WO2005026257A1 - アクリルゾル組成物 - Google Patents
アクリルゾル組成物 Download PDFInfo
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- WO2005026257A1 WO2005026257A1 PCT/JP2004/012396 JP2004012396W WO2005026257A1 WO 2005026257 A1 WO2005026257 A1 WO 2005026257A1 JP 2004012396 W JP2004012396 W JP 2004012396W WO 2005026257 A1 WO2005026257 A1 WO 2005026257A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
Definitions
- the present invention relates to an acrylic sol composition, in particular, has excellent storage stability without generating hydrogen chloride gas or dioxin during incineration, can be cured even at a relatively low temperature, and
- the present invention relates to an acrylic sol composition having excellent adhesion of a coating film to a substrate, cold resistance of the coating film, and coating film strength.
- plastisols that are widely used industrially are prepared by uniformly dispersing polymer particles having a specially adjusted particle size and particle size distribution in a plasticizer together with a filler, in a liquid or liquid form. It is a pasty, viscous composition.
- the plastisol is applied to a substrate and forms a tough coating film by applying an appropriate processing temperature.
- polychlorinated vinyl-based polymers such as a vinyl chloride homopolymer and a copolymer of vinyl chloride and vinyl acetate are generally used in many cases.
- a polyvinyl chloride-based plastisol has good long-term storage stability at room temperature, and has a flexible coating film and excellent durability. For example, steel plate coating, clothing, building materials, daily necessities, sundries, automobile parts, etc. Widely used in the field.
- the polyplastidium-based plastisol is decomposed by heat or light to generate hydrogen chloride gas.
- the hydrogen gas generated here has problems such as being a source of ozone layer destruction, causing acid rain, and accelerating damage to the incinerator during incineration.
- dioxin may be generated, which is not desirable in terms of health and safety and environmental pollution. For this reason, the appearance of a plastisol instead of this polychloride-based plastisol is expected.
- Patent Literature 1 As a plastizonore in place of the polychlorinated vinyl plastizonole, a plastizonole comprising an atalylate polymer and an organic plasticizer is disclosed in Patent Literature 1 listed below. It has insufficient properties, and has disadvantages.
- Patent Document 2 discloses a methyl methacrylate polymer or copolymer, a plasticizer, and a filler.
- a polyvinyl chloride-free plastisol comprising a filler, a blocked polyisocyanate, and a polyamine.
- the plastisol is an urethane, when the processing temperature of the coating is relatively low. Since the curing reaction of the resin does not proceed, the performance of the resulting coating film is not sufficient. Further, if left at about 35 ° C., it will be impractical because gelling will occur in one or two days.
- Patent Document 3 proposes an acryl zone containing acrylic polymer fine particles, a block-type urethane resin, a solid hydrazine-based curing agent, a plasticizer, and a filler.
- Acrylic sols for soundproof undercoats containing acrylic polymer fine particles, plasticizers, fillers, block type urethane resins, curing agents and foaming agents have been proposed.
- these acrylic sols also have disadvantages such as insufficient adhesion to the substrate and insufficient flexibility especially at low temperatures.
- Patent Document 5 discloses a method in which a blocked urethane or a blocked isocyanate and a latent curing agent are blended with a plastisol obtained by dispersing a core-shell type acrylic resin particle and a filler in a plasticizer.
- Patent Document 6 discloses that a plastisol obtained by dispersing an acrylic resin particle and a filler in a plasticizer, a blocked urethane or a blocked isocyanate, and a solid at room temperature.
- thermosetting composition containing a latent curing agent having a melting point of 60 ° C or higher and insoluble in a plasticizer at 40 ° C or lower.
- these thermosetting compositions are still unsatisfactory in terms of viscosity stability and adhesiveness.
- Patent Document 1 Japanese Patent Publication No. 55-16177
- Patent Document 2 Japanese Patent Publication No. 63-66861
- Patent Document 3 JP 2001-329135 A
- Patent Document 4 JP 2001-329208 A
- Patent Document 5 International Publication No. 01 / 88009A1 pamphlet
- Patent Document 6 International Publication No. 01 / 88011A1 pamphlet
- the present invention has been made in view of the above-mentioned situation, and uses hydrogen chloride gas or the like during incineration. It has excellent storage stability without generating dioxin, can be cured even at relatively low temperatures, and has excellent adhesiveness of the coating film to the substrate, cold resistance of the coating film, and coating strength. An object is to provide an acrylic sol composition.
- the present inventors have conducted intensive studies and as a result, as described above, by including a modified product of a polyoxyalkylene polyamine compound in an acrylic sol composition containing acrylic polymer fine particles, block polyurethane and the like.
- the present inventors have found that an acrylic zonole composition having an improved problem can be provided, and arrived at the present invention.
- the present invention is selected from the group consisting of (a) acrylic polymer fine particles, (b) block polyurethane, and (c) a modified product of a polyether polyamine conjugate represented by the following formula (I).
- An acrylic sol composition characterized by comprising a polyamine compound containing at least one polyamine compound, (d) a plasticizer, and (e) a filler.
- X represents a residue obtained by removing m hydroxyl groups from a divalent to hexavalent polyol
- A represents an alkylene group having 2 to 4 carbon atoms
- B represents an alkylene group having 1 to 4 carbon atoms.
- m represents 2 to 6
- n represents 0 to 50. Further, a plurality of A, B and n present in the same molecule may be the same or different.
- a polymer generally used in an acrylic sol composition can be used.
- it is selected from alkyl acrylate, alkyl methacrylate and the like.
- a homopolymer or copolymer of monomers can be used.
- styrene permethylstyrene, methacrylic acid, acrylic acid, itaconic acid, crotonic acid, and the like can be used as the copolymerization component.
- acrylic polymer fine particles it is preferable to use core-shell type acrylic polymer fine particles composed of core and shell forces.
- core-shell type acrylic polymer fine particles composed of core and shell forces.
- the core when (a) the acrylic polymer fine particles are of a core-shell type, the core may be composed of a plasticizer-affinity polymer and the shell may be composed of a plasticizer-incompatible polymer. I like it.
- the polymer strength S of the shell part By covering the polymer strength S of the shell part with poor compatibility with the plasticizer, and the core part with compatibility with the plasticizer, the viscosity increase of the acryl zone composition during storage is suppressed, and the storage stability is improved. Better. Further, by heating such a polymer in the shell portion to an appropriate temperature, the polymer becomes compatible with the plasticizer, and thus no bleeding occurs after heat curing.
- the component of the core portion may contain 50% by mass or more of at least one selected from homopolymers and copolymers of metathalylates such as n-butyl methacrylate, isobutyl methacrylate, and ethyl methacrylate. preferable.
- the component of the core part is highly compatible with the plasticizer in this way, it is possible to suppress the occurrence of bleeding after heat curing.
- the component of the core portion is mainly composed of a copolymer of butyl methacrylate and isobutyl methacrylate.
- the components of the shell portion include homopolymers and copolymers of methacrylates such as methyl methacrylate and benzyl methacrylate, and copolymers of these methacrylates and copolymer components such as styrene. It is preferable that at least one selected from polymer powers is contained in an amount of 50% by mass or more. In this way, by making the shell component a low compatibility with the plasticizer, In addition, an increase in the viscosity of the acrylic sol composition during storage can be suppressed, and storage stability is further improved. In particular, from the viewpoint of further improving the storage stability, it is preferable that the shell component is mainly composed of methyl methacrylate.
- the polymer ratio of the core part and the shell part is 25Z by mass ratio.
- the core part is less than 25 parts by weight with respect to 75 parts by weight of the shell part, the possibility of bleeding after the heat curing is increased as compared with the case of the above-mentioned desirable range. Further, when the core part is less than 30 parts by weight with respect to 70 parts by weight, the core may be insufficiently covered by the shell part as compared with the case of the above-mentioned desirable range, May affect storage stability.
- Examples of the core-shell type acryl polymer fine particles that can be used in the acrylic sol composition of the present invention include, for example, JP-A-6-172734, JP-A-2001-329135, and JP-A-2001-329135.
- Core-shell type acrylic resin fine particles described in 2001-329208, International Publication WO01Z88009 and the like can be mentioned.
- acrylic polymer fine particles having a molecular weight of 100,000 to 1,000,000 in terms of mass average molecular weight are preferably diffused into a plasticizer from the viewpoint of coating film strength, storage stability, and the like. From the viewpoint of stability and storage stability, it is preferable to use those having an average particle size in the range of 0.1—— ⁇ .
- the (b) block polyurethane used in the acrylic sol composition of the present invention is obtained by blocking a polyurethane obtained by reacting a polyisocyanate and an ⁇ -polyol such as a polyether polyol or a polyester polyol with a blocking agent. It can be obtained by
- polyisocyanate examples include propane-1,2-diisocyanate, 2,3-dimethylbutane-1,2,3-diisocyanate, 2-methylpentane_2,4-diisocyanate, octane_3,6-diisocyanate and 3 1,3-dinitropentane-1,5-diisocyanate, octane-1,6-diisocyanate, 1,6-hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, lysine diisocyanate , Tolylene diisocyanate (TDI), Isocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, diphenylmethane-4,4-diisocyanate (MDI), dicyclohexylmethane
- the isocyanurate of polyisocyanate is used, for example, in an inert solvent such as methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, and dioxane, or in getyl phthalate, dibutyl phthalate, Ethylhexyl phthalate, a mixed alkyl phthalate containing 7 to 11 carbon atoms of the alkyl group (hereinafter referred to as C-C), butylbenzyl
- Birds such as trimellitate
- Polymerization in a known manner using a well-known catalyst for example, a tertiary amine, a quaternary ammonium compound, a Mannich base, an alkali metal of a fatty acid, or an alcoholate, in a plasticizer such as a melitate ester.
- a catalyst for example, a tertiary amine, a quaternary ammonium compound, a Mannich base, an alkali metal of a fatty acid, or an alcoholate
- a plasticizer such as a melitate ester.
- polyisocyanates 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexylmethane-1,4,4'-di-succinate (among others) It is preferable to use at least one selected from hydrogenated MDI) because an acrylic sol composition having excellent storage stability can be obtained.
- HDI 1,6-hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- dicyclohexylmethane-1,4,4'-di-succinate among others
- a polyalkylene glycol (molecular weight of about 100 to 5500) adduct of a polyhydric alcohol is preferably used as the polyether polyol which can be used in the production of the (b) block polyurethane together with the polyisocyanate.
- polyhydric alcohol examples include ethylene glycol, propylene glycol,
- Aliphatic dihydric alcohols such as 1,4-butylene glycol and neopentandalcol; glycerin, tris-isobutane, 1,2,3_butane tris, 1,2,3_pentane tris, 2_methyl —1, 2, 3_propanetriol, 2_methyl —2, 3, 4_butanetriol, 2_ Etchinolae 1,2,3_butanetriol, 2,3,4_pentanetriol, 2,3,4-hexanetrione, 4_propyl 3,4,5-heptantriol, 2,4-dimethyl2 Trivalent alcohols such as 3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4 butanetriol, 1,2,4_pentanetriol, and trimethylolpropane; erythritol, pentaerythritol, 1,3 2,3,4—pentanetrol, 2,3,4,5—hexanethrone, 1,2,3,5—p
- the power S for producing the polyether polyol can be increased.
- the alkylene oxide having 2 to 4 carbon atoms it is preferable to use, for example, a force S such as ethylene oxide, propylene oxide, and butylene oxide, particularly, propylene oxide.
- polyester polyol that can be used in the production of the (b) block polyurethane together with the polyisocyanate
- examples of the polyester polyol that can be used in the production of the (b) block polyurethane together with the polyisocyanate include polycarboxylic acids and polyhydric alcohols. And the like obtained from polyester.
- Examples of the above polycarboxylic acids include benzenetricarboxylic acid, adipic acid, succinic acid, suberic acid, sebacic acid, oxalic acid, methyladipic acid, gnoletanoleic acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, It is possible to use isophthalic acid, thiodipropionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid or any suitable carboxylic acid similar thereto.
- polyhydric alcohol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5_pentanediol, 1,6-hexanediol, and bis ( Hydroxymethylchlorohexane), diethylene glycol, 2,2-dimethylpropylene glycol, 1,3,6-hexanetriol, trimethylolpropane, pentaerythritol, sorbitol, glycerin, or any suitable polyvalent similar thereto Alcohol can be used.
- polyhydroxy compound polytetramethylene glycol, polycaprolactone glycol and the like can be used as the polyhydroxy compound.
- polyether polyols particularly trifunctional or higher polyether polyols
- glycerin tris polypropylene glycol
- an acrylic sol composition having excellent adhesion to a substrate is obtained. Most preferred because you can get things.
- the polyurethane constituting the block polyurethane is, for example, a polyhydroxyl conjugate such as a polyether polyol and Z or a polyester polyol as described above, or a mixture thereof with an OH group-containing dalyceride such as castor oil.
- the product can be obtained by reacting the product with the above-described polyisocynate.
- the molar ratio (the former Z the latter) of the above-mentioned polyisocyanate and a polyhydroxy compound such as a high polyol is usually 1.5-3.5 / 1, preferably 2.0-1. 3 ⁇ 5/1.
- the NC ⁇ ⁇ % of the prepolymer (polyurethane) is usually 110% to 20%, preferably 110%.
- the polyurethane can be obtained by a usual method.
- the reaction temperature is usually 40-140 ° C, preferably 60-130 ° C.
- a known urethane polymerization catalyst such as dibutyltin dilaurate, stannous quatoate, stannasoctoate, lead octylate, lead naphthenate, Organometallic compounds such as zinc octoate, and tertiary amine compounds such as triethylenediamine and triethylamine can also be used.
- Block polyurethane is obtained by blocking the above-mentioned polyurethane with a blocking agent.
- the blocking agent include malonic diester (eg, methyl malonate) and acetyl.
- Active methylene compounds such as acetone and acetoacetate (acetyl acetate etc.); oxime compounds such as acetoxime, methylethylketoxime (MEK oxime) and methyl isobutyl ketoxime (MIBK oxime); methyl alcohol, ethyl ethyl alcohol, propinorea Monohydric alcohols such as norecone, butinoleanorecone, heptinoleanorecone, hexinole alcohol, octyl alcohol, 2-ethylhexyl alcohol, isononyl alcohol, stearyl alcohol and isomers thereof; And daricol derivatives such as ethyl alcohol / ethyl alcohol
- the blocking reaction for obtaining the block polyurethane can be performed by a known reaction method.
- the addition amount of the blocking agent in the blocking agent is usually 12 equivalents, preferably 1.00-1.5 equivalents, based on free isocyanate groups.
- the blocking reaction of the polyurethane is usually performed by adding the above-mentioned blocking agent in the final reaction of the polymerization of the polyurethane.
- the blocking agent may be added at an optional stage and reacted.
- the blocking agent may be added at the end of a predetermined polymerization, a force added at the beginning of polymerization, or a method of adding a part at the beginning of polymerization and adding the remainder at the end of polymerization. However, it is preferably added at the end of the polymerization.
- the standard at the end of the predetermined polymerization may be based on the isocyanate% (for example, it can be measured by the method described on page 21 of “Polyurethane”, Bookstore, published in 1960, p. 21).
- the reaction temperature at the time of adding the above-mentioned blocking agent is usually 50-150 ° C, preferably 60-120 ° C.
- the reaction time is usually about 117 hours.
- the above-mentioned known urethane polymerization catalyst can be added to accelerate the reaction.
- an optional amount of a plasticizer described below may be added.
- the blending amount of (b) the block polyurethane is such that the mass ratio of the (a) acrylic polymer fine particles to the (b) block polyurethane (the former / the latter) is 90/10 It is preferable to select from the range of 15/85, especially 90 / 10-50 / 50.
- the amount of the (b) block polyurethane is less than 10 parts by mass with respect to (a) 90 parts by mass of the acrylic polymer fine particles, the adhesion of the coating film to the base material and In addition, the cold resistance and the strength of the coating film may be insufficient.
- the prepared acrylic sol composition is compared with the case of the above-mentioned desirable range. Viscosity may increase, which may affect the workability during application.
- the polyol capable of providing a residue excluding m-hydroxyl group represented by X in the divalent to hexavalent polyol represented by X includes, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, benzenedimethanol, cyclohexanedimethanol, glycerin, trimethylolethane And trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, sorbitol, mannitol, dipentaerythritol and the like.
- Examples of the alkylene group having 2 to 4 carbon atoms represented by A include ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4 — Groups such as butylene, among which ethylene and propylene are preferred.
- Examples of the alkylene group having 1 to 4 carbon atoms represented by B include methylene, ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1, Examples include groups such as 4-butylene, and among them, ethylene and propylene are preferable. Further, m is preferably 2-3 and n is preferably 0-10.
- the polyetheramine compound represented by the above formula (I) is known.
- an alkylene oxide such as ethylene oxide or propylene oxide is added to a polyol giving a residue represented by X.
- it can be produced by a method of aminating the terminal hydroxyl group, or a method of adding acrylonitrile to the terminal hydroxyl group and reducing it to convert a nitrile group to an amino group.
- polyether polyamine conjugate represented by the above formula (I) include the following compound No. 18:
- n1 represents a number of 3 to 100
- n2 and n3 represent a number of 1 to 50
- n4, n5 and n6 represent a number of 0 to 50 .
- the modified polyetheramine compound used as the polyamine conjugate may be an N_H of the polyetheramine compound represented by the above formula (I).
- the reactivity is reduced by crushing a part of the group.
- Modified products, polyamide modified products, Mannich modified products, and the like are included.
- Epoxy compounds (polyglycidinole compounds) capable of providing the above-mentioned epoxy addition modified products include, for example, polyglycidyl ether compounds of mononuclear polyvalent phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol. Dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (o-cresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol-nore A), isopropylidenebis (orthocresol), tetrabromobisphenol Nonole A, 1
- Polyglycidyl ethers of polyhydric alcohols maleic acid, fumaric acid, itaconic acid, succinic acid, gnoletanolic acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid Daricidyl esters of aliphatic, aromatic or alicyclic polybasic acids, such as luric acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endmethylenetetrahydrophthalic acid Homopolymers or copolymers of fine Dali glycidyl meth Tari rate; N Epoxy compounds having a glycidylamino group such as N, diglycidyl diphosphorus, bis (4_ (N-methinole N-glycidylamino) phenyl)
- the method for producing an epoxy addition modified product from the polyether polyamine compound represented by the above formula (I) and the epoxy compound is not particularly limited, but the method is based on 1 mol of the polyether polyamine compound. On the other hand, it can be easily produced by using 0.3 to 1.2 equivalents of the above epoxy compound, using a solvent as necessary, and reacting at 100 to 200 ° C for several minutes to several hours. .
- Examples of the acrylic compound capable of providing the above-mentioned acryl addition modified product include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and methacryl.
- Examples include propyl acrylate, butyl methacrylate, and acrylonitrile. Particularly, alkyl acrylate is preferred.
- the method for producing the acryl addition modified product from the polyether polyamine compound represented by the above formula (I) and the acrylic compound is not particularly limited, but 1 mol of the above polyether polyamine compound is used.
- the reaction was carried out at 100-300 ° C for several minutes and several hours using 0.3-1.2 moles of the above acrylic compound and optionally using a solvent under a catalyst such as p-toluenesulfonic acid. (De-alcoholization) to facilitate production.
- the plastisol composition of the present invention includes, as the (c) polyamine compound, other polyamines in addition to the modified polyether polyamine compound represented by the above formula (I).
- Other polyamine compounds include, for example, aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; isophoronediamine, mensendiamine, bis (4-amino-3-methyldicyclohexyl) methane, Diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9_bis (3-aminopropyl) _2,4,8,10-tetraoxaspiro (5.5) Alicyclic polyamines such as m-phenylenediamine, p-phenylenediamine, tolylene-2,4-diamine,
- a modified product of the polyether polyamine compound represented by the above formula (I) is used as (c) the polyamine compound per 100 parts by mass of the (a) acrylic polymer fine particles.
- the other polyamine compound which is preferably blended in a proportion of 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, comprises 10 parts by mass or less per 100 parts by mass of the (a) acrylic polymer fine particles. It can be blended in any amount.
- plasticizers used in conventional polychlorinated vinyl-based plastizonolates can be used.
- diisononyl phthalate, di (2-ethylhexyl) Phthalate plasticizers such as phthalate, diisodecyl phthalate, and butylbenzyl phthalate; di (2-ethylhexyl) adipate; di_n_decylradiate;
- fatty acid ester plasticizers such as di (2-ethynolehexyl) sebacate, and ester phosphates such as tributyl phosphate, tri_ (2_ethylhexyl) phosphate and 2-ethylhexyldiphenyl phosphate.
- Plasticizers epoxy plasticizers such as epoxidized soybean oil, other polyester plasticizers, benzoic acid plasticizers, etc. It is possible to use. One of these plasticizers may be used alone, or two or more thereof may be used in combination. Especially at low cost From the viewpoint of easy availability, it is preferable to use diisononyl phthalate.
- the plasticizer is blended in a proportion of 50-500 parts by mass, particularly 80-300 parts by mass, per 100 parts by mass of the acrylic polymer fine particles, from the viewpoint of coating film strength, workability and the like. It is preferable that
- the filler (e) constituting the acrylic sol composition of the present invention those commonly used in plastisols can be used.
- calcium carbonate, myriki, talc, kaolin clay, silica In addition to barium sulfate, fibrous fillers such as glass fiber, wollastonite, alumina fiber, ceramic fiber, and various whiskers can be used.
- fibrous fillers such as glass fiber, wollastonite, alumina fiber, ceramic fiber, and various whiskers can be used.
- the filler is blended at a proportion of 50,800 parts by mass, particularly 80,500 parts by mass, per 100 parts by mass of the (a) acrylic polymer fine particles, from the viewpoints of coating film strength, cost and the like.
- the acrylic sol composition of the present invention containing the above-mentioned components (a) to (e) includes a conventionally known additive other than the components (a) to (e), for example, a coloring agent, an oxidizing agent, and the like. Inhibitors, foaming agents, diluents, and ultraviolet absorbers can be added.
- a coloring agent for example, inorganic pigments such as titanium dioxide and carbon black, and organic pigments such as azo and phthalocyanine can be used.
- organic pigments such as azo and phthalocyanine
- the antioxidant for example, a phenol-based antioxidant or the like can be used.
- foaming agent a foaming agent of a type that generates a gas upon heating can be used.
- an azo-based foaming agent such as azodicarbonamide and azobisformamide
- a diluent for example, a solvent such as xylene and mineral terbene can be used, and as the ultraviolet absorber, a benzotriazole-based solvent can be used.
- the method for preparing the acrylic sol composition of the present invention is not particularly limited, and a method commonly used for preparing a conventional plastisol can be used.
- a method commonly used for preparing a conventional plastisol can be used.
- acrylic polymer fine particles, (b) block polyurethane, (c) polyamine compound, (d) plasticizer, (e) filler, and other additives are sufficiently mixed using a known mixer.
- the acrylic zonole composition of the present invention can be prepared.
- a planetary mixer, a kneader, a dren mill, a roll and the like can be used.
- the acrylic sol composition of the present invention can be prepared by a conventionally known coating method, that is, brush coating, coating, It can be applied by color coating, air spray coating, airless spray coating, etc. Then, a coating film can be formed by applying the acrylic sol composition of the present invention and then heating. The heating can be carried out according to a usual method, for example, using a hot air circulating drying oven.
- the acrylic sol composition of the present invention can be applied to paints, inks, adhesives, adhesives, sealing agents, and the like, as well as molded products such as miscellaneous goods, toys, industrial parts, and electric parts.
- molded products such as miscellaneous goods, toys, industrial parts, and electric parts.
- when applied to paper, cloth, etc. artificial leather, rugs, wallpaper, clothing, waterproof sheets, etc. can be obtained, and when applied to metal plates, corrosion-resistant metal plates can be obtained.
- 100-110 were charged with 400 g of diisonophthalate, 472 g of glycerin tris (polypropylene glycol) (molecular weight 4000) and 0.025 g of dibutyltin laurate. C, and dehydrated under reduced pressure at 30 mmHg for 1 hour. This was cooled to 60 ° C, 95 g of dicyclohexylmethane 4,4 'diisocyanate (hydrogenated MDI) was added, and the mixture was reacted under a nitrogen atmosphere at 60-70 ° C for 3 hours.
- diisonophthalate 472 g of glycerin tris (polypropylene glycol) (molecular weight 4000) and 0.025 g of dibutyltin laurate. C, and dehydrated under reduced pressure at 30 mmHg for 1 hour. This was cooled to 60 ° C, 95 g of dicyclohexylmethane 4,4 'diisocyanate
- block polyurethane (BU-1) was obtained.
- block polyurethane (BU-3) was obtained.
- HPA- 1 modified polyamine
- the acrylic polymer fine particles, the block polyurethane and the modified polyamine obtained in the above Production Examples and Comparative Production Examples were blended in the proportions shown in Tables 1 and 2 and mixed and dispersed by a kneader. And the acrylic sol composition of Comparative Example 15 was obtained, respectively.
- the initial viscosity of the acrylic sol composition was measured at a temperature of 20 ° C. using a B-type rotational viscometer. After that, the acrylic sol composition is placed in a sealed container, kept at a temperature of 35 ° C for 10 days, cooled to 20 ° C, and the viscosity is measured in the same manner to calculate the rate of change in viscosity from the beginning.
- the viscosity stability was evaluated according to the following criteria.
- the coloring was visually observed and the coloring property was evaluated according to the following criteria.
- the acrylic sol composition was applied on a mold-releasable plate to a thickness of 2 mm, baked at 130 ° C. for 30 minutes, and punched out with a dumbbell No. 2 mold.
- the dumbbell was pulled at 23 ° C. at a pulling speed of 50 mm / min, and the strength at break (MPa) and elongation (%) were measured.
- PA-1 (Production Example 4) 1 1 1 1 1 1 1 1 Quality PA-2 (Production Example 5) 1
- AR Core-shell type acrylic polymer fine particles whose core is mainly composed of a copolymer of butyl methacrylate and isobutyl methacrylate, and whose shell is mainly composed of methyl methacrylate.
- Sex 180 x30min X X ⁇ X X
- the atalyl sol composition composed of acrylic polymer fine particles, plasticizer and filler does not have sufficient adhesion of the coating film and the coating film strength is completely inadequate (Comparative Example). 1).
- Block isocyanate was used in combination, no improvement in coating adhesion or coating strength was observed (Comparative Example 2), and when block polyurethane was used alone, coating strength was slightly improved. However, no improvement in adhesion was observed (Comparative Example 4).
- a polyamine other than the specific polyamine compound according to the present invention may be used together with the block polyurethane.
- the acrylic sol composition of the present invention comprising acrylic polymer fine particles, block polyurethane, a modified product of a specific polyether polyamine, a plasticizer and a filler, Excellent storage stability, excellent adhesion of coating film, and ability to form tough coating film.
- the acrylic sol composition of the present invention has excellent storage stability that does not generate hydrogen chloride gas or dioxin during incineration, and can be cured even at a relatively low temperature. It excels in adhesion to base materials, cold resistance of coating films, and film strength, and is useful in a wide range of fields such as sealing materials, coating materials, and daily necessities.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/541,400 US20060173110A1 (en) | 2003-09-10 | 2004-08-27 | Acrylic sol composition |
EP04772352A EP1666531B1 (en) | 2003-09-10 | 2004-08-27 | Acrylic sol composition |
KR1020057011717A KR101091474B1 (ko) | 2003-09-10 | 2004-08-27 | 아크릴 졸 조성물 |
DE602004014793T DE602004014793D1 (de) | 2003-09-10 | 2004-08-27 | Acrylsolzusammensetzung |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003317940A JP4480374B2 (ja) | 2003-09-10 | 2003-09-10 | アクリルゾル組成物 |
JP2003-317940 | 2003-09-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005026257A1 true WO2005026257A1 (ja) | 2005-03-24 |
Family
ID=34308503
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2004/012396 WO2005026257A1 (ja) | 2003-09-10 | 2004-08-27 | アクリルゾル組成物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20060173110A1 (ja) |
EP (1) | EP1666531B1 (ja) |
JP (1) | JP4480374B2 (ja) |
KR (1) | KR101091474B1 (ja) |
DE (1) | DE602004014793D1 (ja) |
WO (1) | WO2005026257A1 (ja) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3939287B2 (ja) * | 2003-11-28 | 2007-07-04 | 本田技研工業株式会社 | アクリルゾル組成物 |
EP1792940B1 (en) * | 2004-09-07 | 2008-10-22 | Adeka Corporation | Acrylic sol composition |
EP2220035B1 (de) * | 2007-12-06 | 2019-12-25 | Basf Se | Allophanatgruppenhaltige polyisocyanate |
JP5532284B2 (ja) * | 2008-09-10 | 2014-06-25 | 三菱レイヨン株式会社 | ラテックスの製造方法、及びアクリルゾル組成物 |
US8653171B2 (en) * | 2010-02-22 | 2014-02-18 | Polyone Corporation | Plastisol compositions that are essentially free of polyvinyl halides and phthalates |
MY157219A (en) * | 2011-06-15 | 2016-05-13 | Myriant Corp | Environmentally friendly coalescing agents |
WO2014209968A1 (en) | 2013-06-25 | 2014-12-31 | Polyone Corporation | Acrylic-urethane ipn plastisol |
CN109111642A (zh) * | 2018-06-08 | 2019-01-01 | 苏州西玛家具股份有限公司 | 一种具有防水耐腐蚀环保塑料板 |
CN109337497B (zh) * | 2018-10-11 | 2020-12-08 | 宁波瑞凌新能源材料研究院有限公司 | 一种环境友好型的降温制冷涂料 |
KR102445303B1 (ko) * | 2019-10-31 | 2022-09-20 | 주식회사 엘지화학 | 열 경화성 접착제 조성물과, 접착층을 포함한 구조체 및 이의 제조 방법 |
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JPH03290479A (ja) * | 1990-04-06 | 1991-12-20 | Sanyo Chem Ind Ltd | プラスチゾル組成物 |
JPH1135784A (ja) * | 1997-07-18 | 1999-02-09 | Mitsubishi Rayon Co Ltd | プラスチゾル |
JP2000212237A (ja) * | 1999-01-20 | 2000-08-02 | Takeda Chem Ind Ltd | プラスチゾル組成物 |
JP2000273262A (ja) * | 1999-03-19 | 2000-10-03 | Mitsubishi Rayon Co Ltd | アクリル系プラスチゾル組成物 |
WO2001088011A1 (fr) * | 2000-05-16 | 2001-11-22 | Sunstar Giken Kabushiki Kaisha | Composition de plastisol |
JP2002256155A (ja) * | 2001-03-02 | 2002-09-11 | Sunstar Eng Inc | 電着鋼板板合せ部の腐蝕防止用プラスチゾル組成物 |
JP5073793B2 (ja) * | 2010-08-09 | 2012-11-14 | 株式会社コナミデジタルエンタテインメント | ゲーム端末、ゲーム端末の制御方法、ならびに、プログラム |
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US4210567A (en) * | 1974-11-15 | 1980-07-01 | Teroson G.M.B.H. | Plastisol of an acrylate polymer and a plasticizer |
JPS5736115A (en) * | 1980-08-12 | 1982-02-26 | Mitsui Tekisako Chem Kk | Curing agent composition for polyurethane |
DE3442646C2 (de) * | 1984-11-22 | 1986-10-23 | Dr. Alois Stankiewicz GmbH, 3101 Adelheidsdorf | Polyvinylchloridfreies Plastisol und seine Verwendung |
WO2001088009A1 (fr) * | 2000-05-16 | 2001-11-22 | Sunstar Giken Kabushiki Kaisha | Composition thermodurcissable |
JP3913444B2 (ja) * | 2000-05-23 | 2007-05-09 | アイシン化工株式会社 | 防音アンダーコート用アクリルゾル |
CA2438773C (en) * | 2001-02-17 | 2008-12-30 | Hehr International Inc. | Polyurea polymers prepared from polyamine epoxide adduct |
JP3939287B2 (ja) * | 2003-11-28 | 2007-07-04 | 本田技研工業株式会社 | アクリルゾル組成物 |
-
2003
- 2003-09-10 JP JP2003317940A patent/JP4480374B2/ja not_active Expired - Lifetime
-
2004
- 2004-08-27 DE DE602004014793T patent/DE602004014793D1/de not_active Expired - Fee Related
- 2004-08-27 WO PCT/JP2004/012396 patent/WO2005026257A1/ja active IP Right Grant
- 2004-08-27 KR KR1020057011717A patent/KR101091474B1/ko active IP Right Grant
- 2004-08-27 US US10/541,400 patent/US20060173110A1/en not_active Abandoned
- 2004-08-27 EP EP04772352A patent/EP1666531B1/en not_active Expired - Lifetime
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JPH03290479A (ja) * | 1990-04-06 | 1991-12-20 | Sanyo Chem Ind Ltd | プラスチゾル組成物 |
JPH1135784A (ja) * | 1997-07-18 | 1999-02-09 | Mitsubishi Rayon Co Ltd | プラスチゾル |
JP2000212237A (ja) * | 1999-01-20 | 2000-08-02 | Takeda Chem Ind Ltd | プラスチゾル組成物 |
JP2000273262A (ja) * | 1999-03-19 | 2000-10-03 | Mitsubishi Rayon Co Ltd | アクリル系プラスチゾル組成物 |
WO2001088011A1 (fr) * | 2000-05-16 | 2001-11-22 | Sunstar Giken Kabushiki Kaisha | Composition de plastisol |
JP2002256155A (ja) * | 2001-03-02 | 2002-09-11 | Sunstar Eng Inc | 電着鋼板板合せ部の腐蝕防止用プラスチゾル組成物 |
JP5073793B2 (ja) * | 2010-08-09 | 2012-11-14 | 株式会社コナミデジタルエンタテインメント | ゲーム端末、ゲーム端末の制御方法、ならびに、プログラム |
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Also Published As
Publication number | Publication date |
---|---|
JP4480374B2 (ja) | 2010-06-16 |
KR101091474B1 (ko) | 2011-12-07 |
KR20060061926A (ko) | 2006-06-08 |
EP1666531A4 (en) | 2007-04-11 |
EP1666531B1 (en) | 2008-07-02 |
DE602004014793D1 (de) | 2008-08-14 |
EP1666531A1 (en) | 2006-06-07 |
JP2005082740A (ja) | 2005-03-31 |
US20060173110A1 (en) | 2006-08-03 |
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