WO2022019498A1 - Electrodeposition paint composition - Google Patents

Electrodeposition paint composition Download PDF

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Publication number
WO2022019498A1
WO2022019498A1 PCT/KR2021/007967 KR2021007967W WO2022019498A1 WO 2022019498 A1 WO2022019498 A1 WO 2022019498A1 KR 2021007967 W KR2021007967 W KR 2021007967W WO 2022019498 A1 WO2022019498 A1 WO 2022019498A1
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Prior art keywords
epoxy resin
epoxy
weight
composition
parts
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Application number
PCT/KR2021/007967
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French (fr)
Korean (ko)
Inventor
이규상
김효정
도경해
최재일
김성민
김건태
Original Assignee
주식회사 케이씨씨
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Priority to CN202180029788.7A priority Critical patent/CN115702224B/en
Publication of WO2022019498A1 publication Critical patent/WO2022019498A1/en

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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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints

Definitions

  • the present invention relates to an electrodeposition coating composition capable of forming a coating film having excellent storage stability, filterability and weather resistance, and excellent rust prevention properties at edges.
  • the multi-layer coating is generally formed by applying electrodeposition coating, intermediate coating, top coating, and clear coating to the car body that has undergone a pretreatment process.
  • the electrodeposition coating is a coating method in which a conductor is immersed in an electrodeposition coating solution and a coating film is electrically deposited on the surface of the conductor through an electric current between the conductor and the counter electrode.
  • Epoxy type and acrylic type are mainly used as paints used for this electrodeposition coating, and the epoxy type is mainly applied in the coating specifications that require high corrosion resistance, and the acrylic type is mainly applied in the coating specifications that require weather resistance and appearance characteristics. have.
  • Patent Document 1 discloses polyoxyalkylene amine; glycidoxy alkyl alkoxy silanes; and a semi-porous agent that is an additive comprising a reaction product of a glycidyl compound.
  • the composition of Patent Document 1 has excellent edge coverage, but lacks storage stability and lacks filterability.
  • An object of the present invention is to provide an electrodeposition coating composition capable of forming a coating film having excellent weather resistance and excellent edge rust prevention, and excellent storage stability and filterability.
  • the present invention comprises a resin, a curing agent and a cationic water dispersion additive,
  • the cationic water dispersion additive is prepared from an additive composition comprising a first epoxy resin, a second epoxy resin, and an amine group-containing alkoxysilane,
  • It provides an electrodeposition coating composition
  • the first epoxy resin and the second epoxy resin in a weight ratio of 1:1 to 5:1.
  • the electrodeposition coating composition according to the present invention can form a coating film having excellent storage stability and filterability, excellent weather resistance, and excellent edge rust prevention.
  • the functional group such as 'content of unreacted NCO (NCO%)' may be measured by a method well known in the art, for example, may be a value measured by titration or the like.
  • the electrodeposition coating composition according to the present invention includes a resin, a curing agent, and a cationic water dispersion additive.
  • the resin is the subject of the electrodeposition coating composition, and serves to control the properties of the prepared coating film.
  • the resin is not particularly limited as long as it is a resin applicable as a general electrodeposition paint, and may include, for example, an epoxy resin.
  • the resin may be a bisphenol-type epoxy resin, and the bisphenol-type epoxy resin may be, for example, a bisphenol A-type epoxy resin.
  • the resin may be included in the composition in an amount of 5 to 30 parts by weight, or 10 to 25 parts by weight based on 5 to 30 parts by weight of the curing agent.
  • the content of the resin is less than the above content, the rust prevention property of the composition is insufficient, and when the content exceeds the above content, the problem of insufficient impact resistance of the prepared coating film may occur.
  • the curing agent performs a crosslinking reaction with the resin to cure the composition.
  • the curing agent may be an isocyanate resin, and the isocyanate resin is not particularly limited as long as it is a curing agent commonly used in paints.
  • the isocyanate resin may be, for example, aromatic isocyanate and alicyclic isocyanate, and when the aromatic isocyanate is exposed to UV, decomposition of the double bond of the aromatic ring may occur and weather resistance may be reduced. Therefore, it is preferably an alicyclic isocyanate.
  • the alicyclic isocyanate is, for example, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate, IPDI), 1,4-diisocyanato-3, 3,5-trimethylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,3-diisocyanato-4-methylcyclohexane, 1-isocyanato-1-methyl-4(3) -isocyanatomethyl cyclohexane, 2,4'- or 4,4'-diisocyanatodicyclohexylmethane, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, 4,4' -diisocyanato3,3'-dimethyl dicyclohexylmethane, 4,4'-diisocyanato-3,3',5,5'-tetramethyl dicyclo
  • the isocyanate resin may have an end blocked with a blocking agent.
  • the blocking agent stabilizes the terminal isocyanate group to a specific temperature, and when it exceeds a specific temperature, it is dissociated from the isocyanate group to control the reactivity.
  • the blocking agent is, for example, diethylmalonate, dimethylpyrazole, cyclohexanone oxime, oxime compounds such as methylethyl ketoxime, lactam compounds such as ⁇ -caprolactam and ⁇ -butyrolactam, methanol, It may be an alcohol-based compound such as ethanol.
  • the curing agent may be included in the composition in an amount of 5 to 30 parts by weight, or 10 to 20 parts by weight based on 5 to 30 parts by weight of the resin.
  • the content of the curing agent is less than the above content, a problem of poor curability of the composition may occur.
  • the cationic water dispersion additive controls the flowability at the edge of the composition when forming the coating film, thereby improving the edge coverage and the coating film ascending property.
  • the cationic water dispersion additive is prepared from an additive composition comprising a first epoxy resin, a second epoxy resin, and an amine group-containing alkoxysilane.
  • the additive composition may include the first epoxy resin and the second epoxy resin in a weight ratio of 1:1 to 5:1, or 2:1 to 4:1 by weight.
  • the weight ratio of the first epoxy resin and the second epoxy resin is less than 1:1, that is, when a small amount of the first epoxy resin is included than the second epoxy resin, the edge coating film riseability of the composition is insufficient, and exceeds 5:1; That is, when the first epoxy resin is included in excess based on the second epoxy resin, the resin synthesis stability may be insufficient.
  • the epoxy resin (total amount of the first epoxy resin and the second epoxy resin) and the amine group-containing alkoxysilane may be included in a weight ratio of 5:1 to 1:1, or 3:1 to 1:1 by weight.
  • the weight ratio of the epoxy resin to the amine group-containing alkoxysilane is less than the above range, that is, when a small amount of the epoxy resin is included than the amine group-containing alkoxysilane, there is a problem of re-dissolution of the electrodeposition coating film due to an excess of unreacted amine, exceeding the above range That is, when an excessive amount of the epoxy resin is included, the storage stability of the additive may be insufficient due to an increase in the molecular weight of the prepared cationic water dispersion additive.
  • the first epoxy resin has a lower epoxy group content and a greater viscosity at 25° C. than the second epoxy resin.
  • the first epoxy resin has an epoxy group content of 300 to 2,000 mmol/kg or 500 to 1,100 mmol/kg lower than that of the second epoxy resin, and a viscosity at 25° C. of 40 to 75 mPa ⁇ s or 50 to 70 mPa ⁇ s can be large.
  • the first epoxy resin may have an epoxy group content of 2,500 to 3,500 mmol/kg, or 2,900 to 3,300 mmol/kg.
  • the epoxy group content of the first epoxy resin is less than the above range, the gloss of the coating film is lowered, and when it exceeds the above range, a problem of insufficient edge coverage of the composition may occur.
  • the first epoxy resin may have a viscosity at 25° C. of 50 to 80 mPa ⁇ s, or 55 to 70 mPa ⁇ s.
  • the viscosity at 25° C. of the first epoxy resin is less than the above range, the edge coverage of the composition is reduced, and when it exceeds the above range, the gloss of the coating film may be reduced.
  • the first epoxy resin may have an epoxy equivalent of 250 to 400 g/eq, or 300 to 350 g/eq.
  • the epoxy equivalent of the first epoxy resin is less than the above range, the gloss of the coating film is lowered, and when it exceeds the above range, edge coverage of the composition may be reduced.
  • the second epoxy resin may have an epoxy group content of 3,800 to 4,500 mmol/kg, or 4,000 to 4,300 mmol/kg.
  • the epoxy group content of the second epoxy resin is less than the above range, a problem occurs in the synthetic stability of the additive, and when it exceeds the above range, edge coverage of the composition may be reduced.
  • the second epoxy resin may have a viscosity at 25°C of 3 to 15 mPa ⁇ s, or 5 to 10 mPa ⁇ s.
  • the viscosity at 25° C. of the second epoxy resin is less than the above range, the gloss of the prepared coating film is reduced, and when it exceeds the above range, edge coverage of the electrodeposition coating composition may be reduced.
  • the second epoxy resin may have an epoxy equivalent of 200 to 280 g/eq, or 220 to 260 g/eq.
  • the epoxy equivalent of the second epoxy resin is less than the above range, the reaction rate of the composition increases and the workability of the composition is insufficient, and when it exceeds the above range, a problem of lowering purity may occur.
  • the amine group-containing alkoxysilane reacts with the epoxy group of the epoxy resin to form a cationic resin, and forms silanol from the resin. plays a role in controlling
  • the amine group-containing alkoxysilane may be represented by the following formula (1).
  • R 1 is a substituted or unsubstituted C 1 to C 10 alkylene group
  • R 2 is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.
  • R 1 may be a substituted or unsubstituted C 1 to C 5 alkylene group
  • R 2 may be a substituted or unsubstituted C 1 to C 5 alkoxy group.
  • the alkylene group and the alkoxy group may be linear or branched.
  • the alkylene refers to a branched or straight-chain or cyclic divalent radical derived by the removal of one hydrogen atom from a carbon atom of an alkyl group.
  • the alkylene is methylene (-CH2-), 1,1-ethylene (-CH(CH3)-), 1,2-ethylene (-CH2CH2-), 1,1-propylene (-CH(CH2CH3) )-), 1,2-propylene (-CH2CH(CH3)-), 1,3-propylene (-CH2CH2CH2-), 1,4-butylene (-CH2CH2CH2CH2-), 2,4-butylene (-CH2 (CH3)CH2CH2-), and the like, but is not limited thereto.
  • the cationic water dispersion additive may be a silane-modified epoxy resin containing a silanol group.
  • the cationic water dispersion additive has a solid content of 20 to 30% by weight or 23 to 27% by weight, a degree of neutralization of 10 to 40 mmol/100g or 15 to 35 mmol/100g, and a viscosity at 25°C It may be 10 to 100 cps or 30 to 80 cps.
  • the edge coverage of the composition is lowered, and when it exceeds the above range, the viscosity of the composition is increased and storage properties are lowered.
  • the neutralization degree of the cationic water dispersion additive is less than the above range, the storability of the composition is insufficient, and when it exceeds the above range, the problem of insufficient storability of the composition may occur.
  • the viscosity of the cationic water dispersion additive is less than the above range, edge coverage of the composition is lowered, and when it exceeds the above range, a problem of insufficient storability of the composition may occur.
  • the cationic water dispersion additive may be included in the composition in an amount of 3 to 15 parts by weight, or 5 to 10 parts by weight based on 5 to 30 parts by weight of the resin.
  • content of the cationic water dispersion additive is less than the above content, edge coverage of the composition is lowered, and when the content exceeds the above content, the appearance characteristics and gloss of the prepared coating film may be deteriorated.
  • the electrodeposition paint composition may further include at least one additive selected from the group consisting of an amine compound, a solvent, a neutralizer, an antifoaming agent, an oil removal agent, and a flow control agent.
  • the additives are not particularly limited as long as they can be used in the general electrodeposition coating composition.
  • the electrodeposition coating composition according to the present invention as described above can form a coating film having excellent storage stability and filterability, excellent weather resistance, and excellent edge rust prevention.
  • 112 parts by weight of a first epoxy resin in a reaction vessel (manufacturer: Dow Chemical, product name: DER 732, epoxy content: 3,130 mmol/kg, viscosity at 25°C: 65 ⁇ 5 mPa ⁇ s, epoxy equivalent: 320 g/eq), 36 parts by weight of a second epoxy resin (manufacturer: Hexion, product name: Cardura E-10P, epoxy content: 4,170 mmol/kg, viscosity at 25°C: 7 mPa s, epoxy equivalent: 240 g/eq), 110 parts by weight of an amine group Containing alkoxysilane (manufacturer: Momentive, product name: Silquest A-1100, gamma-aminopropyltriethoxy silane) and 120 parts by weight of isopropyl alcohol were added.
  • a cationic water dispersion additive was prepared in the same manner as in Synthesis Example 3, except that the content of each component was adjusted as shown in Table 1 below.
  • the epoxy equivalent is 1,000 g/eq or more
  • 24 parts by weight of the fourth epoxy resin (manufacturer: Kukdo Chemical, product name: YD-128, epoxy equivalent: 180 to 190 g/eq) is added to react the epoxy, and 19 parts by weight of lactic acid ( Aqueous solution having a concentration of 50% by volume) was added to neutralize, and 576 parts by weight of ionized water was gradually added dropwise to disperse in water to prepare a cationic water dispersion additive-7 having a solid content of 35% by weight and a degree of neutralization (MEQACID) of 25mmol/100g did
  • Part 13 the solvent corresponding to the content of Part 13 was vacuum recovered to obtain a resin reactant.
  • the first aqueous dispersion was carried out while putting the resin reactant into the dispersion tank containing parts 14 to 16, and after stirring for 1 hour, part 17 was added to adjust the viscosity. Thereafter, the temperature was adjusted to 45° C. or less, and part 18 was added to prepare an electrodeposition coating composition.
  • the physical properties of the prepared coating film were measured in the following manner, and the results are shown in Tables 5 and 6.
  • the 60° gloss of the coating was measured vertically and horizontally. At this time, it was determined that the higher the gloss value, the higher the gloss.
  • the number of transfers until the coating film was scratched was measured at 170°C and 175°C using a side sufficiently wetted with methyl isobutyl ketone (MIBK) solvent in the coating film.
  • MIBK methyl isobutyl ketone
  • the hardness of the coating film was measured using a Mitsubishi pencil according to MS652-05 and ISO15184.
  • the maximum hardness that does not damage the final coating film was measured using each of 3B, 2B, B, HB, F, H, 2H, and 3H pencils (3B, 2B, B, HB, F, H, 2H). , 3H: inferior ⁇ excellent).
  • Gloss change was confirmed based on Q-UVA Type 21 days according to ISO 11507. Based on the 60° gloss of the initial coating film before the weather resistance test, if the gloss change rate was less than 10%, it was evaluated as excellent, if it was 10% or more and less than 30%, it was evaluated as normal, and if it was 30% or more, it was evaluated as poor.
  • Specimens were prepared and exposed outdoors for 21 days, and gloss changes were confirmed based on the 60° gloss of the initial coating film before testing. When the gloss change rate was less than 10%, it was evaluated as excellent, when it was 10% or more and less than 30%, it was evaluated as normal, and when it was 30% or more, it was evaluated as poor.
  • the electrodeposition coating composition was coated on the edge portion of the blade (knife) as described above, and the coating film thickness of the edge portion of the blade (knife) was measured with an electron microscope.
  • the electrodeposition coating composition was applied to the punched specimen (manufacturer: Ever Steel) at 240V for 3 minutes, and the coating film thickness of the edge portion of the punched specimen was measured with an electron microscope.
  • the degree of passing of the electrodeposition paint compositions prepared in Examples and Comparative Examples was evaluated using a 100 mesh nylon sieve, and filter properties were evaluated with ⁇ (excellent), ⁇ (normal), and X (poor).
  • the filterability was evaluated in the same manner as described above after the composition was stored at 40° C. for 7 days.
  • compositions of Examples 1 to 5 have excellent filterability even after storage at 40° C. for 7 days, a small size of sieve residue, excellent coating film ascending properties, and physical properties of a coating film prepared therefrom It was excellent.
  • Comparative Example 2 using the cationic water dispersion additive of Synthesis Example 6 without the second epoxy resin and Comparative Example 3 using the cationic water dispersion additive of Synthesis Example 7 without the first epoxy resin were stored at 40° C. It lacked filterability and lacked weather resistance.
  • Comparative Example 5 using a silane-modified epoxy amine compound instead of the cationic water dispersion additive was poor in weather resistance.
  • the electrodeposition coating composition according to the present invention can form a coating film having excellent storage stability and filterability, excellent weather resistance, and excellent edge rust prevention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
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Abstract

The present invention relates to an electrodeposition paint composition comprising a resin, a hardener, and an additive having cations dispersed in water, the additive being produced from an additive composition comprising a first epoxy resin, a second epoxy resin, and an alkoxysilane containing an amine group, wherein the first epoxy resin and the second epoxy resin are comprised at a weight ratio of 1:1 to 5:1.

Description

전착도료 조성물Electrodeposition paint composition
본 발명은 저장 안정성, 필터성 및 내후성이 우수하고 엣지(edge)의 방청성이 우수한 도막을 형성할 수 있는 전착도료 조성물에 관한 것이다.The present invention relates to an electrodeposition coating composition capable of forming a coating film having excellent storage stability, filterability and weather resistance, and excellent rust prevention properties at edges.
통상 자동차의 차체가 완성된 후, 차체의 표면부식을 방지하고 방음 기능의 향상과 함께 미관을 수려하게 하기 위하여 다층 도장을 실시하는 것이 일반적이다. 상기 다층 도장은 전처리 공정을 거친 차체를 전착 도장, 중도 도장, 상도 도장 및 클리어 도막을 도장하여 형성되는 것이 일반적이다.In general, after the vehicle body is completed, it is common to apply multi-layer coating to prevent surface corrosion of the vehicle body and to improve the soundproof function and beautiful appearance. The multi-layer coating is generally formed by applying electrodeposition coating, intermediate coating, top coating, and clear coating to the car body that has undergone a pretreatment process.
상기 전착 도장은 전착 도장액에 피도체를 침지하고 피도체와 대극 사이에 전류를 통하여 피도체의 표면에 전기적으로 도막을 석출시키는 도장방법이고, 전기영동도장, 전영도장, ED도장이라고도 한다. 이러한 전착 도장에 사용되는 도료로는 에폭시 타입과 아크릴 타입이 주로 사용되고 있으며, 고방식성이 요구되는 도장사양에서는 주로 에폭시 타입이 적용되고, 내후성 및 외관 특성이 요구되는 도장사양에는 주로 아크릴 타입이 적용되고 있다.The electrodeposition coating is a coating method in which a conductor is immersed in an electrodeposition coating solution and a coating film is electrically deposited on the surface of the conductor through an electric current between the conductor and the counter electrode. Epoxy type and acrylic type are mainly used as paints used for this electrodeposition coating, and the epoxy type is mainly applied in the coating specifications that require high corrosion resistance, and the acrylic type is mainly applied in the coating specifications that require weather resistance and appearance characteristics. have.
일례로, 한국 등록특허 제713732호(특허문헌 1)에는 폴리옥시알킬렌 아민; 글리시독시 알킬 알콕시 실란; 및 글리시딜 화합물의 반응 생성물을 포함하는 첨가제인 반기공제를 포함하는, 음극 전기 피복 조성물이 개시되어 있다. 그러나, 특허문헌 1의 조성물은 엣지(edge) 피복율이 우수하나, 저장 안정성이 부족하고 필터성이 부족했다.For example, Korean Patent Registration No. 713732 (Patent Document 1) discloses polyoxyalkylene amine; glycidoxy alkyl alkoxy silanes; and a semi-porous agent that is an additive comprising a reaction product of a glycidyl compound. However, the composition of Patent Document 1 has excellent edge coverage, but lacks storage stability and lacks filterability.
따라서, 내후성이 우수하고 엣지(edge)의 방청성이 우수한 도막을 형성할 수 있고, 저장 안정성과 필터성이 우수한 전착도료 조성물에 대한 연구개발이 필요한 실정이다.Therefore, it is possible to form a coating film having excellent weather resistance and excellent rust prevention properties at the edge, and there is a need for research and development on an electrodeposition coating composition having excellent storage stability and filterability.
선행기술문헌: 한국 등록특허 제713732호(공개일: 2002.4.26.)Prior art document: Korean Patent Registration No. 713732 (published date: 2002.4.26.)
본 발명은 내후성이 우수하고 엣지(edge)의 방청성이 우수한 도막을 형성할 수 있고, 저장 안정성과 필터성이 우수한 전착도료 조성물을 제공하고자 한다.An object of the present invention is to provide an electrodeposition coating composition capable of forming a coating film having excellent weather resistance and excellent edge rust prevention, and excellent storage stability and filterability.
본 발명은 수지, 경화제 및 양이온 수분산 첨가제를 포함하고,The present invention comprises a resin, a curing agent and a cationic water dispersion additive,
상기 양이온 수분산 첨가제는 제1 에폭시 수지, 제2 에폭시 수지 및 아민기 함유 알콕시실란을 포함하는 첨가제 조성물로부터 제조되며,The cationic water dispersion additive is prepared from an additive composition comprising a first epoxy resin, a second epoxy resin, and an amine group-containing alkoxysilane,
상기 제1 에폭시 수지와 제2 에폭시 수지를 1:1 내지 5:1의 중량비로 포함하는, 전착도료 조성물을 제공한다.It provides an electrodeposition coating composition comprising the first epoxy resin and the second epoxy resin in a weight ratio of 1:1 to 5:1.
본 발명에 따른 전착도료 조성물은 저장 안정성과 필터성이 우수하고, 내후성이 우수하고 엣지(edge)의 방청성이 우수한 도막을 형성할 수 있다.The electrodeposition coating composition according to the present invention can form a coating film having excellent storage stability and filterability, excellent weather resistance, and excellent edge rust prevention.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에 있어서, '미반응 NCO의 함량(NCO%)'과 같은 작용기가는 당업계에 잘 알려진 방법에 의해 측정할 수 있으며, 예를 들어 적정법(titration) 등으로 측정한 값일 수 있다.In the present invention, the functional group such as 'content of unreacted NCO (NCO%)' may be measured by a method well known in the art, for example, may be a value measured by titration or the like.
본 발명에 따른 전착도료 조성물은 수지, 경화제 및 양이온 수분산 첨가제를 포함한다.The electrodeposition coating composition according to the present invention includes a resin, a curing agent, and a cationic water dispersion additive.
수지Suzy
수지는 전착도료 조성물의 주제로서, 제조되는 도막의 특성을 조절하는 역할을 한다.The resin is the subject of the electrodeposition coating composition, and serves to control the properties of the prepared coating film.
상기 수지는 통상적으로 전착도료의 주제로 적용 가능한 수지라면 특별히 제한되지 않으며, 예를 들어, 에폭시 수지를 포함할 수 있다. 상기 수지는 비스페놀형 에폭시 수지일 수 있으며, 상기 비스페놀형 에폭시 수지는 예를 들어, 비스페놀 A형 에폭시 수지일 수 있다.The resin is not particularly limited as long as it is a resin applicable as a general electrodeposition paint, and may include, for example, an epoxy resin. The resin may be a bisphenol-type epoxy resin, and the bisphenol-type epoxy resin may be, for example, a bisphenol A-type epoxy resin.
상기 수지는 5 내지 30 중량부의 경화제에 대하여 5 내지 30 중량부, 또는 10 내지 25 중량부의 함량으로 조성물에 포함될 수 있다. 수지의 함량이 상기 함량 미만인 경우, 조성물의 방청성이 부족하고, 상기 함량 초과인 경우, 제조된 도막의 내충격성이 부족한 문제가 발생할 수 있다.The resin may be included in the composition in an amount of 5 to 30 parts by weight, or 10 to 25 parts by weight based on 5 to 30 parts by weight of the curing agent. When the content of the resin is less than the above content, the rust prevention property of the composition is insufficient, and when the content exceeds the above content, the problem of insufficient impact resistance of the prepared coating film may occur.
경화제hardener
경화제는 수지와 가교 반응하여 조성물을 경화시키는 역할을 한다.The curing agent performs a crosslinking reaction with the resin to cure the composition.
상기 경화제는 이소시아네이트 수지일 수 있으며, 상기 이소시아네이트 수지는 통상적으로 도료에 사용되는 경화제라면 특별히 제한되지 않는다. 상기 이소시아네이트 수지는, 예를 들어, 방향족 이소시아네이트 및 지환족 이소시아네이트일 수 있으며, 방향족 이소시아네이트는 UV에 노출되면 방향족 고리가 이중결합의 분해가 발생하여 내후성이 저하될 수 있으므로, 바람직하게는 지환족 이소시아네이트일 수 있다.The curing agent may be an isocyanate resin, and the isocyanate resin is not particularly limited as long as it is a curing agent commonly used in paints. The isocyanate resin may be, for example, aromatic isocyanate and alicyclic isocyanate, and when the aromatic isocyanate is exposed to UV, decomposition of the double bond of the aromatic ring may occur and weather resistance may be reduced. Therefore, it is preferably an alicyclic isocyanate. can
상기 지환족 이소시아네이트는 예를 들어, 1-이소시아나토-3,3,5-트리메틸-5-이소시아나토메틸 시클로헥산(이소포론 디이소시아네이트, IPDI), 1,4-디이소시아나토-3,3,5-트리메틸시클로헥산, 1,3-디이소시아나토-2-메틸시클로헥산, 1,3-디이소시아나토-4-메틸시클로헥산, 1-이소시아나토-1-메틸-4(3)-이소시아나토메틸 시클로헥산, 2,4'- 또는 4,4'-디이소시아나토디시클로헥실메탄, 1,3- 또는 1,4-비스(이소시아나토메틸)시클로헥산, 4,4'-디이소시아나토3,3'-디메틸 디시클로헥실메탄, 4,4'-디이소시아나토-3,3',5,5'-테트라메틸 디시클로헥실메탄, 4,4'-디이소시아나토-1,1'-비(시클로헥실), 4,4'-디이소시아나토-3,3'-디메틸-1,1'-비(시클로헥실) 및 4,4'-디이소시아나토2,2',5,5'-테트라메틸-1,1'-비(시클로헥실)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The alicyclic isocyanate is, for example, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate, IPDI), 1,4-diisocyanato-3, 3,5-trimethylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,3-diisocyanato-4-methylcyclohexane, 1-isocyanato-1-methyl-4(3) -isocyanatomethyl cyclohexane, 2,4'- or 4,4'-diisocyanatodicyclohexylmethane, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, 4,4' -diisocyanato3,3'-dimethyl dicyclohexylmethane, 4,4'-diisocyanato-3,3',5,5'-tetramethyl dicyclohexylmethane, 4,4'-diisocyanato- 1,1'-bi(cyclohexyl), 4,4'-diisocyanato-3,3'-dimethyl-1,1'-bi(cyclohexyl) and 4,4'-diisocyanato2,2' , may include at least one selected from the group consisting of ,5,5'-tetramethyl-1,1'-bi (cyclohexyl).
상기 이소시아네이트 수지는 말단이 블록화제로 블록화된 것일 수 있다. 상기 블록화제는 말단 이소시아네이트기를 특정온도까지 안정화시키며, 특정온도 이상이 되면 이소시아네이트기로부터 해리되어 반응성을 조절하는 역할을 한다. 상기 블록화제는 예를 들어, 디에틸말로네이트, 디메틸피라졸, 사이클로헥사논 옥심, 메틸에틸 케톡심 등의 옥심계 화합물, ε-카프로락탐, γ-부티로락탐 등의 락탐계 화합물, 메탄올, 에탄올 등의 알코올계 화합물 등일 수 있다.The isocyanate resin may have an end blocked with a blocking agent. The blocking agent stabilizes the terminal isocyanate group to a specific temperature, and when it exceeds a specific temperature, it is dissociated from the isocyanate group to control the reactivity. The blocking agent is, for example, diethylmalonate, dimethylpyrazole, cyclohexanone oxime, oxime compounds such as methylethyl ketoxime, lactam compounds such as ε-caprolactam and γ-butyrolactam, methanol, It may be an alcohol-based compound such as ethanol.
상기 경화제는 5 내지 30 중량부의 수지에 대하여 5 내지 30 중량부, 또는 10 내지 20 중량부의 함량으로 조성물에 포함될 수 있다. 경화제의 함량이 상기 함량 미만인 경우, 조성물의 경화성이 열세한 문제가 발생하고, 상기 함량 초과인 경우, 제조된 도막의 방청성이 열세한 문제가 발생할 수 있다.The curing agent may be included in the composition in an amount of 5 to 30 parts by weight, or 10 to 20 parts by weight based on 5 to 30 parts by weight of the resin. When the content of the curing agent is less than the above content, a problem of poor curability of the composition may occur.
양이온 수분산 첨가제Cationic Water Dispersion Additives
양이온 수분산 첨가제는 도막 형성시 조성물의 엣지(edge)에서의 흐름성을 제어하여 엣지의 피복율 및 도막 오름성을 향상시키는 역할을 한다.The cationic water dispersion additive controls the flowability at the edge of the composition when forming the coating film, thereby improving the edge coverage and the coating film ascending property.
상기 양이온 수분산 첨가제는 제1 에폭시 수지, 제2 에폭시 수지 및 아민기 함유 알콕시실란을 포함하는 첨가제 조성물로부터 제조된다. 상기 첨가제 조성물은 제1 에폭시 수지와 제2 에폭시 수지를 1:1 내지 5:1의 중량비, 또는 2:1 내지 4:1의 중량비로 포함할 수 있다. 제1 에폭시 수지와 제2 에폭시 수지의 중량비가 1:1 미만, 즉 제2 에폭시 수지 보다 제1 에폭시 수지가 소량 포함될 경우, 조성물의 엣지(edge) 도막 오름성이 부족하고, 5:1 초과, 즉 제2 에폭시 수지를 기준으로 제1 에폭시 수지가 과량 포함될 경우, 수지 합성 안정성이 부족할 수 있다.The cationic water dispersion additive is prepared from an additive composition comprising a first epoxy resin, a second epoxy resin, and an amine group-containing alkoxysilane. The additive composition may include the first epoxy resin and the second epoxy resin in a weight ratio of 1:1 to 5:1, or 2:1 to 4:1 by weight. When the weight ratio of the first epoxy resin and the second epoxy resin is less than 1:1, that is, when a small amount of the first epoxy resin is included than the second epoxy resin, the edge coating film riseability of the composition is insufficient, and exceeds 5:1; That is, when the first epoxy resin is included in excess based on the second epoxy resin, the resin synthesis stability may be insufficient.
상기 에폭시 수지(제1 에폭시 수지 및 제2 에폭시 수지의 총량)와 아민기 함유 알콕시실란은 5:1 내지 1:1의 중량비, 또는 3:1 내지 1:1의 중량비로 포함될 수 있다. 아민기 함유 알콕시실란에 대한 에폭시 수지의 중량비가 상기 범위 미만, 즉 아민기 함유 알콕시실란 보다 에폭시 수지가 소량 포함될 경우, 과량의 미반응 아민으로 인하여 전착 도막의 재용해의 문제가 있고, 상기 범위 초과, 즉 에폭시 수지가 과량 포함될 경우, 제조된 양이온 수분산 첨가제의 분자량 증가로 인하여 첨가제의 저장 안정성이 부족해질 수 있다.The epoxy resin (total amount of the first epoxy resin and the second epoxy resin) and the amine group-containing alkoxysilane may be included in a weight ratio of 5:1 to 1:1, or 3:1 to 1:1 by weight. When the weight ratio of the epoxy resin to the amine group-containing alkoxysilane is less than the above range, that is, when a small amount of the epoxy resin is included than the amine group-containing alkoxysilane, there is a problem of re-dissolution of the electrodeposition coating film due to an excess of unreacted amine, exceeding the above range That is, when an excessive amount of the epoxy resin is included, the storage stability of the additive may be insufficient due to an increase in the molecular weight of the prepared cationic water dispersion additive.
<제1 에폭시 수지><First Epoxy Resin>
상기 제1 에폭시 수지는 제2 에폭시 수지보다 에폭시기 함량(Epoxy Group Content)이 낮고 25℃에서의 점도가 크다. 예를 들어, 상기 제1 에폭시 수지는 제2 에폭시 수지보다 에폭시기 함량이 300 내지 2,000 mmol/kg 또는 500 내지 1,100 mmol/kg 낮고, 25℃에서의 점도가 40 내지 75 mPa·s 또는 50 내지 70 mPa·s 클 수 있다.The first epoxy resin has a lower epoxy group content and a greater viscosity at 25° C. than the second epoxy resin. For example, the first epoxy resin has an epoxy group content of 300 to 2,000 mmol/kg or 500 to 1,100 mmol/kg lower than that of the second epoxy resin, and a viscosity at 25° C. of 40 to 75 mPa·s or 50 to 70 mPa ·s can be large.
상기 제1 에폭시 수지는 에폭시기 함량이 2,500 내지 3,500 mmol/kg, 또는 2,900 내지 3,300 mmol/kg일 수 있다. 제1 에폭시 수지의 에폭시기 함량이 상기 범위 미만인 경우, 도막의 광택이 저하되고, 상기 범위 초과인 경우, 조성물의 엣지 커버성이 부족한 문제가 발생할 수 있다.The first epoxy resin may have an epoxy group content of 2,500 to 3,500 mmol/kg, or 2,900 to 3,300 mmol/kg. When the epoxy group content of the first epoxy resin is less than the above range, the gloss of the coating film is lowered, and when it exceeds the above range, a problem of insufficient edge coverage of the composition may occur.
상기 제1 에폭시 수지는 25℃에서의 점도가 50 내지 80 mPa·s, 또는 55 내지 70 mPa·s일 수 있다. 제1 에폭시 수지의 25℃에서의 점도가 상기 범위 미만인 경우, 조성물의 엣지 커버성이 저하되고, 상기 범위 초과인 경우, 도막의 광택이 저하될 수 있다.The first epoxy resin may have a viscosity at 25° C. of 50 to 80 mPa·s, or 55 to 70 mPa·s. When the viscosity at 25° C. of the first epoxy resin is less than the above range, the edge coverage of the composition is reduced, and when it exceeds the above range, the gloss of the coating film may be reduced.
상기 제1 에폭시 수지는 에폭시 당량이 250 내지 400 g/eq, 또는 300 내지 350 g/eq일 수 있다. 제1 에폭시 수지의 에폭시 당량이 상기 범위 미만인 경우, 도막의 광택이 저하되고, 상기 범위 초과인 경우, 조성물의 엣지 커버성이 저하될 수 있다.The first epoxy resin may have an epoxy equivalent of 250 to 400 g/eq, or 300 to 350 g/eq. When the epoxy equivalent of the first epoxy resin is less than the above range, the gloss of the coating film is lowered, and when it exceeds the above range, edge coverage of the composition may be reduced.
<제2 에폭시 수지><Second Epoxy Resin>
상기 제2 에폭시 수지는 에폭시기 함량이 3,800 내지 4,500 mmol/kg, 또는 4,000 내지 4,300 mmol/kg일 수 있다. 제2 에폭시 수지의 에폭시기 함량이 상기 범위 미만인 경우, 첨가제의 합성 안정성에 문제가 발생하고, 상기 범위 초과인 경우, 조성물의 엣지 커버성이 저하될 수 있다.The second epoxy resin may have an epoxy group content of 3,800 to 4,500 mmol/kg, or 4,000 to 4,300 mmol/kg. When the epoxy group content of the second epoxy resin is less than the above range, a problem occurs in the synthetic stability of the additive, and when it exceeds the above range, edge coverage of the composition may be reduced.
상기 제2 에폭시 수지는 25℃에서의 점도가 3 내지 15 mPa·s, 또는 5 내지 10 mPa·s일 수 있다. 제2 에폭시 수지의 25℃에서의 점도가 상기 범위 미만인 경우, 제조된 도막의 광택이 저하되고, 상기 범위 초과인 경우, 전착 도료 조성물의 엣지 커버성이 저하될 수 있다.The second epoxy resin may have a viscosity at 25°C of 3 to 15 mPa·s, or 5 to 10 mPa·s. When the viscosity at 25° C. of the second epoxy resin is less than the above range, the gloss of the prepared coating film is reduced, and when it exceeds the above range, edge coverage of the electrodeposition coating composition may be reduced.
상기 제2 에폭시 수지는 에폭시 당량이 200 내지 280 g/eq, 또는 220 내지 260 g/eq일 수 있다. 제2 에폭시 수지의 에폭시 당량이 상기 범위 미만인 경우, 조성물의 반응속도가 상승하여 조성물의 작업성이 부족하고, 상기 범위 초과인 경우, 순도 저하 문제가 발생할 수 있다.The second epoxy resin may have an epoxy equivalent of 200 to 280 g/eq, or 220 to 260 g/eq. When the epoxy equivalent of the second epoxy resin is less than the above range, the reaction rate of the composition increases and the workability of the composition is insufficient, and when it exceeds the above range, a problem of lowering purity may occur.
<아민기 함유 알콕시실란><Alkoxysilane containing an amine group>
아민기 함유 알콕시실란은 에폭시 수지의 에폭시기와 반응하여 양이온 수지를 형성하고, 상기 수지에서 실란올을 형성하여 전착 도장 후 건조되면서 점도가 저하될 때 실록산 반응으로 조성물의 점도를 상승시켜 엣지 부위 흐름성을 제어하는 역할을 한다.The amine group-containing alkoxysilane reacts with the epoxy group of the epoxy resin to form a cationic resin, and forms silanol from the resin. plays a role in controlling
아민기 함유 알콕시실란은 하기 화학식 1로 표시될 수 있다.The amine group-containing alkoxysilane may be represented by the following formula (1).
Figure PCTKR2021007967-appb-C000001
Figure PCTKR2021007967-appb-C000001
상기 화학식 1에서,In Formula 1,
R1은 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고,R 1 is a substituted or unsubstituted C 1 to C 10 alkylene group,
R2는 치환 또는 비치환된 탄소수 1 내지 10의 알콕시기이다.R 2 is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.
예를 들어, R1은 치환 또는 비치환된 탄소수 1 내지 5의 알킬렌기이고, R2는 치환 또는 비치환된 탄소수 1 내지 5의 알콕시기일 수 있다.For example, R 1 may be a substituted or unsubstituted C 1 to C 5 alkylene group, and R 2 may be a substituted or unsubstituted C 1 to C 5 alkoxy group.
상기 알킬렌기 및 알콕시기는 선형 또는 분지형일 수 있다. 상기 알킬렌은 알킬기의 탄소원자로부터 1개의 수소 원자가 제거되어 유도되는, 분지쇄 또는 직쇄 또는 고리형인 2가 라디칼을 지칭한다. 예를 들어, 상기 알킬렌은 메틸렌(-CH2-), 1,1-에틸렌(-CH(CH3)-), 1,2-에틸렌(-CH2CH2-), 1,1-프로필렌(-CH(CH2CH3)-), 1,2-프로필렌(-CH2CH(CH3)-), 1,3-프로필렌(-CH2CH2CH2-), 1,4-부틸렌(-CH2CH2CH2CH2-), 2,4-부틸렌(-CH2(CH3)CH2CH2-) 등일 수 있지만, 이에 한정되지는 않는다.The alkylene group and the alkoxy group may be linear or branched. The alkylene refers to a branched or straight-chain or cyclic divalent radical derived by the removal of one hydrogen atom from a carbon atom of an alkyl group. For example, the alkylene is methylene (-CH2-), 1,1-ethylene (-CH(CH3)-), 1,2-ethylene (-CH2CH2-), 1,1-propylene (-CH(CH2CH3) )-), 1,2-propylene (-CH2CH(CH3)-), 1,3-propylene (-CH2CH2CH2-), 1,4-butylene (-CH2CH2CH2CH2-), 2,4-butylene (-CH2 (CH3)CH2CH2-), and the like, but is not limited thereto.
상기 양이온 수분산 첨가제는 실란올기 함유 실란 변성 에폭시 수지일 수 있다. 예를 들어, 상기 양이온 수분산 첨가제는 고형분 함량이 20 내지 30 중량% 또는 23 내지 27 중량%이고, 중화도가 10 내지 40 mmol/100g 또는 15 내지 35 mmol/100g이며, 25℃에서의 점도가 10 내지 100 cps 또는 30 내지 80 cps일 수 있다.The cationic water dispersion additive may be a silane-modified epoxy resin containing a silanol group. For example, the cationic water dispersion additive has a solid content of 20 to 30% by weight or 23 to 27% by weight, a degree of neutralization of 10 to 40 mmol/100g or 15 to 35 mmol/100g, and a viscosity at 25°C It may be 10 to 100 cps or 30 to 80 cps.
양이온 수분산 첨가제의 고형분 함량이 상기 범위 미만인 경우, 조성물의 엣지 커버성이 저하되고, 상기 범위 초과인 경우, 조성물의 점도가 상승하고 저장성이 저하되는 문제가 발생할 수 있다. 또한, 양이온 수분산 첨가제의 중화도가 상기 범위 미만인 경우, 조성물의 저장성이 부족하고, 상기 범위 초과인 경우, 조성물의 저장성이 부족한 문제가 발생할 수 있다. 또한, 양이온 수분산 첨가제의 점도가 상기 범위 미만인 경우, 조성물의 엣지 커버성이 저하되고, 상기 범위 초과인 경우, 조성물의 저장성이 부족한 문제가 발생할 수 있다.When the solid content of the cationic water dispersion additive is less than the above range, the edge coverage of the composition is lowered, and when it exceeds the above range, the viscosity of the composition is increased and storage properties are lowered. In addition, when the neutralization degree of the cationic water dispersion additive is less than the above range, the storability of the composition is insufficient, and when it exceeds the above range, the problem of insufficient storability of the composition may occur. In addition, when the viscosity of the cationic water dispersion additive is less than the above range, edge coverage of the composition is lowered, and when it exceeds the above range, a problem of insufficient storability of the composition may occur.
상기 양이온 수분산 첨가제는 5 내지 30 중량부의 수지에 대하여 3 내지 15 중량부, 또는 5 내지 10 중량부의 함량으로 조성물에 포함될 수 있다. 양이온 수분산 첨가제의 함량이 상기 함량 미만인 경우, 조성물의 엣지 커버성이 저하되고, 상기 함량 초과인 경우, 제조된 도막의 외관 특성 및 광택이 저하될 수 있다.The cationic water dispersion additive may be included in the composition in an amount of 3 to 15 parts by weight, or 5 to 10 parts by weight based on 5 to 30 parts by weight of the resin. When the content of the cationic water dispersion additive is less than the above content, edge coverage of the composition is lowered, and when the content exceeds the above content, the appearance characteristics and gloss of the prepared coating film may be deteriorated.
첨가제additive
상기 전착도료 조성물은 아민 화합물, 용제, 중화제, 소포제, 유분 제거제 및 유동성 조절제로 이루어진 군으로부터 선택된 1종 이상의 첨가제를 추가로 포함할 수 있다.The electrodeposition paint composition may further include at least one additive selected from the group consisting of an amine compound, a solvent, a neutralizer, an antifoaming agent, an oil removal agent, and a flow control agent.
상기 첨가제들은 통상적으로 전착도료 조성물에 사용할 수 있는 것이라면 특별히 한정하지 않는다.The additives are not particularly limited as long as they can be used in the general electrodeposition coating composition.
상술한 바와 같은 본 발명에 따른 전착도료 조성물은 저장 안정성과 필터성이 우수하고, 내후성이 우수하고 엣지(edge)의 방청성이 우수한 도막을 형성할 수 있다.The electrodeposition coating composition according to the present invention as described above can form a coating film having excellent storage stability and filterability, excellent weather resistance, and excellent edge rust prevention.
이하, 실시예를 통해 본 발명을 보다 구체적으로 설명한다. 그러나 이들 실시예는 본 발명의 이해를 돕기 위한 것일 뿐 어떠한 의미로든 본 발명의 범위가 이들 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. However, these examples are only for helping the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.
합성예 1. 경화제-1(블록화된 지환족 이소시아네이트)Synthesis Example 1. Curing agent-1 (blocked alicyclic isocyanate)
온도계 및 냉각기가 구비된 4구 플라스크에 40중량부의 메틸이소부틸케톤, 400중량부의 이소포론 디이소시아네이트 및 0.27중량부의 디부틸주석 라우레이트를 넣고, 질소 대기 하에서 30℃로 승온했다. 이후 360중량부의 2-(2-부톡시에톡시)에탄올을 넣으면서 60℃를 넘지 않도록 온도를 조절한 후 60℃에서 90분간 방치했다. 이후, 120중량부의 메틸에틸케톡심을 첨가한 후 80℃로 승온하고 3시간 동안 유지하여 미반응 NCO%가 0.02중량% 이하가 될 때까지 반응시킨 후, 메틸이소부틸케톤을 첨가하여 고형분 함량을 80중량%로 조절하여 블록화된 지환족 이소시아네이트를 제조하였다.In a four-neck flask equipped with a thermometer and a cooler, 40 parts by weight of methyl isobutyl ketone, 400 parts by weight of isophorone diisocyanate and 0.27 parts by weight of dibutyltin laurate were placed, and the temperature was raised to 30° C. under nitrogen atmosphere. Then, while adding 360 parts by weight of 2-(2-butoxyethoxy)ethanol, the temperature was adjusted not to exceed 60°C, and then left at 60°C for 90 minutes. Then, after adding 120 parts by weight of methyl ethyl ketoxime, the temperature was raised to 80° C. and maintained for 3 hours to react until unreacted NCO % became 0.02 wt % or less, and then methyl isobutyl ketone was added to increase the solid content to 80 A blocked alicyclic isocyanate was prepared by adjusting the weight%.
합성예 2. 경화제-2(블록화된 방향족 이소시아네이트)Synthesis Example 2. Curing agent-2 (blocked aromatic isocyanate)
온도계 및 냉각기가 구비된 4구 플라스크에 1,800중량부의 2-(2-부톡시에톡시)에탄올, 106.6중량부의 메틸이소부틸케톤 및 0.2중량부의 디부틸주석 라우레이트를 넣고, 질소 대기 하에서 30℃로 승온했다. 이후 2,028.6중량부의 방향족 이소시아네이트(제조사: DOW사, 제품명: PAPI PB 7519)를 첨가하면서 60℃를 넘지 않도록 온도를 조절하고, 60℃에서 90분간 방치했다. 이후, 0.1중량부의 디부틸주석 라우레이트 및 200중량부의 트리메틸올 프로판을 첨가하고, 80℃로 승온하고 3시간 동안 유지하여 미반응 NCO%가 0.02중량% 이하가 될 때까지 반응시킨 후, 메틸이소부틸케톤을 첨가하여 고형분 함량을 80중량%로 조정하여 블록화된 방향족 이소시아네이트를 제조하였다.1,800 parts by weight of 2-(2-butoxyethoxy)ethanol, 106.6 parts by weight of methylisobutylketone, and 0.2 parts by weight of dibutyltin laurate were placed in a four-neck flask equipped with a thermometer and a cooler, and heated to 30° C. under nitrogen atmosphere. warmed up Then, while adding 2,028.6 parts by weight of aromatic isocyanate (manufacturer: DOW, product name: PAPI PB 7519), the temperature was adjusted so as not to exceed 60° C., and left at 60° C. for 90 minutes. Thereafter, 0.1 parts by weight of dibutyltin laurate and 200 parts by weight of trimethylol propane are added, the temperature is raised to 80° C. and maintained for 3 hours to react until unreacted NCO% becomes 0.02% by weight or less, and then methyliso A blocked aromatic isocyanate was prepared by adding butyl ketone to adjust the solid content to 80% by weight.
합성예 3. 양이온 수분산 첨가제-1의 제조Synthesis Example 3. Preparation of Cationic Water Dispersion Additive-1
반응 용기에 112중량부의 제1 에폭시 수지(제조사: 다우 케미컬사, 제품명: DER 732, 에폭시 함량: 3,130mmol/kg, 25℃에서의 점도: 65±5mPa·s, 에폭시 당량: 320g/eq), 36중량부의 제2 에폭시 수지(제조사: Hexion, 제품명: Cardura E-10P, 에폭시 함량: 4,170mmol/kg, 25℃에서의 점도: 7mPa·s, 에폭시 당량: 240g/eq), 110중량부의 아민기 함유 알콕시 실란(제조사: Momentive, 제품명: Silquest A-1100, 감마-아미노프로필트리에톡시 실란(gamma-aminopropyltriethoxy silane)) 및 120중량부의 이소프로필알코올을 넣었다. 이후, 무수 질소 대기 하에서 110℃로 가열하여 가드너-홀트(Gardner-Holdt) 점도가 T~W가 될 때까지 반응시켰다. 이후 600중량부의 탈이온수 및 22중량부의 락트산(농도 50부피%의 수용액)을 추가하고 수성 매질에 분산시켜, 고형분 함량이 25중량%이고, 중화도가 25mmol/100g이며, 25℃에서의 점도는 45cps인 양이온 수분산 첨가제-1을 제조하였다.112 parts by weight of a first epoxy resin in a reaction vessel (manufacturer: Dow Chemical, product name: DER 732, epoxy content: 3,130 mmol/kg, viscosity at 25°C: 65±5 mPa·s, epoxy equivalent: 320 g/eq), 36 parts by weight of a second epoxy resin (manufacturer: Hexion, product name: Cardura E-10P, epoxy content: 4,170 mmol/kg, viscosity at 25°C: 7 mPa s, epoxy equivalent: 240 g/eq), 110 parts by weight of an amine group Containing alkoxysilane (manufacturer: Momentive, product name: Silquest A-1100, gamma-aminopropyltriethoxy silane) and 120 parts by weight of isopropyl alcohol were added. Thereafter, it was heated to 110° C. under anhydrous nitrogen atmosphere and reacted until the Gardner-Holdt viscosity became T~W. Then, 600 parts by weight of deionized water and 22 parts by weight of lactic acid (aqueous solution having a concentration of 50% by volume) are added and dispersed in an aqueous medium, the solid content is 25% by weight, the degree of neutralization is 25mmol/100g, and the viscosity at 25℃ is A cationic water dispersion additive-1 of 45 cps was prepared.
합성예 4 내지 8. 양이온 수분산 첨가제-2 내지 -6의 제조Synthesis Examples 4 to 8. Preparation of Cationic Water Dispersion Additives-2 to -6
각 성분들의 함량을 하기 표 1과 같이 조절한 것을 제외하고는, 합성예 3과 동일한 방법으로 양이온 수분산 첨가제를 제조하였다.A cationic water dispersion additive was prepared in the same manner as in Synthesis Example 3, except that the content of each component was adjusted as shown in Table 1 below.
합성예 9. 양이온 수분산 첨가제-7의 제조Synthesis Example 9. Preparation of Cationic Water Dispersion Additive-7
반응용기에 24 중량부의 제3 에폭시 수지(제조사: 국도화학, 제품명: YD-011, 에폭시 당량: 450~490g/eq)를 넣고 52 중량부의 부틸 셀로솔브(BUTYL CELLOSOLVE)를 넣고 가열하여 녹였다. 이후 276중량부의 폴리옥시프로필렌 디아민(제조사: Huntsman, 제품명: Jeffamine D2000, 수평균분자량: 2,000mol/g, 아민 당량: 996.5g/eq), 29중량부의 제2 에폭시 수지(제조사: Hexion, 제품명: Cardura E-10P, 에폭시 함량: 4,170mmol/kg, 25℃에서의 점도: 7mPa·s, 에폭시 당량: 240g/eq)를 넣고 반응시켰다. 에폭시 당량이 1,000g/eq 이상이 되면 24중량부의 제4 에폭시 수지(제조사: 국도화학, 제품명: YD-128, 에폭시 당량: 180~190g/eq)를 추가하여 에폭시를 반응시키고 19중량부의 락트산(농도 50부피%의 수용액)을 추가하여 중화하고 576중량부의 이온수를 서서히 적가하여 수분산하여, 고형분 함량이 35중량%이고, 중화도(MEQACID)가 25mmol/100g인 양이온 수분산 첨가제-7을 제조하였다.24 parts by weight of a third epoxy resin (manufacturer: Kukdo Chemical, product name: YD-011, epoxy equivalent: 450 to 490 g/eq) was put into a reaction vessel, and 52 parts by weight of butyl cellosolve (BUTYL CELLOSOLVE) was put into it and melted by heating. Then 276 parts by weight of polyoxypropylene diamine (manufacturer: Huntsman, product name: Jeffamine D2000, number average molecular weight: 2,000 mol/g, amine equivalent: 996.5 g/eq), 29 parts by weight of a second epoxy resin (manufacturer: Hexion, product name: Cardura E-10P, epoxy content: 4,170 mmol/kg, viscosity at 25°C: 7 mPa·s, epoxy equivalent: 240 g/eq) was added and reacted. When the epoxy equivalent is 1,000 g/eq or more, 24 parts by weight of the fourth epoxy resin (manufacturer: Kukdo Chemical, product name: YD-128, epoxy equivalent: 180 to 190 g/eq) is added to react the epoxy, and 19 parts by weight of lactic acid ( Aqueous solution having a concentration of 50% by volume) was added to neutralize, and 576 parts by weight of ionized water was gradually added dropwise to disperse in water to prepare a cationic water dispersion additive-7 having a solid content of 35% by weight and a degree of neutralization (MEQACID) of 25mmol/100g did
Figure PCTKR2021007967-appb-T000001
Figure PCTKR2021007967-appb-T000001
합성예 10. 실란 변성 에폭시 아민 화합물의 제조Synthesis Example 10. Preparation of silane-modified epoxy amine compound
반응 용기에 1,000중량부의 폴리옥시프로필렌 디아민(제조사: Huntsman, 제품명: Jeffamine D2000, 수평균분자량: 2,000mol/g, 아민 당량: 996.5g/eq), 100중량부의 제2 에폭시 수지(제조사: Hexion, 제품명: Cardura E-10P, 에폭시 함량: 4,170mmol/kg, 25℃에서의 점도: 7mPa·s, 에폭시 당량: 240g/eq), 141.6중량부의 글리시독시 프로필트리메톡시실란(제조사: Momentive, 제품명: Silquest A-187) 및 130중량부의 2-에틸헥산올을 넣었다. 이후 무수 질소 대기 하에서 110℃로 가열하여 가드너-홀트(Gardner-Holdt) 점도가 S-T가 될 때까지 반응시켰다. 이후 4049.6중량부의 탈이온수 및 66.3중량부의 락트산(농도 50부피%의 수용액)을 추가하여 수성 매질에 분산시켜, 고형분 함량이 22중량%인 실란 변성 에폭시 아민 화합물을 제조하였다.In a reaction vessel, 1,000 parts by weight of polyoxypropylene diamine (manufacturer: Huntsman, product name: Jeffamine D2000, number average molecular weight: 2,000 mol/g, amine equivalent: 996.5 g/eq), 100 parts by weight of a second epoxy resin (manufacturer: Hexion, Product name: Cardura E-10P, epoxy content: 4,170 mmol/kg, viscosity at 25°C: 7 mPa s, epoxy equivalent: 240 g/eq), 141.6 parts by weight of glycidoxy propyltrimethoxysilane (manufacturer: Momentive, product name : Silquest A-187) and 130 parts by weight of 2-ethylhexanol were added. Thereafter, it was heated to 110° C. under anhydrous nitrogen atmosphere and reacted until the Gardner-Holdt viscosity became S-T. Thereafter, 4049.6 parts by weight of deionized water and 66.3 parts by weight of lactic acid (aqueous solution having a concentration of 50% by volume) were added and dispersed in an aqueous medium to prepare a silane-modified epoxy amine compound having a solid content of 22% by weight.
실시예 1 내지 5, 및 비교예 1 내지 6. 전착도료 조성물의 제조Examples 1 to 5, and Comparative Examples 1 to 6. Preparation of electrodeposition coating composition
교반기, 냉각기, 가열기 및 온도계를 장착한 분리형 반응기에 표 2 및 3에 기재된 파트 1 내지 4의 원료를 넣고 125℃로 승온하고, 파트 5를 넣고 온도를 145℃로 유지하면서 에폭시 당량을 측정하여 1,110g/eq에 도달할 때까지 유지했다. 이후 온도를 110℃로 조절하고 파트 6 및 7을 순서대로 넣고, 125℃에서 90분간 반응시켰다. 이후 온도를 100℃로 조절하고 파트 8 내지 10을 넣고 70℃로 냉각했다. 이후 파트 11을 사입한 후 파트 12를 넣고 100℃로 1시간 동안 반응시켰다. 이후 파트 13의 함량만큼의 용제를 진공 회수하여 수지 반응물을 수득하였다. 이후 파트 14 내지 16이 담긴 분산조에 상기 수지 반응물을 넣으면서 1차 수분산을 실시하고, 1시간 교반한 후 파트 17을 넣어 점도를 조절하였다. 이후 온도를 45℃ 이하로 조절하고 파트 18를 넣어 전착도료 조성물을 제조하였다.In a separate reactor equipped with a stirrer, a cooler, a heater and a thermometer, the raw materials of parts 1 to 4 listed in Tables 2 and 3 were put, the temperature was raised to 125 ° C, and part 5 was put and the epoxy equivalent was measured while maintaining the temperature at 145 ° C. 1,110 It was held until g/eq was reached. Thereafter, the temperature was adjusted to 110° C., and parts 6 and 7 were put in order, and reacted at 125° C. for 90 minutes. The temperature was then adjusted to 100°C and parts 8 to 10 were added and cooled to 70°C. After adding part 11, part 12 was added and reacted at 100° C. for 1 hour. Thereafter, the solvent corresponding to the content of Part 13 was vacuum recovered to obtain a resin reactant. After that, the first aqueous dispersion was carried out while putting the resin reactant into the dispersion tank containing parts 14 to 16, and after stirring for 1 hour, part 17 was added to adjust the viscosity. Thereafter, the temperature was adjusted to 45° C. or less, and part 18 was added to prepare an electrodeposition coating composition.
Figure PCTKR2021007967-appb-T000002
Figure PCTKR2021007967-appb-T000002
Figure PCTKR2021007967-appb-T000003
Figure PCTKR2021007967-appb-T000003
비교예 및 실시예에서 사용한 각 성분들의 제품명은 하기 표 4에 나타냈다.The product names of each component used in Comparative Examples and Examples are shown in Table 4 below.
Figure PCTKR2021007967-appb-T000004
Figure PCTKR2021007967-appb-T000004
시험예: 물성 평가Test Example: Physical property evaluation
인산아연으로 전처리된 시편(크로메이트 처리된 알루미늄 시편, 가로X세로X두께 = 150mmX70mmX0.8mm)에 상기 실시예 및 비교예에서 제조한 전착도료 조성물을 정류기를 이용하여 240V에서 3분 동안 전착도장하여 도막을 형성하였다. 제조된 도막의 물성을 하기와 같은 방법으로 측정하여 결과를 표 5 및 6에 나타냈다.The electrodeposition coating composition prepared in Examples and Comparative Examples was electrodeposited on a specimen pretreated with zinc phosphate (chromate-treated aluminum specimen, width X length X thickness = 150mmX70mmX0.8mm) using a rectifier at 240V for 3 minutes to make a coating film. was formed. The physical properties of the prepared coating film were measured in the following manner, and the results are shown in Tables 5 and 6.
(1) 광택(1) gloss
도막의 60° 광택을 수직 및 수평에서 측정하였다. 이때, 광택값은 높을수록 고광택인 것으로 판단했다.The 60° gloss of the coating was measured vertically and horizontally. At this time, it was determined that the higher the gloss value, the higher the gloss.
(2) 경화성(2) hardenability
도막에 메틸 이소부틸 케톤(Methyl isobutyl ketone, MIBK) 용제를 충분히 적신 면을 이용하여 도막이 흠집이 발생할 때까지의 이동 횟수를 170℃ 및 175℃에서 측정하였다.The number of transfers until the coating film was scratched was measured at 170°C and 175°C using a side sufficiently wetted with methyl isobutyl ketone (MIBK) solvent in the coating film.
(3) 내충격성(3) Impact resistance
추의 낙하 높이를 20cm부터 50cm까지 변화시키면서 1kg의 추를 최종 도막에 떨어뜨렸을 때, 도막의 외관을 관찰하여 도막에 균열 및 박리 현상이 발생하지 않는 최대 낙하 높이를 측정하여 내충격성을 평가하였다.When a 1 kg weight was dropped on the final coating film while changing the drop height of the weight from 20 cm to 50 cm, the appearance of the coating film was observed and the maximum drop height at which cracks and peeling did not occur in the coating film was measured to evaluate the impact resistance.
(4) 경도(4) hardness
도막을 대상으로 MS652-05 및 ISO15184에 따라 미쯔비시 연필을 이용한 경도를 측정하였다.The hardness of the coating film was measured using a Mitsubishi pencil according to MS652-05 and ISO15184.
구체적으로, 3B, 2B, B, HB, F, H, 2H 및 3H 각각의 연필을 이용하여 최종 도막에 손상을 주지 않는 최대 경도를 측정하였다(3B, 2B, B, HB, F, H, 2H, 3H: 열세⇔우수).Specifically, the maximum hardness that does not damage the final coating film was measured using each of 3B, 2B, B, HB, F, H, 2H, and 3H pencils (3B, 2B, B, HB, F, H, 2H). , 3H: inferior ⇔ excellent).
(5) 내후성-1: Q-UVA(5) Weather resistance-1: Q-UVA
ISO 11507에 따라 Q-UVA Type 21일을 기준으로 광택 변화를 확인하였다. 내후성 테스트 전 초기 도막의 60° 광택을 기준으로 광택 변화율이 10% 미만인 경우 우수, 10% 이상 30% 미만인 경우 보통, 30% 이상인 경우 불량으로 평가하였다.Gloss change was confirmed based on Q-UVA Type 21 days according to ISO 11507. Based on the 60° gloss of the initial coating film before the weather resistance test, if the gloss change rate was less than 10%, it was evaluated as excellent, if it was 10% or more and less than 30%, it was evaluated as normal, and if it was 30% or more, it was evaluated as poor.
(6) 내후성-2: 옥외 폭로(6) Weather resistance-2: outdoor exposure
시편을 제조하고 옥외에 21일 동안 폭로하고 테스트 전 초기 도막의 60° 광택을 기준으로 광택 변화를 확인하였다. 광택 변화율이 10% 미만인 경우 우수, 10% 이상 30% 미만인 경우 보통, 30% 이상인 경우 불량으로 평가하였다.Specimens were prepared and exposed outdoors for 21 days, and gloss changes were confirmed based on the 60° gloss of the initial coating film before testing. When the gloss change rate was less than 10%, it was evaluated as excellent, when it was 10% or more and less than 30%, it was evaluated as normal, and when it was 30% or more, it was evaluated as poor.
(7) 도막 오름성-1: 블레이드(7) Film ascending property-1: Blade
전착도료 조성물을 블레이드(칼날)의 엣지 부위에 상술한 바와 같이 도장하고 전자 현미경으로 블레이드(칼날)의 엣지 부위의 도막 두께를 측정하였다.The electrodeposition coating composition was coated on the edge portion of the blade (knife) as described above, and the coating film thickness of the edge portion of the blade (knife) was measured with an electron microscope.
(8) 도막 오름성-2: 펀치(8) Film ascending property-2: Punch
펀칭 시편(제조사: 에버 스틸)에 전착도료 조성물을 240V로 3분 동안 도장하고 전자 현미경으로 펀칭 시편의 엣지 부위의 도막 두께를 측정하였다.The electrodeposition coating composition was applied to the punched specimen (manufacturer: Ever Steel) at 240V for 3 minutes, and the coating film thickness of the edge portion of the punched specimen was measured with an electron microscope.
(9) 필터성(9) filterability
실시예 및 비교예에서 제조한 전착도료 조성물을 1OOmesh의 나일론 체(sieve)를 이용하여 통과되는 정도를 파악하여, ○(우수), △(보통), X(불량)로 필터성을 평가하였다.The degree of passing of the electrodeposition paint compositions prepared in Examples and Comparative Examples was evaluated using a 100 mesh nylon sieve, and filter properties were evaluated with ○ (excellent), △ (normal), and X (poor).
또한, 상기 조성물을 40℃에서 7일 동안 저장한 후 상술한 바와 동일한 방법으로 필터성을 평가하였다.In addition, the filterability was evaluated in the same manner as described above after the composition was stored at 40° C. for 7 days.
(10) 체 잔여물(sieve residue)(10) sieve residue
실시예 및 비교예에서 제조한 전착도료 조성물 500g을 1OOmesh 나일론 체(sieve)로 거른 후 체에 남은 잔량을 측정하였다.500 g of the electrodeposition coating composition prepared in Examples and Comparative Examples was filtered through a 100 mesh nylon sieve, and the remaining amount of the composition was measured.
또한, 상기 조성물을 40℃에서 7일 동안 저장한 후 체 잔여물을 상술한 바와 동일한 방법으로 측정하였다.In addition, after the composition was stored at 40° C. for 7 days, the sieve residue was measured in the same manner as described above.
Figure PCTKR2021007967-appb-T000005
Figure PCTKR2021007967-appb-T000005
Figure PCTKR2021007967-appb-T000006
Figure PCTKR2021007967-appb-T000006
표 5에서 보는 바와 같이, 실시예 1 내지 5의 조성물은 40℃에서 7일 동안 저장 후에도 필터성이 우수하고 체 잔여물의 크기가 작고, 도막 오름성이 우수하고, 이로부터 제조된 도막의 물성도 우수했다.As shown in Table 5, the compositions of Examples 1 to 5 have excellent filterability even after storage at 40° C. for 7 days, a small size of sieve residue, excellent coating film ascending properties, and physical properties of a coating film prepared therefrom It was excellent.
반면, 양이온 수분산 첨가제를 포함하지 않는 비교예 1 및 아민기 함유 알콕시 실란을 미포함하는 합성예 9의 양이온 수분산 첨가제를 사용한 비교예 6은 경화성이 부족하고, 도막 오름성이 부족하며, 내후성이 부족했다. 또한, 제2 에폭시 수지를 미포함하는 합성예 6의 양이온 수분산 첨가제를 사용한 비교예 2 및 제1 에폭시 수지를 미포함하는 합성예 7의 양이온 수분산 첨가제를 사용한 비교예 3은 40℃에서 저장한 후 필터성이 부족하고, 내후성이 부족했다. 나아가, 제1 에폭시 수지와 제2 에폭시 수지의 중량비가 0.32:1인 합성예 8의 양이온 수분산 첨가제를 사용한 비교예 4는 내후성이 부족했다.On the other hand, Comparative Example 1 not including the cationic water dispersion additive and Comparative Example 6 using the cationic water dispersion additive of Synthesis Example 9 not including the amine group-containing alkoxysilane lacked curability, lacked film rise, and had poor weather resistance. lacked In addition, Comparative Example 2 using the cationic water dispersion additive of Synthesis Example 6 without the second epoxy resin and Comparative Example 3 using the cationic water dispersion additive of Synthesis Example 7 without the first epoxy resin were stored at 40° C. It lacked filterability and lacked weather resistance. Furthermore, Comparative Example 4 using the cationic water dispersion additive of Synthesis Example 8 in which the weight ratio of the first epoxy resin and the second epoxy resin was 0.32:1 was insufficient in weather resistance.
한편, 양이온 수분산 첨가제 대신 실란 변성 에폭시 아민 화합물을 사용한 비교예 5는 내후성이 부족했다.On the other hand, Comparative Example 5 using a silane-modified epoxy amine compound instead of the cationic water dispersion additive was poor in weather resistance.
본 발명에 따른 전착도료 조성물은 저장 안정성과 필터성이 우수하고, 내후성이 우수하고 엣지(edge)의 방청성이 우수한 도막을 형성할 수 있다.The electrodeposition coating composition according to the present invention can form a coating film having excellent storage stability and filterability, excellent weather resistance, and excellent edge rust prevention.

Claims (6)

  1. 수지, 경화제 및 양이온 수분산 첨가제를 포함하고,a resin, a curing agent, and a cationic water dispersion additive;
    상기 양이온 수분산 첨가제는 제1 에폭시 수지, 제2 에폭시 수지 및 아민기 함유 알콕시실란을 포함하는 첨가제 조성물로부터 제조되며,The cationic water dispersion additive is prepared from an additive composition comprising a first epoxy resin, a second epoxy resin, and an amine group-containing alkoxysilane,
    상기 제1 에폭시 수지와 제2 에폭시 수지를 1:1 내지 5:1의 중량비로 포함하는, 전착도료 조성물.An electrodeposition coating composition comprising the first epoxy resin and the second epoxy resin in a weight ratio of 1:1 to 5:1.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 제1 에폭시 수지는 제2 에폭시 수지보다 에폭시기 함량이 낮고 25℃에서의 점도가 큰, 전착도료 조성물.The first epoxy resin has a lower epoxy group content than the second epoxy resin and has a greater viscosity at 25° C., an electrodeposition coating composition.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 제1 에폭시 수지는 에폭시기 함량이 2,500 내지 3,500 mmol/kg이고, 25℃에서의 점도가 50 내지 80 mPa·s이며, 에폭시 당량이 250 내지 400 g/eq인, 전착도료 조성물.The first epoxy resin has an epoxy group content of 2,500 to 3,500 mmol/kg, a viscosity at 25° C. of 50 to 80 mPa·s, and an epoxy equivalent of 250 to 400 g/eq, an electrodeposition coating composition.
  4. 청구항 1에 있어서,The method according to claim 1,
    상기 제2 에폭시 수지는 에폭시기 함량이 3,800 내지 4,500 mmol/kg이고, 25℃에서의 점도가 3 내지 15 mPa·s이며, 에폭시 당량이 200 내지 280 g/eq인, 전착도료 조성물.The second epoxy resin has an epoxy group content of 3,800 to 4,500 mmol/kg, a viscosity at 25° C. of 3 to 15 mPa·s, and an epoxy equivalent of 200 to 280 g/eq, an electrodeposition coating composition.
  5. 청구항 1에 있어서,The method according to claim 1,
    상기 아민기 함유 알콕시실란은 하기 화학식 1로 표시되는, 전착도료 조성물:The amine group-containing alkoxysilane is represented by the following formula (1), electrodeposition coating composition:
    [화학식 1][Formula 1]
    Figure PCTKR2021007967-appb-I000001
    Figure PCTKR2021007967-appb-I000001
    상기 화학식 1에서,In Formula 1,
    R1은 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고,R 1 is a substituted or unsubstituted C 1 to C 10 alkylene group,
    R2는 치환 또는 비치환된 탄소수 1 내지 10의 알콕시기이다.R 2 is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.
  6. 청구항 1에 있어서,The method according to claim 1,
    상기 경화제는 지환족 이소시아네이트인, 전착도료 조성물.The curing agent is an alicyclic isocyanate, the electrodeposition coating composition.
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