TW200914549A - Modified acrylic oligomer and anti-fouling coating containing the same - Google Patents

Abstract

The invention provides a modified acrylic oligomer, which comprises polymerization units derived from the following monomers: (1) an acrylate monomer; (2) a monomer selected from the group consisting of a fluorinated acrylic monomer, a siloxane monomer, and a mixture thereof; and (3) optionally, a tertiary carboxylic ester monomer; wherein said 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 a mixture thereof. The invention also provides an anti-fouling coating comprising the modified acrylic oligomer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified acrylic acid polymer and a coating prepared therefrom, particularly a radiation curable antifouling coating. [Prior Art] Coatings are widely used in buildings, ships, machinery, electronic products, metal products, and wood products. The main purpose is to protect and beautify objects. However due to

涂料 In the environment of use, the paint may be exposed to various external pollution at any time, such as air: floating dust, oily smoke, poorly charged conductors, industrial acid rain, etc. If the anti-fouling properties of the paint are not good, the decorative effect will be short-lived. The deterioration causes the paint to lose its original color and become black or yellow, impairing its appearance or protective properties. Conventional techniques have used organic fluorinated polymers in the coatings industry. The principle is that the surface tension of the fluorinated polymer is low, and the adhesion interface between the coating and the source of contamination or the adhesion is not strong, so that the source of contamination is not easily attached. Low surface energy properties such as polytetrafluoroethylene (PTFE) have long been known. Japanese special, Hira 6-34, the bulletin reveals a kind of fluorinated copolymer resin polymerized with a monomer based on acrylic acid monomer, gas thinner and tetrafluoroethylene monomer, and the resin is further at room temperature. Non-yellowing criminal thoughts scan. The branched isocyanate hardener is hardened by bridge to obtain a coating film, and the coating film is right-handed and has good weather resistance and water repellency. Japanese Patent Laid-Open No. Hei 7-26204 also discloses the polymerization of a fluorine-containing polyurethane urethane prepared from a multi-fermented solution of a 3-unsaturated group (molecular weight 3 〇〇 to 3000) and a perfluoroacrylic acid or a perfluoroethylene monomer. The organic fluoropolymer coating is also better in weather resistance, recording resistance and chemical resistance than before. 123159.doc 200914549 In addition to organic fluorinated polymers, 'organoanthrones are also widely used in antifouling because they also have low surface properties. It is known that the addition of an anthrone additive to a coating can reduce the surface tension and thereby achieve the antifouling effect; ': and because the anthrone additive has a surface migration effect, causing the active ingredient to decrease with time', so the durability of the antifouling effect is limited. . In addition, since the material reaches the nanometer size, τ can have characteristics which are not found in a generally large size. In view of this, many studies have attempted to apply nanotechnology to coatings to enhance the durability of the antifouling effect, for example, to study the nanostructured surface with antifouling effect and apply it to the k-material. . For example, in the known lotus leaf effect (L〇tus, the surface of the lotus leaf has a hydrophobic nano-structure similar to fiber, this hydrophobic nano-structure can not only make the water bead, but also reduce the lotus leaf and the water droplet Or the contact area between the dusts, reducing the strength of each other, so that water droplets or dust are not easy to adhere to the foliage. In addition, the water droplets are easy to adsorb dust particles during the rolling process, which can achieve self-cleaning effect. Taiwan Patent 124845 9 ( Chinese Patent No. 1,266,236 discloses an antifouling coating which applies nanotechnology to a coating, and uses a long-chain fluorine or fluorenone segment on the resin side to reduce the surface tension of the coating and improve the stain resistance of the coating, and utilizes three The grade carbonate further provides compatibility to obtain a fluorine-containing coating film with excellent compatibility. The coating provided by the Taiwan patent case is a conventional heat-curing coating. Because the conventional coating is volatile, the curing speed is slow, and it is not environmentally friendly. Therefore, the current industry actively develops radiation curing technology, which is cured by radiation irradiation (especially ultraviolet light) to cause free radical crosslinking of the coating resin. And as s' of light emitted by the light emitting curing techniques and light source can be divided into solvent type ultraviolet 123159.doc 200914549

(uv) curing technology, non-ultraviolet curing technology, oily photocuring technology, and water photocuring technology. More than 8% of radiation curing technology products use UV-rayization technology. Radiation curing technology has no volatile organic compounds (VOC), low environmental pollution, fast curing speed, high efficiency, energy saving, and excellent performance of cured products. It is suitable for heat-sensitive substrates, suitable for high-speed automatic, production and other advantages. It is widely used in electronics, communication, building materials, packaging and other fields, especially in the plastic material, because the plastic substrate itself is not resistant to the south. ; Ying ' so the use of radiation curing has an absolute advantage. Radiation curing has now gradually replaced traditional curing techniques. Therefore, how to apply nanotechnology in the coatings industry, and the use of conventional fluorin and fluorenone can reduce the surface tension to achieve the anti-fouling effect, while trying to transform the traditional curing mechanism into (four) curing mechanism Active research topics. SUMMARY OF THE INVENTION The main object of the present invention is to provide a modified acrylic acid polymer having a II carbon side bond and/or a scutellite side bond, and thus can be applied to a coating to provide an antifouling effect. _@_The photopolymer has a photoreceptor on the oligomer for the lucky shot curing mechanism. Another object of the present invention is to utilize the incompatibility between the oligomeric gas-carbon side chain and the main chain or other side chain structure, so that the fluorocarbon molecules having a low surface energy (4) are attached to the surface of the coating. The hydrophobic nano microstructure is formed and synergistic with the phase side bonds to enhance the antifouling effect. For the purposes of this disclosure, the present invention provides a modified acrylic oligo which comprises polymerized units derived from the following monomers: 123159.doc 200914549 (1) Acrylic monomers; (2) Free fluorination a monomer composed of an acrylic monomer, a siloxane monomer, and a mixture thereof; and σ (3) a tertiary carboxylic acid ester monomer as needed; & wherein the condensate further comprises a derivative From the group consisting of epoxy (meth) propyl _ - amine hydrazine | ^ 5 acrylic acid, poly vinegar acrylate, (mercapto) propylene West ^ 2 Λ * - 酉 酉 θ and The group of the modifier of the group consisting of the mixture.

The antifouling coating of the present invention has a good and long lasting antifouling effect and is suitable for use in a radiation curing mechanism. [Examples] The acrylic monomer used to form the oligomer of the present invention has the following formula: R1 CH2=C-COOR2 wherein R1 is dentate, H, ch3 or c2h5; and r2 is η, Ch3, C2H5 C3H7 ' C4H9 ' C6H,3 ' C2H4OH ' C3H6OH ' C 〇Hn (isobornyl) or the following groups: CH2 - Examples of the above acrylic monomers, including but not limited to acrylic acid, methacrylic acid, acrylic acid Ester, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-nonyl methacrylate, 2-hydroxypropyl methacrylate, ethyl acrylate Ester, acesulfame isobornyl acrylate or a mixture thereof. 123159.doc 200914549 In order to allow the polymer to be modified with a modifier, thereby attaching the photosensitive group to the oligomer, the acrylic monomer used in the present invention needs to contain at least one hydroxyl group (-OH). a monomer of a reactive group of a carboxyl group (-COOH) or an epoxy group (_A) which is, for example but not limited to, selected from the group consisting of (meth)acrylic acid, epoxy (meth) acrylate, propylene Acid (hydroxyethyl acrylate, HEA), hydroxypropyl acrylate (hydroxypropyl acrylate), 2-hydroxyethyl methacrylate (2-HEMA), hydroxypropyl methacrylate ( A monomer consisting of hydr〇xypr〇pyi methacrylate, hydroxy), 2-hydroxypropyl methacrylate (2-HPMA), and mixtures thereof. Preferably, the acrylic acid monomer used in the present invention comprises at least one monomer having a trans group (-0H)-reactive group selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, and methacrylic acid. A group consisting of 2-hydroxyethyl ester, hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, and mixtures thereof. The amount of the acrylic monomer of the present invention is from 20 to 85% by weight, preferably from 5 to 8 % by weight, based on 1 of the total amount of monomers forming the oligomer. Wherein, the amount of the monomer having a reactive group of a hydroxyl group (-OH), a carboxyl group (-C00H) or an epoxy group is 5% by weight based on the total monomer amount of the acrylic monomer. Good system 1 0-40% by weight. The fluorinated acrylic monomer used to form the polymer of the present invention has the following formula:

RfCH2CH20(0)CC(R)=CH2 wherein Rf is a linear or branched perfluorinated alkyl group: wherein X is an integer from 1 to 2 Å, 叫, C2H5 or C3H7. The invention of the present invention 123159.doc 200914549 The acrylic acid-based monomer is preferably (iv) acid I. The alkyl acrylate acid alkyl ester or a mixture thereof is more preferably fluorinated alkyl vinegar of ruthenium = 6 to 4, fluorinated alkyl thioglycolate or a mixture thereof. According to the present invention, the fluorinated acrylic monomer is used in an amount of 0 to 40% by weight, based on the total weight of the monomers forming the oligomer, preferably 2% by weight. The oxirane monomer used to form the oligomer of the present invention has the following general formula:

Me p!/Ie

Me Ο-έί- ΐΊ/le

Me Ο-έϊ-R8p ιΊλθ where R and R8 are each Η, Me, CH2=CH, NH2, NH2-C3H6, OH C2H4OC3H6, CH2 = CCH3-COO, CH2 = CH-C00, CH2-CCH3-C00C2H4, ch2 =cch3-cooc3h6 or ch2-chch2oc3h6, which yields 1 () to 25 〇. The amount of the "oxyxane monomer" used in the present invention is 0-40% by weight, preferably 2% by weight, based on the total amount of monomers forming the polymer.募 The polymer of the present invention may optionally comprise one or more polymerized units derived from a tertiary carboxylic acid vinegar to adjust the hardness, toughness, etc. of the desired coating. A tertiary carboxylic acid ester having the general formula: RC-COOR6 R4 wherein R, R4 and R5 each represent a straight or branched Ci_c?alkyl group and preferably the sum of the carbon numbers of R, R and R5 is 9, 10 or 11; R6 is selected from the group consisting of: 123159.doc 200914549 ch=ch2

, CH—CH2, CH2—CH—C H2 V CH3 H2C=C—CH2 and H2C=C—CH2 Ο

The preferred secondary acid vinegar car system is selected from the group consisting of saturated tertiary sulphuric acid sulphate, secondary sulphuric acid ethyl ester, saturated tertiary succinyl carbonyl acrylate, and mixtures thereof. . When present, the amount of the tertiary carboxylic acid ester monomer, based on the total amount of monomers forming the oligomer, is 5 to 5 % by weight, preferably i 〇 40% by weight. In order to have a photosensitive group on the nutrient for use in a radiation curing mechanism, the present invention further adds a photosensitive group-containing modifier to modify the oligomer to have a modified C=C after modification. Photosensitive group of double bond. The modified tanning agent used in the present invention can react with a reactive group such as a hydroxyl group (·〇Η) or a carboxyl group (_c〇〇H) 4 epoxy group (—B) in the oligomer, thereby changing the oligomer. Preferably, the modifier is selected from the group consisting of epoxy (mercapto) acrylate, urethane acrylate, polyester acrylate, 2-hydroxyethyl (meth) acrylate or mixtures thereof. The modifier used in the present invention is preferably a urethane acrylate. The urethane acrylate has the following formula:

CCC~〇-(CH2)„-〇-c-NH-G-(CH2)m-NCO where m=0, i, 2 or 3 'n=1 to 5, ... is yang, G is divalent An organic group. Preferably, the G is a divalent aromatic group or a divalent aliphatic group. More preferably, the G group is selected from the group consisting of: \ and (〆, 123i59.doc • 12 · 200914549 wherein Y is independently hydrogen, halogen, c "c4 perfluoroalkyl or Cl-c4 alkyl. In a specific embodiment, G is

According to the invention - 'y is a c!-C2 yard base. - The amount of the modifier used in accordance with the present invention is from 20 to 60% by weight, preferably from 3 to 5% by weight, based on the total weight of the oligomer and modifier. The modified acrylic oligomer of the present invention is polymerized by an acrylic monomer, a fluorochemical acrylic monomer and/or a decyl oxide monomer, and optionally a tertiary carboxylic acid monomer. A modifier modified from a group consisting of epoxy (meth) acrylate, amide phthalic acid acrylate, polyester acrylate, 2-hydroxyethyl acrylate (meth) acrylate, and mixtures thereof And made. According to a preferred embodiment of the present invention, the modified acrylic acid oligomer of the present invention comprises a monomer derived from a propylene oxime monomer, a tertiary carboxylic acid ester monomer, a fluorinated acrylic monomer, and a decane oxide. a polymerized unit of a monomer, and a modifier group derived from an amino phthalate acrylate. According to still another preferred embodiment of the present invention, the modified acrylic acid conjugate of the present invention has the structure of the formula (1):

(1) 123159.doc -13 - 200914549 wherein R11 is halogen, hydrazine, CH3 or C2H5;

R12 is Η, CH3, C2H5, C3H7, C4H9, C2H4OH, C3H6OH C10H174 ch2—ch-ch2 R15 is c4-?, C—O—1 (CH2)n—O—C—NH—G—(CH2) m— NH—C—O—where m=0, 1, 2 or 3, preferably 〇 or 1 'n=l to 5' is preferably 1 or

2, R9 is Η or CH3, and G is the base;

And Y is C]-C2 alkane R3 to R5 are as defined previously herein; R/ is a linear or branched perfluorinated alkyl group CxF2x+1, wherein X is an integer from 1 to 20;

R14 is or

Me -h— fl/1e

Me Ο-έΐ- ti/le 〇-b 8, R8 is Me, CH2 = CH, OH-C2H4OC3H6 p Me CH2"CHCH2〇C3He, P=l〇 to 25 0 z is 0, 1, 2 or 3; a It 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; and e is a value from 0 to 30. It should be noted that the polymerization units in the formula (1) can be arranged in any suitable order 123159.doc -14- 200914549. For example, the oligomer of formula (1) may be a random oligomer in which each polymerized unit constitutes a polymer backbone in a random arrangement, such as, but not limited to, abcde, abecd, and the like. The preparation method of the modified acrylic acid polymer of the present invention is not particularly limited, and the modified acrylic oligomer can be produced in the present invention by any well-known method known to those skilled in the art. A monomer such as an acrylic monomer, a fluorinated acrylic monomer, and/or a siloxane monomer, and optionally a tertiary carboxylic acid ester monomer, is mixed with a suitable initiator and a solvent to carry out a polymerization reaction. The polymerization product is modified with a modifier. The types of the initiators and solvents used in the above polymerization are not particularly limited, and are well known to those skilled in the art to which the present invention pertains. The modified acrylic acid polymer obtained by the invention can provide good water repellency and antifouling property due to the low surface energy fluorocarbon side chain and/or fluorenone side chain, so it can be effectively applied to antifouling In the paint. When the oligomer contains a fluorocarbon side bond, since the fluorocarbon side chain is incompatible with the main chain or other side chain structure and the specific gravity is low, the fluorocarbon side bond is formed when the oligomer is further polymerized to form a coating layer. It will naturally migrate to the surface of the coating to form a hydrophobic nanostructure, which reduces the surface tension. The above coating has structural features similar to the lotus leaf effect, and has the advantages of anti-fouling waterproofing and high durability. In a preferred embodiment of the present invention, the modified acrylic oligomer of the present invention has both an anthracene side chain and a II carbon side chain, and is effective by synergistic action of an anthrone side chain and a fluorocarbon side chain. Improve the anti-fouling effect. In addition, 'Because the modified acrylic oligomer of the present invention has a photosensitive group', in addition to being used for a thermal curing mechanism, it can also be used in a radiation curing mechanism 123159.doc -15-200914549 to provide a radiation-curable anti-fouling coating. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view showing the structure of one embodiment of the modified acrylic acid oligomer of the present invention, wherein the polymer backbone 107 has an anthrone/fluorocarbon side chain 101 and a photocurable group. The side chain of the group 1〇5 and other side chains 10 3 derived from the acrylic monomer. When the g is irradiated with radiation, the oligomer of the present invention generates a crosslinked structure as shown in Fig. 2 by mutual reaction of the photocurable groups.

The invention further provides an antifouling coating comprising the modified acrylic acid polymer of the present invention. According to the present invention, the ruthenium of the modified acrylic oligomer is not particularly limited and may be present in the coating in any suitable ratio. For example, the modified acrylic acid polymer of the present invention can be used directly as an anti-beta soil, or a suitable solvent, a comonomer or a combination of the two can be added as needed to improve the fluidity of the coating. It is good for coating. The types of solvents and comonomers described above are within the skill of the art and are well known to those of ordinary skill in the art. When the coating contains other components, the content of the oligo oligomer is 'by the total weight of the coating'.

Solvents used in jujube coatings π q + cargo corpse / genus technical collar or eight are known to those of ordinary knowledge. Lijia L 7 such as but not limited to benzenes, esters, ketones or mixture. The content of the solvent which falls specifically in the invention (4) is not particularly limited. Preferably, the amount of solvent is %. 3篁 is based on the total weight of the coating, and is 5-50 weights suitable for the benzene-soluble benzene and m-dimethyl phthalate of the present invention. The material is selected from the group consisting of, but not limited to, I, dimethyl ketone >& , the office of the company and its mixture, and into groups. Anthraquinone baths suitable for this month may be selected from, but not limited to, 123159.doc • 16 - 200914549 from ethyl acetate, butyl acetate, diethyl carbonate, ethyl decanoate, decyl acetate, ethoxy acetate A group consisting of ethyl ester, ethoxypropyl acetate, monomethyl ether propylene glycol acetate, and mixtures thereof. The ketone solvent suitable for use in the present invention may be selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof. The comonomers used in the coatings of the present invention may be known to those of ordinary skill in the art to which the present invention pertains, such as, but not limited to, 1,6-hexanediol diacrylate; HDDA), Tripropylene Glycol Diacrylate (TPGDA), Neopentyl Glycol Diacrylate (NPGDA), Ethoxylated Bisphenol-A Diacrylate; BPA4EODA), 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 Tetraacry ate; PET4A), bis-trimethyl methacrylate Ditrimethylolpropane Tetraacrylate (DiTMP4A), Dipentaerythritol Hexaacrylate (DPHA) or a mixture thereof. The amount of comonomer used in the coating of the present invention is not limited to 123159.doc 200914549. The comonomer content is preferably 1 〇 6 〇 % by weight based on the total weight of the coating. When the antifouling coating of the present invention is applied to a radiation curing mechanism, a photoinitiator may be added to the coating of the present invention to provide a radiation curable antifouling coating. The above photoinitiator means after irradiation with light. A radical is generated, and a polymerization reaction is initiated by the transfer of a radical, the kind of which is well known to those of ordinary skill in the art to which the present invention pertains. The photoinitiator suitable for use in the present invention is not particularly limited as long as it is, for example but not limited to, benzophenone, 2-hydroxy-2-methyl-propiophenone (2_hydr〇xy_2_methyl-1-phenyl) -propan-1-one) '2,2-dimethoxy-l,2-diphenylethan-l-one, 1-hydroxyl 1-hydroxycyclohexyl phenyl ketone (eg Irgacure 184 'Eternal), 2,4,6-trimethylbenzoyl diphenylphosphine oxide (2,4,6-trimethylbenzoyl diphenyl) Phosphine oxide) N-based glycine, 9-phenylufluorene. 9-phenylacridine, benzoins 'benzyldimethylketal, 4,4'-bis(diethylamine) benzophenone, 2,4,5-one A 2,4,5-triarylimidazole dimers or a combination thereof. A preferred photoinitiator is benzophenone or hydrazine-hydroxycyclohexyl phenyl ketone, more preferably benzophenone. The photoinitiator used in the coating of the present invention is present in an amount of from 3 to 15% by weight based on the total weight of the coating. Furthermore, the antifouling coating of the present invention may optionally contain a photoinitiating aid such as, but not limited to, a tertiary amine. The antifouling coatings of the present invention may further comprise pigments and/or any additives well known to those of ordinary skill in the art to which the present invention pertains. Additions such as, but not limited to, dispersants, wetting agents, defoamers, accelerators, leveling agents, photosensitizers, UV absorbers, anti-settling agents, slip agents, matting agents, or Its combination. The coating of the present invention may be applied in any manner known to those skilled in the art, for example, by screen printing, shower coating, roll coating, spray coating, etc., to apply a coating to the surface to be coated to form a coating. The coating is then cured by means of heat or radiation or the like. For example, the antifouling coating of the present invention can be applied by radiation curing in the following steps: (1) The modified oligomer of the present invention is optionally combined with a comonomer, a solvent, a photoinitiator, and Mixing other additives to form a coating; (2) applying the coating prepared in the step (1) to the surface to be coated to form a coating; and (3) at normal temperature or under heating, the step (2) The coating illuminates the energy ray to cure it. The energy ray refers to a light source of a certain wavelength range, for example, ultraviolet light, infrared light, visible light or hot wire (radiation heat line or radiant heat line), etc., preferably ultraviolet light. The irradiation intensity may be from 丨〇〇 to 丨〇〇〇mJ/cm 2 (mJ/cm 2 ), preferably from 2 〇〇 to 8 〇〇 mJ/cm 2 . The following examples are provided to further illustrate the invention and are not intended to limit the scope of the invention. Modifications and changes that can be easily made by anyone familiar with the art are included in the scope of the case and the scope of the patent application. The abbreviations used in the examples are defined as follows: AA: Acrylic acid MAA: Mercaptoacrylic acid 123159.doc -19· 200914549 MMA: Ethyl methacrylate IBMA. Isobutyl bromide Methacrylate BA: butyl acrylate n-BMA: n-butyl methacrylate 2-HPMA: 2-hydroxypropyl methacrylate

ZonylTM (trade name): a mixture of 2-(perfluoroalkyl)ethyl acrylate] where the alkyl group is C8, Ci〇 and c12 total smoldering base (DuPont, USA) AS: methyl methacrylic acid Silicone methyl methacrylate (Silaplane, Japan CHISSO)

Veova 10 (trade name): Vinyl ester of neodecanoic acid (Hexion, Singapore) PMA: Propylene glycol monomethyl ether acetate TBPB: Tert-butyl benzoate IPDI: isophorone diisocyanate TDI: toluene diisocyanate HDDA: 1,6-hexanediol diacrylate 2- HEA: Preparation of 2-Ethyl Acrylic Acid Acetate Preparation Polymer: Mix different ratios of monomers, solvents and appropriate starter to prepare a mixture of polymer and solvent for further modification 1 and 2 The preparation conditions are as shown in Table 1 below: 123159.doc -20- 200914549 Table 1 Mixture 1 2 Monomer type and amount (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 Zonyl1M 7.0 3.6 Veova 10 46.6 18.6 n-BMA a 10.5 IBMA -- 21.8 AS — 7.0 Solvent (xylene) (g) 88 111 Solvent (PMA) (g) 17.6 17.6 Starting agent (TBPB) (g) 0.5 3.0 Reaction temperature (° C) 130 ° C 130 ° C time 8 hours 8 hours solid content (% by weight) 56.9 49.1

L

Preparation of J modifiers A and B: Modifier A: 27.5 parts by weight of 2-HEA, 52.5 parts by weight of IPDI are mixed and heated to 40 to 50 ° C, and the modifier (A) is obtained after 2 hours of reaction. Its structure is as follows:

-C- H -C——C-H2

〇 II -c- H -N

NC 〇 Modifier B: 27.5 parts by weight of 2-HEA, 4 1.2 parts by weight of TDI is mixed and heated to 40~50 123159.doc -21 - 200914549 °C, and the modifier (B) can be obtained after 2 hours of reaction. Its structure is as follows Ο Ο Η

H2c=c- H

• C——Ο——C——C——O——C-N H2 h2

NCO CH, Example 1-4 混合物 The above-obtained mixtures 1 and 2 were reacted with modifiers A and B, respectively, to modify the oligomer. Subsequently, the reaction product was mixed with a comonomer and other additives to prepare an antifouling coating of the present invention, and the preparation conditions are shown in Table 2: Table 2 Example 1 2 3 4 Raw material (g) Mixture 1 171 165 - a mixture 2 - — 171 165 Modifier A 80 - 70 - Modifier B - 68.7 - 60.1 HDDA 60 60 60 60 ^termer 231 186.6 186.6 186.6 186.6 ^Irgacure 184 12.44 12.44 12.44 12.44 Benzophenol 12.44 12.44 12.44 12.44 JEtercure 6420 31.1 31.1 31.1 31.1 4Eterslip 70 3.11 3.11 3.11 3.11 BYK 141 (antifoaming agent) 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 °C 45 °C 45 °C 45 〇C time 3 hours 3 hours 3 hours 3 hours solid content (% by weight) 73.5 73.0 75.5 76.2 ^termer 23 1 2Irgacure 184 3Etercure6420 4Eterslip 70 Trihydroxydecylpropane triacrylate (TMPTA) 1-hydroxycyclohexyl ketone (Photoinitiator, Ciba) Tertiary Amine Co-Initiator Slip Agent (Eternal) 123159.doc -22- 200914549 Antifouling Test for Coatings Antifouling Coatings of Examples 1 to 4 Murakami Industrial Co. overlying yl] 'made after curing with UV light Chimera i 57 Table 3 shows the results obtained.仃 resistance / deficient test. Place

Note: Surface cleanliness means:

CJ quality 1 - 2 - 3 - 4 can be found in the results of Table 3, the antifouling coating of the present invention. Good anti-staining property [Simplified description of the drawings] Fig. 1 is a schematic diagram of the modified oligomer of the present invention. Figure 2 is a cross-linking enthalpy of the modified oligomer of the present invention [Description of main component symbols]. No., and map. 100 modified acrylic acid condensate 123159.doc -23- 200914549 101 fluorenone/fluorocarbon side chain 103 other side chain derived from acrylic monomer 105 side chain containing photocurable group 107 main chain 200 crosslinked Modified acrylic acid polymer

123159.doc -24-

Claims (1)

200914549 X. Patent Application Scope·· A modified acrylic oligomer. Unit: It contains poly-, helium-alkane monomers and mixtures derived from the following monomers. (1) an acrylic monomer; (2) a monomer selected from the group consisting of fluorinated acrylic monomers; and (3) a tertiary phthalate monomer, if necessary; The further step comprises derivatization from a group selected from the group consisting of epoxy (meth) acrylate, amino phthalate acrylate, polyester acrylate, (meth) propylene k 2- ethyl acrylate, and mixtures thereof. The beauty agent of the modifier. Soil 2. The modified acrylic oligomer of claim 1 wherein the modifier is an amino phthalate acrylate. 3. The modified acrylic acid polymer of claim 2, wherein the modifier has the following formula: C=C—c—o—(CH2)n—0—C—NH—G—(CH2)m -NCO wherein m = 〇, ι, 2 or 3, n = 1 to 5, R9 is hydrazine or CH3, and G is a divalent organic group. 4. The modified acrylic oligomer as claimed in claim 3 wherein G is a divalent aromatic group or a divalent aliphatic group. 5. The modified acrylic acid polymer of claim 4 wherein G is selected from the group consisting of: 123159.doc 200914549 Each of Y is independently hydrogen, halogen, C--C4 all-air ray or C]-C4 alkyl. 6 _ as claimed in $ modified oligoacrylate, where G is, or , 丫 is CVC2 alkyl. 7. The modified acrylic oligomer as claimed in claim 1 wherein the amount of the modifier is from 2 〇 _ 60% by weight based on the total weight of the oligomer and the modifier. 8 The modified acrylic oligomer according to claim 1, wherein the acrylic monomer has the following formula: Wherein 'R1 is halogen, hydrazine, CH3 or C2H5; and r2 is η, CH3, c2H5, c3H7, C4H9, C6Hn, C2H4〇H, C3H6OH, Ci〇H, 7 or less: K-coupon' wherein the acrylic monomer is a reactive group of a thiol or epoxy group. 9. The modified acrylic acid-polymerized polymer of claim 1 comprising at least one having a hydroxyl group, a carboxyl group or a releasing monomer. 123159.doc 200914549. The modified acrylic acid polymer of claim 9, wherein the acrylic single system having at least one reactive group is selected from the group consisting of (meth)propionic acid, epoxy (曱) Acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl propyl 2-hydroxyethyl ester, hydroxypropyl methacrylate, 2-propyl propyl propyl acrylate and mixtures thereof Group of. 11. The modified acrylic oligomer according to claim 1 , wherein the acrylic monosystem having at least one reactive group is selected from the group consisting of ethyl acrylate, hydroxypropyl acrylate, and 2-hydroxyl methacrylate. A group consisting of ethyl ester, hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, and mixtures thereof. 12. The modified acrylic oligomer according to claim 1, wherein the amount of the acrylic monomer is from 20 to 85% by weight based on the total amount of the monomers forming the oligomer. 13. The modified acrylic oligomer according to claim 9, wherein the amount of the monomer having at least one reactive group is from 5 to 50% by weight based on the total monomer of the acrylic monomer. /0. 14. The modified acrylic oligomer as claimed in claim 3, wherein the tertiary carboxylic acid ester is selected from the group consisting of saturated tertiary carboxylic acid vinyl ester, saturated tertiary fluorinated vinyl carboxylate and saturated tertiary carboxylic acid epoxide a group consisting of propyl esters. 15. A modified acrylic oligomer according to the invention, wherein the amount of the tertiary carboxylic acid ester is from 5 to 50% by weight based on the total amount of monomers forming the oligomer. 1 6. The modified acrylic oligomer of claim 1 wherein the fluorinated acrylic single system has the following formula: R CH2CH2〇(〇)CC(R)=CH2 123159.doc 200914549 wherein Rf# straight A chain or branched perfluorinated alkyl group: Cxf2x+i, wherein x is an integer from 1 to 20, and R is H, CH3, C2H5 or C3H7. A modified acrylic acid oligomer according to claim 16, wherein the fluorinated acrylic single-system fluorinated alkyl acrylate, the fluorinated alkyl methacrylate or a mixture thereof. 1 8. The modified acrylic oligomer of claim i, wherein the amount of fluorinated acrylic monomer is from 0 to 40% by weight based on the total amount of monomers forming the polymer. 19. The modified acrylic oligomer according to claim ,, wherein the oxirane mono system has the general formula: Me R^ii- li/le Me Ο—^i—lile Me Ο-έΐ-R8 .p ΐΊ/le where R7 and R8 are each H, Me, CH2=CH, NH2, NH2-C3H6, 〇H-C2H4OC3H6, CH2=CCH3-COO, CH2=CH-COO, CH2=CCH3-COOC2H4, ch2=cch3 -cooc3h6 or Ci^CHCH2〇C3H6 ' where P=10 to 250. 20. A modified acrylic oligomer according to claim i, wherein the amount of the oxoxane monomer is based on the total amount of monomers forming the polymer, and is 〇 4 〇. /〇. The modified acrylic oligomer according to claim 1, wherein the oligomer comprises a monomer derived from an acrylic monomer, a tertiary carboxylic acid ester monomer, a fluorinated acrylic monomer, and an osmanthus monomer. a polymerization unit, and wherein the modifier is an amino phthalate acrylate. 22. A modified acrylic acid condensate having the structure of formula (1) 123159.doc 200914549, Π η2 -C—丨^c-^rc 卞=0 卞=0 (卞η2) >丨] η11 Λ Η Η 2, / Η 2 f, , Η 2 tc-C"4~(-c-卞- , 11 R 12 c=o R5-〒-R3 (p=0? ?(fH2)z (锫2)Z (1) where R11 is halogen, H, CH3 or C2H5; Γ R12 is H, CH3, C2H5, C3H7, C4H9, C2H4〇H c3h6oh ' C10H17^ CH2—c£hch2 * R15 ^ C=c—c—o—(CH2)n —o—c—NH—G—(CH2) m-NH—C—O — ; m: , 1, 2 or 3, n=l to 5, R9 is H or CH3 or ϋ Y is a C1-C2 hospital base; R3 to R5 each represent a linear or branched 2Cl_C7 alkyl group, and the sum of carbon numbers of R3, 114 and 115 is 9, 10 or 11; R/ is linear or branched Perfluorinated alkyl: CxF2x+1, where X is an integer from 1 to 20; Me R14 is l (/te Ο-έί— lJ/le Me Ο-έΐ-R8 , pd/le R is Me, CH2=CH , OH- C2H4OC3H6* cj^CHCH2OC3H6 ' P=10 to 250 ; z is 0, 1, 2 or 3; 123159.doc 200914549 a is a value from 2 to 20; b is a value from 5 to 50; c is from 0 to 15 The value; d is a value from 5 to 20; and e is a value from 0 to 30. A method for producing a modified acrylic acid oligomer, comprising: a monomer comprising a group consisting of an acrylic monomer, a monomer selected from the group consisting of a propylene monomer, and an oxygen oxidizing monomer, and a mixture thereof If necessary, the tertiary acid § is intended to polymerize the monomer, and then use - selected from the group consisting of epoxy (mercapto) acryl vinegar, amino carboxylic acid glycerin, vinegar vinegar, (methyl) The modified agent of the group consisting of acrylic acid 2 and ethyl vinegar and a mixture thereof is modified. 24. An antifouling coating comprising a modified acrylic acid polymer as claimed. 25. The antifouling coating of claim 24, further comprising a photoinitiator. 26. The coating of claim 25, wherein the photoinitiator is selected from the group consisting of benzophenone '2-hydroxy-2-methyl-i-propiophenone, 2,2-dimethoxy-oxime, 2· Diphenylethyl 1-yl, 1-cyclohexyl phenyl ketone, 2,4,6-trimethyl benzhydryl-based phosphine oxide, fluorenyl-phenylglycine, 9·benzene a group consisting of pyridinium, benzoin, benzyl dimethyl ketal, 4,4 bis bis(diethylamine) benzophenone, 2,4,5-triaryl imidazole dimer, and mixtures thereof group. 27. The coating of claim 25, wherein the modified acrylic oligomer has a content of from 20 to 90% by weight based on the total weight of the coating. 28. The coating of claim 25, wherein the photoinitiator is present in an amount of from 3 to 15% by weight based on the total weight of the coating. The coating of claim 25, further comprising a group selected from the group consisting of photoinitiating aids, solvents, reactive monomers, pigments, additives, and mixtures thereof. 30. The coating of claim 29 wherein the solvent is a stupid, an ester, a ketone or a mixture thereof. 3 1 · The coating of claim 3 wherein the benzene is selected from the group consisting of benzene, o-xylene, m-xylene, p-xylene, trimethylbenzene, styrene, and mixtures thereof. 32. The coating of claim 30, wherein the ester is selected from the group consisting of ethyl acetate, butyl acetate, diethyl carbonate, ethyl formate, methyl acetate, ethoxyethyl acetate, ethoxypropyl acetate a group consisting of monodecyl ether propylene glycol acetate and mixtures thereof. 33. The coating of claim 30, wherein the ketone is selected from the group consisting of acetone, methyl ethyl ketone I, methyl isobutyl ketone, and mixtures thereof. 34. The coating of claim 29, wherein the reactive single system is selected from the group consisting of ruthenium, 6-hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, ethoxylated bisphenol A diacrylic acid Ester, tris(2-hydroxyethyl)isocyanuric acid diacrylate, trihydroxymercaptopropane triacrylate, pentaerythritol triacrylate, ethoxylated trishydroxypropyl propane triacrylate, propoxyglycerol diacrylate, Groups of pentaerythritol tetraacrylate, bis-trimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, and mixtures thereof: groups. 35. The coating of claim 29 wherein the additive is selected from the group consisting of dispersants, wetting agents, defoamers, accelerators, leveling agents, light stabilizers, UV absorbers 123159.doc 200914549, anti-settling agents, matting A group of agents, slip agents, and mixtures thereof. 123159.doc