CN111218201A - Primer material, preparation method and application thereof, automobile glass bracket and bonding combined material - Google Patents
Primer material, preparation method and application thereof, automobile glass bracket and bonding combined material Download PDFInfo
- Publication number
- CN111218201A CN111218201A CN202010126838.0A CN202010126838A CN111218201A CN 111218201 A CN111218201 A CN 111218201A CN 202010126838 A CN202010126838 A CN 202010126838A CN 111218201 A CN111218201 A CN 111218201A
- Authority
- CN
- China
- Prior art keywords
- acrylic resin
- primer
- carbon black
- catalyst
- solvent
- 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.)
- Pending
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- 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
- C09D5/002—Priming paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- 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
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention discloses a primer coating material, a preparation method and application thereof, an automobile glass bracket and an adhesive combined material, and relates to the technical field of adhesive sealing. The priming paint takes acrylic resin and polymethylene polyphenyl isocyanate as main raw materials; wherein the molecular weight of the acrylic resin is 25000-200000g/mol, and the hydroxyl value of the acrylic resin is 0-10 mgKOH/g; the mass ratio of the acrylic resin to the polymethylene polyphenyl isocyanate is 1: 0.6-2.1. The primer material prepared from the raw materials of the primer material has excellent adhesive property, and can form an adhesive combination material with polyurethane to be applied to the adhesion of the side window glass bracket of the automobile and glass.
Description
Technical Field
The invention relates to the technical field of bonding and sealing, in particular to a primer material, a preparation method and application thereof, an automobile glass bracket and a bonding combined material.
Background
In 2019, the automobile production and marketing are respectively completed by 2572.1 thousands and 2576.9 thousands. In the field of automobile safety glass, 7.5 pieces of glass need to be installed on each automobile on average, and the annual demand of automobile glass in China only reaches 2 hundred million pieces. Because the demand for automobile safety glass is huge, the requirements for the production process of the automobile safety glass mounting bracket are increasingly raised.
The traditional bonding process of the automobile safety glass mounting bracket is to adopt a special tool to position and place glass and the bracket, manually glue polyurethane for bonding, and the bottom coating is the key for bonding the automobile safety glass and the bracket. At present, mainstream bracket materials comprise PA66+ 30% GF (polyamide 66+ 30% glass fiber), PBT + 30% GF (polybutylene terephthalate + 30% glass fiber) engineering plastics, the main components of the plastic materials are high polymer materials, and common polyurethane sealant and conventional base coat have poor adhesion with the common polyurethane sealant, so that the development of the bracket base coat with excellent matching performance with the polyurethane sealant is needed for the adhesion of automobile safety glass and a bracket.
The polyurethane adhesive is a polymer with a macromolecule main chain containing repeated carbamate (-NHCOO-) chain segments, has the advantages of high strength, strong tear resistance, good flexibility and wear resistance and the like, and is widely applied to the fields of elastomers, coatings, adhesives or sealants and the like. However, since high strength and high elongation at break are required for bonding safety glass to a bracket, the proportion of the elastic polyether segment is high and the content of isocyanate for bonding is low. The low isocyanate content results in poor wettability of the one-component room temperature curing polyurethane sealant to a bracket base material, thereby causing poor bonding effect. Therefore, a special bracket primer coating is needed to improve the bonding effect of the bracket and the polyurethane sealant.
At present, no patent literature on bracket priming paint is reported, and the traditional priming paint usually adopts a primer with solvent-diluted isocyanate and silane coupling agent as main components, such as CN201010609456.X and CN 200910087090.1. However, the bonding effect of the traditional primer coating material is still not ideal.
Disclosure of Invention
The invention aims to provide a base coating material, aiming at improving the wettability and the bonding effect on a base material.
The invention also aims to provide a preparation method of the base coating material, the prepared base coating material has good wetting property on the base material, and can be matched with the polyurethane glue to improve the bonding effect of the polyurethane glue on the surface of the bracket.
The third purpose of the invention is to provide the application of the primer material or the primer material prepared by the preparation method in the bonding of the side window glass bracket and the glass of the automobile.
The fourth object of the present invention is to provide an automobile glass bracket, wherein the primer material is coated on the automobile glass bracket.
The fifth object of the present invention is to provide an adhesive composition material, which comprises the primer material and polyurethane, and the primer material and the polyurethane are used in combination, so that the adhesive effect between the base materials can be improved.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a primer coating material which takes acrylic resin and polymethylene polyphenyl isocyanate as main raw materials;
wherein the molecular weight of the acrylic resin is 25000-200000 g/mol; the hydroxyl value of the acrylic resin is 0-10 mgKOH/g;
the mass ratio of the acrylic resin to the polymethylene polyphenyl isocyanate is 1: 0.6-2.1.
The invention also provides a preparation method of the base coating material, which is prepared by applying the raw materials of the base coating material.
The invention also provides application of the primer material or the primer material prepared by the preparation method in bonding of the side window glass bracket and glass of the automobile.
The invention also provides an automobile glass bracket, and the primer coating material is coated on the automobile glass bracket.
The invention also provides a bonding combined material which comprises polyurethane and an auxiliary adhesive, wherein the auxiliary adhesive is the primer coating material or the primer coating material prepared by the preparation method.
The embodiment of the invention provides a primer coating material which has the beneficial effects that: acrylic resin and polymethylene polyphenyl isocyanate are used as main raw materials to form a base coating material, particularly, the acrylic resin is used as a film forming agent to be matched with the polymethylene polyphenyl isocyanate to further improve the bonding effect between base materials, and the acrylic resin can be matched with polyurethane glue to improve the bonding effect between an automobile side window glass bracket and glass.
The invention also provides a preparation method of the base coating material, the base coating material is prepared by applying the raw materials of the base coating material, the preparation method is simple and easy to implement, and the prepared base coating material has good wettability to a base material.
The invention also provides an automobile glass bracket, which is coated with the primer material and can be well adhered with the bracket.
The invention also provides an adhesive combination material, which comprises polyurethane and the primer coating material, and the polyurethane and the primer coating material are matched for use, so that the adhesive effect between the base materials can be improved, and the adhesive combination material is particularly suitable for adhering the side window glass bracket of the automobile and the glass.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The primer coating material provided by the embodiment of the invention, the preparation method and the application thereof, and the automobile glass bracket and the bonding combined material are specifically described below.
The primer coating material provided by the embodiment of the invention takes acrylic resin and polymethylene polyphenyl isocyanate as main raw materials. In order to further ensure the bonding performance, the molecular weight and hydroxyl value of the acrylic resin need to be controlled, and the molecular weight of the acrylic resin is 25000-200000 g/mol; the hydroxyl value of the acrylic resin is 0 to 10 mgKOH/g. The mass ratio of the acrylic resin to the polymethylene polyphenyl isocyanate is 1:0.6-2.1, preferably 1: 1.2-1.5.
The primer material provided by the invention has a very excellent wetting effect on base materials, and can be matched with polyurethane glue to improve the bonding effect between the base materials. If the bottom coating material is used for coating the automobile side window glass bracket, and then the polyurethane adhesive is used for bonding the bracket and the glass, the bonding effect is very ideal.
It is emphasized that the acrylic resin and polymethylene polyphenyl isocyanate which are key components in the priming paint have obvious effect of improving the wetting effect on the substrate. The acrylic resin as a film forming agent is a key factor for ensuring the infiltration effect, and the effect is not ideal if polyether or polyester is adopted; the polymethylene polyphenyl isocyanate can further improve the bonding effect of the polyurethane adhesive on the bottom coating surface, and if the bonding effect of the diphenylmethane diisocyanate (MDI) is not ideal, the polymethylene polyphenyl isocyanate plays a role of a bridge after film formation to connect the base material and the polyurethane adhesive.
Preferably, the undercoat further comprises a catalyst; the mass ratio of the acrylic resin to the catalyst is 1:0.005-0.014, more preferably 1: 0.006-0.008. Specifically, the catalyst is selected from at least one of an organobismuth catalyst, an organotin catalyst, a titanate catalyst, and an amine catalyst. The catalysts are applied to the adhesive, so that the bonding acting speed of the polyurethane adhesive on the bottom coating surface is promoted. Specifically, the amine catalyst is selected from one or more of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N' -tetramethylalkylenediamine, triethylamine, N-dimethylbenzylamine, bis (2, 2-morpholinoethyl) ether, and triethylenediamine; the organic bismuth catalyst is selected from one or more of bismuth neodecanoate, bismuth laurate, bismuth isooctanoate and bismuth naphthenate; the organic tin catalyst is one or more selected from dibutyltin dilaurate, dibutyltin didodecyl sulfide and dibutyltin diacetate; the titanate catalyst is selected from one or more of isopropyl titanate, tetraisobutyl titanate and n-butyl titanate.
Preferably, the base coating material also comprises an organic solvent, and the mass ratio of the organic solvent to the acrylic resin is 7-12: 1; more preferably 7-9: 1. In a more preferable embodiment, the organic solvent comprises a first solvent and a second solvent, the amount of the first solvent accounts for 50-100% of the total solvent mass, and the amount of the second solvent accounts for 0-30% of the total solvent mass; wherein the first solvent is at least one selected from toluene, xylene and butanone; the second solvent is selected from at least one of ethyl acetate, propyl acetate and butyl acetate. The inventors have found that it is preferable to use a mixed solvent of an organic solvent containing at least one of toluene, xylene and methyl ethyl ketone, and that it is advantageous to produce a material having uniform properties and good adhesion properties.
Further, the raw materials also comprise carbon black; preferably, the mass ratio of the acrylic resin to the carbon black is 1: 0.35-1; more preferably 1: 0.5-0.9. In order to adapt to the application scene of the priming material, such as the application of the bonding between the side window glass bracket and the glass of an automobile, a coloring agent is required to be added. Preferably, the carbon black is acid carbon black, and the inventor finds that the acid carbon black is more suitable for the formula system provided in the embodiment of the invention, and if the basic carbon black is adopted, the bonding effect of the polyurethane glue on the bracket surface is reduced to a certain extent. Preferably, the specific surface area of the acid carbon black is greater than 40m2(ii)/g; the average primary particle size of the acid carbon black is less than 100 nm; the pH value of the acid carbon black is 2-5. The raw material parameters of the acid carbon black are preferably controlled within the above ranges, so that the coloring can be made uniform, and the adhesion effect of the material is not affected.
Furthermore, the raw materials also comprise a water removal agent for removing water, so that the lasting service performance of the material is improved. Preferably, the mass ratio of the acrylic resin to the water removing agent is 1: 0.04-0.14; more preferably 1: 0.045-0.055; specifically, the water removal agent is at least one selected from molecular sieves, calcium oxide, triethyl orthoformate and p-toluenesulfonyl isocyanate, and the water removal agents are all suitable for the raw material system provided by the invention, so that the water in the system can be effectively removed to prepare the base coating material with excellent bonding performance. If no water removal agent is contained in the raw materials, the stability of the materials is affected, and the shelf life of the materials can be only 1-2 days.
Specifically, polymethylene polyphenyl isocyanates are polymeric MDI; the polymeric MDI is selected from at least one of the group consisting of Tantariowawa PM100, PM130, PM200, PM300, and PM 400. The polymeric MDI with the above brands are more suitable, and the prepared primer material has ideal adhesion.
The invention also provides a preparation method of the base coating material, which is prepared by applying the raw materials of the base coating material, and the prepared base coating material has good adhesive property due to the optimization of the formula.
In order to prepare a material having more excellent adhesive properties, the inventors further optimized the mixing order of the raw materials. Specifically, the preparation method comprises the following steps: the preparation method comprises the steps of uniformly mixing an organic solvent, then mixing the organic solvent with carbon black and a water removing agent to obtain a first mixture, then mixing the first mixture with acrylic resin and polymethylene polyphenyl isocyanate to obtain a second mixture, and then mixing the second mixture with a catalyst. Removing water in the organic solvent and the carbon black by a water removing agent, and mixing with other components to prepare the material with uniform properties.
For more rapid and efficient mixing, the inventor further optimizes the temperature and time parameters of mixing. Preferably, the mixing temperature of the organic solvent is 20-60 ℃, and the mixing is carried out under the protection of nitrogen; the first mixture is prepared by stirring organic solvent, carbon black and water removing agent at 20-60 deg.C for 10-180 min. The second mixture is prepared by mixing the first mixture with acrylic resin and polymethylene polyphenyl isocyanate at 20-60 deg.C, and grinding for 1-3 hr.
The embodiment of the invention also provides an automobile glass bracket, wherein the primer coating material is coated on the automobile glass bracket, and the primer coating material can be well adhered to glass.
The embodiment of the invention also provides a bonding combined material which comprises polyurethane and an auxiliary adhesive, wherein the auxiliary adhesive is the base coat material or the base coat material prepared by the preparation method. The adhesive is particularly suitable for bonding the side window glass bracket of the automobile and glass, the bracket is coated by using a primer material, and then the bracket is bonded by using polyurethane glue. The bonding composition is used separately, and the ratio of the bonding composition to the bonding composition is selected according to specific conditions, and is not limited herein.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a base coating material, which comprises the following steps: 60g of butanone, 30g of toluene and 55g of ethyl acetate are introduced into a reactor with mechanical stirring, nitrogen protection and heating, the temperature is raised to 40 ℃ and stirring is carried out, and then 14g of carbon black (pH 2.5, specific surface 130 m)2(g, average primary particle diameter: 22nm), and 0.9g of p-toluenesulfonyl isocyanate, and stirring was continued for 30 minutes to remove water from the system. Then 16g of acrylic resin (molecular weight of 54000g/mol, hydroxyl value of 1.3mgKOH/g) and 24g of PM100 polymethylene polyphenyl isocyanate are added, stirred, then transferred to a ball mill for grinding for 2h, finally, the grinding is stopped, 0.1g of DMDEE catalyst is added, and the mixture is dispersed for 5min, thus obtaining the primer coating material.
Example 2
The embodiment provides a preparation method of a base coating material, which comprises the following steps: 80g of butanone and 65g of ethyl acetate are added into a reactor with mechanical stirring, nitrogen protection and heating device, the temperature is raised to 45 ℃, stirring is carried out, and then 10g of carbon black (pH value is 2.5, specific surface is 100 m)2(g, average primary particle diameter: 24nm), 0.9g of p-toluenesulfonyl isocyanate, and stirring was continued for 20 minutes to remove water from the system. Then 20g of acrylic resin (molecular weight 200000g/mol, hydroxyl value 9mgKOH/g) and 24g of PM130 polymethylene polyphenyl isocyanate are added, stirred, then the mixture is transferred to a ball mill for grinding for 1 hour, finally the grinding is stopped, 0.1g of DABCO catalyst is added, and the mixture is dispersed for 10min, thus obtaining the primer material.
Example 3
The embodiment provides a preparation method of a base coating material, which comprises the following steps: 40g of butanone, 50g of toluene and 64.8g of propyl acetate are added with mechanical stirring under nitrogenIn the reactor of the protection and heating device, the temperature was raised to 35 ℃ and stirred, then 8g of carbon black (pH 3.0, specific surface 182 m)2(g, average primary particle diameter: 25nm), 0.9g of trimethyl orthoacetate, and stirring was continued for 50 minutes to remove water in the system. Then 22g of acrylic resin (with the molecular weight of 50000g/mol and the hydroxyl value of 9mgKOH/g) and 14g of PM200 polymethylene polyphenyl isocyanate are added, stirred, then transferred to a ball mill for grinding for 1.5h, finally, the grinding is stopped, 0.3g of DABCO catalyst is added, and the mixture is dispersed for 15min, thus obtaining the primer coating material.
Example 4
The embodiment provides a preparation method of a base coating material, which comprises the following steps: 60g of butanone, 20g of toluene and 65g of butyl acetate are added into a reactor with mechanical stirring, nitrogen protection and heating device, the temperature is raised to 50 ℃, stirring is carried out, and then 12g of carbon black (pH value 4.5, specific surface area 260 m)2(g, average primary particle diameter: 15nm) and 1.7g of a 4A molecular sieve, and the mixture was stirred for 60 minutes to remove water from the system. Then 12g of acrylic resin (molecular weight 30000g/mol, hydroxyl value 0mgKOH/g) and 26g of PM300 polymethylene polyphenyl isocyanate are added, stirring is carried out, then the mixture is transferred to a ball mill for grinding for 1.5h, finally, the grinding is stopped, 0.1g of n-butyl titanate catalyst is added, and the mixture is dispersed for 30min, thus obtaining the base coating material.
Example 5
The embodiment provides a preparation method of a base coating material, which comprises the following steps: 60g of butanone, 20g of toluene, 20g of xylene and 45g of ethyl acetate are added into a reactor with mechanical stirring, nitrogen protection and heating device, the temperature is raised to 40 ℃, the mixture is stirred, and then 10g of carbon black (pH value is 3.5, and specific surface area is 62 m)2(g, average primary particle diameter: 31nm) and 0.9g of 4A molecular sieve, and stirring was continued for 60 minutes to remove water from the system. Then 20g of acrylic resin (with the molecular weight of 34000g/mol and the hydroxyl value of 3.2mgKOH/g) and 24g of PM400 polymethylene polyphenyl isocyanate are added, stirred, then the mixture is transferred to a ball mill for grinding for 1 hour, finally, the grinding is stopped, 0.1g of bismuth isooctanoate catalyst is added, and the mixture is dispersed for 30min, thus obtaining the base coating material.
Example 6
The embodiment provides a preparation method of a base coating material, which comprises the following steps: 80g of butanone, 20g of toluene and 45.2g of propyl acetate are added into a reactor with mechanical stirring, nitrogen protection and heating devices, the temperature is raised to 40 ℃, stirring is carried out, then 12g of carbon black (pH value is 2.5, specific surface is 130m2/g, average primary particle size is 22nm) and 0.7g of p-toluenesulfonyl isocyanate are stirred for 30 minutes to remove water in the system. Then 18g of acrylic resin (molecular weight of 54000g/mol, hydroxyl value of 1.3mgKOH/g) and 24g of PM100 polymethylene polyphenyl isocyanate are added, stirred, then transferred to a ball mill for grinding for 2h, finally, the grinding is stopped, 0.1g of DBTDL catalyst is added, and the mixture is dispersed for 15min, thus obtaining the primer coating material.
Example 7
The embodiment provides a preparation method of a base coating material, which comprises the following steps: 90g of butanone, 10g of xylene and 45.2g of propyl acetate are added into a reactor with mechanical stirring, nitrogen protection and heating device, the temperature is raised to 40 ℃, the mixture is stirred, then 10g of carbon black (pH value is 2.5, specific surface is 130m2/g, average primary particle size is 22nm) and 0.6g of p-toluenesulfonyl isocyanate are stirred for 30 minutes to remove water in the system. Then adding 10g of acrylic resin (molecular weight of 54000g/mol, hydroxyl value of 1.3mgKOH/g), 10g of acrylic resin (molecular weight of 30000g/mol, hydroxyl value of 0mgKOH/g) and 24g of PM200 polymethylene polyphenyl isocyanate, stirring, then transferring to a ball mill for grinding for 3h, finally stopping grinding, adding 0.1g of DBTDL catalyst and 0.1g of DMDEE catalyst, and dispersing for 10min to obtain the primer material.
Comparative example 1
This comparative example provides a process for the preparation of a primer, the specific steps being substantially the same as those of example 1, except that: the molecular weight of the acrylic resin is 100000g/mol, and the hydroxyl value is 26 mgKOH/g.
Comparative example 2
This comparative example provides a method of preparing a primer, the specific steps being substantially the same as example 2, except that: the PM130 polymethylene polyphenyl isocyanate was replaced with an equal amount of MDI diphenylmethane diisocyanate.
Comparative example 3
The comparative example provides a preparation method of a base coating material, comprising the specific steps ofThe procedure is substantially the same as in example 3, except that: the carbon black had a pH of 8.0 and a specific surface area of 80m2(ii)/g, average primary particle diameter 28 nm.
Comparative example 4
This comparative example provides a method of preparing a primer, the specific steps being substantially the same as example 4, except that: the acrylic resin was replaced with polyether polyol (Dow DL-2000 polyether polyol, molecular weight 2000, hydroxyl value 56 mgKOH/g).
Comparative example 5
The comparative example provides a preparation method of a base coating material, and the specific steps refer to CN201010609456. X.
Comparative example 6
The comparative example provides a preparation method of a priming paint, and the specific steps refer to CN 200910087090.1.
Test example 1
The adhesion properties of the base coating materials prepared in examples 1 to 7 and comparative examples 1 to 6 were tested, the test results are shown in table 1, test methods: the base material is made of Fuyao side window glass, Fuyao PA66+ 30% glass fiber, PBT + 30% glass fiber plastic bracket. The glass surface is treated by using glass bottom coating of Jiang DT-3000, and the bracket surface is treated by using the bottom coating of the invention. After the bottom coat of the invention is soaked on the surface of the bracket, JS-311 polyurethane adhesive is applied within 5min, and then the bracket is immediately arranged on the glass surface coated with the glass bottom coat. The adhesion value test was carried out after 7 days of curing under standard conditions.
TABLE 1 adhesion Performance test results for base coating materials
From the test data in table 1, it can be seen that the materials prepared using the formulation of the primer material provided by the present invention have good adhesion properties. As can be seen by comparing comparative examples 1 to 6: the molecular weight and hydroxyl value of the acrylic resin need to be controlled within the ranges provided by the embodiments of the present invention, otherwise the adhesive property is significantly reduced; the adoption of diphenylmethane diisocyanate to replace polymethylene polyphenyl isocyanate still can obviously reduce the bonding effect; the adoption of the alkaline carbon black to replace the acid carbon black is not beneficial to ensuring good bonding performance; if the acrylic resin is replaced by other film forming agents, the bonding effect is remarkably reduced; comparative examples 5 to 6 are the existing base coating materials, and it can be seen from the test data that the base coating materials provided by the examples of the present invention have more excellent performance, which may be caused by poor wettability to the bracket substrate and poor adhesion effect due to the high content of the polyol component in the base coating material components in comparative examples 5 to 6.
In summary, according to the primer material provided by the embodiment of the invention, the water removing agent, the acrylic resin, the polymethylene polyphenyl isocyanate and the catalyst are used to form the formula of the primer material, particularly, the acrylic resin is used as the film forming agent to remarkably improve the wettability of the substrate, and the polymethylene polyphenyl isocyanate is matched to further improve the bonding effect between the substrates. Under the synergistic effect of specific content and specific components, the glass fiber bracket has excellent adhesion to PA66+ 30% glass fiber and PBT + 30% glass fiber plastic bracket base materials, the adhesion force is more than 3500N, and the glass fiber bracket can be used for bracket glass installation in glass factories.
The preparation method is simple and easy to implement, the prepared base coating material has good wettability to a base material, and the base coating material can be matched with polyurethane glue to improve the bonding effect of the automobile side window glass bracket and glass.
The invention also provides an automobile glass bracket, which is coated with the primer material and can be well adhered to glass. The invention also provides an adhesive combination material, which comprises polyurethane and the primer coating material, and the polyurethane and the primer coating material are matched for use, so that the adhesive effect between the base materials can be improved.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A priming paint is characterized in that acrylic resin and polymethylene polyphenyl isocyanate are taken as main raw materials;
wherein the molecular weight of the acrylic resin is 25000-200000 g/mol; the hydroxyl value of the acrylic resin is 0-10 mgKOH/g;
the mass ratio of the acrylic resin to the polymethylene polyphenyl isocyanate is 1: 0.6-2.1.
2. The primer according to claim 1, wherein the mass ratio of the acrylic resin to the polymethylene polyphenyl isocyanate is 1:1.2 to 1.5;
preferably, the priming material further comprises a catalyst; the mass ratio of the acrylic resin to the catalyst is 1:0.005-0.014, more preferably 1: 0.006-0.008;
preferably, the catalyst is selected from at least one of organobismuth catalysts, organotin catalysts, titanate catalysts, and amine catalysts;
preferably, the amine catalyst is selected from one or more of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N' -tetramethylalkylenediamine, triethylamine, N-dimethylbenzylamine, bis (2, 2-morpholinoethyl) ether, and triethylenediamine;
preferably, the organic bismuth catalyst is selected from one or more of bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, and bismuth naphthenate;
preferably, the organotin catalyst is selected from one or more of dibutyltin dilaurate, dibutyltin bis (dodecylthio) and dibutyltin diacetate;
preferably, the titanate catalyst is selected from one or more of isopropyl titanate, tetraisobutyl titanate and n-butyl titanate;
preferably, the base coating material further comprises an organic solvent, and the mass ratio of the organic solvent to the acrylic resin is 7-12: 1; more preferably 7-9: 1;
more preferably, the organic solvent comprises a first solvent and a second solvent, wherein the amount of the first solvent accounts for 50-100% of the total solvent by mass, and the amount of the second solvent accounts for 0-30% of the total solvent by mass; wherein the first solvent is selected from at least one of toluene, xylene, and butanone; the second solvent is at least one selected from the group consisting of ethyl acetate, propyl acetate and butyl acetate.
3. The primer coating according to claim 2, wherein the polymethylene polyphenyl isocyanate is polymeric MDI; preferably, the polymeric MDI is selected from at least one of PM100, PM130, PM200, PM300 and PM 400.
4. The primer coating according to claim 2, wherein the starting materials further comprise carbon black;
preferably, the mass ratio of the acrylic resin to the carbon black is 1: 0.35-1; more preferably 1: 0.5-0.9;
preferably, the carbon black is an acid carbon black; more preferably, the specific surface area of the acid carbon black is greater than 40m2(ii)/g; more preferably, the acidic carbon black has an average primary particle size of less than 100 nm; more preferably, the pH of the acidic carbon black is from 2 to 5.
5. The primer coating material according to claim 2, wherein the raw materials further comprise a water scavenger;
preferably, the mass ratio of the acrylic resin to the water removing agent is 1: 0.04-0.14; more preferably 1: 0.045-0.055;
preferably, the water scavenger is selected from at least one of molecular sieves, calcium oxide, triethyl orthoformate and p-toluenesulfonyl isocyanate.
6. A process for the preparation of a primer coating, characterized in that it is prepared from the starting materials of the primer coating according to any one of claims 1 to 5.
7. The process for preparing a base coating material according to claim 6, comprising the steps of:
uniformly mixing an organic solvent, then mixing the organic solvent with carbon black and a water removing agent to obtain a first mixture, then mixing the first mixture with the acrylic resin and the polymethylene polyphenyl isocyanate to obtain a second mixture, and then mixing the second mixture with a catalyst;
preferably, the mixing temperature of the organic solvent is 20-60 ℃, and the mixing is carried out under the protection of nitrogen;
preferably, the first mixture is obtained by stirring the organic solvent, the carbon black and the water removal agent at the temperature of 20-60 ℃ for 10-180 min;
preferably, the second mixture is prepared by mixing the first mixture with the acrylic resin and the polymethylene polyphenyl isocyanate at the temperature of 20-60 ℃ and then grinding for 1-3 h.
8. Use of the primer according to any one of claims 1 to 5 or the primer prepared by the preparation method according to any one of claims 6 to 7 for bonding a side window glass bracket of an automobile to glass.
9. An automobile glass bracket, characterized in that the automobile glass bracket is coated with the priming material of any one of claims 1 to 5 or the priming material prepared by the preparation method of any one of claims 6 to 7; preferably, the automotive glass bracket is further coated with a polyurethane adhesive composition after being coated with the primer.
10. An adhesive composition, characterized by comprising polyurethane and an auxiliary binder, wherein the auxiliary binder is the primer coating material of any one of claims 1-5 or the primer coating material prepared by the preparation method of any one of claims 6-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010126838.0A CN111218201A (en) | 2020-02-28 | 2020-02-28 | Primer material, preparation method and application thereof, automobile glass bracket and bonding combined material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010126838.0A CN111218201A (en) | 2020-02-28 | 2020-02-28 | Primer material, preparation method and application thereof, automobile glass bracket and bonding combined material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111218201A true CN111218201A (en) | 2020-06-02 |
Family
ID=70826245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010126838.0A Pending CN111218201A (en) | 2020-02-28 | 2020-02-28 | Primer material, preparation method and application thereof, automobile glass bracket and bonding combined material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111218201A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01104614A (en) * | 1987-10-19 | 1989-04-21 | Sunstar Giken Kk | Primer composition |
| US6153699A (en) * | 1997-12-19 | 2000-11-28 | The Yokohama Rubber Co., Ltd. | Primer composition for polyvinyl chloride |
| CN101522746A (en) * | 2006-10-05 | 2009-09-02 | 陶氏环球技术公司 | Primer composition for glass bonding |
| CN101547953A (en) * | 2007-04-24 | 2009-09-30 | 陶氏环球技术公司 | One component glass primer including oxazoladine |
| CN102203194A (en) * | 2008-10-29 | 2011-09-28 | 陶氏环球技术有限责任公司 | Low energy surface bonding system containing a primer with long open time |
| US20120064351A1 (en) * | 2010-09-13 | 2012-03-15 | The Yokohama Rubber Co., Ltd. | Primer composition and laminate using the same |
| CN103113819A (en) * | 2013-03-05 | 2013-05-22 | 河南省科学院化学研究所有限公司 | Primer coating for polyurethane sealant and preparation method thereof |
| CN106752838A (en) * | 2016-12-23 | 2017-05-31 | 山东北方现代化学工业有限公司 | A kind of polyurethane sealant silane coupling agent and preparation method thereof |
-
2020
- 2020-02-28 CN CN202010126838.0A patent/CN111218201A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01104614A (en) * | 1987-10-19 | 1989-04-21 | Sunstar Giken Kk | Primer composition |
| US6153699A (en) * | 1997-12-19 | 2000-11-28 | The Yokohama Rubber Co., Ltd. | Primer composition for polyvinyl chloride |
| CN101522746A (en) * | 2006-10-05 | 2009-09-02 | 陶氏环球技术公司 | Primer composition for glass bonding |
| CN101547953A (en) * | 2007-04-24 | 2009-09-30 | 陶氏环球技术公司 | One component glass primer including oxazoladine |
| CN102203194A (en) * | 2008-10-29 | 2011-09-28 | 陶氏环球技术有限责任公司 | Low energy surface bonding system containing a primer with long open time |
| US20120064351A1 (en) * | 2010-09-13 | 2012-03-15 | The Yokohama Rubber Co., Ltd. | Primer composition and laminate using the same |
| CN103113819A (en) * | 2013-03-05 | 2013-05-22 | 河南省科学院化学研究所有限公司 | Primer coating for polyurethane sealant and preparation method thereof |
| CN106752838A (en) * | 2016-12-23 | 2017-05-31 | 山东北方现代化学工业有限公司 | A kind of polyurethane sealant silane coupling agent and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 刘登良: "《涂料工艺 第四版 上册》", 30 June 2015, 化学工业出版社 * |
| 方禹声等: "《聚氨酯泡沫塑料》", 31 August 1994, 化学工业出版社 * |
| 殷立新等: "《胶粘基础与胶粘剂》", 31 August 1988, 航空工业出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101294977B1 (en) | Process for production of urethane resin and adhesive agent | |
| CA2505177C (en) | Moisture-curable, polyether urethanes and their use in sealant, adhesive and coating compositions | |
| CN101173031B (en) | Polyurethane prepolymer, aquosity polyurethane binder and uses thereof | |
| WO2019100357A1 (en) | Method for preparing high temperature-resistant polyurethane hot melt adhesive | |
| JP6336381B2 (en) | Adhesives useful in vehicle window mounting that provide quick travel time | |
| MXPA04012581A (en) | Two-component silylated polyurethane adhesive, sealant, and coating compositions. | |
| WO2005061622A2 (en) | Silane terminated polyurethane | |
| CA2156783C (en) | Primerless urethane adhesive compositions | |
| JP5512529B2 (en) | Polyurethane adhesive composition with high filler level | |
| CN112552863A (en) | Solvent-free bi-component polyurethane adhesive for structural bonding and application | |
| CN108997965A (en) | A kind of reactive polyurethane hot melt and preparation method thereof | |
| CN107384293A (en) | A kind of preparation method of thermoplastic polyurethane hot melt adhesive | |
| CN111690364A (en) | Single-component high-temperature curing adhesive | |
| CN112375484B (en) | Long-acting prime coat on glass surface, preparation method and application thereof, glass sealant and glass product | |
| CN108587550B (en) | Double-component solvent-free reaction type polyurethane hot melt adhesive applied to automobile industry and application method thereof | |
| CN111218201A (en) | Primer material, preparation method and application thereof, automobile glass bracket and bonding combined material | |
| CN102203207A (en) | Dry-to-the-touch moisture-curable compositions and products made therefrom | |
| CN112300745A (en) | Moisture-curing reaction type polyurethane hot melt adhesive and preparation method thereof | |
| CN114958272A (en) | Moisture-curing polyurethane hot melt adhesive for aluminum-plastic compounding | |
| CN114920903A (en) | Closed isocyanate curing agent and preparation method and application thereof | |
| EP1564233B1 (en) | Polyurethaneurea resins with trialkoxysilane groups and processes for the production thereof | |
| CN106883811B (en) | Epoxy modified polyurethane base adhesive composition and thermosetting laminating sheet | |
| WO1993005099A1 (en) | One hundred percent solids acrylic adhesives | |
| JPH09324167A (en) | Solventless type primer composition | |
| CN109575867B (en) | Single-component polyurethane adhesive and preparation method and application thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200602 |
|
| RJ01 | Rejection of invention patent application after publication |