WO2022118684A1 - Adhésif de polyuréthane à deux composants et support d'adhérence - Google Patents

Adhésif de polyuréthane à deux composants et support d'adhérence Download PDF

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Publication number
WO2022118684A1
WO2022118684A1 PCT/JP2021/042657 JP2021042657W WO2022118684A1 WO 2022118684 A1 WO2022118684 A1 WO 2022118684A1 JP 2021042657 W JP2021042657 W JP 2021042657W WO 2022118684 A1 WO2022118684 A1 WO 2022118684A1
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weight
component
polyol
polyurethane adhesive
component polyurethane
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PCT/JP2021/042657
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English (en)
Japanese (ja)
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哲也 島田
恭輔 森本
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三洋化成工業株式会社
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Priority to JP2022539731A priority Critical patent/JP7295341B2/ja
Publication of WO2022118684A1 publication Critical patent/WO2022118684A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09J175/08—Polyurethanes from polyethers

Definitions

  • the present invention relates to a two-component polyurethane adhesive and an adherend.
  • a two-component urethane adhesive composed of a main agent of a polyol composition and a curing agent of an isocyanate composition
  • a two-component curing type composed of a main agent containing a polyurethane polyol as a main component and a curing agent containing a polyurethane polyisocyanate as a main component.
  • Polyurethane adhesives are known. (See, for example, Patent Document 1).
  • it is a two-component curing type urethane adhesive having a main agent containing a urethane prepolymer and a curing agent containing a compound having two or more active hydrogen groups in one molecule, and the curing agent is terpene.
  • Two-component curable urethane adhesives containing compounds are known. (See, for example, Patent Document 2).
  • the adhesive described in Patent Document 1 contains a solvent, there is a problem in safety. Therefore, it has been difficult to use it in applications where solvent content is a problem. Further, the adhesive described in Patent Document 2 is excellent in safety because it does not use a solvent, but has problems in adhesive properties such as adhesive strength (resin strength), heat resistance and durability.
  • Epoxy adhesives are known as two-component adhesives with excellent adhesive strength and heat resistance, but they have low flexibility and may cause problems when used in areas subject to vibration or impact. In addition, the epoxy adhesive has a relatively slow curing speed and easily drips, so that there is a problem in coatability at the time of adhesion.
  • An object of the present invention is to provide a two-component polyurethane adhesive having excellent safety and good resin strength, heat resistance, durability and coatability.
  • the present inventors have found that the above-mentioned problems can be solved, and have reached the present invention. That is, in the present invention, the main agent (X) and the isocyanate component (B) containing the polyol component (A) containing the polyether polyol (a) obtained by adding ethylene oxide and / or propylene oxide to the 6 to 14 functional polyol as an essential component are contained.
  • the cured product obtained by curing the two-component polyurethane adhesive of the present invention has the following effects as compared with the conventional adhesive.
  • Excellent resin strength such as breaking strength and hardness, and excellent durability.
  • It has excellent cold resistance and heat resistance, and has excellent adhesive strength.
  • It is low in odor (no peculiar odor), has little elution, and is low in contamination (non-eluting), so it is excellent in safety.
  • Excellent flexibility and toughness Since the adhesive does not easily drip after coating, it has excellent coatability.
  • the main agent (X) in the present invention contains a polyol component (A) containing a polyether polyol (a) in which ethylene oxide and / or propylene oxide is added to a 6 to 14 functional polyol as an essential component.
  • Examples of the 6 to 14 functional polyols include 6 to 14 valent alcohols having 6 to 20 carbon atoms [aliphatic polyols (sorbitol, mannitol, dipentaerythritol, etc.) and polysaccharides (sucrose, lactose, maltose, trehalose, turanose, etc.). Cellobiose, Raffinose, Melezitose, Malttriose, Acarbose, Stachyose, etc.)]. Of these, sorbitol and sucrose are preferable from the viewpoint of processability (viscosity of the adhesive). When the viscosity of the adhesive is improved, the coatability of the adhesive is improved.
  • the polyether polyol (a) is obtained by adding ethylene oxide (hereinafter, may be referred to as EO) and / or propylene oxide (hereinafter, may be referred to as PO) to the 6 to 14 functional polyol. Obtained.
  • the method for adding EO and / or PO is not particularly limited, but a known method can be used.
  • the total number of ethylene oxide and propylene oxide additions of the polyether polyol (a) is preferably 1.0 to 2.0 per hydroxyl group, more preferably 1.0 to 2.0, from the viewpoint of processability, heat resistance and low elution. It is 1.1 to 1.8, particularly preferably 1.2 to 1.6, and most preferably 1.3 to 1.5.
  • the hydroxyl value of the polyol component (A) is preferably 300 to 900 mgKOH / g, more preferably 300 to 600 mgKOH / g, and particularly preferably 350 to 500 mgKOH, from the viewpoint of processability, heat resistance and coatability. / G.
  • the hydroxyl value is measured according to JIS K 1557-1.
  • the main agent (X) of the present invention can contain other polyol component (a1) in addition to the polyether polyol (a) as the polyol component (A).
  • the other polyol component (a1) include a low molecular weight polyol (a11) having a number average molecular weight (hereinafter abbreviated as Mn) of less than 300, a high molecular weight polyol (a12) having an Mn of 300 or more, and these and later described below.
  • examples thereof include a prepolymer (a13) having a hydroxyl group at the terminal obtained by reacting with an isocyanate (b1), (b2), (b3), (b4) and / or an isocyanate-modified product (b5). It is preferable that the prepolymer (a13) having a hydroxyl group at the terminal does not have an isocyanate group.
  • the other polyol component (a1) one type may be used alone, or two or more types may be used in combination.
  • the number average molecular weight in the present invention is measured by gel permeation chromatography using tetrahydrofuran as a solvent and polyoxypropylene glycol as a standard substance.
  • the sample concentration may be 0.25% by weight
  • the column stationary phase may be one each of TSKgel SuperH2000, TSKgel SuperH3000, and TSKgel SuperH4000 (all manufactured by Tosoh Corporation) connected, and the column temperature may be 40 ° C.
  • the low molecular weight polyol (a11) having a Mn of less than 300 also includes a polyol having a chemical formula of less than 300, specifically, a dihydric alcohol having 2 to 20 carbon atoms and a trivalent to 5 carbon atoms having 3 to 20 carbon atoms. Examples thereof include valent polyhydric alcohols and polyols having 5 to 20 carbon atoms having functional groups other than hydroxyl groups.
  • dihydric alcohol having 2 to 20 carbon atoms examples include aliphatic dihydric alcohols having 2 to 12 carbon atoms (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2,3- , 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 3-methylpentanediol, dodecanediol and other mono- or polyalkylene glycols); containing an alicyclic having 6 to 10 carbon atoms.
  • aliphatic dihydric alcohols having 2 to 12 carbon atoms ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2,3- , 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 3-methylpentanediol
  • Dihydric alcohols (1,4-cyclohexanediol, cyclohexanedimethanol, etc.); aromatic aliphatic dihydric alcohols having 8 to 20 carbon atoms [xylylene glycol, bis (hydroxyethyl) benzene, etc.] and the like can be mentioned.
  • Examples of trihydric to pentahydric polyhydric alcohols having 3 to 20 carbon atoms include (cyclo) alkane polyols and their intramolecular or intermolecular dehydrations [glycerin, trimethylolpropane, pentaerythritol, 1, 2, 6-. Hexatriol, erythritol, cyclohexanetriol, xylitol, sorbitan, diglycerin, etc.], and alkylene oxides of alkylenediamines such as N, N, N', N'-tetrakis (2-hydroxypropyl) ethylenediamine (hereinafter referred to as AO). (May be) Additives, etc. may be mentioned.
  • Examples of the polyol having a functional group other than a hydroxyl group having 5 to 20 carbon atoms include a polyol having a carboxyl group; a polyol having an amino group such as dimethylolpropionic acid and dimethylolbutanoic acid; and a polyol having 2 to 18 carbon atoms of a hydroxyalkyl group. Examples thereof include dialkanol monoamine and diethanolamine.
  • Examples of the polymer polyol (a12) having Mn of 300 or more include a polyether polyol (a121), a polyester polyol (a122), and other polyols (a123).
  • polyether polyol (a121) examples include poly (oxyalkylene) glycol [poly (oxyethylene) glycol, poly (oxypropylene) glycol, poly (oxytetramethylene) glycol, and poly (oxy-3-methyltetramethylene) glycol. Etc.], copolymerized poly (oxyalkylene) diol [EO / PO copolymerized diol, THF / EO copolymerized diol, THF / 3-methyltetrahydrofuran copolymerized diol, etc. (weight ratio is, for example, 1/9 to 9/1)].
  • AO adducts of bisphenol compounds trifunctional or higher functional polyether polyols, eg, AO adducts of trihydric or higher polyhydric alcohols [AO adducts of glycerin, AO adducts of trimethylolpropane, etc.]; and 1 of these.
  • examples include those obtained by coupling seeds or more with methylene dichloride.
  • THF means tetrahydrofuran.
  • Examples of the bisphenol compound in the above include bisphenol A, bisphenol B, bisphenol E, bisphenol F and the like, and more specifically, those described in JP-A-2008-126108.
  • the number of moles of AO added in the above is preferably 2 to 100 mol, more preferably 2 to 50 mol, and particularly preferably 2 to 30 mol from the viewpoint of adhesive strength.
  • the number of moles of the AO adduct of the bisphenol compound is preferably 2 to 10 mol, more preferably 2 to 6 mol, and particularly preferably 2 to 4 mol from the viewpoint of the cohesive force of the adhesive. When the cohesive force of the adhesive is improved, the resin strength is improved.
  • polyester polyol (a122) examples include condensed polyester polyols, polylactone polyols, castor oil-based polyols, and polycarbonate polyols.
  • the condensed polyester polyol includes a low molecular weight polyol (a11) or a polyether polyol (a121) having a Mn of less than 300, and a polycarboxylic acid or an ester-forming derivative thereof (acid anhydride, an alkyl ester having 1 to 4 carbon atoms, etc.). Examples thereof include a polycondensate with.
  • polycarboxylic acid examples include a dicarboxylic acid and a trivalent to tetravalent or higher polycarboxylic acid, and specifically, saturated or saturated with 2 to 30 or more carbon atoms (preferably 2 to 12 carbon atoms).
  • Unsaturated aliphatic polycarboxylic acid [2 to 15 carbon number dicarboxylic acid (succinic acid, succinic acid, malonic acid, adipic acid, suberic acid, azelaic acid, sebatic acid, dodecandicarboxylic acid, maleic acid, fumaric acid and itaconic acid) Etc.) and tricarboxylic acids having 6 to 20 carbon atoms (tricarbaryl acid, hexanetricarboxylic acid, etc.)]; Aromatic polycarboxylic acids having 8 to 15 carbon atoms [dicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid, and trimerits Tri or tetracarboxylic acid such as acid and pyromellitic acid]; alicyclic polycarboxylic acid having 6 to 40 carbon atoms (Dimer acid etc.); and sulfo group-containing polycarboxylic acid [Sulf group introduced into the above
  • polyether polycarboxylic acid for example, carboxymethyl ether of a polyol such as a low molecular weight polyol (a11) having a Mn of less than 300 or a polyether polyol (a121) (monochloroacetic acid in the presence of an alkali). (Etc., etc. obtained by reacting with)]; polyamide and / or polyester polycarboxylic acid [for example, lactam having 4 to 15 carbon atoms (for example, caprolactam, enantractam, laurolactam, undecanolactam, etc.) using the above polycarboxylic acid as an initiator).
  • polyether polycarboxylic acid for example, carboxymethyl ether of a polyol such as a low molecular weight polyol (a11) having a Mn of less than 300 or a polyether polyol (a121) (monochloroacetic acid in the presence of an alkali). (Etc., etc. obtained by
  • polylactam polycarboxylic acid and polylactone polycarboxylic acid obtained by ring-opening polymerization of a lactone having 4 to 15 carbon atoms ( ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, etc.)] and the like can be mentioned.
  • polylactone polyol As the polylactone polyol, ring-opening adduct of a lactone having 4 to 15 carbon atoms ( ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, etc.) starting with water or a low molecular weight polyol (a11) having Mn less than 300 is added. Things etc. can be mentioned.
  • castor oil-based polyol examples include castor oil (lithinol acid triglyceride), partially dehydrated castor oil, partially acylated castor oil, hydrogenated castor oil and modified products thereof [polyether polyol (a121) or low molecular weight Mn of less than 300.
  • Ester polyol obtained by ester exchange reaction between polyol (a11) and castor oil, partially dehydrated castor oil or hydrogenated castor oil, and polyether polyol (a121) or low molecular weight polyol (a11) having Mn less than 300 and castor oil.
  • polycarbonate polyol examples include a ring-opened addition / polycondensate of an alkylene carbonate using a low molecular weight polyol (a11) having a Mn of less than 300 as an initiator, and a weight of a low molecular weight polyol (a11) having a Mn of less than 300 and diphenyl or a dialkyl carbonate. Condensation (ester exchange) products and the like can be mentioned.
  • Examples of other polyols (a123) include polymer polyols, polyolefin polyols, polyalkaziene polyols, acrylic polyols, amino group-containing polyols and the like.
  • the polymer polyol is obtained by dispersing and stabilizing polymer particles obtained by polymerizing a vinyl monomer having 3 to 24 carbon atoms (for example, styrene or acrylonitrile) in one or more polyols in the presence of a radical polymerization initiator.
  • a vinyl monomer having 3 to 24 carbon atoms for example, styrene or acrylonitrile
  • examples thereof include polyols (polymer content is, for example, 5 to 30% by weight).
  • the polyolefin polyol include polyisobutene polyols.
  • Examples of the polyalkaziene polyol include polyisoprene polyols, polybutadiene polyols, hydrogenated polyisoprene polyols, hydrogenated polybutadiene polyols and the like.
  • acrylic polyol examples include a copolymer of an alkyl (meth) acrylic acid (alkyl having 1 to 30 carbon atoms) ester [butyl (meth) acrylate, etc.] and a hydroxyl group-containing acrylic monomer [hydroxyethyl (meth) acrylate, etc.].
  • the Mn of the polymer polyol (a12) having an Mn of 300 or more is preferably 400 to 3000, and more preferably 500 to 2000.
  • the equivalent ratio (NCO / active hydrogen molar ratio) with the active hydrogen in the polyol (a), the low molecular weight polyol (a11) having an Mn of less than 300 and / or the high molecular weight polyol (a12) having an Mn of 300 or more is preferable. 0.25 / 1 to 0.99 / 1, more preferably 0.5 / 1 to 0.95 / 1, particularly preferably 0.6 / 1 to 0.9 / 1, most preferably 0.7 / 1. It is about 0.85 / 1.
  • the other polyol components (a1) it is preferably a high molecular weight polyol (a12) having an Mn of 300 or more, more preferably a polyether polyol (a121), and particularly preferably a 2 to 4 functional polyether polyol. Most preferably, it is an AO adduct of glycerin and an AO adduct of trimethylolpropane. Examples of the AO adduct of glycerin include polyoxypropylene triol. Further, among the other polyol components (a1), a polyester polyol (a122) is also preferable, a castor oil-based polyol is more preferable, and castor oil (refined castor oil) is most preferable.
  • the content of the polyether polyol (a) of the present invention is preferably 50% by weight or more, more preferably 55% by weight or more from the viewpoint of heat resistance, coatability and odor, based on the weight of the polyol component (A). From the viewpoint of heat resistance, odor and flexibility, it is particularly preferably 60% by weight to 90% by weight.
  • the content of the polyol component (a1) other than the polyether polyol (a) is preferably 50% by weight or less, more preferably 45% by weight, based on the weight of the polyol component (A) from the viewpoint of heat resistance. It is the following, and it is particularly preferably 10% by weight to 40% by weight from the viewpoint of heat resistance and flexibility.
  • the content of the small molecule polyol (a11) having a Mn of less than 300 is preferably 20% by weight or less from the viewpoint of heat resistance and low contamination (low elution) based on the weight of the polyol component (A).
  • the curing agent (Y) in the present invention contains an isocyanate component (B).
  • the isocyanate component (B) includes an aliphatic isocyanate (b1) having 2 to 18 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter), an alicyclic isocyanate (b2) having 4 to 15 carbon atoms, and a carbon number of carbon atoms. 8 to 15 aromatic aliphatic isocyanates (b3), 6 to 20 carbon atoms aromatic isocyanates (b4), isocyanurate groups, uretoimine groups, allophanate groups, biuret groups, uretoimine groups of the isocyanates (b1) to (b4).
  • Isocyanate modified product (b5) having a carbodiimide group and / or uretdione group, and excess isocyanate (b1), (b2), (b3), (b4) and / or isocyanate modified product (b5) and Mn are less than 300.
  • Examples thereof include a prepolymer (b6) having an isocyanate group at the terminal obtained from the low molecular weight polyol (a11) and / or the high molecular weight polyol (a12) having Mn of 300 or more. It is preferable that the prepolymer (b6) having an isocyanate group at the terminal does not have a hydroxyl group.
  • the isocyanate component (B) may be used alone or in combination of two or more.
  • Examples of the aliphatic isocyanate (b1) having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4.
  • Examples of the alicyclic isocyanate (b2) having 4 to 15 carbon atoms include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis (2-). Isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- or 2,6-norbornan diisocyanate and the like can be mentioned.
  • aromatic aliphatic isocyanate (b3) having 8 to 15 carbon atoms examples include m- or p-xylylene diisocyanate (XDI), diethylbenzene diisocyanate and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate (TMXDI). Can be mentioned.
  • aromatic isocyanate (b4) having 6 to 20 carbon atoms, 1,3- or 1,4-phenylenediocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'-or 2 , 4'-diphenylmethane diisocyanate (MDI), m- or p-isocyanatophenylsulfonyl isocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3, Examples thereof include 3'-dimethyl-4,4'-diisocyanatodiphenylmethane and 1,5-naphthylene diisocyanate.
  • Examples of the isocyanate modified product (b5) having an isocyanurate group, a uretoimine group, an allophanate group, a biuret group, a uretoimine group, a carbodiimide group and / or a uretdione group include a modified product having a uretoimine group of MDI and a modification having a biuret group of HDI. Examples thereof include a modified product having an isocyanurate group of the body and HDI.
  • the prepolymer (b6) having an isocyanate group at the terminal includes a low molecular weight polyol (a11) having an Mn of less than 300 and / or a high molecular weight polyol (a12) having an Mn of 300 or more, and an excess of isocyanate (b1), (b2). , (B3), (b4) and / or the isocyanate-modified product (b5).
  • the hydroxyl group equivalent of the polyol is preferably 1,000 or less, more preferably 30 to 500, from the viewpoint of the cohesive force of the adhesive and the like.
  • the prepolymer (b6) having an isocyanate group at the terminal include a hydrogenated MDI (2 mol) adduct of glycerin mono (meth) acrylate (1 mol) and TDI (4 mol) of pentaerythritol (1 mol).
  • hydrogenated MDI (2 mol) adducts of AO2 mol adduct (1 mol) of bisphenol A and poly examples thereof include an MDI (2 mol) adduct of oxypropylene) glycol (1 mol).
  • the adhesive is aggregated.
  • aromatic aliphatic isocyanates (b3) having 8 to 15 carbon atoms aromatic isocyanates (b4) having 6 to 20 carbon atoms and their modified products are preferable, and 6 to 6 carbon atoms are more preferable. 20 aromatic isocyanates (b4).
  • the aromatic aliphatic isocyanate (b3) having 8 to 15 carbon atoms, the aromatic isocyanate (b4) having 6 to 20 carbon atoms, and the terminal are preferable.
  • a prepolymer (b6) having an isocyanate group is more preferable, and a prepolymer (b6) having an isocyanate group at the terminal is more preferable.
  • the NCO content of the entire isocyanate component (B) is 18% by weight to 30% by weight, preferably 18% by weight to 28% by weight, and more preferably 18% by weight to 26% by weight. If the NCO content of the entire isocyanate component (B) is less than 18% by weight, heat resistance and low odor are insufficient, and if it exceeds 30% by weight, the adhesive becomes brittle and easily cracked.
  • the NCO content of the entire isocyanate component (B) indicates the isocyanate group content (% by weight) measured according to JIS K 1603-1: 2007.
  • a method for adjusting the NCO content of the entire isocyanate component (B) will be described.
  • the NCO content of each of the isocyanates (b1) to (b6) in the isocyanate component (B) and the respective contents of the isocyanates (b1) to (b6) is adjusted. Can be adjusted.
  • the two-component polyurethane adhesive of the present invention can contain a catalyst used for polyurethane, if necessary, in order to promote the curing reaction.
  • a catalyst used for polyurethane include organic metal compounds [dibutyltin dilaurate, dioctyltinlaurate, bismuth carboxylate, bismuth alkoxide, chelate compounds of bismuth with compounds having a dicarbonyl group, etc.], and inorganic metal compounds [bismuth oxide, water. Bismuth oxide, bismuth halide, etc.]; Amine [triethylamine, triethylenediamine, diazabicycloundecene, etc.] and a combination of two or more thereof can be mentioned.
  • the amount of the catalyst used is not particularly limited, but is preferably 0.0001 to 0.3% by weight, more preferably 0.001 to 0.2, based on the total weight of the main agent (X) and the curing agent (Y). By weight%, particularly preferably 0.01 to 0.1% by weight.
  • the catalyst may be added to either the main agent (X) and / or the curing agent (Y), but it is preferably added to the main agent (X) from the viewpoint of storage stability.
  • the two-component polyurethane adhesive of the present invention comprises the main agent (X) and the curing agent (Y).
  • the two-component polyurethane adhesive of the present invention further contains additives such as a tackifier, an antioxidant, an ultraviolet absorber, a plasticizer, a filler, a pigment and a solvent as long as the effect of the present invention is not impaired. be able to.
  • the above-mentioned additive may be added to either the main agent (X) and / or the curing agent (Y), but it is preferable to add the additive that reacts with the isocyanate component to the main agent (X).
  • tackifier examples include terpene resin, terpene phenol resin, phenol resin, aromatic hydrocarbon-modified terpene resin, rosin resin, modified rosin resin, synthetic petroleum resin (aliphatic, aromatic or alicyclic synthetic petroleum resin, etc.). ), Kumaron-inden resin, xylene resin, styrene resin, dicyclopentadiene resin, and hydrogenated substances having an unsaturated double bond that can be hydrogenated.
  • the tackifier may be used alone or in combination of two or more.
  • those having an acid value and / or a hydroxyl value are preferable from the viewpoint of adhesive strength, and rosin resin, phenol resin, terpene phenol resin, xylene resin and their hydrogen additives are more preferable, and terpene phenol resin and its hydrogen are more preferable. Additives are particularly preferred.
  • the amount of the tackifier used is preferably 100% by weight or less, more preferably 1 to 50, based on the total weight of the main agent (X) and the curing agent (Y) from the viewpoint of the adhesive strength and heat resistance of the adhesive.
  • weight% particularly preferably 3 to 40% by weight, particularly preferably 5 to 35% by weight, most preferably 10 to 30% by weight.
  • Antioxidants include hindered phenol compounds [triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5). -Di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], etc.] and phosphite Ester compounds [Tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, bis (2,6-di-t-) Butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-b
  • antioxidants may be used alone or in combination of two or more.
  • the amount of the antioxidant used is preferably 5% by weight or less, more preferably 0.05, based on the total weight of the main agent (X) and the curing agent (Y) from the viewpoint of the antioxidant effect and the adhesive strength of the adhesive. ⁇ 1% by weight.
  • the ultraviolet absorber examples include salicylic acid derivatives (phenyl salicylate, -P-octylphenyl salicylate, -P-tertiary butylphenyl salicylate, etc.), benzophenone compounds [2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2 , 2'-Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4 -Methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadesiloxybenzophenone, 2,2 ', 4,4'-Tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzoph
  • the ultraviolet absorber one type may be used alone or two or more types may be used in combination.
  • the amount of the ultraviolet absorber used is preferably 5% by weight or less, more preferably 0.1% by weight, based on the total weight of the main agent (X) and the curing agent (Y), from the viewpoint of the ultraviolet absorbing effect and the adhesive strength of the adhesive. ⁇ 1% by weight.
  • plasticizer examples include hydrocarbons [process oil, liquid polybutadiene, liquid polyisobutylene, liquid polyisoprene, liquid paraffin, chlorinated paraffin, paraffin wax, and copolymerization of ethylene and ⁇ -olefin (3 to 20 carbon atoms) (weight ratio).
  • oligomer (weight average molecular weight Mw is 5,000 to 100,000) and ⁇ -olefin (4 to 20 carbon atoms) excluding propylene and ethylene Oligomer (weight ratio 99.9 / 0.1 to 0.1 / 99.9) oligomer (weight average molecular weight Mw is 5,000 to 100,000)]; chlorinated paraffin; ester [phthalate ester [diethylphthalate (diethylphthalate) DEP), dibutylphthalate (DBP), di-2-ethylhexylphthalate (DOP), didecylphthalate, dilaurylphthalate, distealylphthalate, diisononylphthalate, etc.], adiponic acid ester [di (2-ethylhexyl) adipate (DOA) , Dioctyl adipate, etc.] and sevatinic acid ester (di
  • the plasticizer may be used alone or in combination of two or more.
  • the amount of the plasticizer used is preferably 100% by weight or less, more preferably 0.5 to 30 from the viewpoint of the adhesive strength and cohesive strength of the adhesive, based on the total weight of the main agent (X) and the curing agent (Y). It is% by weight.
  • fillers carbonates (magnesium carbonate, calcium carbonate, etc.), sulfates (aluminum sulfate, calcium sulfate, barium sulfate, etc.), sulfites (calcium sulfite, etc.), molybdenum disulfide, silicate (aluminum silicate, etc.) Calcium silicate etc.), diatomaceous soil, silicate powder, talc, silica, zeolite and the like.
  • the filler is fine particles having a volume average particle size of preferably about 0.01 to 5 ⁇ m, and one type may be used alone or two or more types may be used in combination.
  • the amount of the filler used is preferably 250% by weight or less, more preferably 0.5 to 100% by weight, based on the total weight of the main agent (X) and the curing agent (Y) from the viewpoint of the cohesive force of the adhesive. be.
  • Pigments include inorganic pigments (alumina white, graphite, titanium oxide, ultrafine titanium oxide, zinc flower, black iron oxide, mica-like iron oxide, lead white, white carbon, molybdenum white, carbon black, litharge, lithopone, barite, etc.
  • inorganic pigments alumina white, graphite, titanium oxide, ultrafine titanium oxide, zinc flower, black iron oxide, mica-like iron oxide, lead white, white carbon, molybdenum white, carbon black, litharge, lithopone, barite, etc.
  • the pigment is fine particles having a volume average particle size of preferably about 0.01 to 5 ⁇ m, and one type may be used alone or two or more types may be used in combination.
  • the amount of the pigment used is preferably 250% by weight or less, more preferably 0.1 to 50% by weight, based on the total weight of the main agent (X) and the curing agent (Y), from the viewpoint of the cohesive force of the adhesive.
  • solvent examples include toluene, xylene, ethyl acetate, butyl acetate, dimethylformamide, acetone, methyl ethyl ketone, tetrahydrofuran and the like.
  • the adhesive obtained by curing the main agent (X) and the curing agent (Y) in the present invention has a difference in storage elastic modulus (E'-40) at ⁇ 40 ° C. and storage elastic modulus ( E'90 ) at 90 ° C. Since it is small and has little temperature dependence, its physical properties do not change over a wide range of temperatures and stable adhesive strength can be maintained.
  • the cured product obtained by curing the two-component polyurethane adhesive of the present invention has a high storage elastic modulus at -40 ° C to 90 ° C, and has excellent cold resistance and heat resistance because it has little change and is excellent in temperature dependence. Has adhesive strength.
  • the storage elastic modulus (E'90) at 90 ° C. is preferably 200 MPa to 3000 MPa, more preferably 500 MPa to 3000 MPa, and particularly preferably 1000 MPa to 2000 MPa from the viewpoint of flexibility and resin strength.
  • the storage elastic modulus is adjusted by changing the content of the polyether polyol (a) based on the weight of the polyol component (A) and the number of ethylene oxide and propylene oxide added per hydroxyl group of the polyether polyol (a). can do.
  • the ratio of the storage elastic modulus at -40 ° C to the storage elastic modulus at 90 ° C is preferably 0.9 to 10, more preferably 1.0 to 10 from the viewpoint of temperature dependence. It is 5.0, particularly preferably 1.0 to 3.0.
  • the ratio of the storage modulus at -40 ° C to the storage modulus at 90 ° C can be determined, for example, by changing the covalent bond crosslink density of the cured product of the two-component polyurethane adhesive. Can be adjusted.
  • the covalent bond cross-linking density is the number of moles at which the two-component polyurethane adhesive causes cross-linking based on the covalent bond contained in 1 g of the cured urethane resin.
  • the glass transition temperature after curing of the two-component polyurethane adhesive is the peak temperature of tan ⁇ obtained by the following viscoelasticity measuring method using the following test piece.
  • the glass transition temperature of the two-component polyurethane adhesive after curing is 100 ° C. to 150 ° C.
  • the lower limit is preferably 105 ° C., more preferably 110 ° C.
  • the upper limit is preferably 140 ° C., further preferably. Is 130 ° C.
  • the glass transition temperature of the two-component polyurethane adhesive after curing is preferably 105 ° C to 140 ° C, more preferably 110 ° C to 130 ° C.
  • the processability viscosity of the adhesive
  • the main agent (X) containing the polyol component (A) and the curing agent (Y) containing the isocyanate component (B) are uniformly mixed at 50 ° C. at a ratio such that the equivalent ratio (OH / NCO ratio) is 1. After defoaming by centrifugation, molding into a sheet having a thickness of 1 mm, curing at 50 ° C. for 3 days, and cutting into a size of 30 mm in length ⁇ 5 mm in width, a test piece is obtained.
  • ⁇ Viscoelasticity measurement> The storage elastic modulus E', loss elastic modulus E'' and tan ⁇ after curing of the two-component polyurethane adhesive are determined by the following viscoelasticity measurements.
  • ⁇ Viscoelasticity measurement method> Measuring device: Rheogel-E4000 [manufactured by UBM Co., Ltd.] Measuring jig: Pull distance between clamps: 20 mm Power meter: 1kg Static load meter: 2 kg Measurement temperature: -50 ° C to 200 ° C Temperature rise rate: 5 ° C / min Measurement frequency: 10Hz
  • a method for adjusting the glass transition temperature after curing of the two-component polyurethane adhesive will be described.
  • the glass transition temperature after curing for example, increasing the content of urethane groups and / or aromatic rings can increase the glass transition temperature, and decreasing the content of urethane groups and / or aromatic rings lowers the glass transition temperature. Can be done.
  • the content of the urethane group is the number of moles of the urethane group contained in 1 g of the urethane resin obtained by curing the two-component polyurethane adhesive.
  • the content of the aromatic ring is the weight% of the aromatic ring contained in 1 g of the urethane resin obtained by curing the two-component polyurethane adhesive.
  • the two-component polyurethane adhesive of the present invention is particularly useful for adhering adherends such as various plastic films, plastic molded products, rubber molded products, fibrous resins and fiber reinforced resins, as well as inorganic plates and metal plates. It can also be used to bond adherends such as wood and various fibers.
  • plastic film examples include polypropylene film, polyethylene film, polyester film, polyacrylic film, polyvinyl chloride film, polystyrene film, nylon film, ethylene vinyl alcohol copolymer film, polyvinyl alcohol film, fluorine film, and ethylene vinyl acetate weight.
  • plastic molded products include injection molding, extrusion molding, blow molding, and pressing of plastic resins such as ABS resin, polystyrene resin, polyester resin, acrylic resin, urethane resin, polycarbonate resin, polyvinyl chloride resin, melamine resin, and polyolefin resin.
  • plastic resins such as ABS resin, polystyrene resin, polyester resin, acrylic resin, urethane resin, polycarbonate resin, polyvinyl chloride resin, melamine resin, and polyolefin resin.
  • plastic resins such as ABS resin, polystyrene resin, polyester resin, acrylic resin, urethane resin, polycarbonate resin, polyvinyl chloride resin, melamine resin, and polyo
  • Examples of the inorganic board include a slate board, a calcium silicate board, a gypsum board, a wood wool cement board and a foamed concrete board.
  • Examples of the metal plate include a stainless steel plate, a galvanized steel plate, a chemical conversion-treated steel plate, and an aluminum plate.
  • the equivalent ratio (OH / NCO ratio) of the two-component polyurethane adhesive composed of the main agent (X) and the curing agent (Y) for forming the two-component polyurethane adhesive of the present invention is preferable from the viewpoint of heat resistance. Is 0.5 / 1 to 2/1, more preferably 0.7 / 1 to 1.5 / 1, and particularly preferably 0.8 / 1 to 1.2 / 1.
  • the equivalent ratio (OH / NCO ratio) in the present invention can be obtained by the following formula 1. (Hydroxy group value of (X) x weight of (X) / 56100) / (NCO content of (Y) x weight of (Y) / 4200) ... (Equation 1)
  • the content of the polyether polyol (a) contained in the two-component polyurethane adhesive of the present invention is preferably 20 to 60 based on the weight of the two-component polyurethane adhesive from the viewpoint of heat resistance, odor and flexibility. It is% by weight, more preferably 25 to 55% by weight, and particularly preferably 30 to 50% by weight.
  • the content of the polyol component (A) contained in the two-component polyurethane adhesive of the present invention is preferably 25 to 55 weight based on the weight of the two-component polyurethane adhesive from the viewpoint of heat resistance, odor and flexibility. %, More preferably 30 to 50% by weight.
  • the content of the isocyanate component (B) contained in the two-component polyurethane adhesive of the present invention is preferably 45 to 70% by weight based on the weight of the two-component polyurethane adhesive from the viewpoint of heat resistance and odor. Yes, more preferably 50-70% by weight.
  • each component for forming a polyurethane resin can be weighed in a predetermined amount and then mixed with a static mixer, a mechanical mixer, or the like to react to form the polyurethane resin.
  • the gelation time is preferably 3 to 60 minutes, and complete curing takes 1 to 240 hours at room temperature.
  • the point at which the hardness does not change is defined as complete curing (reaction end point). It is also possible to shorten the time until complete curing by raising the curing temperature (for example, 30 ° C to 60 ° C).
  • the D hardness (ASTM D2240; maximum value) of the cured resin obtained by reacting each component for forming the polyurethane resin is preferably 50 to 90, more preferably 50 to 90, from the viewpoint of adhesiveness, resin strength, toughness and flexibility. It is 60 to 85, most preferably 70 to 83.
  • the viscosity (25 ° C.) of the mixture composed of the main agent (X) and the curing agent (Y) is preferably 100 to 50,000 mPa ⁇ s, more preferably 500 to 10,000 mPa ⁇ s, particularly from the viewpoint of coatability. It is preferably 1,000 to 8,000 mPa ⁇ s.
  • the viscosity in the present invention is measured with a B-type rotational viscometer.
  • the NCO content in the mixed solution immediately after mixing the main agent (X) and the curing agent (Y) calculated by the formula 2 shown below is the total of the main agent (X) and the curing agent (Y) from the viewpoint of curability. Based on the weight, it is preferably 2% by weight to 16% by weight, more preferably 5% by weight to 15% by weight, and most preferably 8% by weight to 14% by weight. NCO content of (Y) ⁇ weight of (Y) / (weight of (X) + weight of (Y)) ... (Equation 2)
  • the adherend of the present invention is an adherend bonded with a two-component polyurethane adhesive.
  • the adherend include a plastic film and a plastic molded product, and it is preferable to perform surface treatment such as corona treatment and plasma treatment from the viewpoint of adhesiveness.
  • surface treatment such as corona treatment and plasma treatment from the viewpoint of adhesiveness.
  • the method for producing the adherend a known production method is used.
  • a method for producing a cured product of a two-component polyurethane adhesive a known method for producing a cured product of a two-component polyurethane adhesive can be used.
  • a solvent toluene, xylene, ethyl acetate, butyl acetate, dimethylformamide, acetone
  • a method of reacting a main agent (X) containing a polyol component with a curing agent (Y) containing an isocyanate component can be mentioned.
  • a known reaction device (mixing tank equipped with a stirrer, static mixer, etc.) can be used for the reaction, and the reaction temperature is preferably 10 to 160 ° C., more preferably 25 to 160 ° C. from the viewpoint of reactivity and suppression of thermal deterioration.
  • the temperature is 120 ° C., and it is preferable to replace the gas phase portion with nitrogen from the viewpoint of stability.
  • ⁇ Manufacturing example 1> A stainless steel autoclave equipped with a stirrer, a temperature control device, a heat exchanger as a condensation facility, a raw material supply line and an exhaust line is charged with 385 parts by weight of sorbitol (six-functional) and 3 parts by weight of potassium hydroxide, and then stirred. Was started, and the pressure inside the autoclave and the condensing facility was reduced to 0.005 MPa. Through the raw material supply line, 735 parts by weight of PO was charged while controlling the reaction temperature to be maintained at 90 to 100 ° C. However, the PO was continuously added over 6 hours. A refrigerant at -30 ° C was circulated to condense and recover PO in the condensing facility.
  • ⁇ Manufacturing example 5> Synthesized in the same manner as in Production Example 1 except that 385 parts by weight of sorbitol (6-functional) was changed to 723 parts by weight of sucrose (8-functional) and the amount of PO input was changed from 735 parts by weight to 1465 parts by weight. a-5) was obtained. The hydroxyl value of (a-5) was 432 mgKOH / g, and the number of moles of PO added per hydroxyl group was 1.5.
  • the modified 4,4'-MDI "Lupranate MM103" was changed from 180 parts by weight to 200 parts by weight, and 240 parts by weight of the refined castor oil "ELA-DR" was made into polypropylene glycol (bifunctional) [manufactured by Sanyo Kasei Kogyo Co., Ltd .; " Sannicks PP-1000 "]
  • the isocyanate component (B-3) composed of an NCO group-terminated urethane prepolymer was obtained by synthesizing in the same manner as in Production Example 7 except that the amount was changed to 400 parts by weight.
  • the NCO content of (B-3) was 16% by weight.
  • Examples 1 to 11 and Comparative Examples 1 to 6 As the polyol component (A), a main agent (X) containing a polyether polyol (a-1) to (a-6) and other polyols (a1-1) to (a1-3) described later, and an isocyanate component ( B-1) to (B-3) and a curing agent (Y) containing an isocyanate component (B-4) described later were mixed at the weight ratios shown in Tables 1 and 2, and Examples 1 to 11 were used. And the two-component polyurethane adhesives of Comparative Examples 1 to 6 were obtained.
  • ⁇ Storage modulus> A two-component polyurethane adhesive composed of a main agent (X) containing a polyol component (A) and a curing agent (Y) containing an isocyanate component (B) at 50 ° C. by weight ratio shown in Tables 1 and 2.
  • the mixture was uniformly mixed, centrifugally defoamed, molded into a sheet having a thickness of 1 mm, cured at 50 ° C. for 3 days, and then cut into a size of 30 mm in length ⁇ 5 mm in width to obtain a test piece.
  • -Measuring method In the above-mentioned viscoelasticity measurement, the storage elastic modulus E'at -40 ° C, 25 ° C, 70 ° C and 90 ° C was recorded.
  • a two-component polyurethane adhesive composed of a main agent (X) containing a polyol component (A) and a curing agent (Y) containing an isocyanate component (B) was prepared at 50 ° C. by weight ratios shown in Tables 1 and 2.
  • the viscoelasticity was measured in the same manner as the above viscoelasticity measurement except that the mixture was uniformly mixed, defoamed under reduced pressure, molded into a sheet having a thickness of 1 mm, and cured at 50 ° C. for 3 days.
  • the peak temperature of tan ⁇ (loss elastic modulus / stored elastic modulus ratio) in the range of was determined.
  • the peak temperature of tan ⁇ was defined as the glass transition temperature.
  • a two-component polyurethane adhesive composed of a main agent (X) containing a polyol component (A) and a curing agent (Y) containing an isocyanate component (B) at 50 ° C. in the weight ratios shown in Tables 1 and 2.
  • the mixture was uniformly mixed and defoamed by centrifugation. Twenty minutes after the start of uniform mixing, 0.5 g of an adhesive was applied to one end of a 25 mm ⁇ 100 mm steel sheet, and the steel sheet was placed vertically so that the applied end was on the upper side and allowed to stand. The time from vertical installation until the adhesive drips from the bottom of the steel sheet was recorded, and the coatability was judged according to the following criteria. ⁇ : 10 minutes or more, ⁇ : 7 minutes or more, ⁇ : 3 minutes or more and less than 7 minutes, ⁇ : less than 3 minutes
  • ⁇ D hardness (flexibility and toughness)> A two-component polyurethane adhesive composed of a main agent (X) containing a polyol component (A) and a curing agent (Y) containing an isocyanate component (B) at 50 ° C. in the weight ratios shown in Tables 1 and 2.
  • X main agent
  • Y curing agent
  • B isocyanate component
  • Tables 1 and 2 Uniformly mix, defoam under reduced pressure, weigh 30 g of the mixed solution in a polypropylene cup, cure at 50 ° C for 1 day, remove from the cup, adjust the temperature at 25 ° C for 2 hours, and then polymer meter Co., Ltd.
  • the D hardness (Shore D: instantaneous value) was measured using a Shore D hardness meter manufactured by the same manufacturer. The measurement was performed at 5 points, and the average value was calculated. The instantaneous value is the value immediately after the needle of the hardness tester is pressed against the resin. When the
  • a two-component polyurethane adhesive composed of a main agent (X) containing a polyol component (A) and a curing agent (Y) containing an isocyanate component (B) at 50 ° C. in the weight ratios shown in Tables 1 and 2.
  • X main agent
  • Y curing agent
  • B isocyanate component
  • the adhesive part of the adherend was bonded and fixed with a jig, and the test piece obtained by curing at 50 ° C for 3 days was subjected to shear adhesion strength at 100 ° C and a tensile speed of 100 mm / min using a tensile tester. (Unit: MPa) was measured, and the adhesive strength was judged according to the following criteria. ⁇ : 3 MPa or more, ⁇ : 1.5 MPa or more and less than 3 MPa, ⁇ : 0.5 MPa or more and less than 1.5 MPa, ⁇ : less than 0.5 MPa
  • a two-component polyurethane adhesive composed of a main agent (X) containing a polyol component (A) and a curing agent (Y) containing an isocyanate component (B) at 50 ° C. at the weight ratios shown in Tables 1 and 2.
  • a dumbbell-shaped No. 3 test piece was prepared and used at 23 ° C. using a tensile tester.
  • the breaking strength (unit: MPa) was measured under the condition of a tensile speed of 100 mm / min in an environment of 50% RH. The measurement was performed on 5 test pieces, and the average value was evaluated.
  • a two-component polyurethane adhesive composed of a main agent (X) containing a polyol component (A) and a curing agent (Y) containing an isocyanate component (B) at 50 ° C. in the weight ratios shown in Tables 1 and 2.
  • a two-component polyurethane adhesive composed of a main agent (X) containing a polyol component (A) and a curing agent (Y) containing an isocyanate component (B) at 50 ° C. in the weight ratios shown in Tables 1 and 2.
  • the mixture is uniformly mixed, defoamed under reduced pressure, molded into a sheet having a thickness of 1 cm, cured at 25 ° C. for 48 hours, then 10 g of the obtained cured resin is cut out, sealed in a glass bottle with a lid, and sealed at 60 ° C. for 1 hour.
  • the odor was judged according to the following criteria.
  • ⁇ Slightly peculiar odor
  • ⁇ No peculiar odor.
  • the low odor suggests that the content of the low boiling point component contained in the cured product is low.
  • a two-component polyurethane adhesive composed of a main agent (X) containing a polyol component (A) and a curing agent (Y) containing an isocyanate component (B) at 50 ° C. in the weight ratios shown in Tables 1 and 2.
  • the mixture was uniformly mixed, defoamed under reduced pressure, molded into a sheet having a thickness of 1 cm, and cured at 25 ° C. for 72 hours.
  • About 10 g of a cured resin sample cut into 1 cm squares was placed in a polycup, 100 g of acetone was added, and the mixture was allowed to stand at 40 ° C. for 6 hours.
  • the two-component polyurethane adhesive of the present invention has a small change in elastic modulus from ⁇ 40 ° C. to 90 ° C., good adhesive strength at 100 ° C., and excellent heat resistance. .. Further, since the durability is excellent and the D hardness is in an appropriate range of 50 to 90, it is found that the flexibility and toughness are excellent, and the adhesive strength and the strength of the cured resin can be compatible with each other. Further, the two-component polyurethane adhesive of the present invention is excellent in coatability. Furthermore, since the cured resin has a small odor and the amount of elution is small, it has little effect on the human body and is excellent in safety.
  • the two-component polyurethane adhesive of the present invention is excellent in safety and low stain resistance, has good resin strength, heat resistance and durability, has little odor, and has little elution of low molecular weight substances into the treatment liquid. Therefore, it is particularly useful for applications that come into contact with living organisms and applications related to foods and beverages (medical instruments, water purification applications).
  • the cured resin obtained from the adhesive has excellent electrical insulation, water resistance, and adhesiveness to various substrates, it is used for electrical insulation such as sealing of electronic circuit boards, and water stoppage such as sealing of optical fiber cable connections.
  • applications such as bonding of heat insulating aluminum sashes and bonding of aluminum honeycomb panels, bonding of parts that are exposed to heat around automobile engines and brakes, various films that require heat resistance, and bonding of parts. Can also be suitably used.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

Le but de la présente invention est de fournir un adhésif de polyuréthane à deux composants ayant une sécurité exceptionnelle et une excellente résistance à la résine, une excellente résistance à la chaleur, une excellente durabilité et d'excellentes propriétés de revêtement. La présente invention concerne, entre autres, un adhésif de polyuréthane à deux composants formé à partir : d'un agent principal (X) contenant un composant polyol (A) ayant, en tant que composant essentiel, un polyol de polyéther (a) dans lequel de l'oxyde d'éthylène et/ou de l'oxyde de propylène est ajouté à un polyol à fonctionnalité 6 à 14 ; et d'un agent de durcissement (Y) contenant un composant isocyanate (B), la teneur en NCO de l'ensemble du composant isocyanate (B) étant de 18 à 30 % en poids, et la température de transition vitreuse de l'adhésif de polyuréthane à deux composants après durcissement étant de 100 à 150 °C.
PCT/JP2021/042657 2020-12-01 2021-11-19 Adhésif de polyuréthane à deux composants et support d'adhérence WO2022118684A1 (fr)

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JPH05311146A (ja) * 1990-12-27 1993-11-22 Dainichiseika Color & Chem Mfg Co Ltd 接着剤組成物
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JP2015004052A (ja) * 2013-05-24 2015-01-08 三洋化成工業株式会社 ２液硬化型接着性皮膜形成用組成物
WO2018025702A1 (fr) * 2016-08-02 2018-02-08 横浜ゴム株式会社 Composition adhésive d'uréthane durcissable de type à deux constituants
JP2018204000A (ja) * 2017-06-02 2018-12-27 三洋化成工業株式会社 ２液硬化型ウレタン粘着剤用主剤及び２液硬化型ウレタン粘着剤
JP2019104901A (ja) * 2017-12-12 2019-06-27 三洋化成工業株式会社 ２液硬化型ウレタン粘着剤用主剤及び２液硬化型ウレタン粘着剤
WO2019173058A1 (fr) * 2018-03-07 2019-09-12 Dow Global Technologies Llc Composition adhésive
CN111019588A (zh) * 2019-12-25 2020-04-17 湖北回天新材料股份有限公司 一种耐热性好、且与油墨相溶性好的复膜用聚氨酯胶黏剂
WO2020121993A1 (fr) * 2018-12-11 2020-06-18 三洋化成工業株式会社 Adhésif uréthane durcissable à deux composants
WO2020127439A1 (fr) * 2018-12-20 2020-06-25 Sika Technology Ag Composition de polyuréthane à deux composants

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02206612A (ja) * 1988-12-09 1990-08-16 Mitsubishi Kasei Corp ウレタンプレポリマーの製造法
JPH05311146A (ja) * 1990-12-27 1993-11-22 Dainichiseika Color & Chem Mfg Co Ltd 接着剤組成物
JP2011190309A (ja) * 2010-03-12 2011-09-29 Dic Corp 湿気硬化型ポリウレタンホットメルト接着剤、及びそれを用いて得られる化粧造作部材
JP2015004052A (ja) * 2013-05-24 2015-01-08 三洋化成工業株式会社 ２液硬化型接着性皮膜形成用組成物
WO2018025702A1 (fr) * 2016-08-02 2018-02-08 横浜ゴム株式会社 Composition adhésive d'uréthane durcissable de type à deux constituants
JP2018204000A (ja) * 2017-06-02 2018-12-27 三洋化成工業株式会社 ２液硬化型ウレタン粘着剤用主剤及び２液硬化型ウレタン粘着剤
JP2019104901A (ja) * 2017-12-12 2019-06-27 三洋化成工業株式会社 ２液硬化型ウレタン粘着剤用主剤及び２液硬化型ウレタン粘着剤
WO2019173058A1 (fr) * 2018-03-07 2019-09-12 Dow Global Technologies Llc Composition adhésive
WO2020121993A1 (fr) * 2018-12-11 2020-06-18 三洋化成工業株式会社 Adhésif uréthane durcissable à deux composants
WO2020127439A1 (fr) * 2018-12-20 2020-06-25 Sika Technology Ag Composition de polyuréthane à deux composants
CN111019588A (zh) * 2019-12-25 2020-04-17 湖北回天新材料股份有限公司 一种耐热性好、且与油墨相溶性好的复膜用聚氨酯胶黏剂

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