WO2019182233A1 - Electrodeposition resin composition and electrodeposition paint comprising same - Google Patents

Electrodeposition resin composition and electrodeposition paint comprising same Download PDF

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Publication number
WO2019182233A1
WO2019182233A1 PCT/KR2018/016786 KR2018016786W WO2019182233A1 WO 2019182233 A1 WO2019182233 A1 WO 2019182233A1 KR 2018016786 W KR2018016786 W KR 2018016786W WO 2019182233 A1 WO2019182233 A1 WO 2019182233A1
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Prior art keywords
weight
electrodeposition
parts
compound
epoxy resin
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PCT/KR2018/016786
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French (fr)
Korean (ko)
Inventor
이규상
최재일
김성민
도경해
서외구
Original Assignee
주식회사 케이씨씨
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Publication of WO2019182233A1 publication Critical patent/WO2019182233A1/en

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Classifications

    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4453—Polyepoxides characterised by the nature of the curing agent
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used

Definitions

  • the present invention relates to an electrodeposition resin composition and an electrodeposition paint containing the same.
  • Electrodeposition coating is widely used as a primer coating because it is excellent in paintability and less environmental pollution compared with air spray coating and electrostatic spray coating.
  • the cationic electrodeposition coating can be applied continuously, it has been widely used as a primary coating method for coating objects such as automobile bodies, which are large and require high corrosion resistance.
  • Cationic electrodeposition coating compositions are generally obtained by dispersing a binder component comprising a cationic resin and a curing agent in an aqueous medium containing neutralizing agents such as organic acids. Electrodeposition coating is performed by immersing a coating object as a negative electrode in a cationic electrodeposition coating composition, and applying a voltage. When a voltage is applied between the electrodes in the coating process, an electrodeposition coating film is deposited on the surface of the cathode (coating object) by an electrochemical reaction. Since the electrodeposition coating film formed in this way contains a hardening
  • the cationic resin used for electrodeposition coating there is an advantage in that the physical properties of the coating film can be improved by including a sulfide compound and an epoxy compound, but problems of inferior paintability may occur.
  • the present invention provides an electrodeposition resin composition having improved internal paintability.
  • this invention provides the electrodeposition paint containing the said electrodeposition resin composition and a pigment paste composition.
  • the present invention includes an epoxy resin, a curing agent and an amine compound, wherein the curing agent comprises a first curing agent comprising an isocyanate compound blocked with a monohydric alcohol and a dihydric alcohol, and an isocyanate compound blocked with a monohydric alcohol and a trihydric alcohol. It provides the electrodeposition resin composition containing the 2nd hardening
  • this invention provides the electrodeposition paint containing the said electrodeposition resin composition and a pigment paste composition.
  • the electrodeposition resin composition of the present invention includes dihydric alcohol or trihydric alcohol and two kinds of isocyanate curing agents blocked by monohydric alcohol, thereby improving the internal paintability of the electrodeposition paint formed by using the same, and improving workability.
  • the electrodeposition resin composition of the present invention includes a first epoxy resin and a second epoxy resin in the epoxy resin, it is possible to form a coating film having excellent smoothness and flexibility of the coating film formed by using the same, but also improved rust resistance and adhesion.
  • the present invention provides an electrodeposition resin composition.
  • the electrodeposition resin composition of this invention contains an epoxy resin, a hardening
  • the epoxy resin contained in the electrodeposition resin composition of this invention can contain a 1st epoxy resin and a 2nd epoxy resin as a base resin component which hardens and forms a coating film.
  • the first epoxy resin is a bisphenol-type epoxy resin that imparts excellent physical properties such as rust resistance, adhesion, and heat resistance to the finally formed coating film.
  • the first epoxy resin has an epoxy equivalent weight (EEW) of 150 g / eq. To 2,000 g / eq., An epoxy resin having two or more 1,2-epoxy groups, and may be used without limitation as long as it is commonly used in electrodeposition resin compositions.
  • the first epoxy resin may include a bisphenol type epoxy resin, and for example, may be a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or the like.
  • the second epoxy resin not only improves the smoothness and flexibility of the coating film prepared using the electrodeposition resin composition of the present invention to improve the appearance, but also improves the electrophoresis of the coating film, thereby improving the workability of the coating in the electrodeposition resin.
  • the second epoxy resin may include at least one selected from a unit derived from a compound having a primary amine group at a terminal, a unit derived from a sulfide compound, and a unit derived from an epoxy compound.
  • the second epoxy resin may include at least one selected from a unit derived from a compound having a primary amine group and a unit derived from a sulfide compound, and a unit derived from an epoxy compound.
  • the second epoxy resin may include a unit derived from a compound having a primary amine group at the terminal, a unit derived from a sulfide compound, and a unit derived from an epoxy compound.
  • the second epoxy resin may include a unit derived from a compound having a primary amine group at the terminal and a unit derived from an epoxy compound.
  • the compound having a primary amine group at the terminal may be methanediamine, ethylenediamine, phenylenediamine, dimethylenetriamine, or diethylenetriamine.
  • the compound having a primary amine group at the terminal may have a primary amine group at both terminals.
  • the compound having a primary amine group at the terminal may include a structure represented by the following formula (1).
  • n and m are each a number from 1 to 20.
  • n and m may be the same.
  • the weight average molecular weight (g / mol) of the sulfide compound may be 150 to 8,500, for example, may be 300 to 5,000, may be 500 to 3,000. If the weight average molecular weight of the sulfide compound is less than 150, the flexibility of the reactants is insufficient, and chipping property and mechanical properties are lowered. If the weight average molecular weight of the sulfide compound is greater than 8,500, the viscosity of the final product is high and the high molecular weight may cause gelation during the reaction or storage. Problems may arise.
  • the sulfide compound may be a compound containing two or more mercaptan groups.
  • the sulfide compound may include a structure represented by Formula 2 below.
  • the epoxy compound has a weight average molecular weight (g / mol) of 300 to 2,000, epoxy equivalent (EEW) of 150 g / eq. To 1,000 g / eq.
  • the epoxy compound is a bisphenol A epoxy compound, a bisphenol F epoxy compound, a phenol novolac epoxy compound, a cresol novolac epoxy compound, an alkylphenol novolac epoxy compound, a bisphenol type epoxy compound, a naphthalene type epoxy compound, a dicyclo Pentadiene type epoxy compounds, triglycidyl isocyanates, glycidyl ester epoxy compounds, glycidyl amine epoxy compounds, dimer acid-modified epoxy compounds, acyclic epoxy resins, p-amino phenol type epoxy resins, and the like.
  • the epoxy resin may include the first epoxy resin and the second epoxy resin in a weight ratio of 3: 1 to 7: 1.
  • the weight ratio of the first epoxy resin and the second epoxy resin is less than 3: 1, the content of the bisphenol-type epoxy resin is small, resulting in poor physical properties such as rust resistance, adhesion, and heat resistance of the coating film.
  • the weight ratio of the second epoxy resin is greater than 7: 1 there is a problem that the smoothness and flexibility of the coating film is poor.
  • the curing agent included in the electrodeposition resin composition of the present invention may contain an isocyanate compound as a component that serves to crosslink and cure the base resin (epoxy resin).
  • the curing agent may include a first curing agent including an isocyanate compound blocked with a monohydric alcohol and a dihydric alcohol, and a second curing agent including an isocyanate compound blocked with a monohydric alcohol and a trihydric alcohol.
  • the isocyanate compound is, for example, methyl bisphenyl diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, p-phenylene isocyanate, diphenylmethane-4,4'-diisocyanate, polymethylene polyphenyl isocyanate, triphenylmethane-4,4,4 "-triisocyanate, or mixtures thereof And the like.
  • the isocyanate compound may be blocked (blocked) by alcohol, and the alcohol (blocking agent) is an isocyanate group (-NCO) bonded to the isocyanate compound reacts with active hydrogen at room temperature, and easily self-polymerizes. Block it.
  • the monohydric alcohol may be a linear or branched alkyl alcohol having 1 to 20 carbon atoms, allyl alcohol having 2 to 20 carbon atoms, 6 to 30 carbon atoms, such as methanol, ethanol, propanol, n-butanol, iso-butanol, and tert-butanol. It may be an aryl alcohol and the like, and may be an alcohol containing an ether bond in the middle of the chain, such as butyl carbitol, but may be used without limitation as long as it includes one hydroxyl group in the compound.
  • the dihydric alcohol may be alkylene glycol having 1 to 20 carbon atoms, arylene glycol having 6 to 30 carbon atoms, and the like, and may be used without limitation as long as the compound includes two hydroxyl groups, for example, ethylene glycol and propylene.
  • the trihydric alcohol may be an alkyl triol having 1 to 20 carbon atoms, an aryl triol having 6 to 30 carbon atoms, and the like, and may be used without limitation as long as it includes three hydroxyl groups in the compound.
  • glycerol and trimethylol Propane trimethylol propane, TMP
  • TMP trimethylol propane
  • the curing agent may include the first curing agent and the second curing agent in a weight ratio of 1: 4 to 9: 1, for example, a weight ratio of 1: 1 to 9: 1, 1.5: 1 to 9: 1 It may be included in the weight ratio.
  • the weight ratio of the first curing agent and the second curing agent is less than 1: 4, there is a problem in that the internal paintability of the electrodeposition paint prepared using the electrodeposition resin including the same, the weight ratio of the first curing agent and the second curing agent is 9 If it exceeds 1, the internal paintability of the electrodeposition paint may be inferior and the workability of the electrodeposition paint may be poor.
  • the curing agent may be included in an amount of 50 parts by weight to 80 parts by weight based on 100 parts by weight of the epoxy resin, for example, may be included in an amount of 65 parts by weight to 75 parts by weight.
  • the content of the curing agent is less than 50 parts by weight based on 100 parts by weight of the epoxy resin, the paint may not be sufficiently cured, resulting in low crosslinking density of the epoxy resin, resulting in poor mechanical properties, and content of the curing agent exceeding 80 parts by weight.
  • the water dispersibility is low and there is a fear that precipitation may occur, there may be a problem that the physical properties such as rust resistance, adhesion, heat resistance, etc. due to lack of epoxy content.
  • the amine compound included in the electrodeposition resin composition of the present invention can be used as a polymerization raw material to react with the epoxy resin.
  • the amine compound may be used without limitation as long as it is conventionally used in the electrodeposition resin composition.
  • the amine compound may be, for example, a primary amine, a secondary amine, a ketimine derivative obtained by reacting a primary amine and a secondary amine with a ketone compound, or a mixture thereof.
  • the amine compound may be a monoamine compound, a diamine compound, a triamine compound, a tetraamine compound, or a mixture thereof.
  • the amine compound may be included in an amount of 5 parts by weight to 15 parts by weight based on 100 parts by weight of the epoxy resin, for example, 7 parts by weight to 12 parts by weight.
  • the content of the amine compound is less than 5 parts by weight based on 100 parts by weight of the epoxy resin, the coating film may be degraded, the internal paintability may be deteriorated, and when the content of the amine compound is more than 15 parts by weight, the particles become large and storage problems. As a result, the water dispersibility may be lowered, the film rise and the UF filtrate may be lowered.
  • the electrodeposition resin composition of the present invention may further include at least one selected from the group consisting of an organic solvent, an epoxy neutralizer and an additive.
  • the organic solvent can control the coating film rise and the internal paintability of the electrodeposition coating, for example, 5,8,11,13,16,19-hexaoxatricosane (5,8,11,13,16,19- Ether solvents such as hexaoxatricosane, and alcohols such as 1-methoxy-2-propanol, butyl cellosolve, butyl carbitol, propylene glycol methyl ether, hexyl glycol System solvents and the like can be used.
  • 5,8,11,13,16,19-hexaoxatricosane such as hexaoxatricosane
  • alcohols such as 1-methoxy-2-propanol, butyl cellosolve, butyl carbitol, propylene glycol methyl ether, hexyl glycol System solvents and the like can be used.
  • the organic solvent may be included in an amount of 1 part by weight to 5 parts by weight based on 100 parts by weight of the epoxy resin, for example, may be included in an amount of 1 part by weight to 3 parts by weight, and the stability of the resin is greater than 5 parts by weight. It may fall, and the internal coating may be degraded because a transient film is required.
  • the epoxy neutralizer serves to neutralize the acidity of the cationic epoxy resin of the electrodeposition resin composition, and the epoxy neutralizer may be alkyl sulfonic acid or the like, but is not limited thereto.
  • the epoxy neutralizer may be included in an amount of 1 part by weight to 10 parts by weight based on 100 parts by weight of the epoxy resin.
  • the additive may include an anti-cratering agent or microgel to enhance oil resistance of the electrodeposition resin composition and control fluidity.
  • the pigment paste composition used for this invention contains a dispersion resin and a pigment.
  • the pigment paste composition may have a solid content of 40% to 60% by weight.
  • the solids content of the pigment paste composition is less than 40% by weight, the viscosity of the pigment paste may be so low that the storage stability due to precipitation of relatively heavy pigments may deteriorate, and when the amount of the pigment paste is greater than 60% by weight, the paint may be too high. It may be difficult to use, and the storage stability may be deteriorated due to insufficient content of the dispersion resin.
  • the dispersion resin contained in the pigment paste composition of the present invention functions to improve the wettability of the pigment.
  • the dispersion resin may be a resin having a cationic structure similar to that of the base resin (for example, an amine-modified epoxy resin), and may be, for example, a dispersion resin containing oxazolidone. It may be a dispersion resin having a form of a quaternary ammonium salt, but is not limited thereto.
  • the pigment paste composition used in the present invention may further include a curing catalyst, and the curing catalyst may improve the curability of the pigment paste composition or the final electrodeposited paint.
  • the curing catalyst is not limited to those used in the pigment paste composition, specifically, may be a tin-containing compound, a bismuth-containing compound, or a mixture thereof.
  • the tin-containing compound may be, for example, dibutyl tin oxide, dibutyl tin dilaurylate, dibutyl tin chloride, dioctyl tin chloride, dioctyl tin oxide, or a mixture thereof.
  • the bismuth-containing compound is, for example, Bi 2 O 3 or Bi (OH) divalent , lactic acid (Lactic acid), acetic acid (Acetic acid), formic acid (Formic acid), dimethylolpropionic acid (DMPA), or It may be mixed with an acid such as methanesulfonic acid (MSA).
  • Bi 2 O 3 or Bi (OH) divalent lactic acid (Lactic acid), acetic acid (Acetic acid), formic acid (Formic acid), dimethylolpropionic acid (DMPA), or It may be mixed with an acid such as methanesulfonic acid (MSA).
  • the curing catalyst may be included in an amount of 150 parts by weight to 200 parts by weight based on 100 parts by weight of the dispersion resin, for example, 160 parts by weight to 180 parts by weight.
  • the content of the curing catalyst is less than 150 parts by weight based on 100 parts by weight of the dispersion resin, mechanical properties and corrosion resistance may be lowered due to the lowering of curability of the coating film, and when the content of the curing catalyst is greater than 200 parts by weight, The storage stability may be lowered, resulting in poor appearance and an increase in raw material costs depending on the catalyst content.
  • the pigment contained in the pigment paste composition used for this invention makes the appearance of coating excellent.
  • the pigment a commonly used inorganic pigment may be used.
  • the inorganic pigment may be, for example, titanium oxide, zinc oxide, zinc sulfide, kaolin, clay, calcium carbonate, talc, silica, iron oxide, lead chromate, cadmium, chromium oxide, carbon black, zinc chromate, strontium chromate, Zinc phosphate, phosphate, silicate, and the like, but is not limited thereto.
  • the pigment may be included in an amount of 250 parts by weight to 300 parts by weight based on 100 parts by weight of the dispersion resin, for example, may be included in an amount of 260 parts by weight to 280 parts by weight.
  • the content of the pigment is less than 250 parts by weight based on 100 parts by weight of the dispersion resin, the hiding power to the base and the cover power of the edge (edge) of the vehicle body may be poor, when the content of the coating film is greater than 300 parts by weight This is deteriorated and workability in the electrodeposition process may be deteriorated.
  • the pigment paste composition may further include a solvent for solid content control, acidity, viscosity control and electrodeposition coating of the pigment paste composition.
  • the solvent may be a conventionally known one, for example 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (2,2,4-trimethyl-1,3-pentanediol diisobutyrate) and the like Can be.
  • the pigment paste composition may further include a conventionally known antifoaming agent, surface regulator, dispersant, pH adjuster and the like to increase the physical properties of the coating film formed by using the same.
  • the additive may be included in an amount of 10 parts by weight to 20 parts by weight based on 100 parts by weight of the dispersion resin.
  • this invention provides the electrodeposition paint containing an electrodeposition resin composition and a pigment paste composition.
  • Electrodeposition paint of the present invention is the '1.
  • the electrodeposition coating material of this invention introduce
  • curing agents to an electrodeposition resin composition, and there exists an effect which makes it excellent in the internal coating property and workability of an electrodeposition coating material.
  • the electrodeposition resin composition and the pigment paste composition included in the electrodeposition paint may be mixed in a weight ratio of 5: 1 to 9: 1, for example, in a weight ratio of 6: 1 to 8: 1.
  • the coating film is excellent in rust prevention and adhesion, while improving the internal coating property and workability of the electrodeposition paint, and is useful for electrodeposition coating of automobiles and home appliances. Can be used.
  • Epoxy Amine Value (EPA VALUE) is 2.15, weight average molecular weight is 4,300, viscosity (measured at 25 ° C with Brookfield Viscometer) is 4,200 cPs, solid content is 80% by weight. Epoxy Resin A was prepared.
  • Epoxy Amine Value (EPA VALUE) is 2.15, weight average molecular weight is 4,100, viscosity (measured at 25 ° C with Brookfield Viscometer) is 3,900 cPs, solid content is 80% by weight.
  • Epoxy Resin A-1 was prepared.
  • the resin reactant was transferred to a reactor containing 1.4 parts by weight of 70% by weight of methyl sulfonic acid and 33.5 parts by weight of DIW to carry out the first aqueous dispersion. After water dispersion and stirring for 1 hour, 21.4 parts by weight of DIW was further added to lower the viscosity. 0.51 parts by weight of microgel (microgel rheorol 200, nanocamtack), 0.2 parts by weight of antifoaming agent (SAN NOPCO LTD., SN-180), 0.4 parts by weight of butyl cellosolve, and 0.9 parts by weight of flow below 45 ° C. Put the agents in order.
  • the prepared electrodeposition resin composition had a solid content of 36% by weight.
  • Example 1 an electrodeposition resin composition was prepared in the same manner as in Example 1, except that 4.3 parts by weight of epoxy resin A was added instead of 3.4 parts by weight of epoxy resin A.
  • Example 1 an electrodeposition resin composition was prepared in the same manner as in Example 1, except that 3.4 parts by weight of epoxy resin A-1 was added instead of 3.4 parts by weight of epoxy resin A.
  • the prepared electrodeposition resin composition had a solid content of 36% by weight.
  • Comparative Example 1 an electrodeposition resin composition was prepared in the same manner as in Comparative Example 1, except that only 15.5 parts by weight of curing agent A was added instead of 7.75 parts by weight of curing agent A and 7.75 parts by weight of curing agent B. .
  • Comparative Example 1 an electrodeposition resin composition was prepared in the same manner as in Comparative Example 1, except that only 15.5 parts by weight of curing agent B was added instead of 7.75 parts by weight of curing agent A and 7.75 parts by weight of curing agent B. .
  • Example 1 Example 2
  • Example 3 Example 4 1.YD-128 (Kukdo Chemical) 11.8 11.8 11.8 11.8 1.1.8 2.
  • BPA LG Chemistry
  • BPA Hakdo Chemical
  • BPA Hakogenicity / BSA-60
  • Epoxy Resin A 3.4 4.3 - - 4-1.
  • Epoxy Resin A-1 - - - 3.4 5.
  • Methoxy propanol 1.0 1.0 1.0 1.0 6.Dimethyl benzylamine 0.1 0.1 0.1 0.1 7.
  • Curing agent A 10.0 10.0 10.0 10.0 8.
  • Curing Agent B 6.7 6.7 6.7 6.7 9.Diethanol amine 1.3 1.3 1.3 1.3 10.Diketimine 1.2 1.2 1.2 1.2 11.
  • GA aptitude GA is galvanic specimen, and hydrogen gas generated during electrodeposition coating undergoes air bubbles in the coating film as H 2 decomposed from the surface of galvanic surface with rough surface. At this time, the difference in appearance is compared. ( ⁇ (good), ⁇ (good), ⁇ (bad))
  • T / P The deviation (G / A) between the outer coating and the inner coating can be evaluated in the following way. (The higher the better internal paintability)
  • the electrodeposition coating material using the electrodeposition resin composition of Examples 1 to 4 corresponding to the present invention is excellent in the flexibility of the coating film, compared to Comparative Examples 1 to 3, the T / P (%) value is It can be confirmed that the internal coating property (phenomena in which the electrodeposition paint penetrates into the inside and the coating film rises) is improved in a predominant manner.

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Abstract

The present invention relates to an electrodeposition resin composition comprising an epoxy resin, a curing agent, and an amine compound, and an electrodeposition paint comprising same.

Description

전착 수지 조성물 및 이를 포함하는 전착 도료Electrodeposition resin composition and electrodeposition paint containing same
본 발명은 전착 수지 조성물 및 이를 포함하는 전착 도료에 관한 것이다.The present invention relates to an electrodeposition resin composition and an electrodeposition paint containing the same.
금속 재료를 부식으로부터 보호하고 그 미감을 사용기간 동안 유지하기 위해, 그 표면에는 일반적으로 도장이 행해진다. 전착 도장은 에어 스프레이 도장이나 정전 스프레이 도장과 비교하여, 도장성이 우수하고 환경 오염도 적기 때문에 프라이머 도장으로서 널리 실용화에 이르고 있다. 특히 양이온 전착 도장은 연속적으로 도장할 수 있기 때문에, 자동차 차체 등 대형이고, 높은 내식성이 요구되는 도장 대상물의 초벌 도장 방법으로 범용되고 있다.In order to protect the metal material from corrosion and to maintain its aesthetics for the duration of use, the surface is usually painted. Electrodeposition coating is widely used as a primer coating because it is excellent in paintability and less environmental pollution compared with air spray coating and electrostatic spray coating. In particular, since the cationic electrodeposition coating can be applied continuously, it has been widely used as a primary coating method for coating objects such as automobile bodies, which are large and require high corrosion resistance.
양이온 전착 도료 조성물은 일반적으로 양이온성 수지 및 경화제를 포함하는 바인더 성분을 유기산 등의 중화제를 포함한 수성 매질에 분산시켜 얻어진다. 전착 도장은 양이온 전착 도료 조성물에 도장 대상물을 음극으로서 침지시켜 전압을 인가함으로써 행해진다. 도장 과정에서 전극 사이에 전압을 인가하면, 전기 화학적 반응에 의해 음극(도장 대상물) 표면에 전착 도막이 석출된다. 이렇게 형성된 전착 도막에는 양이온성 수지와 함께 경화제가 포함되므로, 전착 도장 종료 후에 이 도막을 소성하는 것에 의해 도막이 경화하고, 원하는 경화 도막이 형성된다.Cationic electrodeposition coating compositions are generally obtained by dispersing a binder component comprising a cationic resin and a curing agent in an aqueous medium containing neutralizing agents such as organic acids. Electrodeposition coating is performed by immersing a coating object as a negative electrode in a cationic electrodeposition coating composition, and applying a voltage. When a voltage is applied between the electrodes in the coating process, an electrodeposition coating film is deposited on the surface of the cathode (coating object) by an electrochemical reaction. Since the electrodeposition coating film formed in this way contains a hardening | curing agent with cationic resin, a coating film hardens | cures by baking this coating film after completion | finish of electrodeposition coating, and a desired cured coating film is formed.
전착 도장에 이용되는 양이온성 수지로서, 설파이드 화합물과 에폭시 화합물을 포함하여 도막의 물성을 우수하게 할 수 있다는 장점이 있으나, 내부 도장성이 열세한 문제가 생길 수 있다.As the cationic resin used for electrodeposition coating, there is an advantage in that the physical properties of the coating film can be improved by including a sulfide compound and an epoxy compound, but problems of inferior paintability may occur.
이에 따라, 전착 도료의 작업성이나 내부 도장성을 향상시키기 위한 양이온 전착 수지의 개발에 관심이 집중되고 있다.Accordingly, attention has been focused on the development of cationic electrodeposition resins for improving the workability and internal coating properties of electrodeposition paints.
[선행기술문헌][Preceding technical literature]
일본 공개특허공보 특개2012-036314호Japanese Patent Laid-Open No. 2012-036314
본 발명은 내부 도장성이 개선된 전착 수지 조성물을 제공한다.The present invention provides an electrodeposition resin composition having improved internal paintability.
또한 본 발명은 상기 전착 수지 조성물과 안료 페이스트 조성물을 포함하는 전착 도료를 제공한다.Moreover, this invention provides the electrodeposition paint containing the said electrodeposition resin composition and a pigment paste composition.
본 발명은, 에폭시 수지, 경화제 및 아민 화합물을 포함하고, 상기 경화제는 1가 알코올 및 2가 알코올로 차단된 이소시아네이트 화합물을 포함하는 제1 경화제와 1가 알코올 및 3가 알코올로 차단된 이소시아네이트 화합물을 포함하는 제2 경화제를 포함하는 것인 전착 수지 조성물을 제공한다.The present invention includes an epoxy resin, a curing agent and an amine compound, wherein the curing agent comprises a first curing agent comprising an isocyanate compound blocked with a monohydric alcohol and a dihydric alcohol, and an isocyanate compound blocked with a monohydric alcohol and a trihydric alcohol. It provides the electrodeposition resin composition containing the 2nd hardening | curing agent containing.
또한 본 발명은, 상기 전착 수지 조성물과 안료 페이스트 조성물을 포함하는 전착 도료를 제공한다.Moreover, this invention provides the electrodeposition paint containing the said electrodeposition resin composition and a pigment paste composition.
본 발명의 전착 수지 조성물은 2가 알코올 또는 3가 알코올과 1가 알코올로 차단된 이소시아네이트 경화제 2종을 포함함으로써 이를 이용하여 형성된 전착 도료의 내부 도장성을 개선하고, 작업성을 향상시킬 수 있다.The electrodeposition resin composition of the present invention includes dihydric alcohol or trihydric alcohol and two kinds of isocyanate curing agents blocked by monohydric alcohol, thereby improving the internal paintability of the electrodeposition paint formed by using the same, and improving workability.
또한 본 발명의 전착 수지 조성물은 에폭시 수지에 제1 에폭시 수지와 제2 에폭시 수지를 포함함으로써, 이를 이용하여 형성된 도막의 평활성과 유연성이 우수하면서도 방청성과 부착성도 개선된 도막을 형성할 수 있다.In addition, the electrodeposition resin composition of the present invention includes a first epoxy resin and a second epoxy resin in the epoxy resin, it is possible to form a coating film having excellent smoothness and flexibility of the coating film formed by using the same, but also improved rust resistance and adhesion.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
1. One. 전착 수지 조성물Electrodeposition resin composition
본 발명은 전착 수지 조성물을 제공한다.The present invention provides an electrodeposition resin composition.
본 발명의 전착 수지 조성물은 에폭시 수지, 경화제 및 아민 화합물을 포함한다.The electrodeposition resin composition of this invention contains an epoxy resin, a hardening | curing agent, and an amine compound.
<에폭시 수지><Epoxy resin>
본 발명의 전착 수지 조성물에 포함되는 에폭시 수지는 경화되어 도막을 형성하는 베이스 수지 성분으로서, 제1 에폭시 수지와 제2 에폭시 수지를 포함할 수 있다.The epoxy resin contained in the electrodeposition resin composition of this invention can contain a 1st epoxy resin and a 2nd epoxy resin as a base resin component which hardens and forms a coating film.
상기 제1 에폭시 수지는 최종 형성된 도막에 우수한 방청성, 부착성, 내열성 등의 물성을 부여하는 비스페놀형 에폭시 수지이다.The first epoxy resin is a bisphenol-type epoxy resin that imparts excellent physical properties such as rust resistance, adhesion, and heat resistance to the finally formed coating film.
상기 제1 에폭시 수지는 에폭시 당량(Epoxy Equivalent Weight, EEW)이 150 g/eq. 내지 2,000 g/eq.이고, 2개 이상의 1,2-에폭시 그룹을 갖는 에폭시 수지인 것으로서, 전착 수지 조성물에 통상적으로 사용되는 것이면 제한되지 않고 사용될 수 있다. 상기 제1 에폭시 수지는 비스페놀형 에폭시 수지를 포함할 수 있고, 예를 들어 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지 등일 수 있다.The first epoxy resin has an epoxy equivalent weight (EEW) of 150 g / eq. To 2,000 g / eq., An epoxy resin having two or more 1,2-epoxy groups, and may be used without limitation as long as it is commonly used in electrodeposition resin compositions. The first epoxy resin may include a bisphenol type epoxy resin, and for example, may be a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or the like.
상기 제2 에폭시 수지는 본 발명의 전착 수지 조성물을 이용하여 제조한 도막의 평활성과 유연성을 개선하여 외관을 우수하게 할 뿐만 아니라, 도막의 전기영동성을 높여주어 전착 수지에서의 도장의 작업성을 향상시키는 성분이다.The second epoxy resin not only improves the smoothness and flexibility of the coating film prepared using the electrodeposition resin composition of the present invention to improve the appearance, but also improves the electrophoresis of the coating film, thereby improving the workability of the coating in the electrodeposition resin. Ingredient.
상기 제2 에폭시 수지는 말단에 1차 아민기를 갖는 화합물로부터 유래되는 단위, 설파이드 화합물로부터 유래되는 단위 및 에폭시 화합물로부터 유래되는 단위 중에서 선택되는 적어도 하나를 포함할 수 있다.The second epoxy resin may include at least one selected from a unit derived from a compound having a primary amine group at a terminal, a unit derived from a sulfide compound, and a unit derived from an epoxy compound.
예를 들어, 상기 제2 에폭시 수지는 말단에 1차 아민기를 갖는 화합물로부터 유래되는 단위 및 설파이드 화합물로부터 유래되는 단위 중에서 선택되는 적어도 하나, 및 에폭시 화합물로부터 유래되는 단위를 포함할 수 있다.For example, the second epoxy resin may include at least one selected from a unit derived from a compound having a primary amine group and a unit derived from a sulfide compound, and a unit derived from an epoxy compound.
또는, 제2 에폭시 수지는 말단에 1차 아민기를 갖는 화합물로부터 유래되는 단위, 설파이드 화합물로부터 유래되는 단위 및 에폭시 화합물로부터 유래되는 단위를 포함할 수 있다.Alternatively, the second epoxy resin may include a unit derived from a compound having a primary amine group at the terminal, a unit derived from a sulfide compound, and a unit derived from an epoxy compound.
또는, 제2 에폭시 수지는 말단에 1차 아민기를 갖는 화합물로부터 유래되는 단위 및 에폭시 화합물로부터 유래되는 단위를 포함할 수 있다.Alternatively, the second epoxy resin may include a unit derived from a compound having a primary amine group at the terminal and a unit derived from an epoxy compound.
상기 말단에 1차 아민기를 갖는 화합물은 메탄디아민, 에틸렌디아민, 페닐렌디아민, 디메틸렌트리아민, 또는 디에틸렌트리아민 등일 수 있다.The compound having a primary amine group at the terminal may be methanediamine, ethylenediamine, phenylenediamine, dimethylenetriamine, or diethylenetriamine.
상기 말단에 1차 아민기를 갖는 화합물은 양 말단에 1차 아민기를 가질 수 있다. 상기 말단에 1차 아민기를 갖는 화합물은 하기 화학식 1로 표시되는 구조를 포함할 수 있다.The compound having a primary amine group at the terminal may have a primary amine group at both terminals. The compound having a primary amine group at the terminal may include a structure represented by the following formula (1).
[화학식 1][Formula 1]
NH2-(CH2)n-NH-(CH2)m-NH2 NH 2- (CH 2 ) n -NH- (CH 2 ) m -NH 2
(화학식 1에서, n 및 m은 각각 1 내지 20의 수이다.)(In Formula 1, n and m are each a number from 1 to 20.)
상기 화학식 1에서 n과 m은 동일할 수 있다.In Formula 1 n and m may be the same.
상기 설파이드 화합물의 중량평균분자량(g/mol)은 150 내지 8,500일 수 있고, 예를 들어 300 내지 5,000일 수 있고, 500 내지 3,000일 수 있다. 설파이드 화합물의 중량평균분자량이 150 미만인 경우 반응물의 유연성이 충분하지 못하여 치핑성 및 기계적 물성이 저하되고, 8,500 초과인 경우 최종 생성물의 점성도가 높고 고분자량에 의해 반응 또는 저장시에 겔(gel)화의 문제가 발생할 수 있다.The weight average molecular weight (g / mol) of the sulfide compound may be 150 to 8,500, for example, may be 300 to 5,000, may be 500 to 3,000. If the weight average molecular weight of the sulfide compound is less than 150, the flexibility of the reactants is insufficient, and chipping property and mechanical properties are lowered. If the weight average molecular weight of the sulfide compound is greater than 8,500, the viscosity of the final product is high and the high molecular weight may cause gelation during the reaction or storage. Problems may arise.
상기 설파이드 화합물은 2 이상의 머캅탄(mercaptan)기를 함유하는 화합물일 수 있다. 상기 설파이드 화합물은 하기 화학식 2로 표시되는 구조를 포함할 수 있다.The sulfide compound may be a compound containing two or more mercaptan groups. The sulfide compound may include a structure represented by Formula 2 below.
[화학식 2][Formula 2]
HS-(CH2CH2-O-CH2-O-CH2CH2-S-S)a-CH2CH2-O-CH2-O-CH2CH2-SHHS- (CH 2 CH 2 -O-CH 2 -O-CH 2 CH 2 -SS) a -CH 2 CH 2 -O-CH 2 -O-CH 2 CH 2 -SH
(화학식 2에 있어서, a는 0 내지 50의 수이다.)(In Formula 2, a is a number of 0-50.)
상기 에폭시 화합물은 중량평균분자량(g/mol)이 300 내지 2,000이고, 에폭시 당량(EEW)이 150 g/eq. 내지 1,000 g/eq.일 수 있다.The epoxy compound has a weight average molecular weight (g / mol) of 300 to 2,000, epoxy equivalent (EEW) of 150 g / eq. To 1,000 g / eq.
상기 에폭시 화합물은 비스페놀 A형 에폭시 화합물, 비스페놀 F형 에폭시 화합물, 페놀 노볼락형 에폭시 화합물, 크레졸 노볼락형 에폭시 화합물, 알킬페놀 노볼락형 에폭시 화합물, 비스페놀형 에폭시 화합물, 나프탈렌형 에폭시 화합물, 디사이클로펜타디엔형 에폭시 화합물, 트리글리시딜 이소시아네이트, 글리시딜 에스테르계 에폭시 화합물, 글리시딜 아민계 에폭시 화합물, 다이머산 변성 에폭시 화합물, 비환식 에폭시 수지, p-아미노 페놀형 에폭시 수지 등일 수 있다.The epoxy compound is a bisphenol A epoxy compound, a bisphenol F epoxy compound, a phenol novolac epoxy compound, a cresol novolac epoxy compound, an alkylphenol novolac epoxy compound, a bisphenol type epoxy compound, a naphthalene type epoxy compound, a dicyclo Pentadiene type epoxy compounds, triglycidyl isocyanates, glycidyl ester epoxy compounds, glycidyl amine epoxy compounds, dimer acid-modified epoxy compounds, acyclic epoxy resins, p-amino phenol type epoxy resins, and the like.
상기 에폭시 수지는, 상기 제1 에폭시 수지와 상기 제2 에폭시 수지를 3:1 내지 7:1의 중량비로 포함할 수 있다. 상기 제1 에폭시 수지와 상기 제2 에폭시 수지의 중량비가 3:1 미만인 경우 비스페놀형 에폭시 수지의 함량이 적어서 도막의 방청성, 부착성, 내열성 등의 물성이 불량해지는 문제가 있고, 상기 제1 에폭시 수지와 상기 제2 에폭시 수지의 중량비가 7:1 초과인 경우 도막의 평활성과 유연성이 불량해지는 문제가 있다.The epoxy resin may include the first epoxy resin and the second epoxy resin in a weight ratio of 3: 1 to 7: 1. When the weight ratio of the first epoxy resin and the second epoxy resin is less than 3: 1, the content of the bisphenol-type epoxy resin is small, resulting in poor physical properties such as rust resistance, adhesion, and heat resistance of the coating film. And when the weight ratio of the second epoxy resin is greater than 7: 1 there is a problem that the smoothness and flexibility of the coating film is poor.
<경화제><Hardener>
본 발명의 전착 수지 조성물에 포함되는 경화제는 베이스 수지(에폭시 수지)를 가교시켜 경화시키는 역할을 하는 성분으로서, 이소시아네이트 화합물을 포함할 수 있다.The curing agent included in the electrodeposition resin composition of the present invention may contain an isocyanate compound as a component that serves to crosslink and cure the base resin (epoxy resin).
상기 경화제는 1가 알코올 및 2가 알코올로 차단된 이소시아네이트 화합물을 포함하는 제1 경화제와 1가 알코올 및 3가 알코올로 차단된 이소시아네이트 화합물을 포함하는 제2 경화제를 포함할 수 있다.The curing agent may include a first curing agent including an isocyanate compound blocked with a monohydric alcohol and a dihydric alcohol, and a second curing agent including an isocyanate compound blocked with a monohydric alcohol and a trihydric alcohol.
상기 이소시아네이트 화합물은 예를 들어, 메틸 비스페닐 디이소시아네이트, 테트라메틸렌 디이소시아네이트, 헥사메틸렌 디이소시아네이트, 디시클로헥실메탄-4,4'-디이소시아네이트, 이소포론 디이소시아네이트, 2,4-톨루엔 디이소시아네이트, 2,6-톨루엔 디이소시아네이트, p-페닐렌 이소시아네이트, 디페닐메탄-4,4'-디이소시아네이트, 폴리메틸렌 폴리페닐 이소시아네이트, 트리페닐메탄-4,4,4"-트리이소시아네이트, 또는 이들의 혼합물 등일 수 있다.The isocyanate compound is, for example, methyl bisphenyl diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, p-phenylene isocyanate, diphenylmethane-4,4'-diisocyanate, polymethylene polyphenyl isocyanate, triphenylmethane-4,4,4 "-triisocyanate, or mixtures thereof And the like.
또한, 상기 이소시아네이트 화합물은 알코올에 의해 차단(블록화)된 것일 수 있고, 상기 알코올(블록킹제)은 상기 이소시아네이트 화합물에 결합된 이소시아네이트기(-NCO)가 상온에서 활성 수소와 반응하고, 쉽게 자가중합하는 것을 차단한다.In addition, the isocyanate compound may be blocked (blocked) by alcohol, and the alcohol (blocking agent) is an isocyanate group (-NCO) bonded to the isocyanate compound reacts with active hydrogen at room temperature, and easily self-polymerizes. Block it.
상기 1가 알코올은 메탄올, 에탄올, 프로판올, n-부탄올, iso-부탄올, tert-부탄올 등의 직쇄 또는 분지쇄의 탄소수 1 내지 20의 알킬 알코올, 탄소수 2 내지 20의 알릴 알코올, 탄소수 6 내지 30의 아릴 알코올 등일 수 있고, 부틸 카비톨(butyl carbitol)과 같이 사슬 중간에 에테르(ether) 결합이 포함된 알코올일 수 있으나, 화합물 내에 1개의 하이드록시기를 포함하는 것이면 이에 제한없이 사용될 수 있다.The monohydric alcohol may be a linear or branched alkyl alcohol having 1 to 20 carbon atoms, allyl alcohol having 2 to 20 carbon atoms, 6 to 30 carbon atoms, such as methanol, ethanol, propanol, n-butanol, iso-butanol, and tert-butanol. It may be an aryl alcohol and the like, and may be an alcohol containing an ether bond in the middle of the chain, such as butyl carbitol, but may be used without limitation as long as it includes one hydroxyl group in the compound.
상기 2가 알코올은 탄소수 1 내지 20의 알킬렌 글리콜, 탄소수 6 내지 30의 아릴렌 글리콜 등일 수 있고, 화합물 내에 2개의 하이드록시기를 포함하는 것이면 이에 제한없이 사용될 수 있으며, 예를 들어 에틸렌글리콜, 프로필렌글리콜(propylene glycol), 부틸렌글리콜, 에톡시레이티드 비스페놀 A(Ethoxylated BPA) 등일 수 있다.The dihydric alcohol may be alkylene glycol having 1 to 20 carbon atoms, arylene glycol having 6 to 30 carbon atoms, and the like, and may be used without limitation as long as the compound includes two hydroxyl groups, for example, ethylene glycol and propylene. Propylene glycol, butylene glycol, ethoxylated bisphenol A (Ethoxylated BPA), and the like.
상기 3가 알코올은 탄소수 1 내지 20의 알킬 트리올, 탄소수 6 내지 30의 아릴 트리올 등일 수 있고, 화합물 내에 3개의 하이드록시기를 포함하는 것이면 이에 제한없이 사용될 수 있으며, 예를 들어 글리세롤, 트리메틸올프로판(trimethylol propane, TMP) 등일 수 있다.The trihydric alcohol may be an alkyl triol having 1 to 20 carbon atoms, an aryl triol having 6 to 30 carbon atoms, and the like, and may be used without limitation as long as it includes three hydroxyl groups in the compound. For example, glycerol and trimethylol Propane (trimethylol propane, TMP) and the like.
상기 경화제는, 상기 제1 경화제와 상기 제2 경화제를 1:4 내지 9:1의 중량비로 포함할 수 있고, 예를 들어 1:1 내지 9:1의 중량비, 1.5:1 내지 9:1의 중량비로 포함될 수 있다. 상기 제1 경화제와 제2 경화제의 중량비가 1:4 미만인 경우 이를 포함한 전착 수지를 이용하여 제조한 전착 도료의 내부 도장성이 열세한 문제가 있고, 상기 제1 경화제와 제2 경화제의 중량비가 9:1 초과인 경우 전착 도료의 내부 도장성이 열세하고 전착 도료의 작업성이 불량해질 수 있다.The curing agent may include the first curing agent and the second curing agent in a weight ratio of 1: 4 to 9: 1, for example, a weight ratio of 1: 1 to 9: 1, 1.5: 1 to 9: 1 It may be included in the weight ratio. When the weight ratio of the first curing agent and the second curing agent is less than 1: 4, there is a problem in that the internal paintability of the electrodeposition paint prepared using the electrodeposition resin including the same, the weight ratio of the first curing agent and the second curing agent is 9 If it exceeds 1, the internal paintability of the electrodeposition paint may be inferior and the workability of the electrodeposition paint may be poor.
상기 경화제는 상기 에폭시 수지 100 중량부를 기준으로 50 중량부 내지 80 중량부의 함량으로 포함될 수 있고, 예를 들어 65 중량부 내지 75 중량부의 함량으로 포함될 수 있다. 상기 경화제의 함량이 에폭시 수지 100 중량부를 기준으로 50 중량부 미만인 경우 도료가 충분히 경화되지 못하여 에폭시 수지의 가교 밀도가 낮아져, 기계적 물성이 불량해지는 문제가 발생할 수 있고, 경화제의 함량이 80 중량부 초과인 경우 수분산성이 떨어지고 침전이 발생될 우려가 있고, 에폭시 함량의 부족에 따른 방청성, 부착성, 내열성 등의 물성이 떨어지는 문제가 생길 수 있다.The curing agent may be included in an amount of 50 parts by weight to 80 parts by weight based on 100 parts by weight of the epoxy resin, for example, may be included in an amount of 65 parts by weight to 75 parts by weight. When the content of the curing agent is less than 50 parts by weight based on 100 parts by weight of the epoxy resin, the paint may not be sufficiently cured, resulting in low crosslinking density of the epoxy resin, resulting in poor mechanical properties, and content of the curing agent exceeding 80 parts by weight. When the water dispersibility is low and there is a fear that precipitation may occur, there may be a problem that the physical properties such as rust resistance, adhesion, heat resistance, etc. due to lack of epoxy content.
<아민 화합물><Amine Compound>
본 발명의 전착 수지 조성물에 포함되는 아민 화합물은 에폭시 수지와 반응하는 중합 원료로 사용될 수 있다.The amine compound included in the electrodeposition resin composition of the present invention can be used as a polymerization raw material to react with the epoxy resin.
상기 아민 화합물은 전착 수지 조성물에 통상적으로 사용되는 것이면 제한되지 않고 사용될 수 있다. 상기 아민 화합물은 예를 들어, 1급 아민, 2급 아민, 1급 아민과 2급 아민이 케톤 화합물과 반응하여 얻어지는 케티민 유도체, 또는 이들의 혼합물 등일 수 있다. 또한 상기 아민 화합물은 모노아민 화합물, 디아민 화합물, 트리아민 화합물, 테트라아민 화합물, 또는 이들의 혼합물이 사용될 수 있으며, 예컨대, 디메틸아민, 디에틸아민, 디에탄올아민, 메틸에틸렌아민, 디메틸프로판디아민, 벤질아민, n-부틸아민, 아닐린, 사이클로펜탄아민, 사이클로헥실아민, 2-아미노페놀, 2-브로모아닐린, 에틸렌디아민, 헥사메틸디아민, 아미노에틸에탄올아민, N-메틸에탄올아민, 벤질디메틸아민, 케티민, 디케티민, 디에틸렌트리아민, 트리에틸렌테트라아민, 부탄올아민, 또는 이들의 혼합물 등일 수 있다.The amine compound may be used without limitation as long as it is conventionally used in the electrodeposition resin composition. The amine compound may be, for example, a primary amine, a secondary amine, a ketimine derivative obtained by reacting a primary amine and a secondary amine with a ketone compound, or a mixture thereof. In addition, the amine compound may be a monoamine compound, a diamine compound, a triamine compound, a tetraamine compound, or a mixture thereof. For example, dimethylamine, diethylamine, diethanolamine, methylethyleneamine, dimethylpropanediamine, Benzylamine, n-butylamine, aniline, cyclopentanamine, cyclohexylamine, 2-aminophenol, 2-bromoaniline, ethylenediamine, hexamethyldiamine, aminoethylethanolamine, N-methylethanolamine, benzyldimethylamine , Ketimine, diketamine, diethylenetriamine, triethylenetetraamine, butanolamine, or mixtures thereof.
상기 아민 화합물은 상기 에폭시 수지 100 중량부를 기준으로 5 중량부 내지 15 중량부의 함량으로 포함될 수 있고, 예를 들어 7 중량부 내지 12 중량부의 함량으로 포함될 수 있다. 상기 아민 화합물의 함량이 에폭시 수지 100 중량부를 기준으로 5 중량부 미만인 경우 도막의 오름성이 떨어지고, 내부 도장성이 불량해질 수 있고, 아민 화합물의 함량이 15 중량부 초과인 경우 입자가 커져서 저장성 문제, 수분산성이 떨어지고 도막 상승 및 UF 여액이 저하될 수 있다.The amine compound may be included in an amount of 5 parts by weight to 15 parts by weight based on 100 parts by weight of the epoxy resin, for example, 7 parts by weight to 12 parts by weight. When the content of the amine compound is less than 5 parts by weight based on 100 parts by weight of the epoxy resin, the coating film may be degraded, the internal paintability may be deteriorated, and when the content of the amine compound is more than 15 parts by weight, the particles become large and storage problems. As a result, the water dispersibility may be lowered, the film rise and the UF filtrate may be lowered.
<기타><Others>
본 발명의 전착 수지 조성물은 유기 용제, 에폭시 중화제 및 첨가제로 이루어진 군에서 선택되는 적어도 하나를 더 포함할 수 있다.The electrodeposition resin composition of the present invention may further include at least one selected from the group consisting of an organic solvent, an epoxy neutralizer and an additive.
상기 유기 용제는 전착 도장의 도막 오름성과 내부 도장성을 조절할 수 있고, 예를 들어 5,8,11,13,16,19-헥사옥사트리코세인 (5,8,11,13,16,19-Hexaoxatricosane)과 같은 에테르계 용제와, 1-메톡시-2-프로판올, 부틸 셀로솔브(Butyl cellosolve), 부틸 카비톨(Butyl carbitol), 프로필렌 글리콜 메틸 에테르(propylene glycol methyl ether), 헥실글리콜과 같은 알코올계 용제 등을 이용할 수 있다.The organic solvent can control the coating film rise and the internal paintability of the electrodeposition coating, for example, 5,8,11,13,16,19-hexaoxatricosane (5,8,11,13,16,19- Ether solvents such as hexaoxatricosane, and alcohols such as 1-methoxy-2-propanol, butyl cellosolve, butyl carbitol, propylene glycol methyl ether, hexyl glycol System solvents and the like can be used.
상기 유기 용제는 상기 에폭시 수지 100 중량부를 기준으로 1 중량부 내지 5 중량부의 함량으로 포함될 수 있고, 예를 들어 1 중량부 내지 3 중량부의 함량으로 포함될 수 있으며, 5 중량부 초과에서는 수지의 안정성이 떨어지며, 과도막이 필요하여 내부도장성이 떨어질 수 있다.The organic solvent may be included in an amount of 1 part by weight to 5 parts by weight based on 100 parts by weight of the epoxy resin, for example, may be included in an amount of 1 part by weight to 3 parts by weight, and the stability of the resin is greater than 5 parts by weight. It may fall, and the internal coating may be degraded because a transient film is required.
상기 에폭시 중화제는 전착 수지 조성물의 양이온성 에폭시 수지의 산성을 중화시키는 역할을 하고, 상기 에폭시 중화제는 알킬 설폰산 등일 수 있으나 이에 한정되는 것은 아니다.The epoxy neutralizer serves to neutralize the acidity of the cationic epoxy resin of the electrodeposition resin composition, and the epoxy neutralizer may be alkyl sulfonic acid or the like, but is not limited thereto.
상기 에폭시 중화제는 상기 에폭시 수지 100 중량부를 기준으로 1 중량부 내지 10 중량부의 함량으로 포함될 수 있다.The epoxy neutralizer may be included in an amount of 1 part by weight to 10 parts by weight based on 100 parts by weight of the epoxy resin.
상기 첨가제는 전착 수지 조성물의 유분내성을 강화하고 유동성을 조절하기 위한 클레이터링 방지제(anti-cratering agent) 또는 마이크로겔(microgel) 등을 포함할 수 있다.The additive may include an anti-cratering agent or microgel to enhance oil resistance of the electrodeposition resin composition and control fluidity.
2. 2. 안료 페이스트 조성물Pigment paste composition
본 발명에 이용되는 안료 페이스트 조성물은 분산수지 및 안료를 포함한다.The pigment paste composition used for this invention contains a dispersion resin and a pigment.
안료 페이스트 조성물은 고형분 함량이 40 중량% 내지 60 중량%일 수 있다. 상기 안료 페이스트 조성물의 고형분 함량이 40 중량% 미만인 경우에는 안료 페이스트의 점도가 너무 낮아 상대적으로 무거운 안료들의 침전에 의한 저장 안정성이 나빠질 수 있으며, 60 중량% 초과인 경우에는 너무 높은 점도로 인하여 도료의 사용이 어려울 수 있으며, 분산수지의 함량이 부족하여 저장 안정성이 저하될 수 있다.The pigment paste composition may have a solid content of 40% to 60% by weight. When the solids content of the pigment paste composition is less than 40% by weight, the viscosity of the pigment paste may be so low that the storage stability due to precipitation of relatively heavy pigments may deteriorate, and when the amount of the pigment paste is greater than 60% by weight, the paint may be too high. It may be difficult to use, and the storage stability may be deteriorated due to insufficient content of the dispersion resin.
<분산수지><Dispersion Balance>
본 발명의 안료 페이스트 조성물에 포함되는 분산수지는 안료의 웨팅성(wetting)을 향상시키는 기능을 한다.The dispersion resin contained in the pigment paste composition of the present invention functions to improve the wettability of the pigment.
상기 분산수지는 전술한 베이스 수지와 유사한 양이온 구조를 갖는 수지(예를 들어, 아민 변성 에폭시 수지)가 사용될 수 있고, 예를 들어, 옥사졸리돈(oxazolidone)을 함유한 분산수지일 수 있고, 4급 암모늄염의 형태를 가지는 분산수지일 수 있으나, 이에 한정되는 것은 아니다.The dispersion resin may be a resin having a cationic structure similar to that of the base resin (for example, an amine-modified epoxy resin), and may be, for example, a dispersion resin containing oxazolidone. It may be a dispersion resin having a form of a quaternary ammonium salt, but is not limited thereto.
<경화 촉매><Curing Catalyst>
본 발명에 이용되는 안료 페이스트 조성물은 경화 촉매를 더 포함할 수 있고, 상기 경화 촉매는 안료 페이스트 조성물 또는 최종 제조된 전착 도료의 경화성을 향상시킬 수 있다.The pigment paste composition used in the present invention may further include a curing catalyst, and the curing catalyst may improve the curability of the pigment paste composition or the final electrodeposited paint.
상기 경화 촉매는 안료 페이스트 조성물에 사용되는 것이면 이에 한정되지 않으며, 구체적으로 주석 함유 화합물, 비스무스 함유 화합물, 또는 이들의 혼합물 등일 수 있다.The curing catalyst is not limited to those used in the pigment paste composition, specifically, may be a tin-containing compound, a bismuth-containing compound, or a mixture thereof.
상기 주석 함유 화합물은 예를 들어, 디부틸틴옥사이드, 디부틸틴디라우릴레이트, 디부틸틴클로라이드, 디옥틸틴클로라이드, 디옥틸틴옥사이드 또는 이들의 혼합물 등일 수 있다.The tin-containing compound may be, for example, dibutyl tin oxide, dibutyl tin dilaurylate, dibutyl tin chloride, dioctyl tin chloride, dioctyl tin oxide, or a mixture thereof.
상기 비스무스 함유 화합물은 예를 들어, Bi2O3 또는 Bi(OH)2가, 락트산(Lactic acid), 아세트산(Acetic acid), 포름산(Formic acid), 디메틸올프로피온산(Dimethylolpropionic acid, DMPA), 또는 메탄술폰산(Methanesulfonic acid, MSA) 등의 산과 혼합된 것일 수 있다.The bismuth-containing compound is, for example, Bi 2 O 3 or Bi (OH) divalent , lactic acid (Lactic acid), acetic acid (Acetic acid), formic acid (Formic acid), dimethylolpropionic acid (DMPA), or It may be mixed with an acid such as methanesulfonic acid (MSA).
상기 경화 촉매는 상기 분산수지 100 중량부를 기준으로 150 중량부 내지 200 중량부의 함량으로 포함될 수 있고, 예를 들어, 160 중량부 내지 180 중량부의 함량으로 포함될 수 있다. 경화촉매의 함량이 상기 분산수지 100 중량부를 기준으로 150 중량부 미만인 경우에는 도막의 경화성 저하에 따른 기계적 물성 및 내식성이 저하될 수 있고, 경화촉매의 함량이 200 중량부 초과인 경우에는 금속 산화물에 의한 저장 안정성이 저하될 수 있으며, 필요 이상의 촉매 함량에 따른 외관의 불량 및 원재료비의 상승을 초래할 수 있다.The curing catalyst may be included in an amount of 150 parts by weight to 200 parts by weight based on 100 parts by weight of the dispersion resin, for example, 160 parts by weight to 180 parts by weight. When the content of the curing catalyst is less than 150 parts by weight based on 100 parts by weight of the dispersion resin, mechanical properties and corrosion resistance may be lowered due to the lowering of curability of the coating film, and when the content of the curing catalyst is greater than 200 parts by weight, The storage stability may be lowered, resulting in poor appearance and an increase in raw material costs depending on the catalyst content.
<안료><Pigment>
본 발명에 이용되는 안료 페이스트 조성물에 포함되는 안료는 도장의 외관을 우수하게 한다.The pigment contained in the pigment paste composition used for this invention makes the appearance of coating excellent.
상기 안료는 통상적으로 사용되는 무기 안료가 사용될 수 있다. 상기 무기 안료는 예를 들어, 산화티타늄, 산화아연, 황화아연, 카올린, 점토, 탄산칼슘, 탈크(talc), 실리카, 산화철, 크롬산납, 카드뮴, 산화크롬, 카본블랙, 징크크로메이트, 스트론튬크로메이트, 아연포스페이트, 인산염, 규산염 등일 수 있으나, 이에 한정되는 것은 아니다.As the pigment, a commonly used inorganic pigment may be used. The inorganic pigment may be, for example, titanium oxide, zinc oxide, zinc sulfide, kaolin, clay, calcium carbonate, talc, silica, iron oxide, lead chromate, cadmium, chromium oxide, carbon black, zinc chromate, strontium chromate, Zinc phosphate, phosphate, silicate, and the like, but is not limited thereto.
상기 안료는 상기 분산수지 100 중량부를 기준으로 250 중량부 내지 300 중량부의 함량으로 포함될 수 있고, 예를 들어, 260 중량부 내지 280 중량부의 함량으로 포함될 수 있다. 상기 안료의 함량이 상기 분산수지 100 중량부를 기준으로 250 중량부 미만인 경우에는 소지에 대한 은폐력 저하 및 차체의 엣지(edge) 쪽의 커버력이 불량해질 수 있고, 300 중량부 초과인 경우에는 도막의 외관이 저하되며 전착과정에서의 작업성이 저하될 수 있다.The pigment may be included in an amount of 250 parts by weight to 300 parts by weight based on 100 parts by weight of the dispersion resin, for example, may be included in an amount of 260 parts by weight to 280 parts by weight. When the content of the pigment is less than 250 parts by weight based on 100 parts by weight of the dispersion resin, the hiding power to the base and the cover power of the edge (edge) of the vehicle body may be poor, when the content of the coating film is greater than 300 parts by weight This is deteriorated and workability in the electrodeposition process may be deteriorated.
<기타 첨가제><Other additives>
상기 안료 페이스트 조성물은 안료 페이스트 조성물의 고형분 함량 조절, 산성, 점도 제어 및 전착 도장을 위해 용제를 더 포함할 수 있다. 상기 용제는 통상적으로 공지된 것을 사용할 수 있고, 예를 들어 2,2,4-트리메틸-1,3-펜탄다이올 디이소부티레이트(2,2,4-trimethyl-1,3-pentanediol diisobutyrate) 등일 수 있다.The pigment paste composition may further include a solvent for solid content control, acidity, viscosity control and electrodeposition coating of the pigment paste composition. The solvent may be a conventionally known one, for example 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (2,2,4-trimethyl-1,3-pentanediol diisobutyrate) and the like Can be.
또한, 상기 안료 페이스트 조성물은 이를 이용하여 형성되는 도막의 물성을 높이기 위해 통상적으로 공지된 소포제, 표면 조정제, 분산제, pH 조절제 등을 더 포함할 수 있다. 상기 첨가제는 상기 분산수지 100 중량부를 기준으로 10 중량부 내지 20 중량부의 함량으로 포함될 수 있다.In addition, the pigment paste composition may further include a conventionally known antifoaming agent, surface regulator, dispersant, pH adjuster and the like to increase the physical properties of the coating film formed by using the same. The additive may be included in an amount of 10 parts by weight to 20 parts by weight based on 100 parts by weight of the dispersion resin.
3. 전착 도료3. Electrodeposition paint
또한, 본 발명은 전착 수지 조성물과 안료 페이스트 조성물을 포함하는 전착 도료를 제공한다.Furthermore, this invention provides the electrodeposition paint containing an electrodeposition resin composition and a pigment paste composition.
본 발명의 전착 도료는 상기 '1. 전착 수지 조성물' 항목에서 설명한 전착 수지 조성물과 '2. 안료 페이스트 조성물' 항목에서 설명한 안료 페이스트 조성물을 포함할 수 있다.Electrodeposition paint of the present invention is the '1. The electrodeposition resin composition described in the section 'Electrodeling resin composition' and '2. Pigment paste composition described in the section 'Pigment Paste Composition'.
본 발명의 전착 도료는 전착 수지 조성물에 2종의 에폭시 수지를 포함하는 에폭시 수지와, 2종의 경화제를 포함하는 경화제를 도입하여, 전착 도료의 내부 도장성과 작업성을 우수하게 하는 효과가 있다.The electrodeposition coating material of this invention introduce | transduces the epoxy resin containing two types of epoxy resins, and the hardening | curing agent containing two types of hardening | curing agents to an electrodeposition resin composition, and there exists an effect which makes it excellent in the internal coating property and workability of an electrodeposition coating material.
상기 전착 도료에 포함되는 상기 전착 수지 조성물과 상기 안료 페이스트 조성물은 5:1 내지 9:1의 중량비, 예를 들어, 6:1 내지 8:1의 중량비로 혼합될 수 있다. 상기 전착 수지 조성물과 안료 페이스트 조성물의 비율이 상기 범위를 만족하는 경우에, 도막의 방청성과 부착성이 우수하면서도, 전착 도료의 내부 도장성과 작업성을 개선하여, 자동차, 가전 등의 전착 도장 시 유용하게 사용될 수 있다.The electrodeposition resin composition and the pigment paste composition included in the electrodeposition paint may be mixed in a weight ratio of 5: 1 to 9: 1, for example, in a weight ratio of 6: 1 to 8: 1. When the ratio of the electrodeposition resin composition and the pigment paste composition satisfies the above range, the coating film is excellent in rust prevention and adhesion, while improving the internal coating property and workability of the electrodeposition paint, and is useful for electrodeposition coating of automobiles and home appliances. Can be used.
이하 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the invention, the present invention is not limited by the following examples.
[제조예 1] - 에폭시 수지 A의 제조(제2 에폭시 수지)Production Example 1 Preparation of Epoxy Resin A (2nd Epoxy Resin)
12 중량부의 메톡시 프로판올, 7.5 중량부의 디에틸렌트리아민(DETA), 2.5 중량부의 폴리설파이드 화합물을 혼합하여 50~100℃로 승온하고 일정 온도를 유지하면서 55 중량부의 Cardura E10-p를 3시간 적가한다. 적가 후 일정시간 유지하고 15.2 중량부의 에폭시(에폭시 당량 187g/eq.)를 반응시켜 7.8 중량부의 알코올 용제로 희석하여 수지를 제조한다. 제조된 수지의 Epoxy Amine Value(EPA VALUE)가 2.15 이고, 중량평균분자량이 4,300이고, 점도(브룩필드 점도계(Brookfield Viscometer)로 25 ℃에서 측정시)가 4,200 cPs이고, 고형분 함량이 80 중량%인 에폭시 수지 A를 제조하였다.12 parts by weight of methoxy propanol, 7.5 parts by weight of diethylenetriamine (DETA) and 2.5 parts by weight of polysulfide compound were mixed, and the temperature was raised to 50-100 ° C. and 55 parts by weight of Cardura E10-p was added dropwise for 3 hours. do. After dropping, the mixture was kept for a certain time and reacted with 15.2 parts by weight of epoxy (epoxy equivalent 187 g / eq.) To dilute with 7.8 parts by weight of alcohol solvent to prepare a resin. Epoxy Amine Value (EPA VALUE) is 2.15, weight average molecular weight is 4,300, viscosity (measured at 25 ° C with Brookfield Viscometer) is 4,200 cPs, solid content is 80% by weight. Epoxy Resin A was prepared.
[제조예 2] - 에폭시 수지 A-1의 제조(제2 에폭시 수지)Production Example 2 Preparation of Epoxy Resin A-1 (Second Epoxy Resin)
12.6 중량부의 메톡시 프로판올, 6.5 중량부의 디에틸렌트리아민(DETA)을 혼합하여 50~100℃로 승온하고 일정 온도를 유지하면서 57.5 중량부의 Cardura E10-p를 3시간 적가한다. 적가 후 일정시간 유지하고 16 중량부의 에폭시(에폭시 당량 187g/eq.)를 반응시켜 7.4 중량부의 알코올 용제로 희석하여 수지를 제조한다. 제조된 수지의 Epoxy Amine Value(EPA VALUE)가 2.15 이고, 중량평균분자량이 4,100이고, 점도(브룩필드 점도계(Brookfield Viscometer)로 25 ℃에서 측정시)가 3,900 cPs이고, 고형분 함량이 80 중량%인 에폭시 수지 A-1를 제조하였다.12.6 parts by weight of methoxy propanol and 6.5 parts by weight of diethylenetriamine (DETA) are mixed and heated to 50-100 ° C. and 57.5 parts by weight of Cardura E10-p is added dropwise for 3 hours while maintaining a constant temperature. After dropping, the mixture was kept for a certain time and reacted with 16 parts by weight of epoxy (epoxy equivalent 187 g / eq.) To dilute with 7.4 parts by weight of alcohol solvent to prepare a resin. Epoxy Amine Value (EPA VALUE) is 2.15, weight average molecular weight is 4,100, viscosity (measured at 25 ° C with Brookfield Viscometer) is 3,900 cPs, solid content is 80% by weight. Epoxy Resin A-1 was prepared.
[실시예 1]Example 1
기계적 교반기, 냉각기, 가열기 및 온도계를 장착한 분리형 반응기의 상부 반응기에 11.8 중량부의 YD-128(국도화학), 3.5 중량부의 BPA(Bisphenol A), 4.3 중량부의 에톡시 변성 BPA(ethoxylated BPA, 한농화성, BSA-60), 3.4 중량부의 에폭시 수지 A, 1 중량부의 메톡시 프로판올(methoxy propanol)을 넣고 125℃로 승온하고, 0.1 중량부의 디메틸 벤질아민(dimethyl benzylamine)을 넣은 후 온도를 145℃에서 유지하면서 에폭시 당량을 측정하여 목표값에 도달할 때까지 유지하였다.11.8 parts by weight of YD-128 (Kukdo Chemical), 3.5 parts by weight of Bisphenol A (BPA), 4.3 parts by weight of ethoxylated BPA (ethoxylated BPA), concentrated in the upper reactor of a separate reactor equipped with a mechanical stirrer, a cooler, a heater and a thermometer. , BSA-60), 3.4 parts by weight of epoxy resin A, 1 part by weight of methoxy propanol was added to increase the temperature to 125 ℃, 0.1 parts by weight of dimethyl benzylamine (insert dimethyl benzylamine) and the temperature was maintained at 145 ℃ While the epoxy equivalent was measured and maintained until the target value was reached.
에폭시 당량이 도달되면 10.0 중량부의 경화제 A와 6.7 중량부의 경화제 B를 투입한 후 110℃에서 1.3 중량부의 디에탄올아민(diethanol amine)과 1.2 중량부의 디케티민(diketimine)을 넣고 125℃에서 일정 시간을 유지하고, 진공회수로 용제를 회수하였다.When the epoxy equivalent is reached, 10.0 parts by weight of curing agent A and 6.7 parts by weight of curing agent B are added. Then, 1.3 parts by weight of diethanolamine and 1.2 parts by weight of diketimine are added at 110 ° C., and a predetermined time is maintained at 125 ° C. The solvent was recovered by vacuum recovery.
회수가 끝나면 수지 반응물을 70중량%의 메틸설폰산(methyl sulfonic acid) 1.4 중량부와 DIW 33.5 중량부가 담긴 반응기로 이송하면서 1차 수분산을 실시하였다. 수분산하고 1시간 교반한 다음에 추가로 DIW 21.4 중량부를 넣고 점도를 떨어뜨렸다. 온도 45℃이하에서 0.51 중량부의 마이크로겔(microgel rheorol 200, 나노캠택), 0.2 중량부의 소포제(SAN NOPCO LTD., SN-180), 0.4 중량부의 부틸셀로솔브(butyl cellosolve), 0.9 중량부의 Flowing agent를 순서대로 넣는다. 상기 제조된 전착 수지 조성물은 고형분의 함량이 36 중량%였다.After the recovery, the resin reactant was transferred to a reactor containing 1.4 parts by weight of 70% by weight of methyl sulfonic acid and 33.5 parts by weight of DIW to carry out the first aqueous dispersion. After water dispersion and stirring for 1 hour, 21.4 parts by weight of DIW was further added to lower the viscosity. 0.51 parts by weight of microgel (microgel rheorol 200, nanocamtack), 0.2 parts by weight of antifoaming agent (SAN NOPCO LTD., SN-180), 0.4 parts by weight of butyl cellosolve, and 0.9 parts by weight of flow below 45 ° C. Put the agents in order. The prepared electrodeposition resin composition had a solid content of 36% by weight.
[실시예 2]Example 2
상기 실시예 1에 있어서, 3.4 중량부의 에폭시 수지 A 대신 4.3 중량부의 에폭시 수지 A를 첨가하는 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 전착 수지 조성물을 제조하였다.In Example 1, an electrodeposition resin composition was prepared in the same manner as in Example 1, except that 4.3 parts by weight of epoxy resin A was added instead of 3.4 parts by weight of epoxy resin A.
[실시예 3]Example 3
상기 실시예 1에 있어서, 3.4 중량부의 에폭시 수지 A를 첨가하는 것을 생략하고, 나머지는 상기 실시예 1과 동일한 방법으로 전착 수지 조성물을 제조하였다.In the said Example 1, adding 3.4 weight part of epoxy resin A was abbreviate | omitted, and the remainder produced the electrodeposition resin composition by the method similar to the said Example 1.
[실시예 4]Example 4
상기 실시예 1에 있어서, 3.4 중량부의 에폭시 수지 A 대신 3.4 중량부의 에폭시 수지 A-1을 첨가하는 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 전착 수지 조성물을 제조하였다.In Example 1, an electrodeposition resin composition was prepared in the same manner as in Example 1, except that 3.4 parts by weight of epoxy resin A-1 was added instead of 3.4 parts by weight of epoxy resin A.
[비교예 1]Comparative Example 1
기계적 교반기, 냉각기, 가열기 및 온도계를 장착한 분리형 반응기의 상부 반응기에 2.4 중량부의 YD-128(국도화학), 14.2 중량부의 N8010 65% in BC(Butyl Cellosolve)(KCC), 9.5 중량부의 에폭시 수지 A, 0.9 중량부의 메톡시 프로판올(methoxy propanol)을 넣고 80℃로 승온하고, 1.4 중량부의 디에탄올아민(diethanol amine)을 넣고, 0.7 중량부의 디메틸아미노프로필아민(Dimethyl amino propylamine)을 넣고 125℃로 승온하여 90분간 유지하였다.2.4 parts by weight of YD-128 (Kukdo Chemical), 14.2 parts by weight of N8010 65% in BC (Butyl Cellosolve) (KCC), 9.5 parts by weight of epoxy resin A in a top reactor of a separate reactor equipped with a mechanical stirrer, a cooler, a heater and a thermometer. , 0.9 parts by weight of methoxy propanol was added to raise the temperature to 80 ℃, 1.4 parts by weight of diethanolamine (diethanol amine) was added, 0.7 parts by weight of dimethyl amino propylamine (dimethyl amino propylamine) was added to raise the temperature to 125 ℃ Was maintained for 90 minutes.
이어서, 6.8 중량부의 메톡시 프로판올을 회수하고, 7.75 중량부의 경화제 A와 7.75 중량부의 경화제 B를 투입한 후 반응 생성물을 0.6 중량부의 초산(Formic acid)와 28.4 중량부의 DIW가 담긴 분산조로 이송하였다. 수분산 단계에서 온도가 40℃~50℃이 되도록 유지하고, 수분산이 종료되면 추가로 4.0 중량부의 DIW와 14.2 중량부의 DIW를 차례대로 투입하고, 1.5 중량부의 Flowing agent DW-500(KS 케미칼, alkyl type anti-cratering agent), 4.8 중량부의 microgel Rheorol 200(나노캠택)을 순서대로 투입하고 분산을 종료하였다.Subsequently, 6.8 parts by weight of methoxy propanol was recovered, 7.75 parts by weight of curing agent A and 7.75 parts by weight of curing agent B were added, and the reaction product was transferred to a dispersion tank containing 0.6 parts by weight of acetic acid and 28.4 parts by weight of DIW. In the dispersion step, the temperature is maintained at 40 ° C. to 50 ° C., and when the dispersion is completed, additional 4.0 parts by weight of DIW and 14.2 parts by weight of DIW are sequentially added, and 1.5 parts by weight of Flowing agent DW-500 (KS Chemical, Alkyl type anti-cratering agent), 4.8 parts by weight of microgel Rheorol 200 (nanocamtack) was added in order to complete the dispersion.
상기 공정에서 아민 투입 후 자연발열이 심하게 일어나므로, 승온 시 자연발열을 감안하여 온도를 유지시켰다. 상기 제조된 전착 수지 조성물은 고형분의 함량이 36 중량% 였다.Since spontaneous heat generation occurs severely after the amine is added in the above process, the temperature was maintained in consideration of spontaneous heat generation at elevated temperature. The prepared electrodeposition resin composition had a solid content of 36% by weight.
[비교예 2]Comparative Example 2
상기 비교예 1에 있어서, 7.75 중량부의 경화제 A와 7.75 중량부의 경화제 B를 투입하는 것 대신 15.5 중량부의 경화제 A만 투입하는 것을 제외하고는, 상기 비교예 1과 동일한 방법으로 전착 수지 조성물을 제조하였다.In Comparative Example 1, an electrodeposition resin composition was prepared in the same manner as in Comparative Example 1, except that only 15.5 parts by weight of curing agent A was added instead of 7.75 parts by weight of curing agent A and 7.75 parts by weight of curing agent B. .
[비교예 3]Comparative Example 3
상기 비교예 1에 있어서, 7.75 중량부의 경화제 A와 7.75 중량부의 경화제 B를 투입하는 것 대신 15.5 중량부의 경화제 B만 투입하는 것을 제외하고는, 상기 비교예 1과 동일한 방법으로 전착 수지 조성물을 제조하였다.In Comparative Example 1, an electrodeposition resin composition was prepared in the same manner as in Comparative Example 1, except that only 15.5 parts by weight of curing agent B was added instead of 7.75 parts by weight of curing agent A and 7.75 parts by weight of curing agent B. .
상기 실시예 1 내지 3에서 제조된 전착 수지 조성물의 원료와 함량비는 하기 표 1에, 상기 비교예 1 내지 3에서 제조된 전착 수지 조성물의 원료와 함량비는 하기 표 2에 나타내었다.Raw material and content ratios of the electrodeposition resin compositions prepared in Examples 1 to 3 are shown in Table 1 below, and raw material and content ratios of the electrodeposition resin compositions prepared in Comparative Examples 1 to 3 are shown in Table 2 below.
성분ingredient 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4
1. YD-128(국도화학)1.YD-128 (Kukdo Chemical) 11.811.8 11.811.8 11.811.8 11.811.8
2. BPA(LG 화학)2. BPA (LG Chemistry) 3.53.5 3.53.5 3.53.5 3.53.5
3. Ethoxylated BPA(한농화성/BSA-60)3.Ethoxylated BPA (Hanogenicity / BSA-60) 4.34.3 4.34.3 4.34.3 4.34.3
4. 에폭시 수지 A4. Epoxy Resin A 3.43.4 4.34.3 -- --
4-1. 에폭시 수지 A-14-1. Epoxy Resin A-1 -- -- -- 3.43.4
5. Methoxy propanol5. Methoxy propanol 1.01.0 1.01.0 1.01.0 1.01.0
6. Dimethyl benzylamine6.Dimethyl benzylamine 0.10.1 0.10.1 0.10.1 0.10.1
7. 경화제 A7. Curing agent A 10.010.0 10.010.0 10.010.0 10.010.0
8. 경화제 B8. Curing Agent B 6.76.7 6.76.7 6.76.7 6.76.7
9. Diethanol amine9.Diethanol amine 1.31.3 1.31.3 1.31.3 1.31.3
10. Diketimine10.Diketimine 1.21.2 1.21.2 1.21.2 1.21.2
11. 용제 회수11. Solvent Recovery -1.5-1.5 -1.5-1.5 -1.5-1.5 -1.5-1.5
12. MSA(70중량%)12.MSA (70% by weight) 1.41.4 1.41.4 1.41.4 1.41.4
13. DIW13. DIW 33.533.5 33.533.5 33.533.5 33.533.5
14. DIW14. DIW 21.421.4 21.421.4 21.421.4 21.421.4
15. Microgel Rheorol 200(나노캠택)15.Microgel Rheorol 200 (nano cam tag) 0.510.51 0.510.51 0.540.54 0.510.51
16. 소포제(SAN NOPCO LTD./SN-180)16. Defoamer (SAN NOPCO LTD./SN-180) 0.20.2 0.20.2 0.20.2 0.20.2
17. Butyl cellosolve17.Butyl cellosolve 0.40.4 0.40.4 0.40.4 0.40.4
18. Flowing agent(KS 케미칼/DW-500)18.Flowing agent (KS Chemical / DW-500) 0.90.9 0.90.9 0.90.9 0.90.9
TotalTotal 100.11100.11 101.01101.01 96.7496.74 100.11100.11
성분ingredient 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3
1. YD-128(국도화학)1.YD-128 (Kukdo Chemical) 2.42.4 2.42.4 2.42.4
2. N8010 65% in BC(KCC)2.N8010 65% in BC (KCC) 14.214.2 14.214.2 14.214.2
3. 에폭시 수지 A3. Epoxy Resin A 9.59.5 9.59.5 9.59.5
4. Methoxy propanol4. Methoxy propanol 0.90.9 0.90.9 0.90.9
5. Diethanol amine5.Diethanol amine 1.41.4 1.41.4 1.41.4
6. Dimethyl amino propylamine6.Dimethyl amino propylamine 0.70.7 0.70.7 0.70.7
7. Methoxy propanol7. Methoxy propanol -6.8-6.8 -6.8-6.8 -6.8-6.8
8. 경화제 A8. Curing Agent A 7.757.75 15.515.5 --
9. 경화제 B9. Curing agent B 7.757.75 -- 15.515.5
10. Formic acid10.Formic acid 0.60.6 0.60.6 0.60.6
11. DIW11.DIW 28.428.4 28.428.4 28.428.4
12. DIW12.DIW 4.04.0 4.04.0 4.04.0
13. DIW13. DIW 14.214.2 14.214.2 14.214.2
14. Flowing agent(KS 케미칼/DW-500)14.Flowing agent (KS Chemical / DW-500) 1.41.4 1.41.4 1.41.4
15. Microgel Rheorol 200(나노캠택)15.Microgel Rheorol 200 (nano cam tag) 4.84.8 4.84.8 4.84.8
16. DIW16. DIW 8.78.7 8.78.7 8.78.7
TotalTotal 99.999.9 99.999.9 99.999.9
[실험예]Experimental Example
상기 실시예 1 내지 4 및 비교예 1 내지 3에서 제조한 전착 수지 조성물과, 안료 페이스트 조성물을 7:1의 중량비로 혼합하여 전착 도료를 제조한 후, 시편에 도포하고 경화시켜 도막을 형성한 후, 형성된 도막의 물성을 평가하여 하기 표 3에 나타내었다.After the electrodeposition resin composition prepared in Examples 1 to 4 and Comparative Examples 1 to 3 and the pigment paste composition were mixed at a weight ratio of 7: 1 to prepare an electrodeposition paint, the specimen was coated and cured to form a coating film. , The physical properties of the formed coating film was evaluated and shown in Table 3 below.
1. 도막 두께: 높을수록 고광택1. Coating thickness: the higher the gloss
2. GA 적성: GA는 갈바니 시편이며, 전착 도장하면서 발생되는 수소 가스가 표면이 거친 갈바니 표면에서 물 분해된 H2가 빠져나오면서 도막에 기포가 발생하는데, 이 때 외관의 상태에 따른 차이를 비교(○(좋음), △(양호), ×(나쁨))2. GA aptitude: GA is galvanic specimen, and hydrogen gas generated during electrodeposition coating undergoes air bubbles in the coating film as H 2 decomposed from the surface of galvanic surface with rough surface. At this time, the difference in appearance is compared. (○ (good), △ (good), × (bad))
3. T/P: 외곽 도막과 내부 도막의 편차(G/A)는 하기 그림과 같은 방법으로 평가될 수 있음. (높을수록 내부 도장성이 좋음)3. T / P: The deviation (G / A) between the outer coating and the inner coating can be evaluated in the following way. (The higher the better internal paintability)
Figure PCTKR2018016786-appb-I000001
Figure PCTKR2018016786-appb-I000001
4. 경화성: 높을수록 경화성 우수4. Curability: the higher the better the curability
5. 욕액 소포/발포: 기포감소율이 높을수록 좋음5. Bath solution defoaming / foaming: the higher the bubble reduction rate, the better
6. 굴곡성: 높을수록 좋음6. Flexibility: the higher the better
항목Item 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3
도막두께(수직/수평 도막두께(㎛))Coating Thickness (Vertical / Horizontal Coating Thickness (µm)) 240V(직류전류)240 V (DC current) 19.1/19.219.1 / 19.2 20.4/20.120.4 / 20.1 18.3/17.418.3 / 17.4 19.1/18.319.1 / 18.3 21.0/20.521.0 / 20.5 20.6/19.520.6 / 19.5 22.6/20.722.6 / 20.7
광택(수직/수평 도막두께(㎛))Gloss (Vertical / Horizontal Film Thickness (μm)) 60도60 degrees 91/9291/92 87/8387/83 98/9698/96 94/8694/86 86/8686/86 92/8292/82 90/7990/79
GA 적성GA aptitude 200V200 V ○○ ○○ △△ ○○ ○○ △△ △△
220V220 V ХХ ХХ ХХ △△ ХХ ХХ ХХ
T/P(%)(4Box)220VT / P (%) (4Box) 220V AA 15.915.9 16.916.9 17.917.9 19.119.1 20.820.8 21.521.5 22.522.5
DD 11.311.3 11.211.2 12.812.8 13.113.1 15.315.3 14.814.8 15.215.2
GG 9.89.8 9.99.9 10.910.9 11.511.5 1111 11.511.5 11.811.8
D/AD / A 71.171.1 66.366.3 71.571.5 68.668.6 73.673.6 68.868.8 67.567.5
G/AG / A 61.661.6 58.658.6 60.960.9 60.260.2 52.952.9 53.553.5 52.452.4
경화성(MIBK Rubbing 횟수)Curability (MIBK Rubbing Count) 160℃160 ℃ 50↑50 ↑ 50↑50 ↑ 50↑50 ↑ 50↑50 ↑ 50↑50 ↑ 50↑50 ↑ 50↑50 ↑
욕액소포/발포(ml)TestBath solution vesicle / foaming (ml) Test 초기Early 300300 305305 290290 310310 290290 285285 295295
1010 295295 300300 280280 305305 280280 270270 280280
2020 275275 295295 270270 290290 275275 250250 260260
3030 265265 290290 260260 275275 260260 235235 230230
6060 230230 280280 225225 225225 235235 210210 215215
120120 210210 275275 210210 205205 220220 200200 205205
기계적 물성Mechanical properties Impact(1/2inchХ1000g)Impact (1 / 2inchХ1000g) 50cm50 cm 50cm50 cm 50cm50 cm 50cm50 cm 50cm50 cm 50cm50 cm 50cm50 cm
Impact3/8inchХ1000g)Impact3 / 8inchХ1000g) 50cm50 cm 50cm50 cm 50cm50 cm 50cm50 cm 50cm50 cm 50cm50 cm 50cm50 cm
Cross cutCross cut M-1M-1 M-1M-1 M-1M-1 M-1M-1 M-1M-1 M-1M-1 M-1M-1
굴곡성Flexibility 8~9mm8-9mm 8mm8 mm 8~9mm8-9mm 8~9mm8-9mm 7mm7 mm 7mm7 mm 7mm7 mm
전처리 carry over 작업성Pretreatment carry over workability 티없음No tee 티없음No tee 티없음No tee 티없음No tee 티없음No tee 티없음No tee 티없음No tee
상기 표 3을 참조하면, 본 발명에 해당되는 실시예 1 내지 4의 전착 수지 조성물을 이용하는 전착 도료는 비교예 1 내지 3과 비교하여, 도막의 굴곡성이 우수하고, T/P(%) 값이 우세하여 내부 도장성(전착 도료가 내부로 침투되어 도막이 올라 가는 현상)이 향상되는 것을 확인할 수 있다.Referring to Table 3, the electrodeposition coating material using the electrodeposition resin composition of Examples 1 to 4 corresponding to the present invention is excellent in the flexibility of the coating film, compared to Comparative Examples 1 to 3, the T / P (%) value is It can be confirmed that the internal coating property (phenomena in which the electrodeposition paint penetrates into the inside and the coating film rises) is improved in a predominant manner.
이상에서 본 발명은 기재된 실시예에 대해서만 상세히 설명되었지만 본 발명의 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속함은 당연한 것이다.Although the present invention has been described in detail only with respect to the embodiments described, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical spirit of the present invention, and such modifications and variations belong to the appended claims.

Claims (10)

  1. 에폭시 수지, 경화제 및 아민 화합물을 포함하고,Comprising an epoxy resin, a curing agent and an amine compound,
    상기 경화제는 1가 알코올 및 2가 알코올로 차단된 이소시아네이트 화합물을 포함하는 제1 경화제와 1가 알코올 및 3가 알코올로 차단된 이소시아네이트 화합물을 포함하는 제2 경화제를 포함하는 것인 전착 수지 조성물.The curing agent is an electrodeposition resin composition comprising a first curing agent comprising an isocyanate compound blocked with a monohydric alcohol and a dihydric alcohol and a second curing agent comprising an isocyanate compound blocked with a monohydric alcohol and a trihydric alcohol.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 경화제는, 상기 제1 경화제와 상기 제2 경화제를 1:4 내지 9:1의 중량비로 포함하는 것인 전착 수지 조성물.The said hardening | curing agent contains the said 1st hardening | curing agent and the said 2nd hardening | curing agent in the weight ratio of 1: 4-9: 1.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 에폭시 수지는 제1 에폭시 수지와 제2 에폭시 수지를 포함하고,The epoxy resin includes a first epoxy resin and a second epoxy resin,
    상기 제1 에폭시 수지는 비스페놀형 에폭시 수지를 포함하고,The first epoxy resin includes a bisphenol type epoxy resin,
    상기 제2 에폭시 수지는 말단에 1차 아민기를 갖는 화합물로부터 유래되는 단위, 설파이드 화합물로부터 유래되는 단위 및 에폭시 화합물로부터 유래되는 단위 중에서 선택되는 적어도 하나를 포함하는 것인 전착 수지 조성물.The said 2nd epoxy resin is an electrodeposition resin composition containing at least 1 selected from the unit derived from the compound which has a primary amine group at the terminal, the unit derived from a sulfide compound, and the unit derived from an epoxy compound.
  4. 청구항 3에 있어서,The method according to claim 3,
    상기 에폭시 수지는, 상기 제1 에폭시 수지와 상기 제2 에폭시 수지를 3:1 내지 7:1의 중량비로 포함하는 것인 전착 수지 조성물.The said epoxy resin is an electrodeposition resin composition containing the said 1st epoxy resin and the said 2nd epoxy resin in the weight ratio of 3: 1-7: 1.
  5. 청구항 3에 있어서,The method according to claim 3,
    상기 말단에 1차 아민기를 갖는 화합물은 하기 화학식 1로 표시되는 구조를 포함하는 것인 전착 수지 조성물.The electrodeposition resin composition in which the compound which has a primary amine group at the said terminal contains the structure represented by following formula (1).
    [화학식 1][Formula 1]
    NH2-(CH2)n-NH-(CH2)m-NH2 NH 2- (CH 2 ) n -NH- (CH 2 ) m -NH 2
    (화학식 1에서, n 및 m은 각각 1 내지 20의 수이다.)(In Formula 1, n and m are each a number from 1 to 20.)
  6. 청구항 3에 있어서,The method according to claim 3,
    상기 설파이드 화합물은 하기 화학식 2로 표시되는 구조를 포함하는 것인 전착 수지 조성물.The sulfide compound is an electrodeposition resin composition comprising a structure represented by the following formula (2).
    [화학식 2][Formula 2]
    HS-(CH2CH2-O-CH2-O-CH2CH2-S-S)a-CH2CH2-O-CH2-O-CH2CH2-SHHS- (CH 2 CH 2 -O-CH 2 -O-CH 2 CH 2 -SS) a -CH 2 CH 2 -O-CH 2 -O-CH 2 CH 2 -SH
    (화학식 2에 있어서, a는 0 내지 50의 수이다.)(In Formula 2, a is a number of 0-50.)
  7. 청구항 3에 있어서,The method according to claim 3,
    상기 에폭시 화합물은 중량평균분자량이 300 g/mol 내지 2,000 g/mol이고, 에폭시 당량(EEW)이 150 g/eq. 내지 1,000 g/eq.인 것인 전착 수지 조성물.The epoxy compound has a weight average molecular weight of 300 g / mol to 2,000 g / mol, epoxy equivalent (EEW) of 150 g / eq. To 1,000 g / eq. Electrodeposition resin composition.
  8. 청구항 1에 있어서,The method according to claim 1,
    상기 에폭시 수지 100 중량부를 기준으로,Based on 100 parts by weight of the epoxy resin,
    상기 경화제는 50 중량부 내지 80 중량부의 함량으로 포함되고,The hardener is included in an amount of 50 parts by weight to 80 parts by weight,
    상기 아민 화합물은 5 중량부 내지 15 중량부의 함량으로 포함되는 것인 전착 수지 조성물.The amine compound is an electrodeposition resin composition is contained in an amount of 5 parts by weight to 15 parts by weight.
  9. 청구항 1에 있어서,The method according to claim 1,
    상기 전착 수지 조성물은 유기 용제, 에폭시 중화제 및 첨가제로 이루어진 군에서 선택되는 적어도 하나를 포함하는 것인 전착 수지 조성물.The electrodeposition resin composition is an electrodeposition resin composition comprising at least one selected from the group consisting of an organic solvent, an epoxy neutralizer and an additive.
  10. 청구항 1 내지 청구항 9 중 어느 한 항에 따른 전착 수지 조성물과 안료 페이스트 조성물을 포함하는 것인 전착 도료.The electrodeposition coating material containing the electrodeposition resin composition and pigment paste composition of any one of Claims 1-9.
PCT/KR2018/016786 2018-03-23 2018-12-27 Electrodeposition resin composition and electrodeposition paint comprising same WO2019182233A1 (en)

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KR100831205B1 (en) * 2006-12-31 2008-05-21 주식회사 케이씨씨 A cathodic electrodeposition coating compositions having improved appearance, anti-corrosion resistance and flexibility
KR20140140833A (en) * 2013-05-30 2014-12-10 주식회사 케이씨씨 Urethane curing agent for electrodeposition coating with improved appearance and corrosion resistance, and a cationic resin composition for electrodeposition paint and an electrodeposition coating composition comprising the same
JP2015218355A (en) * 2014-05-16 2015-12-07 神東アクサルタコーティングシステムズ株式会社 Coating method of cation electrodeposition paint

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JP4121166B2 (en) * 1996-02-28 2008-07-23 関西ペイント株式会社 Adhesive electrodeposition coating composition for transfer and pattern forming method using the same
JP5606211B2 (en) 2010-08-09 2014-10-15 株式会社シミズ Resin composition for electrodeposition paint, water-based electrodeposition paint, coating method and coated article

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JPH0733848A (en) * 1993-05-17 1995-02-03 Nippon Paint Co Ltd Modified epoxy resin having block isocyanate component and linked cationic group, its production and its use
KR20030017351A (en) * 2001-08-20 2003-03-03 간사이 페인트 가부시키가이샤 Water based intercoat coating composition and multi-layer coating film-forming method by use of the same
KR100831205B1 (en) * 2006-12-31 2008-05-21 주식회사 케이씨씨 A cathodic electrodeposition coating compositions having improved appearance, anti-corrosion resistance and flexibility
KR20140140833A (en) * 2013-05-30 2014-12-10 주식회사 케이씨씨 Urethane curing agent for electrodeposition coating with improved appearance and corrosion resistance, and a cationic resin composition for electrodeposition paint and an electrodeposition coating composition comprising the same
JP2015218355A (en) * 2014-05-16 2015-12-07 神東アクサルタコーティングシステムズ株式会社 Coating method of cation electrodeposition paint

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