WO2023074840A1 - Composition adhésive thermofusible durcissable à l'humidité - Google Patents

Composition adhésive thermofusible durcissable à l'humidité Download PDF

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WO2023074840A1
WO2023074840A1 PCT/JP2022/040329 JP2022040329W WO2023074840A1 WO 2023074840 A1 WO2023074840 A1 WO 2023074840A1 JP 2022040329 W JP2022040329 W JP 2022040329W WO 2023074840 A1 WO2023074840 A1 WO 2023074840A1
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WIPO (PCT)
Prior art keywords
moisture
melt adhesive
adhesive composition
curable hot
urethane prepolymer
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PCT/JP2022/040329
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English (en)
Japanese (ja)
Inventor
甫規 加藤
敦史 宮田
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株式会社イノアックコーポレーション
株式会社イノアック技術研究所
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Priority to JP2023556663A priority Critical patent/JPWO2023074840A1/ja
Publication of WO2023074840A1 publication Critical patent/WO2023074840A1/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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/40—High-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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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 a moisture-curable hot-melt adhesive composition.
  • Moisture-curing hot-melt adhesives that harden by reacting with moisture can be bonded simply by coating an adherend, pressing another adherend onto the coated surface, and then cooling and solidifying. and workability is high. Therefore, moisture-curable hot-melt adhesives are used in various fields including construction, electrical, and automotive fields. Moisture-curable hot-melt adhesives are generally formulated with crystalline ester polyols in order to obtain high initial peel strength (peel strength immediately after bonding). Since the ester polyol is hydrolyzed in a moist and hot environment, the adhesion after bonding may become unstable.
  • Patent Document 1 discloses a moisture-curable polyurethane hot-melt resin composition containing a polycarbonate polyol made from a glycol compound having a branched structure and having excellent initial adhesive strength, final adhesive strength, and hydrolysis resistance. ing.
  • US Pat. No. 5,300,002 discloses an effective amount of one or more non-polymeric diols selected from aromatic diols, aliphatic diols and mixtures thereof, and optionally functional and/or non-functional polymers (acrylic). or mixtures thereof and having improved green strength and hydrolysis resistance.
  • the viscosity of the moisture-curable polyurethane hot-melt resin composition increases, and there is a risk that the coating machine that can be used for coating is limited. .
  • the adhesive composition of Patent Document 2 contains an acrylic polymer, it is necessary to apply the adhesive composition at a higher temperature, which may cause gelation of the adhesive composition.
  • an object of the present invention is to provide a new moisture-curable hot-melt adhesive composition with superior effects.
  • the present inventors conducted intensive research, found that a moisture-curable hot-melt adhesive composition containing a specific urethane prepolymer can solve the above problems, and completed the present invention. That is, the present invention is as follows.
  • Mode (1) of the present invention is A moisture-curable hot-melt adhesive composition comprising a urethane prepolymer, The urethane prepolymer is obtained by reacting a polyol compound and a polyisocyanate compound, The moisture-curable hot-melt adhesive composition is characterized in that the urethane prepolymer has a urethane bond content of 0.90 mol/kg or more.
  • Mode (2) of the present invention is The moisture-curable hot-melt adhesive composition of form (1), further comprising a carbodiimide compound.
  • Mode (3) of the present invention is The moisture-curable hot-melt adhesive composition according to the aspect (2), wherein the carbodiimide compound has a molecular weight or number average molecular weight of 500 or more.
  • Mode (4) of the present invention is The moisture-curable hot-melt adhesive composition according to any one of Embodiments (1) to (3), wherein the polyol compound comprises a polyether polyol compound and a polyester polyol compound.
  • Form (5) of the present invention is The moisture-curable hot-melt adhesive composition according to any one of Embodiments (1) to (4), wherein the urethane prepolymer has an ester bond content of 6.00 mol/kg or less.
  • Mode (6) of the present invention is The moisture-curable hot-melt adhesive composition according to any one of the above modes (1) to (5), which is used as an interior material for automobiles.
  • Form (7) of the present invention is The first base material and the second base material are laminated via an adhesive layer,
  • the adhesive layer is a cured product of the moisture-curable hot-melt adhesive composition of any one of forms (1) to (6),
  • the first substrate and the second substrate are each independently selected from the group consisting of foam, natural leather, synthetic leather, film, woven fabric, and non-woven fabric. is.
  • the method for measuring the number average molecular weight is measured using gel per emission chromatography.
  • an upper limit and a lower limit are listed separately, a numerical range combining any upper limit and any lower limit is substantially disclosed.
  • various measurements are performed at room temperature (25° C.).
  • the moisture curable hot melt adhesive composition of the present disclosure comprises a urethane prepolymer.
  • a urethane prepolymer according to the present disclosure is obtained by reacting a polyol compound and a polyisocyanate compound. Further, the urethane prepolymer preferably has a urethane bond content of 0.90 mol/kg or more, but the present disclosure is not limited to this.
  • the moisture-curable hot-melt adhesive composition can further contain a carbodiimide compound.
  • the moisture-curable hot-melt adhesive composition can contain other additives as needed.
  • the moisture-curable hot-melt adhesive composition of the present disclosure is detailed below.
  • Urethane Prepolymer The urethane prepolymer according to the present disclosure is obtained by reacting a polyol compound and a polyisocyanate compound. The hydroxyl groups contained in the polyol compound react with the isocyanate groups contained in the polyisocyanate compound to form urethane bonds, whereby a urethane prepolymer can be obtained. Moreover, the urethane prepolymer can contain a catalyst as a raw material when the polyol compound and the polyisocyanate compound are reacted.
  • the polyol compound which is the raw material for the urethane prepolymer according to the present disclosure, is not particularly limited as long as the effects of the present disclosure are not hindered.
  • polyether polyol compounds examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc. obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran, respectively, and copolyethers thereof. It can also be obtained by polymerizing the above cyclic ether using a polyhydric alcohol such as glycerin or trimethylolethane.
  • polyester polyol compounds include polyols obtained by a dehydration condensation reaction between a polycarboxylic acid compound (eg, dicarboxylic acid) and a polyol compound (eg, diol).
  • polycarboxylic acid compounds include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; and hexahydrophthalic acid. , hexahydroterephthalic acid and hexahydroisophthalic acid; or acid esters or acid anhydrides thereof.
  • aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid
  • aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid
  • hexahydrophthalic acid hexahydroterephthalic acid and hexahydroisophthalic acid
  • acid esters or acid anhydrides thereof are examples
  • polyol compounds include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, etc., or a mixture thereof.
  • polyester polyols include polylactone diols obtained by ring-opening polymerization of lactone monomers such as ⁇ -caprolactone and methylvalerolactone.
  • polycarbonate polyol compounds include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- At least one polyhydric alcohol such as hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, diethylene carbonate, dimethyl carbonate, and those obtained by reacting with diethyl carbonate or the like.
  • polyhydric alcohol such as hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, diethylene carbonate, dimethyl carbonate, and those obtained by
  • polyester ether polyol compounds include polyols obtained by a dehydration condensation reaction between a polycarboxylic acid compound (eg, dicarboxylic acid) and a polyether polyol.
  • polycarboxylic acid compounds include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and hexahydrophthalic acid.
  • polyether polyols include glycols such as diethylene glycol or propylene oxide adducts, or mixtures thereof.
  • polyhydric phenol compounds include monocyclic polyhydric phenols such as pyrogallol and hydroquinone; bisphenols such as bisphenol A, bisphenol F and bisphenol sulfone; and the like.
  • polystyrene resin can be used alone or in combination.
  • the polyether polyol compound can improve the hydrolysis resistance of the cured product of the moisture-curable hot-melt adhesive composition.
  • the polyester polyol compound has the effect of improving the heat resistance of the cured product of the moisture-curable hot-melt adhesive composition. Since these effects are exhibited at the same time, the polyol compound preferably contains a polyether polyol compound and a polyester polyol compound.
  • the mixing ratio (mass ratio) of the polyether polyol compound and the polyester polyol compound is not particularly limited as long as it does not inhibit the effects of the present disclosure. mass) can be, for example, 20/80 to 80/20, preferably 30/70 to 70/30, more preferably 40/60 to 60/40, and even more preferably 45/55 to 65/35. .
  • mass can be, for example, 20/80 to 80/20, preferably 30/70 to 70/30, more preferably 40/60 to 60/40, and even more preferably 45/55 to 65/35.
  • the mixing ratio of the polyether polyol compound and the polyester polyol compound is within such a range, the wet heat aging resistance of the cured product obtained by curing the moisture-curable hot-melt adhesive composition can be improved. can.
  • polyester ether polyol compounds are treated as polyether polyol compounds.
  • the molecular weight or number average molecular weight of the polyol compound is not particularly limited as long as it does not impair the effects of the present disclosure, and can be freely selected in consideration of the physical properties of the urethane prepolymer.
  • the molecular weight or number average molecular weight of the polyol compound can be, for example, 300-8,000.
  • the hydroxyl value of the polyol compound is not particularly limited as long as the effects of the present disclosure are not hindered, and can be freely selected in consideration of the physical properties of the urethane prepolymer.
  • the hydroxyl value of the polyol compound can be, for example, 50 to 1,000 mgKOH/g.
  • the hydroxyl value is a value measured according to JIS K0070:1992 "Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products".
  • the polyisocyanate compound which is a raw material for the urethane prepolymer according to the present disclosure, is not particularly limited as long as the effects of the present disclosure are not hindered.
  • the polyisocyanate compound may be a bifunctional polyisocyanate compound or a trifunctional or higher polyisocyanate compound. Further, the polyisocyanate compound may be aromatic, aliphatic or alicyclic.
  • bifunctional polyisocyanate compound As aromatic polyisocyanate compounds, 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), m-phenylene diisocyanate, p-phenylene diisocyanate, 4 , 4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′-diphenylmethanedianate (2,4′-MDI), 2,2′-diphenylmethane diisocyanate (2,2′-MDI), hydrogenation MDI, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, polymethylene polyphenyl polyisocyanate, 1,5-naphthalene Diisocyanates, xylylene diisocyanates, x
  • alkylene-based polyisocyanate compounds examples include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and lysine diisocyanate; is mentioned.
  • Tri- or more functional polyisocyanate compounds include 1-methylbenzol-2,4,6-triisocyanate, 1,3,5-trimethylbenzol-2,4,6-triisocyanate, biphenyl-2,4,4' -triisocyanate, diphenylmethane-2,4,4'-triisocyanate, methyldiphenylmethane-4,6,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'tetraisocyanate, tri phenylmethane-4,4′,4′′-triisocyanate, polymeric MDI, lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, 1, 8-diisocyanatomethyloctane, etc.; In addition, these polyisocyanate compounds can contain modified products, derivatives and the
  • the catalyst a known catalyst that promotes the urethane reaction can be used. More specifically, the catalyst includes metal catalysts such as tin-based catalysts and lead-based catalysts; amine-based catalysts; acidic catalysts; basic catalysts; These catalysts can be used alone or in combination.
  • metal catalysts such as tin-based catalysts and lead-based catalysts; amine-based catalysts; acidic catalysts; basic catalysts; These catalysts can be used alone or in combination.
  • the urethane bond amount of the urethane prepolymer according to the present disclosure indicates the amount of urethane bonds contained in the urethane prepolymer.
  • the urethane bond content of the urethane prepolymer can be adjusted by adjusting the hydroxyl value of the polyol compound and the number of isocyanate groups contained in the polyisocyanate compound, which are compounded as raw materials of the urethane prepolymer. That is, the amount of urethane bonds in the urethane prepolymer can be adjusted by adjusting the isocyanate index of the raw material of the urethane prepolymer, which will be described later.
  • the urethane bond content of the urethane prepolymer is preferably 0.90 mol/kg or more, more preferably 1.00 mol/kg or more, 1.10 mol/kg or more, 1.20 mol/kg or more, or 1.30 mol/kg. /kg or more.
  • the upper limit of the amount of urethane bonds contained in the urethane prepolymer is not particularly limited. 2.00 mol/kg or less, or 1.50 mol/kg or less. When the amount of urethane bonds contained in the urethane prepolymer is within this range, the moisture-heat aging resistance of the cured product obtained by curing the moisture-curable hot-melt adhesive composition can be made more excellent.
  • the amount of urethane bonds is calculated by the following method. All polyol compounds and all polyisocyanate compounds that are raw materials for urethane prepolymers are covered. When the mass of the urethane prepolymer is 1 kg, the compounding amount (mass) of each polyol compound and each polyisocyanate compound is determined so that the NCO% of the urethane prepolymer becomes a desired value. The compounding amount (mass) of each polyol compound is divided by the molecular weight of each polyol compound and further multiplied by the number of functional groups of each polyol compound to calculate the number of moles of hydroxyl groups contained in all polyol compounds.
  • the number of moles of this hydroxyl group is regarded as the urethane bond amount of the urethane prepolymer, assuming that all of these hydroxyl groups react with the isocyanate groups of the polyisocyanate compound to form urethane bonds.
  • the ester bond amount of the urethane prepolymer according to the present disclosure indicates the amount of ester bonds contained in the urethane prepolymer.
  • the binding amount of the urethane prepolymer can be adjusted by the blending amount of the polyester polyol compound.
  • the amount of ester bond is measured by the following method. All polyol compounds and all polyisocyanate compounds that are raw materials for urethane prepolymers are covered. When the mass of the urethane prepolymer is 1 kg, the compounding amount (mass) of each polyol compound and each polyisocyanate compound is determined so that the NCO% of the urethane prepolymer becomes a desired value. The compounding amount (number of moles) of each polyester polyol is calculated by dividing the compounding amount (mass) of each compounded polyester polyol compound by the number average molecular weight of each polyester polyol.
  • each polyester polyol Divides the calculated blending amount (number of moles) of each polyester polyol by the molecular weight per 1 structural unit of the repeating structure in each polyester polyol, and the ester contained per 1 structural unit of the repeating structure in each polyester polyol By multiplying the radix, the amount of ester bonds for each polyester polyol is calculated.
  • the ester bond amount of each polyester polyol compound is totaled to calculate the ester bond amount of the urethane prepolymer.
  • a single structure of the repeating structure composed of these compounds is defined as one constituent unit of the repeating structure.
  • the molecular weight per structural unit of the repeating structure is the sum of the molecular weight of the polycarboxylic acid compound and the molecular weight of the polyol compound. , the mass of the structure after subtracting the mass of [(2 hydrogen atoms+1 oxygen atom) ⁇ 2].
  • the amount of ester bonds in the urethane prepolymer is not particularly limited, but the upper limit is 6.00 mol/kg or less, 5.00 mol/kg or less, 4.00 mol/kg or less, and 3,50 mol/kg or less.
  • the lower limit is 0.50 mol/kg or more, 1.00 mol/kg or more, 1.50 mol/kg or more, and 1.70 mol/kg or more.
  • the urethane prepolymer may not contain an ester bond (the amount of ester bond may be 0.00 mol/kg), but if the amount of ester bond contained in the urethane prepolymer is within this range, the moisture-curable A cured product obtained by curing the hot-melt adhesive composition can be made more excellent in wet heat aging resistance.
  • the upper limit of [amount of ester bond of urethane prepolymer]/[amount of urethane bond of urethane prepolymer] is 10.0 or less, 7.5 or less, or 5.0. Below, it is preferably 4.5 or less, 4.0 or less, 3.5 or less, or 3.2 or less, and the lower limit is 0.1 or more. 0.2 or more. It is preferably 0.5 or more, 1.0 or more, or 1.1 or more.
  • the number average molecular weight of the urethane prepolymer is not particularly limited as long as it does not inhibit the effects of the present disclosure, and can be 3,000 to 8,000.
  • properties such as adhesive strength of a cured product obtained by curing the moisture-curable hot-melt adhesive composition can be adjusted.
  • the viscosity of the urethane prepolymer is not particularly limited as long as it does not inhibit the effects of the present invention.
  • the urethane prepolymer can have a melt viscosity of 2,000 to 6,000 mPa ⁇ s at 140°C.
  • properties such as coatability of the moisture-curable hot-melt adhesive composition can be adjusted.
  • the melt viscosity of the urethane prepolymer at 140°C was measured using a rheometer (manufactured by Anton Paar, MCR302) equipped with a parallel plate, heating the sample to 140°C, and measuring it under the conditions of a frequency of 1 Hz and a shear rate of 1 rad/s. shall be measured in
  • the NCO% of the urethane prepolymer is not particularly limited as long as the effects of the present disclosure are not inhibited, but is preferably 0.3% to 3.5%, more preferably 1.2% to 2.5%. 5%.
  • the NCO% of the urethane prepolymer is in such a range, it is possible to promote curing due to moisture while suppressing foaming during operation, and furthermore, it is possible to cure the moisture-curable hot-melt adhesive composition. It is possible to make the wet heat aging property of the cured product more excellent.
  • the NCO% (isocyanate group content) of the prepolymer is JIS K1603-1:2007 "Plastics - Polyurethane raw material aromatic isocyanate test method Part 1: Determination of isocyanate group content" A method (toluene / dibutylamine, hydrochloric acid method).
  • the gel fraction of the urethane prepolymer is not particularly limited as long as the effects of the present disclosure are not hindered, but the lower limit thereof is preferably 30% by mass or more, 40% by mass or more, and 50% by mass. % or more, 60 mass % or more, and 70 mass % or more, and the upper limits are 95 mass % or less, 90 mass % or less, and 85 mass % or less. By setting it to such a range, the wet heat aging property of the cured product obtained by curing the moisture-curable hot-melt adhesive composition can be made more excellent.
  • a gel fraction is calculated by the following method.
  • a predetermined amount e.g., 0.045 g
  • a cured product obtained by curing a moisture-curable hot melt adhesive composition is weighed, immersed in a predetermined amount (e.g., 9 g) of tetrahydrofuran (THF), left to stand for 20 hours, The insoluble portion of the cured product remaining in THF without dissolution is taken out, dried in a vacuum, and its mass is measured.
  • the moisture-curable hot melt adhesive composition of the present disclosure can include a carbodiimide compound.
  • the carbodiimide compound according to the present disclosure is not particularly limited as long as it is a compound having a carbodiimide group.
  • Carbodiimide compounds include, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-[3-(dimethylamino)propyl]carbodiimide, cyanamide, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, N- Cyclohexylcarbodiimide, N'-methylpolystyrene 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, 1-cyclohexyl-3-(2-morpholinoethyl)metho-p-toluenesulfonate carbodiimide, bis(2, 6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, 1-cyclohexyl-3-(2-morpholinoethyl)
  • commercially available products include Carbodilite (registered trademark) E-02, E-03A, E-05, E pellets, HMV-15CA, HMV-5CA-LC, LA-1, SV-02, manufactured by Nisshinbo Chemical Co., Ltd. SW-12G, V-02, V-02B, V-02-L2, V-03, V-04, V-05, V-07, V-09, V-09GB, V-10; Stabaxol (registered trademark) I, P, P100; LUBIO AS 15, LUBIO AS1-SP, LUBIO AS 4 manufactured by Schaefer; and Elastostab H01 manufactured by BASF.
  • These carbodiimide compounds can be used alone or in combination.
  • the moisture-curable hot-melt adhesive composition contains a carbodiimide compound, the wet heat aging resistance of the cured product obtained by curing the moisture-curable hot-melt adhesive composition can be further improved.
  • the molecular weight or number average molecular weight of the carbodiimide compound is not particularly limited as long as it does not inhibit the effects of the present disclosure, but is preferably 300 to 10,000, more preferably 400 to 8,000, even more preferably 500 to 8,000, 500 to 5,000 are particularly preferred.
  • the molecular weight or number average molecular weight of the carbodiimide compound is in the above range, the wet heat aging resistance of the cured product obtained by curing the moisture-curable hot-melt adhesive composition can be further improved.
  • the carbodiimide compound volatilized from the moisture-curable hot-melt adhesive composition or its cured product may adhere to surrounding objects in the environment of use and cloud the surface.
  • the glass of the automobile may be fogged.
  • the molecular weight or number average molecular weight of the carbodiimide compound to 500 or more, it becomes easy to prevent the occurrence of such fogging.
  • the moisture-curable hot melt adhesive composition of the present disclosure can contain other additives as needed.
  • Other additives are not particularly limited, and include known components contained in moisture-curable hot-melt adhesive compositions.
  • Other additives include, for example, fillers, plasticizers, pigments, dyes, antioxidants, antioxidants, antifoaming agents, crystal nucleating agents, antistatic agents, flame retardants, adhesion imparting agents, antibacterial agents, Light stabilizers, stabilizers, dispersants, solvents, hydrophilicity imparting agents, waxes and the like can be mentioned. These can be used singly or in combination.
  • Method for Producing Urethane Prepolymer The method for producing the urethane prepolymer is not particularly limited, and known methods can be used. Specifically, for example, a predetermined amount of polyisocyanate compound is placed in a container and stirred under a nitrogen gas atmosphere. A predetermined amount of polyol compound is added dropwise thereto. Here, a catalyst can be added as necessary to promote the reaction. Stir for the required time to complete the reaction. Here, a portion of the reaction product may be sampled and the isocyanate group content may be measured to confirm that it is within the desired range.
  • the blending amounts of the polyol compound and the polyisocyanate compound are not particularly limited. is preferred, and 1.2 to 1.6 is more preferred.
  • the isocyanate index is the ratio of the number of moles of all active hydrogens in the resin composition, which is the total raw material composition of the urethane prepolymer, to the number of moles of isocyanate groups in the polyisocyanate compound (number of moles of isocyanate groups/activity number of moles of hydrogen).
  • the amount of the catalyst added is not particularly limited, but can be, for example, 0.01 to 5.0 parts by mass when the total amount of the polyol compound is 100 parts by mass.
  • Method for producing moisture-curable hot-melt adhesive composition The method for producing a moisture-curable hot-melt adhesive composition when additives other than urethane prepolymer are added is not particularly limited, and known methods can be used. . Specifically, for example, a predetermined amount of urethane prepolymer is placed in a container, a carbodiimide compound and other additives are added thereto, and the mixture is stirred.
  • the blending amount of the carbodiimide compound is not particularly limited as long as it does not inhibit the effects of the present disclosure.
  • the blending amount of the carbodiimide compound is 0.1 parts by mass or more, 0.5 parts by mass or more, 1.0 parts by mass or more, or 1.5 parts by mass when the total amount of the polyol compound blended in the urethane prepolymer is 100 parts by mass. 6. parts by mass or more, preferably 2.0 parts by mass or more, 2.5 parts by mass or more, or 3.0 parts by mass or more; It is preferably 0 parts by mass or less, or 5.0 parts by mass or less.
  • the total amount of the polyol compound blended in the urethane prepolymer is 100 parts by mass, it can be 0.1 to 10.0 parts by mass, preferably 1.0 to 10.0 parts by mass. 0 to 8.0 parts by mass is more preferable, 1.0 to 6.0 parts by mass is more preferable, 1.0 to 5.0 parts by mass is even more preferable, and 3.0 to 5.0 parts by mass is particularly preferable.
  • the moisture-curable hot-melt adhesive composition contains the carbodiimide compound in such a range, the wet heat aging resistance of the cured product obtained by curing the moisture-curable hot-melt adhesive composition can be further improved. .
  • the blending amount (total blending amount) of other additives is not particularly limited as long as it does not inhibit the effects of the present disclosure.
  • the total amount of the compound is 100 parts by mass, 10.0 parts by mass or less, 5.0 parts by mass or less, 3.0 parts by mass or less, 2.0 parts by mass or less, or 1.0 parts by mass or less 0.1 parts by mass or more, 0.2 parts by mass or more, 0.3 parts by mass or more, 0.4 parts by mass or more, or 0.5 parts by mass or more.
  • Moisture-curable hot-melt adhesive compositions are used, for example, in building interior materials such as decorative sheet coating materials, furniture materials, and interior materials for automobiles, railroads, ships, aircraft, etc. (e.g. It is suitable for bonding the sewn parts of cover pads of seats and headrests, etc.). In particular, it is suitable as an interior material for automobiles used in high-temperature and high-humidity environments.
  • the moisture-curable hot-melt adhesive composition can be applied to an object by being melted by heating.
  • a known method can be used, and examples thereof include coating methods using a brush, a spatula, a syringe, a sealing gun, a dispenser, and the like.
  • the moisture-curable hot-melt adhesive composition of the present disclosure can have a low melt viscosity, it can be applied using a non-contact method (for example, a spray method). From the viewpoint of improving air permeability and improving productivity (for example, it is easy to manufacture even if the object is long), it is preferable to apply it to the object by spray coating.
  • the coating amount of the moisture-curable hot-melt adhesive composition (or the basis weight of the moisture-curable hot-melt adhesive composition) is preferably 1 to 100 g/m 2 , more preferably 3 to 50 g/m 2 is more preferred, and 5 to 30 g/m 2 is particularly preferred.
  • the technology according to the present disclosure may be provided as a cured product of a moisture-curable hot-melt adhesive composition or a laminate containing a cured product of a moisture-curable hot-melt adhesive composition.
  • the technology according to the present disclosure is a laminate in which a first base material and a second base material are laminated via an adhesive layer, and the adhesive layer is a moisture It may be a laminate that is a cured product of a curable hot-melt adhesive composition.
  • the material, shape, etc. of the first base material and the second base material are not particularly limited, but the first base material and the second base material are each independently formed into a foam (for example, urethane foam).
  • Such a laminate can be produced by applying the moisture-curable hot-melt adhesive composition application method described above.
  • Such a laminate can be used as a building interior member such as the decorative sheet coating material described above, a furniture member, a member constituting an interior member for automobiles, railroads, ships, aircraft, and the like.
  • Table 1 shows the raw materials of the moisture-curable hot-melt adhesive compositions produced in Examples and Comparative Examples, and the evaluation results of the obtained moisture-curable hot-melt adhesive compositions.
  • MDI as a polyisocyanate compound was put in a 1-liter four-necked flask equipped with stirring blades in the amounts shown in Table 1, and after purging the inside of the flask with nitrogen gas, the temperature was heated to 80°C.
  • the polyol compounds in the amounts shown in Table 1 are heated and melted at 80°C and charged into the flask in a molten state, and the liquid temperature is maintained at 100°C or lower in a nitrogen gas atmosphere and stirred for 2 hours or longer. bottom.
  • the polyol compound and the polyisocyanate compound reacted to obtain a urethane prepolymer.
  • a carbodiimide compound and other additives were blended according to Table 1 and stirred for 2 hours or longer to obtain moisture-curable hot-melt adhesive compositions of Examples and Comparative Examples.
  • Polyol compound Polyester polyol Polyol 1 reaction product of sebacic acid (SA) and 1,6-hexanediol (HD), number average molecular weight 5,000
  • Polyol 2 reaction product of adipic acid (AA) and 1,6-hexanediol (HD), number average molecular weight 4,500
  • Polyol 3 reaction product of adipic acid (AA) and terephthalic acid with ethylene glycol and 1,4-butylene glycol (BG), number average molecular weight 3,000
  • Polyol 4 reaction product of 1,12-dodecanedioic acid (DDA) and 1,6-hexanediol (HD), number average molecular weight 3,700
  • Polyol 5 reaction product of adipic acid (AA) and 1,4-butanediol (BD), number average molecular weight 2,000
  • Polyether polyol Polyol 6 polypropylene glycol
  • Anti-packing agent (1) Dappo SN348 manufactured by San Nopco ⁇ Antiaging agent (1) IRGANOX1076 manufactured by BASF (2) IRGAFOS168 manufactured by BASF - Catalyst (1) DMDEE (amine-based catalyst, dimorpholinodiethyl ether) ⁇ Crystal nucleating agent (1) NA11 manufactured by ADEKA ⁇ Polyisocyanate compound (1) Monomeric MDI, molecular weight: 250 ⁇ Carbodiimide compound (1) Nisshinbo Chemical Co., Ltd.
  • Carbodilite V04PF number average molecular weight: 2,000 (2) Stabaxol I manufactured by Rhein Chemie, number average molecular weight: 380 (3) Stabaxol P manufactured by Rhein Chemie, number average molecular weight: 2,000 (4) LUBIO AS 15 manufactured by Schaefer, number average molecular weight: 1,500 (5) Nisshinbo Chemical Co., Ltd.
  • Carbodilite HMV-15CA number average molecular weight: 3,400 (6) Elastostab H01 manufactured by BASF Number average molecular weight: 1,900
  • NCO% of urethane prepolymer The NCO% of the urethane prepolymer in each example and comparative example was determined according to JIS K1603-1:2007 "Plastics - Polyurethane raw material aromatic isocyanate test method Part 1: Determination of isocyanate group content" A method (toluene/dibutylamine , hydrochloric acid method).
  • Amount of urethane bonds in urethane prepolymers The amount of urethane bonds in the urethane prepolymers of Examples and Comparative Examples was calculated by the method described above.
  • the moisture-curable hot-melt adhesive composition of each example and comparative example is melted at 130 ° C., and a hand gun is used to make it 20 g / m 2 Urethane foam (EL-67F manufactured by Inoac Corporation ) was sprayed. After that, the urethane foam was attached to a skin composed of a fabric (PET fabric) and cured at room temperature for 12 hours to obtain a laminate. The laminate was processed to have a diameter of 80 mm and a thickness of 250 ⁇ m to obtain a test piece for evaluation. The specimen was placed at the bottom of a 90 mm diameter x 190 mm high glass container (only the top was reluctant to be released).
  • a glass petri dish was placed on the top of the test piece (inside the glass container), and 1 ml of a 0.012 g/ml ethylenediamine aqueous solution was placed in the glass petri dish.
  • the upper part of this glass container was covered with a glass plate having a diameter of 90 mm so as to be hermetically sealed, and the container was left in a constant temperature bath at 80° C. for 72 hours. After that, the glass plate was taken out, and the reflectance of the treated glass plate was measured using a glossiness measuring device. Further, from the previously measured reflectance of the glass plate before the treatment, the glass haze was calculated according to the following formula (1). Each reflectance before and after treatment was measured nine times for each glass plate, and the average value was taken.
  • a test piece was subjected to a 180° peel test in a 25°C environment using a material testing machine (manufactured by Shimadzu Corporation, precision universal testing machine Autograph) to measure the peel strength under each wet heat treatment condition.
  • the peel strength was scored according to the following evaluation criteria when the treatment time was 200 hours, 400 hours, and 600 hours.
  • ⁇ The total evaluation score at 200 hours, 400 hours, and 600 hours is 7 to 9 points
  • ⁇ : The total evaluation score at 200 hours, 400 hours, and 600 hours is 4 to 6 points ⁇ : 200 hours, 400 The total evaluation score in 600 hours is 3
  • the objects to be adhered were changed from urethane foam and fabric to substrates (upper layer and lower layer) shown in Table 2.
  • a laminate was produced in the same manner as described above, except for the above, and the wet heat aging resistance and overall evaluation were evaluated.
  • Table 2 shows the evaluation results.
  • the fabric indicates that of PET fabric.
  • EL-45 is a urethane foam manufactured by INOAC.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une nouvelle composition adhésive thermofusible durcissable à l'humidité dont l'effet est encore meilleur. Un mode de réalisation de la présente invention est une composition adhésive thermofusible durcissable à l'humidité comprenant un prépolymère d'uréthane, caractérisée en ce que le prépolymère d'uréthane est obtenu par réaction d'un composé polyol avec un composé polyisocyanate et présente une teneur en liaison uréthane de 0,90 mol/kg ou plus.
PCT/JP2022/040329 2021-10-29 2022-10-28 Composition adhésive thermofusible durcissable à l'humidité WO2023074840A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004155860A (ja) * 2002-11-05 2004-06-03 Sekisui Chem Co Ltd 湿気硬化型ポリウレタン系ホットメルト接着剤
WO2019163622A1 (fr) * 2018-02-21 2019-08-29 Dic株式会社 Composition de résine thermofusible de polyuréthane durcissable à l'humidité
JP2020002262A (ja) * 2018-06-28 2020-01-09 Dic株式会社 湿気硬化型ポリウレタンホットメルト樹脂組成物
JP2020076018A (ja) * 2018-11-08 2020-05-21 株式会社イノアックコーポレーション 低アウトガス性ウレタンホットメルト接着剤組成物
WO2021025093A1 (fr) * 2019-08-08 2021-02-11 Dic株式会社 Composition de résine thermofusible de polyuréthane durcissable à l'humidité
JP2021116390A (ja) * 2020-01-29 2021-08-10 アイカ工業株式会社 湿気硬化型反応性ホットメルト組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004155860A (ja) * 2002-11-05 2004-06-03 Sekisui Chem Co Ltd 湿気硬化型ポリウレタン系ホットメルト接着剤
WO2019163622A1 (fr) * 2018-02-21 2019-08-29 Dic株式会社 Composition de résine thermofusible de polyuréthane durcissable à l'humidité
JP2020002262A (ja) * 2018-06-28 2020-01-09 Dic株式会社 湿気硬化型ポリウレタンホットメルト樹脂組成物
JP2020076018A (ja) * 2018-11-08 2020-05-21 株式会社イノアックコーポレーション 低アウトガス性ウレタンホットメルト接着剤組成物
WO2021025093A1 (fr) * 2019-08-08 2021-02-11 Dic株式会社 Composition de résine thermofusible de polyuréthane durcissable à l'humidité
JP2021116390A (ja) * 2020-01-29 2021-08-10 アイカ工業株式会社 湿気硬化型反応性ホットメルト組成物

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