Skin-feeling acrylic resin coating emulsion, its preparation method and application

Abstract

The application discloses a skin-feeling acrylic finish emulsion and a preparation method and application thereof. The emulsion is prepared by emulsion polymerization of the following monomer components in a weight ratio: a) 15-70% of ester monomers, b) 1.3-10% of acetoacetoxy-containing olefinically unsaturated monomers, c) 0.5-5% of unsaturated hydrophilic monomers, d) 0.2-5% of reactive silane coupling agents, e) 10-50% of styrene, and f) 14-25% of (4-vinylphenyl)dimethylsilane. The acrylic finish emulsion provided by the application is applied to building interior wall coatings, has a smooth skin feeling, has good anti-graffiti performance, and has synergistically improved water resistance and scrub resistance.

Description

Technical Field

[0001] This invention relates to an acrylic emulsion, and more particularly to a skin-feeling acrylic topcoat emulsion, its preparation method, and its application. Background Technology

[0002] With rapid societal development and rising living standards, people are placing increasingly stringent demands on their living environment. In modern homes, people not only focus on the spatial layout and functionality of their homes but also pursue a high quality of life and a clean living environment. As a crucial component of the home space, the cleanliness and aesthetics of the walls directly impact the overall comfort and quality of the living space.

[0003] Today, people's requirements for walls are no longer limited to a smooth surface, but rather focus on their ability to remain clean over the long term. This is because walls inevitably suffer from various stains in daily life. These stains can come from all sorts of everyday situations, such as spilled tea, cooking fumes, children's water-based pen scribbles, or even minor accidents involving pets. These stains not only ruin the aesthetics of the walls but also reduce the cleanliness and comfort of the living space, seriously affecting people's sensory experience.

[0004] Meanwhile, as living standards improve, people's requirements for their living environment are no longer limited to visual aesthetics and practicality; they also have higher demands for the tactile feel of wall paint. A good tactile feel not only enhances the comfort of residents but also increases the multi-dimensional quality of the paint, transforming the wall from a cold, flat surface into a spatial element with warmth and emotion.

[0005] Currently, skin-friendly anti-graffiti products are relatively scarce in the market, mainly concentrated in the category of two-component anti-graffiti surface coatings. However, two-component products have revealed a series of problems in practical applications. First, these products usually have a relatively strong chemical odor, which poses a certain threat to indoor air quality and the health of residents. Second, the application process for two-component products is relatively complex, requiring precise control of the ratio and mixing of the two components, increasing the difficulty of application and the risk of errors. Third, two-component products dry more slowly, which to some extent affects application efficiency and user experience. Finally, due to increased production and transportation costs, the price of two-component products is often higher, increasing the financial burden on users.

[0006] Patent CN115181442A describes a skin-feel coating cured by UV light, but this method requires UV light irradiation, which is complicated to operate and difficult to implement for indoor coatings.

[0007] Patent CN111763471A achieves a skin-feel effect by using polyurethane microspheres, but the anti-graffiti effect of large-particle polyurethane microspheres is not outstanding, making it difficult to achieve both anti-graffiti and skin-feel effects. Summary of the Invention

[0008] To address the aforementioned technical problems, this invention proposes a skin-feel acrylic overlay emulsion, its preparation method, and its application. The introduction of (4-vinylphenyl)dimethylsilane monomer into the emulsion composition not only provides users with a superior smooth tactile experience but also results in a lower coefficient of friction during friction and sliding, thus exhibiting excellent sliding performance in various application scenarios.

[0009] On the other hand, (4-vinylphenyl)dimethylsilane possesses strong copolymerization properties, which enable it to undergo efficient copolymerization reactions with various polymers during polymerization, thereby significantly improving polymer performance. This performance enhancement is not only reflected in improved mechanical strength and heat resistance, but also in the excellent water resistance and scrub resistance of the polymer through the synergistic combination of (4-vinylphenyl)dimethylsilane and reactive silane coupling agents.

[0010] More importantly, the performance improvement achieved by this invention is not temporary. Through precise formulation design, we have successfully incorporated the properties of (4-vinylphenyl)dimethylsilane maleimide into the polymer in a stable manner, allowing the material to maintain a consistently smooth feel even after long-term use. This long-lasting smooth feel provides users with a durable and stable high-quality experience, further enhancing the material's practicality and market competitiveness.

[0011] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0012] A skin-feel acrylic topcoat emulsion, prepared by emulsion polymerization comprising the following monomer components in the following weight ratios:

[0013] a) 15-70%, preferably 44-66%, of ester monomers.

[0014] b) 1.3-10%, preferably 2-4%, of olefinic unsaturated monomers containing acetoacetic acid groups.

[0015] c) 0.5-5%, preferably 1-5% unsaturated hydrophilic monomers.

[0016] d) 0.2-5%, preferably 0.5-2%, of reactive silane coupling agent.

[0017] e) 10-50%, preferably 20-30% styrene.

[0018] f) 14-25%, preferably 10-15% (4-vinylphenyl)dimethylsilane.

[0019] In the skin-feeling acrylic face mask emulsion provided by the present invention, component a) is selected from alkyl acrylates, allyl acrylates, vinyl acetates and their methyl-substituted derivatives having 1-16 carbon atoms, preferably alkyl acrylates, vinyl acetates and their methyl-substituted derivatives having 1-8 carbon atoms, more preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, methyl 2-methacrylate, isoamyl methacrylate, and heptyl methacrylate, or one or more of these.

[0020] In the skin-feeling acrylic face emulsion provided by the present invention, component b) is selected from one or more of ethyl acetoacetate, propoxy acetoacetate, butoxy acetoacetate, vinyl acetoacetate, allyl acetoacetate and their methyl derivatives, preferably one or two of ethyl acetoacetate and allyl acetoacetate.

[0021] In the skin-feeling acrylic face emulsion provided by the present invention, component c) is selected from at least one of unsaturated compounds containing hydrophilic groups: carboxyl, hydroxyl, amide, sulfonic acid, phosphate, urea, sulfonate, sulfate, and phosphate groups, preferably selected from one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, acrylamide, methacrylamide, ethyl ethylene urea, vinyl alkoxy phosphate, and sodium 2-acrylamide-2-methylpropanesulfonate.

[0022] In the skin-feeling acrylic face emulsion provided by the present invention, component d) is selected from silane coupling agents containing mercapto, vinyl or epoxy functional groups, preferably selected from one or more of vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and mercaptopropyltrimethoxysilane.

[0023] This invention also provides a method for preparing the skin-feeling acrylic face mask emulsion described above, comprising the following steps:

[0024] A. Mix components a), b), c), d), e), f), water, and a portion of the emulsifier evenly to prepare a pre-emulsion;

[0025] B. Divide the initiator into two portions and dissolve them separately in water to obtain a dropwise initiator and a bottom initiator;

[0026] C. Mix the neutralizer, the remaining emulsifier, and water, then add the mixture to the reactor and stir thoroughly. Heat the mixture to 80-90℃. Add a portion of the pre-emulsion, stir evenly, then add all the initiator from the bottom of the reactor. React for 10-20 minutes to obtain the seed emulsion.

[0027] D. Control the temperature inside the reactor to 80-90℃, continue to add the remaining pre-emulsion and all the drop initiator to the seed emulsion, add the material over 2-4 hours, and then keep warm for 20-60 minutes.

[0028] E. Cool the reactor to 70-80℃, gradually add the post-treatment agent to the reactor, add the agent over 2-4 hours, and then keep it warm for 30-60 minutes.

[0029] F. Cool down to below 45℃, add pH adjuster to adjust the pH of the system to 7-9, strip, filter and discharge.

[0030] In the emulsion preparation method provided by the present invention, the amount of emulsifier in step A accounts for 90-99.5% of the total mass of the emulsifier; preferably, the amount of water in step A accounts for 25-35% of the total mass of the water.

[0031] In the emulsion preparation method provided by the present invention, the amount of initiator used in step B for preparing the drop-addition initiator accounts for 25-50% of its total mass, and the amount of initiator used in preparing the bottom initiator accounts for 50-75% of its total mass; preferably, the amount of pre-emulsion used in step C for preparing the seed emulsion is 1-8% of its total mass.

[0032] In the emulsion preparation method provided by the present invention, the amount of water used in step B for preparing the dropwise initiator accounts for 1-6% of the total water mass, and the amount of water used for preparing the bottom initiator accounts for 1-6% of the total water mass.

[0033] In the emulsion preparation method provided by the present invention, the emulsifier is selected from one or more of sodium dodecyl sulfate, sodium p-styrene sulfonate, sodium dodecylbenzene sulfonate, alcohol ether sulfosuccinate, alkyl alcohol ether sulfate, and alkyl alcohol ether phosphate, more preferably sodium dodecyl sulfate and / or sodium dodecylbenzene sulfonate; preferably, the amount of emulsifier is 1-5% of the total mass of components a)-f), more preferably 1-2%;

[0034] Preferably, the initiator is selected from one or more of sodium persulfate, potassium persulfate, and ammonium persulfate, more preferably sodium persulfate and / or potassium persulfate; preferably, the amount of initiator is 0.2-0.6% of the total mass of components a)-f), preferably 0.2-0.4%;

[0035] Preferably, the neutralizing agent is selected from one or more of sodium bicarbonate, diethylenetriamine, diethanolamine, and ethanolamine, more preferably sodium bicarbonate; preferably, the amount of neutralizing agent is 0.1-4% of the total mass of components a)-f), preferably 0.1-0.3%;

[0036] Preferably, the post-treatment agent includes an oxidizing agent and / or a reducing agent, wherein the oxidizing agent is selected from one or more of tert-butyl hydroperoxide, hydrogen peroxide, sodium persulfate, potassium persulfate, and ammonium persulfate, preferably tert-butyl hydroperoxide and / or hydrogen peroxide; the reducing agent is selected from one or more of sodium bisulfite, sodium metabisulfite, and vitamin C, preferably sodium bisulfite and / or sodium metabisulfite; preferably, the total amount of the post-treatment agent is 0.15-0.6% of the total mass of components a)-f), preferably 0.2-0.4%;

[0037] Preferably, the pH adjuster is selected from one or more of diethylenetriamine, diethanolamine, and ethanolamine, more preferably diethylenetriamine and / or ethanolamine;

[0038] Preferably, the total amount of water used is 1-1.5 times the total mass of components a)-f), more preferably 1-1.3 times, and even more preferably, the total amount of water used makes the emulsion have a solid content of 40-45 wt%.

[0039] In the emulsion preparation method provided by the present invention, the stripping conditions in step F are: temperature 55-85℃, pressure -75Kpa to -95Kpa (gauge pressure).

[0040] The present invention also provides the application of the skin-feel acrylic topcoat emulsion as described above or the skin-feel acrylic topcoat emulsion prepared by the method described above in architectural coatings.

[0041] In the emulsion formulation of this invention, (4-vinylphenyl)dimethylsilane not only contains silane groups that provide a smooth, skin-like feel to the polymer, but also possesses strong hydrophobicity and double bond copolymerization ability, allowing it to be stably grafted into the polymer molecular chain and improving the anti-graffiti properties of the coating. Furthermore, it was unexpectedly discovered that the synergistic use of (4-vinylphenyl)dimethylsilane and reactive silane coupling agents has a synergistic effect on improving the water resistance and scrub resistance of the coating. Therefore, the skin-like acrylic topcoat emulsion of this invention has wide applications in the field of interior wall coatings. Detailed Implementation

[0042] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.

[0043] The raw materials used in the following embodiments are shown in Table 1. Unless otherwise specified, all other raw materials are common commercially available materials.

[0044] Table 1. Raw Material Information

[0045]

[0046]

[0047] The following embodiments uniformly adopt the following stripping conditions and processes:

[0048] The emulsion is preheated to 55°C in a buffer vessel and then passed into a stripping tower for stripping (stripping temperature 55°C). The emulsion is fed from the top of the tower, while air and steam are fed from the bottom. The two feed countercurrently and mix rapidly for a short time. The steam and air, carrying VOC components, separate from the emulsion through the vacuum exhaust pipe, and the emulsion is discharged from the bottom. During the stripping process, the relative flow rates of air, steam, and emulsion are 1:0.5:10.

[0049] The main performance testing methods involved in the following embodiments of the present invention are as follows:

[0050] (1) Watercolor Resistancy Assessment: A 100μm wet film was applied to black and white cardstock and allowed to dry at room temperature for 1 day. Lines were then drawn with a M&G 12-color washable watercolor pen. The lines were wiped with a damp cloth immediately, after 1 day, and after 3 days, and the wiping effect was observed. Assessment Criteria:

[0051] 5 points: Erase all.

[0052] 4 points: All except for the red ink containing solvent was erased, leaving only a slight mark of the red pen.

[0053] 3 points: All except for the red ink containing solvent was erased, and the red pen left a clear mark.

[0054] 2 points: Watercolor pen leaves a faint mark, red pen leaves a clear mark.

[0055] 1 point: The watercolor pen left a clear mark.

[0056] 0 points: The paint film is damaged and has not been wiped off at all.

[0057] (2) Water resistance assessment: The water resistance of latex paint was determined according to HG / T 5065-2016.

[0058] (3) VOC: Volatile substances with a boiling point below 250℃ as tested according to GB / T 18582.

[0059] (4)SVOC: Volatile substances with a boiling point of 250-400℃ as tested according to GB / T 18582.

[0060] (5) Olfactory rating: Ten people were randomly selected as the scoring criteria to rate the odor of samples from the same period.

[0061] 0 points: Odorless

[0062] 1 point: Slight odor, barely noticeable.

[0063] 2 points: Slight odor, pleasant smell.

[0064] 3 points: Slight odor, pungent odor.

[0065] 4 points: It has a very distinct odor.

[0066] 5 points: The odor is very strong and causes dizziness and other discomfort.

[0067] (6) Scrub resistance: The scrub resistance of the paint film is tested according to HG / T 5065-2016.

[0068] (7) Skin feel of the coating: Apply 100 micrometers of clear topcoat varnish to the cardstock, cure for 24 hours, and then touch it with your palm to score it:

[0069] 0 points: No skin feel

[0070] 1 point: Slight skin feel, barely noticeable.

[0071] 2 points: Slightly smooth to the touch and with a slightly slippery feel.

[0072] 3 points: It feels like skin, but it's not smooth enough.

[0073] 4 points: It has a very distinct skin feel.

[0074] 5 stars: It not only feels good against the skin, but also has the texture of the skin.

[0075]

Examples 1-8

[0076] Referring to the formula in Table 2, prepare acrylic emulsions uniformly according to the following methods:

[0077] A. Mix components a), b), c), d), e), f) with a portion of water and emulsifier evenly to prepare a pre-emulsion;

[0078] B. Prepare the dropwise initiator and the bottom initiator separately;

[0079] C. Mix the neutralizer, the remaining emulsifier, and water, then add the mixture to the reactor and stir thoroughly. Heat the mixture to 85°C. Add a portion of the pre-emulsion (5% of the total amount), and after stirring evenly, add all the initiator from the bottom of the reactor. React for 10 minutes to obtain the seed emulsion.

[0080] D. Control the temperature inside the reactor to 85℃, and continue to add the remaining pre-emulsion and all the initiator to the seed emulsion at the same time. The total adding time is 4 hours, and then keep warm for 2 minutes.

[0081] E. Cool the reactor to 75°C, gradually add the post-treatment agent to the reactor over a period of 2 hours, and then keep it warm for 30 minutes.

[0082] F) Cool down to below 45℃, add diethylenetriamine as a pH adjuster to adjust the pH of the system to 8, strip, filter through a 100-mesh filter, and discharge.

[0083] Table 2. Raw material formulations for Examples 1-8 (unit: g)

[0084]

[0085]

[0086]

[0087] Comparative Example 1

[0088] An acrylic emulsion was prepared using essentially the same formulation and method as in Example 1, except that component f was not added in step A.

[0089] Comparative Example 2

[0090] An acrylic emulsion was prepared using essentially the same formulation and method as in Example 1, except that the amount of component f in step A was halved.

[0091] Comparative Example 3

[0092] An acrylic emulsion was prepared using essentially the same formulation and method as in Example 1, except that component d was not added.

[0093] Referring to the formulations in Table 3, the acrylic emulsions prepared in each example and comparative example were used as raw materials to prepare coatings, and the performance tests in Tables 4 and 5 were conducted.

[0094] Table 3. Coating Formulation

[0095]

[0096]

[0097] Table 4. Coating performance test results for Examples 1-8

[0098]

[0099] Table 5. Performance test results of coatings in Comparative Examples 1-3

[0100] Comparative Example 1 Comparative Example 2 Comparative Example 3 State of the topcoat coating in the container No clumps No clumps No clumps Topcoat coating properties good good good Does the coating feel smooth to the skin? no no yes Paint film drying time (surface dry, h) 2h 2h 2h Watercolor pen resistance 0 1 4 Water resistance Not passed Not passed Not passed VOC <500ppm <500ppm <500ppm SVOC <500ppm <500ppm <500ppm olfactory level 1 1 1 Scrub resistance (times) 323 1664 1453

[0101] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. A skin-feel acrylic topcoat emulsion, characterized in that, The monomer components, in the following weight ratios, were prepared by emulsion polymerization: a) 15-70%, preferably 44-66%, of ester monomers. b) 1.3-10%, preferably 2-4%, of olefinic unsaturated monomers containing acetoacetic acid groups. c) 0.5-5%, preferably 1-5% unsaturated hydrophilic monomers. d) 0.2-5%, preferably 0.5-2%, of reactive silane coupling agent. e) 10-50%, preferably 20-30% styrene. f) 14-25%, preferably 10-15% (4-vinylphenyl)dimethylsilane.

2. The skin-feel acrylic topcoat emulsion according to claim 1, characterized in that, Component a) is selected from alkyl acrylates, allyl acrylates, vinyl acetates and their methyl-substituted derivatives having 1-16 carbon atoms, preferably alkyl acrylates, vinyl acetates and their methyl-substituted derivatives having 1-8 carbon atoms, more preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, methyl 2-methacrylate, isoamyl methacrylate, and heptyl methacrylate, or one or more of these.

3. The skin-feel acrylic topcoat emulsion according to claim 1 or 2, characterized in that, Component b) is selected from one or more of ethyl acetoacetate, propoxy acetoacetate, butoxy acetoacetate, vinyl acetoacetate, allyl acetoacetate, and their methyl derivatives.

4. The skin-feel acrylic topcoat emulsion according to any one of claims 1-3, characterized in that, Component c) is selected from at least one of the following unsaturated compounds containing hydrophilic groups: carboxyl, hydroxyl, amide, sulfonic acid, phosphate, urea, sulfonate, sulfate, and phosphate groups, preferably selected from one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, acrylamide, methacrylamide, ethyl ethylene urea, vinyl alkoxy phosphate, and sodium 2-acrylamido-2-methylpropanesulfonate.

5. The skin-feel acrylic topcoat emulsion according to any one of claims 1-4, characterized in that, Component d) is selected from silane coupling agents containing mercapto, vinyl or epoxy functional groups, preferably one or more of vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and mercaptopropyltrimethoxysilane.

6. A method for preparing a skin-feel acrylic topcoat emulsion as described in any one of claims 1-5, characterized in that, Includes the following steps: A. Mix components a), b), c), d), e), f), water, and a portion of the emulsifier evenly to prepare a pre-emulsion; B. Divide the initiator into two portions and dissolve them separately in water to obtain a dropwise initiator and a bottom initiator; C. Mix the neutralizer, the remaining emulsifier, and water, then add the mixture to the reactor and stir thoroughly. Heat the mixture to 80-90℃. Add a portion of the pre-emulsion, stir evenly, then add all the initiator from the bottom of the reactor. React for 10-20 minutes to obtain the seed emulsion. D. Control the temperature inside the reactor to 80-90℃, continue to add the remaining pre-emulsion and all the drop initiator to the seed emulsion, add the material over 2-4 hours, and then keep warm for 20-60 minutes. E. Cool the reactor to 70-80℃, gradually add the post-treatment agent to the reactor, add the agent over 2-4 hours, and then keep it warm for 30-60 minutes. F. Cool down to below 45℃, add pH adjuster to adjust the pH of the system to 7-9, strip, filter and discharge.

7. The method for preparing the skin-feel acrylic overcoat emulsion according to claim 6, characterized in that, In step A, the amount of emulsifier accounts for 90-99.5% of the total emulsifier mass; preferably, the amount of water in step A accounts for 25-35% of the total water mass.

8. The method for preparing the skin-feel acrylic topcoat emulsion according to claim 6 or 7, characterized in that, In step B, the amount of initiator used to prepare the dropwise initiator accounts for 25-50% of its total mass, and the amount of initiator used to prepare the bottom initiator accounts for 50-75% of its total mass; preferably, in step C, the amount of pre-emulsion used to prepare the seed emulsion is 1-8% of its total mass.

9. The method for preparing the skin-feel acrylic topcoat emulsion according to any one of claims 6-8, characterized in that, The emulsifier is selected from one or more of sodium dodecyl sulfate, sodium p-styrene sulfonate, sodium dodecylbenzene sulfonate, alcohol ether sulfosuccinate, alkyl alcohol ether sulfate, and alkyl alcohol ether phosphate; preferably, the amount of emulsifier is 1-5% of the total mass of components a)-f), more preferably 1-2%; Preferably, the initiator is selected from one or more of sodium persulfate, potassium persulfate, and ammonium persulfate; preferably, the amount of initiator is 0.2-0.6% of the total mass of components a)-f), more preferably 0.2-0.4%; Preferably, the neutralizing agent is selected from one or more of sodium bicarbonate, diethylenetriamine, diethanolamine, and ethanolamine; preferably, the amount of neutralizing agent used is 0.1-4% of the total mass of components a)-f), more preferably 0.1-0.3%; Preferably, the post-treatment agent includes an oxidizing agent and / or a reducing agent, wherein the oxidizing agent is selected from one or more of tert-butyl hydroperoxide, hydrogen peroxide, sodium persulfate, potassium persulfate, and ammonium persulfate, preferably tert-butyl hydroperoxide and / or hydrogen peroxide; the reducing agent is selected from one or more of sodium bisulfite, sodium metabisulfite, and vitamin C, preferably sodium bisulfite and / or sodium metabisulfite; preferably, the total amount of the post-treatment agent is 0.15-0.6% of the total mass of components a)-f), preferably 0.2-0.4%; Preferably, the pH adjuster is selected from one or more of diethylenetriamine, diethanolamine, and ethanolamine; Preferably, the total amount of water used is used to adjust the emulsion solid content to 40-45 wt%.

10. The use of a skin-feel acrylic topcoat emulsion as described in any one of claims 1-5 or a skin-feel acrylic topcoat emulsion prepared by the method described in any one of claims 6-9 in architectural coatings.

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