WO2023074840A1 - Moisture-curable hot-melt adhesive composition - Google Patents

Moisture-curable hot-melt adhesive composition Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
moisture
melt adhesive
adhesive composition
curable hot
urethane prepolymer
Prior art date
Application number
PCT/JP2022/040329
Other languages
French (fr)
Japanese (ja)
Inventor
甫規 加藤
敦史 宮田
Original Assignee
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 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 filed Critical 株式会社イノアックコーポレーション
Publication of WO2023074840A1 publication Critical patent/WO2023074840A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—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.

Landscapes

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

Abstract

Provided is a new moisture-curable hot-melt adhesive composition having an even better effect. An embodiment of the present invention is a moisture-curable hot-melt adhesive composition including a urethane prepolymer, characterized in that the urethane prepolymer is one obtained by reacting a polyol compound with a polyisocyanate compound and has a urethane bond content of 0.90 mol/kg or higher.

Description

湿気硬化性ホットメルト接着剤組成物Moisture-curable hot-melt adhesive composition
　本発明は、湿気硬化性ホットメルト接着剤組成物に関する。 The present invention relates to a moisture-curable hot-melt adhesive composition.
　湿気と反応して硬化する湿気硬化性ホットメルト接着剤は、被着体に塗工し、この塗工面に別の被着体を圧着後、冷却固化するのみで被着物を接合することが可能であり、作業性が高い。そのため、湿気硬化性ホットメルト接着剤は、建築分野、電気分野、自動車分野をはじめとした種々の分野で使用されている。湿気硬化性ホットメルト接着剤は、一般に、高い初期剥離強度（接合直後の剥離強度）を得るために、結晶性エステルポリオールが処方される。エステルポリオールは、湿熱環境下では加水分解が生じるため、接合後の接着性が不安定になる場合がある。 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.
　特許文献１には、分岐構造を有するグリコール化合物を原料としたポリカーボネートポリオールを含有し、初期接着強度、最終接着強度、及び、耐加水分解性に優れる湿気硬化型ポリウレタンホットメルト樹脂組成物が開示されている。 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.
　特許文献２には、芳香族ジオール、脂肪族ジオール及びこれらの混合物から選択される１種以上の有効量の非重合体ジオールと、任意に官能性及び／又は非官能性のポリマー（アクリル系）又はそれらの混合物とを含み、改良されたグリーン強度及び耐加水分解性を有する接着剤組成物が開示されている。 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.
特開２０２０－０９７６５１号公報JP 2020-097651 A 特開２０１５－１１０７８８号公報JP 2015-110788 A
　しかしながら、特許文献１の湿気硬化型ポリウレタンホットメルト樹脂組成物は、湿気硬化型ポリウレタンホットメルト樹脂組成物の粘度が高くなり、塗工するための使用できる塗工機が制限されるおそれがあった。また、特許文献２の接着剤組成物はアクリルポリマーを含むため、より高温で塗工する必要があり、接着剤組成物がゲル化するおそれがあった。 However, in the moisture-curable polyurethane hot-melt resin composition of Patent Document 1, 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. . Moreover, since 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.
　そこで本発明は、より優れた効果を有する、新しい湿気硬化性ホットメルト接着剤組成物を提供することを課題とする。 Therefore, an object of the present invention is to provide a new moisture-curable hot-melt adhesive composition with superior effects.
　本発明者らは、鋭意研究を行い、特定のウレタンプレポリマーを含む湿気硬化性ホットメルト接着剤組成物が、上記課題を解決可能なことを見出し、本発明を完成させた。即ち、本発明は以下の通りである。 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.
　本発明の形態（１）は、
　ウレタンプレポリマーを含む湿気硬化性ホットメルト接着剤組成物であって、
　前記ウレタンプレポリマーは、ポリオール化合物と、ポリイソシアネート化合物と、を反応させて得られるものであり、
　前記ウレタンプレポリマーのウレタン結合量が、０．９０ｍｏｌ／ｋｇ以上であることを特徴とする、湿気硬化性ホットメルト接着剤組成物である。
　本発明の形態（２）は、
　カルボジイミド化合物をさらに含むことを特徴とする、前記形態（１）の湿気硬化性ホットメルト接着剤組成物である。
　本発明の形態（３）は、
　前記カルボジイミド化合物の分子量又は数平均分子量は、５００以上であることを特徴とする、前記形態（２）の湿気硬化性ホットメルト接着剤組成物である。
　本発明の形態（４）は、
　前記ポリオール化合物は、ポリエーテルポリオール化合物と、ポリエステルポリオール化合物と、を含むことを特徴とする、前記形態（１）～（３）のいずれかの湿気硬化性ホットメルト接着剤組成物である。
　本発明の形態（５）は、
　前記ウレタンプレポリマーのエステル結合量が、６．００ｍｏｌ／ｋｇ以下であることを特徴とする、前記形態（１）～（４）のいずれかの湿気硬化性ホットメルト接着剤組成物である。
　本発明の形態（６）は、
　自動車の内装材用であることを特徴とする、前記形態（１）～（５）のいずれかの湿気硬化性ホットメルト接着剤組成物である。
　本発明の形態（７）は、
　第１の基材と、第２の基材とが、接着剤層を介して積層されており、
　前記接着剤層は、形態（１）～（６）のいずれかの湿気硬化性ホットメルト接着剤組成物の硬化物であり、
　前記第１の基材及び前記第２の基材は、各々独立して、発泡体、天然皮革、合成皮革、フィルム、織布及び不織布からなる群より選択されることを特徴とする、積層体である。 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.
　本発明によれば、より優れた効果を有する、新しい湿気硬化性ホットメルト接着剤組成物を提供することができる。 According to the present invention, it is possible to provide a new moisture-curable hot-melt adhesive composition with superior effects.
　なお、説明した化合物に異性体が存在する場合、特に断らない限り、存在し得る全ての異性体が本発明において使用可能である。 In addition, when isomers exist in the described compounds, all possible isomers can be used in the present invention unless otherwise specified.
　また、本願において、数平均分子量の測定方法は、ゲルパーエミッションクロマトグラフィーを用いて測定される。
　本願において、上限値と下限値とが別々に記載されている場合、任意の上限値と任意の下限値とを組み合わせた数値範囲が実質的に開示されているものとする。
　本願において、特に断らない限り、各種測定は、環境温度を室温（２５℃）として実施する。 Moreover, in this application, the method for measuring the number average molecular weight is measured using gel per emission chromatography.
In this application, when an upper limit and a lower limit are listed separately, a numerical range combining any upper limit and any lower limit is substantially disclosed.
In the present application, unless otherwise specified, various measurements are performed at room temperature (25° C.).
１．湿気硬化性ホットメルト接着剤組成物
　本開示の湿気硬化性ホットメルト接着剤組成物は、ウレタンプレポリマーを含む。本開示にかかるウレタンプレポリマーは、ポリオール化合物と、ポリイソシアネート化合物と、を反応させて得られる。また、ウレタンプレポリマーは、ウレタンプレポリマーに含まれるウレタン結合量が０．９０ｍｏｌ／ｋｇ以上であることが好ましいが、本開示はこれには限定されない。 1. Moisture Curable Hot Melt Adhesive Composition 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.
　湿気硬化性ホットメルト接着剤組成物は、カルボジイミド化合物をさらに含むことができる。また、湿気硬化性ホットメルト接着剤組成物は、必要に応じて、その他の添加物を含むことができる。 The moisture-curable hot-melt adhesive composition can further contain a carbodiimide compound. In addition, the moisture-curable hot-melt adhesive composition can contain other additives as needed.
　以下に、本開示の湿気硬化性ホットメルト接着剤組成物について詳述する。 The moisture-curable hot-melt adhesive composition of the present disclosure is detailed below.
１－１．湿気硬化性ホットメルト接着剤組成物の原料
１－１－１．ウレタンプレポリマー
　本開示にかかるウレタンプレポリマーは、ポリオール化合物と、ポリイソシアネート化合物とを反応させて得られる。ポリオール化合物に含まれる水酸基と、ポリイソシアネート化合物に含まれるイソシアネート基が反応してウレタン結合を形成し、ウレタンプレポリマーを得ることができる。また、ウレタンプレポリマーは、ポリオール化合物と、ポリイソシアネート化合物とを反応させる際、その原料として触媒を含むことができる。 1-1. Raw materials for moisture-curable hot-melt adhesive composition 1-1-1. 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.
・ポリオール化合物
　本開示にかかるウレタンプレポリマーの原料となるポリオール化合物としては、本開示の効果が阻害されない限りにおいて特に限定されず、ポリエーテルポリオール化合物、ポリエステルポリオール化合物、ポリカーボネートポリオール化合物、ポリエステルエーテルポリオール化合物、多価フェノール化合物等を挙げることができる。これらは、単独で、又は、複数を組み合わせて用いることができる。 ・Polyol compound 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 compound, polyester polyol compound, polycarbonate polyol compound, polyester ether polyol compound , polyhydric phenol compounds, and the like. These can be used singly or in combination.
　ポリエーテルポリオール化合物としては、例えば、エチレンオキシド、プロピレンオキシド、テトラヒドロフラン等の環状エーテルをそれぞれ重合させて得られるポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール等、及び、これらのコポリエーテルが挙げられる。また、グリセリン、トリメチロールエタン等の多価アルコールを用い、上記の環状エーテルを重合させて得ることもできる。
　ポリエステルポリオール化合物としては、例えば、ポリカルボン酸化合物（例えば、ジカルボン酸）と、ポリオール化合物（例えば、ジオール）と、の脱水縮合反応で得られるポリオール等を挙げることができる。ポリカルボン酸化合物としては、コハク酸、アジピン酸、セバシン酸及びアゼライン酸等の脂肪族ジカルボン酸や、フタル酸、テレフタル酸、イソフタル酸及びナフタレンジカルボン酸等の芳香族ジカルボン酸や、ヘキサヒドロフタル酸、ヘキサヒドロテレフタル酸及びヘキサヒドロイソフタル酸等の脂環族ジカルボン酸；又は、これらの酸エステルもしくは酸無水物等を挙げることができる。ポリオール化合物としては、エチレングリコール、１，３－プロピレングリコール、１，２－プロピレングリコール、１，４－ブチレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、ネオペンチルグリコール、１，８－オクタンジオール、１，９－ノナンジオール等、もしくは、これらの混合物等を挙げることができる。その他のポリエステルポリオールとしては、例えば、ε－カプロラクトン、メチルバレロラクトン等のラクトンモノマーの開環重合で得られるポリラクトンジオール等を挙げることができる。
　ポリカーボネートポリオール化合物としては、例えば、エチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、ネオペンチルグリコール、１，８－オクタンジオール、１，９－ノナンジオール、ジエチレングリコール等の多価アルコールの少なくとも１種と、ジエチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート等と、を反応させて得られるものを挙げることができる。
　ポリエステルエーテルポリオール化合物としては、ポリカルボン酸化合物（例えば、ジカルボン酸）と、ポリエーテルポリオールと、の脱水縮合反応で得られるポリオール等が挙げられる。ポリカルボン酸化合物としては、例えば、コハク酸、アジピン酸、セバシン酸及びアゼライン酸等の脂肪族ジカルボン酸、フタル酸、テレフタル酸、イソフタル酸及びナフタレンジカルボン酸等の芳香族ジカルボン酸、ヘキサヒドロフタル酸、ヘキサヒドロテレフタル酸及びヘキサヒドロイソフタル酸等の脂環族ジカルボン酸、又は、これらの酸エステルもしくは酸無水物等が挙げられる。ポリエーテルポリオールとしては、ジエチレングリコール、もしくはプロピレンオキシド付加物等のグリコール等、又は、これらの混合物等を挙げることができる。
　多価フェノール化合物としては、例えば、ピロガロール、ハイドロキノン等の単環多価フェノール；ビスフェノールＡ、ビスフェノールＦ、ビスフェノールスルホン等のビスフェノール類；等が挙げられる。 Examples of polyether polyol compounds 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.
Examples of 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). Examples of 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. Examples of 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. Examples of other polyester polyols include polylactone diols obtained by ring-opening polymerization of lactone monomers such as ε-caprolactone and methylvalerolactone.
Examples of 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.
Examples of polyester ether polyol compounds include polyols obtained by a dehydration condensation reaction between a polycarboxylic acid compound (eg, dicarboxylic acid) and a polyether polyol. Examples of 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, hexahydroisophthalic acid, and other alicyclic dicarboxylic acids, or their acid esters or acid anhydrides. Examples of polyether polyols include glycols such as diethylene glycol or propylene oxide adducts, or mixtures thereof.
Examples of 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.
　これらのポリオール化合物は、単独で、又は、複数を組み合わせて用いることができる。特に、ポリエーテルポリオール化合物は湿気硬化性ホットメルト接着剤組成物の硬化物の耐加水分解性を向上させることができる。また、ポリエステルポリオール化合物は湿気硬化性ホットメルト接着剤組成物の硬化物の耐熱性を向上させる効果を有する。これらの効果が同時に奏されることから、ポリオール化合物はポリエーテルポリオール化合物とポリエステルポリオール化合物とを含むことが好ましい。 These polyol compounds can be used alone or in combination. In particular, the polyether polyol compound can improve the hydrolysis resistance of the cured product of the moisture-curable hot-melt adhesive composition. Moreover, 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.
　ポリエーテルポリオール化合物と、ポリエステルポリオール化合物との混合比（質量比）としては、本開示の効果を阻害しない限りにおいて特に限定されず、（全ポリエーテルポリオール化合物の総質量／全ポリエステルポリオール化合物の総質量）として、例えば、２０／８０～８０／２０とすることができ、３０／７０～７０／３０が好ましく、４０／６０～６０／４０がより好ましく、４５／５５～６５／３５がさらに好ましい。ポリエーテルポリオール化合物と、ポリエステルポリオール化合物との混合比がかかる範囲にある場合には、湿気硬化性ホットメルト接着剤組成物を硬化させた硬化物の湿熱老化性をより優れたものとすることができる。なお、本開示において、ポリエステルエーテルポリオール化合物はポリエーテルポリオール化合物として扱う。 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. . When 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. In the present disclosure, polyester ether polyol compounds are treated as polyether polyol compounds.
　ポリオール化合物の分子量又は数平均分子量は、本開示の効果を阻害しない限りにおいて特に限定されず、ウレタンプレポリマーの物性を考慮して自由に選択できる。ポリオール化合物の分子量又は数平均分子量は、例えば、３００～８，０００とすることができる。 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.
　ポリオール化合物の水酸基価は、本開示の効果が阻害されない限りにおいて特に限定されず、ウレタンプレポリマーの物性を考慮して自由に選択できる。ポリオール化合物の水酸基価は、例えば、５０～１，０００ｍｇＫＯＨ／ｇとすることができる。ここで、当該水酸基価は、ＪＩＳ　Ｋ００７０：１９９２「化学製品の酸価、けん化価、エステル価、よう素価、水酸基価及び不けん化物の試験方法」に準じて測定した値である。 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. Here, 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".
・ポリイソシアネート化合物
　本開示にかかるウレタンプレポリマーの原料となるポリイソシアネート化合物は、本開示の効果が阻害されない限りにおいて特に限定されない。
　ポリイソシアネート化合物は、２官能のポリイソシアネート化合物であっても、３官能以上のポリイソシアネート化合物であってもよい。
　また、ポリイソシアネート化合物は、芳香族系、脂肪族系及び脂環族系のいずれでもよい。
　例えば、２官能のポリイソシアネート化合物としては、
　芳香族系のポリイソシアネート化合物として、２，４－トルエンジイソシアネート（２，４－ＴＤＩ）、２，６－トルエンジイソシアネート（２，６－ＴＤＩ）、ｍ－フェニレンジイソシネート、ｐ－フェニレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート（４，４’－ＭＤＩ）、２，４’－ジフェニルメタンジアネート（２，４’－ＭＤＩ）、２，２’－ジフェニルメタンジイソシアネート（２，２’－ＭＤＩ）、水素添加ＭＤＩ、キシリレンジイソシアネート、３，３’－ジメチル－４，４’－ビフェニレンジイソネート、３，３’－ジメトキシ－４，４’－ビフェニレンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート、１，５－ナフタレンジイソシアネート、キシリレンジイソシアネート（ＸＤＩ）、水素添加ＸＤＩ、テトラメチルキシレンジイソシアネート（ＴＭＸＤＩ）、等；
　脂環式のポリイソシアネート化合物として、シクロヘキサン－１，４－ジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、メチルシクロヘキサンジイソシアネート等；
　アルキレン系のポリイソシアネート化合物として、ブタン－１，４－ジイソシアネート、ヘキサメチレンジイソシアネート、イソプロピレンジイソシアネート、メチレンジイソシアネート、リジンジイソシアネート等；
が挙げられる。
　３官能以上のポリイソシアネート化合物としては、１－メチルベンゾール－２，４，６－トリイソシアネート、１，３，５－トリメチルベンゾール－２，４，６－トリイソシアネート、ビフェニル－２，４，４’－トリイソシアネート、ジフェニルメタン－２，４，４’－トリイソシアネート、メチルジフェニルメタン－４，６，４’－トリイソシアネート、４，４’－ジメチルジフェニルメタン－２，２’，５，５’テトライソシアネート、トリフェニルメタン－４，４’，４”－トリイソシアネート、ポリメリックＭＤＩ、リジンエステルトリイソシアネート、１，３，６－ヘキサメチレントリイソシアネート、１，６，１１－ウンデカントリイソシアネート、ビシクロヘプタントリイソシアネート、１，８－ジイソシアナトメチルオクタン等；のイソシアネート化合物を挙げることができる。
　また、これらのポリイソシアネート化合物は、変性体、誘導体等を含むことができる。
　これらのポリイソシアネート化合物は、単独で、又は、複数を組み合わせて用いることができる。
　ポリイソシアネート化合物は、これらのうち、ＭＤＩ、ＴＤＩ、又は、ＭＤＩ若しくはＴＤＩの変性体若しくは誘導体であることが好ましく、モノメリックＭＤＩ及びクルードＭＤＩであることがより好ましい。 - Polyisocyanate compound 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.
For example, as a 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 diisocyanate (XDI), hydrogenated XDI, tetramethylxylylene diisocyanate (TMXDI), etc.;
Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate, etc. as alicyclic polyisocyanate compounds;
Examples of alkylene-based polyisocyanate compounds 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 like.
These polyisocyanate compounds can be used alone or in combination.
Among these, the polyisocyanate compound is preferably MDI, TDI, or a modified or derivative of MDI or TDI, more preferably monomeric MDI and crude MDI.
・触媒
　触媒としては、ウレタン反応を促進する公知の触媒を用いることができる。触媒としては、より具体的には、錫系触媒、鉛系触媒等の金属触媒；アミン系触媒；酸性触媒；塩基性触媒；等を挙げることができる。これらの触媒は、単独で、又は、複数を組み合わせて用いることができる。 - Catalyst As 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.
１－１－２．ウレタンプレポリマーの特性
・ウレタン結合量
　本開示にかかるウレタンプレポリマーのウレタン結合量は、ウレタンプレポリマー中に含まれるウレタン結合の量を示す。ウレタンプレポリマーのウレタン結合量は、ウレタンプレポリマーの原料として配合する、ポリオール化合物の水酸基価と、ポリイソシアネート化合物に含まれるイソシアネート基の数と、により調整することができる。即ち、ウレタンプレポリマーのウレタン結合量は、後述するウレタンプレポリマーの原料のイソシアネートインデックスにより調整することができる。 1-1-2. Properties of Urethane Prepolymer/Urethane Bond Amount 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.
　ウレタンプレポリマーのウレタン結合量は、好ましくは０．９０ｍｏｌ／ｋｇ以上であり、より好ましくは、１．００ｍｏｌ／ｋｇ以上、１．１０ｍｏｌ／ｋｇ以上、１．２０ｍｏｌ／ｋｇ以上、又は、１．３０ｍｏｌ／ｋｇ以上である。ウレタンプレポリマーに含まれるウレタン結合量の上限値は特に限定されるものではないが、例えば、５．００ｍｏｌ／ｋｇ以下、４．００ｍｏｌ／ｋｇ以下、３．００ｍｏｌ／ｋｇ以下、２．５０ｍｏｌ／ｋｇ以下、２．００ｍｏｌ／ｋｇ以下、又は、１．５０ｍｏｌ／ｋｇ以下である。ウレタンプレポリマーに含まれるウレタン結合量がかかる範囲にある場合には、湿気硬化性ホットメルト接着剤組成物を硬化させた硬化物の湿熱老化性をより優れたものとすることができる。 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.
　ウレタン結合量は、以下の方法で算出する。
　ウレタンプレポリマーの原料となる全てのポリオール化合物と、全てのポリイソシアネート化合物とを対象とする。ウレタンプレポリマーの質量が１ｋｇとなる場合について、ウレタンプレポリマーのＮＣＯ％が所望する値となるように、各ポリオール化合物及び各ポリイソシアネート化合物の配合量（質量）を決定する。各ポリオール化合物の配合量（質量）を各ポリオール化合物の分子量で除し、さらに、各ポリオール化合物の官能基数を乗ずることで、全てのポリオール化合物に含まれる水酸基のモル数を算出する。この水酸基のモル数を、これらの水酸基すべてがポリイソシアネート化合物のイソシアネート基と反応しウレタン結合を形成したものとして、ウレタンプレポリマーのウレタン結合量とする。 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.
・エステル結合量
　本開示にかかるウレタンプレポリマーのエステル結合量は、ウレタンプレポリマー中に含まれるエステル結合の量を示す。ウレタンプレポリマーの結合量は、配合する、ポリエステルポリオール化合物の配合量により調整することができる。 - Ester bond amount 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.
　エステル結合量は、以下の方法で測定する。
　ウレタンプレポリマーの原料となる全てのポリオール化合物と、全てのポリイソシアネート化合物とを対象とする。ウレタンプレポリマーの質量が１ｋｇとなる場合について、ウレタンプレポリマーのＮＣＯ％が所望する値となるように、各ポリオール化合物及び各ポリイソシアネート化合物の配合量（質量）を決定する。配合される全てのポリエステルポリオール化合物のそれぞれの配合量（質量）を各ポリエステルポリオールの数平均分子量で除することで、各ポリエステルポリオールの配合量（モル数）を算出する。算出された各ポリエステルポリオールの配合量（モル数）を各ポリエステルポリオール内の繰返構造の１構成単位当たりの分子量で除し、各ポリエステルポリオール内の繰返構造の１構成単位当たりに含まれるエステル基数を乗ずることで、各ポリエステルポリオールそれぞれのエステル結合量を算出する。それぞれのポリエステルポリオール化合物のエステル結合量を合計して、ウレタンプレポリマーのエステル結合量を算出する。
　ここで、例えば、ポリカルボン酸化合物とポリオール化合物とで構成されたポリエステルポリオールの場合について、これらの化合物で構成される繰返構造の単独の構造を繰返構造の１構成単位とする。この場合、一例としてポリカルボン酸をジカルボン酸としポリオール化合物をジオールとした際に、繰返構造の１構成単位当たりの分子量とは、ポリカルボン酸化合物の分子量と、ポリオール化合物の分子量との合計から、［（水素原子２個＋酸素原子１個）×２］の質量を差し引いた構造の質量を示す。 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. Divide 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.
Here, for example, in the case of a polyester polyol composed of a polycarboxylic acid compound and a polyol compound, a single structure of the repeating structure composed of these compounds is defined as one constituent unit of the repeating structure. In this case, as an example, when the polycarboxylic acid is a dicarboxylic acid and the polyol compound is a diol, 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].
　ウレタンプレポリマーのエステル結合量は特に限定されるものではないが、上限値としては、６．００ｍｏｌ／ｋｇ以下、５．００ｍｏｌ／ｋｇ以下、４．００ｍｏｌ／ｋｇ以下、３，５０ｍｏｌ／ｋｇ以下が好ましく、下限値としては０．５０ｍｏｌ／ｋｇ以上、１．００ｍｏｌ／ｋｇ以上、１．５０ｍｏｌ／ｋｇ以上、１．７０ｍｏｌ／ｋｇ以上が好ましい。ウレタンプレポリマーがエステル結合を含まずともよい（エステル結合量が０．００ｍｏｌ／ｋｇであってもよい）が、ウレタンプレポリマーに含まれるエステル結合量がかかる範囲にある場合には、湿気硬化性ホットメルト接着剤組成物を硬化させた硬化物の湿熱老化性をより優れたものとすることができる。
　なお、ウレタンプレポリマーがエステル結合を含む場合、［ウレタンプレポリマーのエステル結合量］／［ウレタンプレポリマーのウレタン結合量］は、上限値が、１０．０以下、７．５以下、５．０以下、４．５以下、４．０以下、３．５以下、又は、３．２以下であることが好ましく、下限値が、０．１以上．０．２以上．０．５以上、１．０以上、又は、１．１以上であることが好ましい。 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. Preferably, 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.
When the urethane prepolymer contains an ester bond, 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.
・数平均分子量
　ウレタンプレポリマーの数平均分子量は、本開示の効果を阻害しない限りにおいて特に限定されず、３，０００～８，０００とすることができる。ウレタンプレポリマーの数平均分子量を調整することで、湿気硬化性ホットメルト接着剤組成物を硬化させた硬化物の接着強度等の特性を調整することができる。ウレタンプレポリマーの数平均分子量の測定は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、測定することができる（標準ポリマー＝ポリスチレンとする）。 · Number average molecular weight 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. By adjusting the number average molecular weight of the urethane prepolymer, properties such as adhesive strength of a cured product obtained by curing the moisture-curable hot-melt adhesive composition can be adjusted. The number average molecular weight of the urethane prepolymer can be measured by a gel permeation chromatography (GPC) method (standard polymer = polystyrene).
・粘度
　ウレタンプレポリマーの粘度は、本発明の効果を阻害しない限りにおいて特に限定されない。例えば、ウレタンプレポリマーの１４０℃における溶融粘度を２，０００～６，０００ｍＰａ・ｓとすることができる。ウレタンプレポリマーの粘度を調整することで、湿気硬化性ホットメルト接着剤組成物の塗工性等の特性を調整することができる。ウレタンプレポリマーの１４０℃における溶融粘度は、レオメータ（アントンパール社製、ＭＣＲ３０２）にパラレルプレートを装着した器具を用いて、サンプルを１４０℃に熱し、周波数１Ｈｚ、ずり速度１ｒａｄ／ｓの条件の下で測定するものとする。 - Viscosity The viscosity of the urethane prepolymer is not particularly limited as long as it does not inhibit the effects of the present invention. For example, the urethane prepolymer can have a melt viscosity of 2,000 to 6,000 mPa·s at 140°C. By adjusting the viscosity of the urethane prepolymer, 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
・イソシアネート基含有率（ＮＣＯ％）
　ウレタンプレポリマーのＮＣＯ％は、本開示の効果が阻害されない限りにおいて特に限定されるものではないが、好ましくは０．３％～３．５％であり、より好ましくは１．２％～２．５％である。ウレタンプレポリマーのＮＣＯ％がかかる範囲にある場合には、作業中の発泡等を抑制しつつも、湿気による硬化を促進することが可能となり、さらに湿気硬化性ホットメルト接着剤組成物を硬化させた硬化物の湿熱老化性をより優れたものとすることができる。プレポリマーのＮＣＯ％（イソシアネート基含有率）は、ＪＩＳ　Ｋ１６０３－１：２００７「プラスチック－ポリウレタン原料芳香族イソシアネート試験方法　第１部：イソシアネート基含有率の求め方」のＡ法（トルエン／ジブチルアミン、塩酸法）に準拠して測定することができる。 ・Isocyanate group content (NCO%)
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%. When 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).
・ゲル分率
　ウレタンプレポリマーのゲル分率は、本開示の効果が阻害されない限りにおいて特に限定されるものではないが、その下限値は、好ましくは３０質量％以上、４０質量％以上、５０質量％以上、６０質量％以上、７０質量％以上であり、上限値は、９５質量％以下、９０質量％以下、８５質量％以下である。このような範囲とすることで、湿気硬化性ホットメルト接着剤組成物を硬化させた硬化物の湿熱老化性をより優れたものとすることができる。 ・Gel fraction 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.
　ゲル分率は、以下の方法により算出される。
　湿気硬化性ホットメルト接着剤組成物を硬化させた硬化物を所定量（例えば、０．０４５ｇ）秤取り、所定量（例えば、９ｇ）のテトラヒドロフラン（ＴＨＦ）に浸漬させ、２０時間静置し、溶解せずにＴＨＦ中に残った硬化物の不溶分を取り出し、真空乾燥させてその質量を測定し、浸漬前の硬化物の質量で除して算出したものゲル分率とする。 A gel fraction is calculated by the following method.
A predetermined amount (e.g., 0.045 g) of 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.
１－２．カルボジイミド化合物
　本開示の湿気硬化性ホットメルト接着剤組成物は、カルボジイミド化合物を含むことができる。本開示にかかるカルボジイミド化合物は、カルボジイミド基を有する化合物であれば特に限定されない。カルボジイミド化合物としては、例えば、ジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、１－エチル－３－［３－（ジメチルアミノ）プロピル］カルボジイミド、シアナミド、Ｎ，Ｎ’－ジイソプロピルカルボジイミド、Ｎ，Ｎ’－ジシクロヘキシルカルボジイミド、Ｎ－シクロヘキシルカルボジイミド，Ｎ’－メチルポリスチレン１－エチル－３－（３－ジメチルアミノプロピル）カルボジイミド塩酸塩、メト－ｐ－トルエンスルホン酸１－シクロヘキシル－３－（２－モルホリノエチル）カルボジイミド、ビス（２，６－ジイソプロピルフェニル）カルボジイミド、ビス(トリメチルシリル)カルボジイミド、１－シクロヘキシル－３－（２－モルホリノエチル）カルボジイミドメト－ｐ－トルエンスルホナート、Ｎ，Ｎ’－ジ－ｔｅｒｔ－ブチルカルボジイミド、１－［３－（ジメチルアミノ）プロピル］－３－エチルカルボジイミドメチオジド等を挙げることができる。
　また、市販品としては、日清紡ケミカル社製のカルボジライト（登録商標）Ｅ－０２、Ｅ－０３Ａ、Ｅ－０５、Ｅペレット、ＨＭＶ－１５ＣＡ、ＨＭＶ－５ＣＡ－ＬＣ、ＬＡ－１、ＳＶ－０２、ＳＷ－１２Ｇ、Ｖ－０２、Ｖ－０２Ｂ、Ｖ－０２－Ｌ２、Ｖ－０３、Ｖ－０４、Ｖ－０５、Ｖ－０７、Ｖ－０９、Ｖ－０９ＧＢ、Ｖ－１０；ラインケミー社製のスタバクゾール（登録商標）Ｉ、Ｐ、Ｐ１００；シェーファー社製ＬＵＢＩＯ　ＡＳ　１５、ＬＵＢＩＯ　ＡＳ１－ＳＰ、ＬＵＢＩＯ　ＡＳ　４；ＢＡＳＦ社製のＥｌａｓｔｏｓｔａｂ　Ｈ０１等を挙げることができる。
　これらのカルボジイミド化合物は、単独で、又は、複数を組み合わせて用いることができる。
　湿気硬化性ホットメルト接着剤組成物がカルボジイミド化合物を含む場合には、湿気硬化性ホットメルト接着剤組成物を硬化させた硬化物の湿熱老化性をさらに優れたものとすることができる。 1-2. Carbodiimide Compound 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)carbodiimide metho-p-toluenesulfonate, N,N'-di-tert-butylcarbodiimide, 1-[3 -(dimethylamino)propyl]-3-ethylcarbodiimide methiodide and the like.
In addition, 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.
When 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.
　カルボジイミド化合物の分子量又は数平均分子量は、本開示の効果を阻害しない限りにおいて特に限定されないが、３００～１０，０００が好ましく、４００～８，０００がより好ましく、５００～８，０００がさらに好ましく、５００～５，０００が特に好ましい。カルボジイミド化合物の分子量又は数平均分子量がかかる範囲にある場合には、湿気硬化性ホットメルト接着剤組成物を硬化させた硬化物の湿熱老化性をさらに優れたものとすることができる。
　また、湿気硬化性ホットメルト接着剤組成物又はその硬化物から揮発したカルボジイミド化合物が使用環境の周辺物に付着してその表面を曇らせることがある。例えば、自動車の内装具の貼り合わせに用いた場合等は、自動車のガラス等を曇らせる場合がある。カルボジイミド化合物の分子量又は数平均分子量を５００以上とすることで、このような曇りの発生を防止し易くなる。 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. When 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.
In addition, 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. For example, when it is used for bonding interior fittings of automobiles, the glass of the automobile may be fogged. By setting 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.
１－３．その他の添加物
　本開示の湿気硬化性ホットメルト接着剤組成物は、必要に応じてその他の添加物を含むことができる。その他の添加剤としては、特に限定されず、湿気硬化性ホットメルト接着剤組成物に含まれる公知の成分が挙げられる。その他の添加物としては、例えば、充填剤、可塑剤、顔料、染料、老化防止剤、酸化防止剤、消泡剤、結晶核剤、帯電防止剤、難燃剤、接着性付与剤、抗菌剤、光安定剤、安定剤、分散剤、溶剤、親水性付与剤、ワックス等が挙げられる。これらは、単独で、又は、複数を組み合わせて用いることができる。 1-3. Other Additives 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.
２．湿気硬化性ホットメルト接着剤組成物の製造方法
２－１．ウレタンプレポリマーの製造方法
　ウレタンプレポリマーの製造方法は特に限定されず、公知の方法を用いることができる。具体的には、例えば、容器に、所定量のポリイソシアネート化合物を入れ、窒素ガス雰囲気下で撹拌する。ここに所定量のポリオール化合物を滴下する。ここで、反応を促進するため、必要に応じて触媒を添加することができる。
　所定の時間撹拌し、反応を完了させる。ここで、反応生成物の一部を抜き取り、イソシアネート基含有率を測定し、所望の範囲内にあることを確認してもよい。 2. Method for producing moisture-curable hot-melt adhesive composition 2-1. 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.
　ポリオール化合物と、ポリイソシアネート化合物の配合量は、特に限定されないが、例えばウレタンプレポリマーのイソシアネートインデックスが０．５～２．０となるよう配合することが可能であり、１．０～２．０が好ましく、１．２～１．６がより好ましい。
　ここで、イソシアネートインデックスとは、ウレタンプレポリマーの全原料配合である樹脂組成物のすべての活性水素のモル数と、ポリイソシアネート化合物中のイソシアネート基のモル数の比（イソシアネート基のモル数／活性水素のモル数）をいう。 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.
Here, 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).
　触媒の添加量は、特に限定されないが、例えば、ポリオール化合物の全配合量を１００質量部とした場合に、０．０１～５．０質量部とすることができる。 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.
２－２．湿気硬化性ホットメルト接着剤組成物の製造方法
　ウレタンプレポリマー以外の添加物を添加する場合の湿気硬化性ホットメルト接着剤組成物の製造方法は特に限定されず、公知の方法を用いることができる。具体的には、例えば、容器に、所定量のウレタンプレポリマーを入れ、ここにカルボジイミド化合物と、その他の添加物とを添加し、攪拌する。 2-2. 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.
　カルボジイミド化合物の配合量は、本開示の効果を阻害しない限りにおいて特に限定されない。カルボジイミド化合物の配合量は、ウレタンプレポリマーに配合したポリオール化合物の全量を１００質量部とした場合に、０．１質量部以上、０．５質量部以上、１．０質量部以上、１．５質量部以上、２．０質量部以上、２．５質量部以上、又は、３．０質量部以上であることが好ましく、また、１０．０質量部以下、８．０質量部以下、６．０質量部以下、又は、５．０質量部以下であることが好ましい。例えば、ウレタンプレポリマーに配合したポリオール化合物の全量を１００質量部とした場合に、０．１～１０．０質量部とすることができ、１．０～１０．０質量部が好ましく、１．０～８．０質量部がより好ましく、１．０～６．０質量部がさらに好ましく、１．０～５．０質量部がさらにより好ましく、３．０～５．０質量部が特に好ましい。湿気硬化性ホットメルト接着剤組成物がかかる範囲のカルボジイミド化合物を含む場合には、湿気硬化性ホットメルト接着剤組成物を硬化させた硬化物の湿熱老化性をさらに優れたものとすることができる。
　その他の添加物（ウレタンプレポリマー、カルボジイミド化合物以外の添加物）の配合量（合計の配合量）は、本開示の効果を阻害しない限りにおいて特に限定されないが、例えば、ウレタンプレポリマーに配合したポリオール化合物の全量を１００質量部とした場合に、１０．０質量部以下、５．０質量部以下、３．０質量部以下、２．０質量部以下、又は、１．０質量部以下とすることができ、また、０．１質量部以上、０．２質量部以上、０．３質量部以上、０．４質量部以上、又は、０．５質量部以上とすることができる。 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. For example, when 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. . When 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 (additives other than urethane prepolymers and carbodiimide compounds) is not particularly limited as long as it does not inhibit the effects of the present disclosure. When 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.
３．湿気硬化性ホットメルト接着剤組成物の用途
　湿気硬化性ホットメルト接着剤組成物は、例えば、化粧シート被覆材料等の建築内装部材、家具部材、自動車、鉄道、船舶、航空機等の内装材（例えば座席やヘッドレストのカバーパッドの縫製部等の接着用等）に用いることが適している。特に、高温かつ高湿度環境で用いられる自動車の内装材用として好適である。 3. Applications of moisture-curable hot-melt adhesive compositions 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.
　湿気硬化性ホットメルト接着剤組成物は、加熱して溶融することにより、対象物に塗布して用いることができる。塗布方法としては、公知の方法を用いることができ、例えば、刷毛、へら、シリンジ、シーリングガン、ディスペンサー、等の塗布方法を挙げることができる。また、本開示の湿気硬化性ホットメルト接着剤組成物は、低溶融粘度とすることが可能であるため非接触方式（例えば、スプレー方式）を用いて塗布することも可能である。通気性を向上させ、生産性を向上させる（例えば、対象物が長尺であっても製造容易である）等の観点から、スプレー塗布によって対象物に塗布することが好ましい。
　湿気硬化性ホットメルト接着剤組成物の塗布量（或いは、湿気硬化性ホットメルト接着剤組成物の目付量）は、１～１００ｇ／ｍ２であることが好ましく、３～５０ｇ／ｍ２であることがより好ましく、５～３０ｇ／ｍ２であることが特に好ましい。 The moisture-curable hot-melt adhesive composition can be applied to an object by being melted by heating. As the coating method, 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. In addition, since 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.
　本開示に係る技術は、湿気硬化性ホットメルト接着剤組成物の硬化物、或いは、湿気硬化性ホットメルト接着剤組成物の硬化物を含む積層体として提供されてもよい。
　例えば、本開示に係る技術は、第１の基材と、第２の基材とが、接着剤層を介して積層された積層体であって、この接着剤層が、本開示に係る湿気硬化性ホットメルト接着剤組成物の硬化物である積層体であってもよい。この場合、第１の基材及び第２の基材の材質や形状等は特に限定されないが、第１の基材及び第２の基材は、各々独立して、発泡体（例えば、ウレタン発泡体）、天然皮革、合成皮革、フィルム（樹脂フィルム）、織布及び不織布からなる群より選択されることが好ましい。
　このような積層体は、前述した湿気硬化性ホットメルト接着剤組成物の塗布方法を適用して製造することができる。
　このような積層体を、前述した化粧シート被覆材料等の建築内装部材、家具部材、自動車、鉄道、船舶、航空機等の内装材を構成する部材等とすることができる。 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.
For example, 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. In this case, 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). body), natural leather, synthetic leather, film (resin film), woven fabric and non-woven fabric.
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.
　以下、実施例により、本開示の湿気硬化性ホットメルト接着剤組成物の効果について、具体的に説明する。
　製造した各実施例及び比較例の湿気硬化性ホットメルト接着剤組成物の原料と、得られた湿気硬化性ホットメルト接着剤組成物の評価結果とを表１に示した。 The effects of the moisture-curable hot-melt adhesive composition of the present disclosure will be specifically described below with reference to examples.
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.
＜湿気硬化性ホットメルト接着剤組成物の製造＞
　撹拌羽を有する１リットル四つ口フラスコ内にポリイソシアネート化合物としてＭＤＩを、表１に示した配合量で投入し、フラスコ内を窒素ガスでパージした後に温度を８０℃まで加熱させた。次に、フラスコ内にポリオール化合物をそれぞれ表１に示した配合量で、８０℃に加熱溶融させて溶融状態で投入し、窒素ガス雰囲気下で液温１００℃以下に保持して２時間以上撹拌した。これにより、ポリオール化合物とポリイソシアネート化合物とが反応して、ウレタンプレポリマーを得た。さらに、カルボジイミド化合物、その他の添加物を表１に従って配合し、さらに２時間以上攪拌し、各実施例及び比較例の湿気硬化性ホットメルト接着剤組成物を得た。 <Production of Moisture Curing Hot Melt Adhesive Composition>
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. Next, 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. As a result, the polyol compound and the polyisocyanate compound reacted to obtain a urethane prepolymer. Further, 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.
　下記に、用いた湿気硬化性ホットメルト接着剤組成物の原料を示す。
・ポリオール化合物
　ポリエステルポリオール
ポリオール１：セバシン酸（ＳＡ）と１，６－ヘキサンジオール（ＨＤ）との反応合成物、数平均分子量５，０００
ポリオール２：アジピン酸（ＡＡ）と１，６－ヘキサンジオール（ＨＤ）との反応合成物、数平均分子量４，５００
ポリオール３：アジピン酸（ＡＡ）及びテレフタル酸と、エチレングリコール及び１，４－ブチレングリコール（ＢＧ）との反応合成物、数平均分子量３，０００
ポリオール４：１，１２－ドデカン二酸（ＤＤＡ）と１，６－ヘキサンジオール（ＨＤ）との反応合成物、数平均分子量３，７００
ポリオール５：アジピン酸（ＡＡ）と１，４－ブタンジオール（ＢＤ）との反応合成物、数平均分子量２，０００
　ポリエーテルポリオール
ポリオール６：ポリプロピレングリコール（ＰＰＧ）、数平均分子量１，０００
ポリオール７：ポリプロピレングリコール（ＰＰＧ）、数平均分子量７００
ポリオール８：ビスフェノールＡ（ＢＰ）とプロピレンオキシド（ＰＯ）との共重合体、数平均分子量５００
・ワックス
（１）日本精蝋社製　マイクロクリスタリンワックスＨｉ－Ｍｉｃ－２０９５
・消包剤
（１）サンノプコ社製　ダッポーＳＮ３４８
・老化防止剤
（１）ＢＡＳＦ社製　ＩＲＧＡＮＯＸ１０７６
（２）ＢＡＳＦ社製　ＩＲＧＡＦＯＳ１６８
・触媒
（１）ＤＭＤＥＥ（アミン系触媒、ジモルホリノジエチルエーテル）
・結晶核剤
（１）ＡＤＥＫＡ社製　ＮＡ１１
・ポリイソシアネート化合物
（１）モノメリックＭＤＩ、分子量：２５０
・カルボジイミド化合物
（１）日清紡ケミカル社製　カルボジライトＶ０４ＰＦ、数平均分子量：２，０００
（２）ラインケミー社製　スタバクゾールＩ、数平均分子量：３８０
（３）ラインケミー社製　スタバクゾールＰ、数平均分子量：２，０００
（４）シェーファー社製　ＬＵＢＩＯ　ＡＳ　１５、数平均分子量：１，５００
（５）日清紡ケミカル社製カルボジライトＨＭＶ－１５ＣＡ、数平均分子量：３，４００
（６）ＢＡＳＦ社製　Ｅｌａｓｔｏｓｔａｂ　Ｈ０１　数平均分子量：１，９００ The raw materials of the moisture-curable hot-melt adhesive compositions used are shown below.
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 (PPG), number average molecular weight 1,000
Polyol 7: polypropylene glycol (PPG), number average molecular weight 700
Polyol 8: Copolymer of bisphenol A (BP) and propylene oxide (PO), number average molecular weight 500
・Wax (1) Microcrystalline wax Hi-Mic-2095 manufactured by Nippon Seiro Co., Ltd.
・ 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
＜評価・測定＞
・ウレタンプレポリマーのＮＣＯ％
　各実施例及び比較例におけるウレタンプレポリマーのＮＣＯ％をＪＩＳ　Ｋ１６０３－１：２００７「プラスチック－ポリウレタン原料芳香族イソシアネート試験方法　第１部：イソシアネート基含有率の求め方」のＡ法（トルエン／ジブチルアミン、塩酸法）に準拠して測定した。 <Evaluation/measurement>
・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).
・ウレタンプレポリマーのイソシアネートインデックス
　各実施例及び比較例のウレタンプレポリマーのイソシアネートインデックスを示した。 - Isocyanate index of urethane prepolymer The isocyanate index of the urethane prepolymer of each example and comparative example is shown.
・相溶性
　カルボジイミド化合物を含む各実施例及び比較例の湿気硬化性ホットメルト接着剤組成物におけるカルボジイミド化合物とウレタンプレポリマーの相溶性を肉眼で観察した。観察は、各実施例及び比較例のウレタンプレポリマーについて、窒素ガス雰囲気下で各実施例及び比較例のカルボジイミド化合物を添加し、１時間攪拌したものを評価試料とした。評価基準は以下とした。また、カルボジイミド化合物を含まない場合については「－」とした。
〇：肉眼でウレタンプレポリマーの懸濁が観察されなかった
×：肉眼でウレタンプレポリマーの懸濁が観察された Compatibility Compatibility between the carbodiimide compound and the urethane prepolymer in the moisture-curable hot-melt adhesive compositions of Examples and Comparative Examples containing the carbodiimide compound was visually observed. Observation was made by adding the carbodiimide compound of each example and comparative example to the urethane prepolymers of each example and comparative example in a nitrogen gas atmosphere and stirring the mixture for 1 hour, which was used as an evaluation sample. The evaluation criteria were as follows. "-" indicates the case where the carbodiimide compound is not contained.
○: Suspension of the urethane prepolymer was not observed with the naked eye ×: Suspension of the urethane prepolymer was observed with the naked eye
・ウレタンプレポリマーのウレタン結合量
　各実施例及び比較例のウレタンプレポリマーのウレタン結合量を上述の方法により算出した。 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.
・ウレタンプレポリマーのエステル結合量
　各実施例及び比較例のウレタンプレポリマーのエステル結合量を上述の方法により算出した。 - Amount of ester bond of urethane prepolymer The amount of ester bond of the urethane prepolymer of each example and comparative example was calculated by the method described above.
・ウレタンプレポリマーのゲル分率
　各実施例及び比較例の湿気硬化性ホットメルト接着剤組成物を離型加工されたＰＥＴフィルム上に塗布し、硬化させて各実施例及び比較例の硬化物を得た。得られた硬化物を０．０４５ｇ秤取り、９ｇのテトラヒドロフラン（ＴＨＦ）に浸漬させ、２０時間静置した。溶解せずにＴＨＦ中に残った硬化物の不溶分を取り出し、真空乾燥させてその質量を測定し、０．０４５ｇで除して算出したものをウレタンプレポリマーのゲル分率とした。 ・Gel fraction of urethane prepolymer The moisture-curable hot-melt adhesive composition of each example and comparative example is applied onto a PET film that has been subjected to mold release processing, and cured to obtain the cured product of each example and comparative example. Obtained. 0.045 g of the obtained cured product was weighed, immersed in 9 g of tetrahydrofuran (THF), and allowed to stand for 20 hours. The insoluble portion of the cured product remaining in THF without dissolving was taken out, dried in a vacuum, and the mass was measured and divided by 0.045 g to obtain the gel fraction of the urethane prepolymer.
・ガラスかすみ度
　各実施例及び比較例の湿気硬化性ホットメルト接着剤組成物を、１３０℃に溶融し、ハンドガンを用いて、２０ｇ／ｍ２となるようにウレタンフォーム（イノアック社製ＥＬ－６７Ｆ）にスプレー塗布した。その後、ウレタンフォームを、ファブリック（ＰＥＴ生地）で構成された表皮と貼り合わせ、常温下で１２時間養生し、積層体を得た。積層体を直径８０ｍｍ×厚み２５０μｍに加工して評価用の試験片とした。試験片を、直径９０ｍｍ×高さ１９０ｍｍのガラス容器（上部のみ解放されたがらず容器）内の底部に設置した。試験片上部（ガラス容器内部）に、ガラスシャーレを設置し、ガラスシャーレ内に０．０１２ｇ／ｍｌのエチレンジアミン水溶液１ｍｌを入れた。このガラス容器の上部を直径９０ｍｍのガラスプレートで密閉状態となるよう蓋をして、８０℃の恒温槽内で７２時間放置する処理を行った。その後、ガラスプレートを取り出し、光沢度測定装置を用いて、処理後のガラスプレートの反射率を測定した。また、予め測定した処理前のガラスプレートの反射率とから、下式１に従い、ガラスかすみ度を算出した。処理前後の各反射率の測定値は、各ガラスプレートについて、９回測定し、その平均値とした。
（式１）
ガラスかすみ度＝処理後のガラスプレートの反射率／処理前のガラスプレートの反射率×１００
　また、ガラスかすみ度について、以下の評価基準で判定した。
〇：９０．０％以上
△：７０．０％以上～９０．０％未満
×：７０．０％未満 ・Glass haziness 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 μm 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.
(Formula 1)
Glass haze=reflectance of glass plate after treatment/reflectance of glass plate before treatment×100
Further, the degree of glass haze was judged according to the following evaluation criteria.
○: 90.0% or more △: 70.0% or more to less than 90.0% ×: less than 70.0%
・湿熱老化性
　各実施例及び比較例の湿気硬化性ホットメルト接着剤組成物を、１３０℃に溶融し、ハンドガンを用いて、２０ｇ／ｍ２となるようにウレタンフォーム（イノアック社製ＥＬ－６７Ｆ）に塗布した。その後、ウレタンフォームを、ファブリック（ＰＥＴ生地）で構成された表皮と貼り合わせ、積層体を得た。各積層体を８５℃及び相対湿度９５％の環境下で、２００時間、４００時間、６００時間の、湿熱処理をそれぞれ行った。処理後の各積層体を幅２５ｍｍ×長さ２５０ｍｍに成形し、常温下で１２時間静置し、評価用の試験片とした。試験片を材料試験機（島津製作所製、精密万能試験機オートグラフ）を用いて、２５℃環境下で１８０°剥離試験を行い、各湿熱処理条件における剥離強度を測定した。
　評価は、処理時間が２００時間、４００時間、６００時間の場合のそれぞれの剥離強度を以下の評価基準で点数評価した。
３点：剥離強度が２．５Ｎ／２５ｍｍ以上である
２点：剥離強度が１．３Ｎ／２５ｍｍ以上～２．５Ｎ／２５ｍｍ未満である
１点：剥離強度が１．３Ｎ／２５ｍｍ未満である
　また、湿熱処理時間が２００時間、４００時間、６００時間の場合のそれぞれの剥離強度の評価点を合計したものを総合評価として、以下の評価基準で評価した。
〇：２００時間、４００時間、６００時間における評価点の合計が７～９点である
△：２００時間、４００時間、６００時間における評価点の合計が４～６点である
×：２００時間、４００時間、６００時間における評価点の合計が３点以下である Wet heat aging property The moisture-curable hot-melt adhesive composition of each example and comparative example was melted at 130 ° C., and using a hand gun, urethane foam (EL-67F manufactured by INOAC Co., Ltd.) was adjusted to 20 g / m 2 ). After that, the urethane foam was attached to a skin composed of a fabric (PET fabric) to obtain a laminate. Each laminate was subjected to wet heat treatment for 200 hours, 400 hours, and 600 hours in an environment of 85° C. and 95% relative humidity. Each laminated body after the treatment was formed into a width of 25 mm and a length of 250 mm, and allowed to stand at room temperature for 12 hours to obtain a test piece for evaluation. 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.
For the evaluation, the peel strength was scored according to the following evaluation criteria when the treatment time was 200 hours, 400 hours, and 600 hours.
3 points: Peel strength is 2.5 N / 25 mm or more 2 points: Peel strength is 1.3 N / 25 mm or more to less than 2.5 N / 25 mm 1 point: Peel strength is less than 1.3 N / 25 mm , and the total evaluation points of the peel strength in the cases where the wet heat treatment time was 200 hours, 400 hours, and 600 hours, and evaluated according to the following evaluation criteria as a comprehensive evaluation.
○: 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 points or less
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　さらに、実施例１、１１、１２に係る湿気硬化性ホットメルト接着剤組成物を用いて、接着する対象物を、ウレタンフォーム及びファブリックから、表２に示す基材（上層及び下層）に変更した以外は前述の方法で積層体を製造し、湿熱老化性及び総合評価を評価した。評価結果を表２に示す。
　表２中、ファブリックはＰＥＴ生地のものを示す。また、ＥＬ－４５は、イノアック社製のウレタンフォームである。 Furthermore, using the moisture-curable hot-melt adhesive compositions according to Examples 1, 11, and 12, 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.
In Table 2, the fabric indicates that of PET fabric. EL-45 is a urethane foam manufactured by INOAC.
Figure JPOXMLDOC01-appb-T000002
 
Figure JPOXMLDOC01-appb-T000002
 

Claims (7)

  1. 　ウレタンプレポリマーを含む湿気硬化性ホットメルト接着剤組成物であって、
    　前記ウレタンプレポリマーは、ポリオール化合物と、ポリイソシアネート化合物と、を反応させて得られるものであり、
    　前記ウレタンプレポリマーのウレタン結合量が、０．９０ｍｏｌ／ｋｇ以上であることを特徴とする、湿気硬化性ホットメルト接着剤組成物。     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,
    A moisture-curable hot-melt adhesive composition, wherein the urethane prepolymer has a urethane bond content of 0.90 mol/kg or more.
  2. 　カルボジイミド化合物をさらに含むことを特徴とする、請求項１に記載の湿気硬化性ホットメルト接着剤組成物。 The moisture-curable hot-melt adhesive composition according to claim 1, further comprising a carbodiimide compound.
  3. 　前記カルボジイミド化合物の分子量又は数平均分子量は、５００以上であることを特徴とする、請求項２に記載の湿気硬化性ホットメルト接着剤組成物。 The moisture-curable hot-melt adhesive composition according to claim 2, wherein the carbodiimide compound has a molecular weight or number average molecular weight of 500 or more.
  4. 　前記ポリオール化合物は、ポリエーテルポリオール化合物と、ポリエステルポリオール化合物と、を含むことを特徴とする、請求項１～３のいずれか一項に記載の湿気硬化性ホットメルト接着剤組成物。 The moisture-curable hot-melt adhesive composition according to any one of claims 1 to 3, wherein the polyol compound comprises a polyether polyol compound and a polyester polyol compound.
  5. 　前記ウレタンプレポリマーのエステル結合量が、６．００ｍｏｌ／ｋｇ以下であることを特徴とする、請求項１～４のいずれか一項に記載の湿気硬化性ホットメルト接着剤組成物。 The moisture-curable hot-melt adhesive composition according to any one of claims 1 to 4, characterized in that the urethane prepolymer has an ester bond content of 6.00 mol/kg or less.
  6. 　自動車の内装材用であることを特徴とする、請求項１～５のいずれか一項に記載の湿気硬化性ホットメルト接着剤組成物。 The moisture-curable hot-melt adhesive composition according to any one of claims 1 to 5, which is used as an interior material for automobiles.
  7. 　第１の基材と、第２の基材とが、接着剤層を介して積層されており、
    　前記接着剤層は、請求項１～６のいずれか一項に記載の湿気硬化性ホットメルト接着剤組成物の硬化物であり、
    　前記第１の基材及び前記第２の基材は、各々独立して、発泡体、天然皮革、合成皮革、フィルム、織布及び不織布からなる群より選択されることを特徴とする、積層体。     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 according to any one of claims 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. .
PCT/JP2022/040329 2021-10-29 2022-10-28 Moisture-curable hot-melt adhesive composition WO2023074840A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-178163 2021-10-29
JP2021178163 2021-10-29

Publications (1)

Publication Number Publication Date
WO2023074840A1 true WO2023074840A1 (en) 2023-05-04

Family

ID=86159985

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/040329 WO2023074840A1 (en) 2021-10-29 2022-10-28 Moisture-curable hot-melt adhesive composition

Country Status (1)

Country Link
WO (1) WO2023074840A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004155860A (en) * 2002-11-05 2004-06-03 Sekisui Chem Co Ltd Moisture curable polyurethane hot-melt adhesive
WO2019163622A1 (en) * 2018-02-21 2019-08-29 Dic株式会社 Moisture-curable polyurethane hot melt resin composition
JP2020002262A (en) * 2018-06-28 2020-01-09 Dic株式会社 Moisture-curable polyurethane hot-melt resin composition
JP2020076018A (en) * 2018-11-08 2020-05-21 株式会社イノアックコーポレーション Low outgassing urethane hot-melt adhesive composition
WO2021025093A1 (en) * 2019-08-08 2021-02-11 Dic株式会社 Moisture-curable polyurethane hot-melt resin composition
JP2021116390A (en) * 2020-01-29 2021-08-10 アイカ工業株式会社 Moisture-curable reactive hot-melt composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004155860A (en) * 2002-11-05 2004-06-03 Sekisui Chem Co Ltd Moisture curable polyurethane hot-melt adhesive
WO2019163622A1 (en) * 2018-02-21 2019-08-29 Dic株式会社 Moisture-curable polyurethane hot melt resin composition
JP2020002262A (en) * 2018-06-28 2020-01-09 Dic株式会社 Moisture-curable polyurethane hot-melt resin composition
JP2020076018A (en) * 2018-11-08 2020-05-21 株式会社イノアックコーポレーション Low outgassing urethane hot-melt adhesive composition
WO2021025093A1 (en) * 2019-08-08 2021-02-11 Dic株式会社 Moisture-curable polyurethane hot-melt resin composition
JP2021116390A (en) * 2020-01-29 2021-08-10 アイカ工業株式会社 Moisture-curable reactive hot-melt composition

Similar Documents

Publication Publication Date Title
JP6947172B2 (en) Moisture-curable reactive hot-melt adhesive composition and its manufacturing method
JP5472525B1 (en) Adhesive composition, laminate and method for producing the same
TWI822795B (en) Moisture curable polyurethane adhesive composition
WO2019163622A1 (en) Moisture-curable polyurethane hot melt resin composition
JP2017527648A (en) Filler-containing polyurethane laminate adhesive
WO2016166978A1 (en) Adhesive composition and layered body using same
EP3029121A2 (en) Surface protective pressure-sensitive adhesive sheet
KR20110098613A (en) Urethane prepolymer
JP7231383B2 (en) Low outgassing urethane hot melt adhesive composition
JP2022185595A (en) Low-outgassing urethane hot-melt adhesive composition
TW202112865A (en) Moisture-curable polyurethane hot-melt resin composition
US20220315817A1 (en) Polyurethane Hot Melt Adhesive Composition, and Preparation Method Thereof
JP7425977B2 (en) Moisture-curing hot melt adhesive composition, adhesive, and clothing
JP7000669B2 (en) Moisture-curing hot melt adhesive and its manufacturing method
WO2023074840A1 (en) Moisture-curable hot-melt adhesive composition
JP6357910B2 (en) OPTICAL POLYURETHANE COMPOSITION, THIN FILM MOLDED BODY, OPTICAL FILM, AND METHOD FOR PRODUCING THIN FILM MOLDED BODY
JP2020023602A (en) Two-pack curable type adhesive
JP7400257B2 (en) Moisture-curable polyurethane hot melt resin composition and cured product thereof
JP7163709B2 (en) Reactive hot-melt adhesive and method for adhering adherend
JP2022189479A (en) Moisture-curable hot-melt adhesive
JP2024069049A (en) Reactive hot melt adhesives and structures
JP6733836B2 (en) Moisture curable polyurethane hot melt resin composition
JP2021107541A (en) Urethane-based hot melt adhesive
WO2023182285A1 (en) Non-sewn clothing manufacturing method
JP2022100680A (en) Moisture-curable reactive hot melt adhesive

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22887165

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023556663

Country of ref document: JP