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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
• • 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 hot melt adhesive containing a thermoplastic urethane resin.
• thermoplastic resin Since the resin strength of a thermoplastic resin usually decreases with an increase in temperature, heat resistance may be a problem when used. From the viewpoint of product quality stability using a thermoplastic resin, a thermoplastic resin having a small temperature dependency in a wide temperature range is desired. In addition, a thermoplastic resin having sharp melt properties (fluidity immediately appears when the melting point is exceeded) is desired for ease of handling when used.
• An object of the present invention is to provide a hot melt adhesive that is less temperature dependent, exhibits fluidity as soon as the melting point is exceeded, and has excellent tensile strength at break.
• the present invention relates to a polyol (A) having an aromatic ring, a diisocyanate (B) having symmetry, a polymethylene glycol (C1) represented by the general formula (1) and / or a polyethylene represented by the general formula (2).
• It is a hot melt adhesive containing a thermoplastic urethane resin (F) whose essential constituent monomer is glycol (C), which is glycol (C2), and polymer polyol (D).
• N is an integer of 2 to 8.
• M is an integer of 2 to 8. ]
• thermoplastic urethane resin contained in the hot melt adhesive of the present invention has little temperature dependence, so it has excellent product quality stability and stable adhesive strength when used as a hot melt adhesive. To do. Further, since it has sharp melt properties (fluidity appears relatively soon when the melting point is exceeded), it is easy to handle. Furthermore, the tensile strength at break is also excellent.
• J bisphenol compound selected from the group consisting of bisphenol A, bisphenol B, bisphenol E and bisphenol F, dihydroxybenzene Ethylene oxide adduct, dihydroxybiphenyl ethylene oxide adduct, bis (hydroxymethyl) benzene, ethylene oxide adduct of the compound, bis (hydroxymethyl) biphenyl, ethylene oxide adduct of the compound, ethylene oxide addition of phthalic acid And a mixture of two or more thereof.
• the average addition mole number of EO of the ethylene oxide (hereinafter referred to as EO) adduct is preferably 0.90 to 1.10, more preferably 0.91 to 1.09, and still more preferably 0.8. 92 to 1.08. If the EO average addition mole number of the EO adduct is 0.90 or more per hydroxyl group, the adhesive strength is improved, and if it is 1.10 or less, the tensile strength at break is improved.
• an ethylene oxide adduct (A1) of at least one bisphenol compound selected from the group consisting of bisphenol A, bisphenol B, bisphenol E and bisphenol F is preferred, and an ethylene oxide adduct (A1), there is further provided an ethylene oxide adduct (A11) having an average ethylene oxide addition mole number of 0.90 to 1.10 per hydroxyl group and a monodispersity of 80% or more represented by the following formula (1): preferable.
• Monodispersity (%) ⁇ [weight of ethylene oxide adduct (A1) having 1 mol of ethylene oxide added per hydroxyl group] / [weight of ethylene oxide adduct (A)] ⁇ ⁇ 100 (1)
• ethylene oxide adducts (A1) an ethylene oxide adduct having an average ethylene oxide addition mole number of 0.90 to 1.10 per hydroxyl group and a monodispersity of 80% or more represented by the above formula (1)
• the adhesive force can be particularly increased, and the tensile strength at break can also be increased.
• bisphenol A is particularly preferable.
• Bisphenol B is 2,2-bis (p-hydroxyphenyl) butane
• phenol E is 1,1-bis (p-hydroxyphenyl) ethane
• bisphenol F is bis (p-hydroxyphenyl) methane. It is.
• the monodispersity of (A11) represented by the above formula (1) is 80% or more, preferably 85% or more, and more preferably 90% or more. If the monodispersity of (A11) is less than 80%, the tensile strength at break is lowered, the temperature dependency is increased, and the adhesive force at high temperature is lowered.
• the monodispersity and EO average addition mole number can be confirmed by gas chromatography (GC) after pretreatment with a silylating agent.
• the measurement conditions are as follows. ⁇ Preparation method of sample> A 1 g sample is taken and then 19 g acetone is added and dissolved. To this sample, 0.1 ml of TMS-H1 (Trimethylchlorosilane silylating agent, manufactured by Tokyo Chemical Industry Co., Ltd.) is added and heated to 50 to 70 ° C. for 2 to 3 minutes to complete the silylation. 1 ⁇ l of this supernatant is sampled and measured with a gas chromatograph.
• TMS-H1 Trimethylchlorosilane silylating agent, manufactured by Tokyo Chemical Industry Co., Ltd.
• diisocyanate (B) having symmetry in the present invention polymethylene diisocyanate (B1) [for example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, etc.]
• polymethylene diisocyanate (B1) is preferable from the viewpoint of crystallinity, and more preferable is polymethylene diisocyanate having an even number of 6 to 10 carbon atoms (excluding carbon in the isocyanate group). .
• Glycol (C) is glycol (C) which is polymethylene glycol (C1) represented by general formula (1) and / or polyethylene glycol (C2) represented by general formula (2), from the viewpoint of crystallinity.
• the polymethylene glycol (C1) and polyethylene glycol (C2) contained in the glycol (C) preferably have an even number of carbon atoms.
• Examples of the polymethylene glycol (C1) in the present invention include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol and the like.
• Examples of the polyethylene glycol (C2) having 2 to 8 repeats include diethylene glycol, triethylene glycol, hexaethylene glycol and the like.
• (C1) is preferable, more preferable is polymethylene glycol having an even number of 4 to 8 carbon atoms, and particularly preferable is 6 to 6 carbon atoms. Polymethylene glycol having an even number of 8.
• thermoplastic urethane resin (F) in the present invention a combination of polymethylene diisocyanate (B1) and polymethylene glycol (C1) is preferable, and the number of carbon atoms excluding carbon in the isocyanate group of (B1). And (C1) preferably have the same number of carbon atoms from the viewpoint of crystallinity.
• B1 polymethylene diisocyanate
• C1 polymethylene glycol
• polymer polyol (D) examples include polyether polyol (D1), polyester polyol (D2), and other polyols (D3).
• Mn number average molecular weight of the polymer polyol (D) is preferably 400 to 10,000, and more preferably 1000 to 5,000.
• polyether polyol (D1) examples include polyalkylene glycol [polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol, poly-3-methyltetramethylene ether glycol, etc.], copolymer polyoxyalkylene diol [EO / PO copolymerization]. Diol, THF / EO copolymerized diol, THF / 3-methyltetrahydrofuran copolymer diol, etc.
• AO adduct of bisphenol compound examples thereof include AO adducts of trihydric or higher polyhydric alcohols [AO adducts of glycerin and AO adducts of trimethylolpropane]; and those obtained by coupling one or more of these with methylene dichloride.
• polyester polyol (D2) examples include condensed polyester polyols, polylactone polyols, castor oil-based polyols, and polycarbonate polyols.
• Condensed polyester polyols are a combination of a low molecular weight polyol or polyether polyol (D1) having an Mn of less than 300 and a polycarboxylic acid or an ester-forming derivative thereof (such as an acid anhydride and an alkyl ester having 1 to 4 carbon atoms). Examples include condensates.
• polycarboxylic acid examples include dicarboxylic acids and trivalent to tetravalent or higher polycarboxylic acids, and specifically, saturated or saturated with 2 to 30 or more carbon atoms (preferably 2 to 12 carbon atoms).
• Unsaturated aliphatic polycarboxylic acids [dicarboxylic acids having 2 to 15 carbon atoms (oxalic acid, succinic acid, malonic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid and itacone Acid) and tricarboxylic acids having 6 to 20 carbon atoms (tricarballylic acid and hexanetricarboxylic acid)]; aromatic polycarboxylic acids having 8 to 15 carbon atoms [dicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid, and trimellit Tri- or tetracarboxylic acid such as acid and
• a polyether polycarboxylic acid for example, a low molecular weight polyol having an Mn of less than 300 or a carboxymethyl ether of a polyol such as a polyether polyol (D1) (obtained by reacting monochloroacetic acid in the presence of alkali)
• Polyamides and / or polyester polycarboxylic acids for example, lactams having 4 to 15 carbon atoms (such as caprolactam, enantolactam, laurolactam, undecanolactam, etc.) or carbon atoms having 4 to 15 carbon atoms using the above polycarboxylic acid as an initiator
• Polylactam polycarboxylic acids and polylactone polycarboxylic acids obtained by ring-opening polymerization of lactones ( ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, etc.).
• polylactone polyol examples include ring-opening adducts of lactones having 4 to 15 carbon atoms ( ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, etc.) that are initiated by water or a low molecular weight polyol having an Mn of less than 300. Can be mentioned.
• Castor oil-based polyols include castor oil (ricinoleic acid triglyceride), partially dehydrated castor oil, partially acylated castor oil, hydrogenated castor oil, and modified products thereof [polyether polyol (D1) or low molecular weight Mn of less than 300 Ester polyol obtained by transesterification reaction between polyol and castor oil, partially dehydrated castor oil or hydrogenated castor oil, and polyether polyol (D1) or low molecular polyol having Mn of less than 300 and castor oil fatty acid or hydrogenated castor oil Ester obtained by esterification reaction with fatty acid, etc.].
• polyether polyol (D1) or low molecular weight Mn of less than 300 Ester polyol obtained by transesterification reaction between polyol and castor oil, partially dehydrated castor oil or hydrogenated castor oil, and polyether polyol (D1) or low molecular polyol having Mn of less than 300 and castor oil fatty acid or hydrogenated castor
• Polycarbonate polyols include ring-opening addition / polycondensation products of alkylene carbonates whose initiator is a low molecular weight polyol having an Mn of less than 300, and polycondensation (transesterification) of a low molecular weight polyol having an Mn of less than 300 and diphenyl or dialkyl carbonate. Thing etc. are mentioned.
• polyols (D3) include polymer polyols, polyolefin polyols, polyalkadiene polyols and acrylic polyols.
• 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 include polyols (polymer content is, for example, 5 to 30% by weight).
• polyolefin polyol examples include polyisobutene polyol.
• polyalkadiene polyol examples include polyisoprene polyol, polybutadiene polyol, hydrogenated polyisoprene polyol, and hydrogenated polybutadiene polyol.
• acrylic polyol examples include a copolymer of an alkyl (meth) acrylate (alkyl 1 to 30 carbon atoms) ester [butyl (meth) acrylate, etc.] and a hydroxyl group-containing acrylic monomer [hydroxyethyl (meth) acrylate, etc.]. Can be mentioned.
• Mn means the number average molecular weight measured by gel permeation chromatography.
• the number average molecular weight is measured by gel permeation chromatography using N, N-dimethylformamide as a solvent and polystyrene as a standard substance.
• the sample concentration may be 0.125% by weight
• the column stationary phase may be TSKgel Guardcolumn ⁇ , TSKgel ⁇ -M (both manufactured by Tosoh Corporation), and the column temperature may be 40 ° C.
• polytetramethylene ether glycol is preferred.
• Polypropylene glycol in which 40 mol% or more, preferably 70 mol% or more of the hydroxypropyl groups located at the terminals is a group (primary OH group) represented by the following chemical formula (3) is preferable. —CH (CH 3 ) —CH 2 —OH (3)
• the weight ratio of the polyol (A) having an aromatic ring, which is an essential constituent monomer of the thermoplastic urethane resin (F), the diisocyanate (B) having symmetry, the glycol (C), and the polymer polyol (D) is ( (A) is preferably 5 to 20% by weight, more preferably 10 to 20% by weight, and (B) is preferably based on the total weight of A), (B), (C) and (D). 15 to 30% by weight, more preferably 20 to 30% by weight, (C) is preferably 1 to 15% by weight, more preferably 3 to 15% by weight, and (D) is preferably 40 to 60% by weight. %, More preferably 45 to 60% by weight.
• the urea group content of the thermoplastic urethane resin (F) is preferably 0.06 mmol / g or less, more preferably 0.03 mmol / g or less, still more preferably 0.02 mmol / g or less from the viewpoint of sharp melt properties. is there.
• thermoplastic urethane resin (F) As a production method of thermoplastic urethane resin (F), for example, polyol (A) having an aromatic ring, glycol (C), and polymer polyol (D) are uniformly mixed. Then, a method of reacting diisocyanate (B) having symmetry is exemplified.
• the water content contained in the mixture of polyol (A), glycol (C) and polymer polyol (D) having an aromatic ring which is an essential constituent monomer of the thermoplastic urethane resin (F) is (A), ( It is preferably 0.00 to 0.10% by weight, more preferably 0.00 to 0.03% by weight based on the total weight of C) and (D).
• a urethanization catalyst may be used.
• Various catalysts can be used as urethanization catalysts such as metal catalysts [tin catalysts [trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate].
• Etc. lead catalysts [lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.], other metal catalysts [metal salts of naphthenate (cobalt naphthenate, etc.), phenylmercuric propionate, etc.] Etc.]; amine catalyst ⁇ triethylenediamine, tetramethylethylenediamine, diazabicycloalkene [1,8-diazabicyclo [5,4,0] undecene-7 [DBU (manufactured by San Apro Co., Ltd., registered trademark)]], etc., dialkyl (C1-3) Aminoalkyl (C2-4) Min [dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, etc.], heterocyclic aminoalkyl (2 to 6 carbon atoms) amine [2- (1
• the hot melt adhesive of the present invention contains a thermoplastic urethane resin (F), but according to various purposes and applications, other resin additives (E) can be arbitrarily added within a range not inhibiting the effects of the present invention. It can be included.
• F thermoplastic urethane resin
• E resin additives
• Additives for resins (E) include tackifiers, antioxidants, UV absorbers, light stabilizers, plasticizers, adsorbents, colorants, fillers, nucleating agents, lubricants, mold release agents, water, Examples include at least one additive selected from the group consisting of a flame retardant and a fragrance.
• 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. ), Coumarone-indene resins, xylene resins, styrene resins, dicyclopentadiene resins, and hydrogenated products of these having hydrogenated unsaturated double bonds.
• Antioxidants include hindered phenol compounds [pentaerystyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t. -Butyl-4-hydroxyphenyl) propionate etc.], phosphorus compound [tris (2,4-di-t-butylphenyl) phosphite etc.], sulfur compound [pentaerythryl-tetrakis (3-laurylthiopropionate) , Dilauryl-3,3′-thiodipropionate, etc.].
• ultraviolet absorbers examples include benzotriazole compounds [2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, etc.] and the like. It is done.
• Examples of the light stabilizer include hindered amine compounds [(bis-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like] and the like.
• Plasticizers include various plasticizers [for example, adhesive technology Vol. 20, (2), 21 (2000), etc.], process oil (paraffin, naphthene or aromatic compound type); liquid resin (Mn 300 to 6,000, for example, liquid polybutene, liquid polybutadiene, liquid Polyisoprene); hydrogenated product of the liquid resin; low molecular weight (Mn 300 to 10,000) polyisobutylene; and mixtures of two or more thereof.
• adsorbent examples include alumina, silica gel, molecular sieve and the like.
• colorant examples include pigments (titanium oxide, carbon black, etc.), dyes (azo, anthraquinone, indigoid, alizarin, acridine, nitroso, aniline dyes, etc.) and the like.
• fillers include talc, mica and calcium carbonate.
• nucleating agent examples include sorbitol, phosphate metal salt, benzoic acid metal salt, and phosphate metal salt.
• lubricant examples include calcium stearate, butyl stearate, oleic acid amide and the like.
• release agent examples include carboxyl-modified silicone oil and hydroxyl-modified silicone oil.
• the flame retardant examples include a halogen-containing flame retardant, a phosphorus-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide-containing flame retardant.
• Perfumes include diterpenes and limonene.
• the total content of the resin additive (E) is preferably 40% by weight or less based on the total weight of the thermoplastic urethane resin (F), and more preferably 0.002 from the viewpoint of the addition effect and adhesiveness. -30% by weight, more preferably 0.1-10% by weight.
• the hot melt adhesive of the present invention has a melting point of preferably 80 ° C. to 150 ° C., more preferably 90 ° C. to 120 ° C., from the viewpoints of temperature dependency and coating properties.
• the hot melt adhesive of the present invention preferably has a low temperature dependency of storage elastic modulus (hereinafter abbreviated as G ′) from the viewpoint of quality stability such as adhesive strength.
• G ′ storage elastic modulus
• the hot melt adhesive of the present invention is excellent in adhesive strength stability. This can be evaluated by the temperature dependence of the storage elastic modulus (G ′). Specifically, it is preferable that the temperature change rate of G ′ represented by the following formula (3) is 100 or less because the temperature dependency is low, and the temperature change rate of G ′ represented by the following formula (4) is 10 or less. More preferably.
• the method for producing the hot melt adhesive of the present invention is not particularly limited, but the components of the hot melt adhesive of the present invention are heated and melted and mixed; and the components of the hot melt adhesive of the present invention are mixed with an organic solvent.
• a method of distilling off the solvent after heating and melting together with (toluene, xylene, etc.) and uniformly mixing can be applied. Of these, the former method is industrially preferred.
• Production Example 4 Synthesis of bisphenol A EO adduct (A-4)
• the amount of EO reacted dropwise in Production Example 1 was 124.8 g (2.84 mol) and the reaction was terminated when 1 mol adduct was 0.1% or less. Reacted.
• the catalyst was neutralized with phosphoric acid, and unreacted EO was distilled off under reduced pressure at 130 to 160 ° C. to obtain an EO product (A-4) of bisphenol A.
• this (A-4) was analyzed by GC, the average added mole number of EO per hydroxyl group of the obtained (A-4) was 0.91, and the monodispersity was 88.3%.
• Production Example 7 Synthesis of bisphenol E EO adduct (A-7)
• the reaction was conducted in the same manner as in Production Example 1 except that bisphenol A used in Production Example 1 was replaced with 321.4 g (1.50 mol) of bisphenol E (“Bisphenol E” manufactured by Honshu Chemical Industry Co., Ltd.). The reaction was terminated when the 1 mol adduct was 0.1% or less. The required EO was 150.6 g (3.42 mol), and the reaction time was 7 hours. After the reaction, unreacted EO, catalyst, solvent and the like were distilled off at 130 to 160 ° C. under reduced pressure to obtain an EO adduct (A-7) of bisphenol E. When this (A-7) was analyzed by GC, the average added mole number of EO per hydroxyl group of the obtained (A-7) was 1.03, and the monodispersity was 96.4%.
• Production Example 8 Synthesis of bisphenol F EO adduct (A-8)
• the reaction was conducted in the same manner as in Production Example 1 except that bisphenol A used in Production Example 1 was replaced with 300.4 g (1.50 mol) of bisphenol F (“Bisphenol F” manufactured by Honshu Chemical Industry Co., Ltd.). The reaction was terminated when the 1 mol adduct was 0.1% or less. The required EO was 150.3 g (3.42 mol), and the reaction time was 7 hours. After the reaction, unreacted EO, catalyst, solvent and the like were distilled off at 130 to 160 ° C. under reduced pressure to obtain bisphenol F EO adduct (A-8). When this (A-8) was analyzed by GC, the average added mole number of EO per hydroxyl group of the obtained (A-8) was 1.02, and the monodispersity was 97.5%.
• Production Example 12 Synthesis of p-phthalic acid EO adduct (A-12)] The reaction was conducted in the same manner as in Production Example 1, except that bisphenol A used in Production Example 1 was replaced with 249.2 g (1.50 mol) of p-phthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). The reaction was terminated when the 1 mol adduct was 0.1% or less. The required EO was 149.2 g (3.39 mol), and the reaction time was 6 hours. After the reaction, unreacted EO, catalyst, solvent and the like were distilled off under reduced pressure at 130 to 160 ° C. to obtain an EO adduct (A-12) of p-phthalic acid.
• Production Example 13 [Synthesis of EO adduct (A-13) of 1,4-dihydroxybenzene] The reaction was carried out in the same manner as in Production Example 1 except that bisphenol A used in Production Example 1 was replaced with 165.2 g (1.50 mol) of 1,4-dihydroxybenzene (Tokyo Chemical Industry Co., Ltd.). The reaction was terminated when the 1 mol adduct was 0.1% or less. The required EO was 151.2 g (3.44 mol), and the reaction time was 7 hours. After the reaction, unreacted EO, catalyst, solvent and the like were distilled off at 130 to 160 ° C. under reduced pressure to obtain an EO adduct (A-13) of 1,4-dihydroxybenzene.
• thermoplastic urethane resins (F-1) to (F-26) and the comparative thermoplastic resins (F′-1) to (F′-3) were reacted by maintaining for 8 hours while maintaining the temperature. Obtained. These were designated as hot melt adhesives (H-1) to (H-26) of the present invention and comparative melt adhesives (H′-1) to (H′-3).
• the moisture content (%) of the polyols [(A) + (C) + (D)] listed in Tables 1 to 3 was measured using a Karl Fischer moisture meter (volumetric titration method).
• a Karl Fischer moisture meter As the Karl Fischer moisture meter, a Karl Fischer moisture meter (MKS-500) manufactured by Kyoto Electronics Industry Co., Ltd. was used. Using methanol as a diluting solvent, about 1 g of a measurement sample was precisely weighed to 4 significant digits, put into methanol, and stirred for 1 minute. After stirring, the water content determined by titration was read. Note that (C) in this calculation includes (C ′).
• Table 1 shows the results of performance evaluation of hot melt adhesives (H-1) to (H-26) and comparative melt adhesives (H'-1) to (H'-3) by the following method. Shown in ⁇ 3.
• the evaluation method is as follows.
• the hot melt adhesives (H-1) to (H-26) and the comparative melt adhesives (H′-1) to (H′-3) are hereinafter simply referred to as adhesives.
• Melt Viscosity The viscosity at 150 ° C. was measured using a B-type viscometer (“RB-80H” manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS-K7117 (1999).
• the storage elastic modulus (G ′) of the adhesive at ⁇ 20 ° C. and 70 ° C. is measured, and G ′ ( ⁇ 20 ° C.) / G ′ (70 ° C.) is calculated.
• the temperature dependence was evaluated. When this value was 100 or less, it was evaluated that the temperature dependency was small.
• the storage elastic modulus (G ′) was determined by pressing a resin film in the same manner as “(3) Tensile strength at break” and cutting out to the following sample size, and measuring viscoelasticity under the following measurement conditions.
• Measuring device Rheogel-E4000 [manufactured by UBM Co., Ltd.] Measuring jig: Solid shear Measurement temperature: -20 to 130 ° C Temperature increase rate: 5 ° C / min Measurement frequency: 10Hz Sample size: about 7mm (length) x about 6mm (width)
• Adhesive strength 80 ° C
• An adhesive was sandwiched between two PET films (thickness: 100 ⁇ m) and bonded to a thickness of 1 mm to prepare a sample.
• the sample was cut into a size of 200 mm ⁇ 25 mm, and a T-type peel strength (unit: N / 25 mm) was measured at a measurement temperature (80 ° C.) under a pulling rate of 100 mm / min using a tensile tester.
• the urea group content is calculated from the N atom content determined by a nitrogen analyzer [ANTEK7000 (manufactured by Antec)] and the ratio of urethane group and urea group determined by 1 H-NMR.
• the 1 H-NMR measurement is carried out by the method described in “Structural study of polyurethane resin by NMR: Takeda Laboratory Report 34 (2), 224-323 (1975)”.
• the urea group was calculated from the ratio of the integral amount of hydrogen derived from a urea group near a chemical shift of 6 ppm and the integral amount of hydrogen derived from a urethane group near a chemical shift of 7 ppm.
• the urethane group and the urea group content are calculated from the weight ratio, the N atom content, the allophanate group and the burette group content.
• the weight ratio of urea group and urethane group is calculated from the ratio of the integral amount of hydrogen derived from urea groups near the chemical shift of 8 ppm and the integral amount of hydrogen derived from urethane groups near the chemical shift of 9 ppm,
• the urea group content is calculated from the weight ratio and the N atom content.
• hot melt adhesives (H-1) to (H-26) have little temperature dependency, they are excellent in product quality stability. And when it uses as a hot-melt-adhesive, adhesive force is stabilized. Furthermore, the tensile strength at break is also excellent.
• the hot melt adhesive of the present invention is particularly useful for apparel use and production of various industrial materials.

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