WO2021111800A1 - 消泡剤及び水系コーティング組成物 - Google Patents
消泡剤及び水系コーティング組成物 Download PDFInfo
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- WO2021111800A1 WO2021111800A1 PCT/JP2020/041458 JP2020041458W WO2021111800A1 WO 2021111800 A1 WO2021111800 A1 WO 2021111800A1 JP 2020041458 W JP2020041458 W JP 2020041458W WO 2021111800 A1 WO2021111800 A1 WO 2021111800A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Definitions
- the present invention relates to antifoaming agents and water-based coating compositions.
- a defoaming agent for water-dilutable paint systems containing a propylene oxide (PO) adduct is known (Patent Document 1).
- An object of the present invention is to provide a defoaming agent having excellent defoaming properties (foaming and defoaming effects) even in a paint to be coated with a roller.
- the characteristic of the defoaming agent of the present invention is that it contains a polyoxyalkylene compound (A) represented by the general formula (1) and a compound (B) represented by the general formula (5).
- the gist is that the weight ratio ⁇ (A): (B) ⁇ of compound (A) to compound (B) is 50:50 to 1:99.
- S 1 is a group represented by the general formula (2)
- S 2 is a group represented by the general formula (3)
- G is a reaction residue of diglycidyl ether having 10 to 50 carbon atoms
- P is a general formula.
- the group represented by (4), q represents 0, 1 or 2.
- Q is a residue obtained by removing a hydrogen atom from t primary hydroxyl groups of a non-reducing di or trisaccharide
- OA is an oxyalkylene group having 2 to 4 carbon atoms
- R 1 is an alkylene or arylene having 2 to 15 carbon atoms.
- O is an oxygen atom
- H is a hydrogen atom
- n is an integer of 2 to 30
- t is an integer of 2 to 4
- m is an integer of 1 to 20
- the total number of OA contained in S 1 unit or S 2 unit are integers of 10 to 50, respectively, and S 1 , S 2 , G, P, (OA) n , (OA) m , Q, n, and m may be the same or different, respectively.
- R 2 is a reaction residue obtained by removing a hydrogen atom from an active hydrogen compound having 3 to 24 carbon atoms
- X is a hydrogen atom or an acyl group having 4 to 23 carbon atoms
- OA is an oxyalkylene group having 2 to 4 carbon atoms
- a is an oxyalkylene group having 2 to 4 carbon atoms.
- An integer of 1 to 50, b is an integer of 1 to 6, and X, (OA) a , and a may be the same or different, respectively.
- the gist of the feature of the water-based coating composition of the present invention is that it consists of a water-based coating material and the above-mentioned defoaming agent.
- the defoaming agent of the present invention exhibits excellent defoaming properties (foaming and defoaming effects) even in a roller-painted paint.
- the water-based coating composition of the present invention contains the above-mentioned defoaming agent, it exhibits excellent defoaming properties even when it is roller-coated.
- the reaction residue (G) of diglycidyl ether having 10 to 50 carbon atoms includes a residue obtained by ring-opening reaction of the epoxy group of diglycidyl ether having 10 to 50 carbon atoms.
- reaction residue of such diglycidyl ether examples include 2,11-dihydroxy-4,9-dioxadodecylene ⁇ -CH 2 CH (OH) CH 2 OCH 2 CH 2 CH 2 CH 2 OCH 2 CH ( OH) CH 2- ⁇ , 2,6,10-trihydroxy-4,8-dioxaundecylene ⁇ -CH 2 CH (OH) CH 2 OCH 2 CH (OH) CH 2 OCH 2 CH (OH) CH 2- ⁇ , 2,10-Dihydroxy-4,8-dioxa-6,6-dimethylundecylene ⁇ -CH 2 CH (OH) CH 2 OCH 2 C (CH 3 ) 2 CH 2 OCH 2 CH (OH) CH 2- ⁇ , 2,13-Dihydroxy-4,11-dioxatetradecylene ⁇ -CH 2 CH (OH) CH 2 OCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 OCH 2 CH (OH) CH 2- ⁇ , 2 , 10-Dihydroxy-4,8-Dioxa
- the di or trisaccharide that can constitute the residue (Q) obtained by removing the hydrogen atom from the t primary hydroxyl groups of the non-reducing di or trisaccharide is Includes sucrose, trehalose, isotrehalose, gentianose, raffinose, meletitos and planteose.
- sucrose, trehalose, gentianose, raffinose and planteose are preferable from the viewpoint of defoaming property, sucrose and raffinose are more preferable, and sucrose is particularly preferable from the viewpoint of supply and cost.
- alkylene or arylene (R 1 ) having 2 to 15 carbon atoms alkylene having 2 to 9 carbon atoms is used as the alkylene, and ethylene and 3-oxapentylene (-CH 2 CH 2 OCH 2 CH 2- ), Propylene, 3-oxa-2,4-dimethylpentylene (-CH 2 CH (CH 3 ) OCH (CH 3 ) CH 2- ), butylene, hexamethylene, cyclohexylene, methylenecyclohexylenemethylene (-CH) 2 C 6 H 10 CH 2- ), methylcyclohexylene, trimethylcyclohexylene and the like can be mentioned.
- R 1 examples of the arylene, used is an arylene such as having 6 to 15 carbon atoms, phenylene, methyl-phenylene, ethylphenylene, tetramethyl phenylene, xylylene, naphthylene, biphenylene, dimethyl biphenylene Li Ren, anthrylene, phenanthrylene, - Group represented by (ph) -CH 2- (ph)-, group represented by-(ph) -C (CH 3 ) 2- (ph)-,-(ph) -CH 2 CH 2- ( Examples thereof include a group represented by ph)-and a group represented by -CH 2- (ch) -CH 2- (ph represents a phenylene group and ch represents a cyclohexylene group).
- examples of the oxyalkylene group (OA) having 2 to 4 carbon atoms include oxyethylene, oxypropylene, oxybutylene, and a mixture thereof.
- oxyethylene and oxypropylene are preferable from the viewpoint of suppressing repellent, and oxypropylene and oxyethylene are more preferably mixed.
- oxypropylene and oxybutylene are preferable, and oxypropylene and oxybutylene are more preferably mixed.
- the content ratio (mol%) of oxyethylene is 4 based on the total number of moles of oxyalkylene groups. It is preferably from 10 to 10, and more preferably 4 to 8. Further, in this case, it is preferable that oxypropylene and / or oxybutylene is located at the end away from the reaction residue (Q). That is, when (OA) n contains an oxyethylene group, it is preferable that the oxyethylene group is directly bonded to the reaction residue (Q). Further, when (OA) n contains a plurality of types of oxyalkylene groups, it may contain either a block form or a random form.
- the content ratio (mol%) of oxyethylene is preferably 5 to 20 based on the total number of moles of the oxyalkylene group. , More preferably 10 to 15. Further, in this case, it is preferable that oxyethylene is located at an end away from alkylene or arylene (R 1). That is, when (OA) m contains an oxyethylene group, it is preferable that the oxyethylene group is bonded to the end portion away from (R 1). Further, when (OA) m contains a plurality of types of oxyalkylene groups, it may contain either a block shape or a random shape.
- N is preferably an integer of 2 to 30, more preferably an integer of 2 to 18, particularly preferably an integer of 5 to 18, and most preferably an integer of 5 to 15. Within this range, the defoaming property is further improved.
- T is preferably an integer of 2 to 4, and more preferably 3. Within this range, the defoaming property is further improved.
- M is preferably an integer of 1 to 20, more preferably an integer of 2 to 18, particularly preferably an integer of 4 to 18, and most preferably an integer of 4 to 16. Within this range, the defoaming property is further improved.
- the total number of OA contained in S 1 unit or S 2 unit is preferably an integer of 10 to 50, more preferably an integer of 15 to 45, particularly preferably an integer of 15 to 40, and most preferably an integer of 20 to 35. It is an integer. Within this range, the defoaming property is further improved.
- the polyoxyalkylene compound (A) represented by the general formula (1) can be produced by a known method, for example, 1 mol part of a non-reducing di or trisaccharide (a1) and an alkylene oxide having 2 to 4 carbon atoms.
- A2 Step (1) of obtaining compound (a12) from a chemical reaction of 10 to 50 mol parts;
- a method including the step (3) of obtaining the alkylene compound (A) is included. That is, the polyoxyalkylene compound (A) produced by these chemical reactions may have a distribution in the number of oxyalkylene groups, n, m, q, etc. In this case, strictly speaking, a plurality of types of polyoxy It becomes a mixture of alkylene compounds, and the polyoxyalkylene compound represented by the general formula (1) is contained in this mixture.
- the amount (molar portion) of the alkylene oxide (a2) used is preferably 10 to 50 with respect to 1 mol part of the non-reducing di or trisaccharide (a1). , More preferably 15 to 45, particularly preferably 15 to 40, and most preferably 20 to 35. Within this range, the defoaming property is further improved.
- the amount (molar portion) of the alkylene oxide (a2) used is preferably 4 to 40 mol with respect to 1 mol part of the glycol (a3) having 2 to 15 carbon atoms. , More preferably 4 to 36, particularly preferably 8 to 36, and most preferably 8 to 32. Within this range, the defoaming property is further improved.
- the amount (molar portion) of the compound (a32) used is preferably 0.5 to 0.75 with respect to 1 mol part of the compound (a12). It is more preferably 0.5 to 0.7, particularly preferably 0.55 to 0.7, and most preferably 0.6 to 0.7. Within this range, the defoaming property is further improved.
- the amount (molar portion) of diglycidyl ether (a4) used is preferably 1 to 1.5, more preferably 1 to 1.4, and particularly preferably 1 with respect to 1 mol part of compound (a12). .2 to 1.4, most preferably 1.2 to 1.35. Within this range, the defoaming property is further improved.
- the non-reducing di or trisaccharide (a1) the same di or trisaccharide that can constitute the reaction residue (Q) can be used, and the preferable range is also the same.
- alkylene oxide (a2) an alkylene oxide having 2 to 4 carbon atoms or the like can be used, and ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO) and Examples thereof include a mixture thereof.
- EO and PO are preferable, and PO and EO are more preferably mixed from the viewpoint of suppressing repellent.
- PO and BO are preferable, and PO and BO are more preferably mixed.
- the reaction order (block shape, random shape and combination thereof) And the usage ratio is not limited, but it is preferable to include a block shape or a combination of a block shape and a random shape.
- the ratio of EO used (mol%) is preferably 4 to 10, more preferably 4 to 8, based on the total number of moles of the alkylene oxide.
- EO and PO and / or BO it is preferable to react PO and / or BO after the reaction of di or trisaccharide (a1) with EO.
- the reaction order (block shape, random shape and combination thereof) and The usage ratio is not limited, but it is preferable to include a block shape or a combination of a block shape and a random shape.
- the ratio of EO used (mol%) is preferably 5 to 20, more preferably 10 to 15, based on the total number of moles of alkylene oxide. Further, in this case, it is preferable to react PO and / or BO and then react with EO.
- glycol (a3) having 2 to 15 carbon atoms examples include alkylenediol ⁇ ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,2-butanediol, hexamethylene glycol, cyclohexyl glycol, and methyl.
- ethylene glycol, propylene glycol, hexamethylene glycol and bisphenol A are preferable, and propylene di
- Examples of the diglycidyl ether (a4) having 10 to 50 carbon atoms include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin diglycidyl ether, and trimethyl propane. Examples thereof include diglycidyl ether and pentaerythritol diglycidyl ether, and further, polyoxyalkylene glycol diglycidyl ether (polyoxyethylene glycol diglycidyl ether, polyoxypropylene glycol diglycidyl ether, polyoxytetramethylene ether glycol diglycidyl ether and the like).
- the chemical reaction of non-reducing di or trisaccharide (a1) and alkylene oxide (a2) and the chemical reaction of glycols (a3) and (a2) having 2 to 15 carbon atoms are anionic polymerization, cationic polymerization or coordination anion. It may be carried out in any form such as polymerization. Further, these polymerization forms may be used alone or in combination depending on the degree of polymerization and the like.
- a reaction catalyst can be used for the chemical reaction with the alkylene oxide (a2).
- the amide described below is used as the reaction solvent, it is not necessary to use a reaction catalyst.
- reaction catalyst a commonly used catalyst for alkylene oxide addition reaction or the like can be used, and hydroxides of alkali metals or alkaline earth metals (potassium hydroxide, rubidium hydroxide, cesium hydroxide, etc.), alkali metal alcoholates, etc. can be used.
- alkali metal or alkaline earth metal carbonates (potassium carbonate, cesium carbonate, barium carbonate, etc.), tertiary amines with 3 to 24 carbon atoms (trimethylamine, trioctylamine, etc.) Triethylenediamine, tetramethylethylenediamine, etc.), Lewis acid (bastin chloride, boron trifluoride, etc.) and the like are used.
- alkali metal hydroxides and tertiary amines are preferred, with potassium hydroxide, cesium hydroxide and trimethylamine being more preferred.
- the amount (% by weight) used is the total weight of the non-reducing di or trisaccharide (a1) and the alkylene oxide (a2), or the total weight of the glycol (a3) and the alkylene oxide (a2). Based on the weight, it is preferably 0.05 to 2, more preferably 0.1 to 1, and particularly preferably 0.2 to 0.6.
- an alkaline adsorbent such as synthetic aluminosilicate ⁇ for example, trade name: Kyoward 700, Kyowa Chemical Industry Co., Ltd., " "Kyoward” is a registered trademark of the same company ⁇ (Japanese Patent Laid-Open No. 53-1234999, etc.), a method of dissolving in a solvent such as xylene or toluene and washing with water (Japanese Patent Publication No. 49-14359, corresponding US publication). Application; US3582491A, etc.), a method using an ion exchange resin (Japanese Patent Laid-Open No. 51-23211, etc.) and a method of filtering an carbonate produced by neutralizing an alkaline catalyst with carbon dioxide gas (Japanese Patent Publication No. 52-33000). And so on.
- an alkaline adsorbent such as synthetic aluminosilicate ⁇ for example, trade name: Kyoward 700, Kyowa Chemical Industry Co.
- the CPR (Controlled Polymerization Rate) value is preferably 20 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2 or less.
- CPR is measured in accordance with JIS K1557-4: 2007 (corresponding international standard; ISO14899: 2001).
- reaction vessel it is preferable to use a pressure-resistant reaction vessel capable of heating, cooling and stirring.
- reaction atmosphere it is preferable to create an atmosphere of a vacuum or dried inert gas (argon, nitrogen, carbon dioxide, etc.) in the reaction apparatus before introducing the alkylene oxide (a2) into the reaction system.
- the reaction temperature (° C.) is preferably 80 to 150, more preferably 90 to 130.
- the reaction pressure (gauge pressure: MPa) is preferably 0.8 or less, more preferably 0.5 or less.
- the end point of the reaction can be confirmed by the following method or the like. That is, when the reaction temperature is kept constant for 15 minutes, if the decrease in reaction pressure (gauge pressure) is 0.001 MPa or less, the reaction end point is set.
- the required reaction time is usually 4 to 12 hours.
- reaction solvent for the chemical reaction of the non-reducing di or trisaccharide (a1) and the alkylene oxide (a2).
- the reaction solvent preferably does not have active hydrogen, and more preferably dissolves non-reducing di or trisaccharide (a1), alkylene oxide (a2) and a product (a12) produced by these reactions. Is preferable.
- an alkyl amide having 3 to 8 carbon atoms, a heterocyclic amide having 5 to 7 carbon atoms, or the like can be used.
- alkylamide examples include N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-N-propylacetamide and 2-dimethylaminoacetaldehyde dimethylacetal.
- DMF N, N-dimethylformamide
- N, N-dimethylacetamide N, N-diethylacetamide
- N-methyl-N-propylacetamide 2-dimethylaminoacetaldehyde dimethylacetal.
- heterocyclic amide examples include N-methylpyrrolidone, N-methyl- ⁇ -caprolactam and N, N-dimethylpyrrole carboxylic acid amide.
- alkylamides and N-methylpyrrolidone are preferred, more preferably DMF, N, N-dimethylacetamide and N-methylpyrrolidone, particularly preferably DMF and N-methylpyrrolidone, and most preferably DMF.
- the amount (% by weight) used is preferably 20 to 200 based on the weight of the compound (a12) produced by the reaction of the di or trisaccharide (a1) with the alkylene oxide (a2). It is more preferably 40 to 180, and particularly preferably 60 to 150.
- the residual amount (% by weight) of the reaction solvent is preferably 0.1 or less, more preferably 0.05 or less, and particularly preferably 0.01 or less, based on the weight of the polyoxyalkylene compound (A). is there.
- the residual amount of the reaction solvent can be determined by a gas chromatography method using an internal standard substance.
- conditions for distillation under reduced pressure conditions such as distillation at 100 to 150 ° C. under a reduced pressure of 0.6 to 27 kPa can be applied.
- a method of treating with an alkaline adsorbent such as synthetic aluminosilicate ⁇ for example, trade name: Kyoward 700, Kyowa Chemical Industry Co., Ltd. ⁇ can be applied.
- Kyoward 700 the amount (% by weight) of the alkaline adsorbent added is about 0.1 to 10 based on the weight of the compound (a12)
- the treatment temperature is about 60 to 120 ° C.
- the treatment time is It takes about 0.5 to 5 hours.
- the residual amount of the reaction solvent can be reduced by removing the alkali adsorbent by filtering using a filter paper or a filter cloth.
- a reaction catalyst can be used for the chemical reaction (epoxy ring-opening reaction) in the step (3), and such a catalyst is the same as that used for the addition reaction of the alkylene oxide (a2) and is known.
- a catalyst Japanese Patent Laid-Open No. 2004-224945, etc. or the like can be applied.
- reaction of compound (a12), compound (a32) and diglycidyl ether (a4) is the same as the reaction of non-reducing di or trisaccharide (a1) and alkylene oxide (a2), and the reaction apparatus The same applies to the catalyst and its removal.
- examples of the active hydrogen compound capable of constituting the reaction residue (R 2 ) obtained by removing the hydrogen atom from the active hydrogen compound having 3 to 24 carbon atoms include a hydroxyl group (-OH) and an imino group (-OH).
- alcohols examples include monool (isopropyl alcohol, butanol, stearyl alcohol, oleyl alcohol, isostearyl alcohol, etc.) and polyols (propylene glycol, glycerin, diglycerin, tetraglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc.). Can be mentioned. In addition to these, non-reducing di or trisaccharides are also included.
- amide examples include monoamide (propionic acid amide, butanoic acid amide, stearyl amide, etc.) and polyamide (malonic acid diamide, ethylene bisbutyl amide, ethylene bisoctyl amide, etc.).
- amines examples include monoamines (isopropylamine, diethylamine, aniline, stearylamine, etc.) and polyamines (propylene diamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, etc.) and the like.
- carboxylic acid examples include monocarboxylic acids (propionic acid, butanoic acid, stearic acid, oleic acid, benzoic acid, etc.) and polycarboxylic acids (malonic acid, maleic acid, hexanedioic acid, benzenedicarboxylic acid, etc.).
- hydroxycarboxylic acid examples include 3-hydroxypropionic acid, tartaric acid, malic acid and 12-hydroxystearic acid.
- aminocarboxylic acid examples include alanine, 4-aminobutyric acid, 6-aminocaproic acid, 12-aminolauric acid and the like.
- the acyl group having 4 to 23 carbon atoms includes a saturated acyl group and an unsaturated acyl group.
- Saturated acyl groups include butanoyl, pentanoyl, hexanoyl, heptanoyle, octanoyl, nonanoyl, decanoyle, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl, and icosanoyl.
- Examples thereof include henicosanoyl, heneicosanoyl, docosanoyl, tricosanoyl, cyclopentanoyl, cyclohexanoyl, cycloheptanoyle, methylcyclopentanoyl, methylcyclohexanoyl and methylcycloheptanoyle.
- Unsaturated acyl groups include crotonoyle, isocrotonoyle, butenoyl, butadienoyle, pentenoyle, hexenoyl, heptenoyl, octenoyl, nonenoyl, decenoyl, undecenoyl, dodecenoyl, tetradecenoyl, oleloyl, ellaidinoyl, cyclopentenoyl, Cyclohexenoyl, 2,4-cyclohexadienoyl, cycloheptenoyl, methylcyclopentenoyl, methylcyclohexenoyl, methylcycloheptenoyl and the like can be mentioned.
- an acyl group having 10 to 20 carbon atoms is preferable, and an acyl group having 12 to 18 carbon atoms is more preferable.
- oxyalkylene groups (OA) having 2 to 4 carbon atoms oxyethylene and oxypropylene are preferable, and oxypropylene and oxyethylene are more preferably mixed.
- the bonding order (block-like, random-like and combination thereof) and content ratio of these oxyalkylene groups are not limited, but may be block-like or block-like. It preferably contains a random combination, more preferably a block.
- A is an integer of 1 to 50, preferably an integer of 2 to 40, and more preferably an integer of 4 to 30. Within this range, the defoaming property is further improved.
- B is an integer of 1 to 6, preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.
- the compound (B) represented by the general formula (5) can be easily obtained by a known method (alkylene oxide addition reaction, esterification reaction, etc.).
- compound (B) can be easily obtained by a chemical reaction between an active hydrogen compound having 4 to 24 carbon atoms, a compound obtained by a chemical reaction with an alkylene oxide having 2 to 4 carbon atoms, and a carboxylic acid.
- the weight ratio of the polyoxyalkylene compound (A) to the compound (B) ⁇ (A) :( B) ⁇ is preferably 50:50 to 1:99, more preferably 40:60 to 10:90, and particularly preferably 40:60 to 10:90. It is from 30:70 to 20:80. Within this range, the defoaming property is further improved.
- the defoaming agent of the present invention preferably contains a hydrophobic liquid (C).
- the hydrophobic liquid (C) includes mineral oil, animal and vegetable oil, and silicone oil.
- Known mineral oils include known mineral oils, such as spindle oils, machine oils, refrigerating machine oils, etc., as well as synthetic lubricating oils ⁇ olefin oils ( ⁇ -olefin oils), polyglycol oils, polybutene oils, alkylbenzene oils (alchelates). Oil) and isoparaffin oil ⁇ .
- the kinematic viscosity (mm 2 / s; 40 ° C.) of the mineral oil is preferably 0.5 to 140, more preferably 1 to 40, and particularly preferably 4 to 35.
- the kinematic viscosity can be measured in accordance with JIS K2283: 2000 "Crude oil and petroleum products-Dynamic viscosity test method and viscosity index calculation method" (corresponding international standards; ISO2909: 1981 and ISO3104: 1994) (the same applies hereinafter). ).
- Animal and vegetable oils include known animal and vegetable oils, such as fish oil, rapeseed oil, soybean oil, sunflower seed oil, cottonseed oil, peanut oil, rice bran oil, corn oil, saflower oil, olive oil, sesame oil, evening primrose oil, palm oil, and shea butter. , Salfat, cacao butter, palm oil, palm kernel oil and the like.
- Fine Oil N Animal and vegetable oils are easily available on the market, and trade names include Fine Oil N, Fine Oil LR-1, Fine Oil ISB-12 (Miyoshi Oil & Fat Co., Ltd.), and the like.
- silicone examples include dimethyl silicone and polyether-modified silicone.
- the kinematic viscosity (mm 2 / s; 25 ° C.) of the silicone is preferably 100 to 60,000, more preferably 100 to 10,000, and particularly preferably 500 to 5,000.
- a part of the methyl group of dimethylsiloxane is an alkoxypolyoxyalkyleneoxypropyl group (alkoxy carbon number 1 to 6, alkylene carbon number 2 to 3, degree of polymerization 2 to 50) or alkoxypolyoxyalkylene. It includes those replaced with a group (alkoxy having 1 to 6 carbon atoms, alkylene having 2 to 3 carbon atoms, and a degree of polymerization of 2 to 50).
- Silicones are readily available on the market and are trade names (numbers in parentheses represent “kinematic viscosity (mm 2 / s, 25 ° C.)"), KF-96 (2500) KF-352A (1600) and KF-615A (920) (Shinetsu Chemical Industry Co., Ltd.); DOWNSIL SH 8700 Fluid (1300) and DOWNSIL SF 8410 Fluid (2900) (Toray Dow Corning Co., Ltd., "DOWNSIL” is registered by The Dow Chemical Company (Trademark); WACKER SILICONE FLUID AKF100-10000 (100-10000) and WACKER TN (1200) (Asahi Kasei Wacker Silicone Co., Ltd., "WACKER” is a registered trademark of Wacker Chemie Actien Gezel Shaft).
- the hydrophobic liquid (C) may contain wax (polyethylene oxide or the like), amide (fatty acid polyamide or the like), metal soap (fatty acid aluminum or the like), hydrophobic silica or the like.
- the viscosity of the hydrophobic liquid (C) (25 °C, B-type viscosity, mPa ⁇ s, 60 rpm) is preferably 10 ⁇ 6.5 ⁇ 10 4, more preferably from 100 ⁇ 1.0 ⁇ 10 4.
- Viscosity is in accordance with JIS K7117-1: 1999 "Plastic-Liquid, Emulsion or Dispersive Resin-Measurement Method of Apparent Viscosity with Brookfield Rotational Viscometer" (corresponding international standard; ISO2555: 1990). Can be measured.
- the content (part by weight) of the hydrophobic liquid (C) is the polyoxyalkylene compound (A) represented by the general formula (1) and the compound represented by the general formula (5) ( With respect to 100 parts by weight of the total weight of B), it is preferably 20 to 10000, more preferably 500 to 3000, and particularly preferably 1000 to 2000.
- the defoaming agent of the present invention is known in addition to the polyoxyalkylene compound (A) represented by the general formula (1), the compound (B) represented by the general formula (5), and the hydrophobic liquid (C).
- Additives viscosity modifiers, wetting agents, dispersants, film-forming modifiers, etc.
- solvents and the like can be contained.
- Viscosity modifiers include SN Sixner 630 and 612 (San Nopco Ltd.), wetting agents include SN Wet 125, 126, 366, 980 and 984 (San Nopco Ltd.), and dispersants.
- film-forming adjusting agents such as SN Dispersant 9228 and Color Sparse 188A (San Nopco Ltd.) include Texanol (Eastman Chemical Company, "Texanol” is a registered trademark of Yoshimura Oil Chemical Co., Ltd.).
- water As the solvent, water, a water-soluble organic solvent, or the like can be used.
- water include ion-exchanged water, distilled water, tap water, industrial water and the like.
- water-soluble organic solvent include alcohols having 1 to 3 carbon atoms (methanol, ethanol, isopropanol, etc.), ketones having 3 to 6 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), and ethers having 2 to 6 carbon atoms (dimethyl ether).
- ether ester having 4 to 6 carbon atoms (butyl cell solve acetate, etc.), and the like, and these may be used in combination.
- the content (% by weight) is preferably 1 to 300% by weight based on the weights of the polyoxyalkylene compound (A) and the compound (B).
- the defoaming agent of the present invention contains the above-mentioned polyoxyalkylene compound (A) and compound (B), there is no limitation on the production method. Further, when the hydrophobic liquid (C), the additive and / or the solvent and the like are contained, there is no limitation on the production method as long as these can be uniformly mixed with the polyoxyalkylene compound (A) and the compound (B).
- the defoaming agent of the present invention can be applied as a defoaming agent for paints and a defoaming agent for various manufacturing processes. Of these, it is suitable as a defoaming agent for paints, and further suitable as a defoaming agent for water-based coating compositions.
- the defoaming agent of the present invention When the defoaming agent of the present invention is applied to a paint, the defoaming agent may be (1) added at the time of pigment dispersion and / or (2) after the paint is prepared. When applied to various manufacturing processes, the defoaming agent is added to (1) the supply of raw materials, (2) before heating and / or decompression treatment, and / or (3) the final finishing step, etc. Either may be used.
- the amount of the defoaming agent added of the present invention can be appropriately determined depending on the application target, application, etc.
- the content (% by weight) of the above-mentioned defoaming agent is Based on the weight of the water-based coating material, it is preferably 0.05 to 5, more preferably 0.1 to 4.5, particularly preferably 0.15 to 4, and most preferably 0.2 to 3. Within this range, the defoaming property and the suppression of cissing are further improved.
- water-based coating material contained in the water-based coating composition examples include acrylic binders, vinyl acetate binders, styrene binders, halogenated olefin binders, urethane binders, acrylic-silicone binders, epoxy binders and fluorine binders.
- the water-based coating composition can be applied to the object to be coated by a usual method, and coating methods such as brush coating, roller coating, air spray coating, airless coating, roll coater coating and flow coater coating can be applied.
- coating methods such as brush coating, roller coating, air spray coating, airless coating, roll coater coating and flow coater coating can be applied.
- the effect is particularly remarkable during brush coating and roller coating.
- parts mean parts by weight and% means% by weight.
- Kyoward 700 is removed by filtration using filter paper ⁇ Toyo Filter Paper Co., Ltd. ⁇ , and further dehydrated at 120 ° C. under reduced pressure of 1.3 to 2.7 kPa for 1 hour (hereinafter, abbreviated as "Kyoward treatment”. ), A raffinose PO 8 mol / EO 3 mol / PO 34 mol adduct (S2) was obtained.
- ⁇ Manufacturing example 7 342 parts (1 mol part) of purified granulated sugar and 1500 parts of DMF were added to the pressure-resistant reaction vessel for "nitrogen substitution”. Then, the temperature was raised to 100 ° C. with stirring, and 88 parts (2 mol parts) of (EO) was added dropwise at the same temperature to "react”. Then, at the same temperature, 1334 parts (23 mol parts) of (PO) was added dropwise and "reacted”. Then, "DMF was removed” to obtain a sucrose / EO2 mol / PO23 mol adduct (S7).
- ⁇ Manufacturing example 9 342 parts (1 mol part) of purified granulated sugar and 1500 parts of DMF were added to the pressure-resistant reaction vessel for "nitrogen substitution”. The temperature was then raised to 100 ° C. with stirring, and 1740 parts (30 mol parts) of (PO) was added dropwise at the same temperature to "react”. Then, at the same temperature, 360 parts (5 mol parts) of (BO) was added dropwise and “reacted”. Then, “DMF was removed” to obtain a sucrose / PO 30 mol / BO 5 mol adduct (S9).
- g2 is 1,6-hexanediol diglycidyl ether ⁇ Epogosei HD (M), Yokkaichi Chemical Co., Ltd., epoxy equivalent 150 g / eq, "Epogosei” is a registered trademark of the company ⁇
- g3 is polyoxypropylene glycol (7 mol) ) Diglycidyl ether ⁇ Glycière PP-300P, Sanyo Kasei Kogyo Co., Ltd., epoxy equivalent 290 g / eq, "Glycière” is a registered trademark of the company ⁇ , and the value obtained by doubling each epoxy equivalent is the molar weight. The number was calculated.
- Hydrophobic liquid hydrophobic liquid (KF-96-500CS ⁇ dimethylsilicone oil ⁇ ] was changed to “KF-96-5000CS ⁇ kinematic viscosity 5000 mm 2 / s, dimethylsilicone oil ⁇ ” in the same manner as in Production Example 37. C4) was obtained.
- Example 1 20 parts of the polyoxyalkylene compound (A9) obtained in Production Example 26 and 80 parts of the compound (B2) obtained in Production Example 31 were uniformly stirred and mixed to obtain the defoaming agent (DF1) of the present invention.
- Example 2 to 3 The defoaming agent (DF2) of the present invention was prepared in the same manner as in Example 1 except that 20 parts of the polyoxyalkylene compound (A9) and 80 parts of the compound (B2) were changed to the types and amounts shown in Table 2. ⁇ (DF3) was obtained.
- Example 4 20 parts of the polyoxyalkylene compound (A1) obtained in Production Example 18, 80 parts of the compound (B1) obtained in Production Example 30, and 1000 parts of the hydrophobic liquid (C1) obtained in Production Example 35 were uniformly stirred and mixed. , The antifoaming agent (DF4) of the present invention was obtained.
- Examples 5 to 19> In the same manner as in Example 4, 20 parts of the polyoxyalkylene compound (A1), 80 parts of the compound (B1) and 1000 parts of the hydrophobic liquid (C1) were changed to the types and amounts shown in Table 2. The antifoaming agents (DF5) to (DF19) of the present invention were obtained.
- Emulsion paints were prepared by the following methods using the antifoaming agents obtained in Examples 1 to 19 and Comparative Examples, and the antifoaming properties and repellent properties of these emulsion paints were evaluated by the following methods.
- Emulsion Base Paint An emulsion base paint was prepared by grinding and letting down using an Excel autohomogenizer equipped with impeller type blades with the raw material composition shown in Table 3.
- Emulsion Paint To 100 parts of emulsion base paint, 0.2 part of any of the antifoaming agents (DF1) to (DF19) or the antifoaming agent (H1) for comparison was added, and Excel Auto equipped with a chores type blade was attached. Each evaluation emulsion coating material was obtained by stirring and mixing with a homogenizer at 25 ° C., 1000 rpm for 5 minutes.
- Emulsion paint for evaluation was roller-coated on a 15 cm x 15 cm tin plate using a medium-hair wool roller (Otsuka Brush Manufacturing Co., Ltd.), and after 15 seconds, a photograph was taken to take a picture of the central part of the tin plate ( The bubbles generated in (1.5 cm ⁇ 1.5 cm) were visually counted and shown in Table 4. The smaller the number, the better the defoaming property.
- the water-based coating composition containing the defoaming agent of the present invention is superior in repelling and defoaming properties to the water-based coating composition containing a comparative defoaming agent, and the coating film obtained by applying the paint is , Did not spoil the appearance.
- the defoaming agent of the present invention can be used for all purposes because it suppresses repelling and can dramatically improve the defoaming property. It is particularly effective when contained in an aqueous foaming liquid, for example, paper pulp manufacturing industry (pulping process, papermaking process, coating process, etc.), construction industry (papermaking process, etc.), dye industry, dyeing industry, fermentation industry, etc. It can be applied to a defoaming agent used for air bubbles generated in various processes such as synthetic resin manufacturing industry, synthetic rubber manufacturing industry, ink, paint industry and textile processing industry. Of these, it is suitable as a defoaming agent for paints, and further suitable as a defoaming agent for water-based paints (emulsion paints).
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Abstract
Description
本発明の目的は、ローラー塗装する塗料においても、消泡性(破泡、抑泡効果)に優れる消泡剤を提供することである。
炭素数2~15のグリコール(a3)1モル部と炭素数2~4のアルキレンオキシド(a2)4~40モル部との化学反応から化合物(a32)を得る工程(2);
化合物(a12)1モル部と、化合物(a32)0.5~0.75モル部と、炭素数10~50のジグリシジルエーテル(a4)1~1.5モル部との化学反応からポリオキシアルキレン化合物(A)を得る工程(3)を含む方法が含まれる。すなわち、これらの化学反応により製造されるポリオキシアルキレン化合物(A)は、オキシアルキレン基やn、m、qの数等に分布を生じる場合があり、この場合、厳密には複数種類のポリオキシアルキレン化合物の混合物となり、この混合物の中に、一般式(1)で表されるポリオキシアルキレン化合物が含まれるものである。
耐圧反応容器に、精製グラニュー糖{台糖株式会社、蔗糖}342部(1モル部)及びN,N-ジメチルホルムアミド{三菱ガス化学株式会社、DMF、以下同じ}1000部を加えた。次いで窒素ガスを用いて、ゲージ圧で0.4MPaになるまで加圧し0.02MPaになるまで排出する操作を3回繰り返した(以下、「窒素置換」と略す)。その後攪拌しつつ100℃まで昇温し、次いで同温度にて(PO)580部(10モル部)を4時間かけて滴下し、さらに同温度にて4時間攪拌を続け残存するPOを完全に反応させた(以下、残存するPO等を完全に反応させる操作の記載を「反応させた」と略す)。次いでオイル拡散式真空ポンプ{MODEL SW-150、佐藤真空株式会社}を用い、120℃にて1.3~13kPaの減圧下にてDMFを除去(以下、「DMFを除去」と略す)し、蔗糖/PO10モル付加物(S1)を得た。
耐圧反応容器に、ラフィノース{試薬特級、富士フイルム和光純薬工業株式会社}504部(1モル部)及びDMF1500部を加えて「窒素置換」した。その後攪拌しつつ100℃まで昇温し、同温度にて(PO)464部(8モル部)を滴下し、「反応させた」。さらに同温度にて(EO)132部(3モル部)を滴下し、「反応させた」。次いで「DMFを除去」し、ラフィノース/PO8モル/EO3モル付加物(S2’)を得た。
耐圧反応容器に、蔗糖/PO10モル付加物(S1)922部(1モル部)及び水酸化カリウム2.0部を加えて「窒素置換」し、さらに「脱水」した。次いで減圧のまま100℃にて、(PO)290部(5モル部)を滴下し、「反応させた」。次いで「キョーワード処理」して、蔗糖/PO15モル付加物(S3)を得た。
耐圧反応容器に、蔗糖/PO10モル付加物(S1)922部(1モル)及び水酸化カリウム3.0部を加えて「窒素置換」し、さらに「脱水」した。次いで減圧のまま100℃にて、(PO)580部(10モル部)を滴下し、「反応させた」。次いで「キョーワード処理」して、蔗糖/PO20モル付加物(S4)を得た。
耐圧反応容器に、蔗糖/PO10モル付加物(S1)922部(1モル)及び水酸化カリウム4.0部を加えて「窒素置換」し、さらに「脱水」した。次いで減圧のまま100℃にて、(PO)1160部(20モル部)を滴下し、「反応させた」。次いで「キョーワード処理」して、蔗糖/PO30モル付加物(S5)を得た。
耐圧反応容器に、蔗糖/PO10モル付加物(S1)922部(1モル)及び水酸化カリウム5.0部を加えて「窒素置換」し、さらに「脱水」した。次いで減圧のまま100℃にて、(PO)1450部(25モル部)を滴下し、「反応させた」。次いで「キョーワード処理」して、蔗糖/PO35モル付加物(S6)を得た。
耐圧反応容器に、精製グラニュー糖342部(1モル部)及びDMF1500部を加えて「窒素置換」した。その後攪拌しつつ100℃まで昇温し、同温度にて(EO)88部(2モル部)を滴下し、「反応させた」。次いで同温度にて(PO)1334部(23モル部)を滴下し、「反応させた」。次いで「DMFを除去」し、蔗糖/EO2モル/PO23モル付加物(S7)を得た。
耐圧反応容器に、蔗糖/EO2モル/PO23モル付加物(S7)1764部(1モル)及び水酸化カリウム7.0部を加えて「窒素置換」し、さらに「脱水」した。次いで減圧のまま100℃にて、(PO)1450部(25モル部)を滴下し、「反応させた」。次いで「キョーワード処理」して、蔗糖/EO2モル/PO48モル付加物(S8)を得た。
耐圧反応容器に、精製グラニュー糖342部(1モル部)及びDMF1500部を加えて「窒素置換」した。その後攪拌しつつ100℃まで昇温し、同温度にて(PO)1740部(30モル部)を滴下し、「反応させた」。次いで同温度にて(BO)360部(5モル部)を滴下し、「反応させた」。次いで「DMFを除去」し、蔗糖/PO30モル/BO5モル付加物(S9)を得た。
耐圧反応容器に、ジエチレングリコール{試薬特級、富士フイルム和光純薬工業株式会社、以下、「deg」と略す}106部(1モル部)及び水酸化カリウム1.0部を投入した後、「窒素置換」した。その後攪拌しつつ100℃まで昇温し、次いで同温度にて(PO)116部(2モル部)を、さらに(BO)144部(2モル部)を滴下し、「反応させた」。次いで「キョーワード処理」して、deg/PO2モル/BO2モル付加物(P1)を得た。
耐圧反応容器に、deg106部(1モル部)及び水酸化カリウム3.0部を投入した後、「窒素置換」した。その後攪拌しつつ100℃まで昇温し、次いで同温度にて(PO)1305部(22.5モル部)を滴下し、「反応させた」。次いで(EO)110部(2.5モル部)を滴下し、「反応させた」。次いで「キョーワード処理」して、deg/PO22.5モル/EO2.5モル付加物(P2)を得た。
耐圧反応容器に、ジプロピレングリコール{試薬特級、富士フイルム和光純薬工業株式会社、以下、「dpg」と略す}134部(1モル部)及び水酸化カリウム1.5部を投入した後、「窒素置換」した。その後攪拌しつつ100℃まで昇温し、次いで同温度にて(PO)464部(8モル部)を滴下し、「反応させた」。次いで「キョーワード処理」して、dpg/PO8モル付加物(P3)を得た。
耐圧反応容器に、dpg134部(1モル部)及び水酸化カリウム4.0部を投入した後、「窒素置換」した。その後攪拌しつつ100℃まで昇温し、次いで同温度にて(PO)1856部(32モル部)を滴下し、「反応させた」。次いで「キョーワード処理」して、dpg/PO32モル付加物(P4)を得た。
耐圧反応容器に、dpg/PO32モル付加物(P4)1990部(1モル部)及び水酸化カリウム5部を投入した後、「窒素置換」し、ついで「脱水」した。その後攪拌しつつ100℃まで昇温し、次いで同温度にて(PO)232部(4モル部)を滴下し、「反応させた」。さらに(EO)176部(4モル部)を滴下し、「反応させた」。次いで「キョーワード処理」して、dpg/PO36モル/EO4モル付加物(P5)を得た。
耐圧反応容器に、dpg/PO8モル付加物(P3)598部(1モル部)及び水酸化カリウム2部を投入した後、「窒素置換」し、さらに「脱水」した。その後攪拌しつつ100℃まで昇温し、次いで同温度にて(PO)290部(5モル部)を滴下し、「反応させた」。さらに(EO)88部(2モル部)を滴下し、「反応させた」。次いで「キョーワード処理」して、dpg/PO13モル/EO2モル付加物(P6)を得た。
耐圧反応容器に、ヘキサメチレングリコール{試薬特級、富士フイルム和光純薬工業株式会社、以下、「hg」と略す}118部(1モル部)及び水酸化カリウム1.5部を投入した後、「窒素置換」した。その後攪拌しつつ100℃まで昇温し、次いで同温度にて(PO)986部(17モル部)を滴下し、「反応させた」。さらに(EO)132部(3モル部)を滴下し、「反応させた」。次いで「キョーワード処理」して、hg/PO17モル/EO3モル付加物(P7)を得た。
耐圧反応容器に、ジプロピレングリコール{試薬特級、富士フイルム和光純薬工業株式会社、以下、「dpg」と略す}134部(1モル部)及び水酸化カリウム1.5部を投入した後、「窒素置換」した。その後攪拌しつつ100℃まで昇温し、次いで同温度にて(PO)464部(8モル部)を滴下し、「反応させた」。さらに(EO)264部(6モル部)を滴下し、「反応させ」、dpg/PO8モル/EO6モル付加物(P9)(EO3モル/PO10モル/EO3モルのプルロニックグリコール)を得た。次いで水酸化カリウム112.2部(2モル部)を50%水溶液として投入した後、脱水した。さらにエピクロルヒドリン{鹿島ケミカル株式会社}189.6部(2.05モル部)を攪拌下40℃にて3時間で滴下した。さらに同温度にて3時間攪拌した後「キョーワード処理」して、プルロニックグリコール(EO3モル/PO10モル/EO3モル)ジグリシジルエーテル(g1)を得た。このジグリシジルエーテル(g1)のエポキシ当量は480(g/eq)であった。なお、エポキシ当量は、JIS K7236:2001(対応する国際規格;ISO3001:1999)に準拠して測定した(以下、同じである。)。
耐圧反応容器に、製造例1で得た蔗糖/PO10モル付加物(S1)2766部(3モル部)、製造例10で得たdeg/PO2モル/BO2モル付加物(P1)732部(2モル部)及び水酸化カリウム7.3部(合計仕込み量のおよそ0.1%量)を仕込み脱水した。その後、製造例17で得たプルロニックグリコール(EO3モル/PO10モル/EO3モル)ジグリシジルエーテル(g1)3840部(4モル部)を加え130℃にて6時間反応させ、次いで「キョーワード処理」してポリオキシアルキレン化合物(A1)を得た。
「蔗糖/PO10モル付加物(S1)2766部(3モル部)」、「deg/PO2モル/BO2モル付加物(P1)732部(2モル部)」及び「プルロニックグリコール(EO3モル-PO10モル-EO3モル)ジグリシジルエーテル(g1)3840部(4モル部)」をそれぞれ表1に示した化合物及び使用モル数に変更したこと以外、製造例18と同様にして、ポリオキシアルキレン化合物(A2)~(A12)を得た。
なお、水酸化カリウムの使用量は、合計仕込み量のおよそ0.1%となるように調整した。
また、表中、(a12)が一般式(1)の「S1」及び「S2」を構成し、(a32)が一般式(1)の「P」を構成し、(a4)が一般式(1)の「G」を構成し、qは一般式(1)の「q」に対応する。
耐圧反応容器に、PGL 03P{ポリグリセリン:グリセリンの約3量体、水酸基価1120mgKOH/g:株式会社ダイセル}236部(1.0モル部)及び水酸化ナトリウム4部を投入した後、「脱水」した。次いで減圧のまま160℃にて、(EO)880部(20モル部)を3時間かけて滴下し、「反応させた」。次いで、「キョーワード処理」して、ポリオキシアルキレン化合物(B1’:ポリグリセリンEO20モル付加体)を得た。
「PGL 03P{ポリグリセリン:グリセリンの約3量体}236部(1.0モル部)」を「DG{日油株式会社、グリセリン(98.5%以上)}92部(1.0モル部)」に変更したこと、「(EO)880部(20モル部)」を「(PO)5220部(90モル部)」に変更したこと及び「ルナック L-98{ラウリン酸}800部(4モル部)」を「NAA34{日油株式会社、オレイン酸、「NAA」は同社の登録商標である。}847.5部(3モル部)」に変更したこと以外、製造例30と同様にして、化合物(B2:グリセリン/PO90モル付加体のオレイン酸3モルエステル化体)を得た。
「PGL 03P{ポリグリセリン:グリセリンの約3量体}236部(1.0モル部)」を「DG{日油株式会社、グリセリン(98.5%以上)}92部(1.0モル部)」に変更したこと及び「(EO)880部(20モル部)」を「(PO)2436部(42モル部)」に変更したこと以外、製造例30と同様にして、ポリオキシアルキレン化合物(B3’:グリセリン/PO42モル付加体)を得た後、耐圧反応容器に、ポリオキシアルキレン化合物B3’(グリセリン/PO42モル付加体)2528部(1モル部)及び水酸化ナトリウム6部を投入した後、「脱水」してから、(EO)660部(15モル部)を3時間かけて滴下し、「反応させた」。次いで「キョーワード処理」して、ポリオキシアルキレン化合物(B3’’:グリセリン/PO42モル/EO15モル付加体)を得た。
耐圧反応容器に、ニューポールPE-61{三洋化成工業株式会社:プルロニックグリコール(EO2.5モル/PO30モル/EO2.5モル)、「ニューポール」は同社の登録商標である。}1960部(1モル部)、ルナック S-98{花王株式会社、ステアリン酸(98%以上)、「ルナック」は同社の登録商標である。}569部(2モル部)及びメタンスルホン酸{試薬特級、富士フイルム和光純薬工業株式会社}5部を仕込み、「窒素置換」したのち、150℃まで昇温した。次いで真空ポンプにより次第に減圧とし、0.6~1.3kPa、150℃×12時間反応させた。次いで「キョーワード処理」して、化合物(B4:プルロニックグリコール(EO2.5モル/PO30モル/EO2.5モル)のステアリン酸2モルエステル化体)を得た。
「ニューポールPE-61{プルロニックグリコール(EO2.5モル/PO30モル/EO2.5モル}1960部(1モル部)」を「ニューポールLB-385{三洋化成工業株式会社:ブタノールのPO25モル付加体、「ニューポール」は同社の登録商標である。}1500部(1.0モル部)」に変更したこと及び「ルナック S-98{ステアリン酸}569部(2モル部)」を「NAA34{オレイン酸}282.5部(1モル部)」に変更したこと以外、製造例33と同様にして、化合物(B5:ブタノール/PO25モル付加体のオレイン酸1モルエステル化体)を得た。
低密度ポリエチレン{EPOLENE E10、酸価17mgKOH/g、ウエストレイク ロングビュー コーポレーション、「EPOLENE」は同社の登録商標である。}70部、コスモニュートラル 150{動粘度32mm2/s、コスモ石油ルブリカンツ株式会社、「コスモ」はコスモエネルギーホールディングス株式会社の登録商標である。}130部を攪拌しつつ100℃まで昇温し、この温度にてさらに15分間加熱攪拌を続けて混合液を得た後、20℃に調節したコスモニュートラル 150の800部を攪拌及び冷却しながら、これに混合液を投入し40℃以下で15分間攪拌した。その後、インペラー型羽根を装着したエクセルオートホモジナイザーにて4000rpmにて15分間攪拌微細化処理して疎水性液体(C1)を得た。
脂肪酸アミド{エチレンビスステアリルアミド、アルフローH-50S、日油株式会社、「アルフロー」は同社の登録商標である。}5部とコスモピュアスピンE{動粘度4.5mm2/s、コスモ石油ルブリカンツ株式会社、「ピュアスピン」はコスモエネルギーホールディングス株式会社の登録商標である。}995部を150℃で均一混合した後、30℃まで撹拌しながら冷却して混合液を得た。その後、インペラー型羽根を装着したエクセルオートホモジナイザーにて4000rpmにて15分間攪拌微細化処理して疎水性液体(C2)を得た。
NIPSIL SS-50{疎水性シリカ、東ソー・シリカ株式会社、M値60、平均粒径(コールターカウンター法}1.5μm、「Nipsil」は同社の登録商標である。}5部とKF-96-500CS{動粘度500mm2/s、ジメチルシリコーンオイル、信越化学工業株式会社}95部を30分間攪拌混合した後、ゴーリンホモジナイザー(マントンゴーリン社)を用いて3500psi(24.1MPa)にて均質化処理して、疎水性液体(C3)を得た。
「KF-96-500CS{ジメチルシリコーンオイル}」を「KF-96-5000CS{動粘度5000mm2/s、ジメチルシリコーンオイル}」に変更したこと以外、製造例37と同様にして、疎水性液体(C4)を得た。
「KF-96-500CS{ジメチルシリコーンオイル}」を「食用大豆油{動粘度32mm2/s、日清オイリオグループ株式会社}」に変更したこと以外、製造例37と同様にして、疎水性液体(C5)を得た。
製造例26で得たポリオキシアルキレン化合物(A9)20部及び製造例31で得た化合物(B2)80部を均一に撹拌混合して、本発明の消泡剤(DF1)を得た。
ポリオキシアルキレン化合物(A9)20部及び化合物(B2)80部を、表2に記載した種類及び使用量に変更したこと以外、実施例1と同様にして、本発明の消泡剤(DF2)~(DF3)を得た。
製造例18で得たポリオキシアルキレン化合物(A1)20部、製造例30で得た化合物(B1)80部及び製造例35で得た疎水性液体(C1)1000部を均一に撹拌混合して、本発明の消泡剤(DF4)を得た。
ポリオキシアルキレン化合物(A1)20部、化合物(B1)80部及び疎水性液体(C1)1000部を、表2に記載した種類及び使用量に変更したこと以外、実施例4と同様にして、本発明の消泡剤(DF5)~(DF19)を得た。
特許文献1の表1の試料V6aの欄に準拠して比較用の消泡剤(H1)を調製した。
1.エマルションベース塗料の調製
表3に記載した原料組成にて、インペラー型羽根を装着したエクセルオートホモジナイザーを用いて、グラインディング及びレットダウンして、エマルションベース塗料を調製した。
※ 2 増粘剤、サンノプコ株式会社
※ 3 酸化チタン、石原産業株式会社、「タイペーク」は同社の登録商標であ る。
※ 4 アクリルエマルション、DIC株式会社、「ボンコート」 は同社の登録商標である。
※ 5 防腐剤、サンノプコ株式会社
※ 6 造膜調整剤、イーストマンケミカル社、「テキサノール」は吉村油化学 株式会社の登録商標である。
エマルションベース塗料100部に、消泡剤(DF1)~(DF19)のいずれか又は比較用の消泡剤(H1)を0.2部加えて、コーレス型羽根を装着したエクセルオートホモジナイザーにて25℃、1000rpm、5分間攪拌混合して、各評価用エマルション塗料を得た。
中毛ウールローラー(大塚刷毛製造株式会社)を用いて評価用エマルション塗料を15cm×15cmのブリキ板上にローラー塗装し、15秒後に写真撮影して、ブリキ板の中央部分(1.5cm×1.5cm)に発生した泡を目視で数えて表4に記載した。数が少ない方が消泡性優れることを意味する。
中毛ウールローラー(大塚刷毛製造株式会社)を用いて評価用エマルション塗料を15cm×15cmのブリキ板上にローラー塗装した後、塗膜表面全体を観察し、目視にて、ハジキ痕の個数を数え、表4に記載した。なお、数値の小さい方がハジキが少ないことを意味し好ましい。
Claims (5)
- 一般式(1)で表されるポリオキシアルキレン化合物(A)と一般式(5)で表される化合物(B)とを含有してなり、ポリオキシアルキレン化合物(A)と化合物(B)との重量比{(A):(B)}が50:50~1:99であることを特徴とする消泡剤。
S1-G(-P-G-S2-G)q-P-G-S1 (1)
ただし、S1は一般式(2)で表される基、S2は一般式(3)で表される基、Gは炭素数10~50のジグリシジルエーテルの反応残基、Pは一般式(4)で表される基、qは0、1又は2を表す。
R2{-(OA)a-X}b (5)
R2は炭素数3~24の活性水素化合物から水素原子を除いた反応残基、Xは水素原子又は炭素数4~23のアシル基、OAは炭素数2~4のオキシアルキレン基、aは1~50の整数、bは1~6の整数であり、X、(OA)a、a、はそれぞれ同じでも異なってもよい。 - 非還元性の二又は三糖類の反応残基(Q)が蔗糖の反応残基である請求項1に記載の消泡剤。
- さらに、疎水性液体(C)を含んでなる請求項1又は2に記載の消泡剤。
- ポリオキシアルキレン化合物(A)及び化合物(B)の合計100重量部に対して、疎水性液体(C)の含有量が20~10000重量部である請求項3に記載の消泡剤。
- 水系コーティング材及び請求項1~4のいずれかに記載された消泡剤からなることを特徴とする水系コーティング組成物。
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