JP2009102627A - Modified acrylic oligomer, and antifouling coating containing the oligomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified acrylic oligomer, and to provide an antifouling coating produced therefrom, a radiation-curable antifouling coating in particular. <P>SOLUTION: The modified acrylic oligomer is provided, comprising polymerization units derived from (1) an acrylate monomer, (2) a monomer selected from the group consisting of a fluorinated acrylate monomer, a siloxane monomer and a mixture thereof, and optionally, (3) a tertiary carboxylic ester monomer; wherein this modified acrylic oligomer further comprises a moiety derived from a modifier selected from the group consisting of epoxy (meth)acrylate, urethane acrylate, polyester acrylate, 2-hydroxyethyl (meth)acryalte and a mixture thereof. An antifouling coating comprising the above modified acrylic oligomer is also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to modified acrylic oligomers and antifouling coatings produced therefrom, in particular radiation curable antifouling coatings.

  Coatings are widely used in buildings, ships, machinery, and electronic, metal, and wooden products for protection and decoration purposes. However, the coating is susceptible to contamination such as airborne dust in the environment, oil-containing smog, poorly charged conductors, and industrial acid rain. If the coating is poorly stain resistant, the ability of the decoration will decline in a short period of time, the coating will lose its original color and darken or yellow, and the appearance and protective properties of the coating will be adversely affected.

  It is customary to use organic fluoropolymers in the paint industry. Organofluoropolymers have a low surface tension and therefore poor adhesion between the coating layer and the soil, which makes it difficult for the soil to adhere to the painted surface. For example, it is well known to those skilled in the art that polytetrafluoroethylene (PTFE) has low surface tension properties. JP 6-345823 discloses a fluorine-containing copolymer resin obtained by polymerizing hydroxyl-containing acrylate monomers, fluoroolefin monomers, and perfluorovinyl monomers. The resulting resin is cured at room temperature with a non-yellowing isocyanate curing agent to form a coating layer. The coating layer provides good weather resistance and water repellency. Japanese Patent Application Laid-Open No. 7-026204 discloses a fluorine-containing polyurethane polymer. This polymer is prepared by polymerization of a polyol having an unsaturated group in the molecule and an average molecular weight of 300 to 3,000, and perfluoroacrylic acid or perfluorovinyl monomer. The organic fluoropolymer coating disclosed in JP-A-7-026204 has better weather resistance, corrosion resistance and chemical resistance than conventional coatings.

  In addition to organofluoropolymers, organosilicones also have a low surface tension and are widely used for antifouling purposes. It is known that the surface tension can be reduced to obtain an antifouling effect by adding silicone additives to the coating. However, surface migration of the silicone causes the amount of active ingredient to decrease with time, which limits the persistence of the antifouling effect of the silicone.

  Nanomaterials have properties that do not appear in the same material of larger size. Therefore, there is a lot of research aimed at applying nanotechnology to coatings to increase the sustainability of silicone antifouling effects. For example, there are studies aimed at the application of nanostructured surfaces with antifouling effects and the coating of such surfaces. Taking the lotus effect as an example, it is known that lotus leaves have fiber-like hydrophobic nanostructures on their surfaces. Hydrophobic nanostructures maintain droplet shape and at the same time reduce the contact area between the lotus leaf and the droplet or dust, thus reducing the adhesion between the lotus leaf surface and the droplet or dust This makes it difficult for droplets or dust to adhere to the surface. In addition, dust particles tend to adhere to the droplets as they roll down the lotus leaf surface, which provides a self-cleaning effect. Taiwan patent TW I248459 (corresponding to Chinese patent CN 1266236) discloses antifouling coatings and the application of nanotechnology to coatings. Taiwan Patent TW I248459 is intended to provide compatibility with long side chain fluorine or silicone segments to reduce the surface tension of the coating layer and increase the antifouling properties of the coating layer, and the resulting fluorine-containing coating thin film A tertiary carboxylate is used. The coating of Taiwan Patent TW I248459 is a conventional thermosetting coating.

  Conventional coatings are volatile, have a slow cure rate, and are not environmentally friendly. Therefore, researchers in this industry have made great efforts in recent years to develop radiation curing techniques. By irradiating the coating with radiation (especially ultraviolet rays), the resin contained in the coating is cured through free radical crosslinking. Generally speaking, radiation curing techniques include ultraviolet curing techniques, non-ultraviolet curing techniques, oil coating photocuring techniques, and aqueous coating photocuring techniques, depending on the type of radiation source and solvent. Over 80% of products with radiation curing technology are manufactured using UV curing technology. Radiation curing technology provides the following advantages. That is, the coating used there does not contain volatile organic compounds and can be cured quickly; the technology itself is highly efficient, energy-saving, suitable for heat sensitive substrates, and in high speed automotive manufacturing processes It can be used; and the cured product has excellent performance. Thus, radiation curing techniques are widely used in electronics, communications, building, and packaging, especially plastic coatings. Plastic coatings cannot withstand high temperatures, so radiation curing techniques have a decisive advantage in their manufacture and are gradually replacing traditional curing techniques.

As shown above, how to apply nanotechnology to coatings and use fluoropolymers and organosilicones to reduce surface tension and get antifouling effects, and how to use traditional curing mechanisms as radiation curing mechanisms It is a problem that has received a lot of attention in this field.
JP-A-6-345823 JP 7-026204 A Taiwan patent TW I248459 Chinese patent CN 1266236

  The main object of the present invention is to provide a modified acrylic oligomer which has fluorocarbon side chains and / or silicone side chains and can be used in coatings to provide an antifouling effect. In addition, the oligomer has a photosensitive group and is suitable for a radiation curing mechanism.

  Another object of the present invention is that the fluorocarbon molecules having low surface energy form a hydrophobic nanostructure on the surface of the coating layer by self-assembly, creating a synergistic effect with the silicone side chain, resulting in an antifouling effect. Is to take advantage of incompatibility between the fluorocarbon side chain and the main chain or other side chains.

To achieve the above object or other objects, the present invention provides the following monomers:
(1) acrylate monomer;
(2) a monomer selected from the group consisting of fluorinated acrylate monomers, siloxane monomers, and mixtures thereof; and
(3) a tertiary carboxylic acid ester monomer, if necessary;
Providing a modified acrylic oligomer comprising polymerized units derived from
Here, the oligomer further comprises a moiety derived from a modifier selected from the group consisting of epoxy (meth) acrylate, urethane acrylate, polyester acrylate, 2-hydroxyethyl (meth) acrylate, and mixtures thereof.

  The antifouling coating of the present invention has an excellent and continuous antifouling effect and is suitable for a radiation curing mechanism.

  The acrylate monomer used to form the oligomer of the present invention has the general formula:

Wherein R ¹ is halogen, H, CH ₃ , or C ₂ H ₅ ; 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 a group of the formula:

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

  In order to react the oligomer with a modifier for attaching a photosensitive group to the oligomer, the acrylate monomer used in the present invention can be hydroxyl (—OH), carboxyl (—COOH), or epoxy.

At least one monomer having a reactive group. For example, monomers having reactive groups include (meth) acrylic acid, epoxy (meth) acrylate, hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), 2-hydroxyethyl methacrylate (2-HEMA), hydroxy Selected from the group consisting of propyl methacrylate (HPMA), 2-hydroxypropyl methacrylate (2-HPMA), and mixtures thereof. Preferably, the acrylate monomer used in the present invention comprises at least one monomer having a hydroxyl (-OH) reactive group, which is hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl Selected from the group consisting of methacrylate, 2-hydroxypropyl methacrylate, and mixtures thereof.

  The amount of acrylate monomer of the present invention ranges from 20 to 85% by weight, preferably from 50 to 80% by weight, based on the total weight of monomers used to form the oligomer. Hydroxyl (-OH), carboxyl (-COOH), or epoxy

The amount of the monomer having the reactive group is in the range of 5 to 50% by weight, preferably 10 to 40% by weight, based on the total weight of the acrylate monomer.

The fluorinated acrylate monomer used to form the oligomer of the present invention has the following general formula:
R ^f CH ₂ CH ₂ O (O) CC (R) = CH ₂
Wherein R ^f is a linear or branched perfluoroalkyl chain C _x F _{2x + 1} , wherein x is an integer in the range of 1 to 20, and R is H, CH ₃ , C ₂ H ₅ , or C ₃ H ₇ . Preferably, the fluorinated acrylate monomer comprises a fluorinated-alkyl acrylate, a fluorinated-alkyl methacrylate, or a mixture thereof. More preferably, the fluorinated acrylate monomer is a fluorinated-alkyl acrylate or fluorinated-alkyl methacrylate, or a mixture thereof, having the above formula, wherein x is in the range of 6-14.

  According to the present invention, the amount of fluorinated acrylate monomer ranges from 0 to 40% by weight, preferably from 1 to 20% by weight, based on the total weight of monomers used to form the oligomer.

  The siloxane monomer used to form the oligomer of the present invention has the following general formula:

In which R ⁷ and R ⁸ are independently 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 ₂ = CCH ₃ -COOC ₂ H ₄ , CH ₂ = CCH ₃ -COOC ₃ H ₆ , or

In the above formula, p = 10 to 250.

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

  The oligomers of the present invention may optionally contain polymerized units derived from tertiary carboxylic acid ester monomers for the purpose of adjusting hardness, robustness, or other properties of the coating. The tertiary carboxylic acid ester used to form the oligomer of the present invention has the general formula

Wherein R ³ , R ⁴ , and R ⁵ independently represent linear or branched C ₁ -C ₇ alkyl, preferably R ³ , R ⁴ , and R ⁵ The total number of carbon atoms is 9, 10, or 11; R ₆ is

Selected from the group consisting of

  Preferred tertiary carboxylic acid ester monomers are selected from the group consisting of saturated tertiary vinyl decanoate, tertiary vinyl nonanoate, and saturated tertiary epoxy decanoate, and mixtures thereof. When present, the amount of tertiary carboxylic acid ester monomer ranges from 5 to 50% by weight, preferably from 10 to 40% by weight, based on the total weight of monomers used to form the oligomer.

  In order to bond a photosensitive group to the oligomer so that the oligomer can be suitable for a radiation curing mechanism, a modifier containing a photosensitive group is further added to modify the oligomer of the present invention, so that C = A photosensitive group such as a C double bond is contained. The modifier used in the present invention is an oligomer reactive group such as hydroxyl (—OH), carboxyl (—COOH), or epoxy.

And then the oligomer can be modified. The modifier is selected from the group consisting of epoxy (meth) acrylate, urethane acrylate, polyester acrylate, 2-hydroxyethyl (meth) acrylate, and mixtures thereof.

  Preferably, the modifier used in the present invention has the general formula

In the above formula, 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

Wherein each Y is independently hydrogen, halogen, C ₁ -C ₄ perfluoroalkyl, or C ₁ -C ₄ alkyl. According to one embodiment of the invention, G is

And Y is C ₁ -C ₂ alkyl.

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

  The modified acrylic oligomers of the present invention are prepared by polymerization of acrylate monomers, fluorinated acrylate monomers, and / or siloxane monomers, and optional tertiary carboxylic acid ester monomers, followed by epoxy (meth) acrylate, urethane acrylate. It is modified with a modifying agent selected from the group consisting of lath, polyester acrylate, 2-hydroxyethyl (meth) acrylate and mixtures thereof.

  According to a preferred embodiment of the present invention, the modified acrylic oligomer of the present invention comprises polymerized units derived from acrylate monomers, tertiary carboxylic acid ester monomers, fluorinated acrylate monomers, and siloxane monomers, and urethane acrylate modifications. The part derived from the agent is included.

  According to another preferred embodiment of the present invention, the modified acrylic oligomer of the present invention has the 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

And R ¹⁵ is

In which m = 0, 1, 2, or 3, preferably 0 or 1; n = 1-5, preferably 1 or 2; R ⁹ is H or CH ₃ ; G is

In it; Y is an C ₁ -C ₂ alkyl;
R ^{3 to} R ⁵ are as defined herein before;
R ^f is a linear or branched perfluoroalkyl chain C _x F _{2x + 1} , where x is an integer ranging from 1 to 20;
R ¹⁴

Where R ⁸ is Me, CH ₂ = CH, OH-C ₂ H ₄ OC ₃ H ₆ , or

P = 10-250;
z is 0, 1, 2 or 3;
a is a value ranging from 2 to 20;
b is a value in the range of 5-50;
c is a value ranging from 0 to 15;
d is a value in the range of 5-20;
e is a value in the range of 0-30.

  It should be noted that the polymerized units of formula (1) can be arranged in any suitable order. For example, the oligomer of the formula (1) may be a random oligomer in which polymerization units are randomly arranged to form an oligomer skeleton, and examples thereof include, but are not limited to, abcde and abecd.

  There are no particular restrictions on the preparation of the modified acrylic oligomer of the present invention. The modified acrylic oligomers of the present invention can be prepared by any method known to those skilled in the art. According to the present invention, polymerization is carried out by mixing acrylate monomer, fluorinated acrylate monomer, and / or siloxane monomer, and optional tertiary carboxylic acid ester monomer with a suitable initiator and solvent, followed by polymerization. The product is modified with a modifying agent. The initiators and solvents used in the above polymerization are not particularly limited and are well known to those skilled in the art.

  The modified acrylic oligomer obtained according to the present invention has a fluorocarbon side chain and / or a silicone side chain and can therefore provide good water repellency and antifouling effect and is useful for antifouling coatings. If the oligomer contains fluorocarbon side chains, the fluorocarbon side chains are incompatible with the main chain or other side chains and have a relatively low specific gravity, so the oligomer further polymerizes to form the coating layer In doing so, the fluorocarbon side chains automatically move to the surface of the coating layer to form hydrophobic nanostructures, and ultimately the surface tension of the coating layer is reduced. The above coating layer has a characteristic structure similar to that having a lotus effect, and has advantages in terms of stain resistance, water repellency, and good durability. In a preferred embodiment of the present invention, the oligomer contains both a fluorocarbon side chain and a silicone side chain, and the antifouling effect can be effectively improved by the synergistic effect of the silicone side chain and the fluorocarbon side chain. .

  Furthermore, since the modified acrylic oligomer of the present invention contains a photosensitive group, it is suitable not only for a heat curing mechanism but also for a radiation curing mechanism, and therefore, a radiation curable coating can be provided.

  FIG. 1 depicts the structure of a modified acrylic oligomer 100 according to one embodiment of the invention, where the oligomer backbone 107 is a silicone / fluorocarbon side chain 101, a side chain 105 containing a photocurable group, and an acrylic chain. Contains other side chains 103 derived from the latex monomer. When exposed to radiation, the photocurable groups of the oligomers of the present invention will react with each other to produce the crosslinked structure 200 shown in FIG.

  The present invention further provides an antifouling coating comprising the modified oligomer of the present invention. The content of the modified oligomer is not particularly limited. The modified oligomer can be present in any suitable ratio in the coating. For example, the modified oligomers of the present invention can be used directly as an antifouling coating; or, optionally, can be used with the addition of a suitable solvent, comonomer, or combinations thereof to improve the flowability of the coating.

  The types of solvents and comonomers described above will be apparent to those skilled in the art. In addition to the modified oligomer, if the coating contains other components, the amount of modified oligomer is preferably in the range of 20-90% by weight, based on the total weight of the coating.

  The solvent used in the present invention will be apparent to those skilled in the art. Examples of solvents include, but are not limited to, benzene compounds, esters, ketones, or mixtures thereof. The amount of solvent in the coating of the present invention is not particularly limited and is preferably in the range of 5-50% by weight based on the total weight of the coating.

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

  The comonomer used in the present invention may be any of those apparent to those skilled in the art. Examples of comonomers include 1,6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), neopentyl glycol diacrylate (NPGDA), ethoxylated bisphenol-A diacrylate (BPA4EODA), tris (2-hydroxyethyl) isocyanurate triacrylate (THEICTA), trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PET3A), ethoxylated trimethylolpropane triacrylate (TMP3EOTA), propoxylated glyceryl These include triacrylate (G3POTA or G3.5POTA), pentaerythritol tetraacrylate (PET4A), ditrimethylolpropane tetraacrylate (DiTMP4A), dipentaerythritol hexaacrylate (DPHA), or mixtures thereof. It is not limited to. The amount of comonomer used in the coating of the present invention is not particularly limited and is preferably in the range of 10 to 60% by weight based on the total weight of the coating.

  When the antifouling coating of the present invention is to be used in a radiation curing mechanism, a photoinitiator can be added to the coating to obtain a radiation curable antifouling coating. When the photoinitiator is irradiated with light, it generates free radicals and then causes polymerization through the transfer of free radicals. The type of photoinitiator will be apparent to those skilled in the art. There are no specific restrictions regarding the type of suitable photoinitiator used in the present invention. Examples of the photoinitiator include benzophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl Phenyl ketone (such as Irgacure 184 from Eternal), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, N-phenylglycine, 9-phenylacridine, benzoin, benzyldimethyl ketal, 4,4'-bis (diethylamine) benzophenone, This includes, but is not limited to, 2,4,5-triarylimidazole dimers, or combinations thereof. Preferably, the photoinitiator is benzophenone or 1-hydroxycyclohexyl phenyl ketone, more preferably benzophenone. The amount of photoinitiator used in the coating of the present invention ranges from 3 to 15% by weight, based on the total weight of the coating. In addition, the antifouling coating of the present invention optionally includes a photoinitiator aid such as, but not limited to, a tertiary amine.

  The antifouling coating of the present invention may further comprise pigments and / or any additives that will be apparent to those skilled in the art. Examples of such additives include dispersants, wetting agents, antifoaming agents, accelerators, leveling agents, light stabilizers, UV absorbers, suspending agents, lubricants, matting agents, or combinations thereof. However, it is not limited to them.

The coatings of the present invention can be applied by any method apparent to those skilled in the art. For example, the coating can be applied onto a desired surface to form a coating layer thereon by methods such as screen printing, curtain coating, roller coating, spray coating, etc .; the coating layer is then cured by heat or radiation. For example, the coating of the present invention may be applied by a method comprising the following steps:
(1) mixing and stirring the modified oligomers of the present invention with optional comonomers, solvents, photoinitiators, and other additives to form a coating;
(2) applying a coating onto the substrate to form a coating layer; and
(3) A step of irradiating the coating layer prepared in step (2) with an energy beam to cure the coating layer.
An energy beam means a light source in a specific wavelength range, which is, for example, ultraviolet light, infrared light, visible light, or heat rays (nuclear rays or radiation), preferably ultraviolet light. The intensity of irradiation was 100 to 1000 mJ / cm ² , preferably 200 to 800 mJ / cm ² .

  The invention will be further described in the following examples. However, the examples do not impose any limitation on the scope of the present invention. Any modification or change in the present invention that can be easily realized by those skilled in the art is included in the disclosure of the present specification and the appended claims.

(Example)
Abbreviation definition:
AA: Acrylic acid
MAA: Methacrylic acid
MMA: Methyl methacrylate
IBMA: Isobornyl methacrylate
BA: Butyl acrylate
n-BMA: n-Butyl methacrylate
2-HPMA: 2-hydroxypropyl methacrylate
Zonyl (TM): 2- (perfluoroalkyl) - mixture containing ethyl acrylate ( "perfluoroalkyl" group C ₈ -, C ₁₀ -, and C ₁₂ - including perfluoroalkyl) (Du Pont Co.)
AS: Silicone methyl methacrylate (Silaplane, CHISSO, Japan)
Veova 10: Vinyl ester of neodecanoic acid (Hexion Specialty Chemicals, Singapore)
PMA: Propylene glycol monomethyl ether acetate
TBPB: t-butyl perbenzoate
IPDI: Isophorone diisocyanate
TDI: Toluene diisocyanate
HDDA: 1,6-hexanediol diacrylate
2-HEA: 2-hydroxyethyl acrylate

Preparative Examples Preparation of oligomers:
Mixtures 1 and 2 containing the oligomer and solvent were prepared from the monomer, solvent, and initiator in the amounts and reaction conditions shown in Table 1.

Preparation of modifiers A and B:
Modifier A
27.5 parts by weight of 2-HEA and 52.5 parts by weight of IPDI were mixed and heated to 40 to 50 ° C. for 2 hours to obtain a modifier A having the following structure.

Modifier B
27.5 parts by weight of 2-HEA and 41.2 parts by weight of TDI were mixed and heated to 40 to 50 ° C. for 2 hours to obtain a modifier B having the following structure.

(Examples 1 to 4)
The oligomers were modified by reacting the resulting mixtures 1 and 2 with modifiers A and B, respectively. The reaction product was then mixed with comonomer and other additives to obtain the antifouling coating of the present invention. The preparation conditions are as shown in Table 2.

Antifouling test of coating The antifouling coating of Examples 1 to 4 was coated on a substrate [PA-757, Chi-Mei Co.], cured by ultraviolet rays, and then subjected to a stain resistance test. The results of the test are shown in Table 3 below.

It is a figure which shows the structure of the modified oligomer of this invention. It is a figure which shows the crosslinked structure of the modified oligomer of this invention.

Explanation of symbols

100 modified acrylic oligomer
101 Silicone / Fluorocarbon side chain
103 Other side chains derived from acrylate monomers
105 Side chains containing photocurable groups
107 main chain
200 Cross-linked structure

Claims (35)

The following monomers
(1) acrylate monomer;
(2) a monomer selected from the group consisting of fluorinated acrylate monomers, siloxane monomers, and mixtures thereof; and
(3) a tertiary carboxylic acid ester monomer, if necessary;
And a portion derived from a modifier selected from the group consisting of epoxy (meth) acrylate, urethane acrylate, polyester acrylate, 2-hydroxyethyl (meth) acrylate, and mixtures thereof. Including modified acrylic oligomer.   The modified acrylic oligomer according to claim 1, wherein the modifying agent is urethane acrylate. The modifier is represented by the following general formula:

Wherein m = 0, 1, 2, or 3, n = 1-5, R ⁹ is H or CH ₃ , and G is a divalent organic group. Modified acrylic oligomer.   The modified acrylic oligomer according to claim 3, wherein G is a divalent aromatic group or a divalent aliphatic group. G is

Is selected from the group consisting of, in the formula, each Y is independently hydrogen, halogen, C ₁ -C ₄ perfluoroalkyl or C ₁ -C ₄ alkyl, modified acrylic oligomer according to claim 4. G is

In it, Y is C ₁ -C ₂ alkyl, modified acrylic oligomer according to claim 5.   The modified acrylic oligomer according to claim 1, wherein the modifier is used in an amount ranging from 20 to 60% by weight, based on the total weight of the oligomer and modifier. The acrylate monomer has the general formula

Wherein R ¹ is halogen, H, CH ₃ , or C ₂ H ₅ ; R ² is H, CH ₃ , ₂₅ , ₃₇ , ₄₉ , ₆₁₃ , ₂₄ , ₃₆ , ₁₀₁₇ , Or a group of the following formula (Chemical Formula 5):

Modified acrylic oligomer listed. The modified acrylic oligomer of claim 1, wherein the acrylate monomer comprises at least one monomer having a hydroxyl, carboxyl, or epoxy reactive group. The acrylate monomer is selected from the group consisting of methacrylic acid, epoxy methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxypropyl methacrylate, and mixtures thereof. The modified acrylic oligomer according to claim 9. The modification of claim 10, wherein the acrylate monomer is selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxypropyl methacrylate, and mixtures thereof. Acrylic oligomer. The modified acrylic oligomer according to claim 1, wherein the acrylate monomer is used in an amount ranging from 20 to 85% by weight, based on the total weight of monomers used to form the oligomer.   The modified acrylic oligomer according to claim 9, wherein the at least one monomer having a reactive group is used in an amount ranging from 5 to 50% by weight, based on the total weight of acrylate monomers used.   The modified acrylic oligomer of claim 1, wherein the tertiary carboxylic acid ester is selected from the group consisting of saturated tertiary vinyl decanoate, saturated tertiary vinyl nonanoate, and saturated tertiary epoxy decanoate. .   The modified acrylic oligomer according to claim 1, wherein the tertiary carboxylic acid ester monomer is used in an amount ranging from 5 to 50% by weight, based on the total weight of monomers used to form the oligomer. The fluorinated acrylate monomer has the general formula
R ^f CH ₂ CH ₂ O (O) CC (R) = CH ₂
Wherein R ^f is a linear or branched perfluoroalkyl chain C _x F _{2x + 1} , 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, modified acrylic oligomer according to claim 1.   The modified acrylic oligomer according to claim 16, wherein the fluorinated acrylate monomer is a fluorinated-alkyl acrylate, a fluorinated-alkyl methacrylate, or a mixture thereof.   The modified acrylic oligomer according to claim 1, wherein the fluorinated acrylate monomer is used in an amount ranging from 0 to 40% by weight, based on the total weight of monomers used to form the oligomer. Siloxane monomer has the following general formula

Wherein R ⁷ and R ⁸ are independently 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 ₂ = CCH ₃ -COOC ₂ H ₄ , CH ₂ = CCH ₃ -COOC ₃ H ₆ , or

The modified acrylic oligomer according to claim 1, wherein p = 10 to 250 in the formula.   The modified acrylic oligomer according to claim 1, wherein the siloxane monomer is used in an amount ranging from 0 to 40% by weight, based on the total weight of monomers used to form the oligomer.   The modified acrylic oligomer according to claim 1, comprising polymerized units derived from an acrylate monomer, a tertiary carboxylic acid ester monomer, a fluorinated acrylate monomer, and a siloxane monomer, wherein the modifier is urethane acrylate. 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

Is;
R ¹⁵ is

Wherein m = 0, 1, 2, or 3; n = 1-5; R ⁹ is H or CH ₃ ; G is

In it; Y is an C ₁ -C ₂ alkyl;
R ^{3 to} R ⁵ independently represent linear or branched C _{1 to} C ₇ alkyl, and the sum of the number of carbon atoms of R ³ , R ⁴ , and R ⁵ is 9, 10, or 11 Yes;
R ^f is a linear or branched perfluoroalkyl chain C _x F _{2x + 1} , wherein x is an integer ranging from 1 to 20;
R ¹⁴

R ⁸ is Me, CH ₂ = CH, OH-C ₂ H ₄ OC ₃ H ₆ , or

P = 10-250;
z is 0, 1, 2, or 3;
a is a value ranging from 2 to 20;
b is a value in the range of 5-50;
c is a value ranging from 0 to 15;
d is a value in the range of 5-20;
e is a value in the range 0-30,
Modified acrylic oligomer.   Polymerizing an acrylate monomer, a monomer selected from the group consisting of a fluorinated acrylate monomer, a siloxane monomer, and mixtures thereof; and an optional tertiary carboxylic acid ester monomer; A modified acrylic oligomer comprising: modifying with a modifier selected from the group consisting of: epoxy (meth) acrylate, urethane acrylate, polyester acrylate, 2-hydroxyethyl (meth) acrylate, and mixtures thereof Method.   An antifouling coating comprising the modified acrylic oligomer according to claim 1 or 22.   25. The antifouling coating of claim 24 further comprising a photoinitiator.   Photoinitiator is benzophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, N-phenylglycine, 9-phenylacridine, benzoin, benzyldimethyl ketal, 4,4'-bis (diethylamine) benzophenone, 2,4,5-triarylimidazole dimer 26. The coating of claim 25, selected from the group consisting of: or a combination thereof.   26. A coating according to claim 25, wherein the modified acrylic oligomer is used in an amount ranging from 20 to 90% by weight, based on the total weight of the coating.   26. A coating according to claim 25, wherein the photoinitiator is used in an amount ranging from 3 to 15% by weight, based on the total weight of the coating.   26. The coating of claim 25, further comprising a component selected from the group consisting of photoinitiator aids, solvents, comonomers, pigments, additives, and mixtures thereof.   30. The coating of claim 29, wherein the solvent is a benzene compound, an ester, a ketone, or a mixture thereof.   32. The coating of claim 30, wherein the benzene compound is selected from the group consisting of benzene, o-xylene, m-xylene, p-xylene, trimethylbenzene, styrene, and mixtures thereof.   The ester is selected from the group consisting of ethyl acetate, butyl acetate, diethyl carboxylate, ethyl formate, methyl acetate, ethoxyethyl acetate, ethoxypropyl acetate, propylene glycol monomethyl ether acetate, and mixtures thereof. 30. Coating according to 30.   32. The coating of claim 30, wherein the ketone is selected from the group consisting of acetone, methyl ethyl ketone, and methyl isobutyl ketone, and mixtures thereof.   Comonomers are 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, ethoxylated bisphenol-A diacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, trimethylol Propane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, and 32. The coating of claim 30, wherein the coating is selected from the group consisting of mixtures thereof.   The additive is selected from the group consisting of dispersants, wetting agents, antifoaming agents, accelerators, leveling agents, light stabilizers, UV absorbers, suspending agents, matting agents, lubricants, and mixtures thereof. 30. The coating of claim 29.

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