WO2014199522A1 - 粘性調整剤及びそれを含有するエマルション樹脂組成物または水系塗料組成物 - Google Patents
粘性調整剤及びそれを含有するエマルション樹脂組成物または水系塗料組成物 Download PDFInfo
- Publication number
- WO2014199522A1 WO2014199522A1 PCT/JP2013/066519 JP2013066519W WO2014199522A1 WO 2014199522 A1 WO2014199522 A1 WO 2014199522A1 JP 2013066519 W JP2013066519 W JP 2013066519W WO 2014199522 A1 WO2014199522 A1 WO 2014199522A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- viscosity modifier
- general formula
- represented
- carbon atoms
- viscosity
- Prior art date
Links
Images
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
- C09D175/08—Polyurethanes from polyethers
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
- C08G18/735—Polyisocyanates or polyisothiocyanates acyclic containing one isocyanate or isothiocyanate group linked to a primary carbon atom and at least one isocyanate or isothiocyanate group linked to a tertiary carbon atom
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- 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
-
- 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
-
- 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
- C09D7/43—Thickening agents
Definitions
- the present invention relates to a viscosity modifier having good low-temperature and high-temperature long-term storage stability of a blended emulsion resin composition or water-based paint composition even when blended in an emulsion resin or water-based paint.
- Viscosity modifiers include natural viscosity modifiers such as carboxymethyl cellulose and hydroxyethyl cellulose, alkali thickening type viscosity modifiers such as polyacrylic acid and polyacrylic acid-containing copolymers, and urethane-modified polyethers. And other urethane type viscosity modifiers are known (see, for example, Patent Documents 1 to 4).
- viscosity modifiers when natural viscosity modifiers or alkali thickening type viscosity modifiers are added to water-based paints, etc., in general, thixotropic viscosity is imparted to the paints to improve leveling. In addition, the water resistance of the paint may deteriorate.
- the urethane type viscosity modifier can obtain a wide range of viscosities from thixotropy to leveling, and the paint has good water resistance. For these reasons, urethane type viscosity modifiers are widely used in various applications or various regions.
- Emulsion resins and paints with added viscosity modifiers are often transported, stored, and sold in containers such as cans and resins, and there is a period of time from when paints are manufactured until they are actually used. In many cases, the length is long, and in many cases, the container is exposed to high or low temperatures for a long time during transportation or storage. Specific examples include storage in midsummer or extremely cold regions, and ocean transportation directly under the equator or in extremely cold regions. Emulsion resin-based paints that contain urethane-type viscosity modifiers are prone to high or low temperatures. When exposed to time, there was a problem that the product viscosity of the paint increased. An increase in product viscosity impairs the basic performance of the paint, which may result in poor painting or problems with the resulting coating.
- JP 10-036720 A Japanese Patent Laid-Open No. 11-199854 JP 2001-295195 A JP 2007-197520 A
- the problem to be solved by the present invention is to provide an emulsion resin composition containing a urethane type viscosity modifier that does not increase the product viscosity of the emulsion resin composition even when stored for a long time at high or low temperatures. .
- the present inventors diligently studied and found a urethane type viscosity modifier that does not increase the product viscosity even when stored at a high temperature or a low temperature for a long period of time, leading to the present invention. That is, the present invention is a viscosity modifier represented by the following general formula (1).
- R 1 to R 4 each represent a linear alkyl group having 1 to 13 carbon atoms
- R 5 and R 6 represent any group represented by the following formula (2) or (3):
- M and n each represent a number of 3 to 15
- x represents a number of 40 to 800
- y represents a number of 1 or more, provided that the sum of the carbon numbers of R 1 and R 2 and R 3 and R ( The sum of 4 carbon atoms must be between 10 and 14.
- a secondary alcohol ethoxylate obtained by adding ethylene oxide to an alcohol described in the following general formulas (4) and (5) is reacted with a compound of the following general formula (6), and the following general formula ( Provided is a viscosity modifier obtained by reacting the diisocyanate represented by 7) and (8).
- R 1 to R 4 each represent a linear alkyl group having 1 to 13 carbon atoms
- R 5 and R 6 represent any group represented by the following formula (2) or (3):
- X represents a number of 40 to 800.
- the sum of the carbon numbers of R 1 and R 2 and the sum of the carbon numbers of R 3 and R 4 must both be 10 to 14.
- the effect of the present invention is that a urethane-type viscosity modifier that does not increase the product viscosity of the emulsion resin composition even when the emulsion resin containing the urethane-type viscosity modifier is stored at high or low temperatures for a long period of time, and an emulsion containing the same A resin composition is provided.
- the chart of the gel permeation chromatography (GPC) of this invention product 3 mentioned later is shown.
- the chart of the gel permeation chromatography (GPC) of this invention product 8 mentioned later is shown.
- the viscosity modifier of the present invention is a compound having the structure of the following general formula (1).
- R 1 to R 4 each represent a linear alkyl group having 1 to 13 carbon atoms
- R 5 and R 6 represent any group represented by the following formula (2) or (3):
- M and n each represent a number of 3 to 15
- x represents a number of 40 to 800
- y represents a number of 1 or more, provided that the sum of the carbon numbers of R 1 and R 2 and R 3 and R ( The sum of 4 carbon atoms must be between 10 and 14.
- R 1 to R 4 in the general formula (1) each represent a linear alkyl group having 1 to 13 carbon atoms.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and a tridecyl group.
- the sum of the carbon number of the group constituting R 1 and the carbon number constituting R 2 must be 10 to 14 carbon atoms, and more preferably 11 to 13 carbon atoms.
- the R 3 and R 4 Similarly, the sum of the number of carbon atoms constituting the carbon number of the group and R 4 constituting the R 3 must be 10-14 carbon atoms, 11 to 13 is more preferred.
- R 5 and R 6 are either a hexamethylene group represented by the formula (2) or a group represented by the formula (3).
- R 5 and R 6 may be the same group or different from each other, but are preferably all the same group in terms of production.
- the values of m and n are each a number from 3 to 15, but a number from 5 to 12 is preferable because of good stability at high and low temperatures. When the value of m or n is less than 3 or exceeds 15, the stability at high and low temperatures is deteriorated. In addition, it is preferable that the value of m and n is the same on a manufacturing method.
- the value of x is a number from 40 to 800, but is preferably a number from 100 to 500 because of good stability at high and low temperatures. If it is less than 40, the solubility in the paint may deteriorate and insoluble matter may be produced, and if it exceeds 800, the product viscosity may increase and the solubility in the paint may deteriorate.
- the value of x corresponds to the average degree of polymerization of polyethylene glycol represented by the general formula (6) described later.
- Y value is a number of 1 or more.
- a method for efficiently obtaining the compound of the general formula (1) will be described later in detail, but compounds having different values of y are formed simultaneously on a preferable production method.
- y is preferably 6 or less. When y is larger than 6, the viscosity of the compound of the general formula (1) itself becomes large, and it may be difficult to add it to a paint as a viscosity modifier.
- the method for producing the viscosity modifier represented by the general formula (1) is not limited and may be produced by a known method. However, since it can be easily produced, secondary alcohol, ethylene oxide, polyethylene glycol and diisocyanate compounds are used as raw materials. It is preferable to synthesize.
- the secondary alcohol as a raw material can be represented by the following general formula (4) and general formula (5).
- R 1 and R 2 each represent a linear alkyl group having 1 to 13 carbon atoms, provided that the sum of the carbon numbers of R 1 and R 2 must be 10 to 14).
- R 3 and R 4 each represent a linear alkyl group having 1 to 13 carbon atoms, provided that the sum of the carbon numbers of R 3 and R 4 must be 10 to 14).
- Raw material polyethylene glycol can be represented by the following general formula (6).
- x represents a number of 40 to 800.
- the raw material diisocyanate compound can be represented by the following general formula (7) and general formula (8).
- R 5 represents the general formula (2) or the general formula (3).
- R 6 represents the general formula (2) or the general formula (3).
- the secondary alcohol ethoxylates obtained by adding ethylene oxide to the raw material alcohol represented by the general formulas (4) and (5) may be the same or different, but the fewer the types of raw materials, the easier the handling, It is preferable to use the same secondary alcohol ethoxylate.
- Commercially available secondary alcohol ethoxylates can be used here.
- Adecatol SO-80, Adecatol SO-105, Adecatol SO-120, Adecatol SO-135, Adecatol SO-145, Adecatol SO-160 (manufactured by ADEKA Corporation) and the like can be mentioned. It is also possible to adjust the values of m and n in the general formula (1) by adding ethylene oxide to a commercially available polyoxyethylene secondary alkyl ether.
- the raw material diisocyanate compounds represented by the general formulas (7) and (8) are preferably the same for the same reason.
- the secondary alcohol ethoxylate obtained by adding ethylene oxide to the raw material alcohol represented by the general formulas (4) and (5) is the same, and the diisocyanate compounds represented by the general formulas (7) and (8) are also the same.
- the raw material polyethylene glycol represented by the general formula (6) is added to 0.2 mol of a secondary alcohol ethoxylate obtained by adding ethylene oxide to the alcohol described in the general formula (4).
- 75 to 1.25 mol, preferably 0.9 to 1.1 mol, and 1.5 to 2.5 mol, preferably 1.8 to 2.2 mol, of raw material diisocyanate may be reacted.
- Specific reaction conditions include a method of adding a raw material diisocyanate to a mixture of a raw material secondary alcohol ethoxylate and a raw material polyethylene glycol and reacting at 60 to 100 ° C. for 1 to 10 hours, or adding a raw material diisocyanate to a raw material polyethylene glycol. And reacting at 60 to 100 ° C. for 1 to 5 hours, adding raw material alcohol and further reacting at the same temperature for 1 to 5 hours.
- the reaction proceeds even without catalyst, but a catalyst may be used.
- the catalyst include titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, gallium chloride, indium chloride, iron chloride, tin chloride, boron fluoride, etc.
- the solid content is about 10 to 50% by mass for easy handling.
- the water-soluble solvent include alcohols such as methanol, ethanol, propanol, and butanol; polyether solvents obtained by adding 1 to 10 moles of ethylene oxide and / or propylene oxide to alcohols having 1 to 10 carbon atoms. Can be used.
- a water-soluble solvent it is preferable to add about 1 to 15% by mass of the total amount of the composition.
- the viscosity modifier of the present invention may be a single product or a mixture.
- y is preferably 6 or less.
- the solubility in paints and the like may deteriorate, making it difficult to use. If the compound with a y value of 7 or more increases, the product viscosity becomes too high, resulting in the application to paints, etc. Solubility may worsen.
- the emulsion resin composition of the present invention is obtained by adding the viscosity modifier of the present invention to an emulsion resin.
- the addition amount is not particularly limited, but it is preferably 0.1 to 5% by mass based on the total amount of the emulsion resin composition, and more preferably 0.2 to 3% by mass.
- the amount is less than 0.1% by mass, the effect as a viscosity modifier may not be obtained.
- the amount exceeds 5% by mass the effect corresponding to the amount added cannot be obtained, or when it cannot be completely dissolved in the emulsion resin. There is.
- Any usable emulsion resin can be used as long as it is a known emulsion resin.
- emulsion resins include urethane emulsions, acrylate emulsions, styrene emulsions, vinyl acetate emulsions, SBR (styrene / butadiene) emulsions, ABS (acrylonitrile / butadiene / styrene) emulsions, BR (butadiene) emulsions, IR (Isoprene) emulsion, NBR (acrylonitrile / butadiene) emulsion, or a mixture thereof.
- urethane emulsions examples include polyether polyols, polyester polyols, and polycarbonate polyols.
- acrylate emulsion examples include (meth) acrylic acid (ester) alone, (meth) acrylic acid (ester) / styrene, (meth) acrylic acid (ester) / vinyl acetate, (meth) acrylic acid (ester) / Acrylonitrile, (meth) acrylic acid (ester) / butadiene, (meth) acrylic acid (ester) / vinylidene chloride, (meth) acrylic acid (ester) / allylamine, (meth) acrylic acid (ester) / vinylpyridine, (meth ) Acrylic acid (ester) / alkylolamide, (meth) acrylic acid (ester) / N, N-dimethylaminoethyl ester, (meth) acrylic acid (ester) / N, N-diethylaminoethyl vinyl ether, cyclohexyl methacrylate, Epoxy modified, urethane modified, etc. Polymerization products thereof.
- styrene emulsion examples include styrene alone, styrene / acrylonitrile, styrene / butadiene, styrene / fumaronitrile, styrene / maleonitrile, styrene / cyanoacrylate, styrene / phenylvinyl acetate, styrene / chloromethylstyrene, styrene / Polymers such as dichlorostyrene, styrene / vinylcarbazole, styrene / N, N-diphenylacrylamide, styrene / methylstyrene, acrylonitrile / butadiene / styrene, styrene / acrylonitrile / methylstyrene, styrene / acrylonitrile / vinylcarba
- vinyl acetate emulsions include vinyl acetate alone, vinyl acetate / styrene, vinyl acetate / vinyl chloride, vinyl acetate / acrylonitrile, vinyl acetate / maleic acid (ester), vinyl acetate / fumaric acid (ester), vinyl acetate / Polymers such as ethylene, vinyl acetate / propylene, vinyl acetate / isobutylene, vinyl acetate / vinylidene chloride, vinyl acetate / cyclopentadiene, vinyl acetate / crotonic acid, vinyl acetate / acrolein, vinyl acetate / alkyl vinyl ether and the like can be mentioned.
- emulsion resins urethane emulsions, acrylate emulsions, and styrene emulsions are preferable because of particularly good stability.
- the aqueous coating composition of the present invention is obtained by adding 0.1 to 5% by mass of the viscosity modifier of the present invention to an emulsion resin-based aqueous coating based on the total amount of the aqueous coating composition. 2 to 3% by mass is preferred. When the amount is less than 0.1% by mass, the effect as a viscosity modifier may not be obtained. When the amount exceeds 5% by mass, the effect corresponding to the addition amount cannot be obtained, or the effect cannot be completely dissolved in the water-based paint. There is.
- any known emulsion-based water-based paint can be used.
- the emulsion resin used in water-based paints the emulsion resins shown above can be used, and pigments, colorants, pearl agents, preservatives, fragrances, plasticizers, antifoaming agents, fillers can be used for these emulsion resins.
- An emulsion-based water-based paint can be obtained by adding one or more of these additives.
- the secondary alcohol having 12 to 14 carbon atoms used for the synthesis of alcohols 1 to 7 is represented by the general formula (4), wherein R 1 and R 2 each represent a linear alkyl group having 1 to 12 carbon atoms, and Only one kind in which the sum of the carbon number of R 1 and R 2 is 11 to 13 is used.
- the viscosity adjusters of the inventive products 2 to 9 and the comparative products 1 to 9 were produced using the following raw materials. Details of each raw material are shown in Tables 1 and 2.
- Alcohol 1 secondary alcohol 3EO having 12 to 14 carbon atoms ( Adekatol SO-80 (manufactured by ADEKA Corporation))
- Alcohol 2 Secondary alcohol 7EO having 12 to 14 carbon atoms (obtained by adding 4 mol of ethylene oxide to 1 mol of alcohol 1)
- Alcohol 3 Secondary alcohol 12EO having 12 to 14 carbon atoms (obtained by adding 9 mol of ethylene oxide to 1 mol of alcohol 1)
- Alcohol 4 Secondary alcohol 15EO having 12 to 14 carbon atoms (obtained by adding 12 moles of ethylene oxide to 1 mole of alcohol 1)
- Alcohol 5 Secondary alcohol 20EO having 12 to 14 carbon atoms (obtained by adding 17 moles of ethylene oxide to 1 mole of alcohol 1)
- Alcohol 6 Secondary alcohol 30EO having 12 to 14 carbon atoms (obtained by adding 27 moles of ethylene oxide to 1 mole of alcohol 1)
- Alcohol 7 Secondary alcohol 50 EO having 12 to 14 carbon atoms (obtained by adding 47 mol of ethylene oxide to 1
- a paint sample was prepared by adding 0.5 parts of the manufactured present invention products 1 to 9 and comparative products 1 to 9 to 100 parts by mass of the test paint, and the viscosity of the paint sample immediately after the addition was measured. Thereafter, the paint sample was divided into three and placed in a sealed container, and each was left in a thermostatic bath at 2 ° C., 25 ° C., and 50 ° C. for 3 months. The viscosity after 3 months was measured and used as an index for long-term storage stability compared to the viscosity measured immediately after production.
- the composition of the test paint and acrylic emulsion resin is shown below. The viscosity was measured by setting the paint sample to 25 ° C. and using a B8H viscometer (rotor number 2) at a rotation speed of 10 rpm.
- composition of test paint A pigment paste having the following composition was prepared and mixed with the following acrylic emulsion and other additives to prepare a test paint.
- Detailed formulation is as follows.
- Acrylic emulsion resin 53.25 parts (see below for details)
- Pigment paste 40.06 parts (see below for details)
- Texanol 2.60 parts (CS-12: Chisso Corporation)
- Propylene glycol 3.80 parts
- Antifoaming agent 0.19 parts (Adecanate B-1015: ADEKA Corporation)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
<サンプルの製造>
温度計、窒素導入管及び攪拌機を付した容量2000mlの4つ口フラスコに重量平均分子量8000のポリオキシエチレングリコールを800g(0.1モル)、炭素数12~14の2級アルコールの混合物(平均炭素数13)のエチレンオキシド3モル付加物(アルコール1)を40.2g(0.2モル)仕込んで混合させた後、ヘキサメチレンジイソシアネート34g(0.2モル)を加え、80~90℃で3時間反応させて本発明品1を得た。なお、アルコール1~7の合成に使用した炭素数12~14の2級アルコールは、一般式(4)において、R1及びR2はそれぞれ炭素数1~12の直鎖アルキル基を表し、且つR1とR2の炭素数の和は11~13である1種のみを使用する。なお同様の装置及び同様の方法で、下記の原料を使用して本発明品2~9及び比較品1~9の粘性調整剤を製造した。各原料の詳細を表1及び2に記載する。
アルコール1:炭素数12~14の2級アルコール3EO(アデカトールSO-80(株式会社ADEKA製))
アルコール2:炭素数12~14の2級アルコール7EO(1モルのアルコール1にエチレンオキサイドを4モル付加して得られる。)
アルコール3:炭素数12~14の2級アルコール12EO(1モルのアルコール1にエチレンオキサイドを9モル付加して得られる。)
アルコール4:炭素数12~14の2級アルコール15EO(1モルのアルコール1にエチレンオキサイドを12モル付加して得られる。)
アルコール5:炭素数12~14の2級アルコール20EO(1モルのアルコール1にエチレンオキサイドを17モル付加して得られる。)
アルコール6:炭素数12~14の2級アルコール30EO(1モルのアルコール1にエチレンオキサイドを27モル付加して得られる。)
アルコール7:炭素数12~14の2級アルコール50EO(1モルのアルコール1にエチレンオキサイドを47モル付加して得られる。)
アルコール8:ラウリルアルコール(炭素数12)10EO
アルコール9:2-ヘキシルデカノール10EO
PEG1:ポリエチレングリコール(分子量4000)
PEG2:ポリエチレングリコール(分子量8000)
PEG3:ポリエチレングリコール(分子量10000)
PEG4:ポリエチレングリコール(分子量20000)
HDI:ヘキサメチレンジイソシアネート
H-MDI:4,4'-ビスシクロヘキシルメタンジイソシアネート
TDI:トリレンジイソシアネート
MDI:4,4'-ジフェニルメタンジイソシアネート
IPDI:イソホロンジイソシアネート
上記発明品3および8について一般式(1)の化合物の分子量分布をGPC(ゲルパーミレーションクロマトグラフィー)を使用して測定した。
なお、測定に使用した機器及び条件は下記の通りである。
使用カラム:TSKgel G4000Hxl、G3000Hxl、G2000Hxl(いずれも東ソー株式会社製)を直列に接続。
溶離液 :THF(テトラヒドロフラン)
流量 :1ml/分
検出器 :HLC-8120GPC(RI)
サンプル濃度:0.1質量%(THF溶液)
サンプル量:200μl
カラム温度:40℃
その結果を図1および2に示す。また、一般式のyの各値に対応するピークの面積から、その配合割合を求めた。結果を表3に示す。
製造した本発明品1~9及び比較品1~9を、試験用の塗料100質量部に対し0.5部添加した塗料サンプルを作製し、添加直後の塗料サンプルの粘度を測定した。その後、塗料サンプルを3つに分けて密閉容器に入れ、それぞれを2℃、25℃、50℃の恒温槽に3ヶ月間放置した。3ヵ月後の粘度を測定し、作製直後に測定した粘度と比較して長期保存安定性の指標とした。試験用の塗料及びアクリル系エマルション樹脂の組成を以下に示す。なお粘度の測定は、塗料サンプルを25℃にしてB8H型粘度計(ローターナンバー2番)を使用して10rpmの回転速度で行った。
下記の組成の顔料ペーストを作製し、下記のアクリルエマルション及びその他の添加剤と混ぜて試験用の塗料を作製した。詳しい配合は以下の通りである。
アクリル系エマルション樹脂 :53.25部 (詳細は下記参照)
顔料ペースト :40.06部 (詳細は下記参照)
テキサノール : 2.60部 (CS-12:チッソ株式会社)
プロピレングリコール : 3.80部
アンモニア水(28%水溶液) : 0.10部
消泡剤 : 0.19部 (アデカネートB-1015:(株)ADEKA)
アクリル酸メチル/アクリル酸エチル/アクリル酸2-ヒドロキシエチル/スチレン/アクリルアミド/メタクリル酸=18.5/56.2/8.3/10/4/3(質量比)を50%水溶液にして乳化重合させたエマルション樹脂。
(顔料ペースト)
トリポリリン酸ソーダ10%水溶液:0.5部
分散剤 :0.5部 (アデカコールW-193:(株)ADEKA製)
酸化チタン :28.7部 (R-930:石原産業株式会社製)
消泡剤 :0.4部 (アデカネートB-1015:(株)ADEKA製)
水 :9.96部
本発明品1~4及び比較品1~3を、上記のアクリル系エマルション樹脂100質量部に対し0.5部添加し、長期保存安定性試験1と同様の試験を行った。
Claims (7)
- 一般式(1)のR5及びR6が同一の基であることを特徴とする請求項1に記載の粘性調整剤。
- 一般式(4)に記載のアルコールにエチレンオキサイドを付加させた2級アルコールエトキシレートと、一般式(5)に記載のアルコールにエチレンオキサイドを付加させた2級アルコールエトキシレートが同一である、請求項3に記載の粘性調整剤。
- 一般式(7)で表されるイソシアネートと、一般式(8)で表されるイソシアネートが同一である、請求項3または4に記載の粘性調整剤。
- 請求項1~5のいずれか1項に記載の粘性調整剤を0.1~5質量%含有することを特徴とするエマルション樹脂組成物。
- 請求項1~5のいずれか1項に記載の粘性調整剤を0.1~5質量%含有することを特徴とする水系塗料組成物。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020157035273A KR102092992B1 (ko) | 2013-06-14 | 2013-06-14 | 점성조정제 및 그를 함유하는 에멀젼 수지 조성물 또는 수계 도료 조성물 |
EP13886661.1A EP3009487B1 (en) | 2013-06-14 | 2013-06-14 | Viscosity modifier, and emulsion resin composition or aqueous coating composition each containing same |
CN201380077396.3A CN105324456B (zh) | 2013-06-14 | 2013-06-14 | 粘度调节剂及含有该粘度调节剂的乳化树脂组合物或水性涂料组合物 |
US14/896,951 US9752055B2 (en) | 2013-06-14 | 2013-06-14 | Viscosity modifier, and emulsion resin composition or aqueous coating composition each containing same |
PCT/JP2013/066519 WO2014199522A1 (ja) | 2013-06-14 | 2013-06-14 | 粘性調整剤及びそれを含有するエマルション樹脂組成物または水系塗料組成物 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2013/066519 WO2014199522A1 (ja) | 2013-06-14 | 2013-06-14 | 粘性調整剤及びそれを含有するエマルション樹脂組成物または水系塗料組成物 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014199522A1 true WO2014199522A1 (ja) | 2014-12-18 |
Family
ID=52021851
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/066519 WO2014199522A1 (ja) | 2013-06-14 | 2013-06-14 | 粘性調整剤及びそれを含有するエマルション樹脂組成物または水系塗料組成物 |
Country Status (5)
Country | Link |
---|---|
US (1) | US9752055B2 (ja) |
EP (1) | EP3009487B1 (ja) |
KR (1) | KR102092992B1 (ja) |
CN (1) | CN105324456B (ja) |
WO (1) | WO2014199522A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021045937A1 (en) * | 2019-09-03 | 2021-03-11 | Dow Global Technologies Llc | Foam formulation |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5480349A (en) * | 1977-12-06 | 1979-06-27 | Rohm & Haas | Polyurethane thickener for latex composition |
JPH0971766A (ja) * | 1995-09-06 | 1997-03-18 | Asahi Denka Kogyo Kk | 粘性調整剤 |
JPH1036720A (ja) | 1996-07-22 | 1998-02-10 | Sekisui Chem Co Ltd | 水系塗料の粘性安定化方法と塗布方法 |
JPH11199854A (ja) | 1998-01-12 | 1999-07-27 | Asahi Denka Kogyo Kk | 粘性調整剤 |
JP2000239120A (ja) * | 1998-12-17 | 2000-09-05 | Shiseido Co Ltd | 化粧料組成物 |
JP2000239649A (ja) * | 1999-02-25 | 2000-09-05 | Asahi Denka Kogyo Kk | 粘性調整剤 |
JP2000303056A (ja) * | 1999-04-21 | 2000-10-31 | Sannopuko Kk | 増粘剤組成物 |
JP2001295195A (ja) | 2000-04-05 | 2001-10-26 | San Nopco Ltd | グラビア印刷用紙用塗工組成物 |
JP2002069430A (ja) * | 2000-08-28 | 2002-03-08 | Asahi Denka Kogyo Kk | 増粘、粘性調整剤 |
JP2007197520A (ja) | 2006-01-25 | 2007-08-09 | Asahi Kasei Chemicals Corp | 水性塗料組成物 |
JP2009280656A (ja) * | 2008-05-20 | 2009-12-03 | Adeka Corp | 粘性調整剤組成物、並びにこれを用いた水溶液の粘性調整方法及びゲルの調整方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100404774B1 (ko) | 1995-09-06 | 2004-04-01 | 아사히 덴카 고교 가부시키가이샤 | 점성조정제 |
-
2013
- 2013-06-14 EP EP13886661.1A patent/EP3009487B1/en active Active
- 2013-06-14 KR KR1020157035273A patent/KR102092992B1/ko active IP Right Grant
- 2013-06-14 WO PCT/JP2013/066519 patent/WO2014199522A1/ja active Application Filing
- 2013-06-14 US US14/896,951 patent/US9752055B2/en active Active
- 2013-06-14 CN CN201380077396.3A patent/CN105324456B/zh active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5480349A (en) * | 1977-12-06 | 1979-06-27 | Rohm & Haas | Polyurethane thickener for latex composition |
JPH0971766A (ja) * | 1995-09-06 | 1997-03-18 | Asahi Denka Kogyo Kk | 粘性調整剤 |
JPH1036720A (ja) | 1996-07-22 | 1998-02-10 | Sekisui Chem Co Ltd | 水系塗料の粘性安定化方法と塗布方法 |
JPH11199854A (ja) | 1998-01-12 | 1999-07-27 | Asahi Denka Kogyo Kk | 粘性調整剤 |
JP2000239120A (ja) * | 1998-12-17 | 2000-09-05 | Shiseido Co Ltd | 化粧料組成物 |
JP2000239649A (ja) * | 1999-02-25 | 2000-09-05 | Asahi Denka Kogyo Kk | 粘性調整剤 |
JP2000303056A (ja) * | 1999-04-21 | 2000-10-31 | Sannopuko Kk | 増粘剤組成物 |
JP2001295195A (ja) | 2000-04-05 | 2001-10-26 | San Nopco Ltd | グラビア印刷用紙用塗工組成物 |
JP2002069430A (ja) * | 2000-08-28 | 2002-03-08 | Asahi Denka Kogyo Kk | 増粘、粘性調整剤 |
JP2007197520A (ja) | 2006-01-25 | 2007-08-09 | Asahi Kasei Chemicals Corp | 水性塗料組成物 |
JP2009280656A (ja) * | 2008-05-20 | 2009-12-03 | Adeka Corp | 粘性調整剤組成物、並びにこれを用いた水溶液の粘性調整方法及びゲルの調整方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3009487A4 |
Also Published As
Publication number | Publication date |
---|---|
KR20160022306A (ko) | 2016-02-29 |
CN105324456A (zh) | 2016-02-10 |
US20160130470A1 (en) | 2016-05-12 |
KR102092992B1 (ko) | 2020-03-24 |
US9752055B2 (en) | 2017-09-05 |
EP3009487B1 (en) | 2018-06-06 |
EP3009487A4 (en) | 2017-03-08 |
CN105324456B (zh) | 2018-05-11 |
EP3009487A1 (en) | 2016-04-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2011219565B2 (en) | Associative monomer based on oxo alcohols, acrylic polymer containing this monomer, use of said polymer as thickener in an aqueous formulation, and formulation obtained | |
US10407385B2 (en) | Ureaurethanes for rheology control | |
AU2016222473B2 (en) | Pigmented paint formulation with a phosphorus acid functionalized latex binder and an associative thickener | |
US20170037262A1 (en) | Storage-stable urea preparations which are suitable as rheology control agents | |
CA2940732C (en) | Pigmented paint formulation with a phosphorus acid functionalized latex binder and an associative thickener | |
US11377553B2 (en) | Polymer suitable as a thickener | |
JP2007332376A (ja) | 新規ポリウレタンおよび水性システムを増粘するためのそれらの使用 | |
JP6438415B2 (ja) | 粘性調整剤組成物 | |
JP5996184B2 (ja) | 粘性調整剤及びそれを含有するエマルション樹脂組成物または水系塗料組成物 | |
WO2014199522A1 (ja) | 粘性調整剤及びそれを含有するエマルション樹脂組成物または水系塗料組成物 | |
JP2003292937A (ja) | 増粘剤組成物 | |
CN114206974B (zh) | 用于温度自适应流变分布的添加剂 | |
JP4528908B2 (ja) | 増粘剤組成物およびアクリル系エマルション型粘着剤組成物 | |
JPH06239957A (ja) | イソシアネート水性エマルジョン組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201380077396.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13886661 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14896951 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20157035273 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013886661 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: JP |