CN101245005A - Modified acrylic oligomer and anti-fouling coating containing oligomer - Google Patents

Abstract

The present invention provides a modified acrylic oligomer comprising polymerized units derived from the following monomers: (1) an acrylic monomer; (2) a monomer selected from the group consisting of fluorinated acrylic monomers, siloxane monomers, and mixtures thereof; and (3) optionally, a tertiary carboxylate monomer; wherein the oligomer also comprises groups derived from a modifier selected from the group consisting of epoxy (meth) acrylates, urethane acrylates, polyester acrylates, 2-hydroxyethyl (meth) acrylate, and mixtures thereof. The invention also provides an anti-fouling coating containing the modified acrylic oligomer.

Description

Modified acrylic oligomer and antifouling paint containing said oligomer

technical field

The invention relates to a modified acrylic acid oligomer and the paint prepared therefrom, especially a radiation-curable antifouling paint.

Background technique

Coatings are widely used in buildings, ships, machinery, electronic products, metal products and wood products, etc. The main purpose is to protect and beautify objects. However, due to the fact that the coating may suffer from various external pollutions at any time in the environment of use, such as floating dust in the air, oily smoke, poorly charged conductors, industrial acid rain, etc., if the anti-fouling property of the coating is not good, its decorative effect will be reduced. Short-term deterioration will cause the paint to lose its original color and become black or yellow, impairing its appearance or protective performance.

Conventional technology has used organic fluorinated polymers in the coating industry. The principle is that the surface tension of fluorinated polymers is low, and the adhesion interface between the coating and pollution sources or adherents is not strong, so pollution sources are not easy to adhere. Low surface energy properties such as polytetrafluoroethylene (PTFE) have long been known. Japanese Patent Application No. 6-345823 discloses a fluorine-containing copolymer resin polymerized with hydroxyl-containing acrylic monomers, fluoroethylene monomers, and perfluorovinyl monomers. The hardener bridges and hardens to obtain a coating film, which has excellent weather resistance and water repellency. Japanese Patent Application Publication No. 7-26204 also discloses a fluorine-containing polyurethane polymer made from polyols containing unsaturated groups (molecular weight 300-3000) and perfluoroacrylic acid or perfluorovinyl monomers. Fluoropolymer coatings are also better in weather resistance, corrosion resistance, and chemical resistance than before.

In addition to organic fluorinated polymers, organosilicone is also widely used in antifouling because of its low surface energy. It is known that the addition of silicone additives to coatings can reduce surface tension and thus achieve antifouling effects. However, the durability of the anti-fouling effect is limited due to the surface migration effect of silicone additives, resulting in the reduction of active ingredients over time.

In addition, when the material reaches the nanometer size, it may have characteristics that it does not have when it is generally larger. In view of this, many studies have attempted to apply nanotechnology to coatings to enhance the durability of the antifouling effect, for example, research on nano-microstructured surfaces with antifouling effects and apply them to coatings. For example, in the known lotus effect (Lotus Effect), the surface of the lotus leaf has a hydrophobic nano-microstructure similar to fibers. This hydrophobic nano-microstructure can not only make water form beads, but also reduce The contact area with water droplets or dust reduces the force of attachment to each other, making it difficult for water droplets or dust to adhere to the leaf surface. In addition, the water droplets are easy to absorb dust particles during the rolling process, which can achieve the effect of self-cleaning. China Taiwan Province patent I248459 (Chinese patent 1266236) promptly discloses a kind of antifouling coating, and it applies nanometer technology to coating, utilizes resin side long-chain fluorine segment or silicone segment to reduce the surface tension of coating and improve the anti-fouling coating of coating. Pollution resistance, and the use of tertiary carbonates to further provide compatibility, to obtain a fluorine-containing coating film with excellent compatibility. The coating provided in this Taiwan patent case is a traditional thermosetting coating.

Because traditional coatings are volatile, slow curing, and unfavorable to environmental protection, the industry is actively developing radiation curing technology, which uses radiation (especially ultraviolet light) to cause free radical crosslinking of coating resins to cure. Generally speaking, radiation curing technology can be divided into ultraviolet (UV) curing technology, non-UV curing technology, oil-based photo-curing technology, and water-based photo-curing technology according to the type of radiation source and solvent. And more than 80% of radiation curing technology products use UV curing technology. Radiation curing technology has the advantages of no volatile organic compounds (VOC), less environmental pollution, fast curing speed, high efficiency, energy saving, excellent performance of cured products, suitable for heat-sensitive substrates, and suitable for high-speed automatic production. Widely used in electronics, communications, building materials, packaging and other fields, especially in the application of plastic coatings, because the plastic substrate itself is not resistant to high temperature, so radiation curing has an absolute advantage. Radiation curing is now gradually replacing traditional curing techniques.

Therefore, how to apply nanotechnology to the coating industry, and use the conventional fluorine and silicone to reduce surface tension to achieve anti-fouling effect, and at the same time try to change the traditional curing mechanism into a radiation curing mechanism has become the active goal of the coating related industries. research topic.

Contents of the invention

In view of this, the main purpose of the present invention is to provide a modified acrylic oligomer, which has a fluorocarbon side chain and/or a silicone side chain, so it can be applied to provide an antifouling effect in coatings; and the oligomer With photosensitive groups on the material, it is suitable for radiation curing mechanism.

Another object of the present invention is to make use of the incompatibility between the oligomer fluorocarbon side chain and the main chain or other side chain structures to make the fluorocarbon molecules with low surface energy self-assemble on the surface of the coating to form a hydrophobic nano-microstructure , and have a synergistic effect with the silicone side chain to enhance the antifouling effect.

To achieve the above disclosure and other purposes, the present invention provides a modified acrylic oligomer comprising polymerized units derived from the following monomers:

(1) Acrylic monomer;

(2) monomers selected from the group consisting of fluorinated acrylic monomers, silicone monomers, and mixtures thereof; and

(3) Optionally, a tertiary carboxylate monomer;

Wherein the oligomer further comprises a group derived from epoxy (meth)acrylate, urethane acrylate, polyester acrylate, 2-hydroxyethyl (meth)acrylate and mixtures thereof Group of modifier groups.

The antifouling coating of the present invention has good and long-lasting antifouling effect, and is suitable for radiation curing mechanism at the same time.

Description of drawings

Figure 1 is a schematic diagram of the structure of the modified oligomer of the present invention.

Fig. 2 is a schematic diagram of the cross-linked structure of the modified oligomer of the present invention.

Detailed ways

The acrylic monomers used to form the oligomers of the present invention have the general formula:

Wherein, R ¹ is halogen, H, CH ₃ or C ₂ H ₅ ; and R ² is H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , C ₆ H ₁₃ , C ₂ H ₄ OH, C ₃ H ₆ OH, C ₁₀ H ₁₇ (isobornyl) or the following groups:

Examples of the aforementioned acrylic monomers include, but are not limited to, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid - 2-Hydroxyethyl ester, 2-hydroxypropyl methacrylate, hexyl ethacrylate, isobornyl methacrylate or mixtures thereof.

的反应性基团的单体，其例如但不限于选自由(甲基)丙烯酸、环氧(甲基)丙烯酸酯、丙烯酸羟乙酯(hydroxyethyl acrylate，HEA)、丙烯酸羟丙酯(hydroxypropyl acrylate，HPA)、甲基丙烯酸-2-羟基乙酯(2-hydroxyethyl methacrylate，2-HEMA)、甲基丙烯酸羟丙酯(hydroxypropylmethacrylate，HPMA)、甲基丙烯酸2-羟基丙酯(2-hydroxypropylmethacrylate，2-HPMA)及其混合物所组成的群组的单体。较佳地，本发明所用丙烯酸类单体包含至少一种具有羟基(-OH)的反应性基团的单体，其系选自由丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸2-羟基丙酯及其混合物所组成的群组。In order to enable the oligomer to react with the modifier for modification, whereby the photosensitive group is attached to the oligomer, the acrylic monomer used in the present invention needs to contain at least one kind of compound having hydroxyl (-OH), carboxyl (-COOH) or epoxy

The monomer of the reactive group, which is for example but not limited to be selected from (meth)acrylic acid, epoxy (meth)acrylate, hydroxyethyl acrylate (hydroxyethyl acrylate, HEA), acrylate (hydroxypropyl acrylate, HPA), 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate, 2-HEMA), hydroxypropyl methacrylate (HPMA), 2-hydroxypropyl methacrylate (2-hydroxypropylmethacrylate, 2- monomers of the group consisting of HPMA) and mixtures thereof. Preferably, the acrylic monomer used in the present invention contains at least one monomer having a hydroxyl (-OH) reactive group selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid-2- The group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate and mixtures thereof.

的反应性基团的单体的用量，以丙烯酸类单体的总单体量计，系5-50重量％，较佳系10-40重量％。The amount of acrylic monomer used in the present invention is 20-85% by weight, preferably 50-80% by weight, based on the total amount of oligomer-forming monomers. Among them, the hydroxyl group (-OH), carboxyl group (-COOH) or epoxy group

The amount of monomers with reactive groups is 5-50% by weight, preferably 10-40% by weight, based on the total amount of acrylic monomers.

The fluorinated acrylic monomers used to form the oligomers of the present invention have the general formula:

R ¹ CH ₂ CH ₂ O(O)CC(R)=CH ₂

Wherein R ¹ is a linear or branched perfluorinated alkyl group: C _x F _2x+3 , wherein x is an integer ranging from 1 to 20, and R is H, CH ₃ , C ₂ H ₅ or C ₃ H ₇ . The fluorinated acrylic monomer of the present invention is preferably fluorinated alkyl acrylate, fluorinated alkyl methacrylate or a mixture thereof, more preferably fluorinated alkyl acrylate, methacrylic acid with x=6 to 14 Fluorinated alkyl esters or mixtures thereof.

According to the present invention, the amount of the fluorinated acrylic monomer is 0-40% by weight, preferably 1-20% by weight, based on the total weight of the oligomer-forming monomers.

The siloxane monomers used to form the oligomers of the present invention have the general formula:

其中p＝10至250。Wherein, each of R ⁷ and R ⁸ is H, Me, CH ₂ =CH, NH ₂ , NH ₂ -C ₃ H ₆ , OH-C ₂ H ₄ OC ₃ H ₆ , CH ₂ =CCH ₃ -COO, CH ₂ =CH-COO, CH ₃ =CCH ₃ -COOC ₂ H ₁ , CH ₂ =CCH ₃ -COOC ₃ H ₆ or

where p=10 to 250.

According to the present invention, the amount of siloxane monomer used is 0-40% by weight, preferably 1-20% by weight, based on the total amount of oligomer-forming monomers used.

The oligomer of the present invention may optionally contain one or more polymerized units derived from tertiary carboxylate monomers to adjust properties such as hardness and toughness of the desired coating. The tertiary carboxylic acid esters used to form the oligomers of the present invention have the following general formula:

wherein R ² , R ⁴ and R ⁵ each represent a straight-chain or branched C ₁ -C ₇ alkyl group, and preferably, the sum of the carbon numbers of R ³ , R ⁴ and R ⁵ is 9, 10 or 11; R ^is selected from the group consisting of the following groups:

and

The preferred tertiary carboxylate monomer system is selected from the group consisting of saturated tertiary decyl carboxylic acid vinyl ester, tertiary nonanoic acid vinyl ester, saturated tertiary decyl carboxylic acid glycidyl ester and mixtures thereof. When present, the tertiary carboxylate monomer is used in an amount of 5-50% by weight, preferably 10-40% by weight, based on the total amount of oligomer-forming monomers.

等活性基团反应，进而将寡聚物改性。上述改性剂系选自环氧(甲基)丙烯酸酯、胺基甲酸酯丙烯酸酯、聚酯丙烯酸酯、(甲基)丙烯酸2-羟乙基酯或其混合物。In order to make the oligomer have a photosensitive group for use in the radiation curing mechanism, the present invention further adds a modifier containing a photosensitive group to modify the oligomer so that it has a C= The photosensitive group of the C double bond. Modifier used in the present invention can be combined with hydroxyl (-OH), carboxyl (-COOH) or epoxy group in the oligomer

and other active groups react to modify the oligomer. The modifier is selected from epoxy (meth)acrylate, urethane acrylate, polyester acrylate, 2-hydroxyethyl (meth)acrylate or mixtures thereof.

The modifier used in the present invention is preferably urethane acrylate. The urethane acrylate system has the general formula:

Wherein, m=0, 1, 2 or 3, n=1 to 5, R ⁹ is H or CH ₃ , and G is a divalent organic group. Preferably, G is a divalent aromatic group or a divalent aliphatic group. More preferably, G is selected from the group consisting of the following groups:

或

且Y为C₁-C₂烷基。wherein each Y is independently hydrogen, halogen, C ₁ -C ₄ perfluoroalkyl or C ₁ -C ₄ alkyl. According to a specific embodiment of the present invention, G is

or

And Y is C ₁ -C ₂ alkyl.

According to the present invention, the amount of the modifying agent is 20-60% by weight, preferably 30-50% by weight, based on the total weight of the oligomer and the modifying agent.

The modified acrylic oligomer of the present invention is firstly polymerized from acrylic monomers, fluorinated acrylic monomers and/or siloxane monomers, and optional tertiary carboxylate monomers, and then undergoes an optional It is prepared by modification with modifiers from the group consisting of epoxy (meth)acrylate, urethane acrylate, polyester acrylate, 2-hydroxyethyl (meth)acrylate and mixtures thereof become.

According to a preferred embodiment of the present invention, the modified acrylic oligomer of the present invention comprises a polymer derived from acrylic monomers, tertiary carboxylate monomers, fluorinated acrylic monomers and siloxane monomers units, and modifier groups derived from urethane acrylate.

According to another preferred embodiment of the present invention, the modified acrylic acid oligomer of the present invention has a structure of formula (1):

Wherein R ¹¹ is halogen, H, CH ₃ or C ₂ H ₅ ;

R ¹² is H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , C ₂ H ₄ OH, C ₃ H ₆ OH, C ₁₀ H ₁₇ or R ¹⁵ is

或

且Y为C₁-C₂烷基；Wherein m=0, 1, 2 or 3, preferably 0 or 1, n=1 to 5, preferably 1 or 2, R ⁹ is H or CH ₃ , G is

or

And Y is C ₁ -C ₂ alkyl;

R ³ to R ⁵ are as previously defined herein;

R ¹ is a linear or branched perfluorinated alkyl group: C _x F _2x+1 , where x is an integer from 1 to 20;

R⁸为Me、CH₂＝CH、OH-C₂H₄OC₃H₆或

p＝10至250；R ¹⁴ is

R ⁸ is Me, CH ₂ ═CH, OH—C ₂ H ₄ OC ₃ H ₆ or

p = 10 to 250;

z is 0, 1, 2 or 3;

a is a value from 2 to 20;

b is a value from 5 to 50;

c is a value from 0 to 15;

d is a value from 5 to 20;

e is a numerical value from 0 to 30.

It should be noted that the polymerized units in formula (1) can be arranged in any suitable order. For example, the oligomer of formula (1) can be a random oligomer (Random oligomer), wherein each polymerization unit is randomly arranged to form the backbone of the oligomer, and its arrangement is such as but not limited to: abcde, abecd, etc. .

The preparation method of the modified acrylic acid oligomer of the present invention is not particularly limited, and the modified acrylic acid oligomer can be prepared by any well-known method of those skilled in the art of the present invention. In the present invention, monomers such as acrylic monomers, fluorinated acrylic monomers and/or siloxane monomers and optional tertiary carboxylate monomers are mixed with appropriate initiators and solvents to carry out Polymerization reaction, and then modify the polymerization product with modifier. The types of initiators and solvents used in the above polymerization reaction are not particularly limited, and are well known to those skilled in the art to which the present invention pertains.

The modified acrylic oligomer prepared by the present invention has fluorocarbon side chains and/or silicone side chains with low surface energy, which can provide good water repellency and antifouling properties, so it can be effectively used in antifouling in paint. When the oligomer contains fluorocarbon side chains, due to the incompatibility between the fluorocarbon side chains and the main chain or other side chain structures and the low specific gravity, when the oligomers are further polymerized to form a coating, the fluorocarbon side chains will Naturally migrate to the surface of the coating to form a hydrophobic nano-microstructure, thereby reducing surface tension. The above-mentioned coating has a structural feature similar to the lotus leaf effect, and has the advantages of anti-fouling, waterproof and high durability. In a preferred embodiment of the present invention, the modified acrylic oligomer of the present invention has both silicone side chains and fluorocarbon side chains, and through the synergistic effect of the silicone side chains and the fluorocarbon side chains, effectively Improve anti-fouling effect.

In addition, since the modified acrylic oligomer of the present invention has a photosensitive group, it can be used not only in the thermal curing mechanism but also in the radiation curing mechanism to provide a radiation curable antifouling coating.

Figure 1 is a schematic structural view of an embodiment of the modified acrylic oligomer 100 of the present invention, wherein the main chain 107 of the oligomer has a silicone/fluorocarbon side chain 101, a side chain 105 containing a photocurable group and other side chains 103 derived from acrylic monomers. When irradiated with radiation, the oligomer of the present invention generates a cross-linked structure 200 as shown in FIG. 2 through the interaction of photocurable groups.

The present invention further provides an antifouling paint comprising the modified acrylic oligomer of the present invention. According to the present invention, the content of the modified acrylic oligomer is not particularly limited, and can be present in the coating in any appropriate proportion. For example, the modified acrylic oligomer of the present invention can be directly used as an antifouling paint alone; or an appropriate solvent, comonomer or a combination of the above two can be added as needed to improve the fluidity of the paint, so that It facilitates coating.

The above-mentioned types of solvents and comonomers are well known to those skilled in the art to which the present invention pertains. When the paint contains other components, the content of the modified oligomer is preferably 20-90% by weight based on the total weight of the paint.

The solvent used in the coating of the present invention can be any known to those having ordinary knowledge in the technical field of the present invention, such as but not limited to benzenes, esters, ketones or mixtures thereof. The content of the solvent used in the paint of the present invention is not particularly limited. Preferably, the content of the solvent is 5-50% by weight based on the total weight of the paint.

The benzene solvent suitable for the present invention may be selected from but not limited to the group consisting of benzene, o-xylene, m-xylene, p-xylene, trimethylbenzene, styrene and mixtures thereof. The ester solvents suitable for the present invention can be selected from but not limited to ethyl acetate, butyl acetate, diethyl carbonate, ethyl formate, methyl acetate, ethoxyethyl acetate, ethoxypropyl acetate, The group consisting of monomethyl ether propylene glycol acetate and mixtures thereof. The ketone solvent suitable for the present invention may be selected from but not limited to the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone and mixtures thereof.

The comonomer used in the coating of the present invention can be anyone known to those skilled in the art of the present invention, such as but not limited to 1,6-Hexanediol Diacrylate (1,6-Hexanediol Diacrylate; HDDA ), Tripropylene Glycol Diacrylate (TPGDA), Neopentyl Glycol Diacrylate (NPGDA), Ethoxylated Bisphenol-A Diacrylate (Ethoxylated Bisphenol-A Diacrylate; BPA4EODA), three ( 2-Hydroxyethyl) Isocyanurate Triacrylate (Tris (2-Hydroxy Ethyl) Isocyanurate Triacrylate; THEICTA), Trimethylolpropane Triacrylate (TMPTA), Pentaerythritol Triacrylate (PET3A) , Ethoxylated Trimethylolpropane Triacrylate (TMP3EOTA), Propoxylated Glyceryl Triacrylate (G3POTA or G3.5POTA), Pentaerythritol Tetraacrylate (PET4A), bis-trimethylol Ditrimethylolpropane Tetraacrylate (DiTMP4A), Dipentaerythritol Hexaacrylate (Dipentaerythritol Hexaacrylate; DPHA) or a mixture thereof. The content of the comonomer used in the coating of the present invention is not particularly limited. The content of the comonomer is preferably 10-60% by weight based on the total weight of the coating.

When the antifouling coating of the present invention is applied in a radiation curing mechanism, a photoinitiator can be added to the coating of the present invention to provide a radiation curable antifouling coating. The above-mentioned photoinitiator refers to one that generates free radicals after being irradiated with light, and initiates a polymerization reaction through the transmission of free radicals, and its type is well known to those with ordinary knowledge in the technical field of the present invention. The photoinitiator that is applicable to the present invention is not particularly limited, and it is for example but not limited to: Benzophenone (benzophenone), 2-hydroxyl-2-methyl-1-propiophenone (2-hydroxy-2-methyl-1 -phenyl-propan-1-one), 2,2-dimethoxy-1,2-diphenylethan-1-one (2,2-dimethoxy-1,2-diphenylethan-1-one), 1 -Hydroxycyclohexyl phenyl ketone (1-hydroxycyclohexyl phenyl ketone) (such as Irgacure 184, Eternal company), 2.4,6-trimethylbenzoyl diphenylphosphine oxide (2,4,6-trimethylbenzoyl diphenylphosphine oxide ), N-phenylglycine, 9-phenylacridine (9-phenylacridine), benzoins (benzoins), benzyldimethylketal (benzyldimethylketal), 4,4'-bis(diethyl Amine) benzophenones, 2,4,5-triarylimidazole dimers (2,4,5-triarylimidazole dimers) or combinations thereof. A preferred photoinitiator is benzophenone or 1-hydroxycyclohexyl phenyl ketone, more preferably benzophenone. The content of the photoinitiator used in the coating of the present invention is 3-15% by weight based on the total weight of the coating. In addition, the antifouling coatings of the present invention may optionally contain photoinitiation aids such as, but not limited to, tertiary amines.

The antifouling paint of the present invention may further comprise pigments and/or any additives known to those skilled in the art to which the present invention pertains. The above-mentioned additives are for example but not limited to dispersants, wetting agents, defoamers, accelerators, leveling agents, light stabilizers, ultraviolet absorbers, anti-settling agents, slip agents, matting agents or combinations thereof.

The construction method of the coating of the present invention can be any mode well-known to those skilled in the art, for example, coating is applied to the surface to be coated by screen printing, flow coating, roller coating, spraying, etc. to form a coating factory and then Curing methods such as heat or radiation cure the coating. By way of example, the antifouling coatings of the present invention can be applied, by radiation curing, in the following steps:

(1) Mix and stir the modified oligomer of the present invention with comonomer, solvent, photoinitiator anti-additive as required to form a coating;

(2) coating the coating prepared in step (1) on the surface to be coated to form a coating;

(3) At normal temperature or under heating, irradiate the coating of step (2) with energy rays to cure it. The energy ray refers to a light source in a certain wavelength range, such as ultraviolet light, infrared light, visible light or heat rays (radiant heat rays or radiant heat rays), etc., preferably ultraviolet light. The irradiation intensity can be 100 to 1000 millijoules/cm 2 (mJ/cm ² ), preferably 200 to 800 mJ/cm ² .

The following examples are used to further illustrate the present invention, but are not intended to limit the scope of the present invention. Modifications and changes that can be easily achieved by any person familiar with this technology are included in the scope of the content disclosed in the description of this case and the scope of the appended patent application.

In the examples, the abbreviations used are defined as follows:

AA: Acrylic

MAA: methacrylic acid

MMA: methyl methacrylate

IBMA: Isobornyl Methacrylate

BA: butyl acrylate

n-BMA: n-butyl methacrylate

2-HPMA: 2-Hydroxypropyl methacrylate

Zonyl ^TM (trade name): a mixture of 2-(perfluoroalkyl)ethyl acrylate, wherein the alkyl group is C ₁₈ , C ₁₀ and C ₁₂ perfluoroalkyl (DuPont, USA)

AS: Silicone methyl methacrylate (Silaplane, Japan CHISSO company)

Veova 10 (trade name): Vinyl ester of neodecanoic acid (Hexion, Singapore)

PMA: Propylene glycol monomethyl etheracetate

TBPB: tertiary butyl perbenzoate

IPDI: isophorone diisocyanate

TDI: toluene diisocyanate

HDDA: 1,6-hexanediol diacrylate

2-HEA: 2-Hydroxyethyl Acrylate

Preparation example

Preparation of oligomers: Take different proportions of monomers, solvents and appropriate initiators to prepare mixtures 1 and 2 of oligomers and solvents for further modification. The preparation conditions are shown in Table 1 below:

Table 1

mixture 1 2   Type and amount of monomer (g) AA 13.4 10.5 MAA 0.6 0.6 MMA 39.6 21.8 BA 17.1 -- 2-HPMA 13.2 31.5 Zonyl ^™ 7.0 3.6 Veova 10 46.6 18.6 n-BMA -- 10.5 IBMA -- 21.8 AS -- 7.0 Solvent (xylene) (g) 88 111 Solvent (PMA) (g) 17.6 17.6 Initiator (TBPB) (g) 0.5 3.0   Reaction temperature (°C) 130℃ 130℃ time 8 hours 8 hours   Solid content (weight%) 56.9 49.1

Preparation of modifiers A and B:

Modifier A:

Mix 27.5 parts by weight of 2-HEA and 52.5 parts by weight of IPDI, heat to 40-50°C, and react for 2 hours to obtain modifier (A), whose structure is as follows:

Modifier B:

Mix 27.5 parts by weight of 2-HEA and 41.2 parts by weight of TDI, heat to 40-50°C, and react for 2 hours to obtain modifier (B), whose structure is as follows:

Example 1-4

The mixtures 1 and 2 prepared above were respectively reacted with modifiers A and B to modify the oligomer. Subsequently, the reaction product is mixed with comonomer and other additives to obtain the antifouling coating of the present invention, and the preparation conditions are as shown in Table 2:

Table 2

Example 1 2 3 4 Raw materials (g) Mixture 1 171 165 -- -- Mixture 2 -- -- 171 165   Modifier A 80 -- 70 --   Modifier B -- 68.7 -- 60.1 HDDA 60 60 60 60 ¹ Etermer 231 186.6 186.6 186.6 186.6 ² Irgacure 184 12.44 12.44 12.44 12.44 Benzophenone (Benzophenol) 12.44 12.44 12.44 12.44 ³ Etercure 6420 31.1 31.1 31.1 31.1 ⁴ Eterslip 70 3.11 3.11 3.11 3.11 BYK 141 (defoamer) 0.6 0.6 0.6 0.6 EFKA5065 (dispersant) 2.5 2.5 2.5 2.5 UV55C (matting powder) 62.2 62.2 62.2 62.2 Reaction temperature (°C) 45℃ 45℃ 45℃ 45℃ time 3 hours 3 hours 3 hours 3 hours Solid content (weight%) 73.5 73.0 75.5 76.2

¹ Etermer 231 Trimethylolpropane Triacrylate (TMPTA)

² Irgacure 1841-hydroxyl cyclohexyl phenyl ketone (photoinitiator, Ciba company)

³ Etereure 6420 tertiary amine co-initiator

⁴ Eterslip 70 slip (Eternal)

Stain Resistance Testing of Coatings

The antifouling coatings of Examples 1 to 4 were coated on the substrate [PA-757, Chi Mei Industrial Co., Ltd.], and the antifouling test was carried out after UV light curing. The obtained results are shown in Table 3.

table 3

NOTE: Surface cleanliness means:

1-Good 2-Fair 3-Fair 4-Poor 5-Extremely poor

As can be seen from the results in Table 3, the antifouling coating of the present invention has good antifouling properties.

Claims (35)

1. modified acrylic acid oligomer, it comprises derived from following monomeric polymerized unit:

(1) acrylic monomer;

(2) be selected from the monomer of the group that is formed by fluorinated acrylamide acids monomer, siloxanyl monomers and composition thereof; And

(3) optionally, three grades of carboxylic acid ester monomers;

Wherein this oligomer further comprises the group derived from the properties-correcting agent that is selected from the group that is made up of epoxy acrylate, epoxy methacrylates, amido formate acrylate, polyester acrylate, vinylformic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester and composition thereof.

2. modified acrylic acid oligomer as claimed in claim 1, wherein properties-correcting agent is the amido formate acrylate.

3. modified acrylic acid oligomer as claimed in claim 2, wherein the properties-correcting agent cording has following general formula:

Wherein, m=0,1,2 or 3, n=1 to 5, R ⁹Be H or CH ₃, G is a divalent organic group.

4. modified acrylic acid oligomer as claimed in claim 3, wherein G is divalence aromatic group or aliphatic divalent group.

5. modified acrylic acid oligomer as claimed in claim 4, wherein G system is selected from by group that following groups constitutes:

And

Each independently is hydrogen, halogen, C for Y ₁-C ₄Perfluoroalkyl or C ₁-C ₄Alkyl.

6. modified acrylic acid oligomer as claimed in claim 5, wherein G is

Or

Y is C ₁-C ₂Alkyl.

7. modified acrylic acid oligomer as claimed in claim 1, wherein the consumption of properties-correcting agent in oligomer and properties-correcting agent gross weight, is 20-60 weight %.

8. modified acrylic acid oligomer as claimed in claim 1, the wherein following general formula of acrylic monomer cording:

Wherein, R ¹Be halogen, H, CH ₃Or C ₂H ₅And R ²Be H, CH ₃, C ₂H ₅, C ₃H ₇, C ₁H ₉, C ₆H ₁₃, C ₂H ₄OH, C ₃H ₆OH, C ₁₀H ₁₇Or following group:

9. modified acrylic acid oligomer as claimed in claim 1, wherein acrylic monomer comprises at least a monomer with reactive group of hydroxyl, carboxyl or epoxy group(ing).

10. modified acrylic acid oligomer as claimed in claim 9, wherein this acrylic monomer system with at least a reactive group is selected from the group that is made up of vinylformic acid, methacrylic acid, epoxy acrylate, epoxy methacrylates, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methacrylic acid-2-hydroxy methacrylate, Rocryl 410, methacrylic acid 2-hydroxy propyl ester and composition thereof.

11. modified acrylic acid oligomer as claimed in claim 10, wherein this acrylic monomer system with at least a reactive group is selected from the group that is made up of Hydroxyethyl acrylate, Propylene glycol monoacrylate, methacrylic acid-2-hydroxy methacrylate, Rocryl 410, methacrylic acid 2-hydroxy propyl ester and composition thereof.

12. modified acrylic acid oligomer as claimed in claim 1, wherein the consumption of acrylic monomer to form the total consumption of monomer of oligomer, is 20-85 weight %.

13. modified acrylic acid oligomer as claimed in claim 9, wherein this has the monomeric consumption of at least a reactive group, in the total monomer amount of acrylic monomer, is 5 to 50 weight %.

14. modified acrylic acid oligomer as claimed in claim 1, wherein three grades of carboxylicesterss system be selected from by saturated three grades the last of the ten Heavenly stems vinyl carboxylates, saturated three grades the ninth of the ten Heavenly Stems vinyl carboxylates and saturated three grades of groups that the last of the ten Heavenly stems, carboxylic acid epoxy propyl ester was formed.

15. modified acrylic acid oligomer as claimed in claim 1, wherein the consumption of three grades of carboxylicesterss to form the total consumption of monomer of oligomer, is 5-50 weight %.

16. modified acrylic acid oligomer as claimed in claim 1, wherein fluorinated acrylamide acids single mass system has following general formula:

R ¹CH ₂CH ₂O(O)CC(R)＝CH ₂

R wherein ¹Be the perfluorinated alkyl of straight chain or tool side chain: C _xF _2x+1, wherein x is 1 to 20 integer, R is H, CH ₃, C ₂H ₅Or C ₃H ₇

17. modified acrylic acid oligomer as claimed in claim 16, wherein fluorinated acrylamide acids single mass system vinylformic acid fluorinated alkyl esters, methacrylic acid fluorinated alkyl esters or its mixture.

18. modified acrylic acid oligomer as claimed in claim 1, wherein the monomeric consumption of fluorinated acrylamide acids to form the total consumption of monomer of oligomer, is 0-40 weight %.

19. modified acrylic acid oligomer as claimed in claim 1, wherein the siloxanyl monomers cording has following general formula:

Wherein, R ⁷And R ⁸Respectively be H, Me, CH ₂=CH, NH ₂, NH ₂-C ₃H ₆, OH-C ₂H ₄OC ₃H ₆, CH ₂=CCH ₃-COO, CH ₂=CH-COO, CH ₂=CCH ₃-COOC ₂H ₄, CH ₂=CCH ₃-COOC ₃H ₆Or P=10 to 250 wherein.

20. modified acrylic acid oligomer as claimed in claim 1, wherein the consumption of siloxanyl monomers to form the total consumption of monomer of oligomer, is 0-40 weight %.

21. modified acrylic acid oligomer as claimed in claim 1, wherein this oligomer comprises the polymerized unit of derived from propylene acids monomer, three grades of carboxylic acid ester monomers, fluorinated acrylamide acids monomer and siloxanyl monomers, and wherein this properties-correcting agent is the amido formate acrylate.

22. a modified acrylic acid oligomer, the structure of tool formula (1)

R wherein ¹¹Be halogen, H, CH ₃Or C ₂H ₅

R ¹²Be H, CH ₃, C ₂H ₅, C ₃H ₇, C ₄H ₉, C ₂H ₄OH, C ₃H ₆OH, C ₁₀H ₁₇Or

R ¹⁵For

M=0,1,2 or 3, n=1 to 5, R ⁹Be H or CH ₃, G is Or

Y is C ₁-C ₂Alkyl;

R ³To R ⁵Each represents the C of straight chain or tool side chain ₁-C ₇Alkyl, and R ₃, R ₄And R ₅The carbon number summation be 9,10 or 11;

R ¹Perfluorinated alkyl for straight chain or tool side chain: C _xF _2x+1, wherein x is 1 to 20 integer;

R ¹⁴For

R ⁸Be Me, CH ₂=CH, OH-C ₂H ₄OC ₃H ₆Or

P=10 to 250;

Z is 0,1,2 or 3;

A is 2 to 20 numerical value;

B is 5 to 50 numerical value;

C is 0 to 15 numerical value;

D is 5 to 20 numerical value; And

E is 0 to 30 numerical value.

23. the manufacture method of a modified acrylic acid oligomer, comprise acrylic monomer, be selected from the monomer of the group that fluorinated acrylamide acids monomer, siloxanyl monomers and composition thereof formed and three grades of carboxylic acid ester monomer polymerizations optionally, re-use a properties-correcting agent that is selected from the group that is formed by epoxy acrylate, epoxy methacrylates, amido formate acrylate, polyester acrylate, vinylformic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester and composition thereof and carry out modification.

24. an anti-pollution paint, it comprises as claim 1 or 22 described modified acrylic acid oligomers.

25. anti-pollution paint as claimed in claim 24, it further comprises light trigger.

26. as coating as described in the claim 25; wherein this light trigger system is selected from by benzophenone, 2-hydroxy-2-methyl-1-Propiophenone, 2; 2-dimethoxy-1; 2-phenylbenzene second-1-ketone, 1-hydroxy-cyclohexyl phenyl ketone, 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide, N-phenyl glycine, 9-phenylacridine, st-yrax class, benzyl dimethyl ketal, 4,4 '-two (diethylamide) benzophenone, 2; 4, the group that 5-triarylimidazoles dipolymer and composition thereof is formed.

27. coating as claimed in claim 25, wherein the content of this modified acrylic acid oligomer in the coating gross weight, is 20-90 weight %.

28. coating as claimed in claim 25, wherein the content of light trigger in the coating gross weight, is 3-15 weight %.

29. coating as claimed in claim 25, it further comprises and is selected from the group that is made up of the initial auxiliary agent of light, solvent, reactive monomer, pigment, additive and composition thereof.

30. coating as claimed in claim 29, wherein this solvent is benzene class, ester class, ketone or its mixture.

31. coating as claimed in claim 30, wherein this benzene class system is selected from the group that is made up of benzene, o-Xylol, m-xylene, p-Xylol, Three methyl Benzene, vinylbenzene and composition thereof.

32. coating as claimed in claim 30, wherein this ester class system is selected from the group that is made up of ethyl acetate, butylacetate, diethyl carbonate, ethyl formate, methyl acetate, ethoxyethyl acetate(EA), acetate oxyethyl group propyl ester, monomethyl ether propylene glycol acetic ester and composition thereof.

33. coating as claimed in claim 30, wherein this ketone system is selected from the group that is made up of acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and composition thereof.

34. coating as claimed in claim 29, wherein this reactive monomer system is selected from by 1,6 hexanediol diacrylate, tripropylene glycol diacrylate, neopentylglycol diacrylate, the ethoxyquin bisphenol a diacrylate, three (2-hydroxyethyl) isocyanuric acid triacrylate, Viscoat 295, pentaerythritol triacrylate, the ethoxyquin Viscoat 295, the glycerol propoxylate triacrylate, tetramethylolmethane is enjoyed tetraacrylate, two-trimethylolpropane tetra-acrylate, the group that dipentaerythritol acrylate and composition thereof is formed.

35. coating as claimed in claim 29, wherein this additive system is selected from by group that dispersion agent, wetting agent, defoamer, promotor, flow agent, light stabilizer, UV light absorber, anti-sedimentation agent, matting agent, lubrication prescription and composition thereof are formed.

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