JP2007211150A - Reactive hot-melt adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reactive hotmelt adhesive composition that can be applied to an adherent without using a special heating apparatus, and can broaden a usable temperature area by controlling increase of viscosity at temperatures lower than 100°C. <P>SOLUTION: The reactive hotmelt adhesive composition comprises an active NCO group-containing urethane prepolymer that can be obtained by reacting an active hydrogen group-containing compound and an isocyanate compound, is in a melt state in a temperature range of 65-100°C and has a viscosity at 100°C of 500-100,000 mPa s, preferably 1,000-50,000 mPa s. The slope of straight line obtained by regression analysis of a common logarithm value of viscosity against temperature is from -0.025 to -0.001, preferably from -0.02 to -0.05. The urethane polymer is obtained by reacting at least one of the compound selected from a crystalline polyester polyol, a polyether polyol, a polycaprolactone diol, and a castor oil based polyol, with an isocyanate compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention melts by heating and becomes ready for use, and after being applied to an adherend, it solidifies by cooling to develop an initial adhesive force, and further reacts with moisture contained in the adherend or air. The present invention relates to a reactive hot melt adhesive composition that cures.

  2. Description of the Related Art Conventionally, hot melt adhesives that are meltable by heating and are ready for use and solidify by cooling to develop initial adhesive strength are known. The conventional hot melt adhesive is composed of a composition such as ethylene vinyl acetate, polyamide diameter, polyester, polyolefin, and thermoplastic rubber.

  However, since the conventional hot melt adhesive has a use temperature in the range of 140 to 200 ° C. and a relatively high temperature, an applicator such as a roll coater, a knife coater, or a hand gun equipped with a dedicated heating device is used for application. There is a problem that it must be used. Further, when the conventional hot melt adhesive is used for an adherend having low heat resistance, there is a problem that the adherend is deformed by heat.

  In order to solve the above problems, a reactive (moisture-curing type) hot melt adhesive that has a relatively low molecular weight urethane prepolymer as a main component and can be used at a relatively low temperature has been proposed in recent years. As such a reactive hot melt adhesive, for example, an adhesive made of a urethane prepolymer obtained by reacting a crystalline polyester polyol and a polyisocyanate compound has been proposed (see, for example, Patent Document 1).

  Specifically, the moisture-curable hot-melt adhesive includes a crystalline polyester polyol having a number average molecular weight in the range of 3000 to 10,000 and a crystalline polyester polyol having a number average molecular weight in the range of 1000 to 3000. It is a urethane prepolymer obtained by reacting a crystalline polyester polyol composed of 10% by weight or more of a polyol with a polyisocyanate compound. The urethane prepolymer contains active isocyanate groups. The reactive hot melt adhesive may be prepared by reacting the two types of crystalline polyester polyols with a polyisocyanate compound to obtain two types of urethane prepolymers. Two kinds of crystalline polyester polyols are mixed, and the mixture may be reacted with a polyisocyanate compound to form a urethane prepolymer.

  The reactive hot-melt adhesive is said to melt at 85 to 90 ° C. and exhibit a melt viscosity in the range of 1400 to 3000 mPa · s at 100 ° C. and in the range of 6000 to 10000 mPa · s at 90 ° C.

  However, the reactive hot melt adhesive has the disadvantage that an applicator such as a roll coater, knife coater, hand gun or the like equipped with a dedicated heating device must be used when applied to the adherend. Further, the reactive hot melt adhesive has a rate of change of Logμ per 1 ° C. in the range of −0.063 to −0.05 when the common logarithm of the melt viscosity is Logμ. There is a disadvantage that the melt viscosity increases exponentially as the value decreases.

The melt viscosity of the conventional moisture curable hot melt adhesive is described in Table 3 on page 7 of Patent Document 1 as “melt viscosity mPa (× 100)”. Is shown as a two-digit number. However, if the above description is interpreted as “actual melt viscosity value multiplied by 100”, for example, if “80” is described, the actual melt viscosity is “0.8 mPa · s”, and “0. The numerical value of “8 mPa · s” is almost the same as the viscosity of water, and thus cannot be used as a hot melt adhesive. Therefore, the above description should be understood as “the value obtained by multiplying the described numerical value by 100 is the actual melt viscosity value”.
JP-A-7-118622 (Claim 1, Claim 2, Table 7 on page 7)

  The present invention eliminates such inconvenience and can be applied to an adherend without using an applicator equipped with a dedicated heating device, and can be used while suppressing an increase in melt viscosity in a temperature range lower than 100 ° C. An object of the present invention is to provide a reactive hot melt adhesive composition capable of widening a wide temperature range.

  In order to achieve this object, the present invention provides an active NCO obtained by reacting an active hydrogen group-containing compound having a plurality of active hydrogen groups in the molecule with an isocyanate compound having a plurality of isocyanate groups in the molecule. A reactive hot-melt adhesive composition containing a group-containing urethane prepolymer, which is in a molten state at a temperature in the range of 65 to 100 ° C., and has a viscosity at 100 ° C. in the molten state of 500 to 100,000 mPa · s, preferably When the logarithmic value of the viscosity is Log μ, the slope of the Log μ line with respect to the temperature determined by regression analysis is −0.025 to −0.001, preferably in the range of 1000 to 50000 mPa · s. Is in the range of -0.02 to -0.005.

  The reactive hot melt adhesive of the present invention is in a molten state at a temperature in the range of 65 to 100 ° C., and the viscosity at 100 ° C. in the molten state is in the range of 500 to 100,000 mPa · s. Without using a large-scale device such as the above, it can be easily used in a factory or a site of a civil engineering that does not have such a device or equipment. When the reactive hot melt adhesive is used at the factory or construction civil engineering site, for example, when a hand gun is used, instead of filling a conventional aluminum tube, an aluminum laminated paper tube or resin having low heat resistance is used. It can be used by filling in a cartridge made of the like.

  When the temperature at which the molten state is reached exceeds 100 ° C., it becomes difficult to use without a device such as an applicator equipped with a heating device. On the other hand, it is extremely difficult for the reactive hot melt adhesive to set the temperature at which the molten state is reached to less than 65 ° C.

  Moreover, when the viscosity at 100 ° C. in the molten state exceeds 100,000 mPa · s, it is difficult to apply to the adherend. On the other hand, it is extremely difficult for the reactive hot melt adhesive to have a viscosity at 100 ° C. in the molten state of less than 500 mPa · s.

  Moreover, it is preferable that the viscosity in 100 degreeC of the said molten state is the range of 1000-50000 mPa * s. If the viscosity at 100 ° C. in the molten state exceeds 50000 mPa · s, it may be difficult to apply to the adherend. On the other hand, setting the viscosity at 100 ° C. in the molten state to less than 1000 mPa · s may be difficult for the reactive hot melt adhesive.

  In the reactive hot melt adhesive of the present invention, the slope of the Logμ line with respect to the temperature determined by the regression analysis indicates the rate of change of Logμ per 1 ° C., and the slope of the straight line is −0. By being in the range of 025 to -0.001, increase in melt viscosity can be suppressed in a temperature range lower than 100 ° C., and the usable temperature range can be widened.

  It is extremely difficult for the reactive hot melt adhesive to make the inclination of the straight line exceed -0.001. On the other hand, when the slope of the straight line is less than −0.025, the viscosity in the molten state increases exponentially in a temperature range lower than 100 ° C., and the usable temperature range becomes narrow.

  The slope of the straight line is preferably in the range of -0.02 to -0.005. It may be difficult for the reactive hot-melt adhesive to make the slope of the straight line exceed -0.005. On the other hand, if the slope of the straight line is less than −0.02, the effect of suppressing the increase in viscosity in the molten state cannot be sufficiently obtained in a temperature range lower than 100 ° C., and the usable temperature range may be narrowed. is there.

  The urethane prepolymer contained in the reactive hot melt adhesive composition of the present invention is an active NCO group-containing urethane prepolymer obtained by reacting the active hydrogen group-containing compound with the isocyanate compound, The NCO group content is preferably in the range of 2 to 6%, more preferably in the range of 3 to 5%. When the active NCO group content is less than 2%, the viscosity of the obtained reactive hot melt adhesive composition becomes high, and when it exceeds 6%, the initial adhesive strength of the obtained reactive hot melt adhesive composition is expressed. Is delayed or the cohesive strength of the resin is reduced.

  The reactive hot-melt adhesive composition of the present invention can be applied to an adherend as a molten state at a temperature in the range of 65 to 100 ° C. by providing the physical properties. Further, the reactive hot melt adhesive composition of the present invention is solidified by being cooled to a temperature lower than the temperature range of the molten state after the application, and the initial strength is expressed in a very short time. The urethane prepolymer can be cured by reacting with moisture in the adherend or moisture in the air to obtain a predetermined adhesive strength.

  Moreover, the reactive hot melt adhesive composition of the present invention is characterized in that the melted state has a viscosity at 85 ° C. of 550 to 220,000 mPa · s. The reactive hot melt adhesive composition of the present invention is filled in an aluminum laminate pack used for retort foods and the like when the viscosity at 85 ° C. in the molten state is in the above range, and the electric laminate etc. together with the aluminum laminate pack It can be melted by immersing it in hot water boiled in. In addition, the reactive hot melt adhesive of the present invention has a viscosity at 85 ° C. in the molten state in the above range, so that even if it is used for a low heat resistant adherend such as a vinyl chloride sheet or polystyrene foam, There is no possibility that the adherend is deformed by heat.

  When the viscosity at 85 ° C. in the molten state exceeds 220,000 mPa · s, the discharge property is lowered and application becomes difficult. On the other hand, when the viscosity at 85 ° C. in the molten state is less than 550 mPa · s, it may be difficult to apply to the adherend.

  In the reactive hot melt adhesive composition of the present invention, the urethane prepolymer may be one obtained by reacting two kinds of polyester polyols and an isocyanate compound. A resin obtained by reacting an isocyanate compound with at least one polyol selected from the group consisting of a reactive polyester polyol, polyether polyol, polycaprolactone diol, and castor oil-based polyol. Here, the crystalline polyester polyol is a resin obtained by reacting diols with dicarboxylic acids, and the polyether polyol is a resin obtained by reacting alkylene oxides with a low molecular weight polyol. .

  Next, embodiments of the present invention will be described in more detail.

  The reactive hot melt adhesive composition of the present embodiment is obtained by reacting an active hydrogen group-containing compound having a plurality of active hydrogen groups in the molecule with an isocyanate compound having a plurality of isocyanate groups in the molecule. A reactive hot melt adhesive composition comprising an active NCO group-containing urethane prepolymer, which is in a molten state at a temperature in the range of 65 to 100 ° C., and has a viscosity at 100 ° C. in the molten state of 500 to 100,000 mPa · s. The range of 1000 to 50000 mPa · s is preferable, and when the common logarithm value of the viscosity is Log μ, the slope of the Log μ line with respect to the temperature obtained by regression analysis is −0.025 to −0.0. 001, preferably in the range of -0.02 to -0.005.

  Furthermore, the reactive hot melt adhesive composition of the present embodiment preferably has a viscosity at 85 ° C. in the molten state of 550 to 220,000 mPa · s, more preferably 1800 to 120,000 mPa · s. preferable.

  In the reactive hot melt adhesive composition of the present embodiment, the active hydrogen group-containing compound may be a compound having two or more active hydrogen groups in the molecule. Mention may be made of monomers or prepolymers having hydroxyl groups or amine groups. More specifically, examples of the active hydrogen group-containing compound include a polymer polyol, a polymer polyamine, and a saccharide.

  Examples of the high-molecular polyol include low molecular glycols, mixtures of the low molecular glycols, polyester polyols, polyether polyols, polycarbonate polyols, acrylic polyols, polyether polyamines, and polymers obtained by ring-opening polymerization of ε-caprolactone. Examples include caprolactone diol and castor oil-based polyol. In the reactive hot melt adhesive composition of the present embodiment, as the polymer polyol, in particular, polyester polyol and at least one compound of polyether polyol, polycaprolactone diol, and castor oil-based polyol are mixed and used. Can do.

  Examples of the polyester polyol include low molecular glycols, a mixture of the low molecular glycols, dicarboxylic acid, an ester of the dicarboxylic acid, an anhydride of the dicarboxylic acid, and a dehydration condensation reaction between the low molecular glycol and the dicarboxylic acid. The polyester polyol of the both terminal hydroxyl group obtained etc. can be mentioned. Examples of the low molecular glycols include ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,2-butane. Diol, neopentyl glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1 , 5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propane Diol, 2-n-butyl-2-ethyl-1,3-propanediol, bisphenol A ethylene Sid adduct, propylene oxide adduct of bisphenol A and the like. Examples of the dicarboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid, naphthylene dicarboxylic acid, and dodecanedioic acid. Can do.

  As the polyester polyol, in this embodiment, it is particularly preferable to use a crystalline polyester polyol having hydroxyl groups at both ends obtained by a dehydration condensation reaction between the low-molecular glycols and the dicarboxylic acid. Examples of the crystalline polyester include polyhexane adipate diol obtained by reacting 1,6-hexanediol and adipic acid, and polyhexane sebate obtained by reacting 1,6-hexanediol and sebacic acid. Examples thereof include bactate diol, polyhexane dodecanedioate diol obtained by reacting 1,6-hexanediol and dodecanedioic acid.

  Examples of the polyether polyol include polyether polyols obtained by polymerizing alkylene oxide with a low molecular weight polyol or water as an initiator, polyether polyols obtained by ring-opening polymerization of a single product or a mixture of alkylene oxides, and tetrahydrofuran. Examples thereof include polytetramethylene glycol obtained by ring-opening polymerization. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Examples of the low molecular polyol used as the polymerization initiator for the alkylene oxide include ethylene glycol, propylene glycol, trimethylolpropane, and glycerin.

  As the polyether polyol, in the present embodiment, it is particularly preferable to use a polyether polyol obtained by polymerizing alkylene oxide using a low molecular polyol as an initiator. Examples of such polyether polyols include copolymers of propylene oxide and ethylene oxide. The copolymer of propylene oxide and ethylene oxide has a molecular weight of 1000 to 4000, and the amount of ethylene oxide in the entire molecule is preferably in the range of 20 to 80% by weight.

  The polycaprolactone diol obtained by ring-opening polymerization of ε-caprolactone is preferably one having 2 functional groups and a molecular weight in the range of 1000 to 4000. When the molecular weight of the polycaprolactone diol is less than 1000, the viscosity of the urethane prepolymer increases. When the molecular weight exceeds 4000, the urethane prepolymer becomes brittle.

  The castor oil-based polyol preferably has a functional group number in the range of 2 to 2.2 and a molecular weight in the range of 500 to 2000. When the molecular weight of the castor oil-based polyol is less than 500 or exceeds 2000, the viscosity of the urethane prepolymer increases.

  In addition, as the active hydrogen group-containing compound, a carbon chain extender, a low molecular alcohol, a diamine, a low molecular amino alcohol, water, or the like can be used for adjusting the molecular weight or introducing a hydroxyl group. Examples of the low molecular alcohol include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, and cyclohexanedimethanol. Examples of the diamine include propylene diamine and hexamethylene diamine.

  Furthermore, examples of the active hydrogen group-containing compound include monoalcohols and monoamines. The low molecular amino alcohol, monoalcohol, monoamine and the like can also be used as a reaction terminator.

  The active hydrogen group-containing compound may be used alone or in combination of two or more, but at least the crystalline polyester polyol, the polyether polyol, polycaprolactone diol, castor oil It is preferable to include at least one polyol selected from the group consisting of system polyols.

  Next, in the reactive hot melt adhesive composition of the present embodiment, the isocyanate compound may be a compound having two or more isocyanate groups in the molecule. Examples of such a compound include aliphatic diisocyanate. , Cycloaliphatic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, dimers, trimers, burettes derived from isocyanate monomers, 2,4,6-oxadi obtained from carbon dioxide and isocyanate monomers Examples thereof include NCO-terminated compounds such as polyisocyanates having a lysine trione ring, adducts of low-molecular polyols and isocyanates, modified products of isocyanate compounds with carbodiimide, and adducts of polymer polyols and isocyanates.

  Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, lysine isocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4-trimethylhexamethylene-1, Examples thereof include 6-diisocyanate and 2,4,4-trimethylhexamethylene-1,6-diisocyanate. Examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), cyclohexyl diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated trimethylxylylene diisocyanate. Can do. Examples of the aromatic diisocyanate include isomers of MDI such as phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4′-diphenylmethane diisocyanate, and polynuclear mixtures of MDI and MDI isomers. Methylene polyphenyl isocyanate (polymeric MDI), 4,4-dibenzyl diisocyanate, 1,5-naphthalene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diene Examples thereof include a mixture of isocyanate and 2,6-tolylene diisocyanate, 4,4-diphenyl ether diisocyanate, and the like. Examples of the araliphatic diisocyanate include tetramethylxylylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene diisocyanate. And the like.

  Examples of the dimer, trimer and burette derived from the isocyanate monomer include triphenylmethane-4,4 ′, 4 ″ -triisocyanate and the like.

  Examples of the low molecular polyol added to the isocyanate include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, and cyclohexanedimethanol.

  The said isocyanate compound may be used individually by 1 type, and may mix and use 2 or more types.

  In the present embodiment, as the isocyanate compound, it is preferable to use the MDI or an isomer of MDI (such as 2,4′-diphenylmethane diisocyanate) from the viewpoint of safety.

  As described above, the reactive hot-melt adhesive composition of the present embodiment includes, in particular, a crystalline polyester polyol having hydroxyl groups at both ends obtained by a dehydration condensation reaction between the low molecular glycols and the dicarboxylic acid, and a low molecular weight. It is preferable to include a urethane prepolymer obtained by reacting a polyether polyol obtained by polymerizing an alkylene oxide using a polyol as an initiator and an isocyanate compound comprising MDI or an isomer of MDI.

  The urethane prepolymer is, for example, 20 to 80 parts by weight of the crystalline polyester polyol, preferably 30 to 60 parts by weight, 5 to 60 parts by weight of the polyether polyol, preferably 20 to 50 parts by weight, and 10 to 30 parts of the isocyanate compound. It can be obtained by mixing and reacting in parts by weight, preferably in the range of 15 to 25 parts by weight. The method for obtaining the urethane prepolymer by reacting the crystalline polyester polyol, the polyether polyol and the isocyanate compound is not particularly limited, and can be carried out by a method known per se.

  Furthermore, the reactive hot melt adhesive composition of the present embodiment may contain various known additives as long as the physical properties relating to the melt viscosity are not impaired and the adhesive performance is not impaired. . The additives include tackifiers for improving adhesiveness and lowering melt viscosity, waxes for improving heat resistance and anti-blocking properties, face dyes, fillers, thixotropic agents, and stability. Agents, antioxidants, UV stabilizers, adhesion-imparting agents, surfactants, curing accelerators, and the like. The additive needs to be dehydrated in advance.

  Examples of the filler include inorganic fillers and organic powders. Examples of the inorganic filler include clay, calcined clay, talc, silica, alumina, calcium carbonate, magnesium oxide, calcium silicate, calcium aluminate, sodium aluminate, magnesium silicate, calcium hydroxide, barium sulfate, and carbon. Examples thereof include black, silica sand, mica, titanium oxide, silica balloon, glass balloon, and zeolite. Examples of the organic powder include vinyl chloride powder, rubber powder, and organic balloons.

  Examples of the thixotropic agent include an inorganic thixotropic agent, an organic thixotropic agent, and calcium carbonate, mica powder, and short fiber polyethylene that have been surface-treated with an amide wax. Examples of the inorganic thixotropic agent include fatty acid amide wax, ultrafine silica, asbestos powder, rock wool powder, sepiolite, Neuburg silica. Examples of the organic thixotropic agent include organic pentonites and fatty acid ester thixotropic agents.

  Examples of the adhesion-imparting agent include various titanate coupling agents, reaction products of coupling agents and isocyanate compounds, reaction products of two or more coupling agents, and the like. Examples of the reaction product of the two or more types of coupling agents include reaction products of various aminosilanes and epoxysilanes, condensation reaction products of two or more molecules of the alkoxy group of the coupling agent, and the like. The said adhesion imparting agent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  Examples of the catalyst include organometallic catalysts and tertiary amines. Examples of the organic metals include dibutyltin dilaurate, tin octenoate, lead octenoate, and lead naphthenate. The tertiary amines include N-triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N′-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl-N′-dimethylaminoethylpiperazine, imidazole substituted secondary amine functional group of imidazole ring with cyanoethyl group A compound etc. can be mentioned.Only the said catalyst may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  The reactive hot-melt adhesive composition of the present embodiment can obtain the above-mentioned physical properties by having the above-mentioned composition, and it is in a molten state at a temperature in the range of 65 to 100 ° C., preferably in the range of 65 to 85 ° C. Can be applied to the dressing. Further, the reactive hot melt adhesive composition of the present embodiment is cured by being cooled to a temperature lower than the temperature range of the molten state after the application, and the initial strength is exhibited in a very short time. A predetermined adhesive strength can be obtained by the urethane prepolymer reacting with moisture in the adherend or moisture in the air.

  The reactive hot melt adhesive composition of the present embodiment can be supplied by being filled into an aluminum laminate pack, a pail can, a drum can, an aluminum tube cartridge, etc., in the same manner as a general reactive hot melt adhesive composition. It can be applied using a dedicated applicator equipped with a heating and melting apparatus for heating and melting the hot melt adhesive composition and a heater for applying the molten hot melt adhesive composition. Examples of the dedicated applicator include a coater such as a roll coater, a knife coater, and a hand gun equipped with a heater dedicated to the hot melt adhesive composition.

  However, since the reactive hot melt adhesive composition of the present embodiment can be melted at a lower temperature than the conventional reactive hot melt adhesive composition, it can be applied without using the dedicated applicator. it can. For example, when a conventional reactive hot-melt adhesive composition is filled in a cartridge and supplied, an aluminum tube cartridge must be used, but the reactive hot-melt adhesive composition of the present embodiment is heat resistant. Low-aluminum laminated paper tubes and cartridges such as resin cartridges can be filled and supplied. In addition, the reactive hot melt adhesive composition of the present embodiment is used when heating the retort food in hot water boiled in an electric pot or the like without using a heating and melting apparatus dedicated to the hot melt adhesive composition. Similarly, it can be heated and melted by dipping an aluminum laminate pack filled with the reactive hot melt adhesive composition of the present embodiment.

  The reactive hot melt adhesive composition of the present embodiment can be used for building material assembly, woodworking, automobile processing, electrical product processing, bookbinding, packaging, and the like. In the construction of building materials and woodworking, the site of architectural civil engineering, doors, access floors, multi-layered floors, furniture assembly, etc. in building manufacturing, bonding of edges, adhesion of profile wrapping, etc., surface repair of wood materials, mortar, etc. Can be used for injection repair. In the processing of automobiles, it can be used for bonding interior materials such as roofs, doors and seats, and bonding exterior materials such as lamps and side moldings. In the processing of electrical products, it can be used for bonding lamp shades, speakers, and the like.

  Next, examples and comparative examples of the present invention are shown.

  In this example, first, 56.7 parts by weight of a crystalline polyester polyol (made by Degussa, trade name: DYNACOLL7831) having a molecular weight of 3500 consisting of a reaction product of 1,6-hexanediol and sebacic acid and a melting point of 65 ° C. , 24.3 parts by weight of polyoxypropylene diol having a molecular weight of 2000 (manufactured by Asahi Glass Co., Ltd., trade name: EXENOL2020) are added, mixed, and heated at 100 ° C. for 1 hour under a vacuum of 1.3 kPa or less to perform vacuum dehydration did. Next, 19 parts by weight of 4,4′-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Millionate MT) is added to the mixture, and the mixture is reacted at 85 ° C. for 3 hours under a nitrogen stream. A light yellow solid reactive hot melt adhesive composition comprising a urethane prepolymer having a group content of 4.0% was obtained.

  Next, the reaction type hot melt adhesive composition obtained in this example was melted by heating, and the reaction type at each temperature of 65 ° C., 70 ° C., 75 ° C., 80 ° C., 85 ° C., 90 ° C., and 100 ° C. The melt viscosity of the hot melt adhesive composition is measured in units of Pa · s using a B-type rotary viscometer, and the logarithmic value of the viscosity is Logμ, and the slope of the Logμ line with respect to temperature is obtained by regression analysis. It was. The slope of the straight line corresponds to the rate of change of Logμ per 1 ° C temperature. Table 1 shows the measurement results of the melt viscosity in mPa · s, and Table 2 shows the Logμ and the slope of the straight line.

  Next, the reaction type hot melt adhesive composition obtained in this example was filled in an aluminum laminate pack, and the aluminum type laminate pack was immersed in hot water at 80 ° C. to heat the reaction type hot melt adhesive composition. After melting, the tip of the aluminum laminate pack was cut to form a discharge port having a diameter of 7 mm. Next, the reactive hot melt adhesive composition is discharged from the discharge port in an atmosphere of 23 ° C. and a relative humidity of 65%, and the resistance at the time of discharge is excellent, good, acceptable, and impossible in four stages. It was evaluated with. The results are shown in Table 3, where “Excellent” is indicated by “◎”, “Good” is indicated by “◯”, “Good” is indicated by “Δ”, and “No” is indicated by “X”.

Next, two 40 mm × 40 mm plywoods were prepared, and the reactive hot melt adhesive composition obtained in this example was applied to one of the plywoods in an amount of about 150 g / m ^{2 in} a beat shape. The other plywood was overlaid and lightly pressure-bonded by hand and left in an atmosphere of 23 ° C. and relative humidity 65% to form a test piece. Next, the adhesive strength of the test piece was measured at regular intervals using a tensile tester, and the time at which an adhesive strength of 0.3 MPa or higher was obtained was defined as the initial adhesive strength expression time (set time). . The results are shown in Table 3.

Next, two 40 mm × 40 mm plywoods were prepared, and the reactive hot melt adhesive composition obtained in this example was applied to one of the plywoods in an amount of about 150 g / m ^{2 in} a beat shape. Immediately after that, the other plywood was superposed and lightly pressure-bonded by hand, and left in an atmosphere of 23 ° C. and relative humidity 65% for 1 week to obtain a test piece. Next, the adhesive strength of the test piece was measured using a tensile tester to obtain a normal adhesive strength. The results are shown in Table 3.

  Next, for the two plywoods, a test piece obtained in exactly the same manner as in the case of the normal adhesive force was immersed in 60 ° C. warm water for 3 hours, and then immersed in room temperature water until cooled. The adhesive strength of the test piece was measured using a tensile tester in the wet state, and was defined as a hot water immersion adhesive strength. The results are shown in Table 3.

Next, a 40 mm × 40 mm plywood and a slate plate were prepared, and the reactive hot melt adhesive composition obtained in this example was applied to the plywood in a beet-like amount of about 150 g / m ² , and immediately Slate plates were stacked and lightly pressure-bonded by hand, and left for 1 week in an atmosphere of 23 ° C. and relative humidity of 65% to obtain test pieces. Next, the adhesive strength of the test piece was measured using a tensile tester to obtain a normal adhesive strength. The results are shown in Table 3.

  Next, for the plywood and slate plate, after immersing a test piece obtained in exactly the same manner as in the case of the normal adhesive force in 60 ° C. warm water for 3 hours, and then cooling in room temperature water until cooled. The adhesive strength of the test piece was measured using a tensile tester in a wet state, and was defined as hot water immersion adhesive strength. The results are shown in Table 3.

  In this example, first, 45.4 parts by weight of a crystalline polyester polyol (made by Degussa, trade name: DYNACOLL7831) having a molecular weight of 3500 and a melting point of 65 ° C. composed of a reaction product of 1,6-hexanediol and sebacic acid. , 14.3 parts by weight of polyoxypropylenediol having a molecular weight of 2000 (Asahi Glass Co., Ltd., trade name: EXENOL2020) and 20 parts by weight of dried calcium carbonate (Shiraishi Kogyo Co., Ltd., trade name: Whiten P-50) Were added, mixed, and vacuum dehydrated in the same manner as in Example 1. Next, 15.2 parts by weight of 4,4′-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Millionate MT) was added to the mixture, and the reaction was carried out in exactly the same manner as in Example 1. A white solid reactive hot melt adhesive composition containing a urethane prepolymer having an NCO group content of 4.0% was obtained.

  Next, in exactly the same manner as in Example 1, the melt viscosity of the reactive hot melt adhesive composition obtained in this example was measured, and the logarithm value of the viscosity was Log μ, and regression analysis was performed with respect to temperature. The slope of the Logμ straight line was determined. Table 1 shows the measurement results of the melt viscosity in mPa · s, and Table 2 shows the Logμ and the slope of the straight line.

  Moreover, while being exactly the same as Example 1, while evaluating the discharge property of the reactive hot-melt-adhesive composition obtained by the present Example, it was obtained by the same as Example 1, and was obtained by the present Example. The set time, normal state adhesive force, and hot water immersion adhesive force of the reactive hot melt adhesive composition were measured. The results are shown in Table 3.

  In this example, first, 28.5 parts by weight of a crystalline polyester polyol (trade name: DYNACOLL 7360, manufactured by Degussa) having a molecular weight of 3500 and a melting point of 55 ° C. composed of a reaction product of 1,6-hexanediol and adipic acid. Non-crystalline polyester polyol having a molecular weight of 2000 including a reaction product of ethylene glycol, neopentyl glycol, adipic acid, and isophthalic acid, and a glass transition temperature (TG) of 10 ° C. (manufactured by Degussa, trade name: DYNACOLL7110) 14. 3 parts by weight, 14.3 parts by weight of polyoxypropylene diol having a molecular weight of 2000 and an ethylene oxide addition rate of 45% (Asahi Glass Co., Ltd., copolymer of propylene oxide and ethylene oxide, trade name: EXENOL 540) and dried carbonic acid Calcium (made by Shiroishi Kogyo Co., Ltd.) Product Name: adding a Whiton P-50) 30 parts by weight, mixed and vacuum dehydration in the same manner as in Example 1. Next, 13 parts by weight of 4,4′-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Millionate MT) is added to the mixture and reacted in the same manner as in Example 1 to obtain active NCO groups. A white solid reactive hot melt adhesive composition containing a urethane prepolymer having a content of 4.0% was obtained.

  Next, in exactly the same manner as in Example 1, the melt viscosity of the reactive hot melt adhesive composition obtained in this example was measured, and the logarithm value of the viscosity was Log μ, and regression analysis was performed with respect to temperature. The slope of the Logμ straight line was determined. Table 1 shows the measurement results of the melt viscosity in units of mPa · s, and Table 2 shows the Logμ and the slope of the straight line.

  Moreover, while being exactly the same as Example 1, while evaluating the discharge property of the reactive hot-melt-adhesive composition obtained by the present Example, it was obtained by the same as Example 1, and was obtained by the present Example. The set time, normal state adhesive force, and hot water immersion adhesive force of the reactive hot melt adhesive composition were measured. The results are shown in Table 3.

  In this example, first, 43.8 parts by weight of a crystalline polyester polyol (made by Degussa, trade name: DYNACOLL7831) having a molecular weight of 3500 consisting of a reaction product of 1,6-hexanediol and sebacic acid and a melting point of 65 ° C. 18.8 parts by weight of polycaprolactone diol having a molecular weight of 1000 (manufactured by Daicel Chemical Industries, Ltd., trade name: PLACEL 210) and 20 weights of dried calcium carbonate (trade name: Shiraishi Kogyo Co., Ltd., trade name: Whiten P-50) Were added and mixed, and vacuum dehydration treatment was performed in exactly the same manner as in Example 1. Next, 17.4 parts by weight of 4,4′-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Millionate MT) was added to the mixture, and the reaction was carried out in exactly the same manner as in Example 1. A white solid reactive hot melt adhesive composition containing a urethane prepolymer having an NCO group content of 4.0% was obtained.

  Next, in exactly the same manner as in Example 1, the melt viscosity of the reactive hot melt adhesive composition obtained in this example was measured, and the logarithm value of the viscosity was Log μ, and regression analysis was performed with respect to temperature. The slope of the Logμ straight line was determined. Table 1 shows the measurement results of the melt viscosity in mPa · s, and Table 2 shows the Logμ and the slope of the straight line.

Moreover, while being exactly the same as Example 1, while evaluating the discharge property of the reactive hot-melt-adhesive composition obtained by the present Example, it was obtained by the same as Example 1, and was obtained by the present Example. The set time, normal state adhesive force, and hot water immersion adhesive force of the reactive hot melt adhesive composition were measured. The results are shown in Table 3.
[Comparative Example 1]
In this comparative example, first, 28.2 parts by weight of a crystalline polyester polyol (trade name: DYNACOLL 7360, manufactured by Degussa) having a molecular weight of 3500 and a melting point of 55 ° C. composed of a reaction product of 1,6-hexanediol and adipic acid. Non-crystalline polyester polyol having a molecular weight of 2000 including a reaction product of ethylene glycol, neopentyl glycol, adipic acid, and isophthalic acid, and a glass transition temperature (TG) of 10 ° C. (trade name: DYNACOLL7110 manufactured by Degussa) 2 parts by weight and 30 parts by weight of dried calcium carbonate (trade name: Whiten P-50, manufactured by Shiraishi Kogyo Co., Ltd.) were added and mixed, and vacuum dehydration treatment was performed in exactly the same manner as in Example 1. Next, 13.7 parts by weight of 4,4′-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Millionate MT) was added to the mixture, and the reaction was carried out in exactly the same manner as in Example 1 to activate the mixture. A white solid reactive hot melt adhesive composition containing a urethane prepolymer having an NCO group content of 4.0% was obtained.

  Next, in exactly the same way as in Example 1, the melt viscosity of the reactive hot melt adhesive composition obtained in this Comparative Example was measured, and the logarithmic value of the viscosity was Log μ, and regression analysis was performed with respect to temperature. The slope of the Logμ straight line was determined. Table 1 shows the measurement results of the melt viscosity in mPa · s, and Table 2 shows the Logμ and the slope of the straight line.

In addition, the ejection property of the reactive hot melt adhesive composition obtained in this comparative example was evaluated exactly the same as in Example 1, and the same as in Example 1 was obtained in this example. The set time, normal state adhesive force, and hot water immersion adhesive force of the reactive hot melt adhesive composition were measured. The results are shown in Table 3.
[Comparative Example 2]
In this comparative example, first, 61.6 parts by weight of a crystalline polyester polyol (Degussa, trade name: DYNACOLL7360) having a molecular weight of 3500 and a melting point of 55 ° C. composed of a reaction product of 1,6-hexanediol and adipic acid. Non-crystalline polyester polyol having a molecular weight of 3500 including a reaction product of ethylene glycol, neopentyl glycol, adipic acid and isophthalic acid, and a glass transition temperature (TG) of 10 ° C. (manufactured by Degussa, trade name: DYNACOLL7210) 4 parts by weight were added, mixed, and vacuum dehydrated in the same manner as in Example 1. Next, 11.9 parts by weight of 4,4′-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Millionate MT) was added to the mixture, and the reaction was carried out in exactly the same manner as in Example 1 to activate the mixture. A white solid reactive hot melt adhesive composition comprising a urethane prepolymer having an NCO group content of 2.0% was obtained.

  Next, in exactly the same way as in Example 1, the melt viscosity of the reactive hot melt adhesive composition obtained in this Comparative Example was measured, and the logarithmic value of the viscosity was Log μ, and regression analysis was performed with respect to temperature. The slope of the Logμ straight line was determined. Table 1 shows the measurement results of the melt viscosity in mPa · s, and Table 2 shows the Logμ and the slope of the straight line.

  In addition, the ejection property of the reactive hot melt adhesive composition obtained in this comparative example was evaluated exactly the same as in Example 1, and the same as in Example 1 was obtained in this example. The set time, normal state adhesive force, and hot water immersion adhesive force of the reactive hot melt adhesive composition were measured. The results are shown in Table 3.

  From Tables 1 to 3, the reactive hot melt adhesive compositions of Examples 1 to 4 are in a molten state at a temperature in the range of 65 to 100 ° C, and the melt viscosity at 100 ° C is 1900 to 12000 mPa · s, 85 ° C. When the melt viscosity in the range of 3100 to 17000 mPa · s and the common logarithm of the melt viscosity is Logμ, the slope of the Logμ line with respect to the temperature determined by regression analysis is −0.0195 to − It is clear that it is in the range of 0.101. And according to the reactive hot melt adhesive composition of Examples 1 to 4, the melt viscosity is in the range of 8500 to 34000 mPa · s even at 65 ° C., and the temperature that can be used in a temperature range lower than 100 ° C. It is clear that the area can be widened, and the discharge property and set time are also good.

  On the other hand, the reactive hot melt adhesive composition of Comparative Example 1 is in a molten state at a temperature in the range of 65 to 100 ° C., and the melt viscosity at 100 ° C. is 17000 mPa · s. Although the melt viscosity at 85 ° C. is increased to 38000 mPa · s, and the melt viscosity at 65 ° C. is increased to 137000, it is difficult to use and is lower than 100 ° C. It is clear that the usable temperature range is narrow in the temperature range. Moreover, it is clear that the reactive hot-melt adhesive composition of Comparative Example 1 has difficulty in ejection properties under the same conditions as the reactive hot-melt adhesive compositions of Examples 1 to 4.

  Further, the reactive hot melt adhesive composition of Comparative Example 2 has a melt viscosity at 100 ° C. of 25000 mPa · s, which is equivalent to the reactive hot melt adhesive composition of Examples 1 to 4, but melted at 85 ° C. The viscosity exceeds 200,000 mPa · s, making it extremely difficult to use, and it is apparent that the usable temperature range is narrow in a temperature range lower than 100 ° C. Moreover, it is clear that the reactive hot melt adhesive composition of Comparative Example 2 cannot be discharged under the same conditions as the reactive hot melt adhesive compositions of Examples 1 to 4.

  Furthermore, from Table 3, according to the reactive hot melt adhesive compositions of Examples 1 to 4, the reactive hot melt adhesive compositions of Comparative Examples 1 and 2 were used in both cases of normal and hot water immersion. It is clear that an equivalent adhesive strength can be obtained.

Claims (7)

Reactive hot melt adhesion comprising an active NCO group-containing urethane prepolymer obtained by reacting an active hydrogen group-containing compound having a plurality of active hydrogen groups in the molecule with an isocyanate compound having a plurality of isocyanate groups in the molecule An agent composition comprising:
When the molten state is at a temperature in the range of 65 to 100 ° C., the viscosity at 100 ° C. in the molten state is in the range of 500 to 100,000 mPa · s, and the common logarithm value of the viscosity is Log μ, the regression analysis The reaction type hot melt adhesive composition, wherein the slope of the Logμ line with respect to the temperature determined by the above is in the range of -0.025 to -0.001.   The reactive hot melt adhesive composition according to claim 1, wherein the melted state has a viscosity at 1000C of 1000 to 50000 mPa · s.   The reactive hot melt adhesive composition according to claim 1 or 2, wherein the slope of the Log μ line with respect to the temperature determined by regression analysis is in the range of -0.02 to -0.005.   The molten state at a temperature in the range of 65 to 85 ° C, and the viscosity at 85 ° C in the molten state is in the range of 550 to 220,000 mPa · s. 5. A reactive hot melt adhesive composition.   The urethane prepolymer is a resin obtained by reacting a crystalline polyester polyol, at least one polyol selected from the group consisting of polyether polyol, polycaprolactone diol, and castor oil-based polyol with an isocyanate compound. The reactive hot melt adhesive composition according to any one of claims 1 to 4, wherein the composition is a reactive hot melt adhesive composition.   6. The reactive hot melt adhesive composition according to claim 5, wherein the crystalline polyester polyol is a resin obtained by reacting a diol with a dicarboxylic acid.   6. The reactive hot melt adhesive composition according to claim 5, wherein the polyether polyol is a resin obtained by reacting an alkylene oxide with a low molecular weight polyol.