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
  • C09D5/4488—Cathodic paints
  • C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
• • 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
  • C09D5/02—Emulsion paints including aerosols
  • C09D5/024—Emulsion paints including aerosols characterised by the additives
  • C09D5/027—Dispersing agents

Definitions

• the present invention relates to a surfactant. More specifically, the present invention relates to a surfactant suitable for an aqueous coating liquid (particularly cationic electrodeposition paint).
• a surfactant comprising a polyoxyalkylene compound having a structure that can be produced by a chemical reaction between 1 mol part of a non-reducing di- or trisaccharide and 20 to 100 mol parts of an alkylene oxide having 2 to 4 carbon atoms is known. (Patent Document 1).
• Aqueous coating liquid (especially cationic electrodeposition paint) has been detoxified by heavy metalization (lead-free) due to environmental problems, etc., and paint performance (high corrosion resistance, low temperature bakeability, VOC content, high throwing power)
• paint performance high corrosion resistance, low temperature bakeability, VOC content, high throwing power
• the foamability of the aqueous coating liquid has changed.
• cationic electrodeposition paints conventionally, rather than the electrodeposition paint itself, emphasis is placed on the foamability of the UF filtrate (the filtrate obtained by ultrafiltration of the electrodeposition paint with an ultrafilter, hereinafter abbreviated as UF filtrate).
• UF filtrate the filtrate obtained by ultrafiltration of the electrodeposition paint with an ultrafilter
• an object of the present invention is to provide a surfactant satisfying excellent foam control and coating film finishing performance regardless of the binder resin-containing aqueous coating liquid.
• the surfactant of the present invention is characterized by a mixture of a polyoxyalkylene compound (Y1) represented by the general formula (1) and a polyoxyalkylene compound (Y2) represented by the general formula (2) (Y ); A multimer (PY1) obtained by reacting the mixture (Y) with a diisocyanate having 6 to 15 carbon atoms; Multimer (PY2) obtained by reaction of mixture (Y) with diglycidyl ether having 10 to 100 carbon atoms; and Multimer (PY3) obtained by reaction of mixture (Y) and epihalohydrin
• the gist is that at least one kind is an essential component.
• the surfactant is produced by reacting 1 mol part of a non-reducing di- or trisaccharide (a1) with 15 to 100 mol parts of an alkylene oxide (a2) having 2 to 3 carbon atoms.
• An adduct is obtained by reacting 1 mol part of a non-reducing disaccharide or trisaccharide (a1) with 15 to 50 mol part of an alkylene oxide (a2) having 2 to 3 carbon atoms, and then adding butylene oxide to the adduct.
• Step (2) for obtaining 2 to 6 mole parts to obtain polyoxyalkylene compound (Y2); and polyoxyalkylene compound (Y1) and polyoxyalkylene compound (Y2) are uniformly mixed to obtain a mixture Step (3) for obtaining (Y)
• the point including
• the aqueous coating liquid of the present invention contains the above surfactant.
• the cationic electrodeposition paint of the present invention contains the above surfactant.
• the surfactant of the present invention exhibits excellent surface activity ⁇ foam control property, water solubility (or water dispersibility), wettability (wetting improvement property and repellency suppression property) ⁇ . Therefore, the surfactant of the present invention satisfies the excellent foam controllability and the finish of the coating film, regardless of the aqueous coating liquid containing any binder resin.
• Examples of di- or trisaccharides that can constitute a reaction residue (Q) obtained by removing a hydrogen atom from t primary hydroxyl groups of non-reducing di- or trisaccharides include sucrose, trehalose, isotrehalose, Examples include isosaccharose, gentianose, raffinose, meretitol and planteose. Of these, sucrose, trehalose, raffinose, and meletitol are preferable from the viewpoint of surface activity and the like, more preferably trehalose and sucrose, and sucrose is particularly preferable from the viewpoint of supply ability and cost. These can be used alone or in combination.
• Examples of the oxyalkylene group (OA) having 2 to 3 carbon atoms include oxyethylene and oxypropylene. Of these, oxypropylene and a mixture of oxypropylene and oxyethylene are preferred, and oxypropylene is more preferred from the viewpoint of surface activity (particularly the finish of the coating film).
• (OA-) n contains oxyethylene and oxypropylene
• the bonding order (block, random and combinations thereof) and the content ratio there is no particular limitation on the bonding order (block, random and combinations thereof) and the content ratio.
• the content ratio (% by weight) of oxyethylene is preferably 2 to 20, more preferably 2 to 15, based on the total weight of oxyethylene and oxypropylene. Particularly preferred is 5 to 15, and most preferred is 5 to 10.
• the oxypropylene is located farthest from the reaction residue (Q).
• the oxyethylene is preferably located as close as possible to the reaction residue (Q), and more preferably, the oxyethylene is directly bonded to the reaction residue (Q).
• the oxybutylene group (OB) is located farthest from the reaction residue (Q).
• a part of the oxybutylene group (OB) may be bonded to oxyethylene and / or oxypropylene at random.
• N is an integer of 1 to 35, preferably an integer of 3 to 30, more preferably an integer of 5 to 25, and particularly preferably an integer of 7 to 20. Within this range, the surface activity (particularly the finish of the coating film) is further improved.
• M is 0 or an integer of 1 to 3, preferably 0, 1 or 2, and more preferably 1 or 2. Within this range, the surface activity (particularly antifoaming property) is further improved. Of the t m, at least one m is an integer of 1 or more.
• T is an integer of 2 to 4, preferably 3 or 4, and more preferably 3. Within this range, the surface activity is further improved. This t corresponds to the number of primary hydroxyl groups of the non-reducing di- or trisaccharide.
• the total number of moles (moles) of the oxyalkylene group (OA) contained in the polyoxyalkylene compound (Y1) represented by the general formula (1) is 15 to 100 per mole of the polyoxyalkylene compound (Y1). It is preferably 15 to 80, more preferably 20 to 70, and particularly preferably 20 to 60. Within this range, the surface activity (particularly the finish of the coating film) is further improved.
• the total number of moles of the oxyalkylene group (OA) contained in the polyoxyalkylene compound (Y2) represented by the general formula (2) is 15 to 50 per mole of the polyoxyalkylene compound (Y2), preferably It is 15 to 45, more preferably 20 to 45, particularly preferably 20 to 40. Within this range, the surface activity (particularly the finish of the coating film) is further improved.
• the total number of moles (mol) of the oxybutylene group (OB) is 2 to 6, preferably 2 to 5, more preferably 2 to 4, particularly preferably 3 to 1 mole per mole of the polyoxyalkylene compound (Y2). 4. Within this range, the surface activity (particularly antifoaming property) is further improved.
• N, m and t may be the same or different.
• the n OA's may be the same or different, and the t (OA-) n may be the same or different. Further, t (OB ⁇ ) m may be the same or different.
• the content (% by weight) of the polyoxyalkylene compound (Y1) is preferably 40 to 90, more preferably 50 to 90, particularly preferably 55 to 85, and most preferably 60, based on the weight of the mixture (Y). ⁇ 80.
• the content (% by weight) of the polyoxyalkylene compound (Y2) is preferably 10 to 60, more preferably 10 to 50, particularly preferably 15 to 45, most preferably 20 based on the weight of the mixture (Y). ⁇ 40. Within these ranges, the surface activity (defoaming property and finish of the coating film) is further improved.
• the polyoxyalkylene compound (Y1) comprises a step (1) of reacting 1 mol part of a non-reducing di- or trisaccharide (a1) with 15 to 100 mol parts of an alkylene oxide (a2) having 2 to 3 carbon atoms, etc. Manufactured by. This reaction causes distribution in the oxyalkylene group of the resulting polyoxyalkylene compound (Y1), but these mixtures may be used as they are.
• the amount (mole parts) of the alkylene oxide (a2) is preferably from 15 to 100, more preferably from 15 to 80, particularly preferably from 20 to 70, based on 1 mole part of the non-reducing di- or trisaccharide (a1). And most preferably 20-60. Within this range, the surface activity is further improved.
• non-reducing di- or trisaccharide (a1) the same disaccharide or trisaccharide that can constitute the reaction residue (Q) in the general formula (1) can be used, and the preferred range is also the same.
• alkylene oxides having 2 to 3 carbon atoms can be used, and examples thereof include ethylene oxide, propylene oxide, and mixtures thereof. Among these, from the viewpoint of surface activity, propylene oxide and a mixture of propylene oxide and ethylene oxide are preferable, and propylene oxide is more preferable.
• the proportion (% by weight) of ethylene oxide is preferably 2 to 20, more preferably 2 to 15, particularly preferably 5 to 15, and most preferably 5 based on the total weight of ethylene oxide and propylene oxide. ⁇ 10.
• the polyoxyalkylene compound (Y2) is obtained by reacting 1 mol part of a non-reducing di- or trisaccharide (a1) with 15 to 50 mol parts of an alkylene oxide (a2) having 2 to 3 carbon atoms. Thereafter, this adduct is produced by reacting 2 to 6 parts by mole of butylene oxide (1,2-butylene oxide and / or 2,3-butylene oxide) (a3) (2). This reaction causes distribution in the oxyalkylene group or oxybutylene group of the polyoxyalkylene compound (Y2), but these mixtures may be used as they are.
• the amount (mole parts) of the alkylene oxide (a2) is preferably 15 to 50, more preferably 15 to 45, particularly preferably 20 to 45, based on 1 mole part of the non-reducing disaccharide or trisaccharide (a1). And most preferably 20-40. Within this range, the surface activity is further improved.
• the amount (mole part) of butylene oxide (a3) is preferably 2 to 6, more preferably 2 to 5, particularly preferably 2 to 4 with respect to 1 mole part of the non-reducing disaccharide or trisaccharide (a1). And most preferably 3-4. Within this range, the surface activity tends to be even better.
• the mixture (Y) is produced by the step (3) of uniformly mixing the polyoxyalkylene compound (Y1) and the polyoxyalkylene compound (Y2).
• this step (3) after producing the polyoxyalkylene compound (Y1), a part of the polyoxyalkylene compound (Y1) and the butylene oxide (a3) are reacted in the same reaction vessel. (Y2) may be produced and mixed uniformly.
• a part of the polyoxyalkylene compound (Y1) is set aside and then the remaining polyoxyalkylene compound (Y1) and butylene oxide (a3) may be reacted to produce a polyoxyalkylene compound (Y2), which may be set aside and mixed uniformly with the polyoxyalkylene compound (Y1).
• the mixture (Y) obtained by uniformly mixing in this way and the polyoxyalkylene compound (Y2) manufactured with another container may be mixed uniformly.
• the polyoxyalkylene compound (Y1) and the polyoxyalkylene compound (Y2) in separate containers they may be uniformly mixed to obtain a mixture (Y).
• AOA reaction Reaction of non-reducing di- or trisaccharide (a1) with alkylene oxide (a2) and reaction product of non-reducing di- or trisaccharide (a1) with alkylene oxide (a2) and butylene oxide (a3) (Hereinafter abbreviated as AOA reaction).
• AOA reaction May be a known method ⁇ for example, Patent Document 1 ⁇ , and may be performed in any form such as anionic polymerization, cationic polymerization, or coordinated anionic polymerization. These polymerization forms may be used alone or in combination according to the degree of polymerization.
• a reaction catalyst can be used for the AOA reaction.
• the reaction catalyst known alkylene oxide addition reaction catalysts described in ⁇ eg, Patent Document 1 ⁇ can be used. Of these, alkali metal hydroxides and tertiary amines are preferable, and potassium hydroxide, cesium hydroxide, and trimethylamine are more preferable.
• the amount used is 0.05 based on the total weight of the raw materials of the AOA reaction ⁇ eg, non-reducing di- or trisaccharide (a1) and alkylene oxide (a2)). To 2, more preferably 0.1 to 1, and particularly preferably 0.2 to 0.6.
• a reaction solvent can be used for the AOA reaction.
• a known solvent for example, Patent Document 1 ⁇ can be used.
• N-alkylamide and N-methylpyrrolidone are preferred, dimethylformamide (DMF), N, N-dimethylacetamide and N-methylpyrrolidone, particularly preferred DMF and N-methylpyrrolidone, most preferred DMF.
• the amount used is preferably 50 to 200, more preferably 60 to 180, particularly preferably 60 to 160, based on the weight of the raw material for the AOA reaction.
• the residual amount (% by weight) of the reaction solvent is preferably 0.1 or less, more preferably 0.05 based on the weight of the polyoxyalkylene compound (Y1) and / or the polyoxyalkylene compound (Y2). Hereinafter, it is particularly preferably 0.01 or less.
• the residual amount of the reaction solvent can be determined by gas chromatography using an internal standard substance.
• a method for removing the reaction solvent a known method ⁇ for example, Patent Document 1 ⁇ can be applied.
• the multimer (PY1) is obtained by reacting the mixture (Y) with a diisocyanate having 6 to 15 carbon atoms.
• the amount (mole) of the diisocyanate having 6 to 20 carbon atoms is preferably 0.5 to 0.8, more preferably 0.67 to 0.8, particularly preferably 0.67, per mole of the mixture (Y). ⁇ 0.75.
• diisocyanate aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate and the like can be used.
• an alkylene diisocyanate having 6 to 8 carbon atoms is used, and examples thereof include 1,4-diisocyanatobutane and hexamethylene diisocyanate (HMDI).
• HMDI hexamethylene diisocyanate
• aromatic diisocyanate arylene diisocyanate having 8 to 15 carbon atoms is used, and paraphenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate ( XDI), 1,5-naphthalene diisocyanate and the like.
• TDI 2,4-tolylene diisocyanate
• MDI 4,4′-diphenylmethane diisocyanate
• XDI xylylene diisocyanate
• 1,5-naphthalene diisocyanate 1,5-naphthalene diisocyanate
• alicyclic diisocyanate cycloalkylene diisocyanate having 12 to 15 carbon atoms is used, and isophorone diisocyanate (IPDI), hydrogenated MDI, trans 1,4-cyclohexane diisocyanate, hydrogenated TDI, hydrogenated 1,5-naphthalene. Diisocyanate etc. are mentioned.
• aliphatic and alicyclic diisocyanates are preferable from the viewpoint of surface activity and the like, more preferably 1,4-diisocyanatobutane, HMDI, IPDI, and hydrogenated MDI, and from the viewpoint of coloring properties and the like. Particularly preferred are HMDI and IPDI.
• the reaction between the mixture (Y) and the diisocyanate is an addition reaction.
• a reaction with a diisocyanate having a low reaction rate such as an aliphatic diisocyanate or an alicyclic diisocyanate
• HMDI or IPDI the reaction time can be shortened.
• a reaction catalyst can be used.
• dibutyltin dilaurate, stannous octoate, triethylenediamine and the like are common.
• reaction temperature (° C.) is preferably 70 to 150, more preferably 90 to 130.
• the reaction atmosphere is preferably a dry inert gas atmosphere.
• the reaction end point can be confirmed by the following method or the like. That is, in the isocyanato group content measurement method using a dioxane solution of di-n-butylamine, the end point of the reaction is the time when the isocyanato group content becomes 0.01% by weight or less.
• the multimer (PY2) is obtained by reacting the mixture (Y) with diglycidyl ether having 10 to 100 carbon atoms.
• the amount (mole) of diglycidyl ether having 10 to 150 carbon atoms is preferably 0.5 to 0.8, more preferably 0.67 to 0.8, particularly preferably 0, per mole of the mixture (Y). .67 to 0.75.
• Examples of the diglycidyl ether having 10 to 100 carbon atoms include tetramethylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyoxypropylene glycol diglycidyl ether, and polyoxyalkylene adducts of various glycols.
• diglycidyl ether compounds diglycidyl ether having 10 to 100 carbon atoms can be mentioned. Of these, hexamethylene glycol diglycidyl ether and polyoxypropylene glycol diglycidyl ether are preferred.
• the reaction between the mixture (Y) and the diglycidyl ether is the same as the reaction between the non-reducing di- or trisaccharide (a1) and the alkylene oxide (a2), and the reaction apparatus, catalyst and removal thereof are the same.
• the multimer (PY3) is obtained by reacting the mixture (Y) with epihalohydrin.
• the amount (mol) of epihalohydrin used is preferably 0.5 to 0.8, more preferably 0.67 to 0.8, and particularly preferably 0.67 to 0.75, per mole of the mixture (Y). .
• Epihalohydrins include epichlorohydrin and epibromohydrin.
• the reaction temperature (° C.) of the epoxy ring-opening reaction in the above steps (1) and (5) is preferably 30 to 150, more preferably 40 to 100.
• the reaction atmosphere is preferably a dry inert gas atmosphere.
• a reaction catalyst in the epoxy ring-opening reaction, can be used, which is the same as that used in the addition reaction of a non-reducing di- or trisaccharide (a1) and an alkylene oxide (a2), and is a known catalyst (special No. 2004-224945 and the like can be applied. The same applies to the removal of the catalyst.
• the end point of the reaction can be performed by the disappearance of the epoxy group.
• the epoxy group is quantified by cetyltrimethylammonium bromide (CTAB) method (JIS K7236) in which hydrogen halide (HB) is generated from perchloric acid and a quaternary ammonium salt (CTAB) and reacted with the epoxy group.
• CTAB cetyltrimethylammonium bromide
• JIS K7236 cetyltrimethylammonium bromide
• HB hydrogen halide
• CTAB quaternary ammonium salt
• the epoxy ring regeneration reaction by the dehydrohalogenation reaction in the above steps (2) and (4) includes a basic substance that neutralizes the generated hydrogen halide, for example, an alkali metal or alkaline earth metal hydroxide ( Lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, etc.) are used as the catalyst. Of these, alkali metal hydroxides are preferred, and sodium hydroxide is more preferred.
• an alkali metal or alkaline earth metal hydroxide Lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, etc.
• alkali metal hydroxides are preferred, and sodium hydroxide is more preferred.
• the amount of the basic substance used is the base equivalent (eq.) Of the basic substance, based on the equivalent (eq.) Of the halogen of the halogenated hydrocarbon, based on the base equivalent of the basic substance / the halogen of the halogenated hydrocarbon.
• the equivalent ratio is preferably 1 to 1.4, more preferably 1.05 to 1.3, and most preferably 1.07 to 1.2.
• reaction catalysts are preferably used as an aqueous solution of about 1 to 20% by weight, and the reaction temperature is preferably about 40 to 80 ° C.
• reaction temperature is preferably about 30 to 70 ° C.
• This removal method includes (1) a method in which the produced neutralized salt is first removed by filtration, and then a remaining basic substance is removed using an adsorbent and the like, and (2) an extraction / water washing method using an organic solvent. And (3) a salting-out method using salt or the like.
• the removal method (1) can be removed in the same manner as the reaction catalyst used in the addition reaction of the alkylene oxide (a2).
• the extraction / washing method in (2) is to add water and an organic solvent (having extremely low solubility in water such as hexane, toluene, xylene, etc.) to the reaction product and mixing the reaction product with the organic solvent.
• an organic solvent having extremely low solubility in water such as hexane, toluene, xylene, etc.
• a basic substance is extracted into an aqueous layer by separating it into layers, and this is separated.
• the organic solvent layer is further washed with deionized water or the like.
• a suitable volume ratio of reaction product: water: organic solvent is approximately 1: 1: 1.
• the reaction product is shaken by adding approximately the same volume of water and an appropriate amount (1 to 5% by weight of sodium chloride) to the reaction product and shaking.
• the basic substance is separated from the aqueous layer by precipitation from the aqueous layer.
• an alkali adsorbent synthetic aluminosilicate, etc .; for example, Kyword 700.
• Examples of the polyoxyalkylene compound (Y1) include compounds shown in Table 1.
• Q, t, and OA correspond to the general formula (1).
• Q1 represents a sucrose reaction residue
• Q2 represents a trehalose reaction residue
• Q3 represents a meletitose reaction residue.
• P represents oxypropylene
• E represents oxyethylene.
• the subscript of P or E represents the number of moles per mole of the non-reducing di- or trisaccharide reaction residue (this sum corresponds to the total number of moles of oxyalkylene groups (OA)).
• / in OA means a block shape
• E is bound to a di- or trisaccharide
• ⁇ in OA means a random shape.
• polyoxyalkylene compounds represented by No. 4, 5, 6, 8, 13, 17 or 18 are preferred, and polyoxyalkylene compounds represented by No. 5 or 17 are more preferred.
• Examples of the polyoxyalkylene compound (Y2) include compounds shown in Table 2.
• Q, t, OA, and OB correspond to the general formula (2).
• Q1 represents a sucrose reaction residue
• Q2 represents a trehalose reaction residue
• Q3 represents a meletitose reaction residue.
• P represents oxypropylene
• E represents oxyethylene
• B represents oxybutylene.
• the subscript P, E or B is the number of moles per mole of the non-reducing di- or trisaccharide reaction residue (the sum of the subscripts P and E is the total number of moles of oxyalkylene groups (OA)).
• the subscript of B represents the total number of oxybutylene groups (OB).
• / in OA means a block shape
• E is bound to a di- or trisaccharide
• ⁇ in OA means a random shape.
• polyoxyalkylene compounds represented by No22, 23, 24 or 29 are preferred, and the polyoxyalkylene compounds represented by No23 or 24 are more preferred.
• Examples of the multimer (PY1) include compounds obtained by reacting the mixture (Y) shown in Table 3 with diisocyanate.
• the mixture (Y) represents a compound shown in Table 1 or 2, and Q1, Q2, Q3, P, B and subscripts correspond to Tables 1 and 2, respectively.
• HMDI represents hexamethylene diisocyanate
• IPDI represents isophorone diisocyanate
• XDI represents xylylene diisocyanate.
• multimers represented by No, 36, 37 or 38 are preferred, and multimers represented by No 36 or 37 are more preferred.
• Examples of the multimer (PY2) include compounds obtained by reacting the mixture (Y) shown in Table 4 with diglycidyl ether.
• the mixture (Y) represents a compound shown in Table 1 or 2, and Q1, Q2, Q3, P, B and each subscript correspond to Tables 1 and 2, respectively.
• G1 represents 1,6-hexamethylene glycol diglycidyl ether
• G2 represents polyoxypropylene (7 mol) glycol diglycidyl ether
• G3 represents polyoxypropylene (20 mol) glycol diglycidyl ether.
• multimers represented by No, 41, 42 or 43 are preferred, and multimers represented by No 41 or 42 are more preferred.
• Examples of the multimer (PY3) include compounds obtained by reacting the mixture (Y) shown in Table 5 with epihalohydrin.
• the mixture (Y) represents a compound shown in Table 1 or 2, and Q1, Q2, Q3, P, B and each subscript correspond to Tables 1 and 2, respectively.
• H1 represents epichlorohydrin and H2 represents epibromohydrin.
• multimers represented by No, 46, 47 or 48 are preferred, and multimers represented by No 46 or 47 are more preferred.
• the surfactant of the present invention includes If necessary, other surfactants and / or solvents can be contained.
• Nonionic surfactants include alkylphenol alkylene oxide adducts, alcohol alkylene oxide adducts, polyhydric alcohol fatty acid esters, alkylamine alkylene oxide adducts, fatty acid amide alkylene oxide adducts, and acetylene glycol alkylene oxide additions. Body and polyoxyalkylene-modified silicone.
• the cationic surfactant include amine salts, quaternary ammonium salts, alkylene oxide addition type ammonium salts, and the like.
• anionic surfactants include fatty acid salts, ⁇ -olefin sulfonates, alkylbenzene sulfonic acids and salts thereof, alkyl sulfate esters, alkyl ether sulfate esters, N-acyl alkyl taurate salts, and alkyl sulfosuccinates. It is done.
• amphoteric surfactants include alanine, imidazolinium betaine, amide betaine, and betaine acetate.
• surfactants include SN Wet 123 and 970 (San Nopco); Lionol TDL-30, 50 and 70 (Lion Corporation, “Lionol” is a registered trademark of the company) Ionette T-80C, S-80, DO-600, etc. (Sanyo Kasei Kogyo Co., Ltd., “Ionette” is a registered trademark of the company); Softanol 30, 30S, MES-5, etc.
• the content is the total weight of the mixture (Y), multimer (PY1), multimer (PY2), multimer (PY3) and other surfactants. Is preferably 1 to 20, more preferably 5 to 15, and particularly preferably 5 to 10.
• water examples include ion exchange water, distilled water, tap water, and industrial water.
• water-soluble organic solvent examples include alcohols having 1 to 3 carbon atoms (such as methanol, ethanol and isopropanol), ketones having 3 to 6 carbon atoms (such as acetone, methyl ethyl ketone and methyl isobutyl ketone), and ethers having 2 to 6 carbon atoms (dimethyl ether). And ethyl cellosolve and butyl cellosolve) and ether esters having 4 to 6 carbon atoms (such as butyl cellosolve acetate).
• the content is 1 to 30 based on the total weight of the mixture (Y), multimer (PY1), multimer (PY2), multimer (PY3) and solvent. More preferably, it is 5 to 25, and particularly preferably 5 to 20.
• the surfactant of the present invention is suitable as a surfactant to be added to an aqueous coating liquid (cationic electrodeposition paint, aqueous architectural paint, aqueous automotive paint, paper coating paint, aqueous ink, etc.).
• an aqueous coating liquid cationic electrodeposition paint, aqueous architectural paint, aqueous automotive paint, paper coating paint, aqueous ink, etc.
• the amount (% by weight) of the surfactant of the present invention is preferably 0.01 to 10, more preferably based on the weight of the aqueous coating solution. It is 0.05 to 5, particularly preferably 0.1 to 3.
• the cationic electrodeposition coating is generally composed of 1) a cationic resin emulsion, 2) a pigment paste, and 3) an aqueous medium.
• the surfactant of the present invention includes (1) a cationic resin emulsion, (2) a pigment paste, (3) an aqueous medium, (4) an electrodeposition coating prepared from these, and (5) You may add to any of UF filtrate.
• the addition amount (% by weight) of the surfactant of the present invention is the amount of the cationic resin emulsion, pigment paste or aqueous medium. Based on the weight, it is preferably 0.01 to 5, more preferably 0.05 to 3, particularly preferably 0.1 to 2.
• the addition amount (% by weight) of the surfactant of the present invention is preferably from 0.01 to 2, more preferably from 0.05 to 2, based on the weight of the electrodeposition paint. 1.5, particularly preferably 0.1 to 1.
• the addition amount (% by weight) of the present invention is preferably 0.001 to 0.3, more preferably 0.002 to 0.2, based on the weight of the UF filtrate. Particularly preferred is 0.003 to 0.15.
• part means “part by weight”
• % means “% by weight”.
• ⁇ Production Example 1> In a pressure-resistant reaction vessel capable of stirring, heating, cooling, dropping, pressurizing with nitrogen, and depressurization with a vacuum pump, 342 parts (1 mol part) of purified granulated sugar ⁇ manufactured by Taiyo Co., Ltd. Chemical Co., Ltd., the same below ⁇ 1000 parts were charged, and then nitrogen gas was used until the gauge pressure was increased to 0.4 MPa and discharged to 0.02 MPa three times ⁇ hereinafter, This operation using nitrogen gas is abbreviated as nitrogen substitution. ⁇ . Thereafter, the temperature was raised to 100 ° C.
• sucrose / (EO) 3 mol / (PO) 40 mol adduct (Y106) 2794 parts (1 mol part) and potassium hydroxide 2.8 parts (0.05 mol part) was dehydrated at 120 ° C. under reduced pressure for 1 hour.
• 222 parts (3 parts by mole) of butylene oxide (BO) was added dropwise over 2 hours at 120 ° C. with the same reduced pressure, and the remaining (BO) was reacted by continuing stirring at the same temperature for 1 hour.
• Kyoward treatment was performed to obtain a polyoxyalkylene compound ⁇ sucrose / (EO) 3 mol / (PO) 40 mol / (BO) 3 mol adduct) ⁇ (Y206).
• the surfactant (S101) of the present invention was obtained by uniformly mixing 60 parts of the polyoxyalkylene compound (Y101) obtained in Production Example 1 and 40 parts of the polyoxyalkylene compound (Y205) obtained in Production Example 17. .
• Example 2 70 parts of the polyoxyalkylene compound (Y102) obtained in Production Example 2 and 30 parts of the polyoxyalkylene compound (Y210) obtained in Production Example 22 were uniformly mixed to obtain the surfactant (S102) of the present invention. .
• the surfactant (S103) of the present invention was obtained by uniformly mixing 90 parts of the polyoxyalkylene compound (Y103) obtained in Production Example 3 and 10 parts of the polyoxyalkylene compound (Y201) obtained in Production Example 13. .
• the surfactant (S104) of the present invention was obtained by uniformly mixing 50 parts of the polyoxyalkylene compound (Y104) obtained in Production Example 4 and 50 parts of the polyoxyalkylene compound (Y204) obtained in Production Example 16. .
• the surfactant (S105) of the present invention was obtained by uniformly mixing 55 parts of the polyoxyalkylene compound (Y105) obtained in Production Example 5 and 45 parts of the polyoxyalkylene compound (Y207) obtained in Production Example 19. .
• Example 6 80 parts of the polyoxyalkylene compound (Y106) obtained in Production Example 6 and 20 parts of the polyoxyalkylene compound (Y202) obtained in Production Example 14 were uniformly mixed to obtain the surfactant (S106) of the present invention. .
• Example 7 85 parts of the polyoxyalkylene compound (Y107) obtained in Production Example 7 and 15 parts of the polyoxyalkylene compound (Y208) obtained in Production Example 20 were uniformly mixed to obtain the surfactant (S107) of the present invention. .
• the surfactant (S108) of the present invention was obtained by uniformly mixing 50 parts of the polyoxyalkylene compound (Y108) obtained in Production Example 8 and 50 parts of the polyoxyalkylene compound (Y209) obtained in Production Example 21. .
• the surfactant (S109) of the present invention was obtained by uniformly mixing 10 parts of the polyoxyalkylene compound (Y109) obtained in Production Example 9 and 90 parts of the polyoxyalkylene compound (Y203) obtained in Production Example 15. .
• Example 10 30 parts of the polyoxyalkylene compound (Y110) obtained in Production Example 10 and 70 parts of the polyoxyalkylene compound (Y206) obtained in Production Example 18 were uniformly mixed to obtain the surfactant (S110) of the present invention. .
• Example 11 30 parts of the polyoxyalkylene compound (Y111) obtained in Production Example 11, 30 parts of the polyoxyalkylene compound (Y103) obtained in Production Example 3 and 40 parts of the polyoxyalkylene compound (Y203) obtained in Production Example 15 were uniformly mixed. To obtain a surfactant (S111) of the present invention.
• Example 13 A reaction vessel similar to Production Example 1 was charged with 2244 parts (1 mole part) of meretito / (PO) 30 mole adduct (Y110) and 3.4 parts (0.06 mole part) of potassium hydroxide under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 290 parts (5 mole parts) of propylene oxide (PO) was added dropwise at 105 ° C. over 5 hours with the same reduced pressure, and the remaining (PO) was allowed to react by continuing stirring at the same temperature for 1 hour. / (PO) 35 mol adduct was obtained. Subsequently, 1269 parts of an amount corresponding to 1 ⁇ 2 of the reaction product was extracted from the reaction vessel, and then dehydrated at 120 ° C.
• PO propylene oxide
• Example 14 In a reaction vessel capable of stirring, heating, cooling, substituting with nitrogen, and depressurizing with a vacuum pump, 1041 parts (0.5 mol parts) of the polyoxyalkylene compound (Y104) obtained in Production Example 4 and obtained in Production Example 16 A mixture (Y104Y204) 2553 parts (1 mol part) uniformly mixed with 1152 parts (0.5 mol part) of a polyoxyalkylene compound (Y204) was charged and dehydrated at 120 ° C. for 2 hours under reduced pressure. Next, hexamethylene diisocyanate (HMDI) ⁇ made by Mitsui Takeda Chemical Co., Ltd., Takenate 700, "Takenate” is a registered trademark of the company at 50 ° C.
• HMDI hexamethylene diisocyanate
• Example 15 In a reaction vessel similar to that in Example 14, 1863 parts (0.7 mol parts) of the polyoxyalkylene compound (Y105) obtained in Production Example 5 and 843 parts (0) of the polyoxyalkylene compound (Y205) obtained in Production Example 17 were used. (3 mol parts) was uniformly mixed with 2706 parts (1.0 mol parts) (Y105Y205) and dehydrated at 120 ° C. for 2 hours under reduced pressure. Next, isophorone diisocyanate (IPDI) ⁇ manufactured by Sumika Bayer Urethane Co., Ltd., Death Module I, "Death Module” is a registered trademark of Bayer Aktiengesellschaft.
• IPDI isophorone diisocyanate
• Example 16> In a reaction vessel similar to that in Example 14, 1481 parts (0.53 mol) of the polyoxyalkylene compound (Y106) obtained in Production Example 6 and 981 parts of polyoxyalkylene compound (Y203) obtained in Production Example 15 (0 (47 mol parts) was uniformly mixed with 2462 parts (1.0 mol parts) (Y106Y203) and dehydrated at 120 ° C. for 2 hours under reduced pressure. Subsequently, 167 parts (0.75 mol part) of isophorone diisocyanate (IPDI) was charged at 60 ° C., and nitrogen substitution was repeated three times while stirring. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 6 hours at the same temperature. After confirming the disappearance of the isocyanate group, a multimer (PY103) was obtained. And this multimer (PY103) was made into the surface active agent (S116) of this invention as it is.
• IPDI isophorone diisocyanate
• Example 17 In a reaction vessel similar to that in Example 14, 1041 parts (0.5 mol parts) of the polyoxyalkylene compound (Y104) obtained in Production Example 4 and 1152 parts (0 of polyoxyalkylene compound (Y204) obtained in Production Example 16) 0.5 mol part) (Y104Y204) 2553 parts (1.0 mol part), potassium hydroxide ⁇ reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd. displayed. same as below. ⁇ 6.0 parts and 1,6-hexamethylene glycol diglycidyl ether ⁇ Epogosei HD, "Epogosei HD” manufactured by Yokkaichi Synthesis Co., Ltd. is a registered trademark of the same company.
• Example 18 In a reaction vessel similar to that in Example 14, 1863 parts (0.7 mol parts) of the polyoxyalkylene compound (Y105) obtained in Production Example 5 and 843 parts (0) of the polyoxyalkylene compound (Y205) obtained in Production Example 17 were used. Mixture (Y105Y205) 2706 parts (1.0 mol part), potassium hydroxide 6.0 parts and polyoxypropylene (7 mol) glycol diglycidyl ether ⁇ Sanyo Chemical Industries, Ltd. Glicier PP-300P, epoxy equivalent: 300, “Gricier” is a registered trademark of the same company. ⁇ After 402 parts (0.67 mole part) was added, dehydration was performed at 80 ° C. under reduced pressure.
• Example 19 In a reaction vessel similar to that in Example 14, 1725 parts (0.83 mol) of the polyoxyalkylene compound (Y110) obtained in Production Example 10 and 434 parts of the polyoxyalkylene compound (Y210) obtained in Production Example 22 (0 (17 mol parts) and 2159 parts (1.0 mol parts), potassium hydroxide 6.0 parts and polyoxypropylene (7 mol) glycol diglycidyl ether (Glicier PP-300P) After adding 300 parts (0.5 mol part), it was dehydrated at 80 ° C. under reduced pressure. Next, the reaction was carried out at 110 ° C. for 4 hours and at 130 ° C. for 8 hours with reduced pressure to confirm the disappearance of the epoxy group. Next, Kyoward treatment and dehydration were performed to obtain a multimer (PY203). And this multimer (PY203) was made into the surfactant (S119) of this invention as it is.
• Example 20> In a reaction vessel similar to that in Example 14, 1041 parts (0.5 mol parts) of the polyoxyalkylene compound (Y104) obtained in Production Example 4 and 1152 parts (0 of polyoxyalkylene compound (Y204) obtained in Production Example 16) 0.55 parts) uniformly mixed (Y104Y204) 2553 parts (1.0 mole parts), sodium hydroxide ⁇ special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd. displayed. same as below. ⁇ After 30.0 parts (0.75 mole part) was added, dehydration was performed at 110 ° C. under reduced pressure.
• Example 21 In a reaction vessel similar to that in Example 14, 1863 parts (0.7 mol parts) of the polyoxyalkylene compound (Y105) obtained in Production Example 5 and 843 parts (0) of the polyoxyalkylene compound (Y205) obtained in Production Example 17 were used. .3 mol parts) and 2706 parts (1.0 mol parts) of a mixture (Y105Y205) and 34.0 parts (0.85 mol parts) of sodium hydroxide were added at 110 ° C. under reduced pressure. Dehydrated. Next, 62.0 parts (0.67 mol part) of epichlorohydrin was added dropwise over 5 hours at 40 ° C. with reduced pressure, and the mixture was further stirred at 40 ° C. for 5 hours.
• Example 22 In a reaction vessel similar to that in Example 14, 910 parts (0.41 mol) of the polyoxyalkylene compound (Y112) obtained in Production Example 12 and 1369 parts (0) of the polyoxyalkylene compound (Y209) obtained in Production Example 21 were used. 259 parts (1.0 mole part) and 34.0 parts (0.85 mole part) of sodium hydroxide, and then at 110 ° C. under reduced pressure. Dehydrated. Next, 74.0 parts (0.8 mole part) of epichlorohydrin was added dropwise over 5 hours at 40 ° C. under reduced pressure, and the mixture was further stirred at 40 ° C. for 5 hours. Thereafter, the temperature was raised to 100 ° C. and stirring was continued for 5 hours and then at 130 ° C. for 3 hours, and the disappearance of the epoxy group was confirmed. Next, Kyoward treatment and dehydration gave a multimer (PY303). And this multimer (PY303) was made into the surfactant (S122) of this invention as it is.
• Surfactant (C3) for comparison was obtained by uniformly mixing 50 parts of the polyoxyalkylene compound (Y103) obtained in Production Example 3 and 50 parts of the polyoxyalkylene compound (Y110) obtained in Production Example 10. .
• a comparative surfactant (C5) was obtained by uniformly mixing 50 parts of the polyoxyalkylene compound (Y203) obtained in Production Example 13 and 50 parts of the polyoxyalkylene compound (Y208) obtained in Production Example 18. .
• Emulsion Epicoat 1004 ⁇ trade name, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 950, “Epicoat” is a registered trademark of Resolution Research Netherland Bethloten Fuennaut Shap. ⁇ 200 parts, Epicoat 828EL ⁇ trade name, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 190 ⁇ , 200 parts, methyl isobutyl ketone (MIBK) 200 parts, N-methylethanolamine 60 parts, diethylenetriamine MIBK diketiminate 75 A base emulsion was obtained by adding 90 parts of MIBK solution containing 1% by weight.
• MIBK methyl isobutyl ketone
• ⁇ Foam control> In an atmosphere of 30 ° C. and 60% relative humidity, 100 ml of the electrodeposition paint for evaluation adjusted to 30 ° C. was added to a flow cup ⁇ JIS K5600-2-2: 1999, No. 4 ⁇ and dropped into a 500 mL glass graduated cylinder (inner diameter: 50.0 mm, cylindrical length: 340 mm) placed under 1.0 m, and almost all of the electrodeposition paint for evaluation dropped into the graduated cylinder. Immediately after the start, when observing from the opening of the graduated cylinder, the time until a part of the foam layer in the graduated cylinder was cut and the coating liquid level in the lower layer started to be seen was defined as the defoaming time (minutes). The blank paint was similarly evaluated.
• ⁇ Finish finish> A test panel in which the evaluation electrodeposition paint or blank paint obtained above was treated with zinc phosphate ⁇ trade name: zinc phosphate-treated steel sheet, manufactured by Nippon Test Panel Co., Ltd., dimensions, 150 mm ⁇ 70 mm ⁇ 0.8 mm ⁇ at 150 V Electrodeposition coating was carried out for 3 minutes, then pulled up from the coating bath, showered with tap water and washed with water. After naturally drying for 5 minutes in an atmosphere of 25 ° C. and 40% relative humidity, after baking for 20 minutes in an electric hot air drier adjusted to 160 ° C., it is cooled to about 25 ° C. and finished according to the following criteria. Was visually evaluated.
• Finishability-1 No occurrence of water droplets on the surface of the coating film 1-2: Very little water droplets on the coating surface (about 1 to 2 places) 3-4: Water droplets on the coating surface Slight occurrence (about 3 to 4 places) 5 ⁇ : Many water drop marks are seen on the coating film surface (more than 5 places)
• the surfactants of the present invention were extremely excellent in foam controllability and finish. On the other hand, with the surfactants of the blank and Comparative Examples 1, 2, and 3, the foam controllability was poor. In addition, the surfactants of Comparative Examples 4, 5, and 6 were inferior in water solubility (water dispersibility) in addition to many water droplet traces.

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