CN114525098A - Single-component water-based flocking adhesive, flocking member and preparation method of flocking member - Google Patents
Single-component water-based flocking adhesive, flocking member and preparation method of flocking member Download PDFInfo
- Publication number
- CN114525098A CN114525098A CN202210201964.7A CN202210201964A CN114525098A CN 114525098 A CN114525098 A CN 114525098A CN 202210201964 A CN202210201964 A CN 202210201964A CN 114525098 A CN114525098 A CN 114525098A
- Authority
- CN
- China
- Prior art keywords
- parts
- flocking
- component water
- flocking adhesive
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
- B05D1/06—Applying particulate materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a single-component water-based flocking adhesive, a flocking member and a preparation method thereof, and relates to the technical field of flocking adhesives. The single-component water-based flocking adhesive is mainly prepared from water-based epoxy resin, a water-based polyurethane dispersion, a film-forming assistant, polyethyleneimine, a thickening agent and other raw materials in specific amounts, and has excellent flocking fastness, wear resistance, heat resistance and cleaning agent scrubbing resistance through the cooperation of the raw materials. The invention also provides a preparation method of the single-component water-based flocking adhesive, which is simple in process, convenient to operate and suitable for industrial mass production. The invention also provides a flocking member which is prepared from the single-component water-based flocking adhesive.
Description
Technical Field
The invention relates to the technical field of flocking adhesives, in particular to a single-component water-based flocking adhesive, a flocking member and a preparation method of the single-component water-based flocking adhesive.
Background
The existing water-based flocking adhesive for automobile flocking interior decoration mainly takes water-based acrylate and water-based polyurethane as main materials. The water-based acrylate emulsion is low in price, but the adhesive film is hard, poor in wear resistance and poor in water resistance and solvent resistance. The aqueous polyurethane adhesive film is softer, so that flocked parts prepared by the aqueous polyurethane adhesive film have general wear resistance. And the water resistance of the urethane is poor because the urethane of the urethane is easily hydrolyzed. In addition, in order to ensure the heat resistance, the heat-resistant composite material is mostly applied in a two-component form, a certain operable time exists, and the complexity of the actual use process is increased.
Accordingly, the present invention is directed to solving at least one of the problems set forth above.
Disclosure of Invention
The first objective of the present invention is to provide a single-component water-based flocking adhesive to alleviate the above technical problems in the prior art.
The second purpose of the invention is to provide a preparation method of the single-component water-based flocking adhesive.
A third object of the present invention is to provide a flocked article.
The fourth purpose of the invention is to provide a preparation method of the flocked member.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a single-component water-based flocking adhesive which comprises the following raw materials in parts by weight:
32-62 parts of waterborne epoxy resin, 32-62 parts of waterborne polyurethane dispersoid, 3-10 parts of film-forming additive, 0.2-1.0 part of polyethyleneimine and 0.1-5 parts of thickening agent.
Further, on the basis of the technical scheme, the raw materials of the single-component water-based flocking adhesive also comprise 0.5-5 parts by weight of an emulsifier;
and/or the raw material of the single-component water-based flocking adhesive also comprises a wetting agent with the weight part of 0.1-5.
Further, on the basis of the technical scheme of the invention, the single-component water-based flocking adhesive comprises the following raw materials in parts by weight:
35-60 parts of waterborne epoxy resin, 35-60 parts of waterborne polyurethane dispersion, 0.5-4 parts of emulsifier, 4-9 parts of film-forming assistant, 0.3-0.9 part of polyethyleneimine, 0.2-4.5 parts of wetting agent and 0.2-4.5 parts of thickening agent.
Further, on the basis of the technical scheme of the invention, the solid content of the waterborne epoxy resin is 30-70%;
preferably, the waterborne epoxy resin comprises a brand Zhan new BECKOPOXTMWaterborne epoxy resins of EP2384w/57 WA;
preferably, the thermal activation temperature of the aqueous polyurethane in the aqueous polyurethane dispersion is 40-90 ℃;
preferably, the aqueous polyurethane dispersion comprises an aqueous polyurethane dispersion under the trade name wanhua chemical Adwel 1630A.
Further, on the basis of the above technical scheme of the present invention, the film-forming assistant comprises any one or a combination of at least two of an alcohol ester film-forming assistant, an alcohol film-forming assistant or an alcohol ether film-forming assistant, preferably comprises an alcohol ester film-forming assistant, and more preferably comprises an alcohol ester twelve;
preferably, the crystallization temperature of the polyethyleneimine is-10 ℃ to 5 ℃;
preferably, the polyethyleneimine comprises polyethyleneimine under the trade name basf Polymin SK;
preferably, the thickener is any one or a combination of at least two of polyurethane associative thickener, polyacrylic acid type thickener or cellulose type thickener;
preferably, the thickener comprises a Rohm and Haas RM-8W.
Further, on the basis of the above technical solution of the present invention, the emulsifier includes any one or a combination of at least two of an anionic emulsifier, a nonionic emulsifier, or a natural emulsifier;
preferably, the emulsifier comprises an emulsifier under the trade name basf AEO-9;
preferably, the wetting agent comprises an anionic wetting agent and/or a non-ionic wetting agent;
preferably, the wetting agent comprises a digat Tego 270 brand wetting agent.
The invention also provides a preparation method of the single-component water-based flocking adhesive, which comprises the following steps:
and mixing the raw materials according to the formula ratio to obtain the single-component water-based flocking adhesive.
Further, on the basis of the technical scheme of the invention, the preparation method of the single-component water-based flocking adhesive comprises the following steps:
(a) mixing the water-based epoxy resin, polyethyleneimine and an optional emulsifier, and reacting to obtain a mixture A;
(b) mixing the aqueous polyurethane dispersion with the mixture A to obtain a mixture B;
(c) and mixing the mixture B, the film-forming aid, the thickening agent and the optional wetting agent to obtain the single-component water-based flocking adhesive.
Further, on the basis of the above technical scheme of the present invention, in the step (a), preferably, in the step (a), the reaction temperature is 35 to 45 ℃, and the reaction time is 30 to 60 min;
preferably, in step (b), the mixing time is 50-60 min;
preferably, in step (c), the mixing time is 50-60 min;
preferably, the viscosity of the single-component water-based flocking adhesive is 3000-5000mPa & s.
The invention also provides a flocking member which is prepared from the single-component water-based flocking adhesive.
The invention also provides a preparation method of the flocked member, which comprises the following steps:
spraying the single-component water-based flocking adhesive on the surface of the pretreated substrate, then carrying out electrostatic flocking, and heating and drying the substrate subjected to electrostatic flocking to obtain a flocked part;
preferably, the wet film thickness of the single-component water-based flocking adhesive sprayed on the surface of the pretreated substrate is 120-150g/m2；
Preferably, the voltage of the electrostatic flocking is 2-4 kv/cm;
preferably, the drying temperature is 75-90 deg.C, and the drying time is 25-35 min.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a single-component water-based flocking adhesive which is mainly prepared from raw materials such as water-based epoxy resin, water-based polyurethane dispersoid, film-forming assistant, polyethyleneimine and thickener, wherein the water-based epoxy resin and the water-based polyurethane dispersoid are compounded, so that the flexibility of the water-based polyurethane is kept, the modulus of an adhesive film is increased by adding the water-based epoxy resin, the hardness of the flocking adhesive is improved, and the flocking fastness and the water resistance of a flocked part are further improved; meanwhile, the polyethyleneimine can modify the waterborne epoxy resin, so that partial epoxy groups in the waterborne epoxy resin react with imino groups, molecular chains of the waterborne epoxy resin are enlarged, and partial IPN interpenetrating network structure is formed after the polyethyleneimine and waterborne polyurethane molecules are intertwined, so that the strength of the glue film body is further increased.
The water-based flocking adhesive is a single-component system, is simple to use and convenient to operate, and can enable a flocking member prepared from the water-based flocking adhesive to achieve excellent flocking fastness, wear resistance, heat resistance and cleaning agent scrubbing resistance without adding a curing agent through the matching of the raw materials.
(2) The invention also provides a preparation method of the single-component water-based flocking adhesive, which has the advantages of simple process and convenient operation and is suitable for industrial mass production.
(3) The invention also provides a flocking member which is prepared from the single-component water-based flocking adhesive. In view of the advantages of the single-component water-based flocking adhesive, the flocking member can achieve excellent flocking fastness, wear resistance, heat resistance and cleaning agent scrubbing resistance.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. Those who do not specify the conditions are performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
According to a first aspect of the invention, a single-component water-based flocking adhesive is provided, which comprises the following raw materials in parts by weight:
32-62 parts of waterborne epoxy resin, 32-62 parts of waterborne polyurethane dispersoid, 3-10 parts of film-forming additive, 0.2-1.0 part of polyethyleneimine and 0.1-5 parts of thickening agent.
The single-component water-based flocking adhesive is mainly prepared from raw materials such as water-based epoxy resin, water-based polyurethane dispersoid, film forming additive, polyethyleneimine and thickener, wherein the water-based epoxy resin and the water-based polyurethane dispersoid are compounded, so that the flexibility of the water-based polyurethane is kept, the modulus of an adhesive film is increased by adding the water-based epoxy resin, the hardness of the flocking adhesive is improved, and the flocking fastness and the water resistance of a flocked part are further improved; meanwhile, the polyethyleneimine can modify the aqueous epoxy resin, so that partial epoxy groups in the aqueous epoxy resin react with imino groups, molecular chains of the aqueous epoxy resin are expanded, and partial IPN interpenetrating network structures are formed after the polyethyleneimine is intertwined with aqueous polyurethane molecules, so that the strength of the adhesive film body is further increased, and the addition of the polyethyleneimine can also increase the adhesive force of the flocking adhesive to fluff and a matrix (such as an automotive interior framework), so that the flocking fastness and the scratch resistance of a flocked part are improved;
the single-component water-based flocking adhesive provided by the invention is a single-component system, and can achieve excellent flocking fastness, wear resistance, heat resistance and cleaning agent scrubbing resistance through the matching of the raw materials without adding a curing agent.
The amount of each raw material used is also limited. Typical but non-limiting parts by weight of the waterborne epoxy resin are 32 parts, 34 parts, 35 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 45 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 55 parts, 56 parts, 58 parts, 60 parts, 61 parts, or 62 parts. If the amount of the water-based epoxy resin is too small (less than 32 parts), the adhesive film is easily soft, and the flocking fastness and the scratch resistance are poor, and if the amount of the water-based epoxy resin is too large (more than 62 parts), the adhesive film is easily brittle and the toughness is insufficient.
Typical but non-limiting parts by weight of the aqueous polyurethane dispersion are 32 parts, 34 parts, 35 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 45 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 55 parts, 56 parts, 58 parts, 60 parts, 61 parts, or 62 parts. If the amount of the aqueous polyurethane dispersion is too small (less than 32 parts), the film tends to become brittle and have insufficient toughness, and if the amount of the aqueous polyurethane dispersion is too large (more than 62 parts), the film tends to be soft and the flock fastness and scratch resistance tend to deteriorate.
Typical but non-limiting parts by weight of polyethyleneimine are 0.2 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts. If the amount of the polyethyleneimine is too small (less than 0.2 parts), the adhesion to the framework is liable to decrease, and the flock fastness is liable to decrease, and if the amount of the polyethyleneimine is too large (more than 10 parts), the system of the flock glue emulsion is liable to be unstable, and small particles appear.
Typical but non-limiting parts by weight of the coalescent are 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts.
Typical but non-limiting parts by weight of the thickener are 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts or 5 parts.
It should be noted that the term "comprising" in the present invention means that it may include other materials in addition to the raw materials, and these components give the one-component water-based flocking adhesive different properties. In addition, the term "comprising" as used herein may be replaced by "being" or "made from … …" in the closed sense.
As an optional embodiment of the invention, the raw material of the single-component water-based flocking adhesive also comprises 0.5-5 parts by weight of an emulsifier;
and/or the raw material of the single-component water-based flocking adhesive also comprises 0.1-5 parts of wetting agent.
The term "and/or" means that the raw materials of the one-component water-based flocking adhesive can only comprise the emulsifier, can also comprise the wetting agent and can also comprise the emulsifier and the wetting agent besides the raw materials (the water-based epoxy resin, the water-based polyurethane dispersion, the film-forming assistant, the polyethyleneimine and the thickening agent).
As a preferred embodiment of the invention, the single-component water-based flocking adhesive comprises the following raw materials in parts by weight:
35-60 parts of waterborne epoxy resin, 35-60 parts of waterborne polyurethane dispersion, 0.5-4 parts of emulsifier, 4-9 parts of film-forming assistant, 0.3-0.9 part of polyethyleneimine, 0.2-4.5 parts of wetting agent and 0.2-4.5 parts of thickening agent.
As an alternative embodiment of the invention, the solid content of the waterborne epoxy resin is from 30 to 70%. Waterborne epoxy resins typically have, but are not limited to, a solids content of 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%.
As an alternative embodiment of the present invention, the waterborne epoxy resin comprises BECKOPOXTMEP2384w/57 WA.
Preferably, the thermal activation temperature of the aqueous polyurethane in the aqueous polyurethane dispersion is 40-90 ℃; typical but non-limiting thermal activation temperatures are 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C or 90 deg.C.
As an alternative embodiment of the invention, the aqueous polyurethane dispersion comprises an aqueous polyurethane dispersion under the trade name wanhua chemical Adwel 1630A.
As an alternative embodiment of the present invention, the coalescent includes any one or a combination of at least two of an alcohol ester-based coalescent, an alcohol coalescent, or an alcohol ether-based coalescent, and preferably includes an alcohol ester-based coalescent.
As a preferred embodiment of the present invention, the coalescent includes an alcohol ester twelve.
As an alternative embodiment of the invention, the crystallization temperature of the polyethyleneimine is-10 ℃ to 5 ℃; typical but not limiting crystallization temperatures for polyethyleneimine are-10 ℃, -8 ℃, -5 ℃, -2 ℃, 0 ℃, 2 ℃, 4 ℃ or 5 ℃.
As an alternative embodiment of the invention, the polyethyleneimine includes polyethyleneimine under the trademark Basff Polymin SK.
As an alternative embodiment of the present invention, the thickener includes any one of a polyurethane associative thickener, a polyacrylic acid type thickener, or a cellulose type thickener, or a combination of at least two thereof.
As an alternative embodiment of the invention, the thickener comprises a Rohm and Haas RM-8W thickener.
As an alternative embodiment of the present invention, the emulsifier comprises any one of an anionic emulsifier, a non-ionic emulsifier or a natural emulsifier or a combination of at least two thereof.
As an alternative embodiment of the invention, the emulsifier comprises a emulsifier under the trade name Pasteur AEO-9.
As an alternative embodiment of the present invention, the emulsifier comprises any one of an anionic emulsifier, a non-ionic emulsifier or a natural emulsifier or a combination of at least two thereof.
As an alternative embodiment of the invention, the wetting agent comprises an anionic wetting agent and/or a non-ionic wetting agent.
As an alternative embodiment of the invention, the wetting agent comprises a digatego 270 brand wetting agent.
The water-based flocking adhesive has better flocking fastness and scraping resistance through the limitation of the specific types of the raw materials.
According to a second aspect of the present invention, there is also provided a preparation method of the above single-component water-based flocking adhesive, including the following steps:
and mixing the raw materials according to the formula ratio to obtain the single-component water-based flocking adhesive.
The preparation method has simple process and convenient operation, and is suitable for industrial production.
As an optional embodiment of the present invention, the preparation method of the single-component water-based flocking adhesive comprises the following steps:
(a) mixing the water-based epoxy resin, polyethyleneimine and an optional emulsifier, and reacting to obtain a mixture A;
(b) mixing the aqueous polyurethane dispersion with the mixture A to obtain a mixture B;
(c) and mixing the mixture B, the film-forming aid, the thickening agent and the optional wetting agent to obtain the single-component water-based flocking adhesive.
By further limiting the steps in the preparation method, the prepared water-based flocking adhesive has better flocking fullness.
The term "optional emulsifier" as used herein means that an emulsifier may or may not be added, and the term "optional wetting agent" means that a wetting agent may or may not be added, and whether or not the emulsifier is added may be determined as necessary.
As an alternative embodiment of the present invention, in the step (a), the reaction temperature is 35-45 ℃ and the reaction time is 30-60 min.
As an alternative embodiment of the present invention, in step (b), the mixing time is 50-60 min.
As an alternative embodiment of the present invention, in step (c), the mixing time is 50-60 min.
In an optional embodiment of the invention, the viscosity of the single-component water-based flocking adhesive is 3000-5000mPa & s.
Typical, but not limiting, single-component aqueous flocking adhesives have a viscosity of 3000 mPas, 3200 mPas, 3400 mPas, 3500 mPas, 3600 mPas, 3800 mPas, 4000 mPas, 4200 mPas, 4400 mPas, 4500 mPas, 4600 mPas, 4800 mPas or 5000 mPas.
Through the further restriction on the viscosity of the single-component water-based flocking adhesive, the water-based flocking adhesive can achieve excellent fullness of flocked parts under the condition of keeping good leveling property.
According to a third aspect of the invention, the flocking member is prepared by adopting the single-component water-based flocking adhesive.
In view of the advantages of the single-component water-based flocking adhesive, the flocking member can achieve excellent flocking fastness, wear resistance, heat resistance and cleaning agent scrubbing resistance.
The flocked member provided by the invention can be used in various fields, such as automobile interiors, spectacle cases, traveling cases and the like.
According to a fourth aspect of the present invention, there is also provided a method for preparing the flocked member, including the following steps:
and spraying the single-component water-based flocking adhesive on the surface of the pretreated substrate, then carrying out electrostatic flocking, and then heating and drying the substrate subjected to electrostatic flocking to obtain the flocked part.
It should be noted that, in the heating and drying of the substrate after electrostatic flocking, the epoxy group in the aqueous epoxy resin will react with the residual amino group in the aqueous polyurethane molecule to generate cross-linking, thereby improving the flocking fastness and heat resistance of the flocked article.
As an optional implementation mode of the invention, the wet film thickness of the single-component water-based flocking adhesive sprayed on the pretreated substrate surface is 120-2。
A typical but non-limiting wet film thickness is 120g/m2、130g/m2、140g/m2Or 150g/m2。
As an alternative embodiment of the invention, the electrostatic flocking is carried out at a voltage of 2-4 kv/cm. Typical but non-limiting electrostatic flocking voltages are 2kv/cm, 2.5kv/cm, 3kv/cm, 3.5kv/cm, or 4 kv/cm.
As an alternative embodiment of the invention, the drying temperature is 75-90 ℃ and the drying time is 25-35 min.
Typical but non-limiting drying temperatures are 75 ℃, 80 ℃, 85 ℃ or 90 ℃, and typical but non-limiting drying times are 25min, 30min or 35 min.
The present invention will be further described with reference to specific examples and comparative examples.
Example 1
The embodiment provides a single-component water-based flocking adhesive, which comprises the following raw materials in parts by weight:
40 parts of waterborne epoxy resin, 54 parts of waterborne polyurethane dispersion, 0.5 part of emulsifier, 4.5 parts of film-forming assistant, 0.5 part of polyethyleneimine, 0.3 part of wetting agent and 0.2 part of thickening agent.
Wherein the waterborne epoxy resin has the brand number Zhanxin BECKOPOXTMEP 386w/52 WA; the aqueous polyurethane dispersion is named as Wanhua chemical Adwel 1633; the emulsifier is under the brand name of Pasteur AEO-9; the film-forming additive is alcohol ester twelve; the grade of polyethyleneimine is basf Polymin SN; the grade of the wetting agent is Digao Tego 270; the thickener is sold under the designation Rohm-8W.
Example 2
This example provides a single-component aqueous flock coating except that the grade of the aqueous epoxy resin in example 1 is replaced with BECKOPOXTMEP2384w/57WA, the trade name of the aqueous polyurethane dispersion WAs replaced by Adwel 1630A, the trade name of the polyethyleneimine WAs replaced by Pasteur Polymin SK and the type and amount of the remaining raw materials were the same as in example 1.
Example 3
This example provides a single-component aqueous flocking adhesive, except that in example 2, the weight parts of the aqueous epoxy resin are replaced by 32 parts and the weight parts of the aqueous polyurethane dispersion are replaced by 54 parts and 62 parts, and the types and the amounts of the other raw materials are the same as those in example 2.
Example 4
This example provides a single-component aqueous flocking adhesive, which is prepared by replacing 40 parts by weight of the aqueous epoxy resin and 54 parts by weight of the aqueous polyurethane dispersion in example 2 with 50 parts by weight of the aqueous epoxy resin and 44 parts by weight of the aqueous polyurethane dispersion, and the types and the amounts of the other raw materials are the same as those in example 2.
Example 5
This example provides a single-component aqueous flocking adhesive, except that the weight part of the aqueous epoxy resin in example 2 is replaced by 62 parts from 40 parts, the weight part of the aqueous polyurethane dispersion is replaced by 32 parts from 54 parts, and the kinds and the amounts of the other raw materials are the same as those in example 2.
Example 6
This example provides a single-component aqueous flocking adhesive, except that the weight parts of the aqueous epoxy resin in example 2 are replaced by 47 parts from 40 parts, the weight parts of the aqueous polyurethane dispersion are replaced by 47 parts from 54 parts, and the types and the amounts of the rest raw materials are the same as those in example 2.
Example 7
This example provides a single-component water-based flocking adhesive, except that no emulsifier is added in example 2, and the types and amounts of the other raw materials are the same as those in example 2.
Example 8
This example provides a single-component water-based flocking adhesive, which has the same kind and amount as example 2, except that no wetting agent is added in example 2.
Example 9
This example provides a single-component aqueous flocking adhesive, which is prepared in the same manner and in the same amount as example 2, except that no emulsifier or wetting agent is added to example 2.
Example 10
The embodiment provides a single-component water-based flocking adhesive, which comprises the following raw materials in parts by weight:
40 parts of waterborne epoxy resin, 54 parts of waterborne polyurethane dispersion, 0.5 part of emulsifier, 3.0 parts of film-forming assistant, 0.2 part of polyethyleneimine, 0.3 part of wetting agent and 0.2 part of thickener.
Wherein the waterborne epoxy resin has the brand number Zhanxin BECKOPOXTMEP2384w/57 WA; the aqueous polyurethane dispersion is under the trade mark of Wanhua chemical Adwel 1630A; the emulsifier is under the brand name of Pasteur AEO-9; the film-forming additive is alcohol ester twelve; the grade of polyethyleneimine is basf Polymin SK; the grade of the wetting agent is Digao Tego 270; the thickener is sold under the trademark Rohm-8W.
Example 11
This example provides a single-component water-based flocking adhesive, which is prepared from the same materials as in example 10 except that the weight parts of the film-forming assistant in example 10 are replaced by 3.0 parts and 10.0 parts, and the weight parts of polyethyleneimine are replaced by 0.2 part and 1.0 part, respectively.
Examples 1-11 provide a method for preparing a one-component aqueous flocking adhesive, comprising the steps of:
(a) adding the water-based epoxy resin and an optional emulsifier into a reaction kettle, adding polyethyleneimine while stirring, controlling the reaction temperature to be lower than 45 ℃, and stirring for 60min to obtain a mixture A;
(b) mixing the mixture A and the aqueous polyurethane dispersion, and stirring for 30min to obtain a mixture B;
(c) and (3) sequentially adding the film-forming aid and the optional wetting agent into the mixture B while stirring, slowly adding the thickening agent after stirring for 30min, controlling the viscosity of the thickening agent to be 3000-5000mPa & s, and uniformly stirring to obtain the single-component water-based flocking adhesive.
Example 12 example 22
Examples 12-22 each provide a flock component, prepared using the one-component aqueous flock glue provided in examples 1-11, respectively.
Specifically, examples 12 to 22 provide a method for preparing a flocked member, including the steps of:
(a) scrubbing the surface of a matrix (polypropylene, PP) by using absolute ethyl alcohol, treating the surface of the PP by flame, and standing for later use;
(b) uniformly spraying the single-component water-based flocking adhesive to the surface of the substrate by adopting a W-71 spray gun, wherein the thickness of the wet adhesive is controlled to be 150g/m2Electrostatic flocking (voltage is 3 kv/cm);
(c) and (3) placing the flocked part in a 75 ℃ oven for 30min, and then placing the flocked part at room temperature for 3 days to obtain the flocked part.
Comparative example 1
This comparative example provides a one-component aqueous flocking adhesive, except that the weight part of the aqueous epoxy resin in example 2 was changed from 40 parts to 0 part (i.e., no aqueous epoxy resin was added), the weight part of the aqueous polyurethane dispersion was changed from 54 parts to 94 parts, and the kinds and amounts of the remaining raw materials were the same as those in example 2.
Comparative example 2
The comparative example provides a single-component water-based flocking adhesive, except that the water-based polyurethane dispersion in the example 2 is replaced by 0 part from 54 parts (namely, the water-based polyurethane dispersion is not added), the water-based epoxy resin is replaced by 94 parts from 40 parts by weight, and the types and the use amounts of the rest raw materials are the same as those in the example 2.
Comparative example 3
The comparative example provides a single-component water-based flocking adhesive, except that the polyethyleneimine in the example 2 is replaced by deionized water with equal weight part, and the types and the use amounts of the other raw materials are the same as those in the example 2.
Comparative example 4
The comparative example provides a single-component water-based flocking adhesive, except that the weight part of the water-based epoxy resin in the example 2 is replaced by 24 parts from 40 parts, the weight part of the water-based polyurethane dispersion is replaced by 70 parts from 54 parts, and the types and the use amounts of the rest raw materials are the same as those in the example 2.
Comparative example 5
The comparative example provides a single-component water-based flocking adhesive, except that the weight part of the water-based epoxy resin in the example 2 is replaced by 70 parts from 40 parts, the weight part of the water-based polyurethane dispersion is replaced by 24 parts from 54 parts, and the types and the use amounts of the rest raw materials are the same as those in the example 2.
Comparative example 6
The comparative example provides a single-component water-based flocking adhesive, except that the weight part of polyethyleneimine in the example 2 is replaced by 0.1 part from 0.5 part, and the types and the use amounts of the other raw materials are the same as those in the example 2.
Comparative example 7
The comparative example provides a single-component water-based flocking adhesive, except that the weight part of polyethyleneimine in the example 2 is replaced by 2.0 parts from 0.5 part, and the types and the use amounts of the other raw materials are the same as those in the example 2.
Comparative example 8
The comparative example provides a single-component water-based flocking adhesive, which comprises the following raw materials in parts by weight:
28 parts of waterborne epoxy resin, 65 parts of waterborne polyurethane dispersion, 0.3 part of emulsifier, 2 parts of film-forming assistant, 1.2 parts of polyethyleneimine, 0.3 part of wetting agent and 0.2 part of waterborne thickener.
Comparative examples 1 to 9 provide a single-component aqueous flocking adhesive which is prepared in the same manner as in examples 1 to 11 and is not described herein.
Comparative example 9
The comparative example provides a water-based flocking adhesive, which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 100: 5;
the component A is the single-component water-based flocking adhesive provided in the embodiment 2, and the component B is an isocyanate water-based curing agent.
The aqueous flocking adhesive is used after the component A and the component B are uniformly mixed according to the proportion before use.
Comparative examples 10 to 18
Comparative examples 10 to 18 each provide a flocked member prepared using the one-component aqueous flocking paste provided in comparative examples 1 to 9.
Specifically, the methods for preparing flocked members provided in comparative examples 10 to 18 are the same as those provided in examples 12 to 22, and are not described in detail herein.
In order to verify the technical effects of the respective examples and comparative examples, the following experimental examples were specifically set.
Examples of the experiments
Flock fastness, abrasion resistance, heat resistance, moisture resistance and cleaning agent scrub resistance of the flocked articles provided in each of examples 12 to 22 and comparative examples 10 to 18 were measured.
The test of flocking fastness of the flocked part refers to GB 9286-88, namely, hundreds of grids are scribed on the flocked part, the distance is 2mm, after the flocked part is completely bonded by using a 3M-600 adhesive tape, the flocked part is as close to an angle of 60 degrees as possible, and the flocked part is stably torn away from the adhesive tape within 0.5-1.0 s. The results were ranked from 0 to 5 and the flock fastness of the flocked article varied from strong to weak according to the fluff on the adhesive tape, according to table 1. Three different positions are taken on the flocked part for testing, and the test results are averaged.
TABLE 1
| Grading | Description of the invention |
| 0 | Non-fluff on adhesive tape |
| 1 | The area of the bonded fluff on the adhesive tape is not more than 5 percent (including 5 percent) |
| 2 | The area of the bonded fluff on the adhesive tape is between 5 percent and 15 percent (including 15 percent) |
| 3 | The area of the fluff adhered on the adhesive tape is between 15 and 35 percent (including 35 percent) |
| 4 | The area of the bonding fluff on the adhesive tape is between 35 percent and 65 percent (including 65 percent) |
| 5 | The area of the fluff adhered on the adhesive tape is more than 65 percent |
The test of the wear resistance of the flocked part refers to QC/T711-2004, a 500g weight is selected, the friction frequency is 60LW/min, the moving stroke is 100mm, and the friction is performed for 250 times. After the test was completed, the friction was checked by visual inspection, the observation was recorded, and the test results were expressed in terms of the rating scale in table 2. The grade is from 1 to 5, and the wear resistance is gradually enhanced. Three different positions are taken on the flocked part for testing, and the test results are averaged.
TABLE 2
The method for testing the heat resistance of the flocked part comprises the following steps: placing the flocked part in an oven at 80 ℃ for 24 hours, then placing the flocked part at room temperature for 4 hours, testing the wear resistance, taking three different positions on the flocked part for testing, and taking an average value of test results. The grade is from 1 to 5, and the heat resistance is gradually enhanced.
The method for testing the moisture resistance of the flocked member comprises the following steps: placing the flocked part in a 35 +/-2 ℃ and 95 +/-5% damp and hot environment for 24 hours, then placing the flocked part at room temperature for 4 hours, testing the wear resistance, taking three different positions on the flocked part for testing, and taking the average value of the test results. The grade is from 1 to 5, and the moisture resistance is gradually enhanced.
The method for testing the scrubbing resistance of the flocked part by using the cleaning agent comprises the following steps: and (3) respectively absorbing neutral soap water, isopropanol, petroleum ether and water by using white cotton cloth, scrubbing the flocked sample piece back and forth for 20 times, and judging the scrubbing performance of the cleaning agent resistance according to the swelling and damage of a rubber film of a flocked part. It is also acceptable that the flocked member is restored after the cleaning agent is volatilized when slight damage, slight swelling or whitening of the adhesive film occurs in the cleaning agent resistant process.
The results of the tests of the examples and comparative examples are shown in Table 3.
TABLE 3
As can be seen from the data in table 3, the examples of the present invention provide flocked articles having overall superior performance in all respects to the comparative examples.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The single-component water-based flocking adhesive is characterized by comprising the following raw materials in parts by weight:
32-62 parts of waterborne epoxy resin, 32-62 parts of waterborne polyurethane dispersoid, 3-10 parts of film-forming additive, 0.2-1.0 part of polyethyleneimine and 0.1-5 parts of thickening agent.
2. The single-component water-based flocking adhesive according to claim 1, wherein the raw material of the single-component water-based flocking adhesive further comprises 0.5-5 parts by weight of an emulsifier;
and/or the raw material of the single-component water-based flocking adhesive also comprises a wetting agent with the weight part of 0.1-5.
3. The single-component water-based flocking adhesive according to claim 1, which is characterized by comprising the following raw materials in parts by weight:
35-60 parts of waterborne epoxy resin, 35-60 parts of waterborne polyurethane dispersion, 0.5-4 parts of emulsifier, 4-9 parts of film-forming assistant, 0.3-0.9 part of polyethyleneimine, 0.2-4.5 parts of wetting agent and 0.2-4.5 parts of thickening agent.
4. The one-component water-based flocking adhesive according to any one of claims 1 to 3, wherein the solid content of the water-based epoxy resin is 30-70%;
preferably, the waterborne epoxy resin comprises a brand Zhan new BECKOPOXTMWaterborne epoxy resins of EP2384w/57 WA;
preferably, the thermal activation temperature of the aqueous polyurethane in the aqueous polyurethane dispersion is 40-90 ℃;
preferably, the aqueous polyurethane dispersion comprises an aqueous polyurethane dispersion under the trade name wanhua chemical Adwel 1630A.
5. The one-component aqueous flocking adhesive according to any one of claims 1 to 3, wherein the film forming agent comprises any one of or a combination of at least two of an alcohol ester type film forming agent, an alcohol film forming agent or an alcohol ether type film forming agent, preferably comprises an alcohol ester type film forming agent, and more preferably comprises an alcohol ester twelve;
preferably, the crystallization temperature of the polyethyleneimine is-10 ℃ to 5 ℃;
preferably, the polyethyleneimine comprises polyethyleneimine under the trade name basf Polymin SK;
preferably, the thickener comprises any one of or a combination of at least two of polyurethane associative thickener, polyacrylic acid type thickener or cellulose type thickener;
preferably, the thickener comprises a Rohm and Haas RM-8W.
6. The single-component water-based flocking glue according to claim 2 or 3, wherein the emulsifier comprises any one or a combination of at least two of an anionic emulsifier, a nonionic emulsifier or a natural emulsifier;
preferably, the emulsifier comprises an emulsifier under the trade name basf AEO-9;
preferably, the wetting agent comprises an anionic wetting agent and/or a nonionic wetting agent;
preferably, the wetting agent comprises a digat Tego 270 brand wetting agent.
7. The method for preparing the single-component water-based flocking adhesive as claimed in any one of claims 1 to 6, which comprises the following steps:
and mixing the raw materials according to the formula ratio to obtain the single-component water-based flocking adhesive.
8. The preparation method of the single-component water-based flocking adhesive as claimed in claim 7, which comprises the following steps:
(a) mixing the waterborne epoxy resin, polyethyleneimine and an optional emulsifier, and reacting to obtain a mixture A;
(b) mixing the aqueous polyurethane dispersion with the mixture A to obtain a mixture B;
(c) mixing the mixture B, a film-forming aid, a thickening agent and an optional wetting agent to obtain a single-component water-based flocking adhesive;
preferably, in the step (a), the reaction temperature is 35-45 ℃, and the reaction time is 30-60 min;
preferably, in step (b), the mixing time is 50-60 min;
preferably, in step (c), the mixing time is 50-60 min;
preferably, the viscosity of the single-component water-based flocking adhesive is 3000-5000mPa & s.
9. A flocked article, characterized in that it is prepared from a one-component aqueous flocking adhesive according to any one of claims 1 to 6.
10. The method of making the flocked article in accordance with claim 9, comprising the steps of:
spraying the single-component water-based flocking adhesive on the surface of the pretreated substrate, then carrying out electrostatic flocking, and heating and drying the substrate subjected to electrostatic flocking to obtain a flocked part;
preferably, the wet film thickness of the single-component water-based flocking adhesive sprayed on the surface of the pretreated substrate is 120-150g/m2；
Preferably, the voltage of the electrostatic flocking is 2-4 kv/cm;
preferably, the drying temperature is 75-90 deg.C, and the drying time is 25-35 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210201964.7A CN114525098B (en) | 2022-03-03 | 2022-03-03 | Single-component water-based flocking adhesive, flocking piece and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210201964.7A CN114525098B (en) | 2022-03-03 | 2022-03-03 | Single-component water-based flocking adhesive, flocking piece and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114525098A true CN114525098A (en) | 2022-05-24 |
| CN114525098B CN114525098B (en) | 2023-09-08 |
Family
ID=81627077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210201964.7A Active CN114525098B (en) | 2022-03-03 | 2022-03-03 | Single-component water-based flocking adhesive, flocking piece and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114525098B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629244A (en) * | 2003-12-15 | 2005-06-22 | 财团法人工业技术研究院 | Adhesive containing aromatic aqueous polyurethane dispersion and flock coating method using same |
| CN109233704A (en) * | 2018-09-05 | 2019-01-18 | 嘉善欣达胶业有限公司 | A kind of flock glue and preparation method thereof |
| CN110144189A (en) * | 2019-05-13 | 2019-08-20 | 苏州北极熊汽车用品有限公司 | A kind of water soluble flocking glue and preparation method thereof |
| US20210188064A1 (en) * | 2018-05-11 | 2021-06-24 | Zhenglin Chen | Hydrophobic automobile rubber seal strip flocking belt and preparation method thereof |
-
2022
- 2022-03-03 CN CN202210201964.7A patent/CN114525098B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629244A (en) * | 2003-12-15 | 2005-06-22 | 财团法人工业技术研究院 | Adhesive containing aromatic aqueous polyurethane dispersion and flock coating method using same |
| US20210188064A1 (en) * | 2018-05-11 | 2021-06-24 | Zhenglin Chen | Hydrophobic automobile rubber seal strip flocking belt and preparation method thereof |
| CN109233704A (en) * | 2018-09-05 | 2019-01-18 | 嘉善欣达胶业有限公司 | A kind of flock glue and preparation method thereof |
| CN110144189A (en) * | 2019-05-13 | 2019-08-20 | 苏州北极熊汽车用品有限公司 | A kind of water soluble flocking glue and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李三军: "水性聚氨酯胶粘剂的制备和应用", 胶体与聚合物, vol. 17, no. 03, pages 22 - 23 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114525098B (en) | 2023-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5425969A (en) | Method of coating articles made of polypropylene with an electrically conductive primer and electrostatically applied overcoat | |
| CN110669419A (en) | Water-based acrylic polyurethane coating and preparation method thereof | |
| WO2019142639A1 (en) | Method for forming multilayer coating film | |
| JP7386680B2 (en) | Water-based multi-component polyurethane coating composition | |
| CN110591483A (en) | High-conductivity water-based automobile bumper primer and preparation method thereof | |
| JP2019167389A (en) | Primer coating composition | |
| KR101438711B1 (en) | Functional matter coated textile fabrics and coating method and its coating matter | |
| CN1989212B (en) | Polyurethane coatings with improved interlayer adhesion | |
| WO2019181990A1 (en) | Multi-layer coating film formation method | |
| AU6555294A (en) | Polyurethane-based aqueous multicolor paint | |
| CN112080185A (en) | Waterborne polyurethane industrial paint and preparation method thereof | |
| JP2002506113A5 (en) | ||
| CN112920693B (en) | High-wear-resistance vacuum coating hydroxyl acrylic coating and preparation method and application thereof | |
| CN114525098A (en) | Single-component water-based flocking adhesive, flocking member and preparation method of flocking member | |
| CN105482765A (en) | Waterborne polyurethane adhesive composition and preparing method thereof | |
| CN108977032B (en) | Water-based dual-component high-gloss finish paint for helmet and preparation method thereof | |
| CN115109510B (en) | Dirty-resistant UV paint and preparation method and application thereof | |
| WO2019188574A1 (en) | Coated body | |
| JP3706971B2 (en) | Low temperature curable touch-sensitive paint composition | |
| WO2018181208A1 (en) | Coating composition | |
| CN102702912B (en) | Vapour vehicle priming paint | |
| EP1172403A1 (en) | Paint composition and its use | |
| JP3283306B2 (en) | Adhesive composition for electrostatic flocking | |
| CN114032058A (en) | Bi-component waterborne polyurethane adhesive and application thereof | |
| JP7078331B2 (en) | Paint composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |