WO2017014188A1 - Composition adhésive et procédé de production de composition adhésive - Google Patents

Composition adhésive et procédé de production de composition adhésive Download PDF

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Publication number
WO2017014188A1
WO2017014188A1 PCT/JP2016/071004 JP2016071004W WO2017014188A1 WO 2017014188 A1 WO2017014188 A1 WO 2017014188A1 JP 2016071004 W JP2016071004 W JP 2016071004W WO 2017014188 A1 WO2017014188 A1 WO 2017014188A1
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WIPO (PCT)
Prior art keywords
adhesive composition
mixture
mixing
paste
group
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PCT/JP2016/071004
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English (en)
Japanese (ja)
Inventor
公範 荒木
Original Assignee
横浜ゴム株式会社
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Publication date
Application filed by 横浜ゴム株式会社 filed Critical 横浜ゴム株式会社
Priority to JP2017529879A priority Critical patent/JPWO2017014188A1/ja
Priority to CN201680041469.7A priority patent/CN107849422B/zh
Publication of WO2017014188A1 publication Critical patent/WO2017014188A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • the present invention relates to an adhesive composition and a method for producing the adhesive composition.
  • Patent Document 1 discloses that “a liquid component (A) containing a polyol compound having two or more hydroxy groups in one molecule and a powder component (B) containing a filler are mixed, and the liquid A mixing step for obtaining a paste-like mixture of the component (A) and the powder component (B), a dehydration step for removing at least a part of residual moisture in the paste-like mixture after the mixing step, and one molecule A polyisocyanate compound (C) having two or more isocyanate groups therein and the paste mixture after the dehydration step are mixed, and the polyisocyanate compound (C) and the polyol compound in the paste mixture are mixed with each other.
  • Another object of the present invention is to provide a method for producing an adhesive composition.
  • the adhesive composition contains a predetermined catalyst, whereby a predetermined effect can be obtained, leading to the present invention.
  • the present invention is based on the above knowledge and the like, and specifically, solves the above problems by the following configuration.
  • a dehydrated paste-like mixture containing a liquid component containing a polyol compound and a powder component containing a filler and dehydrated (or a liquid component containing a polyol compound and a powder component containing a filler are mixed.
  • a one-component moisture-curing adhesive composition containing an amine-based catalyst are mixed.
  • X 1 and X 2 each independently represent a divalent hetero atom, and R 1 and R 2 each independently represent a hydrocarbon group that may have a hetero atom.
  • the divalent heteroatom is at least one selected from the group consisting of an oxygen atom and a sulfur atom.
  • X 1 and X 2 are sulfur atoms, 3.
  • X 1 and X 2 are oxygen atoms, 3.
  • the aliphatic polyisocyanate is at least one selected from the group consisting of a reaction product of hexamethylene diisocyanate and a tri- or higher functional polyol, hexamethylene diisocyanate allophanate, hexamethylene diisocyanate isocyanurate, and hexamethylene diisocyanate biuret. 6.
  • X 1 and X 2 each independently represent a divalent hetero atom, and R 1 and R 2 each independently represent a hydrocarbon group that may have a hetero atom.
  • the mixing process A mixing step 1 of mixing an aromatic polyisocyanate with the dehydrated paste-like mixture; A mixing step 2 in which an aliphatic polyisocyanate and an aminosilane compound are mixed with the mixture obtained in the mixing step 1; 13.
  • the adhesive composition of this invention is excellent in adhesiveness. Moreover, according to the manufacturing method of the adhesive composition of this invention, the adhesive 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 adhesive composition of the present invention (the composition of the present invention) A dehydrated paste mixture comprising a liquid component containing a polyol compound and a powder component containing a filler, and dehydrated; An aromatic polyisocyanate; A predetermined dimethyltin catalyst, An aliphatic polyisocyanate; An aminosilane compound; It is a one-component moisture-curing adhesive composition containing an amine catalyst.
  • the adhesive composition of this invention takes such a structure, it is thought that a desired effect is acquired. The reason is not clear, but it is presumed that it is as follows.
  • the predetermined dimethyltin catalyst is more active than the dioctyltin catalyst, and by containing the predetermined dimethyltin catalyst, the adhesive composition of the present invention has an active hydrogen other than water rather than curing of the adhesive itself by reaction with water.
  • the present inventor presumes that a bond with (for example, a coated plate) is easily generated. Thereby, it is considered that the adhesive composition of the present invention is excellent in adhesiveness to difficult-to-adhere coating plates.
  • each component contained in the composition of this invention is explained in full detail.
  • the dehydrated paste-like mixture contained in the composition of the present invention is a paste-like mixture containing a liquid component containing a polyol compound and a powder component containing a filler and dehydrated.
  • the above “dehydrated” means dehydrated and dried.
  • the dehydrated paste mixture contains at least a polyol compound and a filler.
  • the dehydrated paste-like mixture may further contain a plasticizer.
  • a dehydrated paste-like mixture is obtained by mixing a liquid component containing a polyol compound and a powder component containing a filler to obtain a paste-like mixture, and removing at least a part of residual moisture in the paste-like mixture.
  • One preferred embodiment is a dehydrated paste mixture obtained by the dehydration step.
  • the content of water contained in the dehydrated paste mixture is preferably 500 ppm or less, more preferably 250 ppm or less, and further preferably 230 ppm or less, based on the total amount of the dehydrated paste mixture. In the present invention, the water content was measured at a vaporizer temperature of 200 ° C.
  • the proportion of each component contained in the dehydrated paste mixture can be substantially the same as that of the mixture before being dehydrated (paste mixture).
  • the content of water contained in the dehydrated paste-like mixture should be less than the content of water contained in the mixture (paste-like mixture) before being dehydrated.
  • the content of water contained in the mixture before being dehydrated (paste-like mixture) is not particularly limited.
  • 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 conversion value obtained by GPC (gel permeation chromatography: abbreviation for Gel Permeation Chromatography) method (solvent: using tetrahydrofuran (THF)).
  • GPC gel permeation chromatography: abbreviation for Gel Permeation Chromatography
  • solvent using tetrahydrofuran (THF)
  • the content of the polyol compound is preferably 20 to 80 parts by mass and more preferably 25 to 75 parts by mass with respect to 100 parts by mass of the paste-like mixture from the viewpoint of excellent physical properties of the cured product.
  • 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 of the plasticizer is not particularly limited, but is preferably 2.5 to 50 parts by mass with respect to 100 parts by mass of the paste-like mixture as a whole. More preferred is 25 parts by mass.
  • 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.
  • the filler is preferably carbon black or calcium carbonate because the viscosity and thixotropy of the composition can be easily adjusted.
  • carbon black is used, the physical properties (for example, hardness, elongation, etc.) are excellent.
  • heavy calcium carbonate is used as calcium carbonate, it is excellent in deep part curability. Since carbon black is pellet carbon black, not only the workability is improved, but, as will be described later, dehydration of not only carbon black but also the liquid component is further promoted in mixing with the liquid component. Preferred for reasons.
  • the content of the powder component can be 80 parts by mass or less with respect to 100 parts by mass of the entire paste-like mixture, preferably 5 to 75 parts by mass, and more preferably 15 to 50 parts by mass.
  • Examples of the method for preparing the dehydrated paste-like mixture include a method (mixing / dehydrating method) in which a liquid component and a powder component are mixed and dehydrated.
  • mixing and dehydration can be performed simultaneously or separately, and dehydration after mixing can be mentioned as one of preferred embodiments.
  • dehydration water can be removed from the mixture (paste-like mixture) containing the liquid component and the powder component.
  • One preferred embodiment of the dehydrated paste mixture is a method in which a liquid component containing a polyol compound and a powder component containing a filler are mixed to obtain a paste mixture, and the paste mixture is dehydrated.
  • the method for mixing the liquid component and the powder component is not particularly limited.
  • the method for dehydrating the mixture (paste-like mixture) containing the liquid component and the powder component is not particularly limited.
  • it can be dehydrated by heating.
  • the heating temperature during dehydration can be set to 110 ° C. to 170 ° C. under normal pressure conditions.
  • the paste-like mixture is dried under conditions of vacuum (for example, 1.2 kPa or less, preferably 0.6 to 1.2 kPa) and 30 ° C. (100 ° C.) to 150 ° C. Can be made.
  • 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 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 superior in adhesiveness, and in particular, have a wide range of adhesiveness due to differences in environment during curing (that is, excellent in adhesiveness regardless of differences in the environment during curing (eg, temperature environment)).
  • a modified product of an aliphatic polyisocyanate is preferred.
  • 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 modified aliphatic polyisocyanate 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 polyisocyanate 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 that gives a ratio of 1.1 to 2.5 is preferred.
  • the mass ratio of the aliphatic polyisocyanate to the aromatic polyisocyanate is preferably 0.05 to 1.0, more preferably 0.1 to More preferably, it is 0.7.
  • 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 or imino group and the 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. It has an alkoxysilyl group and an imino group to which an aromatic hydrocarbon group is bonded in one molecule. More preferably, the compound is a compound in which the silyl group and the imino group are bonded via an aliphatic hydrocarbon group.
  • R 1 n —NH 2 —n —R 2 —Si—R 3 3 (I)
  • R 1 represents an aromatic hydrocarbon group
  • n is 0 or 1
  • R 2 represents a divalent aliphatic hydrocarbon group
  • at least one of the 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, a propylene group, and a trimethylene 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 amount is preferably 0.02 to 5.0 parts by weight, more preferably 0.05 to 5.0 parts by weight, based on 100 parts by weight of the total content with the polyisocyanate.
  • the dimethyltin catalyst contained in the adhesive composition of the present invention is a compound represented by the following formula (1).
  • X 1 and X 2 each independently represent a divalent hetero atom
  • R 1 and R 2 each independently represent a hydrocarbon group that may have a hetero atom.
  • Examples of the divalent hetero atom include an oxygen atom and a sulfur atom.
  • Examples of the hetero atom that the hydrocarbon group may have include an oxygen atom, a nitrogen atom, and a sulfur atom.
  • Examples of 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. Examples of the substituent include a carbonyl group and an ester bond. Of the carbon atoms possessed by the hydrocarbon group, carbon atoms located at positions other than both ends of the hydrocarbon group may be replaced with a substituent.
  • the dimethyltin catalyst is excellent in catalytic activity and can suppress an increase in the viscosity of the composition after storage.
  • X 1 and X 2 are oxygen atoms
  • R 1 and R 2 are carbonyl.
  • a dimethyltin dicarboxylate which is an alkyl group having a group and in which the oxygen atom is bonded to the carbonyl group to form an ester bond is preferable.
  • dimethyltin dicarboxylate examples include dimethyltin dicarboxylate represented by the following formula (2).
  • R 3 and R 4 each independently represents a hydrocarbon group.
  • the hydrocarbon group is the same as the hydrocarbon group represented by R 1 and R 2 .
  • dimethyltin dicarboxylate examples include dimethyltin dilaurate represented by the following formula (2-1) and dimethyltin dioctate represented by the following formula (2-2).
  • X 1 and X 2 are each a sulfur atom, and R 1 and R 2 are preferably a thio-based dimethyltin catalyst which is an unsubstituted or alkyl group having an ester bond. In this case, R 1 and R 2 may be the same or different.
  • R 1 and R 2 are unsubstituted or alkyl groups having an ester bond, that R 1 and R 2 are unsubstituted alkyl groups, or R 1 and R 2 are ester bonds. It means that it is an alkyl group having. In the alkyl group having an ester bond, at least one carbon atom of the alkyl group may be replaced with a substituent. Examples of the substituent include a carbonyl group and an ester bond. Of the carbon atoms possessed by the alkyl group, carbon atoms located at positions other than both ends of the alkyl group may be replaced with a substituent.
  • Dimethyltin dimercaptide As the thio-based dimethyltin catalyst in which X 1 and X 2 are sulfur atoms and R 1 and R 2 are unsubstituted alkyl groups in the formula (1), for example, dimethyltin dimercaptide Is mentioned.
  • dimethyltin dimercaptide examples include dimethyltin dimercaptide represented by the following formula (3).
  • R 3 and R 4 each independently represents a hydrocarbon group.
  • the hydrocarbon group is the same as the hydrocarbon group represented by R 1 and R 2 .
  • dimethyltin dimercaptide examples include dimethyltin didecadecyl mercaptide and dibutyltin dioctayl mercaptide represented by the following formula (3-1).
  • Dimethyltin dithioglycolate As the dimethyltin catalyst in which X 1 and X 2 are sulfur atoms and R 1 and R 2 are alkyl groups having an ester bond in the formula (1), for example, dimethyltin dithioglycolate is Can be mentioned.
  • dimethyltin dithioglycolate examples include dimethyltin dimercaptide represented by the following formula (4).
  • R 3 and R 4 each independently represents a hydrocarbon group.
  • the hydrocarbon group is the same as the hydrocarbon group represented by R 1 and R 2 .
  • dimethyltin dithioglycolate examples include dimethyltin bis (2-ethylhexylthioglycolate) represented by the following formula (4-1).
  • the dimethyltin catalyst is not particularly limited for its production. For example, a conventionally well-known thing is mentioned. Moreover, a dimethyltin catalyst can be used individually or in combination of 2 types or more, respectively.
  • the content of the dimethyltin catalyst is excellent in adhesiveness, and in view of excellent curability, storage stability of uncured material, and piping stability, the total content of the dehydrated paste mixture and aromatic polyisocyanate is 100 parts by mass.
  • the amount is preferably 0.0005 to 0.15 parts by mass, and more preferably 0.001 to 0.1 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-based catalyst having a dimorpholinodiethyl ether structure include dimorpholinodiethyl ether (4,4 ′-(oxydi-2,1-ethanediyl) bis-morpholine, bis (2,2 -Morpholinoethyl) ether), di (methylmorpholino) diethyl ether, 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.
  • composition of the present invention can be used as long as it does not impair the purpose of the present invention, if necessary, for example, a silane coupling agent other than an aminosilane compound; a catalyst other than a dimethyltin catalyst and an amine catalyst; Contains additives such as inhibitors, antioxidants, pigments (dyes), thixotropic agents, UV absorbers, flame retardants, surfactants (including leveling agents), dispersants, dehydrating agents, antistatic agents, etc. be able to.
  • the amount of the additive can be appropriately determined.
  • composition of the present invention can be produced, for example, by the method for producing the adhesive composition of the present invention described later.
  • 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 adhesive composition of the present invention can be applied to an adherend without using a primer for the adherend.
  • the adhesive composition of the present invention can be used for difficult-to-adhere coating plates.
  • the paint applied to the hardly adhesive coating plate For example, acrylic / silane-based paints can be mentioned.
  • the A / B paint means A paint and B paint.
  • the paint applied to the hardly-adhesive coating plate is, for example, an acrylic / silane-based paint
  • the paint applied to the hardly-adhesive coating plate is an acrylic paint or a silane-based paint.
  • the adhesive composition of this invention is excellent in the adhesiveness with respect to coating plates other than a difficult adhesion coating plate.
  • the coating plates other than the hard-to-bond coating plates There are no particular restrictions on the coating plates other than the hard-to-bond coating plates. For example, a conventionally well-known thing is mentioned.
  • the coating used for coating plates other than the difficult-to-adhere coating plates include urethane coatings, acid / epoxy coatings, and acrylic / melamine coatings.
  • the method for applying the composition of the present invention to an adherend is not particularly limited.
  • the manufacturing method of the adhesive composition of this invention is demonstrated below.
  • the manufacturing method of the adhesive composition of the present invention (the manufacturing method of the present invention) A mixing / dehydration step of mixing a liquid component containing a polyol compound and a powder component containing a filler and dehydrating to obtain a dehydrated paste-like mixture; To dehydrated paste-like mixture An aromatic polyisocyanate; A dimethyltin catalyst represented by the following formula (1); An aliphatic polyisocyanate; An aminosilane compound; It is a manufacturing method of an adhesive composition which has a mixing process which mixes an amine catalyst and manufactures a one-pack moisture hardening type adhesive composition.
  • X 1 and X 2 each independently represent a divalent hetero atom
  • R 1 and R 2 each independently represent a hydrocarbon group that may have a hetero atom.
  • the dehydrated paste mixture, aromatic polyisocyanate, predetermined dimethyltin catalyst, aliphatic polyisocyanate, aminosilane compound, and amine catalyst used in the production method of the present invention are the same as those of the composition of the present invention.
  • the mixing / dehydrating step of the production method of the present invention is a step in which a liquid component containing a polyol compound and a powder component containing a filler are mixed and dehydrated to obtain a dehydrated paste-like mixture.
  • a liquid component containing a polyol compound and a powder component containing a filler are mixed and dehydrated to obtain a dehydrated paste-like mixture.
  • the liquid component containing the polyol compound and the powder component containing the filler used in the mixing / dehydration step are the same as the composition of the present invention.
  • the polyol compound and the other liquid component may be mixed in advance or may be added separately.
  • the mixing method in the mixing / dehydration step is not particularly limited. For example, it can mix by stirring.
  • the dehydration method and dehydration conditions in the mixing / dehydration step are not particularly limited.
  • the mixing / dehydration process described in the composition of the present invention can be the same.
  • the dehydrated paste mixture used in the mixing step is the dehydrated paste mixture obtained in the mixing / dehydration step.
  • the aromatic polyisocyanate, the dimethyltin catalyst represented by the formula (1), the aliphatic polyisocyanate, the aminosilane compound, or the amine catalyst used in the mixing step are each contained in the composition of the present invention.
  • the method for mixing the above components is not particularly limited. For example, it can mix by stirring.
  • the temperature in the mixing step is not particularly limited. For example, the temperature can be 45 to 65 ° C.
  • the mixing can be performed, for example, under normal pressure or reduced pressure conditions, and is preferably performed under reduced pressure conditions. In the mixing step, it is preferable that the components are not exposed to moisture in the atmosphere, for example.
  • At least an aromatic polyisocyanate is first added to the dehydrated paste-like mixture from the viewpoint of viscosity stability of the final product (adhesive composition) (small variation between lots) and excellent adhesion development. It is preferable to mix. In addition, in the mixing step, it is preferable to finally mix at least an amine catalyst from the viewpoint of excellent viscosity stability (small variation between lots) of the final product (adhesive composition) and excellent adhesion development. .
  • the mixing step is performed from the viewpoint of excellent viscosity stability of the final product (adhesive composition) (small variation between lots) and excellent adhesion development.
  • 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.
  • composition (Dehydration and mixing process) A polyol compound 1 and a plasticizer are added as liquid components to a Ladige mixer (manufactured by Matsubo), and then carbon black and calcium carbonate are further added as powder components and stirred at 110 ° C. for 2 hours to form a paste. A mixture was prepared.
  • the compounding quantity (unit: mass part) of each component is as showing in the following Table 1. The content of water contained in the paste-like mixture prepared as described above was 240 ppm with respect to the total amount of the paste-like mixture.
  • the inside of the Leedige mixer containing the paste-like mixture prepared as described above was dried at 30 to 60 ° C. and 1.2 kPa or less for 30 minutes to obtain a dehydrated paste-like mixture.
  • the content of water contained in the dehydrated paste mixture prepared as described above was 220 ppm with respect to the total amount of the dehydrated paste mixture.
  • Aromatic polyisocyanate2 2. Isocyanate compound 3. Aminosilane compound Metal catalyst, amine catalyst, organic acid
  • 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. The smaller the value, the better the droop resistance.
  • Heat resistant adhesive (Preparation of heat resistant adhesive evaluation sample)
  • One glass (length 25 mm ⁇ width 100 mm ⁇ thickness 8 mm, primer-treated, primer is trade name MS-90, manufactured by Yokohama Rubber Co., Ltd.) was prepared as an adherend.
  • Each composition produced as described above was applied to the glass at room temperature. After coating, the composition on each glass is pressure-bonded to a thickness of 5 mm, cured for 72 hours under conditions of 23 ° C. and 50% relative humidity, and then left in a 120 ° C. environment for 7 days to give a sample for evaluating heat-resistant adhesion. It was.
  • the composition manufactured as described above should not enter air into the hose (diameter 5 mm, length 20 cm, trade name Chuko Flow Tube, manufactured by Chuko Kasei Co., Ltd., polytetrafluoroethylene (PTFE)). After filling, the hose was sealed, and the sealed hose was placed at 50 ° C. for 1 week. One week later, the hose was returned to room temperature, the center of the hose was cut off, the uncured composition was removed from the hose, and the inside of the hose was observed. The case where the composition did not remain in the hose was evaluated as being excellent in piping stability, and this was indicated as “ ⁇ ”.
  • the thickness of the cured composition from any point on the inner surface of the hose toward the center of the cut surface of the hose at the cut surface of the hose was measured. The greater the thickness, the lower the piping stability.
  • Adhesiveness 1 (Preparation of sample for evaluating adhesiveness 1) A hard-to-adhesive coating plate in which an acrylic / silane-based paint was applied to a steel plate was prepared. Each composition prepared as described above was directly applied to the above-mentioned hardly adhesive coating plate without using a primer, cured for 7 days under conditions of 5 ° C. and 50% relative humidity, the composition was cured, and a sample was prepared. Produced. The thickness of the composition after curing was 5 mm. Let the sample produced as mentioned above be a sample for evaluating adhesiveness 1.
  • Adhesion 2 (Preparation of sample for evaluating adhesiveness 2) A hard-to-adhesive coating plate in which an acrylic / silane-based paint was applied to a steel plate was prepared. Moreover, each composition manufactured as mentioned above was stored for 14 days under the conditions of 50 ° C. and 95% relative humidity to prepare a composition after storage. Without applying a primer to the hard-to-adhere coating plate, the composition after storage prepared directly as described above was applied, cured for 7 days under conditions of 5 ° C. and 50% relative humidity, and the composition was cured, A sample was made. The thickness of the composition after curing was 5 mm. Let the sample produced as mentioned above be a sample for evaluating adhesiveness 2.
  • a peel test similar to the peel test in Adhesive 1 was performed except that a sample for evaluating Adhesive 2 was used.
  • the evaluation criteria are the same as those for the adhesiveness 1.
  • Dehydrated paste mixture Dehydrated paste mixture produced as described above
  • Aromatic polyisocyanate Diphenylmethane diisocyanate (MDI) (Cosmonate PH, manufactured by Mitsui Chemicals, Inc.)
  • Aliphatic polyisocyanate 1 Biuret of hexamethylene diisocyanate (HDI) represented by the above formula (7) (D165N, manufactured by Mitsui Chemicals)
  • Aliphatic polyisocyanate 2 HDI isocyanurate represented by the above formula (8), Takenate D170N manufactured by Mitsui Chemicals, Inc. (Comparison) aromatic polyisocyanate: tolylene diisocyanate (TDI) isocyanurate, Desmodur 1351, manufactured by Bayer
  • Dimethyltin catalyst 1 Dimethyltin dilaurate (trade name UL-22, manufactured by Momentive)
  • Dimethyltin catalyst 2 Dimethyltin didodecyl mercaptide (trade name UL-28, manufactured by Momentive)
  • Dimethyltin catalyst 3 dimethyltin bis (2-ethylhexylthioglycolate) (trade name UL-54, manufactured by Momentive)
  • Amine catalyst 1 Triethylenediamine (DABCO, manufactured by Air Products)
  • Amine catalyst 2 dimorpholino diethyl ether (manufactured by San Apro)
  • Organic acid Octylic acid, manufactured by Kanto Chemical Co., Inc.
  • Comparative Example 1 which did not contain an aliphatic polyisocyanate and contained an aromatic polyisocyanate instead (comparative) had low adhesion to a hardly-adhesive coated plate.
  • the comparative example 2 which does not contain an aminosilane compound but contains mercaptosilane instead has low adhesiveness with a difficult-to-adhere coating plate.
  • Comparative Examples 3 to 5 containing a metal catalyst other than the dimethyltin catalyst, the adhesiveness to the hardly adhesive coating plate was low.
  • Comparative Example 6 containing a metal catalyst other than the dimethyltin catalyst and an organic acid, the adhesiveness to the hardly adhesive coating plate was low.
  • Example 10 and 12 are compared about content of a dimethyltin catalyst, content of a dimethyltin catalyst is less than 0.25 mass part with respect to 100 mass parts of total content with a dehydration paste-like mixture and aromatic polyisocyanate. It was confirmed that this was superior in storage stability, heat resistant adhesiveness, and piping stability.
  • Examples 1, 4, and 7 were compared with respect to the dimethyltin catalyst content, it was confirmed that the smaller the dimethyltin catalyst content, the lower the viscosity increase rate.
  • the comparison of Examples 2, 5, and 8, the comparison of Examples 3, 6, and 9 and the comparison of Examples 10 and 12 showed similar results.

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

Abstract

L'objet de la présente invention est de fournir une composition adhésive présentant d'excellentes propriétés adhésives. La présente invention concerne : une composition adhésive durcissable à l'humidité à un constituant, comprenant un constituant liquide contenant un composé polyol et un constituant poudreux contenant une matière de charge; et son procédé de production. La composition adhésive contient : un mélange pâteux déshydraté qui a été déshydraté; un polyisocyanate aromatique; un catalyseur de diméthylétain indiqué par la formule (1); un polyisocyanate aliphatique; un composé amino silane; et un catalyseur à base d'amine. Dans la formule (1), X1 et X2 représentent chacun indépendamment un hétéroatome divalent et R1 et R2 représentent chacun indépendamment un groupe hydrocarbure qui peut comprendre un hétéroatome.
PCT/JP2016/071004 2015-07-17 2016-07-15 Composition adhésive et procédé de production de composition adhésive WO2017014188A1 (fr)

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JP2018168309A (ja) * 2017-03-30 2018-11-01 ベック株式会社 改質剤
WO2020157854A1 (fr) * 2019-01-30 2020-08-06 横浜ゴム株式会社 Composition d'agent adhésif à base d'uréthane

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