TWI618764B - Microcapsule structure containing antibacterial agent which can be used for paint - Google Patents

Abstract

The invention discloses a microcapsule structure containing an antibacterial agent which can be used for a paint, comprising: a hydrophobic core formed by polymerizing a hydrophobic monomer containing at least one unsaturated bond; a co-crosslinked shell surrounding the hydrophobic core, And an antibacterial agent is a hydrophobic compound; wherein the hydrophobic core and the co-crosslinked shell are coated with an unsaturated bond hydrophobic monomer and a hydrophilic monomer having at least one unsaturated bond; The dispersed antibacterial agent. Thereby, the antibacterial agent is released from the microcapsule core, so that the paint coating has the advantages of long-term, long-lasting anti-biofouling.

Description

Microcapsule structure containing antibacterial agent which can be used for paint

The present invention relates to a microcapsule structure containing an antibacterial agent, and more particularly to an antibacterial agent microcapsule structure which can be used for a paint.

When the underwater part of the hull is attached by marine organisms, the surface roughness of the hull will increase the navigational resistance, resulting in a significant decrease in the speed of the ship and an increase in fuel consumption. When the marine life in the submarine door and the cooling pipe system is serious, it will cause Blockage, resulting in a decrease in cooling rate and even mechanical failure. At the same time, the secretions produced by the attachment of marine organisms are susceptible to corrosion of marine coatings and hull steel plates, which accelerates the degree of corrosion of underwater parts of marine vessels, so preventing biofouling is very important for shipping of ships.

Marine ship antifouling technology often uses heavy metals as antifouling agents. For example, the US military used mercury chloride and zinc oxide as antifouling agents in the past 1960s. Commercial fishing vessels or cargo ships often used tributyltin (TBT). Antifouling paint. Due to the antifouling coating containing tributyltin, the marine organisms will be mutated. After January 1, 2008, the use of antifouling coatings containing organotins is completely banned. At present, heavy metals such as cuprous oxide are used as bio-anti-fouling. The agent is used, but the amount of use is too high and it will cause environmental hazards.

In the release of antibacterial agents, antibacterial agents that are not coated with microcapsules, When a large amount of paint is present, it will react with the rubber binder, thus increasing the viscosity of the paint, causing the properties of the paint to change and affecting the painting operation. When the antibacterial agent not coated with the microcapsules is mixed with the paint, when it is applied as a coating, it will ooze out from the coating under the environmental condition of the concentration difference, so that a large concentration is released at the beginning. In the environment, the waste of the antibacterial agent is caused and the burden of the environment is increased; and then the concentration is rapidly lowered, causing the subsequent drug release concentration to be lower than the effective concentration, resulting in an ineffective concentration, as shown in the first figure.

In the prior art of antibacterial agent microcapsule design, U.S. Patent Application Serial No. 60/782,990, the disclosure of which is incorporated herein by reference to the entire disclosure of the entire disclosures of Modulation of release rate of biocide from microcapsules; U.S. Patent No. 6,365,066, which describes various uses of microcapsule-coated antimicrobial agents in combination with polymeric forming polymers; however, these compositions are still The inability to solve the release of the antibacterial agent applied in the paint can ensure the effective antibacterial concentration and long-term antibacterial purpose to deal with the problem of microbial growth control.

Therefore, the present invention develops an antibacterial agent microcapsule structure which can be used for a paint, so that the antibacterial agent coated in the microcapsule can release the antibacterial agent from the microcapsule core, so that the paint coating can have a long length. The anti-biofouling advantage of the effective concentration of the long-acting antibacterial agent.

The main object of the present invention is to provide a microcapsule structure containing an antibacterial agent which can be used for a paint, which is passed through a core of a polymer microcapsule. And further shell design, so that the antibacterial agent coated in the microcapsule can release the antibacterial agent slowly and at a moderate concentration from the microcapsule core, so that the paint coating has a long time and long-lasting effect. The effective concentration of the antibacterial agent releases the advantage of biofouling.

The invention discloses an antibacterial agent microcapsule structure which can be used for a paint material, adopts single-stage or multi-stage polymer polymerization cross-linking, to achieve a high unit of antibacterial agent coated in the microcapsule core, and further adopts hydrophobic antibacterial agent. The agent can prevent the antibacterial agent from being released into the environment quickly and in large quantities due to dissolution of the aqueous solution. The antibacterial agent is selected to be less than 2% by weight (more specifically less than 1% by weight) of a hydrophobic compound or a combination thereof, such as 2-n-octyl-3(2H)-isothiazolone (OIT), benzopyrene Thiazolone (BIT), 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone (DCOIT) or other alkane compounds, which can be microencapsulated with analogs and derivatives. Used in marine paints for anti-biofouling purposes.

The invention relates to a microcapsule structure containing an antibacterial agent which can be used for a paint, and can be used for the anti-biofouling microcapsule structure used for a paint topcoat. Due to the limitation of the thickness of the topcoat coating, the particle size of the antibacterial microcapsule containing antibacterial agent used in the coating needs to be less than 5 μm, so as not to be too large to destroy the compactness of the topcoat layer itself. In order to make the antifouling microcapsules more suitable for the application level, the present invention coats the antibacterial agent with an emulsifier-free emulsion polymerization method to prepare microcapsules having a submicron order, a uniform particle size and a solvent resistance and a high coating amount. In addition, microcapsules of uniform particle size are one of the factors for achieving stable long-acting release (zero-order release).

Atom transfer radical polymerization (Atom-transfer radical-polymerization, abbreviated as ATRP), using free radicals as an initiator, free radicals attack the unsaturated bonds of monomers after high temperature (>90 ° C) in the solution, causing free radicals The base is polymerized. In this polymerization reaction, the carbon-carbon unsaturated bond is attacked by free radicals to form a new carbon-carbon single bond, and the original unsaturated bond is also attacked by free radicals, which also generates new free radicals. A series of monomers are polymerized into a polymer reaction until the free radicals in the solution are consumed.

The invention can further achieve the effect of resisting the solvent and controlling the release control of the coated drug by controlling the crosslinking density by introducing the crosslinking agent.

In order to achieve the above object, according to the solution of the present invention, there is provided an antibacterial agent microcapsule structure which can be used for a paint, comprising: a hydrophobic core, which contains at least one unsaturated group under the action of a radical initiator The hydrophobic monomer is polymerized; and an antibacterial agent is a hydrophobic compound; wherein the hydrophobic core coats the dispersed antibacterial agent to achieve storage and release of the antibacterial agent.

In the above, the unsaturated bond hydrophobic single system is further polymerized with a crosslinking agent to form a crosslinked hydrophobic core; wherein the crosslinking agent is a compound containing a plurality of unsaturated bonds. In the above, the method further comprises a crosslinked hydrophilic shell surrounding the hydrophobic core or the crosslinked hydrophobic core; wherein the crosslinked hydrophilic shell is polymerized by a hydrophilic monomer having at least one unsaturated bond and another crosslinking agent The other crosslinking agent is a compound containing a plurality of unsaturated bonds.

The invention also provides an antibacterial agent microcapsule structure and a preparation method thereof for use in a paint, comprising: a hydrophobic core, the one containing at least one An unsaturated bond hydrophobic monomer is polymerized; a co-crosslinked shell surrounding the hydrophobic core is formed by copolymerizing an unsaturated bond hydrophobic monomer with a hydrophilic monomer having at least one unsaturated bond; The antibacterial agent is a hydrophobic compound; wherein the hydrophobic core and the co-crosslinked shell coat the dispersed antibacterial agent to achieve storage and release of the antibacterial agent. Wherein the hydrophobic core is formed by a hydrophobic monomer containing at least one unsaturated bond, which is polymerized by a radical initiator, and when the conversion rate of the hydrophobic monomer reaches 20-80%, Adding an unsaturated bond hydrophilic monomer, a crosslinking agent and the remaining hydrophobic monomer to form the co-crosslinked shell; wherein, before the action of the radical initiator, or the hydrophobic single When the bulk conversion rate is 20-80%, the antibacterial agent is added to prepare the microcapsule structure containing the antibacterial agent.

The monomer conversion according to the present invention is defined as a degree of consumption of a monomer which is subjected to a radical addition polymerization reaction by a radical, and a monomer is polymerized into a polymer. The invention adopts a radical addition polymerization reaction, and the initial rate of the polymerization reaction is greater than the termination rate, so as the reaction time increases, the monomer decreases, and gradually changes into a polymer, and the conversion rate is a percentage. The form indicates how many monomers have been converted into polymers. The relationship between the conversion ratio and the reaction time is as shown in the second graph. It can be seen that the conversion rate rises slowly in the initial stage of the reaction, and then the conversion rate rises rapidly. At this time, the radical polymerization is formed, and the monomer is rapidly consumed. Finally, the monomer concentration decreases and the conversion tends to be flat. The invention utilizes the appropriate conversion rate of the first monomer, and then adds the second monomer, thereby controlling the polymerization degree of the polymer material of the microcapsule core and the shell wall.

The invention also provides an antibacterial agent microcapsule structure which can be used for a paint, comprising: a hydrophilic core, which is polymerized by a hydrophilic monomer having at least one unsaturated bond by a radical initiator; An antibacterial agent is a hydrophobic compound; wherein the hydrophilic core coats the dispersed antibacterial agent to achieve storage and release of the antibacterial agent.

The invention can also directly adopt a hydrophilic monomer to form a hydrophilic core to coat a hydrophobic antibacterial agent after being polymerized; the reason is that the hydrophilic monomer has an unsaturated bond after polymer polymerization reaction. After being attacked by free radicals, a saturated carbon-carbon covalent bond is formed, so the long-chain hydrocarbon chain end can serve as a hydrophobic end, and will aggregate to form a core resembling a micelle. The long carbon chain is on the inside of its core, while the hydrophilic end functional groups are arranged on the outside of the core. The hydrophobic end on the inner side of the core can be used to coat the hydrophobic antibacterial agent, while the hydrophilic end on the outer side of the core can react with the high molecular monomer of the outer shell to form a core-shell structure.

In the above, the unsaturated bond hydrophilic single system is further polymerized with a crosslinking agent to form a crosslinked hydrophilic core; wherein the crosslinking agent is a compound containing a plurality of unsaturated bonds. In the above, the method further comprises a crosslinked hydrophilic shell surrounding the hydrophilic core or the crosslinked hydrophilic core; wherein the crosslinked hydrophilic shell is polymerized by a hydrophilic monomer having at least one unsaturated bond and another crosslinking agent The other crosslinking agent is a compound containing a plurality of unsaturated bonds.

The invention also provides an antibacterial agent microcapsule structure and a preparation method thereof for use in a paint, comprising: a hydrophilic core, the one containing at least one An unsaturated bond hydrophilic monomer is polymerized; a hydrophilic co-crosslinked shell surrounding the hydrophilic core is formed by copolymerizing a first unsaturated bond hydrophilic monomer and a second unsaturated bond hydrophilic monomer And an antibacterial agent, which is a hydrophobic compound; wherein the hydrophilic core and the hydrophilic co-crosslinked shell coat the dispersed antibacterial agent to achieve storage and release of the antibacterial agent. Wherein, the hydrophilic core is formed by a first unsaturated bond hydrophilic monomer, which is polymerized by a radical initiator, and is added when the hydrophilic monomer conversion rate is 20-80%. a second unsaturated bond hydrophilic monomer, a crosslinking agent and the remaining first unsaturated bond hydrophilic monomer are copolymerized to form the hydrophilic co-crosslinked shell; wherein, the free radical initiator The antibacterial agent is added before the action or when the conversion rate of the hydrophilic monomer reaches 20-80% to prepare the microcapsule structure containing the antibacterial agent.

In the above, the unsaturated bond hydrophobic monomer structure contains at least one or more unsaturated bonds, and the unsaturated bond contains a double bond and a triple bond, which can be attacked by a radical and then subjected to an addition polymerization reaction, preferably styrene. The antibacterial agent is a hydrophobic compound or a combination thereof having a water solubility of less than 2% by weight (more specifically less than 1% by weight), such as 2-n-octyl-3(2H)-isothiazolone (OIT), benzo Isothiazolone (BIT), 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone (DCOIT) or other alkane compound, preferably 4,5-dichloro-2-positive Octyl-3-(2H)-isothiazolone (4,5-dichloro-2-n-octyl-3-(2H)-isothiazolone, DCOIT); the free radical initiator is conditioned or heated The lower free radical is selected from potassium persulfate, benzammonium peroxide, azobisisobutyronitrile or one of the group consisting of potassium persulfate; the crosslinker has at least two Or multiple unsaturated keys; the unsaturated key contains The double bond and the triple bond may be subjected to free radical attack and then subjected to addition polymerization reaction, and are selected from divinylbenzene, 1,4-butanediol diacrylate or one of the group, preferably divinylbenzene; The unsaturated bond hydrophilic monomer structure contains at least one or more unsaturated bonds; the unsaturated bond contains double bonds and triple bonds, and can be subjected to free radical attack and then subjected to addition polymerization reaction, which may be methyl methacrylate, One of the group consisting of methacrylic acid, acrylic acid or the like is preferably methyl methacrylate.

In the microcapsule structure containing the antibacterial agent of the present invention, when the hydrophobic antibacterial agent is present in the aqueous phase system, the antibacterial agent tends to combine with the polymer which is also hydrophobic, and the antibacterial agent is coated in the core of the polymer microcapsule. Therefore, in the present invention, a hydrophobic monomer is polymerized to form a hydrophobic core, which can stabilize and coat the hydrophobic antibacterial agent. The invention further introduces a hydrophilic shell (shell or wall), which is formed by hydrophilic polymerization of a hydrophilic monomer to form a hydrophilic shell wall, and is surrounded by the original hydrophobic core, thereby avoiding the hydrophobic core and the coating The hydrophobic antibacterial agent directly contacts the less polar organic solvent in the paint, causing the core or antibacterial agent to dissolve quickly and release in large quantities.

The invention relates to an antibacterial agent microcapsule structure which can be used for paints, and the microcapsule structure design concept comprises: (1) adopting single-stage or multi-stage polymer polymerization cross-linking, so as to achieve high unit antibacterial agent coating. In the microcapsule core; (2) the present invention employs a hydrophobic antibacterial agent, so that the antibacterial agent can be quickly released into the environment without being dissolved by the aqueous solution; (3) the core of the microcapsule of the present invention is hydrophobic The monomer is polymerized into a hydrophobic polymer or a polymer compound having a hydrophobic terminal functional group (for example, a long hydrocarbon chain), which is stable and abundant. The hydrophobic antibacterial agent is stored; (4) In addition, the shell of the microcapsule of the present invention is polymerized into a hydrophilic polymer by a hydrophilic monomer, so that the hydrophobic antibacterial agent can be released into the paint without being too fast. In the material, the outer shell of the hydrophilic polymer can form a similar shielding effect, and the hydrophobic antibacterial agent is directly contacted with the paint solvent; (5) depending on the use requirement, the cross-linking agent is appropriately added to carry out the microcapsule polymer core or the shell wall. Perform polymer cross-linking to enhance the stable setting of the polymer core or shell wall structure of the microcapsule and increase the solvent resistance of the solvent in the paint. (6) The microcapsule polymer core can also be adjusted by adjusting the cross-linking agent content. Or the degree of cross-linking of the shell wall can be controlled, thereby controlling the release amount of the microcapsule coated antibacterial agent.

The above summary, the following detailed description and the accompanying drawings are intended to further illustrate the manner, the Other objects and advantages of the present invention will be described in the following description and drawings.

100‧‧‧microcapsule structure

20‧‧‧hydrogen nucleus

30‧‧‧Common cross-shell

40‧‧‧Antibacterial agent

The first figure is a correlation diagram of the concentration of the drug release and the time; the second figure is a typical monomer conversion rate diagram; the third figure is a schematic diagram of the structure of the microcapsule containing the antibacterial agent according to the embodiment of the present invention; The antibacterial agent microcapsule thermogravimetric analysis chart is shown in the embodiment; the fifth figure is an experimental photograph of the antibacterial ring containing the antibacterial agent microcapsule paint coating film according to the embodiment of the invention.

The embodiments of the present invention are described by way of specific examples, and those skilled in the art can readily appreciate the advantages and effects of the present invention from the disclosure herein.

The invention relates to a microcapsule structure containing an antibacterial agent which can be used for a paint material, which adopts single-stage or multi-stage polymer polymerization cross-linking, so as to achieve a high unit of antibacterial agent coated in the microcapsule core, and adopts hydrophobic antibacterial agent. The agent can prevent the antibacterial agent from being released into the environment quickly and in large quantities due to dissolution of the aqueous solution.

Please refer to the third figure, which is a schematic diagram of the structure of the microcapsule containing the antibacterial agent according to an embodiment of the present invention. As shown in the figure, an embodiment of the microcapsule structure containing an antibacterial agent which can be used for a paint material comprises: a hydrophobic core formed by polymerizing a hydrophobic monomer containing at least one unsaturated bond; a shell surrounding the hydrophobic core, wherein the hydrophobic monomer is copolymerized with a hydrophilic monomer having at least one unsaturated bond; and an antibacterial agent is a hydrophobic compound; wherein the hydrophobic core The dispersed antibacterial agent is coated with the co-crosslinked shell to achieve storage and release of the antibacterial agent.

Wherein the hydrophobic core is formed by a hydrophobic monomer containing at least one unsaturated bond, which is polymerized by a radical initiator, and when the conversion rate of the hydrophobic monomer reaches 20-80%, Adding an unsaturated bond hydrophilic monomer, a crosslinking agent and the remaining hydrophobic monomer to form the co-crosslinked shell; wherein, before the action of the radical initiator, or the hydrophobic single When the bulk conversion rate is 20-80%, the antibacterial agent is added to prepare the microcapsule structure containing the antibacterial agent.

In addition, in the examples exemplified in the present invention, when the microcapsule core is formed by polymerization of a hydrophobic monomer, since the reaction proceeds in an aqueous solution, the efficiency of the free radical in the aqueous solution to attack the unsaturated bond of the hydrophobic monomer is biased. Low, so that the free radicals generated by the initiator may not have attacked the monomeric unsaturated bonds, and they are eliminated in the aqueous solution by themselves. Therefore, the hydrophobic monomer polymerization reaction can be carried out by adding a little (within 5%) of a hydrophilic monomer, such as acrylic acid, to the solution, thereby increasing the polymerization point of the monomer in the solution and improving the polymerization efficiency of the hydrophobic monomer.

Example 1A: Hydrophobic core coated antimicrobial microcapsules

10 g of styrene, 0.5 g of acrylic acid, 8.57 g of antibacterial agent DCOIT were added to the double neck bottle, followed by deionized water until the total solution weight was 100 g. The double neck bottle was placed in an oil bath for reflux heating. After the solution began to boil, 0.13 g of potassium persulfate was further added and reacted for 2 hours. After the reaction is completed, the solution is centrifuged and the upper layer liquid is removed, and left to stand at room temperature to obtain a hydrophobic core-coated antimicrobial microcapsule.

Example 1B: Hydrophobic core coated antimicrobial microcapsules

First, 10 g of styrene and about 0.5 g of acrylic acid are heated and boiled in an aqueous solution, and 0.13 g of potassium persulfate is added to carry out radical polymerization to form a polymer hydrophobic core (embryo), and then an antibacterial agent DCOIT is added. The microcapsules are coated. After the reaction is finished, the solution is centrifuged and the upper layer liquid is removed, and the mixture is allowed to stand at room temperature to obtain a hydrophobic core-coated antibacterial agent microcapsule.

Example 2: Crosslinked hydrophobic core coated antibacterial agent microcapsule

In this embodiment, the cross-linking agent divinylbenzene is mixed with styrene. Joint reaction. 10 grams of styrene, about 0.5 grams of acrylic acid, 8.57 grams of antimicrobial DCOIT, 2 grams of divinylbenzene were added to the double neck bottle, followed by deionized water until the total solution weight was 100 grams. The double neck bottle was placed in an oil bath for reflux heating. After the solution began to boil, 0.13 g of potassium persulfate was further added and reacted for 2 hours. After the reaction is completed, the solution is centrifuged and the upper layer liquid is removed, and left to stand at room temperature to obtain a crosslinked hydrophobic core-coated antimicrobial microcapsule. The purpose of this embodiment is to add a crosslinking agent and a monomer to crosslink to polymerize the crosslinked polymer, so that it is included in the scope of the present embodiment regardless of the order in which the crosslinking agent and the antibacterial agent are added to the reaction.

Example 3A: Crosslinked hydrophilic shell/hydrophobic core coated antibacterial agent microcapsule

The experimental procedure of Example 1A or 1B is first carried out to complete the hydrophobic core-coated antibacterial microcapsule as the core structure of the microcapsule, and then 8 g of methyl methacrylate, 2 g of divinylbenzene and 0.13 g are further added to the reaction solution. Potassium persulfate. After reacting for 1.5 hours, it can be polymerized to form a crosslinked hydrophilic shell surrounded by a hydrophobic core. After the reaction is finished, the solution is centrifuged and the upper layer liquid is removed, and left to stand at room temperature to obtain a crosslinked hydrophilic shell/hydrophobic core coated antibacterial. Microcapsules. The purpose of this embodiment is to add a hydrophilic monomer and a crosslinking agent to surround the original hydrophobic core, and the equal embodiments are included in the scope of the present embodiment.

Example 3B: Crosslinked hydrophilic shell/crosslinked hydrophobic core coated antibacterial agent microcapsule

The experimental procedure of Example 2 was first carried out to complete the cross-linked hydrophobic core-coated antibacterial microcapsule as the core structure of the microcapsule, and then 8 g of methyl methacrylate, 2 g of divinylbenzene and 0.13 g were further added to the reaction solution. Potassium persulfate. After 1.5 hours of reaction, a cross-linked hydrophilic shell/crosslinking can be obtained after centrifugal drying. Water core coated antibacterial agent microcapsules.

Example 4: Co-crosslinked shell/hydrophobic core coated antimicrobial microcapsules

10 grams of styrene, about 0.5 grams of acrylic acid, and 8.57 grams of the antimicrobial agent DCOIT were added to the double neck flask, followed by deionized water until the total solution weight was 100 grams. The double neck bottle was placed in an oil bath for reflux heating. After the solution began to boil, 0.13 g of potassium persulfate was further added to carry out a radical polymer polymerization reaction. The reaction is carried out for 10-30 minutes (hydrocarbon monomer conversion rate is 20-80%), at which time a hydrophobic core is pre-formed in the solution, but unreacted free radicals remain in the solution. Further, 8 g of methyl methacrylate and 2 g of divinylbenzene were added and reacted for 1.5 hours. The post-added methyl methacrylate monomer can be copolymerized with the remaining portion of the styrene monomer in the solution to form a crosslinked shell. After the reaction, the solution is centrifuged and the upper layer liquid is removed, and left to dry at room temperature to obtain a co-crosslinked shell/hydrophobic core-coated antibacterial microcapsule, and the antibacterial agent is dispersed and coated in the hydrophobic core and the co-crosslinked shell. . The purpose of this embodiment is to add a hydrophilic monomer, a crosslinking agent and a part of the hydrophobic monomer to co-crosslink to form a co-crosslinked shell, which is surrounded by the original hydrophobic core, so the order of reaction with the antibacterial agent is added. Irrelevant; the antibacterial agent may also be added together with the methyl methacrylate monomer, which is an equal embodiment and is therefore included in the scope of the present embodiment.

In this embodiment, the core monomer is styrene, and the shell wall material is a co-crosslinked shell formed by copolymerization of styrene, methyl methacrylate and a cross-linking agent divinylbenzene. Among them, styrene and divinylbenzene are easily copolymerized, so that it is easy to produce a non-uniform copolymer during copolymerization, so that a part is easily generated. The region with low crosslink density is suitable as the core of the coated hydrophobic antibacterial agent, and methyl methacrylate can be copolymerized with styrene and divinylbenzene as the shell wall material of the microcapsule.

In this embodiment, the initiator is potassium persulfate and the core monomer is styrene. The vinyl group on the styrene monomer is attacked by free radicals, and the double bond is opened to bond to form a new carbon-carbon single bond, forming the core of polystyrene. There is still free radicals in the solution. When the polymer conversion rate of styrene monomer is about 20-80%, the shell wall monomer methyl methacrylate is added; the free radical on the styrene vinyl group in the solution, or The free radical generated by potassium persulfate attacks the vinyl group on the monomer methyl methacrylate, and the double bond is opened to bond to form a new carbon-carbon single bond, which can form a copolymer of methyl methacrylate and styrene. (copolymer). If a double-bonded cross-linking agent divinylbenzene is added, the free radicals on the styrene vinyl group in the solution, as well as the free radicals generated by potassium persulfate or the free radicals on the methyl methacrylate vinyl group, The two-double chain on the cross-linking agent divinylbenzene is attacked, and the copolymer polymer is further formed into a network polymer. However, the hydrophobic antibacterial agent DCOIT coated in the present embodiment tends to be combined with the same hydrophobic polymer because of its hydrophobic property in an aqueous solution, so the hydrophobic antibacterial agent DCOIT is formed in the entire microcapsule structure forming reaction. It will enter the core of the microcapsule structure by means of dissolution and permeation, and then be coated with a network structure of methyl methacrylate and divinylbenzene.

Example 5A: Hydrophilic core coated antimicrobial microcapsules

Add 10 grams of methyl methacrylate, 8.57 to the double neck bottle. The antibacterial agent DCOIT was added followed by deionized water until the total solution weight was 100 grams. The double neck bottle was placed in an oil bath for reflux heating. After the solution began to boil, 0.13 g of potassium persulfate was further added and reacted for 2 hours. After the reaction is completed, the solution is centrifuged and the supernatant liquid is removed, and the mixture is allowed to stand at room temperature to obtain a hydrophilic core-coated antimicrobial microcapsule.

Example 5B: Hydrophilic core coated antibacterial agent microcapsule

First, 10 g of methyl methacrylate is heated and boiled in an aqueous solution, and 0.13 g of potassium persulfate is added to carry out radical polymerization to form a polymer hydrophilic nuclear (embryo), and then an antibacterial agent DCOIT is added for microcapsules. Coating is also included in the scope of the embodiments of the present invention.

Example 6: Crosslinked hydrophilic core coated antibacterial agent microcapsule

In this embodiment, a crosslinking agent, divinylbenzene, and methyl methacrylate are added to carry out a crosslinking reaction. 10 g of methyl methacrylate 8.57 g of antibacterial agent DCOIT, 2 g of divinylbenzene were added to the double neck bottle, followed by deionized water until the total solution weight was 100 g. The double neck bottle was placed in an oil bath for reflux heating. After the solution began to boil, 0.13 g of potassium persulfate was further added and reacted for 2 hours. After the reaction is completed, the solution is centrifuged and the upper layer liquid is removed, and left to stand at room temperature to obtain a crosslinked hydrophilic core-coated antibacterial agent microcapsule. The purpose of this embodiment is to add a crosslinking agent and a monomer to crosslink to polymerize the crosslinked polymer, so that it is included in the scope of the present embodiment regardless of the order in which the crosslinking agent and the antibacterial agent are added to the reaction.

Example 7A: Crosslinked hydrophilic shell/hydrophilic core coated antibacterial agent microcapsule

The experimental procedure of Example 5A or 5B is first performed to complete the hydrophilicity. The core coated antibacterial microcapsules were used as the core structure of the microcapsules, and then 8 g of methyl methacrylate, 2 g of divinylbenzene and 0.13 g of potassium persulfate were further added to the reaction solution. After reacting for 1.5 hours, it can be polymerized to form a crosslinked hydrophilic shell surrounded by a hydrophilic core. After the reaction is finished, the solution is centrifuged and the upper layer liquid is removed, and the mixture is allowed to stand at room temperature to obtain a crosslinked hydrophilic shell/hydrophilic core coated antibacterial. Microcapsules. The purpose of this embodiment is to add a hydrophilic monomer and a crosslinking agent to surround the original hydrophilic core, and the equal embodiments are included in the scope of the present embodiment.

Example 7B: Crosslinked hydrophilic shell/crosslinked hydrophilic core coated antibacterial agent microcapsule

The experimental procedure of Example 6 was first carried out to complete the cross-linked hydrophilic core-coated antibacterial microcapsule as the core structure of the microcapsule, and then 8 g of methyl methacrylate, 2 g of divinylbenzene and 0.13 g were further added to the reaction solution. Potassium persulfate. After reacting for 1.5 hours, a crosslinked hydrophilic shell/crosslinked hydrophilic core coated antimicrobial microcapsule can be obtained.

Example 8: Hydrophilic co-crosslinked shell/hydrophilic core coated antibacterial agent microcapsule

10 grams of methyl methacrylate and 8.57 grams of the antimicrobial agent DCOIT were added to the double neck flask, followed by deionized water until the total solution weight was 100 grams. The double neck bottle was placed in an oil bath for reflux heating. After the solution began to boil, 0.13 g of potassium persulfate was further added to carry out a radical polymer polymerization reaction. The reaction is carried out for 10-30 minutes (the hydrophilic monomer conversion rate is 20-80%), and a hydrophilic core is preliminarily formed in the solution, but unreacted free radicals remain in the solution. Further, 8 g of methyl methacrylate and 2 g of divinylbenzene were added and reacted for 1.5 hours. The post-added methyl methacrylate monomer can be added to the solution with the remaining part of methacrylic acid. The acid methyl ester monomer is copolymerized to form a hydrophilic co-crosslinked shell. After the reaction, the solution is centrifuged and the upper layer liquid is removed, and left to dry at room temperature to obtain a total hydrophilic cross-linked shell/hydrophilic core-coated antibacterial microcapsule, and the antibacterial agent is dispersed and coated on the hydrophilic core and the hydrophilic co-intersection. In the shell. The purpose of this embodiment is to add a hydrophilic monomer, a crosslinking agent and a part of the hydrophilic monomer added first to co-crosslink to form a hydrophilic co-crosslinked shell, which is surrounded by the original hydrophobic core, so the antibacterial agent The order of addition to the reaction is irrelevant; the antibacterial agent may also be added together with the methyl methacrylate monomer added later, which is an equal embodiment and is therefore included in the scope of the present embodiment.

Example 9: Microcapsule thermogravimetric analysis and identification

Please refer to the fourth figure, which is a thermogravimetric analysis diagram of an antibacterial agent microcapsule according to an embodiment of the present invention. As shown in the figure, the co-crosslinked shell/hydrophobic core coated antibacterial agent microcapsule of the embodiment 4 of the invention has an antibacterial agent DCOIT coating amount of 30 wt% (heat loss before 250 ° C), and a polymer content of 70 wt. % (250 ° C - 600 ° C thermogravimetric loss), confirmed that a high content of antibacterial agent microcapsule structure has been prepared.

Example 10: Release test of microcapsules containing antibacterial agents

In this embodiment, a release test experiment of an antibacterial agent microcapsule was carried out. The microcapsule samples containing the antibacterial agent of Examples 1, 3A and 4 were immersed in an organic solvent toluene at a ratio of 5 wt%, and the organic solvent was taken out one day after the immersion time (one day of microcapsule immersion time), and then the same was added. Volume organic solvent, and then immersed for two days (microcapsule immersion time for three days); take out the organic solvent, take a quantitative volume of the microcapsule organic solvent for pyrolysis gas chromatography mass spectrometry (PyGC/MS) analysis, the results show In Table 1. Example 1 without a hydrophilic shell and then coated outside the hydrophobic core, hydrophobic The antibacterial agent (DCOIT) will be released faster, while Examples 3A and 4 are protected by a cross-linked hydrophilic shell on the periphery, which slows the release rate and release of the hydrophobic antibacterial agent DCOIT. The microcapsule structure containing the antibacterial agent of the invention can be modulated through a structure such as a hydrophobic core or a hydrophilic shell, and can achieve the purpose of regulating the release control of the coated object.

Example 11: Microcapsules containing antibacterial agents for use and testing of paints

In the present embodiment, the microcapsule containing the antibacterial agent of the present invention is used in a lacquer, so that it can be used as an antifouling paint for biofouling. The amount of microcapsules added in a ratio of 5 wt% is mixed with the commercial paint, and the microcapsules are mixed and blended according to the ratio of the dosage forms of the paints and the manner of application; if the microcapsules are compatible with the paint, the dispersion is not In the best case, the amount of the diluent can be adjusted in a timely manner or a physical mode such as a three-roller can be used to uniformly disperse the microcapsules in the paint.

A microcapsule paint coating operation was uniformly performed on the test piece using a square coater. After the coating film is completed, it is allowed to stand at room temperature for 7 days, and after drying is completed, the experiment can be carried out. The dried paint coating film was scraped off from the test piece, and 10 mg and 1 mg were respectively weighed for antibacterial experiments. The experimental strain was Pseudoalteromonas sp. (sbt), using the examples and experimental dose control sample names are shown in Table 2. In this experiment, the antibacterial test of the microcapsule-containing paint was carried out by the method of inhibiting the bacteria circle, and the sample containing the microcapsule paint was placed in the middle, and the sample coated with the microcapsule paint slowly released the antibacterial coated therein. The agent forms a zone of inhibition zone, and the larger the zone of inhibition zone, the greater the bacteriostatic efficacy. Please refer to the fifth figure, which is an experimental photograph of the inhibition zone of the antibacterial agent microcapsule paint coating film according to an embodiment of the present invention. As shown in the figure, as the concentration of the paint containing the microcapsule of the present invention increases, the range of the zone of inhibition zone is larger, and it is confirmed that the microcapsule containing the antibacterial agent of the present invention can be mixed into the paint to be used as an antifouling paint. use.

Example 12: Ocean exposure experiment with microcapsule paint coating film

The microcapsule addition amount is mixed with the commercial paint at a ratio of 1%, and the microcapsules are added and mixed according to the ratio of the paint dosage forms and the application manner, and then the microcapsule paint is sprayed, brushed or sprayed. The method was applied to a stainless steel substrate and allowed to stand at room temperature for more than 7 days until the coating was dry. The substrate containing the microcapsule paint film was suspended at the seaside of Kaohsiung Harbor, about 1 meter below the sea surface, and subjected to a one-month marine exposure test.

After 1 month, the substrate was taken out, and the substrate containing the microcapsule paint coating film was observed and compared with the substrate to which the microcapsule paint coating film was not added. As a result, it was revealed that the substrate containing the microcapsule paint coating film did not have obvious green algae adhered thereto; and the substrate on which the microcapsule paint coating film was not added had green algae attached thereto. It shows a coating film containing microcapsule paint, which has anti-biofouling performance for at least 1 month.

The microcapsule structure containing the antibacterial agent which can be used for the paint material adopts single-stage or multi-stage polymer polymerization cross-linking to achieve a high unit of antibacterial agent coated in the microcapsule core, so that the antibacterial agent can not be prevented The large amount of release into the environment, and further the use of hydrophobic antibacterial agents, allows the antibacterial agent to be released into the environment quickly and in large quantities due to dissolution of the aqueous solution. The microcapsule structure containing the antibacterial agent of the invention can realize the long-term and long-acting release of the antibacterial agent in the paint, and has the effect of preventing biofouling, and has economic and energy-saving benefits, so that it can be more widely applied in the future.

The above-described embodiments are merely illustrative of the features and effects of the present invention and are not intended to limit the scope of the technical scope of the present invention. Modifications and variations of the above-described embodiments can be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention should be as set forth in the scope of the claims described below.

Claims (14)

An antibacterial agent microcapsule structure for use in a paint, comprising: a hydrophobic core, polymerized by a hydrophobic monomer having at least one unsaturated bond by a radical initiator; a crosslinked hydrophilic shell Surrounding the hydrophobic core; and an antibacterial agent, which is a hydrophobic compound; wherein the crosslinked hydrophilic shell is formed by polymerizing a hydrophilic monomer having at least one unsaturated bond with a crosslinking agent; The crosslinking agent is a compound containing a plurality of unsaturated bonds; wherein the hydrophobic core coats the dispersed antibacterial agent to achieve storage and release of the antibacterial agent. The antibacterial agent microcapsule structure according to claim 1, wherein the unsaturated bond hydrophobic single system is further polymerized with another crosslinking agent to form a crosslinked hydrophobic core; wherein the other crosslinking agent is a A compound containing a plurality of unsaturated bonds. An antibacterial agent microcapsule structure which can be used for paints, comprising: a hydrophobic core formed by polymerizing a hydrophobic monomer containing at least one unsaturated bond; a co-crosslinked shell surrounding the hydrophobic core a saturated bond hydrophobic monomer is copolymerized with a hydrophilic monomer containing at least one unsaturated bond; and an antibacterial agent is a hydrophobic compound; Wherein, the hydrophobic core and the co-crosslinked shell coat the dispersed antibacterial agent to realize storage and release of the antibacterial agent. A method for preparing a microcapsule-containing microcapsule structure for use in a paint according to claim 3, the method comprising the steps of: (a) providing a hydrophobic monomer having at least one unsaturated bond, and a radical initiator Under the action, the polymerization starts to form the hydrophobic core; (b) when the conversion rate of the hydrophobic monomer reaches 20-80%, adding an unsaturated bond hydrophilic monomer, a crosslinking agent and the remaining hydrophobic single The body is copolymerized to form the co-crosslinked shell; wherein an antibacterial agent is added in the step (a) or the step (b) to prepare the microcapsule-containing structure containing the antibacterial agent. An antibacterial agent microcapsule structure for use in a paint, comprising: a hydrophilic core, polymerized by a hydrophilic monomer having at least one unsaturated bond by a radical initiator; a crosslinked hydrophilic shell Surrounding the hydrophilic core; and an antibacterial agent, which is a hydrophobic compound; wherein the crosslinked hydrophilic shell is formed by polymerizing a hydrophilic monomer having at least one unsaturated bond with a crosslinking agent; The crosslinking agent is a compound containing a plurality of unsaturated bonds; wherein the hydrophilic core coats the dispersed antibacterial agent to achieve storage and release of the antibacterial agent. The antibacterial agent microcapsule structure according to claim 5, wherein the unsaturated layer The bond hydrophilic single system is further polymerized with another crosslinking agent to form a crosslinked hydrophilic core; wherein the other crosslinking agent is a compound containing a plurality of unsaturated bonds. An antibacterial agent microcapsule structure which can be used for a paint material, comprising: a hydrophilic core formed by polymerizing a hydrophilic monomer containing at least one unsaturated bond; and a hydrophilic co-crosslinked shell surrounding the hydrophilic core a first unsaturated bond hydrophilic monomer is copolymerized with a second unsaturated bond hydrophilic monomer; and an antibacterial agent is a hydrophobic compound; wherein the hydrophilic core and the hydrophilic co-crosslinked shell The dispersed antibacterial agent is applied to achieve storage and release of the antibacterial agent. A method for preparing a microcapsule-containing microcapsule structure for use in a paint according to claim 7, wherein the step comprises: (1) providing a first unsaturated bond hydrophilic monomer, acting as a radical initiator Next, starting to polymerize into the hydrophilic core; (2) adding a second unsaturated bond hydrophilic monomer, a crosslinking agent and the remaining first when the hydrophilic monomer conversion rate is 20-80% The saturated bond hydrophilic monomer is copolymerized to form the hydrophilic co-crosslinked shell; wherein an antibacterial agent is added in the step (1) or the step (2) to prepare the microcapsule-containing structure containing the antibacterial agent. The antibacterial agent microcapsule structure according to claim 1, 2, 3 or 4, wherein the unsaturated bond hydrophobic single system is styrene. The antibacterial agent microcapsule structure and the preparation method thereof according to claim 1, 3, 4, 5, 7 or 8, wherein the antibacterial agent is a hydrophobic compound having a water solubility of less than 2% by weight or a combination thereof. The antibacterial agent microcapsule structure and the preparation method thereof according to claim 1, 3, 4, 5, 7 or 8, wherein the antibacterial agent is 4,5-dichloro-2-n-octyl-3- (2H)-isothiazolone (4,5-dichloro-2-n-octyl-3-(2H)-isothiazolone, DCOIT). The antibacterial agent microcapsule structure and the preparation method thereof according to claim 1, 4, 5 or 8, wherein the radical initiator is selected from the group consisting of potassium persulfate, benzammonium peroxide, and azobisisoindole. Nitrile or one of the group consisting of. The antibacterial agent microcapsule structure and the preparation method thereof according to claim 2, 4, 6 or 8, wherein the crosslinking agent is divinylbenzene. The antibacterial agent microcapsule structure and the preparation method thereof according to any one of claims 3 to 8, wherein the unsaturated bond hydrophilic single system is composed of methyl methacrylate, methacrylic acid, acrylic acid or the like. One of the groups.