KR20130092075A - Acryl resin, preparing method thereof and coating composition comprising the same - Google Patents
Acryl resin, preparing method thereof and coating composition comprising the same Download PDFInfo
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- KR20130092075A KR20130092075A KR1020120013567A KR20120013567A KR20130092075A KR 20130092075 A KR20130092075 A KR 20130092075A KR 1020120013567 A KR1020120013567 A KR 1020120013567A KR 20120013567 A KR20120013567 A KR 20120013567A KR 20130092075 A KR20130092075 A KR 20130092075A
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- LUPHJKMTKIVJCY-UHFFFAOYSA-N CNO[NH+](N(C)N=C)[O-] Chemical compound CNO[NH+](N(C)N=C)[O-] LUPHJKMTKIVJCY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/22—Esters containing halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
Abstract
Description
The present invention relates to an acrylic resin, a preparation method thereof, and a coating composition including the same. More specifically, the present invention is an acrylic resin used in a coating composition which is excellent in adhesiveness, weather resistance, hydrophilicity, and stain resistance of a silane and a coating material when crosslinking, and is formed with a single coating, a manufacturing method thereof, and a coating composition comprising the same. It is about.
The coating (coating) has a difference in speed and late with time, but deteriorates (degradation of performance) by the action of the internal and external factors of the coating. Among the factors influencing the deterioration of the coating film, the weather resistance of the coating film varies depending on internal factors such as the chemical structure, polymerization degree, molecular weight distribution, physical and chemical properties of the coating film according to the type and compounding ratio of the polymer, pigment, and additive. In addition, external deterioration factors such as ultraviolet rays, oxygen, heat, moisture, seawater, sulfurous acid gas, hydrogen sulfide, hydrocarbons and microorganisms, as well as pretreatment of the material, thickness and drying conditions of the coating film also affect the weather resistance of the coating film.
Due to deterioration of the coating film, coating defects such as glossiness, discoloration, whitening, swelling, rust, cracking, detachment, abrasion, contamination adhesion, and lowering of electrical resistance occur. If a coating defect occurs, the thickness and weight of the coating are reduced, and thus, repainting is required because the coating needs to be replaced. Therefore, the cost of repainting and environmental pollution due to volatiles in the paint.
The recent research direction of paints is focused on the development of high-performance paints that require various uses and characteristics. In particular, in order to reduce environmental problems and health and maintenance costs, development of highly weatherable paints is urgently required. Accordingly, as a weather resistant paint for minimizing deterioration, silicone resin paints and fluorine resin paints having a large bond energy between atoms have been recently developed, and their application to various fields has been expanded.
Silicone paint is a generic term for resin paints containing silicone resins, silicone modified resins and alkoxysilanes. Silicone modified resins having organic functional groups in the backbone can be classified into organic and inorganic composite resins, and silicone resins and alkoxysilane-containing resins composed mostly of Si-O-Si can be classified as inorganic resins.
Such silicone resins, silicone modified resins and alkoxysilane-containing resins have strong siloxane bonds in the bonding structure and thus exhibit excellent weatherability compared to general organic resins, and thus are known to be suitable for high weatherability paints. Silicone resins and alkoxysilane-containing resins have excellent physical properties such as weather resistance, heat resistance, water repellency, solvent resistance, and chemical resistance, but when cured, they require high-temperature energy and are extremely expensive in terms of price, and they are limited in expressing various advantages. There is. Specifically, the alkoxysilane-containing resin is a situation in which the storage stability and crack stability are poorly used only in a field that is not universally used and requires special fields such as heat resistance and water repellency.
On the other hand, silicone modified resins using silicone intermediates and silicone intermediates having reactive functional groups can be used in various fields because they can control various curing conditions, are inexpensive in price, exhibit not only advantages of organic resins but also have excellent weather resistance. It is known to be applicable to. In particular, silicone modified acrylic resin paint is a combination of silicone resin and acrylic resin which has excellent weather resistance among general organic resins. It not only expresses high weather resistance comparable to fluorine resin paint, but also adheres to coating materials, chemical resistance, stain resistance and solvent resistance. Since the physical properties of the same paints are excellent, research and development on high weathering paints using these are being actively conducted.
Until the 1980s, weather-resistant paints were mainly made of fluororesin paint, a copolymer of fluoroethylene and vinyl ether. The fluororesin paint is designed in a two-component system in which a higher alkyl group is introduced into a molecular structure to impart flexibility and solubility to a solvent, and a hydroxyl group is introduced to form a crosslink with a polyisocyanate at heat drying or at room temperature.
However, fluorine resin paints are expensive, poor pollution resistance to environmental changes, weak hardness, and difficult to form a thick coating film with a single coating, so the working conditions are difficult. come.
Inorganic ceramic paints have received new attention for architectural interiors and exteriors since the 1990s. Inorganic ceramic paints are nonflammable and have good stain resistance since inorganic pigments of pure ceramic components are used. However, it is easy to cause cracks and has a disadvantage of heating for 30 minutes at 180 ° C to 200 ° C.
To date, as the stain-resistant paints, paints made of silicone and acrylic resins (silicon / acrylic resins), fluororesin paints and emulsion resin paints are known. However, the silicone / acrylic resin paint is difficult to cure according to the presence of catalyst and water, and the fluororesin paint is low polarized by a higher alkyl group introduced into the structure, so that lipophilic organic pollutants can be easily adsorbed onto the coating film. In addition, there is a problem in that it is difficult to remove the traces of contamination and thus cannot maintain aesthetic appearance for a long time. In addition, the emulsion resin paint is an aqueous paint using an emulsion resin using an acrylic monomer as a binder and a blending technique such as pigments, fillers and additives. Due to poor weather resistance, there is a problem in that it needs to be repainted, and it is not suitable for use as an exterior finishing material for difficult repainting work.
Therefore, in order to fundamentally improve the fouling resistance of the paint, the surface of the coating is made hydrophilic to weaken the binding force of lipophilic substances such as automobile exhaust, tire wear and soot, which are the main causes of contamination on the surface of the coating, and the crosslinking density of the coating. It is not only difficult to penetrate the contaminants by increasing the efficiency, but also the attached contaminants can be easily removed by rainwater, even if they become contaminated. Research and development of this excellent non-polluting paint is absolutely required.
Topcoat paints, which have weather resistance and non-pollution resistance and can form a coating film of 50㎛ or more at a time, do not require separate maintenance and repair, so they can be widely used in automobile coatings, bridges, large structures, especially long bridges. In addition, the existing manufacturing and coating equipment can be used as it is, the content of volatile organic compounds (Volatile Organic Compounds (VOC)) can be reduced in the resin and paint industry with respect to environmental problems.
However, there is a technical problem to overcome the deterioration of the appearance performance of the coating film, such as poor flowability and smoothness of the paint caused by adjusting the crosslinking degree of the resin for imparting weather resistance and non-pollution characteristics over a long period of time.
As to weathering paint, Korean Patent No. 895197 discloses 30 to 70 parts by weight of an acrylic resin containing a tertiary amine group and a hydroxyl group, and 5 to 20 parts by weight of a silicone resin or silicon intermediate containing any one of a methoxy functional group or a silanol functional group. A main part comprising 20 to 30 parts by weight of a white pigment, 5 to 20 parts by weight of an additive and a diluent; And 20 to 70 parts by weight of polyisocyanate, 20 to 50 parts by weight of functional epoxy silane, and 10 to 30 parts by weight of diluent, wherein the curing agent part may further include a functional isocyanate silane. A functional silane curable urethane modified polysiloxane coating composition configured to have a weight ratio of from 15 to 1 is disclosed. However, the composition does not crosslink to a uniform crosslinking density when crosslinking with a curing agent by simply mixing a silicone resin or a silicone intermediate containing any one of a methoxy functional group or a silanol functional group without reacting the polymer backbone, Some molecules which do not participate in the binding are present, and the coating film performance such as water resistance, scratch resistance, and chemical resistance is lowered, and there is a problem of poor fouling resistance.
One embodiment of the present invention is to provide an acrylic resin and a coating composition comprising the same to form a coating film having excellent adhesion to weathered materials and / or non-pollution upon crosslinking.
Another embodiment of the present invention is to provide an acrylic resin and a coating composition including the same, which can form a thick film by one coating.
Another embodiment of the present invention is to provide a method for producing an acrylic resin according to the embodiment of the present invention.
According to the first aspect of the present invention,
Methacrylate repeating units having aliphatic functional groups, methacrylate repeating units having tertiary amine groups, methacrylate repeating units having hydroxy groups, silicon repeating units, styrene repeating units having fluorine atoms, acrylate repeating units and methacrylates There is provided an acrylic resin comprising a repeating unit having at least one fluorine atom selected from the group consisting of repeating units, and a (meth) acrylate repeating unit having an acid functional group.
According to a second aspect of the present invention,
The acrylic resin is provided with an acrylic resin comprising the following repeating units.
[Formula 1]
(Methacrylate repeating unit having an aliphatic functional group)
[Formula 2]
(Methacrylate repeating unit having a tertiary amine group)
(3)
(Methacrylate repeating unit having a hydroxyl group)
[Formula 4]
(Silicone Repeating Unit)
[Chemical Formula 5]
(Repeat unit with fluorine atom)
[Formula 6]
((Meth) acrylate repeating units having acid functionality)
According to the third aspect of the present invention,
The acrylic resin is 50 to 80 parts by weight of methacrylate monomer having an aliphatic functional group, 2 to 10 parts by weight of methacrylate monomer having a tertiary amine group, 10 to 40 parts by weight of methacrylate monomer having a hydroxy group Parts, 1 to 20 parts by weight of the silicone monomer, 1 to 20 parts by weight of at least one fluorine-containing monomer selected from the group consisting of fluorine-containing styrene monomers, acrylate monomers and methacrylate monomers, Provided is an acrylic resin prepared by polymerizing a polymerization reaction composition comprising 1 to 5 parts by weight of a acrylate monomer, 1 to 5 parts by weight of a chain transfer agent having a hydroxyl group, and 1 to 5 parts by weight of a radical polymerization initiator. do.
According to the fourth aspect of the present invention,
The methacrylate monomer having an aliphatic group is normal butyl methacrylate, normal propyl methacrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, glycidyl methacrylate At least one acrylic resin selected from the group consisting of lauryl methacrylate, and isobornyl methacrylate is provided.
According to the fifth aspect of the present invention,
The methacrylate monomer having a tertiary amine group is provided with at least one acrylic resin selected from the group consisting of dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
According to the sixth aspect of the present invention,
The methacrylate monomer having a hydroxyl group is provided by at least one acrylic resin selected from the group consisting of 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate. do.
According to the seventh aspect of the present invention,
The silicone monomers are 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropyltriisobutoxysilane, 3-methacryloxypropyltrioctoxysilane, vinyltriisobutoxysilane, vinyltri- n -decock Selected from the group consisting of cysilane, vinyltri- t -butoxysilane, methacrylatoalkylalkoxysilane, vinylalkoxysilane, 3-mercaptopropyltriisobutoxysilane, and 3-mercaptopropyltrimethoxysilane At least one kind of acrylic resin is provided.
According to the eighth aspect of the present invention,
The fluorine-containing monomers are 1,2,2-trifluorostyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacryl Rate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate, hexafluoro-2- (4-fluorophenyl) -2- Propyl acrylate, hexafluoro-2- (4-fluorophenyl) -2-propyl methacrylate, 1,1-dihydroperfluoroheptyl acrylate, 1,1-dihydroperfluorooctyl acrylate, 2 Provided is an acrylic resin that is at least one selected from the group consisting of-(N-ethyl perfluorooctane sulfonamido) ethyl methacrylate, and 2- (N-ethyl perfluorooctane sulfonamido) ethylacrylate do.
According to the ninth aspect of the present invention,
The (meth) acrylate monomer having the acid functional group is provided with at least one acrylic resin selected from the group consisting of acrylic acid and methacrylic acid.
According to the tenth aspect of the present invention,
The chain transfer agent having a hydroxyl group is provided with at least one acrylic resin selected from the group consisting of 2-mercaptoethanol, and 2-hydroxyethyl-3-mercaptopropionate.
According to the eleventh aspect of the present invention,
The radical polymerization initiator is composed of benzoyl peroxide, tertiary butyl peroxy benzoate, tertiary butyl peroxy-2-ethyl hexanoate, tertiary mill peroxy-2-ethyl hexanoate, and tertiary mill peroxide. At least one kind of acrylic resin selected from the group provided is provided.
According to the twelfth aspect of the present invention,
The acrylic resin is provided with an acrylic resin having a number average molecular weight of 5000 to 15000.
According to the thirteenth aspect of the present invention,
The acrylic resin is provided with an acrylic resin having a glass transition temperature of 20 ° C to 60 ° C.
According to a fourteenth aspect of the present invention,
The acrylic resin is provided with an acrylic resin having a viscosity of 1500 mPa · s to 3000 mPa · s.
According to a fifteenth aspect of the present invention,
The acrylic resin is provided with an acrylic resin having an acid value of 10 mgKOH / g to 25 mgKOH / g.
According to a sixteenth aspect of the present invention,
The acrylic resin is provided with an acrylic resin having a hydroxyl group content of 2 parts by weight to 6 parts by weight based on 100 parts by weight of the polymerization composition.
According to a seventeenth aspect of the present invention,
The acrylic resin has a number average molecular weight of 5,000 to 15,000, glass transition temperature of 20 ℃ to 60 ℃, viscosity of 1500 mPa · s to 3000 mPa · s, acid value of 10 mgKOH / g to 25 mgKOH / g, hydroxyl group content 2 parts by weight to 6 parts by weight of the acrylic resin is provided based on 100 parts by weight of the polymerization composition.
According to an eighteenth aspect of the present invention,
50 parts by weight to 80 parts by weight of a methacrylate monomer having an aliphatic functional group, 2 parts to 10 parts by weight of a methacrylate monomer having a tertiary amine group, 10 parts to 40 parts by weight of a methacrylate monomer having a hydroxyl group, and a silicone monomer 1 to 20 parts by weight, 1 to 20 parts by weight of at least one fluorine-containing monomer selected from the group consisting of fluorine-containing styrene monomers, acrylate monomers and methacrylate monomers, and (meth) acrylate monomers having an acid functional group Acrylic resin which polymerizes the polymerization reaction composition which contains 1 weight part-5 weight part, 1 weight part-5 weight part of a chain transfer agent which has a hydroxyl group, and 1 weight part-5 weight part of a radical polymerization initiator in 80 degreeC-100 degreeC in a solvent. Provided is a method for preparing.
According to a nineteenth aspect of the present invention,
According to one aspect of the present invention, there is provided an acrylic resin coating composition comprising 60 parts by weight to 90 parts by weight of an acrylic resin, and 30 parts by weight to 70 parts by weight of a silane curing agent composition.
According to a twentieth aspect of the present invention,
The acrylic resin coating composition is provided with an acrylic resin coating composition having a viscosity of 100 cps to 500 cps.
According to a twenty-first aspect of the present invention,
The silane curing agent composition is provided with an acrylic resin coating composition, which is a mixture of isocyanate silane and epoxysilane.
According to a twenty-second aspect of the present invention,
The silane curing agent composition is provided with an acrylic resin coating composition further comprises an inorganic ceramic material in an amount of 10 to 20 parts by weight based on 100 parts by weight of the silane curing agent composition.
Coating composition comprising an acrylic resin according to an embodiment of the present invention forms a coating film excellent in adhesion, weather resistance and / or non-pollution property to the coating material when crosslinking. Furthermore, the coating film formed of the coating composition containing the acrylic resin according to one embodiment of the present invention is hydrophilic, and furthermore, a thick coating film, in particular, a thickness of 50 µm or more, preferably 60 µm to 80 in one coating. A thick coating film having a thickness can be formed.
Specifically, the acrylic resin included in the coating composition of the present invention is a high-solid-based compound having a smaller content of volatile organic compounds (VOC) than the acrylic resin used in conventional acrylic resin paints, and has a relatively small number average molecular weight. Due to the molecular structure, a cross-linking reaction with silane forms a coating film having excellent mechanical properties such as adhesion to coatings, water resistance, solvent resistance, etc., having excellent appearance quality, gloss and hardness, and having non-pollution characteristics with weather resistance. It is a top coat paint that can form a coating film of 50㎛ or more at a time, so it does not require separate maintenance and repair, so it can be widely used in automobile coatings, bridges, large structures, especially long bridges, etc. , Painting equipment can be used as it is, painting in that it can reduce the content of VOC It is a useful invention capable of low pollution in terms of human protection and atmospheric environment of the operator.
According to one embodiment of the present invention, an acrylic resin that is used as a main resin in a coating composition and has excellent adhesion, weather resistance and / or non-pollution property and forms a thick coating film when applied to a coating material.
The acrylic resin according to the present invention is a methacrylate repeating unit having an aliphatic functional group, a methacrylate repeating unit having a tertiary amine group, a methacrylate repeating unit having a hydroxy group, a silicon repeating unit, a styrene repeating unit having a fluorine atom, and an acryl A repeating unit having at least one fluorine atom selected from the group consisting of a rate repeating unit and a methacrylate repeating unit, and a (meth) acrylate repeating unit having an acid functional group.
Furthermore, the acrylic resin according to the present invention includes the following repeating unit.
[Formula 1]
[Formula 2]
(3)
[Formula 4]
[Chemical Formula 5]
[Formula 6]
On the other hand, the acrylic resin according to the present invention is a methacrylate monomer having an aliphatic functional group 50 parts by weight to 80 parts by weight, methacrylate monomer having a tertiary amine group 2 parts by weight to 10 parts by weight, methacrylate monomer having a hydroxyl group 10 parts by weight to 40 parts by weight, 1 to 20 parts by weight of silicone monomer, 1 to 20 parts by weight of at least one fluorine-containing monomer selected from the group consisting of fluorine-containing styrene monomers, acrylate monomers and methacrylate monomers, 1 to 5 parts by weight of a (meth) acrylate monomer having an acid functional group, 1 to 5 parts by weight of a chain transfer agent having a hydroxy group, and 1 to 5 parts by weight of an initiator may be prepared by polymerizing a polymerization composition. have.
Specifically, the acrylic resin is prepared by radical polymerization of various kinds of monomers having a vinyl double bond of acrylic ester or methacrylic ester in a solution using a thermal decomposition initiator.
Examples of the methacrylate monomer having an aliphatic group include normal butyl methacrylate, normal propyl methacrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, and glycidyl methacrylate. At least one selected from the group consisting of latex, lauryl methacrylate, and isobornyl methacrylate can be used. These may be used alone or two or more together. The methacrylate monomer having an aliphatic group may be used in an amount of 50 parts by weight to 80 parts by weight based on the content of other components constituting the polymerization composition described herein.
At least one selected from the group consisting of dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate may be used as the methacrylate monomer having a tertiary amine group.
The methacrylate monomer having a tertiary amine group is 2 parts by weight to 10 parts by weight with respect to the content of other components constituting the polymerization reaction composition described herein in consideration of crosslinking with an epoxy silane used as a curing agent. May be used in 2 parts by weight to 8 parts by weight. When the content of the methacrylate monomer having a tertiary amine group is less than 2 parts by weight, the crosslinking density with the epoxy silane may be insufficient, resulting in a decrease in coating properties such as solvent resistance and wash resistance. If it exceeds 10 parts by weight, yellowing and / or cracking may occur due to hardening of the coating film, shortening of pot life and / or deterioration of weather resistance due to excessive increase in the crosslinking density.
As the methacrylate monomer having a hydroxy group, at least one selected from the group consisting of 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate may be used. These may be used alone or two or more together.
The methacrylate monomer having a hydroxy group is 10 parts by weight to 40 parts by weight, preferably 10 parts by weight based on the content of other components constituting the polymerization composition described herein in consideration of crosslinking with an isocyanate silane used as a curing agent. It can be used in parts by weight to 35 parts by weight. When the content of the methacrylate monomer having a hydroxy group is less than 10 parts by weight, the crosslinking density with the isocyanate silane is insufficient, the hardness is low, and the coating film properties may be lowered, such as poor solvent resistance. If the content exceeds 40 parts by weight, the resin itself will have an increase in viscosity and an excessive increase in crosslinking density, resulting in problems such as hardening of the coating film, lowering of water resistance and chemical resistance, and poor compatibility with a crosslinking agent and a nonpolar solvent.
The silicone monomer replaces the coating surface with a hydrophilic component, whereby fine particulate adhesive substances mainly composed of black carbon such as automobile exhaust gas, tire wear and soot, which are the main causes of contamination, are fixed by chemically and physically adhering to the coating surface. It is used to prevent the contaminants from penetrating and increasing the crosslinking density of the coating film, and to make it easier to remove the contaminants attached by the rainwater even if it is contaminated.
Examples of the silicone monomers include 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropyltriisobutoxysilane, 3-methacryloxypropyltrioctoxysilane, vinyltriisobutoxysilane and vinyltri- n- . Deoxyoxysilane, vinyltri- t -butoxysilane, acrylatoalkylalkoxysilane, methacrylatoalkylalkoxysilane, vinylalkoxysilane, 3-mercaptopropyltriisobutoxysilane, and 3-mercaptopropyltrimethoxysilane At least one selected from the group consisting of can be used. These may be used alone or two or more together. Here, alkoxysilanes having a high steric hindrance effect that contributes to reaction stability and storage stability are suitable.
The silicone monomer may be used in an amount of 1 part by weight to 20 parts by weight, and preferably 1 part by weight to 10 parts by weight, based on the content of other components constituting the polymerization composition described herein. If the content of the silicone monomer is less than 1 part by weight, fouling resistance may be lowered. If it is more than 20 parts by weight, the viscosity may increase, storage stability may be poor, and scratch resistance may be lowered.
The fluorine-containing monomer is blended to enhance the hardness and stain resistance of the coating film. As the fluorine-containing monomer, at least one selected from the group consisting of fluorine-containing styrene monomers, acrylate monomers and methacrylate monomers can be used. Examples of the fluorine-containing monomer include 1,2,2-trifluorostyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, trifluoroethyl methacrylate, 2,2,3,3- Tetrafluoropropyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate, hexafluoro-2- (4-fluoro Phenyl) -2-propyl acrylate, hexafluoro-2- (4-fluorophenyl) -2-propyl methacrylate, 1,1-dihydroperfluoroheptyl acrylate, 1,1-dihydroperfluorooctyl acrylic At least one selected from the group consisting of latex, 2- (N-ethyl perfluorooctane sulfonamido) ethyl methacrylate, 2- (N-ethyl perfluorooctane sulfonamido) ethylacrylate can be used. have. These may be used alone or two or more together.
The fluorine-containing monomer is 1 part by weight to 20 parts by weight, preferably 1 part by weight to 10 parts by weight, in consideration of reactivity, hardness, fouling resistance and weather resistance, relative to the content of other components constituting the polymerization composition described herein. Can be used. The fluorine-containing monomer is used in the content of the above range in terms of hardness, scratch resistance, stain resistance, reactivity and adhesion of the polymerization composition.
Both silicone monomers and fluorine-containing monomers are highly hydrophobic and their electrical properties are different, so they are incompatible with each other and cause phase separation.However, when a copolymer of silicon and fluorine is formed, this problem is eliminated and the characteristics of each monomer are different. It exhibits better non-pollution properties than polymers. This is because the distance between the fluorine moiety and the water molecule is longer than that of the fluorine monomer alone, and the interaction energy is significantly reduced when the interaction between the hydrophobic heteropolymer and the water is calculated by the molecular orbital method. The distance between the hydrogen atom of the silicone monomer and the oxygen atom of the water is slightly shorter, but the interaction energy is almost 1/2. This ensures that copolymers of fluorine and silicon have low interactions with water so that when hydrophobic groups approach water, the arrangement of water takes the position of the lowest energy level suitable for it, so that hydrophilic forces can repel water and approach water. It is non-polluting because there is no.
At least one selected from the group consisting of acrylic acid and methacrylic acid may be used as the (meth) acrylate monomer having an acid functional group. These may be used alone or two or more together.
The (meth) acrylate monomer having an acid functional group may be used in an amount of 1 to 5 parts by weight based on the content of other components constituting the polymerization reaction composition described herein. The (meth) acrylate monomer having an acid functional group is preferably used in the above content in terms of reaction stability, coating hardness, adhesion, viscosity, water resistance, storage stability.
The chain transfer agent having a hydroxyl group plays an important role in lowering the molecular weight of the resin during the polymerization reaction, and is finally bonded to the terminal of the synthetic polymer to increase the density of the hydroxyl group, which is a crosslinking point with the crosslinking agent when forming a coating film, and then cures the polymer. To form a chain.
As the chain transfer agent including the hydroxyl group, for example, at least one selected from the group consisting of 2-mercaptoethanol and 2-hydroxyethyl-3-mercaptopropionate may be used. These may be used alone or two or more together.
The chain transfer agent including the hydroxyl group may be used in an amount of 1 part by weight to 5 parts by weight, preferably 1 part by weight to 3 parts by weight, based on the content of other components constituting the polymerization reaction composition described herein. The chain transfer agent including the hydroxyl group may be used in the content of the above range in consideration of viscosity control, molecular weight control, coating properties, and odor by the sulfur component.
The radical polymerization initiator is added to adjust the molecular weight of the acrylic resin. Examples of the radical polymerization initiator include benzoyl peroxide, tertiary butyl peroxy benzoate, tertiary butyl peroxy-2-ethyl hexanoate, tertiary mill peroxy-2-ethyl hexanoate, and tertiary mill peroxide. At least one selected from the group consisting of organic peroxides and azo compounds such as 2-azobisisobutyronitrile (AIBN) can be used. The radical polymerization initiator may be used alone or two or more together.
The radical polymerization initiator may be used in an amount of 1 part by weight to 5 parts by weight, preferably 2 parts by weight to 4 parts by weight, more than the amount of the common acrylic resin initiator with respect to the content of other components constituting the polymerization composition described herein. have. The radical polymerization initiator is preferably used in the above content in consideration of viscosity, molecular weight, workability, and coating film properties.
An acrylic resin can be obtained by polymerizing the said polymerization composition. Specifically, the polymerization may be carried out at a temperature of 80 ℃ to 100 ℃ in a solvent, preferably a solvent having a middle boiling point, according to another embodiment of the present invention a method for producing an acrylic resin by polymerization of the polymerization reaction composition This is provided. More specifically, the acrylic polymer may be prepared by polymerizing the polymerization composition in the solvent at a temperature of 80 ° C. to 100 ° C. for 8 hours to 11 hours. For example, when the polymerization composition is polymerized in the solvent at a temperature of 80 ° C. to 100 ° C. for 8 hours to 11 hours, the polymerization composition may be added dropwise to the solvent for 6 hours to 8 hours. .
As the solvent, esters such as aromatic hydrocarbons such as toluene and xylene, ethyl acetate, normal butyl acetate, ethylene glycol ethyl ether acetate, and ketones such as methyl isobutyl ketone and methyl normal amyl ketone may be used. The solvent may be used alone or two or more together. In consideration of the effect of the reaction temperature on the molecular weight and final viscosity of the resin, the synthesis temperature of the resin, solubility parameters, evaporation rate, etc., polymerization was carried out at a temperature of 80 ℃ to 100 ℃ using a medium boiling point solvent having a boiling point of 100 ℃ to 160 ℃ It is desirable to. By using a medium boiling point solvent, it is possible to stably synthesize acrylic resin at a given reaction temperature by preventing reflux. The content of the solvent can be adjusted so that the viscosity of the acrylic resin obtained is 1500 mPa · s to 3000 mPa · s. The acrylic resin of the present invention exhibits this viscosity at a nonvolatile content (solid content) of about 60% by weight.
By dropwise addition of the polymerization reaction composition to the solvent for a long time of 6 hours to 8 hours, reflux of the middle boiling point solvent, which can generally be caused upon dropping of the monomer mixture in the conventional general acrylic resin synthesis, can be prevented.
By polymerization under the above reaction conditions, not only the composition ratio of each repeating unit of the acrylic resin and the distribution of the repeating unit are uniform, but also the chain transfer agent having a hydroxyl group is bonded to the terminal of the acrylic resin molecular structure. Therefore, when the acrylic resin according to one embodiment of the present invention is crosslinked to form a coating film, the polymer structure of the resin is polymerized in a linear direction to ultimately exhibit excellent gloss and clarity, as well as excellent chemical properties. An acrylic resin according to one embodiment of the present invention is provided.
Acrylic resin according to an embodiment of the present invention may have a number average molecular weight (Mn) of 5,000 to 15,000. The acrylic resin may have a glass transition temperature of 20 ℃ to 60 ℃. The acrylic resin may have a viscosity of 1500 mPa · s to 3000 mPa · s. The acrylic resin may have an acid value of 10 mgKOH / g to 25 mgKOH / g. The acrylic resin may have a hydroxyl content in the range of 2 parts by weight to 6 parts by weight based on 100 parts by weight of the polymerization composition. The acrylic resin may have a nonvolatile content of about 60% by weight. The acrylic resin has a number average molecular weight of 5,000 to 15,000, glass transition temperature of 20 ℃ to 60 ℃, viscosity of 1500 mPa · s to 3000 mPa · s, acid value of 10 mgKOH / g to 25 mgKOH / g, hydroxyl group content 2 parts by weight to 6 parts by weight based on 100 parts by weight of the polymerization composition.
According to another embodiment of the present invention, there is provided an acrylic resin coating composition comprising 60 parts by weight to 90 parts by weight of an acrylic resin and 30 parts by weight to 70 parts by weight of a silane curing agent composition according to one embodiment of the present invention.
The silane curing agent composition is a mixture of an isocyanate silane and an epoxy silane, and may be mixed with 60 parts by weight to 90 parts by weight with 30 parts by weight to 70 parts by weight of an acrylic resin.
More specifically, the isocyanate silane is used such that the equivalent ratio of NCO / OH in the acrylic resin is about 1.2 / 1 and the epoxysilane is such that the epoxy group / amine group equivalent ratio is about 1/1 with respect to the amine in the acrylic resin.
In the silane curing agent composition, the isocyanate silane and the epoxy silane are used to match the functional group equivalents of the isocyanate group and the epoxy group in the silane as the curing agent corresponding to the hydroxyl group and the amine group in the main acrylic resin. If the isocyanate group or the hydroxyl group remains in the equivalent ratio of NCO / OH without participating in the crosslinking reaction, the coating film properties are lowered because it does not form a dense crosslink. When NCO / OH <1, the flexibility of the coating film is increased, but water resistance, chemical resistance and hardness are lowered. On the contrary, when NCO / OH> 1, the water resistance, chemical resistance and hardness is increased, but flexibility is decreased. Therefore, in order to eliminate the unreacted state, the equivalent ratio of NCO / OH should be 1/1, but an isocyanate group is usually used in excess since the isocyanate group reacts with moisture in the air. Therefore, the isocyanate silane is used in an NCO / It is used such that the equivalent ratio of OH is about 1.2 / 1. That is, 20% excess.
The equivalent ratio of the epoxy group / amine group is low in crosslinking density if one component does not participate in the reaction and is low in drying, resulting in poor drying and poor physical properties such as water resistance and weather resistance. Thus, epoxysilane is used such that the epoxy group / amine group equivalent ratio is about 1/1 to the amine in the acrylic resin.
In order to improve the non-contamination properties of the coating film, an alkali silicate compound containing an alkoxy group is generally blended into the coating composition as a hydrophilic inorganic ceramic material, and the coating composition according to the present invention may further include a hydrophilic inorganic ceramic material. . As the hydrophilic inorganic ceramic material, an alkali silicate, specifically methyl silicate, more specifically Mitsubishi chemical MS-57 may be used.
The hydrophilic inorganic ceramic material is preferably used in an amount of 10 parts by weight to 20 parts by weight based on 100 parts by weight of the silane curing agent composition. Or it is preferable to use 3 weight part-10 weight part with respect to 100 weight part of solid content of coating composition. If the hydrophilic inorganic ceramic material is less than 3 parts by weight based on 100 parts by weight of solids of the paint composition, the antifouling function is lowered. If the hydrophilic inorganic ceramic material is more than 10 parts by weight, the price increases and the compatibility of the paint is poor. It is difficult to produce a transparent paint.
The acrylic resin coating composition may further include a reaction catalyst as a curing accelerator. At least one selected from the group consisting of an organic tin compound and an acid catalyst may be used as the reaction catalyst. Examples of the organic tin compound include dibutyl tin dilaurate, dibutyl tin dichloride, dimethyl tin dilaurate, dimethyl tin dichloride, dibutyl tin diacetate, and the like, and these may be used alone or in combination of two or more. Paratoluene sulfonic acid etc. are mentioned as an example of the said acid catalyst.
The reaction catalyst may be additionally added as necessary in 0.001 parts by weight to 0.01 parts by weight, preferably 0.003 parts by weight to 0.008 parts by weight, based on 100 parts by weight of the solid content of the acrylic resin coating composition. The 'solid content of the coating composition' refers to the content of solids excluding the solvent component in the coating composition.
The acrylic resin coating composition may further include a solvent as necessary. The solvent may be used such that the viscosity of the acrylic resin coating composition is 100 cPs to 500 cPs. In this case, the content of the acrylic resin coating composition is approximately 60% by weight. The type of the solvent is the same as the type of solvent that can be used in the synthesis of the acrylic resin.
The acrylic resin coating composition may have a viscosity of 100 cPs to 500 cPs (Gardner Holdt: D˜S). In general, the conventional paint had to adjust the solid content concentration to 50% by weight by adding an excessive amount of volatile organic solvent in order to achieve a viscosity of 100 cPs to 500 cPs, but in the present invention, the viscosity of the solid content using a relatively small amount of volatile organic solvent was used at 60% by weight. There is an advantage that can be adjusted to 100cPs to 500cPs.
Hereinafter, the present invention will be described in more detail with reference to the present invention. The following examples are provided to aid the understanding of the present invention and thus do not limit the present invention.
( Example 1 to 5 and Comparative example )
To a four-necked flask equipped with a stirrer, 127.3 g of normal butyl acetate and 127.3 g of xylene were added as a solvent, replaced with nitrogen gas, and the temperature was maintained at 90 ° C. while stirring. As the methacrylate monomer having an aliphatic functional group in the solvent, 252.8 g of normal butyl methacrylate, as a methacrylate monomer having a tertiary amine group, 20 g of dimethylaminoethyl methacrylate and 2-hydroxy as a methacrylate monomer having a hydroxyl group 83.2 g of ethyl methacrylate, 4 g of acrylic acid as a (meth) acrylate monomer having an acid functional group, 4.0 g of 2-mercaptoethanol as a chain transfer agent containing a hydroxyl group, 6 g of AIBN as a radical polymerization initiator, of the contents shown in Table 1 below. A mixture of a silicone monomer and a mixture of fluorine-containing monomers of the contents shown in Table 1 was added dropwise at a uniform rate over 4 hours, further aged for 3 hours after completion of the dropping, and then additionally 2 g of AIBN was added for 3 hours. The reaction was completed by further reacting the unreacted monomer while stirring to prepare an acrylic resin.
[Table 1]
( Experimental Example )
In order to find out the properties of the coating film formed of the coating composition comprising the acrylic resin of Examples 1 to 5 and Comparative Examples, as shown in Table 2 below, the acrylic resin and the curing agent composition of Examples 1 to 5 and Comparative Examples were mixed The composition was prepared. As the curing agent composition, Desmodur N-3300 from Bayer, which is an epoxy silane, an isocyanate silane and a sulfur-free polyisocyanate, was used. At this time, the equivalence ratio of epoxy / amine was 1/1, and the equivalence ratio of NCO / OH was 1.2 / 1.
[Table 2]
In order to evaluate the coating properties formed of the coating composition comprising the acrylic resin using cold rolled steel sheet (KS D 3512) test method 4.4 of KS M 5000-1111 (manufacturing method of the test iron plate of paint), that is, mechanical pretreatment A specimen coating film was formed in accordance with the specifications of the specimen. The coating composition was applied to the steel sheet at a time using a spray coating machine so that the dry coating thickness was 60 μm, and the physical properties of the coating film formed by drying at room temperature for 7 days were evaluated as follows.
[Physical Properties Evaluation of Coating Film]
1. Adhesive test
The cross-hatch adhesion test of the paint was carried out in accordance with ISO 2409 on the specimen coating fabricated above, in a crosswise shape, 11 lines horizontally and vertically, with a distance of 1 mm, taped on it, and then peeled off and then 100 pieces on the coating film. The adhesion was evaluated as the number of pieces remaining in the coating of. The number of pieces remaining in the coating film was visually evaluated. The larger the value obtained, the better the adhesion.
2. Pencil Hardness
Hardness was measured by the pencil hardness method of JIS K 5400 (8.4.1). The pencil hardness method is scratched when drawn at a 45 ° angle by the type of pencil (3B, 2B, B, HB, F, H, 2H, 3H, 4H) on the specimen coating film formed as described in the experimental example on a glass plate. This I appreciate the hardness. The degree of scratching was evaluated visually. Normally, the hardness of the coating film is about HB to 2H, and the higher the H value, the better the hardness and the better the wear resistance.
3. Promoting weather resistance test
The accelerated weather resistance test was evaluated by the sunshine weather-Ometer (Atlas Electric Devices Co., Ci65A type) according to the accelerated weather resistance test method of KS M 5000-3231 with the gloss preservation value and color difference of the coating film after 3,000 hours.
(1) Gloss preservation value measurement
Gloss preservation value was calculated by the following formula using a Glossmeter (Pacific Scientific Co., Glossgard Type II).
(2) color difference measurement
Color difference expresses the difference between two colors from visual to numerical concept. That is, the geometric distance of the two colors in the color space coordinates is expressed numerically. Spectro Color Meter (Dippon Denshoku Kogyo Co., SZ-∑ 80 type), which is a diffuse reflectance measuring device, was used for measurement. The color difference was calculated by the following equation.
Color difference (ΔE) = [(ΔL) 2 + (Δa) 2 + (Δb) 2 ] 1/2
Where L = Hunter color indicator
a, b = chromaticity coefficients of the Hunter colorimeter
4. Promoting pollution
Accelerated fouling test was carried out by spraying the coating film with 20% of black carbon dispersed in mineral spirits, immersing and drying for 5 hours at 80 ± 2 ° C, and then using the water washing test to determine the brightness index difference before and after water washing. ΔL).
[Table 3]
As shown in the table above, when the amount of silicon and fluorine monomers was changed while adding 2 g of each of them to less than 1 part by weight, which is the range of the present invention, the stain resistance was slightly lowered in the accelerated fouling test. It can be confirmed, in the case of Example 1 added 20g each to 1 to 20 parts by weight within the scope of the present invention can be confirmed that all excellent in adhesiveness, pencil hardness, accelerated weather resistance and accelerated fouling, the scope of the present invention In Examples 3 and 5, in which 90 g each was added so as to exceed 20 parts by weight of phosphorus, it was confirmed that the pencil hardness was increased and the adhesiveness was slightly decreased.
On the other hand, in the comparative examples without using the silicon and fluorine monomer, although the coating film hardness is slightly lower, but the adhesion is good, it can be seen that the weather resistance is degraded in the accelerated weather resistance test. In particular, in the case of Comparative Example 2 in which a curing agent was used as the non-yellowing polyisocyanate, it was confirmed that the accelerated weather resistance was rapidly decreased. This phenomenon was found to be caused by the decrease of the content of the inorganic silicone in the total components of the paint. Moreover, in the case of the comparative example 3 which does not use the methyl silicate which gives hydrophilicity of a coating film to a hardening | curing agent part, it can confirm that accelerating fouling property falls rapidly.
Claims (13)
The methacrylate monomer having a tertiary amine group is at least one selected from the group consisting of dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate;
The methacrylate monomer having a hydroxyl group is at least one selected from the group consisting of 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate;
The silicone monomers are 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropyltriisobutoxysilane, 3-methacryloxypropyltrioctoxysilane, vinyltriisobutoxysilane, vinyltri- n -decock Acrylatoalkylalkoxysilane, methacrylatoalkylalkoxysilane, vinylalkoxysilane, 3-mercaptopropyltriisobutoxysilane, and 3-mercaptopropyltrimethoxy, such as cysilane, vinyltri- t -butoxysilane At least one selected from the group consisting of silanes;
The fluorine-containing monomers are 1,2,2-trifluorostyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacryl Rate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate, hexafluoro-2- (4-fluorophenyl) -2- Propyl acrylate, hexafluoro-2- (4-fluorophenyl) -2-propyl methacrylate, 1,1-dihydroperfluoroheptyl acrylate, 1,1-dihydroperfluorooctyl acrylate, 2 At least one selected from the group consisting of-(N-ethyl perfluorooctane sulfonamido) ethyl methacrylate, and 2- (N-ethyl perfluorooctane sulfonamido) ethylacrylate;
The (meth) acrylate monomer having an acid functional group is at least one selected from the group consisting of acrylic acid and methacrylic acid;
The chain transfer agent having a hydroxyl group is at least one selected from the group consisting of 2-mercaptoethanol, and 2-hydroxyethyl-3-mercaptopropionate;
The radical polymerization initiator is composed of benzoyl peroxide, tertiary butyl peroxy benzoate, tertiary butyl peroxy-2-ethyl hexanoate, tertiary mill peroxy-2-ethyl hexanoate, and tertiary mill peroxide. At least one acrylic resin selected from the group consisting of.
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