CN111334137A - Waterproof spray, preparation method and application thereof - Google Patents
Waterproof spray, preparation method and application thereof Download PDFInfo
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- CN111334137A CN111334137A CN202010345631.2A CN202010345631A CN111334137A CN 111334137 A CN111334137 A CN 111334137A CN 202010345631 A CN202010345631 A CN 202010345631A CN 111334137 A CN111334137 A CN 111334137A
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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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to the technical field of waterproof spraying, in particular to a waterproof spraying agent, a preparation method and application thereof, wherein the waterproof spraying agent comprises the following raw materials in parts by weight: 20-32 parts of fluorocarbon resin, 0-8 parts of acrylic resin, 1-3 parts of polysilazane, 0-3 parts of other auxiliaries and 78-78 parts of organic solvent A55. Fluorocarbon resin is taken as main resin and dissolved in the organic solvent A, the fluorocarbon resin can be used at normal temperature, the organic solvent A volatilizes after coating to enable the fluorocarbon resin to form a waterproof breathable film, the waterproof effect is improved, polysilazane is mixed in the fluorocarbon resin to play a role in reinforcement, and the waterproof aging of the waterproof breathable film is improved; furthermore, if less than 8 parts by weight of acrylic resin is added, the acrylic resin and fluorocarbon resin have synergistic effect, so that the adhesiveness and the film-forming property of the waterproof spray coated on the surface of the carrier are improved, and the flexibility of the waterproof breathable film is improved.
Description
Technical Field
The invention relates to the technical field of waterproof spraying, in particular to a waterproof spraying agent, and a preparation method and application thereof.
Background
Ordinary clothes, shoes, bags and other articles are not waterproof and antifouling, and once the articles are contacted with water, the articles are easily soaked, wetted and stained. At present, mature waterproof products exist in the market, but the application process is complex, professional equipment and strict temperature control are needed, and the waterproof effect and the aging are poor.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the waterproof spray which can be used at normal temperature, forms a waterproof breathable film after being coated, improves the waterproof effect and has longer waterproof time-effect.
The second purpose of the invention is to provide a preparation method of the waterproof spray, which has the advantages of simple operation, convenient control, high production efficiency and low production cost and can be used for large-scale production.
The invention also aims to provide the application of the waterproof spray, and the waterproof spray is applied to a spray can, acts on the surface of fabric for water prevention, the surface of leather for water prevention and the surface of a shoe bag for water prevention, is convenient to use and is suitable for household use.
One of the purposes of the invention is realized by the following technical scheme: a waterproof spray comprises the following raw materials in parts by weight:
the waterproof spray takes fluorocarbon resin as main resin and is dissolved in the organic solvent A, and can be used at normal temperature, after coating, the organic solvent A volatilizes to enable the fluorocarbon resin to form a waterproof breathable film, so that the waterproof effect is improved, polysilazane is mixed into the fluorocarbon resin to play a role in reinforcement, and the waterproof aging of the waterproof breathable film is improved; furthermore, if less than 8 parts by weight of acrylic resin is added, the acrylic resin and fluorocarbon resin have synergistic effect, so that the adhesiveness and the film-forming property of the waterproof spray coated on the surface of the carrier are improved, and the flexibility of the waterproof breathable film is improved.
Preferably, the fluorocarbon resin is fluoroether resin and acrylic fluorinated resin in a weight ratio of 5: 1-2, mixing; the weight average molecular weight of the fluorocarbon resin is 5000-.
By adopting the technical scheme, the fluorocarbon resin can be dissolved in the organic solvent A at normal temperature, and the organic solvent A volatilizes after coating to enable the fluorocarbon resin to form the waterproof breathable film. The weight average molecular weight of the fluorocarbon resin is controlled to be 5000-20000, and if the molecular weight of the fluorocarbon resin is too small, a spray prepared from the fluorocarbon resin is easy to exude free compounds in the using process, so that the film forming property of the waterproof spray is adversely affected; if the molecular weight is too large, the spray curing film forming speed is reduced, and the film forming property of the waterproof spray is adversely affected. Further, the fluoroether resin is trifluoroethylene-vinyl ether copolymer or tetrafluoroethylene-vinyl ether copolymer.
Preferably, the acrylic fluorinated resin is prepared by the following method:
(R1) weighing 25-28 parts of butyl acrylate, 30-40 parts of styrene, 5-10 parts of glycidyl methacrylate, 10-25 parts of hydroxypropyl acrylate, 1-3 parts of acrylic acid, 2-3 parts of initiator, 10-25 parts of fluorine-containing acrylic acid monomer and 80-100 parts of organic solvent B according to parts by weight for later use;
(R2), taking butyl acrylate, styrene, glycidyl methacrylate, hydroxypropyl acrylate, acrylic acid, part of initiator and part of organic solvent B, and uniformly mixing to obtain a component A;
(R3), uniformly mixing the fluorine-containing acrylic monomer, the rest of initiator and the rest of organic solvent B to obtain a component B;
(R4), heating a part of the component A to 78-80 ℃, stirring for a certain time, maintaining the temperature of 80-85 ℃, adding the component B and the rest of the component A, stirring for a certain time, and cooling to room temperature to obtain the acrylic fluorinated resin.
By adopting the technical scheme, the prepared acrylic acid fluorinated resin is transparent liquid, has good compatibility with the fluoroether resin, is easy to dissolve in the organic solvent A, promotes the fluoroether resin to be dissolved in the organic solvent A, and has synergistic effect with the fluoroether resin, so that the hydrophobicity and the air permeability of the waterproof spray after film formation are jointly improved, and the adhesiveness and the film forming property of the waterproof spray coated on the surface of a carrier are improved. Wherein, monomers such as butyl acrylate, styrene, glycidyl methacrylate, hydroxypropyl acrylate, acrylic acid and the like are used for locally initiating polymerization, and then fluorine-containing acrylic acid monomer is introduced, so that the obtained acrylic acid fluorinated resin has the solid content of 60-63 percent, the hydroxyl value is moderate, and the weight average molecular weight can be controlled to be 5000-20000. In the step (R4), after the temperature is raised to 78-80 ℃ and the mixture is stirred for 30-60min, the monomer of the component A is prepolymerized, the heat dissipation of the heat effect is controlled, the component B and the rest of the component A are added under the condition of maintaining the temperature of 80-85 ℃, and the mixture is stirred for 80-100min, so that the component A and the component B are fully reacted, and the solid content of the acrylic fluorinated resin is improved. The weight ratio of the initiator used in the step (R2) to the initiator used in the step (R3) is 1: 0.5 to 1; the weight ratio of the using amount of the organic solvent B in the step (R2) to the using amount of the organic solvent B in the step (R3) is 1: 1-2; in the step (R4), the ratio of the amount of a part of component a to the amount of the remaining component a in parts by weight is 1: 4-6.
Preferably, the initiator is azobisisobutyronitrile or benzoyl peroxide; the fluorine-containing acrylic monomer is at least one of dodecafluoroheptyl acrylate, dodecafluoroheptyl methacrylate, perfluoroalkyl ethyl acrylate, hexafluorobutyl acrylate and trifluoroethyl acrylate; the organic solvent B is xylene and propylene glycol monomethyl ether acetate according to a weight ratio of 2: 3-5, mixing.
By adopting the technical scheme, the initiator is adopted to improve the stability and the reaction activity, the effect of initiating the monomer polymerization is better, the residue of the monomer is greatly reduced, and the reaction conversion rate of the monomer is improved. With the above fluorine-containing acrylic monomer, more preferably, the fluorine-containing acrylic monomer is selected from the group consisting of dodecafluoroheptyl acrylate and dodecafluoroheptyl methacrylate in a weight ratio of 1: 3-5, the obtained acrylic acid fluorinated resin is transparent liquid, has good compatibility with the fluoroether resin, is easy to dissolve in the organic solvent A, promotes the fluoroether resin to dissolve in the organic solvent A, and improves the hydrophobicity and the air permeability of the waterproof spray after film formation and the adhesiveness and the film forming property of the waterproof spray coated on the surface of a carrier under the synergistic effect of the acrylic acid fluorinated resin and the fluoroether resin. The xylene and the propylene glycol monomethyl ether acetate are mixed according to a specific proportion to promote the monomer to be dissolved in the organic solvent B for polymerization and complete reaction, and the obtained acrylic fluorinated resin has moderate hydroxyl value and can control the weight average molecular weight to be 5000-20000.
Preferably, the acrylic resin is thermoplastic acrylic resin with the relative molecular weight of 85000-120000, the viscosity of 200-250s, the acid value of 1-3mgKOH/g and the Tg value of 40-42 ℃.
By adopting the technical scheme, the acrylic resin and fluorocarbon resin have synergistic effect, the adhesiveness and the film forming property of the waterproof spray coated on the surface of a carrier are improved, the flexibility of a waterproof breathable film is improved, the acrylic resin is quick-drying, and the drying rate of the waterproof spray is improved. Further, the viscosity was measured at 25 ℃ in a paint-4 cup.
Preferably, the organic solvent a is at least one of isohexane, n-heptane, cyclohexane, xylene, butyl acetate and n-butyl ether.
By adopting the technical scheme, the fluorocarbon resin, the acrylic resin and the polysilazane are promoted to be dissolved, so that the spray can be conveniently prepared and used as a spray in a spray can. More preferably, the organic solvent A is isohexane and butyl acetate in a weight ratio of 1: 2-3, has better dissolving effect and lower harm to human body than other solvents.
Preferably, each part of the other auxiliary agent comprises 1-2 parts of dispersant and 1-2 parts of defoaming agent.
By adopting the technical scheme, the dispersibility and the defoaming property of the waterproof spray are improved, the spray can be conveniently prepared and used for spraying in a spray can, the influence of foam generated by coating on the surface of a carrier on the film forming effect is avoided, and the blockage caused by the foam remained in a nozzle of the spray can is avoided. More preferably, the dispersant is sodium dodecyl benzene sulfonate, polyethylene glycol 2000 or polysorbate-80; the defoaming agent is BYK-085, BYK-070 or BYK-1730.
The second purpose of the invention is realized by the following technical scheme: the preparation method of the waterproof spray comprises the following steps:
(S1), weighing the raw materials in parts by weight for later use;
(S2), adding fluorocarbon resin into the organic solvent A, stirring for a certain time at the rotating speed of 600-1000rpm, adding other raw materials, and stirring for a certain time at the rotating speed of 400-600rpm to obtain the waterproof spray.
Wherein, the fluorocarbon resin is added into the organic solvent A and stirred for 30-35min at the rotating speed of 600-1000rpm, and then other raw materials are added and stirred for 10-20min at the rotating speed of 400-600rpm, so as to promote the dissolution of the raw materials, shorten the stirring time and save the stirring energy consumption.
The third purpose of the invention is realized by the following technical scheme: the application of the waterproof spraying agent is to be applied to a spraying tank, and the waterproof spraying agent is used for preventing water on the surface of fabric, leather, bags or shoes.
The invention has the beneficial effects that: the waterproof spray can be used at normal temperature, and a waterproof breathable film is formed after the waterproof spray is coated, so that the waterproof effect is improved, and the waterproof aging is longer.
The preparation method of the waterproof spray is simple to operate, convenient to control, high in production efficiency, low in production cost and applicable to large-scale production.
The waterproof spray is applied to a spray can, acts on fabric surface waterproofing, leather surface waterproofing, bag surface waterproofing or shoe material surface waterproofing, is convenient to use, and is suitable for household use.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A waterproof spray comprises the following raw materials in parts by weight:
the fluorocarbon resin is fluoroether resin and acrylic acid fluorinated resin according to the weight ratio of 5: 1.5 mixing; the fluoroether resin has a weight average molecular weight of 8000, and the acrylic fluorinated resin has a weight average molecular weight of 15000.
The fluoroether resin is trifluoroethylene-vinyl ether copolymer.
The acrylic fluorinated resin is prepared by the following method:
(R1) weighing 26 parts of butyl acrylate, 35 parts of styrene, 8 parts of glycidyl methacrylate, 18 parts of hydroxypropyl acrylate, 2 parts of acrylic acid, 2.5 parts of initiator, 18 parts of fluorine-containing acrylic acid monomer and 90 parts of organic solvent B according to parts by weight for later use;
(R2), taking butyl acrylate, styrene, glycidyl methacrylate, hydroxypropyl acrylate, acrylic acid, part of initiator and part of organic solvent B, and uniformly mixing to obtain a component A;
(R3), uniformly mixing the fluorine-containing acrylic monomer, the rest of initiator and the rest of organic solvent B to obtain a component B;
(R4), heating a part of the component A to 79 ℃, stirring for 45min, maintaining the temperature of 82 ℃, adding the component B and the rest of the component A, stirring for 90min, and cooling to room temperature to obtain the acrylic fluorinated resin.
The weight ratio of the initiator used in the step (R2) to the initiator used in the step (R3) is 1: 0.8; the weight ratio of the using amount of the organic solvent B in the step (R2) to the using amount of the organic solvent B in the step (R3) is 1: 1.5; in the step (R4), the ratio of the amount of a part of component a to the amount of the remaining component a in parts by weight is 1: 5.
the initiator is benzoyl peroxide; the fluorine-containing acrylic monomer is selected from dodecafluoroheptyl acrylate and dodecafluoroheptyl methacrylate in a weight ratio of 1: 4, mixing; the organic solvent B is xylene and propylene glycol monomethyl ether acetate according to a weight ratio of 2: 4, and mixing.
The acrylic resin is thermoplastic acrylic resin with the relative molecular weight of 105000, the viscosity of 230s, the acid value of 2mgKOH/g and the Tg value of 41 ℃.
The organic solvent A is isohexane and butyl acetate according to the weight ratio of 1: 2.5 mixing.
The other auxiliary agents comprise 1.5 parts of dispersing agent and 1.5 parts of defoaming agent by weight.
The dispersing agent is sodium dodecyl benzene sulfonate; the defoaming agent is BYK-085.
The preparation method of the waterproof spray comprises the following steps:
(S1), weighing the raw materials in parts by weight for later use;
(S2), adding fluorocarbon resin into the organic solvent A, stirring at the rotating speed of 800rpm for 32min, adding other raw materials, and stirring at the rotating speed of 500rpm for 15min to obtain the waterproof spray.
The waterproof spraying agent is applied to a spraying tank, and acts on the surface of a shoe material to prevent water.
Example 2
A waterproof spray comprises the following raw materials in parts by weight:
20 parts of fluorocarbon resin
1 part of polysilazane
55 parts of an organic solvent A.
The fluorocarbon resin is fluoroether resin and acrylic acid fluorinated resin according to the weight ratio of 5: 1, mixing; the weight average molecular weight of the fluoroether resin is 5000, and the weight average molecular weight of the acrylic fluorinated resin is 5000.
The fluoroether resin is tetrafluoroethylene-vinyl ether copolymer.
The acrylic fluorinated resin is prepared by the following method:
(R1) weighing 25 parts of butyl acrylate, 30 parts of styrene, 5 parts of glycidyl methacrylate, 10 parts of hydroxypropyl acrylate, 1 part of acrylic acid, 2 parts of initiator, 10 parts of fluorine-containing acrylic acid monomer and 80 parts of organic solvent B according to parts by weight for later use;
(R2), taking butyl acrylate, styrene, glycidyl methacrylate, hydroxypropyl acrylate, acrylic acid, part of initiator and part of organic solvent B, and uniformly mixing to obtain a component A;
(R3), uniformly mixing the fluorine-containing acrylic monomer, the rest of initiator and the rest of organic solvent B to obtain a component B;
(R4), heating a part of the component A to 78 ℃, stirring for 30-60min, maintaining the temperature at 80 ℃, adding the component B and the rest of the component A, stirring for 80min, and cooling to room temperature to obtain the acrylic fluorinated resin.
The weight ratio of the initiator used in the step (R2) to the initiator used in the step (R3) is 1: 0.5; the weight ratio of the using amount of the organic solvent B in the step (R2) to the using amount of the organic solvent B in the step (R3) is 1: 1; in the step (R4), the ratio of the amount of a part of component a to the amount of the remaining component a in parts by weight is 1: 4.
the initiator is azobisisobutyronitrile; the fluorine-containing acrylic monomer is dodecafluoroheptyl methacrylate; the organic solvent B is xylene and propylene glycol monomethyl ether acetate according to a weight ratio of 2: 3, and mixing.
The organic solvent A is isohexane.
The organic solvent A is isohexane and butyl acetate according to the weight ratio of 1: 2, mixing the components.
The preparation method of the waterproof spray comprises the following steps:
(S1), weighing the raw materials in parts by weight for later use;
(S2), adding fluorocarbon resin into the organic solvent A, stirring at the rotating speed of 600rpm for 30min, adding other raw materials, and stirring at the rotating speed of 400rpm for 10min to obtain the waterproof spray.
The waterproof spraying agent is applied to a spraying can, and acts on the surface of a bag to prevent water.
Example 3
A waterproof spray comprises the following raw materials in parts by weight:
the fluorocarbon resin is fluoroether resin and acrylic acid fluorinated resin according to the weight ratio of 5: 2, mixing; the weight average molecular weight of the fluoroether resin is 20000, and the weight average molecular weight of the acrylic fluorinated resin is 20000.
The fluoroether resin is trifluoroethylene-vinyl ether copolymer.
The acrylic fluorinated resin is prepared by the following method:
(R1) weighing 28 parts of butyl acrylate, 40 parts of styrene, 10 parts of glycidyl methacrylate, 25 parts of hydroxypropyl acrylate, 3 parts of acrylic acid, 3 parts of initiator, 25 parts of fluorine-containing acrylic acid monomer and 100 parts of organic solvent B according to parts by weight for later use;
(R2), taking butyl acrylate, styrene, glycidyl methacrylate, hydroxypropyl acrylate, acrylic acid, part of initiator and part of organic solvent B, and uniformly mixing to obtain a component A;
(R3), uniformly mixing the fluorine-containing acrylic monomer, the rest of initiator and the rest of organic solvent B to obtain a component B;
(R4), heating a part of the component A to 80 ℃, stirring for 60min, maintaining the temperature of 85 ℃, adding the component B and the rest of the component A, stirring for 100min, and cooling to room temperature to obtain the acrylic fluorinated resin.
The weight ratio of the initiator used in the step (R2) to the initiator used in the step (R3) is 1: 1; the weight ratio of the using amount of the organic solvent B in the step (R2) to the using amount of the organic solvent B in the step (R3) is 1: 2; in the step (R4), the ratio of the amount of a part of component a to the amount of the remaining component a in parts by weight is 1: 6.
the initiator is benzoyl peroxide; the fluorine-containing acrylic monomer is selected from dodecafluoroheptyl acrylate and dodecafluoroheptyl methacrylate in a weight ratio of 1: 5, mixing; the organic solvent B is xylene and propylene glycol monomethyl ether acetate according to a weight ratio of 2: 5, mixing the components.
The acrylic resin is thermoplastic acrylic resin with the relative molecular weight of 120000, the viscosity of 250s, the acid value of 3mgKOH/g and the Tg value of 42 ℃.
The organic solvent A is isohexane and butyl acetate according to the weight ratio of 1: 3, and mixing.
Each part of the other auxiliary agents comprises 2 parts of dispersing agent and 2 parts of defoaming agent.
The dispersant is polysorbate-80; the defoaming agent is BYK-1730.
The preparation method of the waterproof spray comprises the following steps:
(S1), weighing the raw materials in parts by weight for later use;
(S2), adding fluorocarbon resin into the organic solvent A, stirring at the rotating speed of 1000rpm for 35min, adding other raw materials, and stirring at the rotating speed of 600rpm for 20min to obtain the waterproof spray.
The waterproof spray is applied to a spray can, and acts on the surface of fabric to prevent water.
Example 4
A waterproof spray comprises the following raw materials in parts by weight:
the fluorocarbon resin is fluoroether resin and acrylic acid fluorinated resin according to the weight ratio of 5: 1.2 mixing; the weight average molecular weight of the fluoroether resin is 12000, and the weight average molecular weight of the acrylic fluorinated resin is 8000.
The fluoroether resin is trifluoroethylene-vinyl ether copolymer.
The acrylic fluorinated resin is prepared by the following method:
(R1) weighing 27 parts of butyl acrylate, 38 parts of styrene, 6 parts of glycidyl methacrylate, 22 parts of hydroxypropyl acrylate, 1.2 parts of acrylic acid, 2.2 parts of initiator, 23 parts of fluorine-containing acrylic acid monomer and 95 parts of organic solvent B according to parts by weight for later use;
(R2), taking butyl acrylate, styrene, glycidyl methacrylate, hydroxypropyl acrylate, acrylic acid, part of initiator and part of organic solvent B, and uniformly mixing to obtain a component A;
(R3), uniformly mixing the fluorine-containing acrylic monomer, the rest of initiator and the rest of organic solvent B to obtain a component B;
(R4), heating a part of the component A to 80 ℃, stirring for 32min, maintaining the temperature of 85 ℃, adding the component B and the rest of the component A, stirring for 85min, and cooling to room temperature to obtain the acrylic fluorinated resin.
The weight ratio of the initiator used in the step (R2) to the initiator used in the step (R3) is 1: 0.9; the weight ratio of the using amount of the organic solvent B in the step (R2) to the using amount of the organic solvent B in the step (R3) is 1: 1.8; in the step (R4), the ratio of the amount of a part of component a to the amount of the remaining component a in parts by weight is 1: 4.5.
the initiator is benzoyl peroxide; the fluorine-containing acrylic monomer is selected from dodecafluoroheptyl acrylate and dodecafluoroheptyl methacrylate in a weight ratio of 1: 4, mixing; the organic solvent B is xylene and propylene glycol monomethyl ether acetate according to a weight ratio of 2: 3.5 mixing.
The acrylic resin is thermoplastic acrylic resin with the relative molecular weight of 90000, the viscosity of 220s, the acid value of 1.5mgKOH/g and the Tg value of 40 ℃.
The organic solvent A is isohexane and butyl acetate according to the weight ratio of 1: 3, and mixing.
The other auxiliary agents comprise 1.2 parts of dispersing agent and 1.2 parts of defoaming agent by weight.
The dispersing agent is sodium dodecyl benzene sulfonate; the defoaming agent is BYK-085.
The preparation method of the waterproof spray comprises the following steps:
(S1), weighing the raw materials in parts by weight for later use;
(S2), adding fluorocarbon resin into the organic solvent A, stirring at 680rpm for 34min, adding other raw materials, and stirring at 450rpm for 18min to obtain the waterproof spray.
The waterproof spraying agent is applied to a spraying tank, and acts on the surface of a shoe material to prevent water.
Comparative example 1
This comparative example differs from example 1 in that: the waterproof spray does not contain polysilazane.
Comparative example 2
This comparative example differs from example 1 in that: in the waterproof spray, the weight part of polysilazane is 5 parts.
Comparative example 3
This comparative example differs from example 1 in that: the fluorocarbon resin is a trifluoroethylene-vinyl ether copolymer and a fluorinated acrylate resin CN4200, and the weight ratio of the fluorocarbon resin to the fluorinated acrylate resin is 5: 1.5 mixing.
Example 5
After the waterproof sprays prepared in examples 1 to 4 and comparative examples 1 to 3 were filled in a spray can, the waterproof breathable films were tested for their waterproofness, breathability and long-lasting waterproofness; wherein, a spraying experiment is carried out on the tin plate, and after the tin plate is illuminated and dried into a waterproof breathable film, the waterproof performance and the long-acting waterproof performance of the tin plate are tested; the surface of the woven fabric was subjected to a spraying test, and after the surface was subjected to illumination drying, the air permeability difference before and after spraying was measured (air permeability difference is air permeability of the woven fabric before spraying — air permeability of the woven fabric after spraying), and the measurement method was as follows:
water resistance: the water droplet size was 5. mu.L as a static contact angle of the film layer with respect to water, measured by a contact angle measuring instrument model JC2000C1, and the average value was obtained in degrees after 3 measurements.
Long-acting water resistance: the tinplate with the waterproof breathable film is respectively treated in an oven at 60 ℃ for 72h and 168h, and then the waterproof property of the tinplate is respectively tested.
Air permeability: the air permeability was measured and calculated in mm/s at a pressure drop of 100Pa according to the measurement of the air permeability of the GB/T5453 fabric.
The test results are shown in table 1 below:
TABLE 1
As can be seen from the above table 1, the waterproof breathable film sprayed by the waterproof spray of the invention has good waterproof effect and good breathable effect.
Compared with the comparative example 1, the contact angle of the waterproof breathable film in the example 1 is reduced by 5.2 percent after the waterproof breathable film is baked at 60 ℃ for 168 hours, and the contact angle of the waterproof breathable film in the comparative example 1 is reduced by 59.2 percent, which shows that the added polysilazane has a great promotion effect on the aging of the waterproof effect.
Compared with the comparative example 2, the contact angle of the waterproof breathable film in the example 1 is 153 degrees, and the contact angle of the waterproof breathable film in the comparative example 2 is 142 degrees, which shows that the polysilazane has an inhibiting effect on the waterproof effect, so that the polysilazane is controlled to be 1-3 parts by weight, which is beneficial to the waterproof effect and the waterproof aging.
Compared with comparative example 3, the water-proof effect, the water-proof aging and the air permeability of example 1 are all better than those of comparative example 3, which shows that the fluoroether resin and the special acrylic fluorinated resin of the invention are better mixed according to the weight ratio.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. A waterproof spray characterized by: the feed comprises the following raw materials in parts by weight:
2. the water-resistant spray according to claim 1, wherein: the fluorocarbon resin is fluoroether resin and acrylic acid fluorinated resin according to the weight ratio of 5: 1-2, mixing; the weight average molecular weight of the fluorocarbon resin is 5000-.
3. The waterproof spray according to claim 2, wherein: the acrylic fluorinated resin is prepared by the following method:
(R1) weighing 25-28 parts of butyl acrylate, 30-40 parts of styrene, 5-10 parts of glycidyl methacrylate, 10-25 parts of hydroxypropyl acrylate, 1-3 parts of acrylic acid, 2-3 parts of initiator, 10-25 parts of fluorine-containing acrylic acid monomer and 80-100 parts of organic solvent B according to parts by weight for later use;
(R2), taking butyl acrylate, styrene, glycidyl methacrylate, hydroxypropyl acrylate, acrylic acid, part of initiator and part of organic solvent B, and uniformly mixing to obtain a component A;
(R3), uniformly mixing the fluorine-containing acrylic monomer, the rest of initiator and the rest of organic solvent B to obtain a component B;
(R4), heating a part of the component A to 78-80 ℃, stirring for a certain time, maintaining the temperature of 80-85 ℃, adding the component B and the rest of the component A, stirring for a certain time, and cooling to room temperature to obtain the acrylic fluorinated resin.
4. A water-resistant spray according to claim 3, wherein: the initiator is azobisisobutyronitrile or benzoyl peroxide; the fluorine-containing acrylic monomer is at least one of dodecafluoroheptyl acrylate, dodecafluoroheptyl methacrylate, perfluoroalkyl ethyl acrylate, hexafluorobutyl acrylate and trifluoroethyl acrylate; the organic solvent B is xylene and propylene glycol monomethyl ether acetate according to a weight ratio of 2: 3-5, mixing.
5. The water-resistant spray according to claim 1, wherein: the acrylic resin is thermoplastic acrylic resin with the relative molecular weight of 85000-120000, the viscosity of 200-250s, the acid value of 1-3mgKOH/g and the Tg value of 40-42 ℃.
6. The water-resistant spray according to claim 1, wherein: the organic solvent A is at least one of isohexane, n-heptane, cyclohexane, xylene, butyl acetate and n-butyl ether.
7. The water-resistant spray according to claim 1, wherein: each part of the other auxiliary agents comprises 1-2 parts of dispersing agent and 1-2 parts of defoaming agent.
8. The water-resistant spray according to claim 7, wherein: the dispersant is sodium dodecyl benzene sulfonate, polyethylene glycol 2000 or polysorbate-80; the defoaming agent is BYK-085, BYK-070 or BYK-1730.
9. A method of preparing a waterproof spray according to any one of claims 1 to 8, wherein: the method comprises the following steps:
(S1), weighing the raw materials in parts by weight for later use;
(S2), adding fluorocarbon resin into the organic solvent A, stirring for a certain time at the rotating speed of 600-1000rpm, adding other raw materials, and stirring for a certain time at the rotating speed of 400-600rpm to obtain the waterproof spray.
10. Use of a water-resistant spray according to any one of claims 1 to 8, characterized in that: the waterproof spraying agent is applied to a spraying tank, and acts on fabric surface waterproofing, leather surface waterproofing and shoe and bag surface waterproofing.
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| US4824728A (en) * | 1987-10-09 | 1989-04-25 | Desoto, Inc. | Multilayer durable fluorocarbon coatings |
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| US4824728A (en) * | 1987-10-09 | 1989-04-25 | Desoto, Inc. | Multilayer durable fluorocarbon coatings |
| CN102532397A (en) * | 2010-12-10 | 2012-07-04 | 深圳市嘉达高科产业发展有限公司 | Resin for low surface energy organic fluorine silicone antifouling coating, and preparation process thereof |
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