WO2014199527A1 - Aqueous primer composition for paint removal use, and paint removal method - Google Patents

Aqueous primer composition for paint removal use, and paint removal method Download PDF

Info

Publication number
WO2014199527A1
WO2014199527A1 PCT/JP2013/078518 JP2013078518W WO2014199527A1 WO 2014199527 A1 WO2014199527 A1 WO 2014199527A1 JP 2013078518 W JP2013078518 W JP 2013078518W WO 2014199527 A1 WO2014199527 A1 WO 2014199527A1
Authority
WO
WIPO (PCT)
Prior art keywords
paint
polyurethane resin
primer composition
cationic polyurethane
aqueous primer
Prior art date
Application number
PCT/JP2013/078518
Other languages
French (fr)
Japanese (ja)
Inventor
修太郎 山本
和也 吉村
Original Assignee
株式会社ネオス
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社ネオス filed Critical 株式会社ネオス
Priority to JP2015522467A priority Critical patent/JPWO2014199527A1/en
Publication of WO2014199527A1 publication Critical patent/WO2014199527A1/en

Links

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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
    • C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
    • 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
    • C09D5/008—Temporary coatings

Definitions

  • the present invention is a paint that enables efficient removal of a hardened or uncured paint or paint film that adheres to and accumulates on coating equipment used in the painting process of various objects including the painting process of automobiles.
  • the present invention relates to a stripping aqueous primer composition and a coating stripping method.
  • Paint equipment is used in various painting processes, including the painting process of automobiles. If paint adheres to and accumulates on these painting equipment, workability and function will deteriorate, so every fixed period of time. In addition, it is necessary to peel and remove the hardened or uncured paint from the coating equipment.
  • masking jigs, slats, and painting booths may be used as painting instruments used in painting processes for painting objects such as automobiles.
  • various methods have been proposed as a coating film method that adheres to these coating instruments.
  • a method using a paint remover mainly composed of an organic solvent such as dichloromethane or thinner (ii) a method comprising heating an aqueous detergent mainly composed of caustic, (iii) incineration treatment And (iv) a method of applying a physical vibration or impact using a hammer, a scraper or the like, and (v) a method of coating a silicone resin or a fluororesin for preventing adhesion of a paint.
  • method (ii) there is a problem in safety because the concentration of the alkali component is high.
  • concentration of caustic alkali that is often used is 5% or more
  • handling is complicated because it is designated as a deleterious substance in the Poisonous and Deleterious Poison Control Law.
  • method (iii) has a problem in terms of air pollution because it involves generation of toxic exhaust gas.
  • the method (iv) not only is it difficult to completely peel off the details, but there is a high risk of deforming and damaging the coating instruments, and there is a problem that the working efficiency is extremely low.
  • a primer is coated in advance on the part of the coating equipment to which the paint adheres, and after the paint has adhered to and deposited to some extent in the painting process, a water-soluble paint remover (Patent Document 1) or a solvent is used. Some peel. When peeling with a water-soluble paint remover, polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble acrylic resin, etherified cellulose, etc. (Patent Documents 2, 3, 4, 5, 6) do not have sufficient peeling performance.
  • High viscosity grease is widely used as an oil-type paint peeling primer because it is inexpensive and effective, but it is easily dissolved in solvent-based paints, and water-based paints have repellency and do not adhere. Contamination of the surrounding environment also becomes a problem because it causes a decrease in productivity, such as leading to defective paint products due to dropped paint, and the grease itself is highly contaminated.
  • the present invention provides a cured or uncured paint or coating film that adheres to and accumulates on coating equipment used in various painting processes including automobile painting processes.
  • An object of the present invention is to provide an aqueous primer composition for stripping paint that enables efficient removal when stripping using a water-soluble paint stripper.
  • this invention relates to the water-based primer composition for paint peeling containing the following component.
  • Item 1. An aqueous primer composition for peeling paints, comprising at least one cationic polyurethane resin and water.
  • Item 2. The paint peeling agent according to Item 1, wherein the cationic polyurethane resin is a polyurethane resin having at least one cationic functional group selected from a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group.
  • Aqueous primer composition Item 3. Item 3.
  • Item 4. Item 4. The paint peeling according to any one of Items 1 to 3, wherein the cationic polyurethane resin is a polyether cationic polyurethane resin, a polyester cationic polyurethane resin, a polycarbonate cationic polyurethane resin, or a polycaprolactone cationic polyurethane resin.
  • Aqueous primer composition Item 5.
  • Item 6 The step of applying the aqueous primer composition for stripping paint according to any one of Items 1 to 5 to a coating device before coating, and applying a cured or uncured coating from the coating device using a coating stripper after coating A method for removing paint, comprising a step of removing.
  • water-based primer for removing paint cationic polyurethane resin
  • the attached paint will crack. Since the water-soluble paint remover penetrates into the cracks and dissolves and swells the coating, the adhering paint emerges from the surface of the coating equipment and peels easily and completely. Therefore, according to the water-based primer for removing paint of the present invention, it is possible to easily peel off the adhered and deposited paint even in a relatively difficult part such as a corner or a bent part of a painting tool in a short time. can do.
  • the aqueous primer composition for peeling paint according to the present invention contains a cationic polyurethane resin and water.
  • Cationic polyurethane resin is a reaction product of primary amino group, secondary amino group, tertiary amino group or phosphino group with acid such as hydrochloric acid, acetic acid, sulfuric acid, quaternary ammonium group, quaternary phosphonium group, etc.
  • acid such as hydrochloric acid, acetic acid, sulfuric acid, quaternary ammonium group, quaternary phosphonium group, etc.
  • Examples thereof include a polyurethane resin having a functional group, which is a polyurethane resin having at least one cationic functional group selected from a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group. It is preferable.
  • the cationic functional group may be contained in any of polyol, polyisocyanate, and urethane prepolymer.
  • the cationic polyurethane resin may be used alone or in combination of two or more.
  • Examples of the primary amino group, secondary amino group, and tertiary amino group include, for example, R 1 R 2 N— (C 2 H 4 —O) n — (C 3 H 6 —O) m — (in the formula, R 1 and R 2 are the same or different and are a hydrogen atom, an alkyl having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, preferably a straight chain or branched chain having 1 to 2 carbon atoms.
  • alkanolamines such as methyldiethanolamine, preferably quaternary ammonium groups, [R 1 R 2 R 3 N + - (C 2 H 4 - O) n- (C 3 H 6 -O) m ]-(wherein R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, Preferably an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, having a straight or branched chain, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, preferably carbon
  • the carbon number of the alkyl group and hydroxyalkyl group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 2.
  • Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and hydroxyalkyl includes hydroxylethyl, 2-hydroxypropyl, hydroxyisobutyl, hydroxypentyl, Hydroxyhexyl etc. can be mentioned.
  • the number of carbon atoms in the quaternary alkyl or hydroxyalkyl group is 11 or more, the water solubility of the resin is remarkably lowered and unstable, and the film formability is lowered.
  • the cationic polyurethane resin can be obtained by polycondensation of at least a part of the polyol substituted with the amino group or ammonium group and an aliphatic, alicyclic or aromatic polyisocyanate. As long as it has at least one cationic functional group, the polyol, polyisocyanate, and polymerization method are not particularly limited.
  • the skeleton of the polyurethane resin is classified into a polyether cationic polyurethane resin, a polyester cationic polyurethane resin, a polycarbonate cationic polyurethane resin, a polycaprolactone cationic polyurethane resin, etc., depending on the polyol component used. Any of them may be used and is not particularly limited.
  • polyol compound examples include a low molecular weight polyol having a molecular weight of 400 or less, a polyester polyol, a polyether polyol, a castor oil-based polyol, a polycarbonate polyol, or a hydrocarbon-based polyol.
  • a polyol compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Low molecular weight polyols having a molecular weight of 400 or less include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butane.
  • propane etc. can be mentioned, a trimethylol propane is preferable.
  • polyester polyol examples include a hydroxyl group-terminated esterified condensate obtained by reacting a low molecular weight polyol and a polyvalent carboxylic acid.
  • polyvalent carboxylic acid examples include succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrofuran acid, endomethine tetrahydrofuran acid, and hexahydrophthalic acid. It is done.
  • polyether polyol examples include those obtained by addition polymerization of alkylene oxide to the low molecular weight polyol such as bisphenol A, pentaerythritol, sorbitol, or sucrose.
  • alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide and the like.
  • Castor oil-based polyols include castor oil, hydrogenated castor oil, castor oil fatty acid, or hydrogenated hydrogenated castor oil fatty acid hydrogenated to castor oil, and the like. Moreover, the esterification reaction product of a castor oil fatty acid and a polyhydric alcohol, the polyol which carried out the addition polymerization of the alkylene oxide to these, etc. are mentioned.
  • polycarbonate polyol examples include conventionally known ones.
  • the polycarbonate polyol can be obtained, for example, by a reaction between the low molecular weight polyol and diphenyl carbonate or a reaction between the low molecular weight polyol and phosgene.
  • polyester polyol or polyether polyol is preferable from the viewpoint of corrosion resistance.
  • Polyester polyol obtained by reacting 1,4-butanediol and adipic acid, and polyether polyol obtained by adding alkylene oxide to bisphenol A are more preferable. preferable.
  • isocyanate compound examples include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate. In terms of being able to suppress discoloration of the resin, aliphatic polyisocyanate or Alicyclic polyisocyanates are preferred.
  • the isocyanate compounds may be used alone or in combination of two or more.
  • Aliphatic polyisocyanates include tetramethylene diisocyanate, dodecamethylene isocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine isocyanate, 2-methylpentane- Examples thereof include 1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate.
  • alicyclic polyisocyanates examples include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. be able to.
  • Aromatic polyisocyanates include tolylene diisocyanate, 2,2-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate (MDI), 4,4-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate.
  • MDI 4,4-diphenylmethane diisocyanate
  • Xylylene diisocyanate 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and the like.
  • araliphatic polyisocyanate examples include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, ⁇ , ⁇ , ⁇ , ⁇ -tetramethylxylylenezoisocyanate.
  • isocyanate compound dimers or trimers of the above polyisocyanates, modified products such as burette isocyanate, polymethylene polyphenyl polyisocyanate (polymeric MDI), and the like can be used.
  • isocyanate compound Preferred as the isocyanate compound are hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane.
  • the content of the cationic functional group of the cationic polyurethane resin is not particularly limited as long as the cationic polyurethane resin can form a stable dispersion without dissolving in the aqueous medium.
  • the cationic group of the conductive polyurethane resin is preferably contained in an amount of about 0.001 to 10 equivalent / kg, more preferably about 0.005 to 5 equivalent / kg, and still more preferably 0.01 to 3 equivalent / kg.
  • the cationic polyurethane resin can be neutralized with an inorganic acid such as hydrochloric acid and sulfuric acid, or an acid such as organic carboxylic acid such as formic acid and acetic acid. Further, it can be quaternized with a quaternizing agent such as alkyl halides such as methyl chloride and methyl bromide, and dialkyl sulfuric acid such as dimethyl sulfate.
  • an inorganic acid such as hydrochloric acid and sulfuric acid
  • an acid such as organic carboxylic acid such as formic acid and acetic acid.
  • a quaternizing agent such as alkyl halides such as methyl chloride and methyl bromide, and dialkyl sulfuric acid such as dimethyl sulfate.
  • cationic polyurethane resin a commercially available product can be used, or a commercially available product can be synthesized as a raw material.
  • Each component can be produced by a conventionally known general method, and can be synthesized, for example, in the presence of an organic solvent.
  • aqueous dispersions of cationic polyurethane resins include, for example, “Superflex 600”, “Superflex 620”, “Superflex 650” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “Adekabon titer HUX-” manufactured by ADEKA 680 ".
  • the weight average molecular weight (Mw) of the cationic polyurethane resin is usually preferably from 1,000 to 5,000,000, more preferably from 2,000 to 3,000,000, and even more preferably from 3,000 to 2,000,000.
  • Mw weight average molecular weight
  • limiting in particular as a measuring method of a weight average molecular weight It can select suitably from well-known methods, For example, a gel permeation chromatography method (GPC method), a viscosity method, a light-scattering method etc. are mentioned. .
  • the aqueous primer composition for peeling paint according to the present invention is an aqueous dispersion in which a cationic polyurethane resin is dispersed in water, and the balance contains water.
  • the ratio of the cationic polyurethane resin in the aqueous primer composition for peeling paint according to the present invention is not particularly limited, but is usually 1 to 50% by weight, preferably 2 to 20% by weight, more preferably 4 to 4%. 10% by weight.
  • the ratio of components other than the cationic polyurethane resin in the aqueous primer composition for peeling paint according to the present invention is not particularly limited, but is usually about 99 to 50% by weight, preferably about 98 to 80% by weight, More preferably, it is about 96 to 90% by weight.
  • the water-based primer composition for peeling paint according to the present invention includes, as components other than the cationic polyurethane resin, a surfactant such as a hydrophilicity imparting agent and a nonionic surfactant in addition to water, a leveling agent, an antibacterial agent and an antifungal agent.
  • Antifoam additives such as agents, thickeners, rust inhibitors, etc. may be included.
  • these additives conventionally known additives can be used.
  • the compounding amount of these additives is usually about 0 to 10% by weight, preferably about 0.5 to 5% by weight, more preferably about 1 to 3% by weight.
  • the aqueous primer composition for peeling paint according to the present invention is preliminarily treated on the surface of the painting equipment before coating the painting equipment. Specifically, after the above-described aqueous primer for removing a paint according to the present invention is attached to the surface of a coating instrument by a dipping method, spraying method, shower coating method, etc., it is naturally dried or heat dried (for example, 60 to 90 ° C.) A film is formed on the surface of the coating tools by evaporating the water.
  • painting tools examples include hangers, jigs, tools such as slats, painting equipment, painting robot arms, painting booth inner walls and floor members.
  • the thickness of the coating is not particularly limited, but is usually about 1 to 100 ⁇ m, preferably about 10 to 80 ⁇ m, and more preferably about 15 to 50 ⁇ m. If the film is too thin, the peeling effect cannot be obtained and the paint cannot be completely removed. In addition, when the film thickness was too thick, the drying property was deteriorated, the removability of the film itself was deteriorated, and a physical impact was applied in a state where the paint adhered and deposited on the film of the aqueous primer composition for paint peeling. Occasionally, the occurrence of defective products due to paint peeling (chipping) occurs.
  • paint remover may be appropriately selected from the paint removers conventionally used in the field according to the kind of attached paint, the attached thickness, the material of the object to be treated, and the like.
  • paint removers include water, aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium polyphosphate, and sodium carbonate, aromatic alcohols such as benzyl alcohol, aromatic ethers such as phenylmethyl ether, and alkanols such as ethanolamine.
  • glycols such as amine, ethylene glycol and propylene glycol, alkoxyaryl such as DMF, DMSO, glycol ether, glycol acetate and anisole, and aryl sulfonate such as sodium benzenesulfonate and sodium toluenesulfonate.
  • alkoxyaryl such as DMF, DMSO, glycol ether, glycol acetate and anisole
  • aryl sulfonate such as sodium benzenesulfonate and sodium toluenesulfonate.
  • the paint remover may be either an alkaline type (pH above 8) or a neutral type (pH 6-8).
  • the peeling temperature is 5 ° C. to 100 ° C., preferably 50 ° C. to 90 ° C., more preferably 70 ° C. to 90 ° C.
  • the aqueous primer composition for peeling paint according to the present invention can be applied to general uncured coating films adhering to coating instruments.
  • the test piece was pulled up and dried (60 ° C., 60 minutes) to form a film on the surface.
  • the test piece was immersed in a paint for painting automobile parts (white paint OP-70-P, manufactured by Kansai Paint Co., Ltd.), and the paint was applied by pulling up, followed by baking (140 ° C., 30 minutes). After baking, it was immersed in a water-soluble paint remover heated to 50 ° C., and the time until the paint was completely removed was measured.
  • the results of peel performance evaluation are shown in Table 1, and the composition of the water-soluble paint remover is shown in Table 2.
  • the peeling time of the paint or coating film was short, and even a neutral release material had sufficient peeling performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The present invention provides an aqueous primer composition for paint removal use, which is characterized by comprising at least one cationic polyurethane resin and water.

Description

塗料剥離用水性プライマー組成物および塗料剥離方法Aqueous primer composition for paint stripping and paint stripping method
　本発明は、自動車の塗装工程をはじめとし、各種被塗装物の塗装工程に使用される塗装用器具類に付着、堆積する硬化もしくは未硬化の塗料もしくは塗膜の効率的除去を可能にする塗料剥離用水性プライマー組成物および塗料剥離方法に関する。 The present invention is a paint that enables efficient removal of a hardened or uncured paint or paint film that adheres to and accumulates on coating equipment used in the painting process of various objects including the painting process of automobiles. The present invention relates to a stripping aqueous primer composition and a coating stripping method.
　自動車の塗装工程をはじめとし、様々な塗装工程に塗装用器具類が使用されているが、これら塗装用器具類に塗料が付着、堆積すると、作業性や機能が低下することから、一定期間ごとに塗装用器具類から硬化もしくは未硬化の塗料を剥離除去する必要がある。 Painting equipment is used in various painting processes, including the painting process of automobiles. If paint adheres to and accumulates on these painting equipment, workability and function will deteriorate, so every fixed period of time. In addition, it is necessary to peel and remove the hardened or uncured paint from the coating equipment.
　自動車をはじめ、被塗装物を塗装する塗装工程において使用される塗装用器具類としては、例えば、マスキング治具、スノコおよび塗装ブース等が挙げられる。これら塗装用器具類に付着する塗膜法としては、従来より種々の方法が提案されている。(i)ジクロロメタンやシンナー等の有機溶剤を主成分とする塗料剥離剤を使用する方法、(ii)苛性アルカリを主成分とする水性洗浄剤を加温して使用する方法、(iii)焼却処理する方法、および(iv)ハンマーやスクレーパー等を用いて物理的な振動や衝撃を与える方法、(v)塗料の付着を防止するシリコーン樹脂やフッ素樹脂をコーティングする方法等が知られている。 For example, masking jigs, slats, and painting booths may be used as painting instruments used in painting processes for painting objects such as automobiles. Conventionally, various methods have been proposed as a coating film method that adheres to these coating instruments. (i) a method using a paint remover mainly composed of an organic solvent such as dichloromethane or thinner, (ii) a method comprising heating an aqueous detergent mainly composed of caustic, (iii) incineration treatment And (iv) a method of applying a physical vibration or impact using a hammer, a scraper or the like, and (v) a method of coating a silicone resin or a fluororesin for preventing adhesion of a paint.
　しかしながら、方法(i)の場合には、溶剤で剥離するものは、塗料剥離剤として溶剤にキシレン、ケトン等の引火性溶剤、あるいはジクロロメタン等の塩素系溶剤を使用するため、作業環境の保全と引火防止対策が必要となる。この方法は、毒性、臭気、引火性および廃液処理等の作業衛生性や環境汚染の点で多くの問題がある。特にジクロロメタンを主成分とする塗料剥離剤の使用は従来技術としては広く知られており、活用されてきたが、胆管癌の発症など人体への影響が懸念される現在では使用し難くなっている。方法(ii)の場合には、アルカリ成分の濃度が高いことから安全性に問題がある。なおかつよく使用されている苛性アルカリについては、その濃度が５％以上である場合、毒物及び劇毒物取締法における劇物として指定されることから取り扱いが煩雑となる。また方法(iii)は有毒な排ガスの発生を伴うので大気汚染の点で問題がある。さらに方法(iv)の場合には、細部までの完全な剥離が困難なだけでなく塗装用器具類を変形被損させる危険性が高く、作業効率が極めて低いという難点がある。(v)の場合には、塗料の付着を完全には防止できず、コストが高いことや塗装はじきが懸念されることから普及していない。前記の方法(i)から方法(v)を通じて、全体に付着塗料が除去しにくいという欠点があった。 However, in the case of method (i), those that are peeled off with a solvent use a flammable solvent such as xylene or ketone, or a chlorine-based solvent such as dichloromethane as the paint remover, so that the work environment is protected. Inflammation prevention measures are required. This method has many problems in terms of work hygiene such as toxicity, odor, flammability and waste liquid treatment, and environmental pollution. In particular, the use of a paint stripper mainly composed of dichloromethane is widely known and used as a prior art, but it has become difficult to use at present when there are concerns about the effects on the human body such as the development of bile duct cancer. . In the case of the method (ii), there is a problem in safety because the concentration of the alkali component is high. In addition, when the concentration of caustic alkali that is often used is 5% or more, handling is complicated because it is designated as a deleterious substance in the Poisonous and Deleterious Poison Control Law. In addition, method (iii) has a problem in terms of air pollution because it involves generation of toxic exhaust gas. Furthermore, in the case of the method (iv), not only is it difficult to completely peel off the details, but there is a high risk of deforming and damaging the coating instruments, and there is a problem that the working efficiency is extremely low. In the case of (v), the adhesion of the paint cannot be completely prevented, and it is not popular because of high costs and concerns about paint repelling. Through the method (i) to the method (v), there is a drawback that it is difficult to remove the adhered paint as a whole.
　その他の方法として、塗装用器具類の塗料が付着する部分に予めプライマーをコーティングしておき、塗装工程で塗料がある程度、付着、堆積したあと、水溶性塗料剥離剤（特許文献1）や溶剤で剥離するものがある。水溶性塗料剥離剤で剥離する場合、ポリビニルアルコール、ポリビニルピロリドン、水溶性アクリル系樹脂、エーテル化セルロースなど（特許文献２，３，４，５，６）では剥離性能が十分でない。 As another method, a primer is coated in advance on the part of the coating equipment to which the paint adheres, and after the paint has adhered to and deposited to some extent in the painting process, a water-soluble paint remover (Patent Document 1) or a solvent is used. Some peel. When peeling with a water-soluble paint remover, polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble acrylic resin, etherified cellulose, etc. (Patent Documents 2, 3, 4, 5, 6) do not have sufficient peeling performance.
　油タイプの塗装剥離用プライマーとしては、高粘度のグリースが、安価で効果もあるため広く用いられているが、溶剤系塗料に溶解され易かったり、また水性塗料にはハジキがあり、付着せず落下した塗料による塗装品不良につながる等生産性低下を引き起こすことやグリース自体が高汚染性のため、周囲の環境の汚染も問題となる。 High viscosity grease is widely used as an oil-type paint peeling primer because it is inexpensive and effective, but it is easily dissolved in solvent-based paints, and water-based paints have repellency and do not adhere. Contamination of the surrounding environment also becomes a problem because it causes a decrease in productivity, such as leading to defective paint products due to dropped paint, and the grease itself is highly contaminated.
特開2002-275394JP2002-275394 特開2000-191961JP2000-191961 特開平8-134386JP-A-8-134386 特開平4-149284JP 4-149284 A 特開昭63-209771JP 63-209771 特開昭62-246973JP 62-246973
　本発明は上述したような当該分野の実情に鑑み、自動車の塗装工程をはじめとし、様々な塗装工程に使用されている塗装用器具類に付着、堆積する硬化もしくは未硬化の塗料もしくは塗膜を水溶性塗料剥離剤を使用し剥離する場合の効率的除去を可能にする塗料剥離用水性プライマー組成物を提供することを目的とする。 In view of the situation in the field as described above, the present invention provides a cured or uncured paint or coating film that adheres to and accumulates on coating equipment used in various painting processes including automobile painting processes. An object of the present invention is to provide an aqueous primer composition for stripping paint that enables efficient removal when stripping using a water-soluble paint stripper.
 前記課題を解決するために、本発明者は鋭意検討を重ねた結果、本発明に至った。つまり、本発明は次の成分を含有する塗料剥離用水性プライマー組成物に関する。
項１．　
少なくとも１種のカチオン性ポリウレタン樹脂および水を含有することを特徴する塗料剥離用水性プライマー組成物。
項２．　
カチオン性ポリウレタン樹脂が１級アミノ基、２級アミノ基、３級アミノ基および４級アンモニウム基から選ばれた少なくとも1種のカチオン性官能基を有するポリウレタン樹脂である項１に記載の塗料剥離用水性プライマー組成物。
項３．　
カチオン性ポリウレタン樹脂が４級アンモニウム基を有するポリウレタン樹脂である項１又は２に記載の塗料剥離用水性プライマー組成物。
項４．　
カチオン性ポリウレタン樹脂が、ポリエーテル系カチオン性ポリウレタン樹脂、ポリエステル系カチオン性ポリウレタン樹脂、ポリカーボネート系カチオン性ポリウレタン樹脂、ポリカプロラクトン系カチオン性ポリウレタン樹脂である、項１～３のいずれかに記載の塗料剥離用水性プライマー組成物。
項５．　
カチオン性ポリウレタン樹脂の濃度が１～５０重量％である項１～４のいずれかに記載の塗料剥離用水性プライマー組成物。
項６．　
項１～５のいずれかに記載の塗料剥離用水性プライマー組成物を塗装前に塗装用器具類に塗布する工程、塗装後に塗料剥離剤を用いて塗装用器具類から硬化もしくは未硬化の塗料を除去する工程を含む、塗料の剥離方法。 In order to solve the above-mentioned problems, the present inventor has intensively studied and, as a result, has reached the present invention. That is, this invention relates to the water-based primer composition for paint peeling containing the following component.
Item 1.
An aqueous primer composition for peeling paints, comprising at least one cationic polyurethane resin and water.
Item 2.
Item 2. The paint peeling agent according to Item 1, wherein the cationic polyurethane resin is a polyurethane resin having at least one cationic functional group selected from a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group. Aqueous primer composition.
Item 3.
Item 3. The aqueous primer composition for peeling paints according to Item 1 or 2, wherein the cationic polyurethane resin is a polyurethane resin having a quaternary ammonium group.
Item 4.
Item 4. The paint peeling according to any one of Items 1 to 3, wherein the cationic polyurethane resin is a polyether cationic polyurethane resin, a polyester cationic polyurethane resin, a polycarbonate cationic polyurethane resin, or a polycaprolactone cationic polyurethane resin. Aqueous primer composition.
Item 5.
Item 5. The aqueous primer composition for removing a paint according to any one of Items 1 to 4, wherein the concentration of the cationic polyurethane resin is 1 to 50% by weight.
Item 6.
The step of applying the aqueous primer composition for stripping paint according to any one of Items 1 to 5 to a coating device before coating, and applying a cured or uncured coating from the coating device using a coating stripper after coating A method for removing paint, comprising a step of removing.
　塗料剥離用水性プライマー（カチオン性ポリウレタン樹脂）の皮膜を表面に有する塗装用器具類は、不要な塗料が付着、堆積しても、水溶性塗料剥離剤を用いて処理すると付着塗料に亀裂が生じ、亀裂内へ水溶性塗料剥離剤が浸透して皮膜を溶解、膨潤させるので、付着塗料は塗装用器具類の表面から浮かび上がって容易かつ完全に剥離する。従って、本発明の塗料剥離用水性プライマーによると短時間で塗装用器具類の隅部や屈曲部等のように、塗料剥離が比較的困難な部位においても、付着、堆積した塗料を容易に剥離することができる。 For coating equipment that has a coating of water-based primer for removing paint (cationic polyurethane resin) on its surface, even if unnecessary paint adheres and accumulates, if it is treated with a water-soluble paint remover, the attached paint will crack. Since the water-soluble paint remover penetrates into the cracks and dissolves and swells the coating, the adhering paint emerges from the surface of the coating equipment and peels easily and completely. Therefore, according to the water-based primer for removing paint of the present invention, it is possible to easily peel off the adhered and deposited paint even in a relatively difficult part such as a corner or a bent part of a painting tool in a short time. can do.
　また、塗料剥離処理後は一般に水洗処理が行われるが、本発明によるプライマーから形成される皮膜は水で溶解除去されるので新たな皮膜形成に際して、塗料の密着不良は発生しない。 In addition, after the paint peeling treatment, a water washing treatment is generally performed. However, since the film formed from the primer according to the present invention is dissolved and removed with water, no poor adhesion of the paint occurs when a new film is formed.
　以下、本発明の塗料剥離用水性プライマー組成物について詳述する。本発明の塗料剥離用水性プライマー組成物はカチオン性ポリウレタン樹脂および水を含有することを特徴とする。 Hereinafter, the aqueous primer composition for peeling paint according to the present invention will be described in detail. The aqueous primer composition for peeling paint according to the present invention contains a cationic polyurethane resin and water.
　カチオン性ポリウレタン樹脂は、１級アミノ基、２級アミノ基、３級アミノ基やホスフィノ基の塩酸、酢酸、硫酸等の酸との反応物、４級アンモニウム基、４級ホスホニウム基などのカチオン性官能基を有するポリウレタン樹脂を挙げることができるが、１級アミノ基、２級アミノ基、３級アミノ基、４級アンモニウム基から選ばれた少なくとも1種のカチオン性官能基を有するポリウレタン樹脂であることが好ましい。カチオン性官能基は、ポリオール、ポリイソシアネート、ウレタンプレポリマーのいずれに含まれていてもよい。 Cationic polyurethane resin is a reaction product of primary amino group, secondary amino group, tertiary amino group or phosphino group with acid such as hydrochloric acid, acetic acid, sulfuric acid, quaternary ammonium group, quaternary phosphonium group, etc. Examples thereof include a polyurethane resin having a functional group, which is a polyurethane resin having at least one cationic functional group selected from a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group. It is preferable. The cationic functional group may be contained in any of polyol, polyisocyanate, and urethane prepolymer.
　カチオン性ポリウレタン樹脂は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The cationic polyurethane resin may be used alone or in combination of two or more.
　１級アミノ基、２級アミノ基、３級アミノ基としては、例えば、R1R2N-(C2H4-O)n-(C3H6-O)m-（式中、R1、R2は同一又は異なって、水素原子、炭素数1～10、好ましくは炭素数1～6、好ましくは炭素数1～4、好ましくは炭素数1～2の直鎖又は分岐を有するアルキル基、炭素数1～10、好ましくは炭素数1～6、好ましくは炭素数1～4、好ましくは炭素数1～2の直鎖又は分岐を有するヒドロキシアルキル基を示し、1≦n+m≦50、ｎは0～50の整数、ｍは0～50の整数を示す）で表される１級、２級又は３級アルカノールアミノ基、例えば2－アミノエタノール、２－（メチルアミノ）エタノール、ジメチルアミノエタノール、メチルジエタノールアミン等のアルカノールアミンを挙げることができるが、４級アンモニウム基が好ましく、［R1R2R3N＋-(C2H4-O)n-(C3H6-O)m]－（式中、R1、R2、R3は同一又は異なって、水素原子、炭素数1～10、好ましくは炭素数1～6、好ましくは炭素数1～4、好ましくは炭素数1～2の直鎖又は分岐を有するアルキル基、炭素数1～10、好ましくは炭素数1～6、好ましくは炭素数1～4、好ましくは炭素数1～2の直鎖又は分岐を有するヒドロキシアルキル基を示し、1≦n+m≦50、ｎは0～50の整数、ｍは0～50の整数を示す）で表される４級アンモニウム基が挙げられ、好ましくはヒドロキシアルキル基を有し、炭素数が４～１０の４級アンモニウム基が好ましい。 Examples of the primary amino group, secondary amino group, and tertiary amino group include, for example, R 1 R 2 N— (C 2 H 4 —O) n — (C 3 H 6 —O) m — (in the formula, R 1 and R 2 are the same or different and are a hydrogen atom, an alkyl having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, preferably a straight chain or branched chain having 1 to 2 carbon atoms. A straight or branched hydroxyalkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, and 1 ≦ n + m ≦ 50, n represents an integer of 0 to 50, and m represents an integer of 0 to 50). For example, 2-aminoethanol, 2- (methylamino) ethanol, dimethylaminoethanol, there may be mentioned alkanolamines such as methyldiethanolamine, preferably quaternary ammonium groups, [R 1 R 2 R 3 N + - (C 2 H 4 - O) n- (C 3 H 6 -O) m ]-(wherein R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, Preferably an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, having a straight or branched chain, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, preferably carbon A quaternary ammonium represented by a linear or branched hydroxyalkyl group of 1 or 2 and represented by 1 ≦ n + m ≦ 50, n is an integer of 0 to 50, and m is an integer of 0 to 50) A quaternary ammonium group having a hydroxyalkyl group and having 4 to 10 carbon atoms is preferred.
　分子内にヒドロキシアルキル基、エーテル基等の親水性基を有する場合、水溶性塗料剥離用プライマーの水中における分散安定性をより高めることができるため好適である。アルキル基、ヒドロキシアルキル基の炭素数は、好ましくは１～６、より好ましくは１～４であり、さらに好ましくは１～２である。アルキル基の具体例としては、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシルが挙げられ、ヒドロキシアルキルとしては、ヒドロキシルエチル、２-ヒドロキシプロピル、ヒドロキシイソブチル、ヒドロキシペンチル、ヒドロキシヘキシルなどを挙げることができる。４級アルキルもしくはヒドロキシアルキル基炭素数が１１以上になると樹脂の水溶性が著しく低下し、不安定にあり、成膜性が低下する。 It is preferable to have a hydrophilic group such as a hydroxyalkyl group or an ether group in the molecule because the dispersion stability of the water-soluble paint peeling primer in water can be further increased. The carbon number of the alkyl group and hydroxyalkyl group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 2. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and hydroxyalkyl includes hydroxylethyl, 2-hydroxypropyl, hydroxyisobutyl, hydroxypentyl, Hydroxyhexyl etc. can be mentioned. When the number of carbon atoms in the quaternary alkyl or hydroxyalkyl group is 11 or more, the water solubility of the resin is remarkably lowered and unstable, and the film formability is lowered.
　カチオン性ポリウレタン樹脂は少なくとも一部が上記アミノ基またはアンモニウム基で置換されたポリオールと脂肪族、脂環族もしくは芳香族ポリイソシアネートとを縮重合させることにより得ることができる。少なくとも一つのカチオン性官能基を有する限り、ポリオールとポリイソシアネートや重合方法は特に限定されない。ポリウレタン樹脂の骨格は、使用するポリオール成分に応じて、ポリエーテル系カチオン性ポリウレタン樹脂、ポリエステル系カチオン性ポリウレタン樹脂、ポリカーボネート系カチオン性ポリウレタン樹脂、ポリカプロラクトン系カチオン性ポリウレタン樹脂などに分類されるが、いずれであってもよく特に限定されるものではない。 The cationic polyurethane resin can be obtained by polycondensation of at least a part of the polyol substituted with the amino group or ammonium group and an aliphatic, alicyclic or aromatic polyisocyanate. As long as it has at least one cationic functional group, the polyol, polyisocyanate, and polymerization method are not particularly limited. The skeleton of the polyurethane resin is classified into a polyether cationic polyurethane resin, a polyester cationic polyurethane resin, a polycarbonate cationic polyurethane resin, a polycaprolactone cationic polyurethane resin, etc., depending on the polyol component used. Any of them may be used and is not particularly limited.
　ポリオール化合物としては、分子量４００以下の低分子量ポリオール、ポリエステルポリオール、ポリエーテルポリオール、ひまし油系ポリオール、ポリカーボネートポリオール、又は炭化水素系ポリオール等を挙げることができる。ポリオール化合物は1種単独で用いてもよいし2種以上を組み合わせて用いてもよい。 Examples of the polyol compound include a low molecular weight polyol having a molecular weight of 400 or less, a polyester polyol, a polyether polyol, a castor oil-based polyol, a polycarbonate polyol, or a hydrocarbon-based polyol. A polyol compound may be used individually by 1 type, and may be used in combination of 2 or more type.
　分子量４００以下の低分子量ポリオールは、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２－プロピレングリコール、1，3－プロピレングリコール、ネオペンチルグリコール、１，３－ブタンジオール、１，４－ブタンジオール、３－メチルペンタンジオール、１，６－ヘキサンジオール、１，８－オクタンジオール、２－メチル－１，３－プロパンジオール、ビスフェノールA、水添ビスフェノールA、シクロヘキサンジメタノール、グリセリン、又はトリメチロールプロパン等を挙げることができるが、トリメチロールプロパンが好ましい。 Low molecular weight polyols having a molecular weight of 400 or less include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butane. Diol, 3-methylpentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,3-propanediol, bisphenol A, hydrogenated bisphenol A, cyclohexanedimethanol, glycerin, or trimethylol Although propane etc. can be mentioned, a trimethylol propane is preferable.
　ポリエステルポリオールとしては、低分子量ポリオールと多価カルボン酸とを反応させてなる水酸基末端エステル化縮合物を挙げることができる。多価カルボン酸としては、例えば、コハク酸、グルタル酸、アジピン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、テトラヒドロフラン酸、エンドメチンテトラヒドロフラン酸、又はヘキサヒドロフタル酸等が挙げられる。 Examples of the polyester polyol include a hydroxyl group-terminated esterified condensate obtained by reacting a low molecular weight polyol and a polyvalent carboxylic acid. Examples of the polyvalent carboxylic acid include succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrofuran acid, endomethine tetrahydrofuran acid, and hexahydrophthalic acid. It is done.
　ポリエーテルポリオールとしては、ビスフェノールA等の前記低分子量ポリオール、ペンタエリスリトール、ソルビトール、又はショ糖等にアルキレンオキサイドを付加重合したものを挙げることができる。アルキレンオキサイドとしては、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド等が挙げられる。 Examples of the polyether polyol include those obtained by addition polymerization of alkylene oxide to the low molecular weight polyol such as bisphenol A, pentaerythritol, sorbitol, or sucrose. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and the like.
　ひまし油系ポリオールとしては、ひまし油、ひまし油に水素付加した水添付加した、水添ひまし油、ひまし油脂肪酸又はこれに水素付加した水添ひまし油脂肪酸を用いて製造されたポリオール等が挙げられる。また、ひまし油脂肪酸と多価アルコールとのエステル化反応物、又はこれらにアルキレンオキサイドを付加重合したポリオール等が挙げられる。 Castor oil-based polyols include castor oil, hydrogenated castor oil, castor oil fatty acid, or hydrogenated hydrogenated castor oil fatty acid hydrogenated to castor oil, and the like. Moreover, the esterification reaction product of a castor oil fatty acid and a polyhydric alcohol, the polyol which carried out the addition polymerization of the alkylene oxide to these, etc. are mentioned.
 ポリカーボネートポリオールとしては、従来公知のものが挙げられ、該ポリカーボネートポリオールは、例えば、前記低分子量ポリオールとジフェニルカーボネートとの反応により、又は、前記低分子量ポリオールとホスゲンとの反応により得られる。 Examples of the polycarbonate polyol include conventionally known ones. The polycarbonate polyol can be obtained, for example, by a reaction between the low molecular weight polyol and diphenyl carbonate or a reaction between the low molecular weight polyol and phosgene.
　ポリオール化合物としては、耐食性の点からポリエステルポリオール又はポリエーテルポリオールが好ましく、１，４－ブタンジオールとアジピン酸とを反応させてなるポリエステルポリオール、及びビスフェノールＡにアルキレンオキサイドを付加したポリエーテルポリオールがより好ましい。 As the polyol compound, polyester polyol or polyether polyol is preferable from the viewpoint of corrosion resistance. Polyester polyol obtained by reacting 1,4-butanediol and adipic acid, and polyether polyol obtained by adding alkylene oxide to bisphenol A are more preferable. preferable.
　イソシアネート化合物としては、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香族ポリイソシアネート、又は芳香脂肪族ポリイソシアネート等を挙げることができるが、樹脂の変色を抑制できるという点で、脂肪族ポリイソシアネート又は脂環族ポリイソシアネートが好ましい。イソシアネート化合物は、1種単独で用いてもよいが、2種以上組み合わせて用いてもよい。 Examples of the isocyanate compound include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate. In terms of being able to suppress discoloration of the resin, aliphatic polyisocyanate or Alicyclic polyisocyanates are preferred. The isocyanate compounds may be used alone or in combination of two or more.
　脂肪族ポリイソシアネートとしては、テトラメチレンジイソシアネート、ドデカメチレンイソシアネート、ヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、リジンイイソシアネート、２－メチルペンタン－１，５－ジイソシアネート、３－メチルペンタン－１，５－ジイソシアネート等を挙げることができる。 Aliphatic polyisocyanates include tetramethylene diisocyanate, dodecamethylene isocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine isocyanate, 2-methylpentane- Examples thereof include 1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate.
　脂環族ポリイソシアネートとしては、イソホロンジイソシアネート、水添キシリレンジイソシアネート、４，４－ジシクロヘキシルメタンジイソシアネート、１，４－シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、１，３－ビス(イソシアネートメチル)シクロヘキサン等を挙げることができる。 Examples of alicyclic polyisocyanates include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. be able to.
　芳香族ポリイソシアネートとしては、トリレンジイソシアネート、２，２－ジフェニルメタンジイソシアネート、２，４－ジフェニルメタンジイソシアネート、４，４－ジフェニルメタンジイソシアネート(ＭＤＩ)、４，４－ジベンジルジイソシアネート、１，５－ナフチレンジイソシアネート、キシリレンジイソシアネート、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネート等を挙げることができる。 Aromatic polyisocyanates include tolylene diisocyanate, 2,2-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate (MDI), 4,4-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate. Xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and the like.
　芳香脂肪族ポリイソシアネートとしては、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、α,α,α,α－テトラメチルキシリレンゾイソシアネート等を挙げることができる。 Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylylenezoisocyanate.
　また、前記イソシアネート化合物として、上記のポリイソシアネートの２量体もしくは３量体、ビューレット化イソシアネート等の変性体、ポリメチレンポリフェニルポリイソシアネート（ポリメリックＭＤＩ）等を用いることもできる。 Also, as the isocyanate compound, dimers or trimers of the above polyisocyanates, modified products such as burette isocyanate, polymethylene polyphenyl polyisocyanate (polymeric MDI), and the like can be used.
　イソシアネート化合物として好ましいのは、ヘキサメチレンジイソシアネート、４，４－ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサンである。 Preferred as the isocyanate compound are hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane.
　カチオン性ポリウレタン樹脂が有するカチオン性官能基の含有量としては、カチオン性ポリウレタン樹脂が水性媒体中で溶解することなく安定な分散体を形成できる範囲であれば特に限定されるものでないが、例えばカチオン性ポリウレタン樹脂のカチオン性基は、好ましくは０．００１～１０当量／ｋｇ程度、より好ましくは０．００５～５当量／ｋｇ程度、さらに好ましくは０．０１～３当量／ｋｇ含有される。 The content of the cationic functional group of the cationic polyurethane resin is not particularly limited as long as the cationic polyurethane resin can form a stable dispersion without dissolving in the aqueous medium. The cationic group of the conductive polyurethane resin is preferably contained in an amount of about 0.001 to 10 equivalent / kg, more preferably about 0.005 to 5 equivalent / kg, and still more preferably 0.01 to 3 equivalent / kg.
　カチオン性ポリウレタン樹脂は、塩酸および硫酸等の無機酸、ギ酸および酢酸等の有機カルボン酸等の酸で中和することができる。また、塩化メチルおよび臭化メチル等のハロゲン化アルキル、ジメチル硫酸等のジアルキル硫酸等の四級化剤で四級化することができる。 The cationic polyurethane resin can be neutralized with an inorganic acid such as hydrochloric acid and sulfuric acid, or an acid such as organic carboxylic acid such as formic acid and acetic acid. Further, it can be quaternized with a quaternizing agent such as alkyl halides such as methyl chloride and methyl bromide, and dialkyl sulfuric acid such as dimethyl sulfate.
　カチオン性ポリウレタン樹脂は、市販されているものを用いたり、市販されているものを原料として用いて合成することができる。各成分はそれぞれ従来公知の一般的な方法によって製造でき、例えば有機溶剤の存在下で合成することができる。 As the cationic polyurethane resin, a commercially available product can be used, or a commercially available product can be synthesized as a raw material. Each component can be produced by a conventionally known general method, and can be synthesized, for example, in the presence of an organic solvent.
　カチオン性ポリウレタン樹脂の水分散液の市販品としては、例えば、第一工業製薬（株）製の「スーパーフレックス６００」「スーパーフレックス６２０」「スーパーフレックス６５０」、ADEKA社製「アデカボンタイターHUX-680」などを挙げることができる。 Commercially available aqueous dispersions of cationic polyurethane resins include, for example, “Superflex 600”, “Superflex 620”, “Superflex 650” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “Adekabon titer HUX-” manufactured by ADEKA 680 ".
　カチオン性ポリウレタン樹脂の重量平均分子量(Ｍｗ)としては、通常１０００～５００００００が好ましく、２０００～３００００００がより好ましく、３０００～２００００００がさらに好ましい。重量平均分子量の測定方法としては、特に制限はなく、公知の方法の中から適宜選択することができ、例えば、ゲルパーミエーションクロマトグラフ法（ＧＰＣ法）、粘度法、光散乱法などが挙げられる。 The weight average molecular weight (Mw) of the cationic polyurethane resin is usually preferably from 1,000 to 5,000,000, more preferably from 2,000 to 3,000,000, and even more preferably from 3,000 to 2,000,000. There is no restriction | limiting in particular as a measuring method of a weight average molecular weight, It can select suitably from well-known methods, For example, a gel permeation chromatography method (GPC method), a viscosity method, a light-scattering method etc. are mentioned. .
　本発明の塗料剥離用水性プライマー組成物は、カチオン性ポリウレタン樹脂を水に分散させた水性分散体であり、残部に水が含まれる。 The aqueous primer composition for peeling paint according to the present invention is an aqueous dispersion in which a cationic polyurethane resin is dispersed in water, and the balance contains water.
　本発明の塗料剥離用水性プライマー組成物のカチオン性ポリウレタン樹脂が占める割合は特に限定されるものではないが、通常１～５０重量％であり、好ましくは２～２０重量％、より好ましくは４～１０重量％である。 The ratio of the cationic polyurethane resin in the aqueous primer composition for peeling paint according to the present invention is not particularly limited, but is usually 1 to 50% by weight, preferably 2 to 20% by weight, more preferably 4 to 4%. 10% by weight.
　本発明の塗料剥離用水性プライマー組成物のカチオン性ポリウレタン樹脂以外の成分が占める割合は特に限定されるものではないが、通常９９～５０重量％程度であり、好ましくは９８～８０重量％程度、より好ましくは９６～９０重量％程度である。 The ratio of components other than the cationic polyurethane resin in the aqueous primer composition for peeling paint according to the present invention is not particularly limited, but is usually about 99 to 50% by weight, preferably about 98 to 80% by weight, More preferably, it is about 96 to 90% by weight.
　本発明の塗料剥離用水性プライマー組成物は、カチオン性ポリウレタン樹脂以外の成分として、水の他に親水性付与剤、非イオン性界面活性剤等の界面活性剤、レベリング剤、抗菌剤、抗カビ剤、増粘剤、防錆剤等、消泡剤の添加剤を含み得る。これら添加剤としては、従来公知のものを用いることができる。これらの添加剤の配合量は、通常０～１０重量％程度であり、好ましくは０．５～５重量％程度、より好ましくは１～３重量％程度である。 The water-based primer composition for peeling paint according to the present invention includes, as components other than the cationic polyurethane resin, a surfactant such as a hydrophilicity imparting agent and a nonionic surfactant in addition to water, a leveling agent, an antibacterial agent and an antifungal agent. Antifoam additives such as agents, thickeners, rust inhibitors, etc. may be included. As these additives, conventionally known additives can be used. The compounding amount of these additives is usually about 0 to 10% by weight, preferably about 0.5 to 5% by weight, more preferably about 1 to 3% by weight.
　本発明の塗料剥離用水性プライマー組成物は、塗装用器具類を塗装する前に、塗装用器具類の表面に予め処理する。具体的には、塗装用器具類の表面に浸漬法、噴霧法、シャワー塗布法等によって上記本発明の塗料剥離用水性プライマーを付着させた後、自然乾燥または加熱乾燥（例えば６０～９０℃）によって水分を蒸発させることによって塗装用器具類の表面に皮膜を形成させる。 The aqueous primer composition for peeling paint according to the present invention is preliminarily treated on the surface of the painting equipment before coating the painting equipment. Specifically, after the above-described aqueous primer for removing a paint according to the present invention is attached to the surface of a coating instrument by a dipping method, spraying method, shower coating method, etc., it is naturally dried or heat dried (for example, 60 to 90 ° C.) A film is formed on the surface of the coating tools by evaporating the water.
　塗装用器具類としてはハンガー、治具、スノコ等の塗装用具、塗装装置、塗装ロボットアーム及び塗装ブースの内壁や床部材等を挙げることができる。 Examples of painting tools include hangers, jigs, tools such as slats, painting equipment, painting robot arms, painting booth inner walls and floor members.
　皮膜の厚さは特に限定はされないが、通常は１～１００μｍ程度、好ましくは１０～８０μｍ程度、さらに好ましくは１５～５０μｍ程度である。皮膜の厚さが薄すぎると剥離効果が得られず塗料が完全に除去できない。また、皮膜の厚さが厚すぎると乾燥性の低下や皮膜自体の除去性の悪化、また、塗料剥離用水性プライマー組成物の皮膜の上に塗料が付着堆積した状態で物理的衝撃が加わったときに塗料はがれ(チッピング)が起こることによる不良品の発生が問題となる。 The thickness of the coating is not particularly limited, but is usually about 1 to 100 μm, preferably about 10 to 80 μm, and more preferably about 15 to 50 μm. If the film is too thin, the peeling effect cannot be obtained and the paint cannot be completely removed. In addition, when the film thickness was too thick, the drying property was deteriorated, the removability of the film itself was deteriorated, and a physical impact was applied in a state where the paint adhered and deposited on the film of the aqueous primer composition for paint peeling. Occasionally, the occurrence of defective products due to paint peeling (chipping) occurs.
　プライマー被膜を表面に有する塗装用器具類を、各々の目的に応じて塗装工程で使用すると、該プライマー被膜表面上に塗装膜が形成され、該塗装用器具類は塗料剥離剤を含有する溶液で洗浄処理に付される。塗料剥離剤としては、従来から当該分野において使用されている塗料剥離剤から、付着塗料の種類や付着厚および被処理対象物の材質等に応じて適宜選択すればよい。塗料剥離剤としては、例えば水、水酸化ナトリウム、水酸化カリウム、ポリリン酸ナトリウム、炭酸ナトリウムなどのアルカリ水溶液、ベンジルアルコールなどの芳香族アルコール、フェニルメチルエーテルなどの芳香族エーテル、エタノールアミンなどのアルカノールアミン、エチレングリコール、プロピレングリコールなどのグリコール類、ＤＭＦ，ＤＭＳＯ、グリコールエーテル、グリコールアセテート、アニソールなどのアルコキシアリール、ベンゼンスルホン酸ナトリウム、トルエンスルホン酸ナトリウムなどのアリールスルホン酸塩などが挙げられる。 When coating equipment having a primer coating on the surface is used in the painting process according to each purpose, a coating film is formed on the surface of the primer coating, and the coating equipment is a solution containing a paint release agent. It is subjected to a cleaning process. The paint remover may be appropriately selected from the paint removers conventionally used in the field according to the kind of attached paint, the attached thickness, the material of the object to be treated, and the like. Examples of paint removers include water, aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium polyphosphate, and sodium carbonate, aromatic alcohols such as benzyl alcohol, aromatic ethers such as phenylmethyl ether, and alkanols such as ethanolamine. Examples thereof include glycols such as amine, ethylene glycol and propylene glycol, alkoxyaryl such as DMF, DMSO, glycol ether, glycol acetate and anisole, and aryl sulfonate such as sodium benzenesulfonate and sodium toluenesulfonate.
　塗料剥離剤は、アルカリ性タイプ（ｐＨ８超）、中性タイプ（ｐＨ６～８）のいずれでもよい。 The paint remover may be either an alkaline type (pH above 8) or a neutral type (pH 6-8).
　塗料剥離剤の使用方法としては塗装用器具類を浸漬して用い、剥離温度としては、5℃～１００℃、好ましくは５０℃～９０℃、さらに好ましくは７０℃～９０℃である。 As a method of using the paint remover, a coating tool is immersed and used, and the peeling temperature is 5 ° C. to 100 ° C., preferably 50 ° C. to 90 ° C., more preferably 70 ° C. to 90 ° C.
　本発明の塗料剥離用水性プライマー組成物は、塗装用器具類に付着した未硬化塗膜一般に対して適用できるものである。 The aqueous primer composition for peeling paint according to the present invention can be applied to general uncured coating films adhering to coating instruments.
以下、本発明を実施例によってさらに説明する。 The invention is further illustrated by the following examples.
　剥離性能評価
［実施例１～１０及び比較例１～６］
実施例、比較例の塗料剥離用水性プライマー組成物は各種市販のポリウレタン樹脂水分散体の水を加え、不揮発成分20wt%に調整したものを用いた。 Peeling performance evaluation [Examples 1 to 10 and Comparative Examples 1 to 6]
The aqueous primer compositions for peeling paints in Examples and Comparative Examples were prepared by adding water of various commercially available polyurethane resin aqueous dispersions to a non-volatile component of 20 wt%.
 冷間圧延鋼板(ＳＰＣＣ－ＳＤ)の平板テストピース（70ｍｍ×50ｍｍ×0.8mm）をアセトン脱脂後、＃240の紙やすりで研磨し、表1の配合処方によって調整した塗料剥離用水性プライマー組成物に浸漬した。 Cold strip steel plate (SPCC-SD) flat plate test piece (70mm x 50mm x 0.8mm) is degreased with acetone and then polished with # 240 sandpaper and adjusted according to the formulation shown in Table 1. Soaked in.
　テストピースを引き上げ、乾燥処理(60℃，60分)することによって表面上に皮膜を形成させた。このテストピースを、自動車部品塗装用塗料（白色塗料OP-70-P 関西ペイント株式会社製）に浸漬、引き上げることより塗料を塗布し、その後、焼付け（140℃，30分）を行った。焼付け塗装後、50℃に加温した水溶性塗料剥離剤に浸漬し、塗料が完全に剥離除去されるまでの時間を測定した。剥離性能評価の結果を表１に、水溶性塗料剥離剤の組成を表２に示した。 The test piece was pulled up and dried (60 ° C., 60 minutes) to form a film on the surface. The test piece was immersed in a paint for painting automobile parts (white paint OP-70-P, manufactured by Kansai Paint Co., Ltd.), and the paint was applied by pulling up, followed by baking (140 ° C., 30 minutes). After baking, it was immersed in a water-soluble paint remover heated to 50 ° C., and the time until the paint was completely removed was measured. The results of peel performance evaluation are shown in Table 1, and the composition of the water-soluble paint remover is shown in Table 2.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明のプライマー組成物を用いれば、塗料もしくは塗膜の剥離時間が短く、中性の剥離材でも十分な剥離性能を有していた。 When the primer composition of the present invention was used, the peeling time of the paint or coating film was short, and even a neutral release material had sufficient peeling performance.

Claims (6)

  1. 少なくとも１種のカチオン性ポリウレタン樹脂および水を含有することを特徴する塗料剥離用水性プライマー組成物。 An aqueous primer composition for peeling paints, comprising at least one cationic polyurethane resin and water.
  2. カチオン性ポリウレタン樹脂が１級アミノ基、２級アミノ基、３級アミノ基および４級アンモニウム基から選ばれた少なくとも1種のカチオン性官能基を有するポリウレタン樹脂である請求項１に記載の塗料剥離用水性プライマー組成物。 The paint peeling according to claim 1, wherein the cationic polyurethane resin is a polyurethane resin having at least one cationic functional group selected from a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group. Aqueous primer composition.
  3. カチオン性ポリウレタン樹脂が４級アンモニウム基を有するポリウレタン樹脂である請求項１又は２に記載の塗料剥離用水性プライマー組成物。 The aqueous primer composition for paint stripping according to claim 1 or 2, wherein the cationic polyurethane resin is a polyurethane resin having a quaternary ammonium group.
  4. カチオン性ポリウレタン樹脂が、ポリエーテル系カチオン性ポリウレタン樹脂、ポリエステル系カチオン性ポリウレタン樹脂、ポリカーボネート系カチオン性ポリウレタン樹脂、ポリカプロラクトン系カチオン性ポリウレタン樹脂である、請求項１～３のいずれかに記載の塗料剥離用水性プライマー組成物。 The paint according to any one of claims 1 to 3, wherein the cationic polyurethane resin is a polyether cationic polyurethane resin, a polyester cationic polyurethane resin, a polycarbonate cationic polyurethane resin, or a polycaprolactone cationic polyurethane resin. An aqueous primer composition for peeling.
  5. カチオン性ポリウレタン樹脂の濃度が１～５０重量％である請求項１～４のいずれかに記載の塗料剥離用水性プライマー組成物。 The aqueous primer composition for removing paints according to any one of claims 1 to 4, wherein the concentration of the cationic polyurethane resin is 1 to 50% by weight.
  6. 請求項１～５のいずれかに記載の塗料剥離用水性プライマー組成物を塗装前に塗装用器具類に塗布する工程、塗装後に塗料剥離剤を用いて塗装用器具類から硬化もしくは未硬化の塗料を除去する工程を含む、塗料の剥離方法。 A step of applying the aqueous primer composition for removing paints according to any one of claims 1 to 5 to coating tools before painting, a cured or uncured paint from the coating tools using a paint remover after painting A method for removing a paint, comprising a step of removing water.
PCT/JP2013/078518 2013-06-10 2013-10-22 Aqueous primer composition for paint removal use, and paint removal method WO2014199527A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015522467A JPWO2014199527A1 (en) 2013-06-10 2013-10-22 Aqueous primer composition for paint stripping and paint stripping method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-122197 2013-06-10
JP2013122197 2013-06-10

Publications (1)

Publication Number Publication Date
WO2014199527A1 true WO2014199527A1 (en) 2014-12-18

Family

ID=52021856

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/078518 WO2014199527A1 (en) 2013-06-10 2013-10-22 Aqueous primer composition for paint removal use, and paint removal method

Country Status (2)

Country Link
JP (1) JPWO2014199527A1 (en)
WO (1) WO2014199527A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017066309A (en) * 2015-09-30 2017-04-06 株式会社ネオス Aqueous primer composition for coating detachment and coating detachment method
JPWO2023282003A1 (en) * 2021-07-07 2023-01-12
WO2023282004A1 (en) * 2021-07-07 2023-01-12 Dic株式会社 Composition for forming separable coating film

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002030294A (en) * 2000-06-08 2002-01-31 Ausimont Spa Polyurethane having low friction coefficient
JP2005213502A (en) * 2004-01-27 2005-08-11 Solvay Solexis Spa Polyurethane
JP2007197669A (en) * 2005-12-26 2007-08-09 Dainippon Ink & Chem Inc Coating agent for metal
JP2007270036A (en) * 2006-03-31 2007-10-18 Sanyo Chem Ind Ltd Polyurethane resin aqueous dispersion
JP2008088396A (en) * 2006-09-29 2008-04-17 Construction Research & Technology Gmbh Functionalized polyurethane (pu) resin, its production process and its use
JP2008303291A (en) * 2007-06-07 2008-12-18 Dic Corp Aqueous paint composition for wood, and dirt prevention-treated wood using the same
JP2010138274A (en) * 2008-12-11 2010-06-24 Dic Corp Aqueous coating agent
JP2012092311A (en) * 2010-09-28 2012-05-17 Dic Corp Primer coating agent and laminate
JP2012211284A (en) * 2011-03-31 2012-11-01 Dic Corp Cationic urethane resin composition and metal coating agent

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002030294A (en) * 2000-06-08 2002-01-31 Ausimont Spa Polyurethane having low friction coefficient
JP2005213502A (en) * 2004-01-27 2005-08-11 Solvay Solexis Spa Polyurethane
JP2007197669A (en) * 2005-12-26 2007-08-09 Dainippon Ink & Chem Inc Coating agent for metal
JP2007270036A (en) * 2006-03-31 2007-10-18 Sanyo Chem Ind Ltd Polyurethane resin aqueous dispersion
JP2008088396A (en) * 2006-09-29 2008-04-17 Construction Research & Technology Gmbh Functionalized polyurethane (pu) resin, its production process and its use
JP2008303291A (en) * 2007-06-07 2008-12-18 Dic Corp Aqueous paint composition for wood, and dirt prevention-treated wood using the same
JP2010138274A (en) * 2008-12-11 2010-06-24 Dic Corp Aqueous coating agent
JP2012092311A (en) * 2010-09-28 2012-05-17 Dic Corp Primer coating agent and laminate
JP2012211284A (en) * 2011-03-31 2012-11-01 Dic Corp Cationic urethane resin composition and metal coating agent

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017066309A (en) * 2015-09-30 2017-04-06 株式会社ネオス Aqueous primer composition for coating detachment and coating detachment method
JPWO2023282003A1 (en) * 2021-07-07 2023-01-12
WO2023282004A1 (en) * 2021-07-07 2023-01-12 Dic株式会社 Composition for forming separable coating film
WO2023282003A1 (en) * 2021-07-07 2023-01-12 Dic株式会社 Composition for forming separable coating film
JPWO2023282004A1 (en) * 2021-07-07 2023-01-12
JP7327702B2 (en) 2021-07-07 2023-08-16 Dic株式会社 Detachable film-forming composition
JP7364109B2 (en) 2021-07-07 2023-10-18 Dic株式会社 Detachable film-forming composition

Also Published As

Publication number Publication date
JPWO2014199527A1 (en) 2017-02-23

Similar Documents

Publication Publication Date Title
US4812255A (en) Paint removing compositions
EP1130068B1 (en) Removable coating composition and preparative method
EP2162498B1 (en) Method for protecting substrates and removing contaminants from such substrates
US5565136A (en) Water based wood stripping compositions
US5035829A (en) Paint removing compositions
US5494702A (en) Protective solvent free liquid masking compounds and related method
JP4527435B2 (en) CURABLE COMPOSITION AND COATING METHOD USING THE COMPOSITION
CA3033906C (en) Composition and method for removing a coating from a surface
WO2014199527A1 (en) Aqueous primer composition for paint removal use, and paint removal method
JP6693720B2 (en) Aqueous primer composition for paint stripping and paint stripping method
US20220195219A1 (en) Methods of reducing the adhesion of a maskant
WO2003072270A1 (en) Carboxylic acid containing protective coating compositions and methods of use thereof
JP2016069633A (en) Aqueous primer composition for coating material peeling and coating material peeling method
AU2018348025A1 (en) Automotive paint remover composition and method of making
TWI829681B (en) Compositions and methods for cleaning and stripping
JP4826689B2 (en) Aqueous active energy ray-curable resin composition
JP6153435B2 (en) Aqueous primer composition for paint stripping and paint stripping method
EP1642940B1 (en) Removable coating composition and preparative method
NO884633L (en) COMPOSITIONS FOR REMOVING PAINT.

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13887013

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015522467

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13887013

Country of ref document: EP

Kind code of ref document: A1