H, the impact property is 20-30 cm, the flexibility is 1-2 mm, the wear resistance is 0.03-0.034 g, the polyurethane gloss white finish also has good chemical stability, the yellowing resistance is 2.3-2.6, the water resistance, the alcohol resistance, the alkali resistance and the stain resistance are good, and the dry heat resistance is 1-2 grades, meanwhile, the polyurethane gloss white finish provided by the invention has high brightness, and has no miliaria and dark bubbles in one-time thick coating construction under a high temperature condition, so that the polyurethane gloss white finish can achieve a good coating effect, and is suitable for being used as a wood coating.
Compared with example 1, if the synthetic fatty acid resin is prepared by using only the combination of trimethylolpropane and acrylamide as a modifier (example 4), or the synthetic fatty acid resin is prepared by using only the combination of diethylene glycol and acrylamide as a modifier (example 5), or the synthetic fatty acid resin is prepared by using only the combination of diethylene glycol and trimethylolpropane as a modifier (example 6), the molecular chain of the synthetic fatty acid resin is short, and the polyurethane brilliant white finish prepared has poor adhesion, hardness, impact performance, flexibility and abrasion resistance, and miliaria is generated during thick coating construction, and the yellowing resistance and alcohol resistance are poor. Therefore, the polyurethane gloss white finish prepared by the invention through the matching use of diethylene glycol, trimethylolpropane and acrylamide has better mechanical property, chemical stability and coating effect.
Compared with example 1, if the content of the modifier in the synthetic fatty acid resin is too low (example 9), the molecular chain of the prepared synthetic fatty acid resin is shorter, and the mechanical property of the prepared polyurethane bright white finish paint is poorer, and miliaria can be generated during thick coating construction; if the content of the modifier in the synthetic fatty acid resin is too high (example 10), the adhesion of the polyurethane brilliant white finish prepared is poor.
If the content of dehydrating agent in component B is too low (comparative example 1), the storage stability of the polyurethane glossy white finish prepared is inferior to that of example 1; if the content of the dehydrating agent in the B component is too high (comparative example 2), the production cost of the polyurethane glossy surface paint increases and the waste of raw materials is caused.
In conclusion, the polyurethane gloss white finish prepared by the invention has excellent mechanical properties and higher fullness through the design of the components of the polyurethane gloss white finish, the design of the preparation raw materials of the synthetic fatty acid resin and the use of the modifier, and miliaria and dark bubbles are avoided during one-step thick coating construction under the high-temperature condition, so that a better coating effect can be achieved, and the polyurethane gloss white finish is suitable for being used as a woodware coating.
The applicant states that the present invention is illustrated by the above examples to show the detailed process flow of the present invention, but the present invention is not limited to the above detailed process flow, which means that the present invention does not depend on the above detailed process flow to be implemented. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (26)
1. The polyurethane gloss white finish is characterized by comprising a component A, a component B and a component C;
the component A comprises the following components in parts by weight: 65-70 parts of synthetic fatty acid resin, 1-3 parts of propylene glycol monomethyl ether acetate, 25-30 parts of titanium dioxide and 1-4 parts of butyl acetate;
the component B comprises the following components in parts by weight: 45-60 parts of butyl acetate, 0.3-0.7 part of a dehydrating agent, 25-35 parts of hexamethylene diisocyanate and 15-20 parts of toluene diisocyanate trimer;
the component C comprises the following components in parts by weight: 25-35 parts of dimethylbenzene, 20-30 parts of butyl acetate, 8-12 parts of sec-butyl acetate, 5-8 parts of cyclohexanone and 25-35 parts of propylene glycol monomethyl ether acetate;
the preparation raw materials of the synthetic fatty acid resin comprise the following components in parts by weight: 20-25 parts of isooctanoic acid, 2-4 parts of benzoic acid, 6-10 parts of neopentyl glycol, 18-22 parts of pentaerythritol, 20-30 parts of phthalic anhydride, 3-6 parts of a modifier and 3-7 parts of xylene;
the modifier comprises the following components in percentage by mass: 25-35% of diethylene glycol, 10% of trimethylolpropane and 55-65% of acrylamide;
the mass ratio of the component A, the component B and the component C is 1 (0.8-0.9) to 0.4-0.5.
2. The polyurethane glossy white finish according to claim 1, characterized in that the raw materials for preparing the synthetic fatty acid resin further comprise 0.1-0.5 parts of an antioxidant.
3. The polyurethane white top coating of claim 2, wherein the antioxidant is antioxidant M-070.
4. The polyurethane white top-coat according to claim 1, wherein the raw materials for preparing the synthetic fatty acid resin further comprise 0.01-0.03 parts of a catalyst.
5. Polyurethane brilliant white top coat according to claim 4, characterised in that the catalyst is selected from CaO and/or LiOH.
6. The polyurethane white top-coat according to claim 1, wherein the raw materials for preparing the synthetic fatty acid resin further comprise 4-7 parts of a solvent.
7. The polyurethane brilliant white finish of claim 6, characterized in that the solvent is selected from xylene.
8. The polyurethane brilliant white finish according to claim 1, characterized in that the preparation method of the synthetic fatty acid resin comprises the following steps:
(1) mixing isooctanoic acid, benzoic acid, neopentyl glycol, pentaerythritol and an optional catalyst, and carrying out esterification reaction to obtain an esterified substance;
(2) And (2) mixing the esterified substance obtained in the step (1) with phthalic anhydride, dimethylbenzene, a modifier and an optional antioxidant, carrying out polyester reaction, and adding an optional solvent for dilution to obtain the synthetic fatty acid resin.
9. The polyurethane brilliant white finish of claim 8, characterized in that the esterification reaction is carried out in the presence of an inert gas.
10. The polyurethane white topcoat with gloss according to claim 8, wherein the esterification reaction temperature is 200-230 ℃.
11. The polyurethane brilliant white finish of claim 8, characterized in that the polyester reaction is carried out in the presence of an inert gas.
12. The polyurethane white top-coat according to claim 8, wherein the temperature of the polyester reaction is 180-220 ℃.
13. The polyurethane brilliant white finish according to claim 1, characterized in that the titanium dioxide is rutile titanium dioxide.
14. The polyurethane white top-coat according to claim 1, wherein the component A further comprises 0.3-0.8 part of wetting dispersant.
15. The polyurethane brilliant white finish of claim 14, wherein the wetting dispersant is selected from dispersant BYK-110 and/or dispersant BYK-103.
16. The polyurethane white top-coat according to claim 1, wherein the component A further comprises 0.2-0.5 parts of a defoaming agent.
17. The polyurethane brilliant white finish of claim 16, wherein the defoamer is selected from Deform 5300 defoamer and/or defoamer BYK-141.
18. The polyurethane white top coating according to claim 1, wherein the component A further comprises 0.2-0.5 parts of a leveling agent.
19. The polyurethane brilliant white finish of claim 18, wherein the leveling agent comprises a combination of a silicone leveling agent and an acrylate leveling agent.
20. The polyurethane white top-coat paint according to claim 19, wherein the amount of the organic silicon leveling agent in the component A is 0.1-0.3 parts by weight.
21. The polyurethane glossy white top coat according to claim 19 wherein the silicone leveling agent is selected from the leveling agents BYK-333 and/or the leveling agent TEGO-450.
22. The polyurethane glossy white finish according to claim 19, wherein the acrylic leveling agent in the component a is 0.1 to 0.3 parts by weight.
23. The polyurethane glossy white finish according to claim 19, wherein the acrylate leveling agent is selected from leveling agents BYK-358N and/or leveling agents BYK-354.
24. The polyurethane brilliant white finish according to claim 1, characterized in that the dehydrating agent is selected from TI dehydrating agents and/or BF-5 dehydrating agents.
25. A process for the preparation of a polyurethane brilliant white finish according to any one of claims 1 to 24, characterized in that it comprises the following steps:
(A) uniformly mixing the synthetic fatty acid resin, propylene glycol monomethyl ether acetate, titanium dioxide, butyl acetate, an optional wetting dispersant, a leveling agent and an antifoaming agent to obtain a component A;
uniformly mixing butyl acetate, a dehydrating agent, hexamethylene diisocyanate and toluene diisocyanate tripolymer to obtain a component B;
uniformly mixing xylene, butyl acetate, sec-butyl acetate, cyclohexanone and propylene glycol monomethyl ether acetate to obtain a component C;
(B) and (B) uniformly mixing the component A, the component B and the component C obtained in the step (A) to obtain the polyurethane bright white finish.
26. Use of a polyurethane gloss white finish according to any one of claims 1 to 24 in a wood coating.
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| CN103614060A (en) * | 2013-11-22 | 2014-03-05 | 广东巴德士化工有限公司 | Polyurethane brilliant white finish based on construction tolerance |
| CN103694874A (en) * | 2013-12-06 | 2014-04-02 | 上海富臣化工有限公司 | Nanoscale barium sulfate-containing polyurethane bright white finish for furniture |
| CN106752855A (en) * | 2016-11-22 | 2017-05-31 | 展辰新材料集团股份有限公司 | A kind of furniture polyurethane Brilliant white paint |
| CN108503756B (en) * | 2017-02-28 | 2020-12-18 | 常州华科聚合物股份有限公司 | Vinyl monomer modified polyester resin, low shrinkage agent and preparation method |
| CN107418417A (en) * | 2017-08-30 | 2017-12-01 | 展辰新材料集团股份有限公司 | A kind of polyurethane Brilliant white paint |
| CN110951057A (en) * | 2018-09-26 | 2020-04-03 | 万华化学（北京）有限公司 | Preparation method of alkyd resin and prepared resin, preparation method of acrylic acid modified alkyd resin and prepared resin |
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