JP2005314445A - Reactive hot-melt adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a reactive hot-melt adhesive that keeps a long adhesion time after application, improves initial adhesive power, thereby prevents a strain adherend from separating and peeling, especially prevents an adherend in a working environment (atmosphere at 35°C) in the summer from separating and peeling, extremely shortens a curing time before the cutting work of a bonded body and does not contaminate a working environment and to provide a method for purifying a polyether, which has increased productivity and reduces an amount of an adsorbent used. <P>SOLUTION: The reactive hot-melt adhesive comprises a urethane prepolymer (A) obtained by reacting a polyisocyanate (a) with a polyol (b) and a rosin (c) containing active hydrogen to be reacted with an isocyanate and a thermoplastic elastomer (D) as essential components. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a reactive hot melt adhesive. More specifically, the present invention relates to a hot melt adhesive suitably used for manufacturing construction members (floor materials, panels, boards, cloths, metals, etc.) and clothing members (fibers, woven fabrics, films, etc.).

Hot melt adhesives are solid and solvent-free at room temperature, and are easy to use and useful, such as being usable only with a heating operation. Reactive hot melt adhesives have attracted attention in recent years as further improved in heat resistance and adhesiveness.
Conventionally, as a reactive hot melt adhesive, one made of a polyester-based or polyether-based urethane prepolymer and a low molecular weight xylene resin is known (for example, Patent Document 1).
Japanese Patent No. 2651640

However, although this reactive hot melt adhesive is excellent in the length of time that can be adhered after application and the elasticity after curing, the initial adhesive force immediately after application is expressed mainly by tackiness. In addition, because the resin strength is weak both before and after curing, the adherend may float and peel before it is completely cured when bonding adherends with distortion (such as construction members). It was. In addition, for applications in which the bonded body is cut after curing (adhesion of construction members and clothing members), during cutting, resin fusion occurs on the blade, and the curing time until cutting is 1 There were problems such as poor production efficiency because it took more than a week. Furthermore, since the low molecular weight xylene resin is partially decomposed when exposed to a high temperature of 120 ° C. or more to generate odor and smoke, there is also a problem in terms of working environment.
The object of the present invention is to maintain the length of time that can be adhered after coating and to improve the initial adhesive force, thereby preventing the distorted adherend from floating and peeling off, especially in the summer working environment (at 35 ° C atmosphere) It is an object of the present invention to provide a reactive hot-melt adhesive that does not contaminate the working environment that can prevent the floating and peeling of the adherend in the lower part and can significantly shorten the curing time until the cutting of the adhesive.

The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention relates to a urethane prepolymer (A) obtained by reacting a polyisocyanate (a), a polyol (b), and a rosin (c) having active hydrogen that reacts with an isocyanate, and a thermoplastic elastomer (D ) As an essential component.

The reactive hot melt adhesive of the present invention has the following effects.
Compared to conventional hot melt adhesives composed of polyester-based or polyether-based urethane prepolymers and low molecular weight xylene resins, the melt viscosity at the coating temperature is low and the coating property is excellent, without contaminating the work environment, In addition, prevention of floating and peeling after adherence of distorted adherends, especially prevention of floatation and peeling of adherends in the summer working environment (35 ° C atmosphere) and shortening of the curing time until cutting of the adherends. Is possible.

In the present invention, the polyisocyanate (a) is an aromatic polyisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), an aliphatic polyisocyanate having 2 to 18 carbon atoms, or 4 to 15 carbon atoms. Alicyclic polyisocyanates, araliphatic polyisocyanates having 8 to 15 carbon atoms, modified products of these polyisocyanates, and mixtures of two or more of these.
Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, and 2,4′-. And / or 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4, Examples include 4'-diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate.

Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine. Diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc. Is mentioned.
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2- And isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.

Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.
Polyisocyanate modified products include modified MDIs (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI), urethane modified TDI, biuret modified HDI, isocyanurate modified HDI, isocyanurate modified IPDI and the like. And a mixture of two or more thereof [for example, combined use of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)].
Among these, HDI, IPDI, TDI, MDI, XDI and TMXDI are preferable, and HDI and MDI are particularly preferable.

The polyol (b) is preferably one or more selected from the following (b1) to (b3).
(B1): phenols or alcohols added with alkylene oxides having 2 to 4 carbon atoms (b2): condensed polyester polyols of dicarboxylic acids and (b1) (b3): (b1) and / or (b2 ) Polymer polyol obtained by polymerizing ethylenically unsaturated monomers in (b1), and (b3) is more preferable among these.

  Specific examples of the phenols (b11) include dihydric phenols having 6 to 30 carbon atoms, such as catechol, resorcinol, hydroquinone, dihydroxymethylbenzene, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, dihydroxydiphenyl. Examples thereof include thioether, binaphthol, and alkyls (having 1 to 10 carbon atoms) or halogen substituents thereof. Bisphenol A and bisphenol F are preferable.

As specific examples of the alcohols (b12), dihydric or higher alcohols having 2 to 20 carbon atoms are preferable. For example, dihydric alcohols (ethylene glycol, diethylene glycol, 1,
2-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,3-hexanediol, 1,4-hexanediol, 1, 6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecanediol, 1,20-eicosanediol and alkyldi Alkanolamines, etc.), low molecular diols having a cyclic group [1-hydroxymethyl-1-cyclobutanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1-methyl-3 , 4-cyclohexanediol, 2-hydroxymethylcyclohexanol, 4-hydroxy Droxymethylcyclohexanol, 1,4-cyclohexanedimethanol, 1,4-bis (hydroxymethyl) cyclohexane, m- and p-xylylene glycol, 1,4-bis (2-hydroxyethoxy) benzene, 1,4 -Bis (α-hydroxyisopropyl) benzene, 2,2-bis (4-hydroxyethoxyphenyl) propane, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, 2-benzyl- 1,3-propanediol, triphenylethylene glycol, tetraphenylethylene glycol, benzopinacol, etc.], trihydric alcohols (glycerin, trimethylolpropane, hexanetriol, etc.), tetrafunctional or higher polyhydric alcohols (sorbitol, sugar) -Close etc.). More preferred are dihydric alcohols and trihydric alcohols.

Examples of the alkylene oxide (b13) include alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, 1,2-, 1,3-, 2,3-, or 1,4-butylene oxide, and these 2 More than one type of combined system [block addition (chip type, balance type, active secondary type, etc.), random addition, or a mixed system thereof] can be mentioned. Of these, ethylene oxide and propylene oxide are preferred.
The number of added moles of (b13) is preferably 1 to 100 moles, more preferably 2 to 50 moles.
The addition of the alkylene oxide can be carried out by a known method, in the absence of a catalyst, or in the presence of a catalyst (an alkali catalyst, an amine catalyst, an acidic catalyst) (especially in the latter half of the addition), at normal pressure or under an applied pressure. The reduction is performed in one stage or in multiple stages.

As the dicarboxylic acids (b14) constituting the condensed polyester polyol, dicarboxylic acids having 2 to 20 carbon atoms are preferable. For example, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids are used.
Aliphatic dicarboxylic acids include saturated aliphatic dicarboxylic acids (for example, oxalic acid, malonic acid, succinic acid, glutaric acid, methyl succinic acid, dimethyl malonic acid, β-methyl glutaric acid, ethyl succinic acid, isopropyl malonic acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, icosane dicarboxylic acid, etc.) and unsaturated Aliphatic dicarboxylic acids (for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.) can be mentioned.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, and biphenyl-2. 2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid and the like.
Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid. Examples include acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, dicyclohexyl-4,4-dicarboxylic acid and the like.
Of these, aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferable, and succinic acid, adipic acid, terephthalic acid, and phthalic acid are more preferable.

  The molar ratio of (b1) to dicarboxylic acids (b14) is preferably 101/100 to 2/1, and more preferably 51/50 to 3/2. The esterification reaction may be non-catalyzed or may use an esterification catalyst. Examples of esterification catalysts include protonic acids such as phosphoric acid, alkali metals, alkaline earth metals, transition metals, 2B metals, 4A metals, 4B metals, and 5B metals having 2 to 4 carbon carboxylates, carbonates, Examples thereof include sulfates, phosphates, oxides, chlorides, hydroxides, and alkoxides. Among these, 2B metal, 4A metal, 4B metal, and 5B metal are preferably C2-C4 organic carboxylates and oxides, and more preferably antimony trioxide and monobutyltin from the viewpoint of product color tone. Oxide, tetrabutyl titanate, tetrabutyl zirconate, zirconyl acetate, and zinc acetate. The amount of esterification catalyst used is not particularly limited as long as a desired molecular weight can be obtained. However, from the viewpoint of reactivity and color tone, the amount of esterification catalyst is 0. 005-5 mass% is preferable, More preferably, it is 0.1-1.0 mass%.

The esterification reaction is performed in the presence of an inert gas such as nitrogen or under reduced pressure (for example, 133 Pa or less). In order to accelerate the reaction, an organic solvent can be added and refluxed. After completion of the reaction, the organic solvent is removed. The organic solvent is not particularly limited as long as it has no active hydrogen such as a hydroxyl group. For example, hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate, An ester solvent such as butyl acetate can be used.
The reaction temperature is preferably 120 to 250 ° C, more preferably 150 to 230 ° C. The reaction time is preferably 1 to 40 hours, more preferably 3 to 24 hours.
The end point of the reaction can be measured by acid value (AV). The acid value at the end point is preferably 3 or less, more preferably 2 or less. The hydroxyl value of the resulting condensed polyester polyol is preferably 5 to 450, more preferably 10 to 280. The number average molecular weight (hereinafter referred to as Mn) is preferably 500 to 20,000, more preferably 800 to 10,000. Mn is a value measured by a gel permeation chromatography method (GPC method). The same applies hereinafter.

Measurement of Mn by the GPC method can be performed under the following conditions.
Solvent: Tetrahydrofuran Reference material: Polyethylene glycol (PEG)
Sample concentration: 0.25 wt / vol%
Column temperature: 23 ° C

Examples of the polymer polyol (b3) include a polymer polyol obtained by polymerizing an ethylenically unsaturated monomer in the aforementioned (b1) and / or (b2).
Examples of the ethylenically unsaturated monomer include α-olefins having 3 to 30 carbon atoms (hexene, octene, decene, dodecene, tetradecene, hexadecene, octadecene, aicosene, heneicosene, docosene, tricosene, tetracosene, pentacosene, hexacosene. Etc.), C8-C15 aromatic hydrocarbon monomers (styrene, α-methylstyrene, etc.), unsaturated nitriles [(meth) acrylonitrile, etc.], (meth) acrylic acid esters {(meth) Acrylic acid alkyl ester (alkyl group having 1 to 30 carbon atoms) [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) Acrylate, dodecyl (meth) acrylate, tridecyl ( Acrylate), tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, etc.], (meth) acrylic acid hydroxyalkyl ester [Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc.]}, ethylenically unsaturated carboxylic acid and its derivatives [(meth) acrylic acid, (meth) acrylamide, etc.], aliphatic hydrocarbon monomer (ethylene , Propylene, etc.), fluorine-containing vinyl monomers [perfluorooctylethyl (meth) acrylate, etc.], nitrogen-containing vinyl monomers (diaminoethyl methacrylate, morpholinoethyl methacrylate, etc.), glycidyl (meth) acrylate Relay - door, and the like.
Of these, preferred are aromatic hydrocarbon monomers, unsaturated nitriles [(meth) acrylonitrile, etc.] and (meth) acrylic acid esters, and more preferred are styrene, (meth) acrylonitrile, ( It is a (meth) acrylic acid alkyl ester.

  The content of the ethylenically unsaturated monomer constituting the polymer polyol is preferably 0.1 to 90% by weight, more preferably 5 to 80% by weight, particularly preferably 10%, based on the polymer polyol. ~ 70 wt%. The average functional group number of the polymer polyol is preferably 2 to 8, and more preferably 2 to 4. The Mn of the polymer polyol is preferably 300 to 30,000, more preferably 500 to 20,000.

  As a method for producing a polymer polyol, for example, a method in which an ethylenically unsaturated monomer is polymerized in a polyol in the presence of a polymerization initiator (radical generator, etc.) (Japanese Patent Publication No. 39-24737, Japanese Patent Publication No. 47-). No. 47999, Japanese Patent Laid-Open No. 50-15894, etc.).

Examples of rosins (c) having active hydrogen capable of reacting with isocyanate include, for example, wood rosin, gum rosin, hydrogenated rosin, disproportionated rosin, tall oil rosin, wood-based polymerized rosin, gum-based polymerized rosin, and tall oil-based polymer. Polymerized rosin such as polymerized rosin, and mixtures thereof. Moreover, it is preferable to use rosins having a hydroxyl group as the rosins. For example, there are polyester polyols or polyether polyols having a rosin skeleton, which can be obtained by reacting with polyols using rosins as the acid component of the polyester, or compounds having glycidyl groups in the molecule and rosins. It can be obtained by reaction. In this case, the number of hydroxyl groups is preferably 1 to 5 in one molecule. The hydroxyl value is preferably 5 to 1200, more preferably 10 to 570. Mn is preferably 200 to 10,000, and more preferably 300 to 5,000.
The above rosins having a hydroxyl group are preferred because they can react with (a) to form a urethane prepolymer. The rosins can be obtained from Arakawa Chemical Company under trade names such as “Pine Crystal D-6011” and “KE-615-3”.
Mn of (c) is preferably 300 to 15,000, and more preferably 500 to 5,000. Mn is a value obtained by the GPC method.

The equivalent ratio of [(b), (c), total OH (hydroxyl group)] / [(a) NCO (isocyanate group)] is preferably 1 / 1.01 to 1/5, more preferably 1. /1.2 to 1/4, particularly preferably 1 / 1.5-1 to 1/3. By making the isocyanate group of (a) excessive, it becomes an NCO-terminated urethane prepolymer (A) and is reactive when used as a hot melt adhesive.
The blending ratio of each of the above (b) and (c) is preferably 10 to 95% by weight of (b) and 5 to 90% by weight of (c) with respect to the total of (b) and (c). %, More preferably (b) is 20 to 90% by weight, and (c) is 10 to 80% by weight. When (b) is 95% by weight or less, the obtained adhesive has good thermal stability, and when it is 10% by weight or more, there is no problem that the adhesive strength after curing of the obtained adhesive is reduced. When (c) is 90% by weight or less, the viscosity of the obtained adhesive is further lowered, and when it is 5% by weight or more, the initial adhesive force of the obtained adhesive is further improved.
The manufacturing method of a urethane prepolymer (A) is not specifically limited, The following two types of methods can be illustrated.
(I): A method in which (a) and (b) and (a) and (c) are individually reacted and then kneaded.

(Ii) A process for producing a mixture of (b) and (c) and (a).
Among the above methods, the method (ii) is preferable from the viewpoint of the simplicity of the production process and the thermal stability of the obtained adhesive.

When the urethane prepolymer (A) is produced, a urethanization catalyst may be used. As the urethanization catalyst, those conventionally used for polyurethane production can be used.
Metal catalysts such as tin catalysts [trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate, etc.], lead catalysts [lead oleate, 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.], other metal catalysts [naphthalic acid metal salts such as cobalt naphthenate, phenylmercury propionate, etc.]; and amine catalysts such as triethylenediamine, tetramethyl Ethylenediamine, diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7 [DBU (manufactured by San Apro, registered trademark)], etc.]; dialkylaminoalkylamines [dimethylaminoethylamine, dimethylaminopropyl Amines, Ethylaminopropylamine, dipropylaminopropylamine, etc.] or heterocyclic aminoalkylamines [2- (1-aziridinyl) ethylamine, 4- (1-piperidinyl) -2-hexylamine, etc.] carbonates and organic acids Salts (such as formate salts) and the like; N-methylmorpholine, N-ethylmorpholine, triethylamine, diethylethanolamine, dimethylethanolamine, and the like; and combinations of two or more of these.

The use amount of the urethanization catalyst is preferably 1% by weight or less, more preferably 0.05% by weight or less, particularly preferably 0.01% by weight or less, based on the total weight of (a) to (c). . When it is 1% by weight or less, the thermal stability of the finally obtained adhesive is not impaired.
As reaction conditions, for example, (a) to (c) and a urethanization catalyst are charged into a reaction vessel equipped with a temperature control function, and continuously reacted at a temperature of 50 to 200 ° C. for 30 to 1,000 minutes. There are a method, a method in which (a) to (c) and the urethanization catalyst are poured into, for example, a biaxial excluder, and preferably reacted continuously at a temperature of 100 to 220 ° C.
The content of isocyanate groups in the urethane prepolymer (A) comprising (a) to (c) is preferably 0.2 to 10% by weight, more preferably 0.5 to 5% by weight. . When it is 0.2% by weight or more, the heat resistance is good, and when it is 10% by weight or less, the thermal stability at the time of heating and melting is good.

The thermoplastic elastomer (D) is an elastomer having a glass transition temperature much lower than room temperature, maintaining a highly elastic rubber state at room temperature without intermolecular crosslinking, and having microphase separation. It can be molded at high temperatures and can be recycled, unlike ordinary crosslinked elastomers.
(D) includes one or more selected from the group consisting of polyolefin resins, diene (co) polymers, polyester resins, polyurethane resins and polyamide resins. Of these, polyolefin resins, polyurethane resins, and polyamide resins are preferable, and polyolefin resins are more preferable.
Mn of (D) is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000.

Examples of the polyolefin resin (D1) include ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-vinyl acetate copolymers, α-olefin homopolymers, and the like and graft reaction products of these with vinyl monomers. be able to. Of these, preferred are ethylene-propylene copolymer, ethylene-butene copolymer, α-olefin homopolymer, and graft reaction product of these with vinyl monomer.
Examples of the diene (co) polymer (D2) include butadiene rubber, isoprene rubber, natural rubber, butyl rubber, nitrile rubber, acrylic rubber, acrylonitrile-butadiene copolymer rubber (NBR), and styrene-butadiene-styrene block copolymer rubber. Hydrogen in which part or all of the diene part of (SBS), styrene-isoprene-styrene block copolymer rubber (SIS), styrene-butadiene random copolymer rubber (SBR), and diene (co) polymer rubber is hydrogenated [Styrene- (ethylene-propylene) -styrene block copolymer rubber (SEPS; hydrogenated SIS), styrene- (ethylene-butene) -styrene block copolymer rubber (SEBS; hydrogenated SBS), styrene -Ethylene- (ethylene-propylene) -styrene block copolymer Body rubber (SEEPS; hydrogen embodying the SIBS), hydrogenated SBR, etc.] and the like. Of these, preferred are SBS, SIS, SEPS, SEBS, and SEEPS.

As the polyester resin (D3), those obtained by polymerizing at least one polyester forming monomer selected from the group consisting of the following (1) to (3) by a conventional method can be used.
(1) Carbonic acid or dicarboxylic acids (d31) and / or ester-forming derivatives thereof (E32) and diol (d33)
(2) Lactone (d34)
(3) Hydroxycarboxylic acid (d35)
As dicarboxylic acid (d31), the same thing as said (b14) can be used.

The ester-forming derivative (d32) includes an ester (b14), an acid anhydride, and an acid halide. Examples thereof include carbonic acid and dialkyl (carbon number 1 to 4) ester (dimethyl ester, diethyl ester, dibutyl ester) and diphenyl ester of the above dicarboxylic acid, and acid anhydrides (for example, phthalic anhydride).
Dicarboxylic acids and ester-forming derivatives may be used alone or in combination of two or more.
Of these, preferred are sebacic acid, icosandiic acid, 1,4-cyclohexanedicarboxylic acid, diphenyl carbonate, dimethyl adipate, dimethyl 1,4-cyclohexanedicarboxylate, and sodium 5-sulfoisophthalate. More preferred are adipic acid, terephthalic acid, isophthalic acid, phthalic acid, sodium 5-sulfoisophthalate, dimethyl carbonate, dimethyl terephthalate, dimethyl isophthalate and 5-sulfoisophthalic acid sodium salt dimethyl ester.

As the diol (d33), glycol and / or polyoxyalkylene diol and phenol can be used.
As glycol, the same thing as said (b12) can be used.
The polyoxyalkylene glycol is represented by the following general formula (1), and R has two active hydrogen atoms selected from the group consisting of alcohol, phenol, amine, carboxyl group-containing compound, thiol and phosphorus-containing acid. A residue obtained by removing active hydrogen from a compound. R-[-(AO) p-H] ₂ (1)
A is an alkylene group having 2 to 12 carbon atoms which may be substituted with a halogen, an aryl group, a halo-substituted aryl group or a cycloalkyl group; p is an integer of 1 to 200, preferably 2 to 100, more preferably 1-80.
(D33) may be used alone or in combination of two or more.
Of these, propylene glycol, neopentyl glycol, cyclohexanediol, bisphenol A, and polypropylene glycol are preferred. More preferred are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polytetramethylene glycol, EO adduct of bisphenol A and PO adduct of bisphenol A.
Mn of (d33) is not particularly limited, but is preferably 10,000 or less, more preferably 4,000 or less, and particularly preferably 62 to 3,000, from the viewpoint of the melt viscosity of the hot melt adhesive. .

As the lactone (d34), a lactone having 4 to 20 carbon atoms can be used. For example, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-pimerolactone, γ-caprolactone, γ- Examples include decanolactone, enanthlactone, laurolactone, undecanolactone, and eicosanolactone. (E34) may be used alone or in combination of two or more. Of these, γ-butyrolactone, ε-caprolactone, δ-valerolactone, enanthlactone and laurolactone are preferred.
As the hydroxycarboxylic acid (d35), a hydroxycarboxylic acid having 2 to 20 carbon atoms can be used. For example, hydroxyacetic acid, lactic acid, ω-hydroxycaproic acid, ω-hydroxyenanthic acid, ω-hydroxycaprylic acid, ω-hydroxy Examples include pergonic acid, ω-hydroxycapric acid, 11-hydroxyundecanoic acid, 12-hydroxydodecanoic acid and 20-hydroxyeicosanoic acid. (D35) may be used alone or in combination of two or more. Of these, preferred are ω-hydroxycaproic acid, 11-hydroxyundecanoic acid and 12-hydroxydodecanoic acid.

  Specific examples of the (D3) include, for example, polyethylene adipate, polyethylene isophthalate, polyethylene terephthalate, polybutylene terephthalate, polycyclohexyl dimethyl terephthalate, polyethylene terephthalate and polycyclohexyl dimethyl terephthalate copolymer and hexamethylene adipate. Can be mentioned.

  The polyurethane resin (D4) is not particularly limited as long as it is a polyisocyanate compound and a polyhydric alcohol synthesized by a conventional polyaddition reaction. For example, as the polyisocyanate and the polyhydric alcohol, The same as a) and (b) can be used.

As the polyamide-based resin (D5), those obtained by polymerizing at least one polyamide-forming monomer selected from the group consisting of the following (4) to (6) by a conventional method can be used.
(4) Aminocarboxylic acid (d51)
(5) Lactam (d52)
(6) Nylon salt consisting of diamine (d53) and dicarboxylic acid

As the aminocarboxylic acid (d51), an aminocarboxylic acid having 2 to 20 carbon atoms can be used, for example, glycine, alanine, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid. , Ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 20-aminoeicosanoic acid and the like. These may be used alone or in combination of two or more.
As the lactam (d52), a lactam having 4 to 20 carbon atoms can be used. , Laurolactam, undecanolactam, eicosanolactam, 5-phenyl-2-piperidone and the like. These may be used alone or in combination of two or more.
As the diamine (d53), a diamine having 2 to 20 carbon atoms can be used. For example, ethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, eicosanediamine, xylylenediamine And cyclohexyldiamine.
Examples of the dicarboxylic acid include (d31).

Specific examples of the (D5) include, for example, nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12, hexamethylenediamine / dimer acid type Examples thereof include polyamide.
Further, as these (D5), polyether ester amides and / or polyester amides obtained by copolymerizing polyether polyols and / or polyester polyols may be used.
The content (% by weight) of (D) is preferably 1% or more based on the weight of the hot melt adhesive of the present invention, from the viewpoint of compatibility with each component in the hot melt adhesive and cohesive strength. Preferably it is 10% or more, and 50% or less is preferable, More preferably, it is 40% or less.
The addition method of (D) is not specifically limited, The following two types of methods can be illustrated.
(I): A method of kneading and producing (A) and (D).
(Ii): (D) A process for producing (A) in the presence.
Of the above methods, the method (ii) is preferred from the viewpoint of the simplicity of the production process and the thermal stability of the resulting adhesive.

The hot melt adhesive of the present invention can contain a tackifying resin (E) that does not contain an active hydrogen such as a hydroxyl group for the purpose of improving the initial adhesive force in the production process or at any stage after production.
As (E), those generally used for hot melt adhesives can be used, and examples thereof include petroleum resins, styrene resins, terpene resins and coumarone resins. The number average molecular weight of these resins is not particularly limited, but is preferably 200 or more and 15,000 or less, more preferably 300 or more and 5,000 or less.
Examples of petroleum resins include aliphatic petroleum resins (polymers based on C4 to C5 mono- or diolefins such as isobutylene, butadiene, 1,3-pentadiene, isoprene, and piperidine), and alicyclic petroleum resins (spent C4). Resin obtained by cyclization and dimerization polymerization of diene component in C5 fraction, resin hydrogenated with aromatic hydrocarbon resin, etc., aromatic petroleum resin (vinyl toluene, indene, α-methylstyrene, C9, etc.) And polymers having a vinyl aromatic hydrocarbon of C10 as a main component), petroleum resins such as aliphatic-aromatic copolymers, and hydrides thereof.

The ring and ball softening point (measurement method: conforming to JAI-7-1991) of (E) is selected depending on the use temperature of the adhesive, but is preferably 30 to 160 ° C, more preferably 60 to 140 ° C.
If a liquid at room temperature is used alone, the cohesive force may be too low, but it can be used in combination with a solid at room temperature.
The addition amount of (E) is preferably 0 to 70% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 50% by mass with respect to the entire hot melt adhesive of the present invention. . When the addition amount exceeds 70% by mass, the adhesive strength after curing is insufficient.

In the hot melt adhesive of the present invention, a softening agent can be added for the purpose of adjusting the viscosity, the adhesive strength, the solidification speed, etc. in the production process or at any stage after the production.
Examples of the softening agent include process oil, plasticizer, liquid rubber, and wax. These may be used alone or in combination of two or more. A softener is a liquid or solid at room temperature and melts at the time of use to lower the melt viscosity of a hot melt adhesive, plasticize it to give an adhesive force, or delay or accelerate the solidification rate. is there.
Examples of the process oil include those having a kinematic viscosity (100 ° C.) of 1 to 100 mm ² / s, such as paraffinic oil, naphthenic oil, and aroma oil.
Examples of the plasticizer include those having a weight average molecular weight (hereinafter referred to as Mw) of 100 to 5,000, such as phthalic acid ester, benzoic acid ester, phosphoric acid ester, aliphatic glycol polyester, and toluenesulfonamide.
Examples of the liquid rubber include those having an Mw of 200 to 10,000, such as liquid polybutene, liquid polybutadiene, liquid polyisoprene, and hydrogenated products thereof.
Examples of the wax include those having an Mw of 100 to 10,000. For example, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, oxidized wax obtained by oxidative decomposition thereof, and (anhydrous) And acid-modified wax obtained by graft-modifying unsaturated carboxylic acid (anhydride) such as maleic acid, fumaric acid and (meth) acrylic acid.
Mw is a value measured by the GPC method described above.

Furthermore, the reactive hot melt adhesive of the present invention can be optionally added with other resin additives in the production process or at any stage after production as long as the properties of the composition are not impaired depending on various purposes and applications. Can be added. The addition amount is preferably 0 to 30% by mass and more preferably 5 to 20% by mass with respect to the entire hot melt adhesive of the present invention.
Examples of the additive include pigments (for example, titanium oxide, carbon black, etc.), dyes, fillers (for example, talc, mica, calcium carbonate, etc.), nucleating agents (for example, sorbitol, phosphate metal salts, benzoic acid metal salts, Metal phosphates, etc.), lubricants (eg, calcium stearate, butyl stearate, oleic amide, etc.), mold release agents (eg, carboxyl-modified silicone oil, hydroxyl-modified silicone oil, etc.), antioxidants (eg, phenol-based) Antioxidants, phosphite antioxidants, thioether antioxidants, amine antioxidants, etc.), light stabilizers (eg benzotriazole, hindered amine, benzoate, benzotriazole, etc.) and flame retardants (eg halogen series) Flame retardant, phosphorus flame retardant, antimony flame retardant, metal hydroxide -Based flame retardants and the like) and the like.

In the reaction of the above (b), (c) and (a), in addition to the urethanization catalyst and solvent, softener, pigment, dye, filler, nucleating agent, lubricant, mold release agent, antioxidant, You may contain a light stabilizer, a flame retardant, etc.
In producing the hot melt adhesive of the present invention, it is sufficient that the constituent components of the adhesive can be heated, melted and kneaded, and ordinary hot melt production equipment can be used.
For example, a mixer, a reaction mixing tank, a single or twin screw extruder, a sigma blade mixer, a butterfly mixer, a kneader, etc., equipped with a highly compressible screw or ribbon stirrer.
The mixing temperature is preferably 60 to 250 ° C., more preferably 80 to 200 ° C., and it is preferably performed in an inert gas atmosphere such as nitrogen gas for preventing resin deterioration.

The adhesive of the present invention thus obtained is appropriately formed into a desired shape such as a block, pellet, powder, sheet or film, and can be used as a hot melt adhesive.
The method for using the hot melt adhesive of the present invention is not particularly limited. For example, when the adhesive is in the form of a block or a pellet, the adhesive is melted and then bonded to a substrate to be bonded. Used by applying.
As an apparatus used for application, an applicator for a normal hot melt adhesive, [for example, a roll coater having a heatable melting tank (gravure roll, reverse roll, etc.), curtain coater, bead, spiral, spray, slot] and Extruders [for example, single screw extruders, twin screw extruders, kneader ruders, etc.].
In the case of an apparatus such as the former, an adhesive is applied to one or both of the adherends and bonded together before cooling and solidification, or after cooling and solidification, the adherends are combined, heated again, and bonded. When bonding, it is better to pressurize, and the pressure can be released after cooling and solidification.
In the case of an apparatus like the latter, it extrudes to one or both of a to-be-adhered body, and after cooling and solidifying, a to-be-adhered body is match | combined, and it heats and bonds again. When bonding, it is better to pressurize, and the pressure can be released after cooling and solidification.
Moreover, it can coextrude between adherends and can perform bonding simultaneously.

When the adhesive is powder, it is used after being applied to the adherend and then heated and bonded. The heating temperature is not particularly limited, but is preferably 10 to 20 ° C. higher than the melting point (or softening point). When bonding, it is better to pressurize, and the pressure can be released after cooling and solidification. The pressure to be applied is not particularly limited as long as sufficient adhesion can be obtained, and is preferably 10 kPa to 5 MPa. The basis weight of the powder is not particularly limited as long as a desired adhesive force can be obtained, but is preferably 10 to 500 g / m ² .

When the adhesive is a sheet or a film, the adhesive is sandwiched between substrates to be bonded together, heated and melted and bonded, or placed on one or both, heated and melted, and before cooling and solidification Or after cooling and solidification, the adherends are combined, heated again and bonded together. The heating temperature at the time of heating and melting is not particularly limited, but is preferably higher by 10 to 20 ° C. than the melting point (or softening point), and the heating temperature at the time of heating again is not particularly limited, but the melting point (or The temperature is preferably 10 to 20 ° C. higher than the softening point). Moreover, it is better to pressurize when bonding, and the pressure can be released after cooling and solidification. The pressure to be applied is not particularly limited as long as a desired adhesive force can be obtained, and is preferably 10 kPa to 5 MPa.
The size of the sheet or film is not particularly limited as long as it has a desired area. Although the thickness of a sheet | seat or a film does not have a restriction | limiting in particular, Preferably it is 10-500 micrometers, More preferably, it is 30-300 micrometers.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In the examples, “parts” represents parts by weight, and “%” represents% by weight.

Production Example 1
In a separable flask equipped with a thermometer controller, a reflux dehydrator and a stirrer, 310.1 parts of adipic acid, “New Pole BPE-20” (manufactured by Sanyo Chemical Industries, Ltd .; bisphenol A ethylene oxide adduct, hydroxyl value = 343) 0.0) 766.3 parts was charged, the temperature was raised to 150 ° C., and stirring was started after the raw material was melted and stirred, and the temperature was gradually raised from 150 ° C. to 230 ° C. over 8 hours. The reaction was carried out at 230 ° C. for 4 hours, and further under a reduced pressure of 133 Pa or less for 4 hours. As a result, the polyester polyol having an acid value = 0.9, a hydroxyl value = 31.9, and Mn = 3,400 [B2-1] was obtained.

Production Example 2
A separable flask equipped with the same apparatus as in Example 1 was charged with 500.0 parts of “SANNICS GP-4000” (manufactured by Sanyo Chemical Industries; glycerin propylene oxide adduct, hydroxyl value = 42.0), and the temperature was raised. To 100 ° C., and a mixture of 30.0 parts of ethyl methacrylate, 120.0 parts of acrylonitrile, 350.0 parts of styrene and 10.0 parts of 2,2′-azobisisobutyronitrile (AIBN) is taken over 1 hour. It was dripped. Thereafter, 5.0 parts of AIBN was charged and aged at 100 ° C. for 2 hours to obtain a polymer polyol [b3-1] (polymer content: 50%, 23 ° C. viscosity: 5,000 mPa · s).

(Description of abbreviations used in the following examples)
[B1-1]: “New Pole BPE-100” (manufactured by Sanyo Chemical Industries, Ltd .; bisphenol A ethylene oxide adduct, hydroxyl value = 168.0)
[B1-2]: “Sanix PP-2000” (manufactured by Sanyo Chemical Industries, Ltd .; polyoxypropylene glycol, hydroxyl value = 55.2)
[C-1]: “Pine Crystal D-6011” (manufactured by Arakawa Chemical Industries, Ltd .; rosin-containing polyol, hydroxyl value = 119.5, Mn = 950)
[C-2]: “Pine Crystal KE-359” (manufactured by Arakawa Chemical Industries, Ltd .; rosin ester, hydroxyl value = 42.8, Mn = 2,600)
[D-1]: “Evaflex EV410” (manufactured by Mitsui DuPont Polychemical Co., Ltd .; ethylene-vinyl acetate copolymer, vinyl acetate content 19% by weight, Mn = 50,000)
[D-2]: “Clayton D-1155” (manufactured by Kraton Polymer Japan; styrene-butadiene-styrene block copolymer rubber, styrene content 40% by weight, Mn = 90,000)
[D-3]: “Byron GM900” (manufactured by Toyobo Co., Ltd .; polyester resin, Mn = 25,000)
[D-4]: “T-1190” (manufactured by Dainippon Ink & Chemicals, Inc .; urethane resin, Mn = 20,000)
[D-5]: “Thermelt 867” (manufactured by Aron Evergrip Limited; polyamide resin, Mn = 25,000)
[E-1]: “Clearon P-85” (manufactured by Yasuhara Chemical; hydrogenated terpene resin, hydroxyl value = 0, Mn = 630)
[E-2]: “YS resin TO-85” (manufactured by Yasuhara Chemical Co., Ltd .; aromatic modified terpene resin, hydroxyl value = 0, Mn = 750)
[F-1]: “Nicanol KL-05” (manufactured by Fudou; xylene resin, hydroxyl value = 6.3, Mn = 4,500)

Example 1
In a separable flask equipped with a temperature controller and a stirrer, 25.0 parts of [b1-1], 5.0 parts of [b1-2], 50.0 parts of [c-1] and [D-1] 20.0 The parts were charged and dissolved at 120 ° C., followed by dehydration under reduced pressure (120 ° C., 133 Pa, 1 hour). In a nitrogen atmosphere, 47.0 parts of MDI was added, and after aging at 80 ° C. for 4 hours, the hot melt adhesive (NCO%: 5.38%, 120 ° C. melt viscosity: 22,000 mPa · s) of the present invention was removed. Obtained.

Examples 2-8
With the compositions and parts by weight shown in Table 1, the same operations as in Example 1 were performed to obtain the hot melt adhesives of the present invention.

Comparative Examples 1-4
With the composition and parts by weight as shown in Table 1, the same operations as in Example 1 were performed to obtain comparative hot melt adhesives.

<Sample evaluation method>
1) Melt viscosity: The temperature of a sample was controlled at 120 ° C. for 15 minutes, and then measured using a B-type viscometer at the same temperature.
2) Adhesive time after coating; each of the above hot melt adhesives was melted at a temperature of 120 ° C., and was used in a 23 ° C. atmosphere using a curtain spray coating machine (hot air pressure 1.5 kg / cm ² , It is applied on MDF (medium density fiber board) at a hot air temperature of 140 ° C., a gun head temperature of 130 ° C., a distance of 10 cm between the gun head and the adherend, and a coating amount of 100 g / m ^2. Time).
3) Initial adhesive strength; applied onto MDF (length 10 cm, width 10 cm, thickness 1 cm) in the same manner as 2), and after 2 minutes, a wooden thin plate (length 10 cm, width 10 cm, thickness 0.5 mm, The shape was slightly wavy, and was bonded together under a 23 ° C. atmosphere under a press pressure of 5 kgf / cm ² and a press time of 2 minutes. Thereafter, the press was released and left for 5 hours in an atmosphere of 35 ° C. and 50% RH, and the state of the adhesive was observed and evaluated according to the following criteria.
Evaluation criteria A: The area of the floating or peeling part of the wooden thin plate is 0 cm ² or more and less than 1 cm ²
○: The area of the floating and peeling parts of the wooden thin plate is 1 cm ² or more and less than 3 cm ²
X: The area of the floating and peeling part of the wooden thin plate is 3 cm ² or more.

4) Adhesive strength after curing: pasted in the same manner as in 3), left in a constant temperature and humidity chamber at 23 ° C. and 50% RH for 1 week, and then measured 180 ° peel strength. At this time, the destruction state was also observed.
The post-curing adhesive strength was measured under the condition of a tensile speed of 100 mm / min using an autograph according to JIS K6854-1999.
5) Workability of the bonded body: Bonded in the same manner as in 3), and left in a constant temperature and humidity chamber at 23 ° C. and 50% RH for 1 day. The bonded body was cut out using a saw, and the state at the time of cutting was observed and evaluated according to the following criteria.
Evaluation criteria ○: No adhesive fusion to the saw blade
X: Adhesive fusion on the saw blade 6) Thermal stability: The hot melt adhesive of the present invention and the comparative hot melt adhesive were left in an incubator at 120 ° C. for 8 hours in an air atmosphere, and the viscosity The change (expressed after the test / initial viscosity ratio) was measured and defined as thermal stability. The closer the value is to 1, the better the thermal stability.
7) Odor, 8) Smoke; The hot melt adhesive of the present invention and the comparative hot melt adhesive were allowed to stand in an incubator at 120 ° C. for 3 hours in an air atmosphere, and the odor and smoke state (viewed) by five panelists. Evaluation) was confirmed.
The above results are shown in Table 2.

* 1 (I): Material destruction of wooden thin plate, (II): Cohesive failure of adhesive layer * 2 Adhesion cannot be measured because of high melt viscosity and cannot be applied with curtain spray coating machine

The use of the hot melt adhesive of the present invention is not particularly limited. For example, wood, synthetic wood, wooden decorative board, various plastic molded products (molded article, film, sheet), various plastic foams (polyurethane foam, polyolefin foam), It can be used for adhesion of the same or different materials such as metal products (copper, aluminum, stainless steel, steel plate, etc.), fiber products (natural fibers, synthetic fibers, nonwoven fabrics, etc.), paper, natural or synthetic leather.
Specifically, it can be suitably used for adhesion of construction members (floor materials, panels, boards, cloths, metals, etc.), clothing materials (fibers, woven fabrics, films, etc.), etc., but is not limited thereto. It is not something.

Claims (9)

The urethane prepolymer (A) and the thermoplastic elastomer (D) formed by reacting the polyisocyanate (a), the polyol (b), and the rosin (c) having an active hydrogen that reacts with the isocyanate are essential components. Reactive hot melt adhesive characterized. The adhesive according to claim 1, wherein (b) is one or more selected from the following (b1) to (b3).
(B1): phenols or alcohols added with alkylene oxides having 2 to 4 carbon atoms (b2): condensed polyester polyols of dicarboxylic acids and (b1) (b3): (b1) and / or (b2 ) Polymer polyol obtained by polymerizing ethylenically unsaturated monomer in The adhesive according to claim 1 or 2, wherein (c) is a rosin having a hydroxyl group. The adhesive according to any one of claims 1 to 3, wherein (D) is at least one selected from the group consisting of a polyolefin resin, a diene (co) polymer, a polyester resin, a polyurethane resin, and a polyamide resin. The adhesive according to any one of claims 1 to 4, wherein (A) is obtained by reacting in (D). Furthermore, tackifying resin (E) is added, The adhesive agent in any one of Claims 1-5. The adhesive according to any one of claims 1 to 6, further comprising at least one selected from the group consisting of a pigment, a dye, a filler, a nucleating agent, a release agent, an antioxidant, a light stabilizer, and a flame retardant. Hardened | cured material formed by hardening the adhesive agent in any one of Claims 1-7. An adherend bonded with the adhesive according to claim 1.