WO2016002335A1 - 反応性ホットメルト接着剤組成物 - Google Patents
反応性ホットメルト接着剤組成物 Download PDFInfo
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- WO2016002335A1 WO2016002335A1 PCT/JP2015/063200 JP2015063200W WO2016002335A1 WO 2016002335 A1 WO2016002335 A1 WO 2016002335A1 JP 2015063200 W JP2015063200 W JP 2015063200W WO 2016002335 A1 WO2016002335 A1 WO 2016002335A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4891—Polyethers modified with higher fatty oils or their acids or by resin acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/6715—Unsaturated monofunctional alcohols or amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
- C08G18/8166—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with unsaturated monofunctional alcohols or amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
Definitions
- the present invention relates to a reactive hot melt adhesive composition.
- Patent Document 1 a polyurethane hot melt adhesive composition containing an isocyanate and an acrylic polymer, wherein the acrylic polymer is a high molecular weight acrylic polymer.
- an object of this invention is to provide the reactive hot-melt-adhesive composition which is excellent in water-resistant adhesiveness.
- the present inventor contains a urethane prepolymer having an isocyanate group, a (meth) acrylic resin, and an adhesion-imparting agent containing at least an isocyanate group-containing (meth) acrylamide compound.
- the present inventors have found that the composition can be a moisture-curable reactive hot melt adhesive having excellent water-resistant adhesion (particularly excellent in hot water-resistant adhesion), and completed the present invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
- a urethane prepolymer having an isocyanate group (Meth) acrylic resin, A moisture-curable reactive hot-melt adhesive composition containing an adhesion promoter containing at least an isocyanate group-containing (meth) acrylamide compound.
- the amount of the adhesion-imparting agent is 1 to 5 parts by mass with respect to a total of 100 parts by mass of the polyol and polyisocyanate 2 used in the production of the urethane prepolymer and the (meth) acrylic resin.
- the urethane prepolymer is a compound produced by reacting a bifunctional polyol and / or a trifunctional polyol with polyisocyanate 2, The reactive hot melt adhesive according to any one of (1) to (3), wherein the bifunctional polyol is at least one selected from the group consisting of polyoxypropylene diol, polyoxyethylene diol, and castor oil-based polyol. Agent composition.
- the reactive hot melt adhesive composition according to (4), wherein the trifunctional polyol has a weight average molecular weight of 5,000 or more.
- the reactive hot melt adhesive composition of the present invention is excellent in water-resistant adhesion.
- the reactive hot melt adhesive composition of the present invention (the composition of the present invention) A urethane prepolymer having an isocyanate group; (Meth) acrylic resin, A moisture-curable reactive hot-melt adhesive composition containing an adhesion-imparting agent containing at least an isocyanate group-containing (meth) acrylamide compound.
- the composition of this invention is excellent in water-resistant adhesiveness by containing the adhesion imparting agent which contains an isocyanate group containing (meth) acrylamide compound at least.
- the adhesion imparting agent which contains an isocyanate group containing (meth) acrylamide compound at least.
- the reason is not clear, but it is presumed that it is as follows. That is, since the isocyanate group-containing (meth) acrylamide compound contained in the reactive hot melt adhesive composition of the present invention has an isocyanate group and a (meth) acrylamide group, the isocyanate group is a urethane prepolymer in the composition, etc.
- the (meth) acrylamide group improves the wettability with the substrate.
- the isocyanate group-containing (meth) acrylamide compound functions as an adhesion-imparting agent that improves the adhesion between the composition and the substrate.
- the composition of the present invention is excellent in adhesiveness, and it is considered that the adhesiveness is maintained even when immersed in warm water (that is, excellent in water-resistant adhesiveness). This is also inferred from the fact that the shear strength retention after water aging is low when the isocyanate group-containing (meth) acrylamide compound is not contained (Comparative Example 1), as shown in Comparative Examples described later.
- the urethane prepolymer contained in the composition of the present invention has an isocyanate group.
- One preferred embodiment of the urethane prepolymer is a urethane prepolymer containing a plurality of isocyanate groups in one molecule at the molecular end.
- a conventionally well-known thing can be used as a urethane prepolymer.
- a polyisocyanate and a compound having two or more active hydrogen-containing groups in one molecule hereinafter abbreviated as “active hydrogen compound” are used so that the isocyanate groups are excessive with respect to the active hydrogen-containing groups.
- active hydrogen compound a compound having two or more active hydrogen-containing groups in one molecule
- the reaction product obtained by making it react can be used.
- the active hydrogen-containing group means a group containing active hydrogen. Examples of the active hydrogen-containing group include a hydroxy group, an amino group, and an imino group.
- polyisocyanate 2 The polyisocyanate used in the production of the urethane prepolymer (this polyisocyanate is hereinafter referred to as polyisocyanate 2) is not particularly limited as long as it has two or more isocyanate groups in the molecule.
- polyisocyanate 2 examples include tolylene diisocyanate (TDI, eg, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), diphenylmethane diisocyanate (MDI, eg, 4,4′-diphenylmethane diisocyanate, 2, 4'-diphenylmethane diisocyanate), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI) ), Aromatic polyisocyanates such as triphenylmethane triisocyanate; hexamethylene diisocyanate (HDI), trimer Le hexamethylene diisocyanate (TMHDI), lysine diis
- Polyisocyanate 2 is preferably an aromatic polyisocyanate and more preferably MDI because of its excellent curability. Polyisocyanate 2 can be used alone or in combination of two or more.
- the compound (active hydrogen compound) which has two or more active hydrogen containing groups in 1 molecule used in the case of manufacture of a urethane prepolymer is not specifically limited.
- the active hydrogen-containing group include a hydroxyl group (OH) group, an amino group, and an imino group.
- the active hydrogen compound for example, a polyol having two or more hydroxyl (OH) groups in one molecule, a polyamine compound having two or more amino groups and / or imino groups in one molecule, etc. are preferable. Among them, a polyol is preferable.
- the active hydrogen compounds can be used alone or in combination of two or more.
- Polyol is a compound having two or more OH groups in one molecule.
- polystyrene resin examples include polyether polyols; castor oil-based polyols; polyester polyols; polymer polyols having a carbon-carbon bond in the main chain skeleton such as acrylic polyols, polybutadiene diols, and hydrogenated polybutadiene polyols; low molecular weight polyhydric alcohols
- polyether polyols and castor oil-based polyols are mentioned as one of preferred embodiments.
- the polyether polyol is not particularly limited as long as it is a compound having polyether as a main chain and having two or more hydroxy groups.
- the polyether is a group having two or more ether bonds. Specific examples thereof include a group having two or more structural units —R a —O—R b — in total.
- R a and R b each independently represent a hydrocarbon group.
- the hydrocarbon group is not particularly limited. For example, a linear alkylene group having 1 to 10 carbon atoms can be mentioned.
- polyether polyol examples include polyoxyethylene diol (polyethylene glycol), polyoxypropylene diol (polypropylene glycol: PPG), polyoxypropylene triol, ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG). And polyoxyalkylene polyols such as polytetraethylene glycol; sorbitol-based polyols and the like.
- Castor oil-based polyol is not particularly limited.
- the polyol is preferably a bifunctional polyol (a compound having two hydroxyl groups in one molecule) and / or a trifunctional polyol (a compound having three hydroxyl groups in one molecule).
- the bifunctional polyol is preferably a polyoxyalkylene diol and / or a castor oil-based diol, and more preferably at least one selected from the group consisting of polyoxypropylene diol, polyoxyethylene diol and castor oil-based diol.
- the weight average molecular weight of the bifunctional polyol is preferably 5,000 or less, and more preferably 2,000 to 4,000.
- the weight average molecular weight of the polyol is a polystyrene equivalent value obtained by the GPC method (solvent: tetrahydrofuran (THF)).
- the amount of the bifunctional polyol is preferably 30 to 80 parts by mass in a total of 100 parts by mass of the polyol and polyisocyanate 2 used in the production of the urethane prepolymer and the (meth) acrylic resin.
- the bifunctional polyol it is preferable to use castor oil-based polyol (particularly castor oil-based diol) for the reason of better adhesion to the substrate (particularly olefin resin).
- the amount of castor oil-based polyol is preferably 5 to 30% by mass based on the total amount of polyol used for the production of the urethane prepolymer.
- the trifunctional polyol is preferably polyoxyalkylene triol, more preferably polyoxyethylene triol or polyoxypropylene triol.
- the weight average molecular weight of the trifunctional polyol is preferably 3,000 or more, and more preferably 5,000 to 10,000 from the viewpoint of excellent viscosity, strength, and adhesiveness.
- the amount of the trifunctional polyol is preferably 5 to 50% by mass, and more preferably 5 to 45% by mass, based on the total amount of polyol used for the production of the urethane prepolymer.
- the method for producing the urethane prepolymer is not particularly limited.
- polyisocyanate is used so that 1.3 to 2.5 mol of an isocyanate group reacts with respect to 1 mol of an active hydrogen-containing group (for example, a hydroxy group) of the active hydrogen compound, and these are mixed and reacted.
- an active hydrogen-containing group for example, a hydroxy group
- the urethane prepolymers can be used alone or in combination of two or more.
- the (meth) acrylic resin will be described below.
- the (meth) acrylic resin contained in the composition of the present invention is not particularly limited.
- the composition of this invention can express high adhesiveness in an initial stage by containing a (meth) acrylic resin.
- (meth) acryl means acryl or methacryl.
- (Meth) acrylic resin will not be restrict
- (meth) acrylic monomers include (meth) acrylate monomers, acid functional group-containing (meth) acrylic monomers, tertiary amine-containing (meth) acrylic monomers, and hydroxy group-containing (meth) acrylic monomers. Can be mentioned.
- the (meth) acrylic resin may be either a homopolymer or a copolymer.
- the (meth) acrylic resin is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
- the (meth) acrylic resins can be used alone or in combination of two or more.
- the amount of (meth) acrylic resin is preferably 20 to 50 parts by mass with respect to 100 parts by mass of the urethane prepolymer from the viewpoint of excellent initial strength.
- the adhesion imparting agent will be described below.
- the adhesion-imparting agent contained in the composition of the present invention contains at least an isocyanate group-containing (meth) acrylamide compound.
- One preferred embodiment is that a part of the adhesion-imparting agent is an isocyanate group-containing (meth) acrylamide compound.
- All of the adhesion-imparting agents may be isocyanate group-containing (meth) acrylamide compounds.
- the isocyanate group-containing (meth) acrylamide compound will be described below.
- the isocyanate group-containing (meth) acrylamide compound contained in the adhesion-imparting agent is not particularly limited as long as it is a compound having at least one isocyanate group and at least one (meth) acrylamide group in one molecule.
- the (meth) acrylamide group refers to a group represented by CH 2 ⁇ CR—CO—N (R is a hydrogen atom or a methyl group).
- R is a hydrogen atom or a methyl group.
- the isocyanate group and the (meth) acrylamide group can be bonded via, for example, a hydrocarbon group that may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
- adhesion-imparting agent contained in the composition of the present invention does not contain a (meth) acrylic resin.
- the adhesion-imparting agent is mentioned as one of preferred embodiments that is produced by reacting a hydroxyl group-containing compound having a hydroxyl group and a (meth) acrylamide group with polyisocyanate 1. It is done.
- the polyisocyanate 1 used for the production of the adhesion promoter is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule.
- the thing similar to the polyisocyanate 2 is mentioned.
- a modified product of aliphatic polyisocyanate can be mentioned.
- the modified product of the aliphatic polyisocyanate include an allophanate-modified product, an isocyanurate-modified product, and a modified product with trimethylolpropane.
- an allophanate-modified product of aliphatic polyisocyanate is preferable from the viewpoint of excellent workability (easy handling of the imparting agent itself).
- an allophanate modified body of aliphatic polyisocyanate the allophanate modified body of hexamethylene diisocyanate is mentioned, for example.
- the hydroxyl group-containing compound used for the production of the adhesion-imparting agent is not particularly limited as long as it is a compound having at least one hydroxyl group and at least one (meth) acrylamide group in one molecule.
- the hydrocarbon group having a hydroxy group include an alkyl group having a hydroxy group.
- the number of hydroxy groups contained in the hydroxyl group-containing compound is preferably one per molecule.
- hydroxyl group-containing compound examples include N-hydroxyethyl (meth) acrylamide (HEAA) and N-hydroxymethyl (meth) acrylamide.
- adhesion-imparting agent for example, a hydroxyl group-containing compound and polyisocyanate 1 are mixed in an amount such that the index (molar ratio of NCO / OH) is 2 to 10, and these are reacted in a nitrogen atmosphere.
- An adhesion-imparting agent can be produced.
- the isocyanate group-containing (meth) acrylamide compound contained in the adhesion-imparting agent for example, at least one (but not all) of the plurality of isocyanate groups possessed by polyisocyanate 1 reacts with the hydroxyl group of the hydroxyl group-containing compound.
- the produced compound in which one molecule can have an allophanate bond in addition to a (meth) acrylamide group, a urethane bond and an isocyanate group) can be mentioned.
- R 1 represents a hydrogen atom or a methyl group.
- R 2 represents a hydrogen atom or a hydrocarbon group.
- R 2 is preferably a hydrogen atom.
- R 3 and R 4 each independently represent a hydrocarbon group which may have a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom.
- R 3 at least one carbon atom in the hydrocarbon group may be substituted with an allophanate bond.
- the allophanate bond is not particularly limited.
- R 4 is preferably an aliphatic hydrocarbon group.
- m and n are each independently 1 or more, and preferably 1 or 2.
- m + n is preferably from 2 to 3, more preferably 2.
- the hydrocarbon group is not particularly limited.
- the hydrocarbon group may have 1 to 30 carbon atoms.
- Examples of the hydrocarbon group include an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and combinations thereof.
- the hydrocarbon group may be linear or branched and may have an unsaturated bond.
- the hydrocarbon group is exemplified as being monovalent or divalent or higher. The same applies to the following examples of various hydrocarbon groups.
- Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and an eicosyl group.
- Examples of the alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group.
- Examples of the aromatic hydrocarbon group include a phenyl group, a naphthalene ring, and an anthracene ring.
- the hydrocarbon group has a hetero atom
- at least one of the carbon atoms in the hydrocarbon group is a hetero atom or a functional group having a hetero atom (for example, a divalent or higher functional group). May be substituted and / or at least one of the hydrogen atoms in the hydrocarbon group (in which case the number of carbon atoms is not limited) is substituted with a functional group containing a hetero atom (eg, a monovalent functional group). Also good.
- Examples of the functional group include monovalent functional groups such as hydroxy group, amino group, mercapto group, isocyanate group, and alkoxysilyl group; divalent groups such as carbonyl group, urethane bond, urea bond, allophanate bond, and ester bond.
- monovalent functional groups such as hydroxy group, amino group, mercapto group, isocyanate group, and alkoxysilyl group
- divalent groups such as carbonyl group, urethane bond, urea bond, allophanate bond, and ester bond.
- heteroatom can form, for example, an ether bond, a secondary amine, a tertiary amine, a sulfide bond.
- the adhesion-imparting agent can further contain a (meth) acrylamide compound not containing an isocyanate group, in addition to the isocyanate group-containing (meth) acrylamide compound.
- a (meth) acrylamide compound not containing an isocyanate group for example, in the reaction of a hydroxyl group-containing compound and polyisocyanate 1, a compound produced by reacting all isocyanate groups of polyisocyanate 1 with a hydroxyl group-containing compound is used. Can be mentioned.
- the adhesion-imparting agent can further contain polyisocyanate 1 that has not reacted with the hydroxyl group-containing compound, in addition to the isocyanate group-containing (meth) acrylamide compound.
- Polyisocyanate 1 that has not reacted with the hydroxyl group-containing compound may be in an unreacted state or an oligomer of polyisocyanate 1.
- the amount of the adhesion-imparting agent is preferably 1 to 5 parts by mass with respect to 100 parts by mass in total of the urethane prepolymer and the (meth) acrylic resin from the viewpoint of being superior in water-resistant adhesion.
- the composition of the present invention can further contain a reaction catalyst from the viewpoint of excellent curability.
- the reaction catalyst is not particularly limited as long as it promotes the reaction of isocyanate groups.
- An example is dimorpholinodiethyl ether.
- the amount of the reaction catalyst is not particularly limited. For example, it can be the same amount as conventionally known.
- the composition of the present invention can be used as long as it does not impair the purpose of the present invention, if necessary, for example, an adhesion imparting agent other than the adhesion imparting agent contained in the composition of the present invention, a filler (for example, carbon black, carbonic acid Calcium), plasticizers, anti-aging agents, antioxidants, pigments, thixotropic agents, UV absorbers, flame retardants, surfactants, dispersants, dehydrating agents, antistatic agents, etc. it can.
- the amount of the additive is not particularly limited. For example, it can be the same as conventionally known.
- the production method of the composition of the present invention is not particularly limited.
- the polyol and (meth) acrylic resin used in the production of the urethane prepolymer are stirred at 120 ° C. under reduced pressure, and the polyol and the (meta ) The mixture with the acrylic resin is dehydrated, and then the polyisocyanate 2 used for the production of the urethane prepolymer is added to the mixture after dehydration under the condition of 120 ° C.
- a (meth) acrylic resin mixture, and an adhesion-imparting agent, which can be added as necessary, to the mixture, a reaction catalyst and additives are added and mixed to produce the composition of the present invention. Can do.
- the composition of the present invention can be a one-component type or a two-component type.
- the composition of the present invention is used as a main agent (first liquid), and the set includes the main agent and a curing agent (curing agent in a broad sense; second liquid).
- the hardener in the broad sense (second liquid) includes a hardener (hardener in the narrow sense) as a curing component, and the hardener in the narrow sense is not particularly limited as long as it is a compound that can react with the urethane prepolymer. For example, a conventionally well-known thing is mentioned.
- Examples of the substrate to which the composition of the present invention can be applied include plastic, glass, rubber, metal and the like.
- plastics include olefin resins such as polypropylene and polyethylene, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polymethyl methacrylate resin (PMMA resin), polycarbonate resin, polystyrene resin, acrylonitrile / styrene.
- Examples thereof include hard-to-adhere resins such as polymerization resin, polyvinyl chloride resin, acetate resin, ABS resin, and polyamide resin.
- the substrate may be surface treated.
- Examples of the surface treatment include flame treatment, corona treatment, and plasma treatment. These processes are not particularly limited. For example, a conventionally well-known thing is mentioned.
- the composition of the present invention is a moisture curable reactive hot melt adhesive composition, and can be applied to a substrate by heating and melting the composition of the present invention.
- the temperature for heating the composition of the present invention is preferably 110 to 130 ° C.
- the application method to the substrate is not particularly limited. For example, a conventionally well-known thing is mentioned.
- the composition of the present invention is a moisture curable reactive hot melt adhesive composition, which can be reacted and cured by moisture.
- the composition of the present invention can be cured under conditions of 5 to 90 ° C. and a relative humidity of 5 to 95 (% RH).
- the composition of this invention is not hardened
- composition of the present invention can be used in a field where moisture-curing hot melt adhesives are conventionally used.
- moisture-curing hot melt adhesives are conventionally used.
- attachment of the interior material and exterior material for motor vehicles, etc. are mentioned.
- polyisocyanate 2-1 shown in the column of urethane prepolymer in Table 1 is added to the mixture after dehydration in the amount (parts by mass) shown in the same table, and 1 at normal pressure.
- the mixture was reacted for an hour and further stirred for 1 hour under reduced pressure to produce a mixture of urethane prepolymer and (meth) acrylic resin.
- the said urethane prepolymer has an isocyanate group at the terminal.
- composition For the mixture of urethane prepolymer produced as described above (the amount of urethane prepolymer is the total amount of each component in the column of urethane prepolymer in Table 1) and (meth) acrylic resin, The adhesion imparting agent and reaction catalyst shown in Table 1 were added in the amounts (parts by mass) shown in Table 1, and these were mixed with a stirrer to produce a composition.
- the melt viscosity of the composition was measured on 120 degreeC conditions using the Brookfield viscometer (Brooksfield company DV2T viscometer, No. 27 rotor, rotation speed 5.0rpm). Specifically, the composition is preheated to 120 ° C., and 11 g is weighed in a viscometer cup. Set in a viscometer and heat at 120 ° C. for 15 minutes, then set the rotor and heat for another 15 minutes. Thereafter, the measurement was started, and the value after 2 minutes was defined as the initial viscosity.
- Brookfield viscometer Brookfield company DV2T viscometer, No. 27 rotor, rotation speed 5.0rpm
- the composition produced as described above was melted at 120 ° C and applied to polypropylene (with plasma treatment) having a width of 2.5 cm and a length of 5 cm.
- the above polypropylene is pressure-bonded to a polycarbonate having a width of 2.5 cm and a length of 5 cm, and a lap surface (width 2.5 cm, length 1 cm; composition thickness on the wrap surface 5 mm) to produce a test piece. did.
- the test piece was cured for 1 hour under the conditions of 20 ° C. and 50% RH to obtain an initial sample.
- the initial shear strength (initial shear strength) of the initial sample was measured at a tensile speed of 50 mm / min and at 20 ° C.
- Adhesion imparting agent 1 9.4 g of HEAA (N- (2-hydroxyethyl) acrylamide, manufactured by Kojin Co., Ltd.) and polyisocyanate 1-1 (hexamethylene diisocyanate (HDI) allophanate, trade name Takenate D-178NL, Mitsui) Made by Chemical Co., Ltd. 89.6 g (having two isocyanate groups in one molecule) (NCO / OH was a molar ratio of 5 at this time) and these were mixed at 12 ° C. at 60 ° C. under a nitrogen atmosphere.
- HEAA N- (2-hydroxyethyl) acrylamide, manufactured by Kojin Co., Ltd.
- polyisocyanate 1-1 hexamethylene diisocyanate (HDI) allophanate, trade name Takenate D-178NL, Mitsui) Made by Chemical Co., Ltd. 89.6 g (having two isocyanate groups in one molecule) (
- the reaction product was obtained by reacting for a period of time.
- the resulting reaction product is a compound formed by reacting one of the two isocyanate groups of polyisocyanate 1-1 with HEAA (in one molecule, allophanate bonds in addition to acrylamide groups, urethane bonds, isocyanate groups).
- HEAA in one molecule, allophanate bonds in addition to acrylamide groups, urethane bonds, isocyanate groups.
- HEAA a compound formed by reacting both of two isocyanate groups of polyisocyanate 1-1 with HEAA, and HEAA is a mixture containing unreacted polyisocyanate 1-1.
- the mixture produced as described above was used as the adhesion promoter 1.
- the obtained reaction product includes both a compound formed by reacting one of two isocyanate groups of polyisocyanate 1-1 with N-hydroxymethylacrylamide and two isocyanate groups of polyisocyanate 1-1. Is a mixture containing a compound formed by reacting with N-hydroxymethylacrylamide and N-hydroxymethylacrylamide is unreacted polyisocyanate 1-1. The mixture produced as described above was used as the adhesion promoter 2.
- -Reaction catalyst DMDEE Dimorpholino diethyl ether, manufactured by Mitsui Chemicals Fine
- Comparative Example 1 containing no adhesion-imparting agent had low water-resistant adhesion. That is, the shear strength retention after water aging (shear strength after hot water test / shear strength after normal test (measured under 20 ° C. condition)) was low.
- the comparative example 2 which does not contain a (meth) acrylic resin did not harden in the initial stage, and the adhesiveness, heat-resistant adhesiveness, and water-resistant adhesiveness after a normal test were low.
- Examples 1 to 7 were excellent in water-resistant adhesion. Shear strength retention after water aging (shear strength after hot water test / shear strength after normal test (measured under 20 ° C. condition)) was high. Moreover, when Example 1 and Example 5 are compared about the weight average molecular weight of the polyoxyalkylene triol used for manufacture of a urethane prepolymer, Example 1 where the weight average molecular weight of polyoxyalkylene triol is larger is Example. More excellent than 5 in water-resistant adhesion. When Example 1 and Example 7 were compared about the hydroxyl-containing compound used when manufacturing an adhesion
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Abstract
Description
そこで、本発明は耐水接着性に優れる反応性ホットメルト接着剤組成物を提供することを目的とする。
すなわち、本発明者らは、以下の構成により上記課題が解決できることを見出した。
(メタ)アクリル樹脂と、
イソシアネート基含有(メタ)アクリルアミド化合物を少なくとも含む接着付与剤とを含有する、湿気硬化型の反応性ホットメルト接着剤組成物。
(2) 上記接着付与剤が、水酸基と(メタ)アクリルアミド基とを有する水酸基含有化合物と、ポリイソシアネート1とを反応させることによって製造される、上記(1)に記載の反応性ホットメルト接着剤組成物。
(3) 上記接着付与剤の量が、上記ウレタンプレポリマーの製造に使用されるポリオール及びポリイソシアネート2並びに上記(メタ)アクリル樹脂の合計100質量部に対して、1~5質量部である、上記(1)又は(2)に記載の反応性ホットメルト接着剤組成物。
(4) 上記ウレタンプレポリマーが、2官能ポリオール及び/又は3官能ポリオールとポリイソシアネート2とを反応させることによって製造される化合物であり、
上記2官能ポリオールが、ポリオキシプロピレンジオール、ポリオキシエチレンジオール及びひまし油系ポリオールからなる群から選ばれる少なくとも1種である、上記(1)~(3)のいずれかに記載の反応性ホットメルト接着剤組成物。
(5) 上記3官能ポリオールの重量平均分子量が、5,000以上である、上記(4)に記載の反応性ホットメルト接着剤組成物。
(6) 上記3官能ポリオールの量が、上記ウレタンプレポリマーの製造に使用されるポリオール全量中、5~50質量%である、上記(4)又は(5)に記載の反応性ホットメルト接着剤組成物。
本発明の反応性ホットメルト接着剤組成物(本発明の組成物)は、
イソシアネート基を有するウレタンプレポリマーと、
(メタ)アクリル樹脂と、
イソシアネート基含有(メタ)アクリルアミド化合物を少なくとも含む接着付与剤とを含有する、湿気硬化型の反応性ホットメルト接着剤組成物である。
その理由は明らかではないが、およそ以下のとおりと推測される。
すなわち、本発明の反応性ホットメルト接着剤組成物に含有されるイソシアネート基含有(メタ)アクリルアミド化合物はイソシアネート基と(メタ)アクリルアミド基とを有するため、イソシアネート基は組成物中のウレタンプレポリマーなどの他の成分と反応し、また、(メタ)アクリルアミド基は基材との濡れ性を良好にする。すなわち、上記イソシアネート基含有(メタ)アクリルアミド化合物は組成物と基材とを接着性を向上させる接着付与剤として機能する。結果として、本発明の組成物は接着性に優れ、また、温水などに浸漬した場合であっても接着性が保持される(すなわち、耐水接着性に優れる)ものと考えられる。このことは後述する比較例が示すように上記イソシアネート基含有(メタ)アクリルアミド化合物を含有しない場合(比較例1)には耐水老化後の剪断強度保持率が低くなることからも推測される。
ウレタンプレポリマーは、1分子内に複数のイソシアネート基を分子末端に含有するウレタンプレポリマーであるのが好ましい態様の1つとして挙げられる。
ウレタンプレポリマーとしては、従来公知のものを用いることができる。例えば、ポリイソシアネートと1分子中に2個以上の活性水素含有基を有する化合物(以下、「活性水素化合物」と略す。)とを、活性水素含有基に対してイソシアネート基が過剰となるように反応させることにより得られる反応生成物等を用いることができる。
本発明において、活性水素含有基は活性水素を含有する基を意味する。活性水素含有基としては例えば、ヒドロキシ基、アミノ基、イミノ基が挙げられる。
ウレタンプレポリマーの製造の際に使用されるポリイソシアネート(このポリイソシアネートを以下ポリイソシアネート2という。)は、分子内にイソシアネート基を2個以上有するものであれば特に限定されない。
ポリイソシアネート2としては、例えば、トリレンジイソシアネート(TDI。例えば、2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート)、ジフェニルメタンジイソシアネート(MDI。例えば、4,4′-ジフェニルメタンジイソシアネート、2,4′-ジフェニルメタンジイソシアネート)、1,4-フェニレンジイソシアネート、ポリメチレンポリフェニレンポリイソシアネート、キシリレンジイソシアネート(XDI)、テトラメチルキシリレンジイソシアネート(TMXDI)、トリジンジイソシアネート(TODI)、1,5-ナフタレンジイソシアネート(NDI)、トリフェニルメタントリイソシアネートのような芳香族ポリイソシアネート;ヘキサメチレンジイソシアネート(HDI)、トリメチルヘキサメチレンジイソシアネート(TMHDI)、リジンジイソシアネート、ノルボルナンジイソシアネート(NBDI)、トランスシクロヘキサン-1,4-ジイソシアネート、イソホロンジイソシアネート(IPDI)、ビス(イソシアネートメチル)シクロヘキサン(H6XDI)、ジシクロヘキシルメタンジイソシアネート(H12MDI)のような、脂肪族及び/又は脂環式のポリイソシアネート;これらのカルボジイミド変性ポリイソシアネート、イソシアヌレート変性ポリイソシアネート、アロファネート変性体が挙げられる。
ポリイソシアネート2は、それぞれ単独でまたは2種以上を組み合わせて使用することができる。
ウレタンプレポリマーの製造の際に使用される1分子中に2個以上の活性水素含有基を有する化合物(活性水素化合物)は特に限定されない。活性水素含有基としては、例えば、水酸(OH)基、アミノ基、イミノ基が挙げられる。
活性水素化合物はそれぞれ単独で又は2種以上を組み合わせて使用することができる。
ポリエーテルポリオールとしては、例えば、ポリオキシエチレンジオール(ポリエチレングリコール)、ポリオキシプロピレンジオール(ポリプロピレングリコール:PPG)、ポリオキシプロピレントリオール、エチレンオキサイド/プロピレンオキサイド共重合体、ポリテトラメチレンエーテルグリコール(PTMEG)、ポリテトラエチレングリコールのようなポリオキシアルキレンポリオール;ソルビトール系ポリオール等が挙げられる。
本発明において、ポリオールの重量平均分子量は、GPC法(溶媒:テトラヒドロフラン(THF))により得られたポリスチレン換算値である。
ウレタンプレポリマーはそれぞれ単独でまたは2種以上を組み合わせて使用することができる。
本発明の組成物は(メタ)アクリル樹脂を含有することによって、初期段階において高い接着性を発現させることができる。
本発明において、(メタ)アクリルはアクリル又はメタクリルを意味する。
(メタ)アクリル樹脂は単独重合体、共重合体のいずれであってもよい。
(メタ)アクリル樹脂はそれぞれ単独でまたは2種以上を組み合わせて使用することができる。
本発明の組成物に含有される接着付与剤は、イソシアネート基含有(メタ)アクリルアミド化合物を少なくとも含む。
接着付与剤の一部がイソシアネート基含有(メタ)アクリルアミド化合物であるのが好ましい態様の1つとして挙げられる。接着付与剤のすべてがイソシアネート基含有(メタ)アクリルアミド化合物であってもよい。
接着付与剤に含まれるイソシアネート基含有(メタ)アクリルアミド化合物は、1分子中に、少なくとも1個のイソシアネート基と、少なくとも1個の(メタ)アクリルアミド基とを有する化合物であれば特に制限されない。
本発明において、(メタ)アクリルアミド基は、CH2=CR-CO-Nで表される基(Rは水素原子又はメチル基である。)をいう。
イソシアネート基と(メタ)アクリルアミド基とは、例えば、酸素原子、窒素原子、硫黄原子のようなヘテロ原子を有してもよい炭化水素基を介して結合することができる。
例えば、(メタ)アクリルアミド基が有する窒素原子にヒドロキシ基を有する炭化水素基が少なくとも1個結合する化合物が挙げられる。ヒドロキシ基を有する炭化水素基としては例えば、ヒドロキシ基を有するアルキル基が挙げられる。
水酸基含有化合物が有するヒドロキシ基の数は1分子中1個であるのが好ましい。
式(1)中、R2は、水素原子、炭化水素基を示す。R2は水素原子であるのが好ましい。
式(1)中、R3、R4はそれぞれ独立に、例えば、酸素原子、窒素原子、硫黄原子のようなヘテロ原子を有してもよい炭化水素基を示す。R3は、炭化水素基の中の炭素原子の少なくとも1個がアロファネート結合に置換されていてもよい。アロファネート結合は特に制限されない。R4は脂肪族炭化水素基であるのが好ましい。
式(1)中、m、nはそれぞれ独立に1以上であり、1~2であるのが好ましい。m+nは2~3であるのが好ましく、2であるのがより好ましい。
なお炭化水素基は、1価又は2価以上のものとして例示する。以下の各種炭化水素基の例示についても同様である。
脂環式炭化水素基としては、例えば、シクロペンチル基、シクロヘキシル基が挙げられる。
芳香族炭化水素基としては、例えば、フェニル基、ナフタレン環、アントラセン環が挙げられる。
イソシアネート基を含有しない(メタ)アクリルアミド化合物としては、例えば、水酸基含有化合物とポリイソシアネート1との反応において、ポリイソシアネート1が有するすべてのイソシアネート基が水酸基含有化合物と反応することによって製造される化合物が挙げられる。
反応触媒の量は特に制限されない。例えば、従来公知と同様の量とすることができる。
本発明の組成物を2液型に使用する場合、本発明の組成物を主剤(第1液)とし、当該主剤と硬化剤(広義の硬化剤。第2液)とを有するセットとすることができる。
広義の硬化剤(第2液)は硬化成分としての硬化剤(狭義の硬化剤)を含み、狭義の硬化剤はウレタンプレポリマーと反応しうる化合物であれば特に制限されない。例えば、従来公知のものが挙げられる。
プラスチックとしては例えば、ポリプロピレン、ポリエチレンのようなオレフィン樹脂、ポリエチレンテレフタレート(PET)やポリブチレンテレフタレート(PBT)などのポリエステル樹脂、ポリメチルメタクリレート樹脂(PMMA樹脂)、ポリカーボネート樹脂、ポリスチレン樹脂、アクリロニトリル・スチレン共重合樹脂、ポリ塩化ビニル樹脂、アセテート樹脂、ABS樹脂、ポリアミド樹脂のような難接着性樹脂が挙げられる。
本発明の組成物を加熱する温度は、110~130℃であるのが好ましい。
基材への適用方法は特に制限されない。例えば、従来公知のものが挙げられる。
なお、本発明において、紫外線等の光を照射することによって本発明の組成物を硬化させないのが好ましい態様の1つとして挙げられる。
<ウレタンプレポリマーの製造>
第1表のウレタンプレポリマーの欄に示す各成分(ポリイソシアネート2-1を除く。)及び(メタ)アクリル樹脂を同表に示す量(質量部)で反応容器に仕込み、120℃で減圧下2時間攪拌して、ポリオールと(メタ)アクリル樹脂との混合物を脱水した。次に、120℃の条件下で、脱水後の混合物に、第1表のウレタンプレポリマーの欄に示すポリイソシアネート2-1を同表に示す量(質量部)で添加し、常圧下で1時間反応させ、さらに減圧下で1時間攪拌して、ウレタンプレポリマーと(メタ)アクリル樹脂との混合物を製造した。なお、上記ウレタンプレポリマーは、末端にイソシアネート基を有する。
上記のとおり製造されたウレタンプレポリマー(ウレタンプレポリマーの量は第1表のウレタンプレポリマーの欄の各成分の量の合計である。)と(メタ)アクリル樹脂との混合物に対して、第1表に示す接着付与剤と反応触媒とを第1表に示す量(質量部)で添加し、これらを攪拌機で混合して、組成物を製造した。
上記のとおり製造された組成物を用いて以下の評価を行った。結果を第1表に示す。
ブルックフィールド粘度計(ブルックスフィールド社製DV2T粘度計、No.27ローター、回転数5.0rpm)を用いて120℃の条件下で組成物の溶融粘度を測定した。具体的には、組成物を予め120℃に加温し、粘度計カップに11g秤量する。粘度計にセットし120℃で15分加温後ローターをセットしさらに15分加温する。その後測定を開始し、2分後の数値を初期粘度とした。
初期粘度を測定した後、120℃の条件下で90分置き、粘度測定を開始した。開始から2分後の数値を読み取り、老化後の溶融粘度とした。そして、下記の式に当てはめて老化後の増粘率を算出した。
老化後増粘率(%)=[(老化後の溶融粘度-初期粘度)/初期粘度]×100
上記のとおり製造された組成物を120℃で溶融し、これを幅2.5cm、長さ5cmのポリプロピレン(プラズマ処理あり)に塗布した。上記ポリプロピレンを、幅2.5cm、長さ5cmのポリカーボネートと、ラップ面(幅2.5cm、長さ1cm;ラップ面での組成物の厚さ5mm)となるように圧着し、試験片を製造した。
試験片を20℃、50%RHの条件下で1時間養生させ、初期サンプルとした。
上記のとおり得られた初期サンプルを20℃、65%RHの条件下に7日間養生させて、常態試験用サンプルを得た。
上記常態試験用サンプルを用いて引張速度50mm/分で、20℃又は120℃の条件下で剪断強度を測定した。
上記のとおり得られた常態試験用サンプルを120℃の条件下に7日間置く耐熱性試験を行った。7日経過後、得られたサンプルを耐熱性評価用サンプルを得た。
上記耐熱性評価用サンプルを用いて引張速度50mm/分で、20℃の条件下で剪断強度を測定した。耐熱試験後の剪断強度(20℃条件下で測定)は常態の剪断強度(上記の常態試験後の剪断強度(20℃条件下で測定))の70%以上あれば良好とした。
上記のとおり得られた常態試験用サンプルを40℃の温水に7日間浸漬させる耐温水試験を行った。7日経過後、サンプルを温水から引き揚げて耐水接着性評価用サンプルを得た。
上記耐水接着性評価用サンプルを用いて引張速度50mm/分で、20℃の条件下で剪断強度を測定した。
なお、常態の剪断強度(上記の常態試験後の剪断強度(20℃条件下で測定))に対する耐温水試験後の剪断強度(20℃条件下で測定)の保持率(第1表中の「耐水老化後の剪断強度保持率」)が70%以上であれば、耐水接着性に優れると言える。
・接着付与剤1:HEAA(N-(2-ヒドロキシエチル)アクリルアミド、興人社製)9.4gとポリイソアネート1-1(ヘキサメチレンジイソシアネート(HDI)のアロファネート体、商品名タケネートD-178NL、三井化学社製。1分子中にイソシアネート基を2個有する。)89.6gとを混合し(このときNCO/OHはモル比で5であった。)、これらを窒素雰囲気下で60℃で12時間反応させ、反応生成物を得た。
得られた反応生成物は、ポリイソシアネート1-1が有する2つのイソシアネート基のうち1つがHEAAと反応して生成した化合物(1分子中に、アクリルアミド基、ウレタン結合、イソシアネート基の他、アロファネート結合を有する。)と、ポリイソシアネート1-1が有する2つのイソシアネート基の両方がHEAAと反応して生成した化合物と、HEAAとは未反応のポリイソシアネート1-1とを含む混合物である。
上記のとおりにして製造された混合物を接着付与剤1として使用した。
得られた反応生成物は、ポリイソシアネート1-1が有する2つのイソシアネート基のうち1つがN-ヒドロキシメチルアクリルアミドと反応して生成した化合物と、ポリイソシアネート1-1が有する2つのイソシアネート基の両方がN-ヒドロキシメチルアクリルアミドと反応して生成した化合物と、N-ヒドロキシメチルアクリルアミドとは未反応のポリイソシアネート1-1とを含む混合物である。
上記のとおりにして製造された混合物を接着付与剤2として使用した。
・反応触媒 DMDEE:ジモルフォリノジエチルエーテル、三井化学ファイン社製
(メタ)アクリル樹脂を含有しない比較例2は、初期段階で硬化せず、常態試験後の接着性、耐熱接着性、耐水接着性が低かった。
また、ウレタンプレポリマーの製造に使用されるポリオキシアルキレントリオールの重量平均分子量について実施例1と実施例5とを比較すると、ポリオキシアルキレントリオールの重量平均分子量が大きい実施例1のほうが、実施例5よりも耐水接着性により優れた。
接着付与剤を製造する際に使用される水酸基含有化合物について実施例1と実施例7とを比較すると、実施例1のほうが実施例7よりも耐水接着性により優れた。
Claims (6)
- イソシアネート基を有するウレタンプレポリマーと、
(メタ)アクリル樹脂と、
イソシアネート基含有(メタ)アクリルアミド化合物を少なくとも含む接着付与剤とを含有する、湿気硬化型の反応性ホットメルト接着剤組成物。 - 前記接着付与剤が、水酸基と(メタ)アクリルアミド基とを有する水酸基含有化合物と、ポリイソシアネート1とを反応させることによって製造される、請求項1に記載の反応性ホットメルト接着剤組成物。
- 前記接着付与剤の量が、前記ウレタンプレポリマーの製造に使用されるポリオール及びポリイソシアネート2並びに前記(メタ)アクリル樹脂の合計100質量部に対して、1~5質量部である、請求項1又は2に記載の反応性ホットメルト接着剤組成物。
- 前記ウレタンプレポリマーが、2官能ポリオール及び/又は3官能ポリオールとポリイソシアネート2とを反応させることによって製造される化合物であり、
前記2官能ポリオールが、ポリオキシプロピレンジオール、ポリオキシエチレンジオール及びひまし油系ポリオールからなる群から選ばれる少なくとも1種である、請求項1~3のいずれか1項に記載の反応性ホットメルト接着剤組成物。 - 前記3官能ポリオールの重量平均分子量が、5,000以上である、請求項4に記載の反応性ホットメルト接着剤組成物。
- 前記3官能ポリオールの量が、前記ウレタンプレポリマーの製造に使用されるポリオール全量中、5~50質量%である、請求項4又は5に記載の反応性ホットメルト接着剤組成物。
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CN113493670A (zh) * | 2020-03-19 | 2021-10-12 | 深圳市润贝化工有限公司 | 一种航空级阻燃聚氨酯压敏胶及其制备方法 |
CN114250054B (zh) * | 2021-12-22 | 2024-02-09 | 广州白云科技股份有限公司 | 尼龙粘接用反应型聚氨酯热熔胶及其制备方法 |
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