CN108753013B - A kind of water-soluble antifouling and anti-graffiti additive and its application - Google Patents

Abstract

The invention discloses a water-soluble antifouling and anti-graffiti auxiliary agent and its application. The auxiliary agent introduces a polysiloxane chain segment, a water-soluble organic chain segment containing a tertiary amino group, a light Curing active groups and ‑CO‑NH‑ and other groups improve the compatibility and adhesion of additives with water-based UV paint films, and make the perfluoropolyether segment migrate more thoroughly, thereby making the paint film with good Anti-fouling performance and wear resistance; Application: Its application in anti-fouling and anti-graffiti water-based UV light-curing coatings.

Description

A kind of water-soluble antifouling and anti-graffiti additive and its application

technical field

The invention belongs to the field of macromolecular materials, in particular to a water-soluble auxiliary agent suitable for water-based UV light-curing coatings, in particular to a water-soluble antifouling and anti-graffiti auxiliary agent and its application.

Background technique

Water-based UV light-curing coatings have the advantages of fast curing speed, energy saving, less environmental pollution, good cured product performance, and suitability for high-speed automated production. attention in the paint industry. However, since the paint film formed by the water-based UV coating contains a large number of polar functional groups such as carbonyl and amino groups, the anti-fouling and anti-graffiti performance of the paint film is poor. Improving the anti-fouling, anti-sticking and anti-graffiti properties of existing water-based UV coatings has always been a hot and difficult point in coatings research, especially 3C coatings applied to surfaces such as computers, communications and consumer electronics, as well as displays and touch controls. Hardening coatings on the surface of optical films such as screens, as well as low surface energy coatings such as anti-graffiti coatings for the prevention and treatment of urban psoriasis. From a technical point of view, there are two main ways to realize the hydrophobic and oleophobic function of the material surface. One is to add low surface energy substances on the surface of the material, mainly organic fluorine and silicone; the other is to build a rough structure on the surface of the material. Undoubtedly, it is a quick, efficient and practical method to study the addition of an efficient antifouling additive to the existing paint formulation without changing other properties of the original paint.

Perfluoropolyether (PFPE) does not contain PFOA, PFCS and other environmental cumulative chemical components, and is a safe and environmentally friendly fluorine source. It has poor compatibility with other hydrocarbon components in the coating, and will float on the surface of the paint film during the film-forming process, thereby reducing the surface energy of the paint film, and finally realizing the functions of oil-proof, waterproof and dust-proof. Chinese invention patent CN106220839A discloses a perfluoropolyether-based anti-graffiti additive and a preparation method thereof. The structural formula is as follows:

其中，n为自然数且2≤n≤30；X为R¹N(R²)-或-HN-R²，R¹、R²分别为含有聚氨酯结构的取代基，且X的末端含有醇羟基。然而此化合物主要是含有聚氨酯结构等基团，其难以应用于UV光固化涂料中，在UV光固化涂料中相容性差，难以发挥其防污防涂鸦功能。

Wherein, n is a natural number and 2≤n≤30; X is R ¹ N(R ² )- or -HN-R ² , R ¹ and R ² are substituents containing polyurethane structure respectively, and the end of X contains an alcoholic hydroxyl group . However, this compound mainly contains groups such as polyurethane structure, which is difficult to be used in UV light-curing coatings, and has poor compatibility in UV light-curing coatings, so it is difficult to exert its anti-fouling and anti-graffiti functions.

Another example is the invention patent CN2005800145739, which discloses a perfluoropolyether-modified acrylate with antifouling effect. However, after the compound disclosed in this patent is applied to the coating, the coating will be cured by UV light, and the oxygen in the air will cure it. Oxygen inhibition is produced, and at the same time, the adhesion and compatibility of this compound and the paint film are poor, and then the perfluoropolyether will be continuously separated from the surface of the paint film during the use of the product, which will eventually lead to the antifouling function of the paint film. The durability of the compound deteriorates, so although it achieves a certain anti-fouling and wear resistance, the effect is still unsatisfactory, and the compound cannot be dissolved in water-based UV coatings, that is, it cannot be applied to water-based UV coatings to improve the anti-fouling and anti-graffiti properties. .

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a water-soluble anti-fouling and anti-graffiti additive, which is suitable for water-based UV light-curing coatings, and can achieve long-term stable anti-fouling and anti-graffiti effects, wear-resisting good sex.

The invention also provides an anti-fouling and anti-graffiti water-based UV light-curing coating.

In order to solve the above technical problems, a kind of technical scheme adopted in the present invention is as follows:

A water-soluble anti-fouling and anti-graffiti auxiliary, the water-soluble anti-fouling and anti-graffiti auxiliary has the following general structural formula:

wherein, R _f is a perfluoropolyether acyl group;

X ₁ is an organic group containing a secondary amino group, and R _f is connected to the nitrogen atom of the secondary amino group;

X ₂ is a water-soluble organic group containing a tertiary amino group;

R ^A is an organic group containing a photocurable active group and -CO-NH-, and the R ^A is connected to the tertiary amino group in the X through the carbon atom _on the -CO-NH- it contains. the nitrogen atoms are connected;

R ^C is -C _n H _2n-1 , and n is a positive integer;

a, b, and c are each independently selected from an integer greater than or equal to 1.

According to some preferred aspects of the present invention, the R _f is a combination of one or more selected from the following groups:

其中，50≥d≥2；

Among them, 50≥d≥2;

其中，50≥e≥2；

Among them, 50≥e≥2;

其中，50≥f≥2，50≥g≥2；

Among them, 50≥f≥2, 50≥g≥2;

其中，50≥h≥2，50≥i≥2。

Among them, 50≥h≥2, 50≥i≥2.

According to some preferred aspects of the present invention, the X ₁ is -R ₁ -NH-, wherein R ₁ is a C _1-20 alkylene group. More preferably, R ₁ is a C _1-10 alkylene group. According to some specific _{aspects of} the invention, _{R1 can be -CH2-} , _{-CH2CH2- , -CH2CH2CH2- , -CH2CH2CH2CH2- , -CH2CH2CH 2CH2CH2-} , _{-CH2CH2CH2CH2CH2CH2-} , _{-CH ( CH3 ) CH2- , -C ( CH3 ) 2CH2- .}

其中，R₂为C_1-20的亚烷基基团。更优选地，R₂为C_1-10的亚烷基基团。根据本发明的一些具体方面，R₂可以为-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂CH₂-、-CH(CH₃)CH₂-、-C(CH₃)₂CH₂-。According to some preferred aspects of the present invention, the X ₂ is

wherein, R ₂ is a C _1-20 alkylene group. More preferably, R ₂ is a C _1-10 alkylene group. According to some specific _aspects of the _invention , _{R2 can be -CH2-} , _{-CH2CH2- , -CH2CH2CH2- , -CH2CH2CH2CH2- , -CH2CH2CH 2CH2CH2-} , _{-CH2CH2CH2CH2CH2CH2-} , _{-CH ( CH3 ) CH2- , -C ( CH3 ) 2CH2- .}

According to some preferred aspects of the present invention, the photocurable reactive group is an unsubstituted acrylate functional group and/or a C _1-10 alkyl-substituted acrylate functional group. The structural formula of the acrylate functional group is CH ₂ =CHCOO, and the alkyl substituted acrylate functional group can be CH ₂ =C(CH ₃ )COO, CH ₂ =C(CH ₂ CH ₃ )COO, CH ₂ =C(CH ₂ CH ₂ CH ₃ )COO, CH ₂ =C(CH ₂ CH ₂ CH ₂ CH ₃ )COO, and the like.

According to some specific and preferred aspects of the present invention, the photocurable reactive group has at least three and is located at the end of the ^RA structure.

According to some preferred aspects of the present invention, the -CO-NH- has a plurality. It is beneficial to introduce other groups or to form longer segments.

R₄为-(CH₂)_j-C(CH₂OOC-CH＝CH₂)₃，或，According to some preferred aspects of the present invention, the R ^A is -CO-NH-R ₃ -NH-COO-R ₄ , wherein the R ₃ is

R ₄ is -(CH ₂ ) _j -C(CH ₂ OOC-CH=CH ₂ ) ₃ , or,

-(CH ₂ ) _k -C(CH ₂ OOC-CH=CH ₂ ) ₂ -CH ₂ -O-CH ₂ -C(CH ₂ OOC-CH=CH ₂ ) ₃ , where j and k are independently selected A self-positive integer; more preferably, j, k are independently selected from integers in the range of 1-100.

R ₅ and R ₆ are each independently -NH-CO-OR ₇ -O-CO-NH-, R ₇ is an alkylene group selected from C _1-10 , -(C _m H _2m O) _r1 -C _m A combination of one or more of H _2m -, -(C _p H _2p O) _r2 -(C _s H _2s O) _r3- C _m H _2m -, m, p, s, r1, r2 and r3 respectively Independently selected from positive integers, p and s are different. Specifically, m, p, s, r1, r2 and r3 are each independently selected from an integer from 1-50. According to some specific aspects of the invention, the _{C1-10 alkylene} group _{may be -CH2-} , _{-CH2CH2- , -CH2CH2CH2- , -CH2CH2CH2CH2- , -CH2CH2CH2CH2CH2- , -CH2CH2CH2CH2CH2CH2- , -CH ( CH3 ) CH2- , -C ( CH3 ) 2CH2- .} According to further specific aspects of the invention, m, p, s, r1, r2 and r3 are each independently selected from integers from 1-20.

所示位置处表示会连接有其它基团。In the present invention,

The positions shown indicate that other groups will be attached.

According to some preferred aspects of the present invention, the R ^C is a C _1-10 alkyl group. According to some specific _{aspects of} the _invention , ^RC _{can be -CH3 , -CH2CH3 , -CH2CH2CH3 , -CH2CH2CH2CH3 , -CH2CH2CH2CH2CH 3} , _{-CH2CH2CH2CH2CH2CH3} , -CH _{( CH3 ) CH3} or _{-C ( CH3 ) 2CH3 .}

According to some preferred aspects of the present invention, a, b are independently selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, respectively.

According to some preferred aspects of the present invention, c is an integer selected from 3-30. More preferably, c is an integer selected from 3-20. According to some specific aspects of the invention, c is an integer selected from 3-15.

According to some specific and preferred aspects of the present invention, the water-soluble antifouling and antigraffiti adjuvant is one selected from the following structural formula:

Among them, 50≥d≥2, a, b, c and t1 are independently positive integers;

Among them, 50≥d≥2, a, b, c and t2 are independently positive integers;

Among them, 50≥d≥2, a, b, c and t3 are independently positive integers;

Among them, 50≥d≥2, a, b, c, t4 and t5 are independently positive integers;

Wherein, 50≥d≥2, and a, b, c, t6 and t7 are each independently positive integers.

According to some specific aspects of the invention, tl, t2, t3, t4, t5, t6, and t7 are each independently selected from integers from 1-50.

Another technical solution provided by the present invention is an anti-fouling and anti-graffiti water-based UV light-curing coating, the raw material of which contains the above-mentioned water-soluble anti-fouling and anti-graffiti auxiliary.

In the present invention, in parts by weight, the raw material formulation of the antifouling and anti-graffiti water-based UV light-curing coating includes:

Wherein, the UV active compound can be selected from one or more of water-based polyurethane acrylate, water-based epoxy acrylate, water-based polyester acrylate, 2-functional acrylate monomer, 3-functional acrylate monomer, etc. combination.

The pH regulator can be selected from one or more combinations of triethylamine, ammonia water, diethanolamine, triethanolamine, methylethanolamine, etc.

The photoinitiator can be selected from one or a combination of Irgacure500, Irgacure819, Irgacure2959, Irgacure754 and Irgacure819DW.

In the present invention, all the above-mentioned raw materials can be obtained by commercial purchase and/or by known means, and all meet the requirements of standard chemical products unless otherwise specified.

Due to the implementation of the above-mentioned technical solutions, the present invention has the following advantages compared with the prior art:

The water-soluble antifouling and anti-graffiti auxiliary provided by the invention has good compatibility with the raw materials of the water-based UV light-curing coating, and has strong migration in the paint film, so that the perfluoropolyether group contained in the auxiliary can be used in the coating composition. In the process of filming, it quickly and thoroughly migrates to the surface of the paint film to achieve excellent anti-fouling and anti-graffiti effects. At the same time, it can also achieve stronger adhesion with the paint film and will not fall off during the use of the product, thereby ensuring that Long-term stable anti-fouling and anti-graffiti effects of the paint film, and better wear resistance.

Description of drawings

FIG. 1 is a nuclear magnetic H ¹ NMR analysis spectrum of PFPE-1 of Example 1. FIG.

Detailed ways

The preparation method of the water-soluble antifouling and anti-graffiti adjuvant provided by the present invention comprises the following steps:

1) Mix the silane coupling agent 1 containing the primary amino group and the silane coupling agent 2 containing the secondary amino group, hydrolysis reaction and condensation reaction occur to obtain the initial product, and then in the presence of the first catalyst, the obtained initial product is mixed with siloxane. The ring body and the organosilicon end capping agent undergo a polycondensation reaction to generate aminosilicone oil product 1;

2) carrying out amidation reaction of amino silicone oil product 1 prepared in step 1) with perfluoropolyether compound to generate product 2;

3) in the presence of the second catalyst, in the presence of a polymerization inhibitor, in a solvent, the isocyanate compound and the hydroxyacrylate compound are reacted to generate product 3;

4) Add the product 3 prepared in step 3) to the product 2 prepared in step 2), and react to generate the water-soluble antifouling and anti-graffiti adjuvant.

The preparation method is simple and easy to operate, the reaction conditions are mild, and the preparation process is safe and environmentally friendly.

According to some specific and preferred aspects of the present invention, the primary amino group-containing silane coupling agent 1 can be selected from γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldiethoxysilane, - a combination of one or more of aminopropylethyldimethoxysilane and gamma-aminopropylethyldiethoxysilane.

According to some specific and preferred aspects of the present invention, the secondary amino group-containing silane coupling agent 2 can be selected from γ-piperazinylpropylmethyldimethoxysilane, γ-piperazinylpropylmethyldiethoxysilane Silane, γ-Piperazinylpropylethyldimethoxysilane, γ-Piperazinylpropylethyldiethoxysilane, N-(n-butyl)-γ-aminopropylmethyldimethyl dimethyl A combination of one or more of oxysilane, 3-piperazinylpropylmethyldimethoxysilane, and N-(n-butyl)-gamma-aminopropylmethyldiethoxysilane.

Preferably, in step 1), the hydrolysis reaction and the condensation reaction are carried out in desalinated water.

Preferably, the first catalyst is a basic catalyst, and the basic catalyst is a combination of one or more selected from catalysts such as potassium hydroxide, sodium hydroxide, and tetramethylammonium hydroxide.

Preferably, the siloxane ring body is a combination of one or more selected from octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane and decamethylcyclopentasiloxane.

Preferably, the silicone end-capping agent is a combination of one or more selected from hexamethyldisiloxane, octamethyltrisiloxane and decamethyltetrasiloxane.

Preferably, in step 1), the hydrolysis reaction and the condensation reaction are carried out at 10°C to 200°C, and the reaction time is 1 to 12 hours. More preferably, in step 1), the hydrolysis reaction and the condensation reaction are carried out at 10°C to 100°C, and the reaction time is 2 to 8 hours.

Preferably, in step 1), the polycondensation reaction is carried out at 10°C to 200°C, and the reaction time is 1 to 12 hours. More preferably, in step 1), the polycondensation reaction is carried out at 80°C to 200°C, and the reaction time is 2 to 8 hours.

Preferably, the amidation reaction in step 2) is carried out in the presence of a protective gas (for example, nitrogen, etc.).

Preferably, the general structural formula of the perfluoropolyether compound is R _f OR ₈ , wherein R ₈ is a C1-10 alkyl group. According to some specific _{aspects of} the _invention , _{R8 can be -CH3 , -CH2CH3 , -CH2CH2CH3 , -CH2CH2CH2CH3 , -CH2CH2CH2CH2CH 3} , _{-CH2CH2CH2CH2CH2CH3} , -CH _{( CH3 ) CH3} or _{-C ( CH3 ) 2CH3 .}

Preferably, in step 2), the amidation reaction is carried out at 50°C to 200°C, and the reaction time is 1 to 12 hours. More preferably, in step 2), the amidation reaction is carried out at 50°C to 150°C, and the reaction time is 3 to 12 hours. Further preferably, in step 2), the amidation reaction is carried out at 50°C to 120°C, and the reaction time is 3 to 10 hours.

Preferably, the second catalyst can be selected from triethylamine, tetrabutyl titanate, dibutyltin dilaurate, stannous octoate, dibutyltin bis(dodecyl sulfide) and dibutyltin diacetate. a combination of one or more.

Preferably, the polymerization inhibitor is selected from hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone and 2,5-di-tert-butyl paraquinone A combination of one or more of the diphenols.

Preferably, in step 3), the solvent is one selected from ethyl acetate, ethyl propyl ester, butyl acetate, amyl acetate, methyl ethyl ketone, methyl butyl ketone and methyl isobutyl ketone or a combination of more than one.

Preferably, the isocyanate compound is selected from isophorone diisocyanate and its trimer, toluene diisocyanate and its dimer and trimer, hexamethylene diisocyanate and its dimer and trimer , a combination of one or more of dicyclohexylmethane diisocyanates. It can also be the reaction product of the above-mentioned isocyanate and a hydrophilic double-ended hydroxyl compound, wherein the hydrophilic double-ended hydroxyl compound is selected from the group consisting of polytetrahydrofuran ether glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol A combination of one or more of the alcohol-polypropylene glycol copolymers. When the isocyanate compound is the reaction product of the above-mentioned isocyanate and the hydrophilic double-ended hydroxyl compound, the specific implementation of step 3) is: firstly make the above-mentioned isocyanate and the hydrophilic double-ended hydroxyl compound in the presence of the second catalyst The following reaction generates an NCO-terminated prepolymer product (for the convenience of description, referred to as step a), and then adds a polymerization inhibitor and a hydroxy acrylate compound, and reacts (for the convenience of description, referred to as step b) to generate a product containing NCO and acrylate Product 3 of the functional group.

Preferably, the hydroxyacrylate compound is selected from pentaerythritol triacrylate and/or dipentaerythritol tetraacrylate.

Preferably, in step 3), the reaction is carried out at 20-150° C., and the reaction time is 1-12 hours.

Preferably, in step 3), when the isocyanate compound is the reaction product of the above-mentioned isocyanate and a hydrophilic double-ended hydroxyl compound, step a is carried out at 60-150°C.

Preferably, in step 3), when the isocyanate compound is the reaction product of the above-mentioned isocyanate and a hydrophilic double-ended hydroxyl compound, step b is carried out at 20-80°C.

Preferably, in step 4), the reaction is carried out at 0°C to 80°C, and the reaction time is 2 to 12 hours.

According to some specific aspects of the present invention, the embodiment of step 4) is: slowly drop the product 3 prepared in step 3) into the product 2 prepared in step 2), and react.

The above scheme will be further described below in conjunction with specific examples; it should be understood that these examples are used to illustrate the basic principles, main features and advantages of the present invention, and the present invention is not limited by the scope of the following examples; The implementation conditions can be further adjusted according to specific requirements, and the unspecified implementation conditions are usually those in routine experiments.

Unless otherwise specified below, all raw materials are commercially available or prepared by conventional methods in the art.

Example 1

This embodiment provides a water-soluble antifouling and antigraffiti additive 1# sample (PFPE-1), and the structural formula of PFPE-1 is as follows:

Among them, a=1, b=1, c=8, d=11, and PEG represents a polyethylene glycol molecular segment.

Its preparation method is as follows:

In a 1L three-necked flask, γ-aminopropylmethyldimethoxysilane (5.25g), 3-piperazinylpropylmethyldimethoxysilane (5.8g) and 10g of desalted water were added, and the temperature was heated at 50°C. The hydrolysis reaction was stirred under the conditions for 5 hours, and the negative pressure was slowly turned on and dehydrated to obtain a dry silane low boiler; then potassium hydroxide powder (0.01g), octamethylcyclotetrasiloxane (15g) and hexamethyldisiloxane were added. Alkane (4.05g) was slowly heated to 130°C, and the stirring reaction time was 4 hours. Finally, the low boilers were removed by vacuum to obtain dry amino silicone oil; under nitrogen protection, perfluoropolyether methanol ester ( 50g, the structural formula is as follows, wherein R _f selects hexafluoropropylene oxide polymerization unit, provided by Taicang Sinochem Environmental Protection Chemical Co., Ltd.), slowly warming up to 80 ° C, the reaction time is 8 hours, and obtains perfluoropolyether modified amino silicone oil .

In a 1L three-necked flask, add dibutyltin tin dilaurate (2g), isophorone diisocyanate (11g), polyethylene glycol (25g, molecular weight is 1000g/mol, polymerization unit is _{CH2CH2O )} and Butyl acetate (100g) was slowly heated to 80°C under nitrogen protection, and the reaction was stirred for 2 hours to obtain an isocyanate prepolymer; the reaction system was cooled to 50°C, and the polymerization inhibitor p-hydroxyanisole (0.25g) was added, Slowly add pentaerythritol triacrylate (7.75g) under stirring conditions, and the reaction time is 4 hours to obtain an acrylate compound containing NCO, and then add solvent butyl acetate (188g); control the reaction temperature to be 10 ° C, under stirring conditions The above product is slowly dropped into the perfluoropolyether modified amino silicone oil, the reaction time is 4 hours, the NCO peak disappears after sampling for infrared spectrum analysis, and the solvent is removed from the reaction product under reduced pressure to obtain the water-soluble anti-fouling and anti-graffiti additive PFPE -1.

The structure of R _f in the raw material perfluoropolyether methyl ester R _f OCH ₃ involved in the preparation method is:

其中，d＝11；

Among them, d=11;

The product PFPE-1 compound was subjected to nuclear magnetic H ¹ NMR analysis. The H ¹ NMR analysis results of PFPE-1 are shown in Figure 1. It can be seen from Figure 1 that the chaotic chemical shift peaks in the range of 0ppm to 0.2ppm belong to polydimethyl Absorption peaks of silyl methyl protons on siloxane side groups; chaotic chemical shift peaks in the range of 1.0 ppm to 2.0 ppm are attributed to silyl methylene groups and isophorone molecular rings on polydimethylsiloxane side groups The proton absorption peak of 3.5ppm is attributed to the methylene group on the middle segment of polyethylene glycol; other chaotic chemical shift peaks in the range of 2.0ppm to 4.5ppm are attributed to piperazine and isophorone molecules The methylene group connected with the urea group (or the amide group and the urethane bond) on the ring, and the absorption peak of the methylene group on the pentaerythritol; the double bond in the acrylate structure appeared in the range of 5.5-6.5ppm The proton chemical shift peaks prove that the acrylate functional group has been successfully introduced into the PFPE molecular chain.

Example 2

This embodiment provides a 2# sample (PFPE-2) of a water-soluble antifouling and antigraffiti additive.

According to the steps and processes shown in Example 1, the mass of isophorone diisocyanate was replaced with 22 g, the mass of polyethylene glycol was replaced with 50 g, the supplementary amount of solvent butyl acetate was replaced with 300 g, and the mass of pentaerythritol triacrylate was replaced with 15.5 g g, the mass of 3-piperazinylpropylmethyldimethoxysilane was changed to 11.6g, and the rest conditions and mass were the same as those in Example 1, and the water-soluble antifouling and antigraffiti additive 2# sample (PFPE-2 ).

Example 3

This embodiment provides a 3# sample (PFPE-3) of a water-soluble antifouling and antigraffiti additive.

According to the steps and processes shown in Example 1, the mass of isophorone diisocyanate was replaced by 22g, the molecular weight of polyethylene glycol was replaced by 2000g/mol, the mass of polyethylene glycol was replaced by 100g, and the supplementary amount of solvent butyl acetate was replaced It is 425g, the mass of pentaerythritol triacrylate is replaced by 15.5g, the mass of 3-piperazinyl propylmethyldimethoxysilane is replaced by 11.6g, and the other conditions and quality are the same as those in Example 1. Graffiti Auxiliary 3# sample (PFPE-3).

Comparative Example 1

The present embodiment provides a preparation method of a water-soluble antifouling and antigraffiti additive 4# sample (PFPE-4), which is as follows:

In a 1L three-necked flask, add perfluoropolyether methyl ester (100g, the specification is the same as Example 1) and aminoethanol (10g, the specification is the same as Example 1), slowly heat up to 80 ° C, the reaction time is 8 hours, sampling infrared analysis The infrared absorption peak (1792cm ^-1 ) of measuring the ester bond disappeared, and the amide bond absorption peak (1712cm ^-1 ) appeared; the reaction product crude product was stirred and washed with anhydrous methanol, left to stand for stratification, and the lower layer liquid was taken out, repeated 3 times, at 80 ℃ Decompression and low boiling drying at ℃ to obtain pure perfluoropolyether amidoethanol.

In a 1L three-necked flask, add dibutyltin tin dilaurate (5g), isophorone diisocyanate (11g), polyethylene glycol (200g, molecular weight is 4000g/mol, polymerization unit is _{CH2CH2O )} and Butyl acetate (800g) was slowly heated to 80°C under nitrogen protection, and the reaction was stirred for 2 hours to obtain an isocyanate prepolymer; the reaction system was cooled to 50°C, and the polymerization inhibitor p-hydroxyanisole (0.50g) was added, Slowly add pentaerythritol triacrylate (15.50g) under stirring conditions, the reaction time is 4 hours to obtain an acrylate compound containing NCO, and then add solvent butyl acetate (188g); control the reaction temperature to be 10 ° C, under stirring conditions The above product is slowly dropped into the pure product of perfluoropolyether amidoethanol, the reaction time is 4 hours, the NCO peak disappears after sampling for infrared spectrum analysis, and the reaction product is decompressed and the solvent is removed to obtain a water-soluble antifouling and anti-graffiti assistant. agent PFPE-4.

where a=11 and q=45.

Preparation of coatings

UV 2282科思创公司提供，HDDA代表1,6-己二醇二丙烯酸酯(百灵威公司提供)，Irgacure2959代表光固化引发剂巴斯夫提供；Compounded according to the formula shown in Table 1 (the addition amount of each component is in parts by weight), dispersed at a high speed for 20 minutes to prepare a UV coating, and then sprayed the coating on a polycarbonate (PC) plastic coating test plate, and painted The film was first leveled at room temperature for 5 minutes, then placed in a 50°C oven for 30 minutes, and finally placed in a RW-UVA201-20 UV light curing machine for curing. In the table, UV2282 represents water-based UV-curable polyurethane dispersions

UV 2282 is provided by Covestro, HDDA stands for 1,6-Hexanediol diacrylate (provided by Bailingwei), and Irgacure2959 is provided by BASF for light curing initiator;

Performance test of paint film

Evaluation of graffiti resistance: After graffiti on the surface of the paint film with a powerful oily black marker and dried at room temperature for 4 hours, wipe the stains on the surface of the paint film with a dry paper towel to observe whether there are any stains on the surface of the paint film. Grading is done according to the following standards:

Level 1: Indicates that the stains can be easily wiped off, and there is no residue inside the paint film;

Level 2: It means that the stain can be wiped off, but it is laborious, and there is no residue inside the paint film;

Level 3: Indicates that the stain can be wiped off, but there is ink infiltrated inside the paint film;

Level 4: Indicates that the stain cannot be wiped off.

Contact angle test method: place the test piece without any wear on the contact angle meter (model: DSA30, provided by Klusch Co., Ltd., Germany), with deionized water and dodecane as the test medium, and the test droplet volume is 4 μL, record the contact angle value of 3 droplets, and take the arithmetic mean of 3 test data.

Friction durability evaluation: fix the test piece on the abrasion resistance tester (ESIDA-NM-002, provided by Shenzhen Yi Shida Instrument Equipment Co., Ltd.), and bundle the polypropylene non-woven fabric (model: B95) on the friction probe of the contact head , Jiangxi Haorui Industrial Materials Co., Ltd.); a test load of 500g is applied above the probe, the test stroke is 20mm, and the sample speed is 10 times/min; after the wear test is carried out for 20 minutes, the experiment is stopped and the contact angle of the surface is lost.

The test results of graffiti resistance, contact angle, and friction durability are shown in Table 1.

Table 1 shows the formulation and performance test results of the coatings

By comparing the paint samples S1, S2, S3, S4, S5, S6 with the blank sample paint S7, it can be seen that the introduction of PFPE into the water-based paint formulation can significantly improve the anti-graffiti performance, and the paint film without PFPE has no anti-fouling properties. , oleic acid can spread completely on the surface of the paint film, oily marker ink can contaminate the paint film and cannot be erased; compared with S6, the paint film surface of S1, S2, S3, S4 and S5 has higher water and The contact angle of oleic acid is due to the introduction of multiple acrylate UV-curable reactive functional groups and polysiloxane segments in the waterborne coatings S1, S2, S3, S4 and S5, which have a higher phase with the waterborne coating bulk. Solubility and adhesion, the water-based paint has higher wear resistance, and the perfluoropolyether segment migrates more thoroughly, which greatly improves the anti-fouling and anti-graffiti performance; at the same time, through the water-based paint samples S1, S4 and S5 By comparison, it is found that the increase in the content of PFPE-based anti-fouling and anti-graffiti additives in the paint film helps to improve the anti-fouling performance, but the change of the increase rate with the content is not obvious, which proves that when the PFPE-based anti-fouling and anti-graffiti additives in the water-based coating formulations After the content reaches a certain level, the anti-fouling property is not significantly improved. The experimental results show that the water-soluble antifouling and anti-graffiti adjuvant provided by the present invention with both water-solubility and UV light curing activity can have good compatibility and adhesion with the water-based UV paint film, and can make the perfluoropolyether segment migrate. It is more thorough, so the paint film added with it has good anti-fouling performance and abrasion resistance.

The present invention has been described in detail above, and its purpose is to enable those skilled in the art to understand the content of the present invention and implement it, and cannot limit the scope of protection of the present invention by this, and the present invention is not limited to the above-mentioned embodiments, All equivalent changes or modifications made according to the spirit of the present invention should be included within the protection scope of the present invention.

Claims (5)

1. a water-soluble antifouling anti-graffiti auxiliary, is characterized in that, described water-soluble antifouling anti-graffiti auxiliary has the following general structural formula:

wherein, R _f is a perfluoropolyether acyl group; X ₁ is -R ₁ -NH-, wherein R ₁ is a C _1-20 alkylene group, and R _f is connected to the nitrogen atom of the secondary amino group; X ₂ is a water-soluble organic group containing a tertiary amino group represented by the following formula,

Wherein, R ₂ is a C _1-20 alkylene group; R ^A is -CO-NH-R ₃ -NH-COO-R ₄ , wherein the R ₃ is

R ₄ is -(CH ₂ ) _j -C(CH ₂ OOC-CH=CH ₂ ) ₃ , or, -(CH ₂ ) _k -C(CH ₂ OOC-CH=CH ₂ ) ₂ -CH ₂ -O-CH ₂ -C(CH ₂ OOC-CH=CH ₂ ) ₃ , where j and k are independently selected positive integer; R ₅ and R ₆ are each independently -NH-CO-OR ₇ -O-CO-NH-, R ₇ is an alkylene group selected from C _1-10 , -(C _m H _2m O) _r1 -C _m A combination of one or more of H _2m -, -(C _p H _2p O) _r2 -(C _s H _2s O) _r3 -C _m H _2m -, m, p, s, r1, r2 and r3 respectively Independently selected from positive integers, p and s are different, and the R ^A is connected to the nitrogen atom of the tertiary amino group in the X ₂ through the carbon atom on the -CO-NH- it contains; R ^C is -C _n H _2n-1 , and n is a positive integer; a, b, and c are each independently selected from an integer greater than or equal to 1. 2. water-soluble antifouling anti-graffiti auxiliary agent according to claim 1, is characterized in that, described R _f is the combination of one or more selected from the following groups:

Among them, 50≥d≥2;

Among them, 50≥e≥2;

Among them, 50≥f≥2, 50≥g≥2;

Among them, 50≥h≥2, 50≥i≥2. 3. The water-soluble antifouling and antigraffiti adjuvant according to claim 1, wherein the R ^C is an alkyl group of C _1-10 ; and/or, a and b are independently selected from 1-10 Integer, c is an integer selected from 3-30. 4. water-soluble antifouling anti-graffiti auxiliary agent according to claim 1, is characterized in that, described water-soluble antifouling anti-graffiti auxiliary agent is a kind of selected from following structural formula:

Among them, 50≥d≥2, a, b, c and t1 are independently positive integers;

Among them, 50≥d≥2, a, b, c and t2 are independently positive integers;

Among them, 50≥d≥2, a, b, c and t3 are independently positive integers;

Among them, 50≥d≥2, a, b, c, t4 and t5 are independently positive integers;

Wherein, 50≥d≥2, and a, b, c, t6 and t7 are each independently positive integers. 5. An anti-fouling and anti-graffiti water-based UV light-curable coating, wherein the raw material contains the water-soluble anti-fouling and anti-graffiti auxiliary according to any one of claims 1 to 4.

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