CN107868200B

CN107868200B - Bathroom antiskid aerosol composition and preparation method thereof

Info

Publication number: CN107868200B
Application number: CN201711238140.2A
Authority: CN
Inventors: 方弘; 梁山河
Original assignee: Suzhou Primebond Glue Co ltd
Current assignee: Suzhou Primebond Glue Co ltd
Priority date: 2017-11-30
Filing date: 2017-11-30
Publication date: 2020-12-08
Anticipated expiration: 2037-11-30
Also published as: CN107868200A

Abstract

The scheme relates to a bathroom antiskid aerosol composition and a preparation method thereof, and the bathroom antiskid aerosol composition comprises a water-based polyurethane adhesive and a propellant; the waterborne polyurethane adhesive comprises a component A, a component B, a component C, an auxiliary agent and a filler, wherein the component A comprises a polyurethane prepolymer containing a chain extender, the component B comprises a water-insoluble enclosed isocyanate curing agent, and the component C comprises tridecafluorooctyltrimethoxysilane, phospholipid and a 2-2.5% carrageenan aqueous solution; the polyurethane aerosol composition based on the aqueous polyurethane dispersion provided by the invention has high transparency and good water resistance; the shelf life can reach more than one year, the polyurethane film can be conveniently sprayed on the base material, the formed polyurethane film still can show better adhesion on the surface of the moist and watery ceramic tile, the friction coefficient of the surface of the base material is not greatly changed after the polyurethane film meets water, and a user feels comfortable.

Description

Bathroom antiskid aerosol composition and preparation method thereof

Technical Field

The invention belongs to the technical field of anti-skid adhesive materials, and particularly relates to a bathroom anti-skid aerosol composition and a preparation method thereof.

Background

Polyurethanes are synthetic polymers that find widespread use in the modern synthetic gum industry. The urethane linkages of these polymers are made by reacting a polyfunctional isocyanate with a diol or polyol in the presence of a suitable catalyst. Thermoplastic polyurethanes are characterized by linear polymer chains that form self-assembled block structures, while thermoset polyurethanes form covalently bonded crosslinked networks. By proper selection of the diisocyanate and diol or polyol components, the polyurethane can be designed to resist moisture and chemical degradation while also exhibiting good flexibility.

The comprehensive performance of the waterborne polyurethane system is best when the waterborne polyurethane is applied to the most extensive polyurethane synthetic adhesive; the waterborne polyurethane system comprises a single-component waterborne polyurethane system and a double-component waterborne polyurethane system, and compared with the single-component waterborne polyurethane system, the double-component waterborne polyurethane system greatly improves the crosslinking density of the product and has the superior performances of strong adhesive force, good wear resistance, high hardness, good chemical resistance, good weather resistance and the like. Therefore, the double-component waterborne polyurethane adhesive is a novel material which not only has the advantages of the traditional solvent system, but also conforms to the environmental regulations.

The two components of the bi-component polyurethane system are usually packaged separately, and are prepared according to a certain proportion before use, the two components must be prepared at present, the operation has certain time limitation, the generally prepared adhesive can not be used after more than 2-4 hours, bubbles are easily generated when the adhesive with higher viscosity is prepared, the bubbles are difficult to eliminate quickly, the component B used as the fixing agent is generally stored under a strict anhydrous oxygen-free system, and the cost is generally higher. Moreover, aziridine double-component systems, carbodiimide double-component systems and the like have toxicity higher than neutral and can cause great harm to human bodies; the reaction rate is slow, the solvent type curing agent is difficult to dissolve in a water-based system, the prepared adhesive is a two-phase system, the water-based curing agent contains hydrophilic groups, and the water resistance of the material is influenced to a certain extent after the hydrophilic groups are introduced.

Modern polyurethane films can be applied to substrates by aerosol spraying. Aerosol spray coating is the encapsulation of a liquid composition and a volatile propellant in a common container, followed by the use of a positive pressure generated by the propellant to drive the composition from the container, which then cures to form a transparent and durable protective coating. Aerosol products are attractive to home users because they are easy to use, shelf stable, do not require mixing, and can form very smooth and uniform films.

Although polyurethane aerosol compositions have many advantages, they are also limited by certain technical problems. A major problem with aqueous polyurethane aerosol compositions is that exposure to precipitation, cleaning or even moisture before the polyurethane is fully or substantially fully dried can cause the resulting film to lose its transparency and become hazy or even opaque.

Disclosure of Invention

The invention provides a bathroom antiskid aerosol composition, which comprises a water-based polyurethane adhesive and a propellant; the waterborne polyurethane adhesive comprises a component A, a component B, a component C, an auxiliary agent and a filler, wherein the component A comprises a polyurethane prepolymer containing a chain extender, the component B comprises a water-insoluble enclosed isocyanate curing agent, and the component C comprises tridecafluorooctyltrimethoxysilane, phospholipid and a 2-2.5% carrageenan aqueous solution; the mass ratio of the component A to the component B to the component C is 18-20:1: 45-55; the mass ratio of the tridecafluorooctyltrimethoxysilane to the phospholipid to the 2-2.5% carrageenan aqueous solution in the component C is 1:1-2: 20-25.

Preferably, said bathroom skid resistant aerosol composition wherein said chain extender comprises a reactive chain extender and a hydrophilic chain extender.

Preferably, the bathroom anti-slip aerosol composition wherein the reactive chain extender is adipic acid dihydrazide or oxalyl hydrazide.

Preferably, the bathroom anti-slip aerosol composition, wherein the hydrophilic chain extender is sulfonic acid type hydrophilic chain extender sodium N, N-bis (2-hydroxyethyl) -2-aminopropanesulfonate.

Preferably, the bathroom antiskid aerosol composition comprises one or more of mica powder, glass fiber powder and hollow glass bead powder.

Preferably, the bathroom antiskid aerosol composition is characterized in that the auxiliary agents are ultraviolet absorbers, antifoaming agents and antioxidants, and are selected from the agents commonly used in aqueous polyurethane adhesives.

Preferably, the preparation method of the polyurethane prepolymer is to mix polyol with isocyanate reactive groups, diisocyanate and a chain extender, perform a prepolymerization reaction to obtain the polyurethane prepolymer, and add a neutralizer to neutralize the polyurethane prepolymer.

A method of making the bathroom anti-slip aerosol composition, comprising: dehydrating 5-10 parts of polyol at the temperature of 100-120 ℃ for 1-1.5 hours, adding 3-6 parts of diisocyanate, reacting at the temperature of 90-100 ℃ for 4-5 hours, adding 1-2 parts of hydrophilic chain extender, 1-2 parts of reaction chain extender and 6-8 parts of acetone or butanone, and reacting at the temperature of 80-90 ℃ for 3-4 hours to obtain a component A; mixing the component A, the component B and the component C in a mass ratio of 8-10:1:1-2, shearing the component A and the component B at a high speed of 2800-;

adding the auxiliary agent and the component C into a mixture of the component A and the component B, and mixing the water-insoluble enclosed isocyanate curing agent with the polyurethane prepolymer to obtain an emulsifying system of the water-based polyurethane adhesive with the water-insoluble enclosed isocyanate curing agent as a core and the polyurethane prepolymer as a shell; adding filler, mixing uniformly, and adding propellant to obtain the anti-skid aerosol composition for the bathroom.

Preferably, the bathroom anti-slip aerosol composition, wherein the propellant comprises butane.

Advantageous effects

The polyurethane aerosol composition based on the aqueous polyurethane dispersion provided by the invention has high transparency and good water resistance; the shelf storage time can reach more than one year, and the polyurethane film can be conveniently sprayed on a base material and can form a uniform polyurethane film after being cured. These films were found to exhibit excellent water, heat and uv resistance, optical clarity and mechanical properties compared to known aerosol compositions. Advantageously, it has also been found that these polyurethane films still exhibit good adhesion to moist, watery tile surfaces, so that the coefficient of friction of the substrate surface does not change significantly upon contact with water, resulting in comfort for the user; while still being able to be manually removed from the tile with oil and detergent as it ages without damaging the tile surface, making the compositions provided by the present invention very suitable for bathroom and other similar wet environment applications.

Detailed Description

The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.

It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.

Example 1:

under laboratory conditions, 100.00g of polycaprolactone diol was added to a 500mL three-necked flask, dehydrated at 110 ℃ for 1h and then cooled to 90 ℃. Adding 25g of isophorone diisocyanate into a three-neck flask, stirring for reaction at 90 ℃ for 2h, adding 4.3g of oxalyl hydrazine, 3.7g N, N-bis (2-hydroxyethyl) -2-aminopropanesulfonic acid sodium and 90.00 g of butanone, magnetically stirring at 80 ℃ at constant temperature, adding 5g of chemical mr-310 enclosed solvent isocyanate crosslinking agent after reacting for 4 h, stirring and mixing uniformly, transferring the reaction product into a high-speed disperser, dispersing at 3000r/min for 2min, adding 6g of tridecafluorooctyl trimethoxysilane, 8g of phospholipid, 150g of 2% carrageenan aqueous solution, dispersing at 1500r/min for 5min, adding 6g of tridecafluorooctyl trimethoxysilane, 8g of phospholipid, 150g of 2% carrageenan aqueous solution, stirring at 600r/min for 30 min, transferring the reaction product into a rotary evaporator, removing butanone under the vacuum condition of 50 ℃ and 6KPa, finally, 0.5g of 2-hydroxy-4-n-octoxy benzophenone ultraviolet absorbent, 3g of Dow Corning AFE-0050 organic silicon defoaming agent, 0.5g of diphenylamine antioxidant and 20g of glass fiber powder are added, and the mixture is stirred at 600r/min for 10 minutes to obtain the waterborne polyurethane adhesive. 120 grams of the aqueous polyurethane adhesive was transferred to an aerosol can, then glass mixing beads were added and the can was crimped closed with an internally threaded valve, then 40 grams of methane was added to the aerosol can using a pressure filler and an externally threaded actuator was fitted to the internally threaded valve.

Example 2:

under laboratory conditions, 100.00g of diethylene glycol was charged into a 500mL three-necked flask, dehydrated at 100 ℃ for 1 hour, and cooled to 90 ℃. Adding 25g of toluene diisocyanate into a three-neck flask, stirring and reacting at 80 ℃ for 2h, adding 4.3g of adipic dihydrazide, 3.7g N, N-bis (2-hydroxyethyl) -2-aminopropanesulfonic acid sodium and 100.00g of acetone, magnetically stirring at 80 ℃ at constant temperature, reacting for 4 h, adding 4g of molar chemical mr-310 closed solvent isocyanate cross-linking agent, stirring and mixing uniformly, transferring the reaction product into a high-speed disperser, dispersing at 3000r/min for 2min, adding 5g of tridecafluorooctyl trimethoxysilane, 6g of phospholipid, 150g of 2% carrageenan aqueous solution, dispersing at 1500r/min for 5min, adding 5g of tridecafluorooctyl trimethoxysilane, 6g of phospholipid, 150g of 2.5% carrageenan aqueous solution, stirring at 600r/min for 30 min, transferring the reaction product into a rotary evaporator, and reacting at 50 ℃ for 50 ℃, Removing acetone under the vacuum condition of 5KPa, finally adding 0.5g of 2, 4-dihydroxy benzophenone ultraviolet absorbent, 3g of Dow Corning AFE-0050 organic silicon defoaming agent, 0.5g of 2, 6-di-tert-butyl-p-cresol antioxidant, then adding 20g of hollow glass bead powder, and stirring for 10 minutes at 600r/min to obtain the waterborne polyurethane adhesive emulsion. 120 grams of the aqueous polyurethane adhesive was transferred to an aerosol can, then glass mixing beads were added and the can was crimped closed with an internally threaded valve, then 40 grams of butane was added to the aerosol can using a pressure filler and an externally threaded actuator was fitted to the internally threaded valve.

Example 3

The aerosol prepared in the example 1 is sprayed on a pure white Fushan Gauss ceramic tile to form a film, the film is placed for 48 hours at the temperature of 25 ℃, and after water is slowly volatilized, hot air drying treatment at the temperature of 70-80 ℃ is carried out on the surface of the ceramic tile by using a Koff KF-9544 electric hair drier, so that a polyurethane colloidal film with the maximum thickness of about 160 microns is obtained. The gel film was colorless and transparent in a dry state and slightly yellow in a wet state.

Comparative example 1:

in addition to example 1, 0%, 0.5%, 1%, 1.5%, 3%, and 4% carrageenan aqueous solution was added instead of each other to obtain A, B, C, D, E, F.

Comparative example 2:

on the basis of example 1, tridecafluorooctyltrimethoxysilane was not added.

Comparative example 3:

no phospholipid was added to example 1.

Comparative example 4:

on the basis of example 1, no reaction chain extender was added.

Test panels were prepared by spraying the above aerosol composition onto pure white tiles of the forskog gaussian tiles and drying at 25 ℃ for 48 hours followed by 70 ℃ for 1 hour, the dried polyurethane film having a maximum thickness of about 160 microns. The performance parameters obtained for the test panels using the aerosol compositions in the dry and surface water spray environments are shown in tables 1 and 2, respectively. And (3) testing environment: temperature: 25 ℃, humidity: 72 percent.

TABLE 1

TABLE 2

Aerosol composition	Coefficient of friction in the dry state	Coefficient of friction under water holding state
			Composition A	0.62	0.45
Composition B	0.61	0.51
			Composition C	0.61	0.54
Composition D	0.62	0.60
			Composition E	0.63	0.75
Composition F	0.60	0.86

The addition of the low surface energy tridecyl octyl trimethoxy silane results in a significant improvement in stain resistance of the present invention.

Adding 2-2.5% carrageenan solution, after meeting water, the water absorption rate of the carrageenan is higher than that of the aqueous polyurethane film, so that the water absorption deformation of the carrageenan is larger than that of the aqueous polyurethane film, and innumerable elastic cavities are formed on the aqueous polyurethane film by the carrageenan after the water absorption deformation, and the elastic cavities generate adsorption force on objects acting on the elastic cavities due to pressure deformation. The friction coefficient of the water-based polyurethane film can not change greatly before and after water absorption, and discomfort of people caused by overlarge change of the friction coefficient of the surface of the common anti-skid glue before and after water absorption is avoided.

The addition of phospholipid enhances the stability of the aerosol emulsifying system, so that the shelf life of the commodity prepared by the method can reach more than one year.

While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the embodiments shown and described without departing from the generic concept as defined by the claims and their equivalents.

Claims

1. A bathroom anti-slip aerosol composition comprising an aqueous polyurethane adhesive and a propellant; the waterborne polyurethane adhesive comprises a component A, a component B, a component C, an auxiliary agent and a filler, and is characterized in that: the component A comprises a polyurethane prepolymer containing a chain extender, the component B comprises a water-insoluble blocked isocyanate curing agent, and the component C comprises tridecafluorooctyltrimethoxysilane, phospholipid and 2-2.5% carrageenan aqueous solution; the mass ratio of the component A to the component B to the component C is 18-20:1: 45-55; the mass ratio of the tridecafluorooctyltrimethoxysilane to the phospholipid to the 2-2.5% carrageenan aqueous solution in the component C is 1:1-2: 20-25;

the chain extender comprises a reaction chain extender and a hydrophilic chain extender;

the reaction chain extender is adipic acid dihydrazide or oxalyl hydrazine.

2. A bathroom skid resistant aerosol composition according to claim 1, wherein: the hydrophilic chain extender is sulfonic acid type hydrophilic chain extender N, N-bis (2-hydroxyethyl) -2-aminopropanesulfonic acid sodium.

3. A bathroom skid resistant aerosol composition according to claim 1, wherein: the filler is one or more of mica powder, glass fiber powder and hollow glass bead powder.

4. A bathroom skid resistant aerosol composition according to claim 1, wherein: the auxiliary agent is an ultraviolet absorbent, a defoaming agent and an antioxidant.

5. A bathroom skid resistant aerosol composition according to claim 1, wherein: the preparation method of the polyurethane prepolymer comprises the step of mixing the polyol with the isocyanate reactive group, the diisocyanate and the chain extender, and carrying out prepolymerization reaction to obtain the polyurethane prepolymer.

6. A method of making the bathroom anti-slip aerosol composition of any of claims 1-5, comprising: dehydrating 5-10 parts of polyol at 100-120 ℃ for 1-1.5 hours, adding 3-6 parts of diisocyanate, reacting at 90-100 ℃ for 4-5 hours, adding 1-2 parts of hydrophilic chain extender, 1-2 parts of reaction chain extender and 6-8 parts of acetone or butanone, and reacting at 80-90 ℃ for 3-4 hours to obtain a component A; mixing the component A, the component B and the component C according to the mass ratio of 8-10:1:1-2, firstly mixing the component A and the component B in a high-speed dispersion machine, then shearing at a high speed of 2800-, and the polyurethane prepolymer is an aqueous polyurethane adhesive of the shell, 2-3 parts of filler is added and mixed uniformly, and then the propellant is added to obtain the bathroom antiskid aerosol composition.

7. A method of preparing a bathroom anti-slip aerosol composition according to claim 6, characterized in that: the propellant comprises butane.