WO2016199751A1 - Composition d'uréthane et procédé de production de composition d'uréthane - Google Patents

Composition d'uréthane et procédé de production de composition d'uréthane Download PDF

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Publication number
WO2016199751A1
WO2016199751A1 PCT/JP2016/066863 JP2016066863W WO2016199751A1 WO 2016199751 A1 WO2016199751 A1 WO 2016199751A1 JP 2016066863 W JP2016066863 W JP 2016066863W WO 2016199751 A1 WO2016199751 A1 WO 2016199751A1
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Prior art keywords
mixture
urethane composition
group
catalyst
mixing
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PCT/JP2016/066863
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English (en)
Japanese (ja)
Inventor
公範 荒木
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横浜ゴム株式会社
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Application filed by 横浜ゴム株式会社 filed Critical 横浜ゴム株式会社
Priority to JP2017523642A priority Critical patent/JP6965744B2/ja
Priority to CN201680032984.9A priority patent/CN107636037B/zh
Publication of WO2016199751A1 publication Critical patent/WO2016199751A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • 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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • 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

Definitions

  • the present invention relates to a urethane composition and a method for producing the urethane composition.
  • Patent Document 1 has been proposed as a method for producing a composition that can be used for a body (painted steel plate).
  • Another object of the present invention is to provide a method for producing a urethane composition.
  • the present inventor has found that the urethane composition contains an aminosilane compound, whereby a predetermined effect can be obtained, and the present invention has been achieved.
  • the present invention is based on the above knowledge and the like, and specifically, solves the above problems by the following configuration.
  • Dehydration obtained by a mixing / dehydration process in which a liquid component containing a polyol compound and a powder component containing a filler are mixed to obtain a paste-like mixture, and at least a part of residual moisture in the paste-like mixture is removed.
  • a paste-like mixture An aromatic polyisocyanate; At least one metal catalyst selected from the group consisting of bismuth-based catalysts and titanium-based catalysts; An aliphatic polyisocyanate; An aminosilane compound; A tin-based catalyst; A one-component moisture-curing urethane composition containing an amine-based catalyst.
  • the urethane composition according to 1 above wherein the aminosilane compound has an imino group, and the imino group is bonded to at least one aromatic hydrocarbon group. 3. 3. The urethane composition according to 1 or 2 above, wherein the content of the aminosilane compound is 0.2 to 5.0 parts by mass with respect to 100 parts by mass of the total content of the dehydrated paste mixture and the aromatic polyisocyanate.
  • a liquid component containing a polyol compound and a powder component containing a filler are mixed to obtain a paste-like mixture, and at least a part of residual moisture in the paste-like mixture is removed to obtain a dehydrated paste-like mixture.
  • An aromatic polyisocyanate To dehydrated paste-like mixture An aromatic polyisocyanate; At least one metal catalyst selected from the group consisting of bismuth-based catalysts and titanium-based catalysts; An aliphatic polyisocyanate; An aminosilane compound; A tin-based catalyst; The manufacturing method of a urethane composition which has a mixing process which mixes an amine catalyst and manufactures a one-component moisture hardening type urethane composition. 5.
  • the mixing process A mixing step 1 of mixing an aromatic polyisocyanate with the dehydrated paste-like mixture; After the mixing step 1, the mixing step 2 for mixing the metal catalyst, the aliphatic polyisocyanate and the aminosilane compound, and after the mixing step 2, the mixing step 3 for mixing the tin-based catalyst and the amine-based catalyst are provided.
  • the method for producing a urethane composition as described in 4 above. 6). 6.
  • the urethane composition of the present invention is excellent in adhesiveness. Moreover, according to the manufacturing method of the urethane composition of this invention, the urethane composition excellent in adhesiveness can be provided.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • content of the said component refers to the total content of 2 or more types of substances.
  • the urethane composition of the present invention (the composition of the present invention) Dehydration obtained by a mixing / dehydration process in which a liquid component containing a polyol compound and a powder component containing a filler are mixed to obtain a paste-like mixture, and at least a part of residual moisture in the paste-like mixture is removed.
  • a paste-like mixture An aromatic polyisocyanate; At least one metal catalyst selected from the group consisting of bismuth-based catalysts and titanium-based catalysts; An aliphatic polyisocyanate; An aminosilane compound; A tin-based catalyst; A one-component moisture-curing urethane composition containing an amine-based catalyst.
  • composition of this invention takes such a structure, it is thought that a desired effect is acquired. The reason is not clear, but the present inventor presumes this as follows.
  • a urea reaction in which at least one isocyanate component selected from the group consisting of an aromatic polyisocyanate, an aliphatic polyisocyanate, and these urethane prepolymers reacts with an aminosilane compound, and an aromatic Urethane reaction in which polyisocyanate and aliphatic polyisocyanate react with a polyol compound, and bonding (adhesion) between an aminosilane compound and glass may occur.
  • the slower curing of the composition is advantageous in order for the aminosilane compound to adhere to the glass.
  • the slower reaction of the aminosilane compound in the urea reaction is more advantageous.
  • the aminosilane compound can react with any of the above-described isocyanate components in the urea reaction.
  • the isocyanate component is a plurality of types, the urea reaction is considered to proceed moderately as a whole. And it is thought that hardening of the whole composition becomes late
  • an aminosilane compound can react more with a urethane prepolymer, hardening of a composition is suppressed more and it is thought that it is excellent by adhesiveness.
  • the present inventor has found that a desired effect cannot be obtained when a reaction product of an aliphatic polyisocyanate and an aminosilane compound is contained, that is, when the composition is rapidly cured.
  • the above findings are thought to support that the rapid urea reaction inhibits the aminosilane compound from adhering to the glass.
  • the dehydrated paste-like mixture contained in the composition of the present invention is obtained by mixing a liquid component containing a polyol compound and a powder component containing a filler to obtain a paste-like mixture, which contains residual moisture in the paste-like mixture. It is a dehydrated paste-like mixture obtained by a mixing / dehydration process that removes at least a part.
  • the liquid component is not particularly limited as long as it contains a polyol compound, and may contain only the polyol compound.
  • the liquid component further contains, for example, a plasticizer. There may be. From the viewpoint of the viscosity in the mixing step, the melting point of the polyol compound is preferably 80 ° C. or less, and more preferably 60 ° C. or less.
  • the polyol compound is not particularly limited in its molecular weight and skeleton as long as it is a compound having two or more hydroxy groups (OH groups).
  • examples thereof include low-molecular polyhydric alcohols, polyether polyols, polyester polyols, other polyols, and mixed polyols thereof. Of these, polyether polyol is preferred.
  • polyether polyol examples include polyoxyethylene diol (polyethylene glycol), polyoxypropylene diol (polypropylene glycol: PPG), polyoxypropylene triol, ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG). , Polytetraethylene glycol, sorbitol-based polyol, and the like.
  • the polyether polyol is preferably polypropylene glycol or polyoxypropylene triol from the viewpoint of excellent compatibility with the polyisocyanate.
  • the weight average molecular weight of the polyether polyol is preferably 500 to 20,000 from the viewpoint that the viscosity of the urethane prepolymer obtained by the reaction with isocyanate has an appropriate fluidity at room temperature.
  • the weight average molecular weight is a polystyrene equivalent value obtained by the GPC method (solvent: tetrahydrofuran (THF)).
  • the polyol compounds can be used alone or in combination of two or more.
  • the content of the polyol compound is preferably 20 to 80 parts by mass, and preferably 25 to 75 parts by mass with respect to 100 parts by mass of the paste-like mixture or dehydrated paste-like mixture, from the viewpoint of excellent physical properties of the cured product. Is more preferable.
  • plasticizer examples include, for example, diisononyl adipate (DINA); diisononyl phthalate (DINP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, acetylricinoleic acid Examples include methyl; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol adipate polyester, and the like. These may be used alone or in combination of two or more. Of these, it is preferable to use diisononyl adipate (DINA) and diisononyl phthalate (DINP) for reasons of excellent cost and compatibility.
  • DINA diisononyl adipate
  • DIFP diisononyl phthalate
  • the content thereof is not particularly limited, but is 20 to 20 parts per 100 parts by mass of the total content of the polyol compound, aromatic polyisocyanate and aliphatic polyisocyanate. 80 parts by mass is preferable, and 30 to 70 parts by mass is more preferable.
  • the powder component is not particularly limited as long as it contains a filler, and may contain only the filler.
  • an anti-aging agent for example, an antioxidant, etc.
  • Contains various additives such as pigments (dyes), thixotropic agents, UV absorbers, flame retardants, surfactants (including leveling agents), dispersants, dehydrating agents, adhesion-imparting agents, and antistatic agents. It may be a thing.
  • the additive is not particularly limited. For example, a conventionally well-known thing is mentioned.
  • the filler include organic or inorganic fillers of various shapes. Specifically, for example, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; calcium carbonate (for example, heavy calcium carbonate , Precipitated calcium carbonate (light calcium carbonate), colloidal calcium carbonate), magnesium carbonate, zinc carbonate; wax stone clay, kaolin clay, calcined clay; carbon black; treated with these fatty acids, treated with resin acid, treated with urethane compound Processed fatty acid ester; etc., and these may be used alone or in combination of two or more.
  • carbon black and calcium carbonate are preferable because the viscosity and thixotropy of the composition can be easily adjusted.
  • the physical properties for example, hardness, elongation, etc.
  • heavy calcium carbonate it is excellent in deep part curability.
  • the carbon black is preferably pellet carbon black because the workability is improved and the dehydration of the liquid component is further promoted.
  • the content of the powder component is preferably 50 to 150 parts by mass, more preferably 70 to 130 parts by mass with respect to 100 parts by mass of the total content of the polyol compound, aromatic polyisocyanate and aliphatic polyisocyanate.
  • the mixing method in the mixing / dehydration step is not particularly limited. For example, it can mix by stirring.
  • the dehydrating method in the mixing / dehydrating step is not particularly limited. For example, it can be dehydrated by heating. The heating temperature during dehydration can be set to 110 ° C. to 170 ° C. Further, at the time of dehydration, the pasty mixture can be dried under conditions of vacuum (for example, 1.2 kPa or less, preferably 0.6 to 1.2 kPa) and 150 ° C. or less.
  • the ratio of each component contained in the dehydrated paste mixture is substantially the same as that of the paste mixture.
  • the aromatic polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups bonded to an aromatic hydrocarbon group in one molecule.
  • the aromatic hydrocarbon group is not particularly limited.
  • aromatic polyisocyanates examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), and tetramethylxylylene diisocyanate (TMXDI). , Tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), and triphenylmethane triisocyanate.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • XDI xylylene diisocyanate
  • TMXDI tetramethylxylylene diisocyanate
  • TODI Tolidine diisocyanate
  • NDI 1,5-naphthalene diisocyanate
  • triphenylmethane triisocyanate triphen
  • the content of the aromatic polyisocyanate is from 1 to 100 parts by mass with respect to a total content of 100 parts by mass of the dehydrated paste-like mixture and the aromatic polyisocyanate, from the viewpoint of excellent balance of handleability (viscosity) and physical properties after curing.
  • the amount is preferably 10 parts by mass, and more preferably 2 to 7 parts by mass.
  • the metal element catalyst contained in the composition of the present invention is at least one selected from the group consisting of a bismuth catalyst and a titanium catalyst.
  • the metal catalyst can accelerate the reaction of isocyanate groups such as urethane reaction.
  • the bismuth-based catalyst is preferably bismuth (metal bismuth) from the viewpoint that the reaction does not run away and a gel is not easily generated.
  • the titanium-based catalyst is not particularly limited as long as it is a compound containing titanium.
  • an organotitanium catalyst is mentioned.
  • the organic titanium catalyst include titanium carboxylate, alkoxide, and complex.
  • the carboxylic acid, alkoxy group and ligand constituting the organic titanium catalyst are not particularly limited.
  • Specific examples of the titanium-based catalyst include tetrapropyl titanate, tetrabutyl titanate, tetraoctyl titanate, and titanium diisopropoxy bis (ethyl acetoacetate).
  • Metal catalysts can be used alone or in combination of two or more.
  • the production of the metal catalyst is not particularly limited. For example, a conventionally well-known thing is mentioned.
  • the content of the metal catalyst is preferably 0.001 to 0.05 parts by mass, preferably 0.002 to 0.02 parts per 100 parts by mass of the total content of the dehydrated paste-like mixture and the aromatic polyisocyanate. More preferred is part by mass.
  • the aliphatic polyisocyanate contained in the composition of the present invention is not particularly limited as long as it is a compound having two or more isocyanate groups bonded to an aliphatic hydrocarbon group in one molecule.
  • the aliphatic hydrocarbon group that the aliphatic polyisocyanate has is not particularly limited. It may be linear, branched or cyclic, and is preferably linear.
  • the aliphatic hydrocarbon group may be saturated or unsaturated, and is preferably saturated.
  • the number of isocyanate groups that the aliphatic polyisocyanate has in one molecule is preferably 2 or more, more preferably 2 to 3 from the viewpoint of superior adhesion.
  • Aliphatic polyisocyanates are hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanate methyl).
  • HDI hexamethylene diisocyanate
  • TMHDI trimethylhexamethylene diisocyanate
  • NBDI norbornane diisocyanate
  • IPDI isophorone diisocyanate
  • bis isocyanate methyl
  • Aliphatic polyisocyanates such as cyclohexane (H 6 XDI) and dicyclohexylmethane diisocyanate (H 12 MDI) (excluding modified products; hereinafter, the above aliphatic polyisocyanate may be referred to as aliphatic polyisocyanate b); aliphatic Examples include modified polyisocyanates.
  • Aliphatic polyisocyanates are preferred from the viewpoint of excellent adhesiveness, and in particular, from the viewpoint of a wide range of adhesiveness due to differences in environment during curing.
  • the modified product of the aliphatic polyisocyanate is a reaction product of a trifunctional or higher functional polyol and an aliphatic polyisocyanate, an allophanate of an aliphatic polyisocyanate, a fat, from the viewpoint of excellent adhesion and physical property balance of the adhesive after curing. It is preferably at least one aliphatic isocyanate-modified product a selected from the group consisting of an isocyanurate of an aliphatic polyisocyanate and a biuret of an aliphatic polyisocyanate.
  • the aliphatic polyisocyanate used in the modified aliphatic isocyanate a is not particularly limited as long as it is an aliphatic hydrocarbon compound having at least two isocyanate groups in one molecule.
  • the thing similar to aliphatic polyisocyanate b is mentioned.
  • linear aliphatic polyisocyanates are preferable, and HDI is more preferable, from the viewpoint that the adhesiveness is excellent and foaming hardly occurs due to the addition amount.
  • reaction product of a trifunctional or higher polyol and an aliphatic polyisocyanate examples include a reaction product of a trifunctional polyol such as trimethylolpropane (TMP) or glycerin and an aliphatic polyisocyanate b (for example, HDI). It is done.
  • a reaction product of TMP and HDI for example, a compound represented by the following formula (5)
  • a reaction product of glycerin and HDI for example, a compound represented by the following formula (6).
  • Examples of the allophanate body of aliphatic polyisocyanate include HDI allophanate body.
  • biuret body of the aliphatic polyisocyanate examples include an HDI biuret body.
  • a compound represented by the following formula (7) is preferably exemplified.
  • Examples of the isocyanurate form of the aliphatic polyisocyanate include an HDI isocyanurate form. Specifically, the compound represented by following formula (8) is mentioned, for example.
  • the aliphatic polyisocyanate is selected from the group consisting of an isocyanurate body of an aliphatic polyisocyanate and a biuret body of an aliphatic polyisocyanate, from the viewpoint that the composition has a small variation in viscosity, excellent adhesion, and excellent storage stability. It is preferable that it is at least one kind.
  • the aliphatic polyisocyanate is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
  • the aliphatic polyisocyanates can be used alone or in combination of two or more.
  • the total content of aromatic polyisocyanate and aliphatic polyisocyanate is, for example, the number of moles of hydroxy group (OH) of the polyol compound relative to the total number of moles of isocyanate group of aromatic polyisocyanate and isocyanate group of aliphatic polyisocyanate.
  • An amount with a ratio of 1.1 to 2.5 is preferred.
  • the mass ratio of aliphatic polyisocyanate to aromatic polyisocyanate is 0.2 to 0.6 from the viewpoint of superior adhesion (particularly adhesion to glass). Is more preferable, and 0.3 to 0.4 is more preferable.
  • the aminosilane compound used in the composition of the present invention is a compound having at least one selected from the group consisting of an amino group (—NH 2 ) and an imino group (—NH—) and a hydrolyzable silyl group.
  • the amino group, imino group and hydrolyzable silyl group can be bonded via an organic group.
  • the group bonded to the imino group is preferably an aromatic hydrocarbon group.
  • the aromatic hydrocarbon group is not particularly limited as long as it is a hydrocarbon group having at least an aromatic ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring.
  • the aromatic ring may have a substituent. Examples of the substituent include an alkyl group.
  • hydrolyzable silyl group examples include those in which at least one hydrolyzable group is bonded to one silicon atom. When one or two hydrolyzable groups are bonded to one silicon atom, other groups that can be bonded to the silicon atom are not particularly limited. For example, a hydrocarbon group is mentioned. The hydrocarbon group is not particularly limited, but an alkyl group is preferable. Examples of the hydrolyzable silyl group include an alkoxysilyl group.
  • Specific examples include a methoxysilyl group (monomethoxysilyl group, dimethoxysilyl group, trimethoxysilyl group) and ethoxysilyl group (monoethoxysilyl group, diethoxysilyl group, triethoxysilyl group).
  • the organic group is not particularly limited.
  • the hydrocarbon group which may have a hetero atom like an oxygen atom, a nitrogen atom, and a sulfur atom is mentioned.
  • the hydrocarbon group include an aliphatic hydrocarbon group (which may be linear, branched or cyclic, may have an unsaturated bond), an aromatic hydrocarbon group, or these. The combination of is mentioned. At least one of the carbon atom or hydrogen atom of the hydrocarbon group may be replaced with a substituent.
  • an aliphatic hydrocarbon group is preferable.
  • the aminosilane compound is preferably a compound having an alkoxysilyl group and an imino group in one molecule from the viewpoint of excellent adhesion, excellent storage stability of the adhesive, and droop resistance. More preferably, it is a compound having a silyl group and an imino group to which an aromatic hydrocarbon group is bonded. An alkoxysilyl group, an imino group to which an aromatic hydrocarbon group is bonded in one molecule, an alkoxysilyl group, More preferably, the compound is bonded to the imino group via an aliphatic hydrocarbon group.
  • R 1 n NH 2 —n —R 2 —Si—R 3 3
  • R 1 represents an aromatic hydrocarbon group
  • n is 0 or 1
  • R 2 represents a divalent aliphatic hydrocarbon group
  • at least one of three R 3 is It is an alkoxy group
  • three R 3 s may be the same or different.
  • the remaining R 3 is preferably an alkyl group.
  • Examples of the aromatic hydrocarbon group include a phenyl group.
  • Examples of the divalent aliphatic hydrocarbon group include a methylene group, an ethylene group, and a propylene group.
  • Examples of the alkoxy group include a methoxy group and an ethoxy group.
  • Examples of the alkyl group include a methyl group and an ethyl group.
  • aminosilane compound examples include N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane.
  • the aminosilane compound is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
  • the aminosilane compounds can be used alone or in combination of two or more.
  • the amount of the aminosilane compound is superior in terms of adhesiveness, excellent storage stability when uncured, small variations in the viscosity of the composition, and appropriate length of tack-free time.
  • the content is preferably 0.2 to 5.0 parts by mass, more preferably 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the total content with the polyisocyanate.
  • the tin-based catalyst contained in the composition of the present invention is not particularly limited as long as it is a compound having tin.
  • an organotin catalyst can be used.
  • the organic group that the organotin catalyst has is not particularly limited.
  • organotin catalysts include tin carboxylates, alkoxides, and complexes.
  • the carboxylic acid, alkoxy group and ligand constituting the organotin catalyst are not particularly limited.
  • organotin catalysts include dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin maleate, stannous octate, dibutyltin diacetylacetonate, dioctyltin maleate; 1,3-diacetoxy-1,1,3,3- Examples thereof include a reaction product obtained by reacting tetrabutyl-distanoxane and ethyl silicate so that the molar ratio is 1: 0.8 to 1: 1.2.
  • Tin-based catalysts can be used alone or in combination of two or more.
  • the production of the tin-based catalyst is not particularly limited. For example, a conventionally well-known thing is mentioned.
  • the content of the tin-based catalyst is 0.001 to 0.05 parts by mass with respect to 100 parts by mass of the total content of the dehydrated paste-like mixture and the aromatic polyisocyanate from the viewpoint of excellent curability and adhesion development.
  • the amount is preferably 0.002 to 0.02 parts by mass.
  • the amine catalyst contained in the composition of the present invention is a compound having a nitrogen atom and promoting the reaction of an isocyanate group.
  • Amine-based catalysts are tertiary amino groups (one nitrogen atom is single-bonded to three carbon atoms, or one nitrogen atom is single-bonded to one carbon atom and double-bonded to another carbon atom.
  • Examples of the amine-based catalyst (tertiary amine) having a tertiary amino group include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, trioctylamine, trilaurylamine, dimethylethylamine.
  • the amine-based catalyst preferably contains a dimorpholinodiethyl ether structure in that it is excellent due to the effects of the present invention and is excellent in moisture curability, storage stability, and sag resistance.
  • the dimorpholinodiethyl ether structure is a structure having dimorpholinodiethyl ether as a basic skeleton.
  • the hydrogen atom of the morpholine ring may be substituted with a substituent.
  • the substituent is not particularly limited.
  • an alkyl group is mentioned. Examples of the alkyl group include a methyl group and an ethyl group.
  • Examples of the amine-based catalyst having a dimorpholinodiethyl ether structure include a compound represented by the following formula (9).
  • R 1 and R 2 are each independently an alkyl group, and m and n are each independently 0, 1 or 2.
  • Specific examples of the amine catalyst containing a dimorpholino diethyl ether structure include dimorpholino diethyl ether, di (methylmorpholino) diethyl ether, and di (dimethylmorpholino) diethyl ether.
  • Amine-based catalysts can be used alone or in combination of two or more.
  • the content of the amine catalyst is 0.05 to 1 with respect to 100 parts by mass of the total content of the dehydrated paste-like mixture and the aromatic polyisocyanate from the viewpoint of excellent curability and storage stability of the uncured product.
  • the amount is preferably 0.0 parts by mass, more preferably 0.07 to 0.5 parts by mass.
  • the composition of the present invention includes a silane coupling agent other than an aminosilane compound; a catalyst other than a predetermined metal catalyst, a tin-based catalyst, and an amine-based catalyst; Anti-sagging agent, anti-aging agent, antioxidant, pigment (dye), thixotropic agent, UV absorber, flame retardant, surfactant (including leveling agent), dispersant, dehydrating agent, antistatic agent, etc. Additives can be included. The amount of the additive can be appropriately determined.
  • the composition of the present invention is a one-component type.
  • the composition of the present invention can be moisture cured. For example, it can be cured under conditions of ⁇ 20 to + 50 ° C. by atmospheric humidity.
  • the composition of the present invention is excellent in adhesiveness even at an environmental temperature as low as ⁇ 20 ° C. to + 5 ° C.
  • the adherend to which the composition of the present invention can be applied is not particularly limited.
  • metal including a coated plate
  • plastic including a coated plate
  • rubber can be used.
  • the composition of the present invention can be directly applied to the glass without using a primer for the glass.
  • the method for applying the composition of the present invention to an adherend is not particularly limited.
  • composition of the present invention can be produced, for example, by the method for producing the urethane composition of the present invention described later.
  • the manufacturing method of the urethane composition of this invention is demonstrated below.
  • the production method of the urethane composition of the present invention production method of the present invention
  • a liquid component containing a polyol compound and a powder component containing a filler are mixed to obtain a paste-like mixture, and at least a part of residual moisture in the paste-like mixture is removed to obtain a dehydrated paste-like mixture.
  • Dehydration process To dehydrated paste-like mixture An aromatic polyisocyanate; At least one metal catalyst selected from the group consisting of bismuth-based catalysts and titanium-based catalysts; An aliphatic polyisocyanate; An aminosilane compound; A tin-based catalyst; It is a manufacturing method of a urethane composition which has a mixing process which mixes an amine catalyst and manufactures a one-pack moisture hardening type urethane composition.
  • At least one metal catalyst selected from the group consisting of dehydrated paste-like mixture, aromatic polyisocyanate, bismuth catalyst and titanium catalyst used in the production method of the present invention, aliphatic polyisocyanate, aminosilane compound, tin system
  • the catalyst and the amine catalyst are the same as in the composition of the present invention.
  • the mixing / dehydrating step of the production method of the present invention is the same as the mixing / dehydrating step in the composition of the present invention.
  • the method for mixing the above components is not particularly limited.
  • it can mix by stirring.
  • the temperature in the mixing step is not particularly limited.
  • the temperature can be 45 to 65 ° C.
  • it is preferable that the components are not exposed to moisture (for example, moisture in the atmosphere).
  • At least aromatic polyisocyanate is first mixed with the dehydrated paste-like mixture from the viewpoint of viscosity stability of the final product (urethane composition) (small variation between lots) and excellent adhesion development. It is preferable to do this.
  • the mixing step is from the viewpoint of excellent viscosity stability (small variation between lots) of the final product (urethane composition), excellent adhesion development,
  • the mixing step 2 of mixing the metal catalyst, the aliphatic polyisocyanate, and the aminosilane compound with the mixture obtained in the mixing step 1 After the mixing step 2, the mixture obtained in the mixing step 2 preferably has a mixing step 3 in which a tin-based catalyst and an amine-based catalyst are mixed.
  • the adhesiveness is excellent at low temperatures (specifically, after curing for 7 days at 5 ° C. and 50% RH, a manual peeling test with a cutter knife was performed, and as a result, an adhesive was obtained. In the case where the layer breaks up and breaks down, it is assumed that the adhesive developability at low temperature is excellent.)
  • the aminosilane compound is mixed. Is preferred.
  • the order of mixing the metal catalyst, the aliphatic polyisocyanate, and the aminosilane compound with the mixture obtained in the mixing step 1 is, for example, (1) Metal catalyst, aliphatic polyisocyanate, aminosilane compound (2) Aliphatic polyisocyanate, metal catalyst, aminosilane compound (3) Aliphatic polyisocyanate, aminosilane compound, metal catalyst.
  • composition (Dehydration and mixing process) Add polyol compounds 1 and 2 and plasticizer as liquid components to Ladige mixer (Matsubo), then add carbon black and calcium carbonate as powder components, stir at 110 ° C. for 2 hours and paste A mixture was prepared.
  • the compounding quantity (unit: mass part) of each component is as showing in the following Table 1.
  • the inside of the Ladige mixer containing the paste mixture was reduced to 30-60 ° C. and 1.2 kPa or less and dried for 30 minutes to obtain a dehydrated paste mixture.
  • Polyol compound 1 bifunctional polypropylene glycol (EXCENOL 2020, manufactured by Asahi Glass Co., Ltd.)
  • Polyol compound 2 trifunctional polypropylene glycol (EXCENOL 5030, manufactured by Asahi Glass Co., Ltd.)
  • Calcium carbonate Heavy calcium carbonate (Super S, manufactured by Maruo Calcium)
  • Aromatic polyisocyanate2 2.
  • Metal catalyst Aliphatic polyisocyanate4.
  • SOD viscosity (initial viscosity) of the composition produced as described above was measured using a pressure viscometer (ASTM D 1092) in accordance with JASO M338-89.
  • SOD viscosity variation (%) [(maximum value ⁇ minimum value) / average value] ⁇ 100
  • the composition produced as described above was sealed in a container, measured for SOD viscosity (Pa ⁇ s) after storage at 40 ° C for 7 days, and increased from SOD viscosity (initial viscosity) before storage. The rate was calculated. The SOD viscosity was measured using a pressure viscometer (ASTM D 1092) according to JASO M338-89. When the thickening rate is 30% or less, it can be evaluated that the storage stability is excellent.
  • Each composition produced as described above was extruded on a glass plate with a right triangle bead having a base of 6 mm and a height of 10 mm, and then the hypotenuse of the composition extruded into the shape of the right triangle.
  • the glass plate was set up vertically (90 ° angle) so that the side of the composition having a height of 10 mm was horizontal, the glass plate was fixed, and the glass plate was held vertically, , And left at 65% relative humidity for 30 minutes.
  • the distance h (mm) at which the apex of the right triangle of each composition hangs down was measured within 30 minutes after the glass plate was made vertical, and the sag resistance was evaluated with this value.
  • ⁇ TFT (tack free time) A polyethylene film is placed between the surface of the cured product and the finger under the conditions of 23 ° C. and 50% RH, and the surface of the cured product is pressed with the finger through the polyethylene film. Thus, the stickiness of the surface of the cured product was confirmed. The time (minutes) from the start of the test until the cured product did not adhere to the polyethylene film was measured.
  • the sample for initial adhesion evaluation obtained as described above was placed under a condition of 110 ° C for 2 weeks to prepare a sample for heat-resistant adhesiveness evaluation.
  • a hand peeling test with a cutter knife was performed in the same manner as in the evaluation of initial adhesiveness using the above heat-resistant adhesive evaluation sample.
  • the evaluation criteria are the same as the evaluation of the initial adhesion development.
  • composition produced as described above was stored in a sealed state at 50 ° C. for 2 weeks to obtain a composition after storage.
  • a sample was prepared and evaluated in the same manner as the initial adhesion development property except that the composition after storage obtained as described above was used.
  • the evaluation criteria are the same as the evaluation of the initial adhesion development.
  • the sample for initial-curing evaluation obtained as described above was placed under a condition of 50 ° C for 2 weeks to prepare a sample for accelerating-curing adhesiveness evaluation.
  • a manual peeling test using a cutter knife was carried out in the same manner as in the evaluation of initial adhesion development using the sample for evaluating accelerated curing adhesion.
  • the evaluation criteria are the same as the evaluation of the initial adhesion development.
  • Dehydrated paste mixture Dehydrated paste mixture produced as described above
  • Bi catalyst Inorganic bismuth (Neostan U-600, manufactured by Nitto Kasei)
  • Ti catalyst Titanium acetoacetate ethyl chelate (Orgatechs TC-750, manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • HDI-biuret hexamethylene diisocyanate (HDI) biuret represented by the above formula (7)
  • HDI-isocyanurate body HDI isocyanurate body represented by the above formula (8)
  • HDI-TMP modified product HDI-TMP adduct represented by the above formula (5) (synthetic product). The synthesis was performed by dropping TMP with stirring in an equivalent ratio at which NCO / OH was 2.0 in a flask to which HDI had been added in advance, and then reacting at 80 ° C. for 24 hours.
  • -TDI modified product isocyanurate of tolylene diisocyanate (TDI), Death Module 1351, manufactured by Bayer
  • KBM573 N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM903 3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM803 3-mercaptopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. Made by company
  • (Comparison) Reaction product 1 a compound produced by mixing 2 parts by mass of the HDI-biuret and 1 part by mass of the KBM573 and reacting the resulting mixture at 50 ° C. for 10 hours. The obtained compound was used as reaction product 1 as it was.
  • (Comparison) Reaction product 2 Compound prepared by mixing 2 parts by mass of the above HDI-isocyanurate and 1 part by mass of KBM573 and reacting the resulting mixture at 50 ° C. for 10 hours. . The obtained compound was directly used as reaction product 2.
  • Ti catalyst Same as the above Ti catalyst
  • DMDMEE dimorpholino diethyl ether (manufactured by Sun Apro)
  • -TEDA Triethylenediamine (DABCO, manufactured by Air Products)
  • Example 1 containing a bismuth-based catalyst has a lower viscosity of the composition and a viscosity variation than Example 16 containing a titanium-based catalyst. Small, excellent storage stability and short TFT.
  • Example 19 produced under standard production conditions was tack-free than Example 20 produced with simultaneous addition 1 while maintaining excellent adhesion. I was able to shorten my time. Moreover, when Example 19 and Example 21 were compared, Example 19 was excellent in droop resistance than Example 21 produced by simultaneous addition 2.
  • Comparative Example 1 in which no aliphatic polyisocyanate was used had low adhesiveness.
  • the comparative example 2 which uses a mercaptosilane instead without using an aminosilane compound had low adhesiveness.
  • Comparative Examples 3 and 4 in which no tin-based catalyst was used, the adhesiveness was low.
  • Comparative Examples 5 and 6 in which the reaction product of the aliphatic polyisocyanate and the aminosilane compound was used instead of the aliphatic polyisocyanate and the aminosilane compound, the adhesiveness was low.
  • Comparative Example 7 in which no aliphatic polyisocyanate was used, the adhesiveness was low.
  • the comparative example 8 which does not use an aminosilane compound had low adhesiveness.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'objectif de la présente invention est de fournir une composition d'uréthane ayant une excellente adhérence et un procédé de production de la composition d'uréthane. La présente invention concerne une composition d'uréthane durcissable par l'eau à liquide unique qui contient : un mélange de pâte déshydraté obtenu à partir d'une étape de mélange/déshydratation pour mélanger un composant liquide contenant un composé polyol et un composant en poudre contenant une charge pour obtenir un mélange de pâte, et éliminer au moins une partie de l'eau résiduelle dans le mélange de pâte ; un polyisocyanate aromatique ; au moins un catalyseur métallique choisi dans le groupe constitué de catalyseurs à base de bismuth et catalyseurs à base de titane ; un polyisocyanate aliphatique ; un composé aminosilane ; un catalyseur à base d'étain ; et un catalyseur à base d'amine. La présente invention concerne en outre un procédé de production de la composition d'uréthane.
PCT/JP2016/066863 2015-06-10 2016-06-07 Composition d'uréthane et procédé de production de composition d'uréthane WO2016199751A1 (fr)

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JP2021509415A (ja) * 2017-12-27 2021-03-25 ダウ グローバル テクノロジーズ エルエルシー ポリマーバリア基材への接着のための二成分無溶剤接着剤組成物
EP3919581A4 (fr) * 2019-01-30 2022-08-24 Sika Hamatite Co., Ltd. Composition d'agent adhésif à base d'uréthane

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WO2014097905A1 (fr) * 2012-12-20 2014-06-26 横浜ゴム株式会社 Procédé de production d'une composition de polyuréthane monoconstituant durcissant à l'humidité
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JP7223002B2 (ja) 2017-12-27 2023-02-15 ダウ グローバル テクノロジーズ エルエルシー ポリマーバリア基材への接着のための二成分無溶剤接着剤組成物
EP3919581A4 (fr) * 2019-01-30 2022-08-24 Sika Hamatite Co., Ltd. Composition d'agent adhésif à base d'uréthane
US11479700B2 (en) 2019-01-30 2022-10-25 Sika Hamatite Co., Ltd. Urethane adhesive composition

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