WO2015186555A1 - 2液ウレタン系接着剤組成物 - Google Patents
2液ウレタン系接着剤組成物 Download PDFInfo
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- WO2015186555A1 WO2015186555A1 PCT/JP2015/064931 JP2015064931W WO2015186555A1 WO 2015186555 A1 WO2015186555 A1 WO 2015186555A1 JP 2015064931 W JP2015064931 W JP 2015064931W WO 2015186555 A1 WO2015186555 A1 WO 2015186555A1
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- adhesive composition
- acrylamide
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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
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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
- C08G18/4825—Polyethers containing two 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
- C08G18/08—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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2081—Heterocyclic amines; Salts thereof containing at least two non-condensed heterocyclic rings
-
- 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
- C08G18/4829—Polyethers containing 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
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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
- C09J11/04—Non-macromolecular additives inorganic
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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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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
Definitions
- the present invention relates to a two-component urethane-based adhesive composition.
- resin materials for example, olefin resin and fiber reinforced plastic (FRP) matrix resin
- FRP fiber reinforced plastic
- the resin material and the dissimilar material are bonded by using a primer after the frame treatment of the resin material (see, for example, Patent Documents 1 and 2).
- a direct glazing agent (DG) is employed as a material for adhering automobile window glass to a painted vehicle body.
- DG direct glazing agent
- the present applicant has previously proposed a one-component moisture-curable urethane composition that can be used as a direct glazing material (Patent Document 3).
- this invention makes it a subject to provide the 2 liquid urethane type adhesive composition excellent in adhesiveness with a base material (mainly resin base material, especially olefin resin), without using a primer.
- a base material mainly resin base material, especially olefin resin
- the said adhesiveness can include initial stage adhesiveness and / or warm water-resistant adhesiveness, for example.
- the present inventors have found that a two-component urethane adhesive composition using a (meth) acrylamide compound is excellent in adhesiveness, and completed the present invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
- a two-component urethane-based adhesive composition having a main agent containing a urethane prepolymer having an isocyanate group and a curing agent containing a compound having two or more active hydrogen-containing groups in one molecule, A two-component urethane-based adhesive composition in which one or both of the main agent and the curing agent contains a (meth) acrylamide compound.
- 2. The two-component urethane-based adhesive composition according to 1 above, wherein at least one alkyl group that may have a hetero atom is bonded to the nitrogen atom of the amide bond of the (meth) acrylamide compound. 3. 3.
- the two-component urethane-based adhesive composition of the present invention is excellent in adhesion to a substrate without using a primer.
- the two-component urethane-based adhesive composition of the present invention includes a main agent containing a urethane prepolymer having an isocyanate group and two in one molecule.
- a two-component urethane adhesive composition comprising a curing agent containing a compound having the above active hydrogen-containing group, wherein one or both of the main agent and the curing agent comprises a (meth) acrylamide compound. It is a two-component urethane-based adhesive composition.
- the adhesion to the substrate becomes good without using a primer.
- the (meth) acrylamide compound easily penetrates into the substrate, and the urethane prepolymer and / or the active hydrogen-containing group when the (meth) acrylamide compound penetrates into the substrate. Therefore, after the adhesive composition of the present invention is cured, it is considered that the adhesiveness between the adhesive layer and the substrate is improved.
- the said mechanism is a guess of the present inventors, and even if a mechanism differs, it is in the scope of the present invention.
- the main ingredient of the adhesive composition of the present invention contains a urethane prepolymer having an isocyanate group.
- the urethane prepolymer contained in the main component of the adhesive composition of the present invention is a polymer containing a plurality of isocyanate groups in one molecule at the molecular terminals.
- a conventionally well-known thing can be used as such a urethane prepolymer.
- an isocyanate group is excessive with respect to the active hydrogen-containing group.
- 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.
- the polyisocyanate compound used in the production of the urethane prepolymer is not particularly limited as long as it has two or more isocyanate groups in the molecule.
- the polyisocyanate compound include tolylene diisocyanate (TDI, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), diphenylmethane diisocyanate (MDI, for example, 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 trip
- Such polyisocyanate compounds can be used alone or in combination of two or more.
- aromatic polyisocyanate is preferable and MDI is more preferable because of excellent curability.
- 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 compound 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 compound is preferable.
- the polyol compound is a compound having two or more OH groups
- the molecular weight and skeleton thereof are not particularly limited.
- Specific examples thereof include polyether polyol; polyester polyol; acrylic polyol, polybutadiene diol, and hydrogenated.
- Polymer polyols having a carbon-carbon bond in the main chain skeleton such as polybutadiene polyol; low molecular polyhydric alcohols; and mixed polyols thereof.
- polyether polyol is mentioned as one of the preferable aspects.
- 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). , Polytetraethylene glycol, sorbitol-based polyol, and the like.
- the polyether polyol is preferably polypropylene glycol or polyoxypropylene triol from the viewpoint of excellent compatibility with the polyisocyanate compound.
- the weight average molecular weight of the polyether polyol is preferably 500 to 20,000 from the viewpoint that the viscosity of the urethane prepolymer obtained by the reaction with the isocyanate compound has appropriate fluidity at room temperature.
- the weight average molecular weight is a polystyrene equivalent value obtained by the GPC method (solvent: tetrahydrofuran (THF)).
- the active hydrogen compounds can be used alone or in combination of two or more.
- the urethane prepolymer is preferably a urethane prepolymer obtained by reacting a polyether polyol and an aromatic polyisocyanate compound from the viewpoint of excellent adhesion and excellent curability.
- the urethane prepolymers can be used alone or in combination of two or more.
- the method for producing the urethane prepolymer is not particularly limited.
- a polyisocyanate compound is used so that 1.5 to 2.5 mol of an isocyanate group reacts with 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 curing agent of the adhesive composition of the present invention contains a compound having two or more active hydrogen-containing groups in one molecule.
- the compound having two or more active hydrogen-containing groups in one molecule contained in the curing agent (curing agent in a broad sense) of the adhesive composition of the present invention cures the urethane prepolymer contained in the main agent described above.
- Examples of the compound having two or more active hydrogen-containing groups in one molecule contained in the curing agent include the same compounds as the active hydrogen compounds used in the production of the urethane prepolymer.
- a polyol compound is preferable.
- the polyol compound is the same as described above.
- the polyol compound is preferably a polyether polyol from the viewpoint of better adhesion and excellent curability.
- the polyether polyol is the same as described above.
- the compounds having two or more active hydrogen-containing groups in one molecule contained in the curing agent can be used alone or in combination of two or more.
- the molar ratio (isocyanate group / active hydrogen-containing group) of the isocyanate group that the urethane prepolymer has and the active hydrogen-containing group that the compound having two or more active hydrogen-containing groups in one molecule contained in the curing agent has is preferably 1.0 to 20, and more preferably 1.4 to 10.
- the (meth) acrylamide compound contained in the adhesive composition of the present invention is a compound having at least one group represented by CH 2 ⁇ CR—CO—N in one molecule (R is a hydrogen atom or a methyl group) Is not particularly limited.
- a (meth) acrylamide compound does not contain the polymer obtained by superposing
- Examples of the (meth) acrylamide compound include a compound represented by the following formula (1).
- R 1 represents a hydrogen atom or a methyl group.
- R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group that may have a hetero atom.
- the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.
- n is 1 and R 2 and / or R 3 is a hydrocarbon group which may have a hetero atom, R 2 and R 3 may be bonded to each other to form a ring structure.
- n is 1 or more, and preferably 1 or 2.
- the hydrocarbon group is not particularly limited.
- the hydrocarbon group may have 1 to 20 carbon atoms.
- Examples of the hydrocarbon group include an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and combinations thereof.
- the hydrocarbon group may be linear or branched and may have an unsaturated bond.
- Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, and eicosyl group.
- Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopentyl group and a cyclohexyl group.
- Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a naphthalene ring, and an anthracene ring.
- the hydrocarbon group is preferably an aliphatic hydrocarbon group.
- 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 or higher functional groups such as carbonyl group, urethane bond, urea bond, and allophanate bond. Groups.
- heteroatom can form, for example, an ether bond, a secondary amine, a tertiary amine, a sulfide bond.
- examples of the hydrocarbon group in which at least one carbon atom in the hydrocarbon group is substituted with a hetero atom include tertiary amines such as N, N-dimethylaminopropyl group; —CH 2 CH 2 —O— An ether bond such as CH 2 CH 2 — may be mentioned.
- the hydrocarbon group in which at least one carbon atom in the hydrocarbon group is substituted with a functional group containing a hetero atom has a carbonyl group as a functional group, such as a 1,1-dimethyl-3oxobutyl group, for example.
- a hydrocarbon group is mentioned.
- R 2 and R 3 when R 2 and R 3 are bonded to each other to form a ring structure, the bonded R 2 and R 3 are, for example, a divalent hydrocarbon group that may have an ether bond. Is mentioned.
- the divalent hydrocarbon group having an ether bond include —R 4 —O—R 5 —.
- R 4 and R 5 in the above formula are each independently a divalent hydrocarbon group.
- the divalent hydrocarbon group as R 4 and R 5 preferably has 1 to 20 carbon atoms.
- the divalent hydrocarbon group as R 4 and R 5 is preferably a divalent aliphatic hydrocarbon group.
- Examples of the divalent aliphatic hydrocarbon group include a methylene group, an ethylene group, and a trimethylene group.
- Examples of the divalent aliphatic hydrocarbon group having an ether bond include —CH 2 CH 2 —O—CH 2 CH 2 —.
- examples of the ring structure include a morpholino group.
- the (meth) acrylamide compound is excellent in adhesion and is compatible with a matrix component such as a urethane prepolymer and / or a compound having two or more active hydrogen-containing groups in one molecule (for example, a polyol).
- a matrix component such as a urethane prepolymer and / or a compound having two or more active hydrogen-containing groups in one molecule (for example, a polyol).
- a matrix component such as a urethane prepolymer and / or a compound having two or more active hydrogen-containing groups in one molecule (for example, a polyol).
- a matrix component such as a urethane prepolymer and / or a compound having two or more active hydrogen-containing groups in one molecule (for example, a polyol).
- R 2 in the formula (1) , R 3 is more preferably a hydrocarbon group which may have a hetero atom.
- a urethane prepolymer is liquid at
- R 2, R 3 in the formula (1) is, as the compound is a hydrocarbon group which may have a hetero atom, for example, with a N- alkyl (meth) acrylamide, hydroxy N- Examples thereof include alkyl (meth) acrylamide and N-alkyl (meth) acrylamide having an ether bond.
- N-alkyl (meth) acrylamide includes N-monoalkyl (meth) acrylamide and N, N-dialkyl (meth) acrylamide.
- N-alkyl (meth) acrylamide at least one carbon atom of the alkyl group may be substituted with the heteroatom.
- N-alkyl (meth) acrylamide having a hydroxy group can have a hydroxy group at least one alkyl group bonded to the nitrogen atom of the acrylamide group.
- a (meth) acrylamide compound in which the alkyl group bonded to the nitrogen atom of the acrylamide group has a hydroxy group is referred to as an N-hydroxy group-containing alkyl (meth) acrylamide.
- the N-alkyl (meth) acrylamide having an ether bond can have an ether bond at least one alkyl group bonded to the nitrogen atom of the acrylamide group.
- a (meth) acrylamide compound in which the alkyl group bonded to the nitrogen atom of the acrylamide group has an ether bond is referred to as an N-ether bond-containing alkyl (meth) acrylamide.
- N-ether bond-containing alkyl (meth) acrylamide an alkyl group having an ether bond that is bonded to the nitrogen atom of the acrylamide group is bonded to the nitrogen atom, and the alkyl group having an ether bond and the nitrogen atom form a ring structure. May be.
- R 2 and R 3 in Formula (1) are a hydrocarbon group optionally having a hetero atom
- R 2 and R 3 in Formula (1) include, for example, Unsubstituted N-alkyl (meth) acrylamides such as N, N-dimethyl (meth) acrylamide (DMAA), N, N-diethyl (meth) acrylamide (DEAA);
- N-tertiary amine-containing alkyl (meth) acrylamides such as N- (N, N-dimethylaminopropyl) (meth) acrylamide (DMAPAA);
- N-ether bond-containing alkyl (meth) acrylamide represented by the following formula (2)
- R 1 represents a hydrogen atom or a methyl group
- R 4 and R 5 each independently represents a divalent aliphatic hydrocarbon group. Divalent aliphatic as R 4 and R 5
- the hydrocarbon group is the same as described above.
- Specific examples of the N-ether bond-containing alkyl (meth) acrylamide include acryloylmorpholine (ACMO) and methacryloylmorpholine represented by the following formula. ;
- N-hydroxy group-containing alkyl (meth) acrylamide represented by the following formula (3)
- R 1 represents a hydrogen atom or a methyl group
- R 6 represents a divalent aliphatic hydrocarbon group.
- the divalent aliphatic hydrocarbon group as R 6 represents R 4 , R 5.
- the N-hydroxy group-containing alkyl (meth) acrylamide is specifically exemplified by N-hydroxyethylacrylamide (HEAA), N-hydroxyethylmethacrylamide, and the like. Can be mentioned. ;
- N-carbonyl group-containing alkyl (meth) acrylamides such as N- (1,1-dimethyl-3oxobutyl) acrylamide (DAAM: diacetone acrylamide) represented by the following formula ;
- a reaction product of a polyisocyanate compound and an N-hydroxy group-containing alkyl (meth) acrylamide may be mentioned.
- Examples of the reaction product of a polyisocyanate compound and an N-hydroxy group-containing alkyl (meth) acrylamide include a reaction product of a modified aliphatic polyisocyanate and an N-hydroxy group-containing alkyl (meth) acrylamide.
- the modified product of the aliphatic polyisocyanate is mentioned as one of the preferred embodiments having two or more isocyanate groups in one molecule, and the number of isocyanate groups is preferably two.
- Examples of the modified product of the aliphatic polyisocyanate include an allophanate-modified product of an aliphatic polyisocyanate, and specifically, an allophanate-modified product of hexamethylene diisocyanate (HDI).
- HDI hexamethylene diisocyanate
- N-hydroxy group-containing alkyl (meth) acrylamide is a (meth) acrylamide having an alkyl group having at least one hydroxy group.
- the number of hydroxy groups possessed by the compound is preferably one per molecule.
- Examples of the N-hydroxy group-containing alkyl (meth) acrylamide include N-hydroxyethyl (meth) acrylamide (HEAA).
- a reaction product of a polyisocyanate compound and an N-hydroxy group-containing alkyl (meth) acrylamide is a compound obtained by reacting at least one or all of the isocyanate groups of the polyisocyanate compound with an N-hydroxy group-containing alkyl (meth) acrylamide. Or a mixture thereof may be used.
- N-alkyl Preferred are (meth) acrylamide, N-alkyl (meth) acrylamide having a hydroxy group, and N-ether bond-containing alkyl (meth) acrylamide.
- N-hydroxy group-containing alkyl (meth) acrylamide represented by the formula (3), N-ether bond-containing alkyl (meth) acrylamide represented by the formula (2) is more preferred, DMAA, DEAA, HEAA, and ACMO are more preferable.
- the (meth) acrylamide compound has N-alkyl (meth) acrylamide, N-alkyl (meth) acrylamide having a hydroxy group, and N-ether bond-containing alkyl (meth) acrylamide from the viewpoint of excellent hot water adhesion.
- N-alkyl (meth) acrylamide having a hydroxy group and N-ether bond-containing alkyl (meth) acrylamide are more preferable, More preferred are N-hydroxy group-containing alkyl (meth) acrylamides represented by the formula (3), N-ether bond-containing alkyl (meth) acrylamides represented by the formula (2), HEAA and ACMO are particularly preferable.
- the (meth) acrylamide compound is contained in the curing agent.
- the (meth) acrylamide compound is preferably an N-ether bond-containing alkyl (meth) acrylamide having an ether bond from the viewpoint of excellent initial adhesion, and an N-ether bond-containing alkyl represented by the formula (2) ( More preferred is (meth) acrylamide and even more preferred is ACMO.
- a (meth) acrylamide compound is contained in the main agent.
- (Meth) acrylamide compounds can be used alone or in combination of two or more.
- the (meth) acrylamide compound is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
- the content of the (meth) acrylamide compound is superior in adhesiveness, and the viscosity of the main agent and / or curing agent containing the (meth) acrylamide compound (for example, viscosity at room temperature) becomes appropriate and excellent in workability.
- the content is preferably 0.01 to 30% by mass, more preferably 0.1 to 5% by mass in the two-component urethane-based adhesive composition.
- the adhesive composition of the present invention is superior in adhesiveness and has excellent physical properties of the cured product of the two-component urethane adhesive composition such as hardness, the main agent and / or the curing agent is further carbon black and / or It is preferable to contain calcium carbonate.
- the carbon black that can be used in the adhesive composition of the present invention is not particularly limited. For example, a conventionally well-known thing is mentioned. Carbon blacks can be used alone or in combination of two or more. In the present invention, the content of carbon black is preferably 10 to 80 parts by mass, and more preferably 15 to 60 parts by mass, in 100 parts by mass of the two-component urethane adhesive composition.
- Calcium carbonate that can be used in the adhesive composition of the present invention is not particularly limited. Examples include heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), and colloidal calcium carbonate.
- the calcium carbonate may be surface-treated with, for example, a fatty acid, a fatty acid ester, or the like. Calcium carbonate can be used alone or in combination of two or more.
- the content of calcium carbonate is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, in 100 parts by mass of the two-component urethane adhesive composition.
- the adhesive composition of the present invention can be used as long as it does not impair the object of the present invention, if necessary, fillers other than carbon black and calcium carbonate, curing catalyst, plasticizer, anti-aging agent, antioxidant, pigment (dye ), Thixotropy imparting agent, ultraviolet absorber, flame retardant, surfactant (including leveling agent), dispersant, dehydrating agent, adhesion imparting agent, antistatic agent, and the like.
- the amount of the additive is not particularly limited. For example, it can be the same as conventionally known.
- the adhesive composition of this invention is not aqueous.
- the quantity of water can be 10 mass% or less in a 2 liquid urethane type adhesive composition.
- the production method of the adhesive composition of the present invention is not particularly limited.
- a main agent containing a urethane prepolymer is put in one container and contains a compound having two or more active hydrogen-containing groups in one molecule. It can manufacture by putting the hardening
- the adhesive composition of the present invention is a two-component type.
- one or both of the main agent and the curing agent contains a (meth) acrylamide compound.
- one of the main agent and the curing agent contains a (meth) acrylamide compound.
- the curing agent contains at least a (meth) acrylamide compound, it is preferable because it is excellent in adhesiveness (particularly hot water-resistant adhesiveness) and storage stability. It is preferable that at least the main agent contains a (meth) acrylamide compound because of excellent adhesiveness (particularly initial adhesiveness). What is necessary is just to mix and use a main ingredient and a hardening
- the mixing method is not particularly limited. For example, a conventionally well-known thing is mentioned.
- Examples of the substrate to which the adhesive composition of the present invention can be applied include plastic, glass, rubber, metal and the like.
- the plastic include polymers of propylene, ethylene, and cycloolefin monomers.
- the polymer may be a homopolymer, a copolymer, or a hydrogenated product.
- plastics include, for example, olefin resins such as polypropylene, polyethylene, COP, and COC, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polymethyl methacrylate resin (PMMA resin), polycarbonate resin, Examples thereof include hardly adhesive resins such as polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin (acrylonitrile / butadiene rubber / styrene copolymer), and polyamide resin.
- olefin resins such as polypropylene, polyethylene, COP, and COC
- polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polymethyl methacrylate resin (PMMA resin), polycarbonate resin
- PET polyethylene terephthalate
- PBT polybutylene tere
- COC means a cycloolefin copolymer such as a copolymer of tetracyclododecene and an olefin such as ethylene.
- COP means, for example, a cycloolefin polymer such as a polymer obtained by ring-opening polymerization of norbornene and hydrogenation.
- the base material may be surface-treated. Examples of the surface treatment include frame treatment, corona treatment, and itro treatment. These processes are not particularly limited. For example, a conventionally well-known thing is mentioned.
- the method for applying the adhesive composition of the present invention to a substrate is not particularly limited. For example, a conventionally well-known thing is mentioned.
- the adhesive composition of the present invention can be cured by moisture.
- the adhesive 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 adhesive composition of this invention is not hardened
- Examples of the use of the adhesive composition of the present invention include direct glazing agents, automotive sealants, and building member sealants.
- Each component of the following Table 1 was mixed with the composition (parts by mass) shown in Table 1 using a stirrer to prepare each main agent and each curing agent. Next, 100 g of the main agent produced as described above and the curing agent produced as described above were mixed at a main agent / curing agent mixing ratio shown in Table 1 to obtain an adhesive composition. About each manufactured adhesive composition, adhesiveness was evaluated by the following method. The results are shown in Table 1.
- the obtained reaction product is a compound formed by reacting one of the two isocyanate groups of the isocyanate compound with a hydroxyl group of HEAA (in one molecule, in addition to an acrylamide group and an allophanate bond, a urethane bond, an isocyanate group). And two isocyanate groups of the isocyanate compound react with a hydroxyl group of HEAA and a mixture containing at least an unreacted isocyanate compound.
- Plasticizer DINP diisononyl phthalate, manufactured by J-Plus Catalyst DMDEE: Compound name dimorpholino diethyl ether, trade name UCAT-660M, manufactured by San Apro Co., Ltd.
- (meth) acrylate compound 1 butyl acrylate (BA) -(Meth) acrylate compound 2: hydroxyethyl acrylate (HEA) -Polymer of (meth) acrylamide compound: Dissolve 2.0 g of dimethylacrylamide and 23.0 g of butyl acrylate in 200 ml of ethanol in a 500 ml reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, After purging with nitrogen while stirring at room temperature for 30 minutes, 0.162 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the polymerization reaction was performed at 60 ° C.
- AIBN azobisisobuty
- the polymer obtained as mentioned above be a polymer of a (meth) acrylamide compound. Polymers of (meth) acrylamide compounds do not have double bonds.
- the adhesive composition containing the (meth) acrylamide compound was excellent in adhesiveness (Examples 1 to 12). It was also found that the adhesive composition containing the (meth) acrylamide compound has high shear strength and good adhesion to the substrate without using a primer (Examples 1 to 12). From the results of Examples 1 to 12, it was found that the (meth) acrylamide compound can be added to the main agent and / or the curing agent. When at least one alkyl group that may have a hetero atom is bonded to the nitrogen atom of the amide bond of the (meth) acrylamide compound (Examples 1 to 6, 8 to 12), a hydrogen atom is bonded to the nitrogen atom.
- the shear strength was higher and the adhesiveness was better than when two were bonded (Example 7). Comparing Examples 1 and 2 in which the ratio of the isocyanate group in the main agent to the hydroxy group in the curing agent is equal, when the alkyl group substituted for the nitrogen atom of the (meth) acrylamide compound is an ethyl group, the shearing is greater than the methyl group. Excellent strength.
- the results of Examples 5 and 6 were the same. From the results of Examples 3 and 9 (the fracture state after the tensile test evaluated after immersion in hot water is CF 100%), when the (meth) acrylamide compound has a hydroxy group, it was more excellent in resistance to hot water.
- Example 11 From the results of Examples 11 and 12, it was found that when the (meth) acrylamide compound has an ether bond, it is more excellent in adhesiveness. Specifically, when Example 11 and Examples 1, 2, 4, and 7 in which a (meth) acrylamide compound is contained in a curing agent are compared for resistance to hot water, the (meth) acrylamide compound has an ether bond. Example 11 had a better fracture state and superior hot water adhesion than Examples 1, 2, 4, and 7 that did not have an ether bond. Further, when Example 12 and Examples 5, 6, and 8 in which the (meth) acrylamide compound is contained in the main agent are compared in terms of initial adhesiveness, Example 12 in which the (meth) acrylamide compound has an ether bond is ether. The fracture state was better than in Examples 5, 6, and 8 having no bond, and the initial water adhesion was excellent.
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Abstract
Description
このような樹脂材料と異種材料(例えば、ガラス)との接着には、樹脂材料をフレーム処理した後、プライマーを用いて接着させるのが一般的であった(例えば、特許文献1および2など参照)。
本願出願人は以前ダイレクトグレージング材として使用することができる1液湿気硬化型ウレタン組成物を提案した(特許文献3)。
また、生産性の向上を目的にDG用途の接着剤に硬化剤を適用し、硬化速度を速めるという要求が近年高まっている。
しかし、DG用途の接着剤に硬化剤を適用して硬化速度を高めようとすると、基材(主に樹脂基材、特にオレフィン樹脂)に対する接着性(例えば、初期接着性、耐温水接着性が挙げられる。以下同様。)が損なわれる場合があることを本発明者らは見出した。
そこで、本発明は、プライマーを用いずとも基材(主に樹脂基材、特にオレフィン樹脂)との接着性に優れた2液ウレタン系接着剤組成物を提供することを課題とする。なお、プライマーを用いずとも基材との接着性に優れることを、以下、接着性に優れるということがある。また、当該接着性は例えば、初期接着性及び/又は耐温水接着性を含むことができる。
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。
前記主剤と前記硬化剤のうちの一方又は両方が、(メタ)アクリルアミド化合物を含有する、2液ウレタン系接着剤組成物。
2. 前記(メタ)アクリルアミド化合物が有するアミド結合の窒素原子に、ヘテロ原子を有してもよいアルキル基が少なくとも1個結合する、上記1に記載の2液ウレタン系接着剤組成物。
3. 前記イソシアネート基と前記活性水素含有基のモル比(イソシアネート基/活性水素含有基)が、0.8~20.0である、上記1又は2に記載の2液ウレタン系接着剤組成物。
4. 前記ウレタンプレポリマーが、ポリエーテルポリオールと芳香族ポリイソシアネートとを反応させてなるウレタンプレポリマーである、上記1~3のいずれか1つに記載の2液ウレタン系接着剤組成物。
5. 前記主剤及び/又は前記硬化剤が、更にカーボンブラック及び/又は炭酸カルシウムを含有する、上記1~4のいずれか1つに記載の2液ウレタン系接着剤組成物。
6. 前記(メタ)アクリルアミド化合物の含有量が、当該2液ウレタン系接着剤組成物中の0.01~30質量%である、上記1~5のいずれか1つに記載の2液ウレタン系接着剤組成物。
7. 湿気によって硬化する、上記1~6のいずれか1つに記載の2液ウレタン系接着剤組成物。
8. オレフィン基材を接着するために使用される、上記1~7のいずれか1つに記載の2液ウレタン系接着剤組成物。
9. 前記(メタ)アクリルアミド化合物が、ヒドロキシ基を有するN-アルキル(メタ)アクリルアミド及びエーテル結合を有するN-アルキル(メタ)アクリルアミドからなる群から選ばれる少なくとも1種である、上記1~8のいずれかに記載の2液ウレタン系接着剤組成物。
これは、詳細には明らかではないが、(メタ)アクリルアミド化合物が、基材に浸み込みやすく、(メタ)アクリルアミド化合物が基材に浸み込む際にウレタンプレポリマー及び/又は活性水素含有基を有する化合物を伴うため、本発明の接着剤組成物が硬化したのち、接着剤層と基材との接着性が良好になると考えられる。
なお上記メカニズムは本発明者らの推測であり、メカニズムが異なっていても本発明の範囲内である。
本発明の接着剤組成物の主剤は、イソシアネート基を有するウレタンプレポリマーを含有する。
本発明の接着剤組成物の主剤に含有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ポリマーである。
このような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化合物と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、これを「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化合物は、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化合物としては、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;これらのイソシアヌレート変性ポリイソシアネートが挙げられる。
これらのうち、硬化性に優れる理由から、芳香族ポリイソシアネートが好ましく、MDIがより好ましい。
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。
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、ソルビトール系ポリオール等が挙げられる。
ポリエーテルポリオールは、ポリイソアネート化合物との相溶性に優れるという観点から、ポリプロピレングリコール、ポリオキシプロピレントリオールが好ましい。
ポリエーテルポリオールの重量平均分子量は、イソシアネート化合物との反応によって得られるウレタンプレポリマーの粘度が常温において適度な流動性を有するという観点から、500~20,000であるのが好ましい。本発明において上記重量平均分子量は、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。
活性水素化合物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方法は特に制限されない。例えば、活性水素化合物が有する活性水素含有基(例えばヒドロキシ基)1モルに対し、1.5~2.5モルのイソシアネート基が反応するようにポリイソシアネート化合物を使用し、これらを混合して反応させることによってウレタンプレポリマーを製造することができる。
本発明の接着剤組成物の硬化剤は、1分子中に2個以上の活性水素含有基を有する化合物を含有する。
本発明の接着剤組成物の硬化剤(広義の硬化剤)に含有される1分子中に2個以上の活性水素含有基を有する化合物は、上述した主剤に含有される上記ウレタンプレポリマーを硬化させる成分(狭義の硬化剤成分)である。
硬化剤に含有される1分子中に2個以上の活性水素含有基を有する化合物としては、上記ウレタンプレポリマーの製造に用いる活性水素化合物と同様の化合物が挙げられる。なかでも、ポリオール化合物であるのが好ましい。ポリオール化合物は上記と同様である。
特に、ポリオール化合物は、接着性がより優れ、硬化性に優れるという観点からポリエーテルポリオールが好ましい。ポリエーテルポリオールは上記と同様である。
硬化剤に含有される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。
本発明の接着剤組成物に含有される(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CH2=CR-CO-Nで表される基を有する化合物(Rは水素原子又はメチル基である。)であれば特に制限されない。
なお、本発明において、(メタ)アクリルアミド化合物は、(メタ)アクリルアミド化合物をモノマーとし、(メタ)アクリルアミド化合物が有する、ビニル基又はイソプロペニル基が重合して得られる重合体を含まない。
式(1)中、R2、R3はそれぞれ独立に、水素原子、又は、ヘテロ原子を有してもよい炭化水素基を示す。ヘテロ原子としては例えば、酸素原子、窒素原子、硫黄原子が挙げられる。nが1であり、R2及び/又はR3がヘテロ原子を有してもよい炭化水素基である場合、R2、R3は互いに結合して環構造を形成してもよい。
式(1)中、nは1以上であり、1~2であるのが好ましい。
炭素数1~20の脂肪族炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、エイコシル基が挙げられる。
炭素数3~20の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。
炭素数6~20の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。
炭化水素基は、なかでも、脂肪族炭化水素基であることが好ましい。
炭化水素基の中の炭素原子の少なくとも1つがヘテロ原子に置換された炭化水素基としては、例えば、N,N-ジメチルアミノプロピル基のような第3級アミン;-CH2CH2-O-CH2CH2-のようなエーテル結合が挙げられる。
R2、R3が互いに結合して環構造を形成した場合、環構造としては例えば、モルホリノ基が挙げられる。
N,N-ジメチル(メタ)アクリルアミド(DMAA)、N,N-ジエチル(メタ)アクリルアミド(DEAA)のような無置換のN-アルキル(メタ)アクリルアミド;
(式(2)中、R1は水素原子又はメチル基を示し、R4、R5はそれぞれ独立に2価の脂肪族炭化水素基を示す。R4、R5としての2価の脂肪族炭化水素基は上記と同様である。)N-エーテル結合含有アルキル(メタ)アクリルアミドとしては具体的には例えば、下記式で表されるアクリロイルモルホリン(ACMO)、メタクリロイルモルホリンが挙げられる。
;
(式(3)中、R1は水素原子又はメチル基を示し、R6は2価の脂肪族炭化水素基を示す。R6としての2価の脂肪族炭化水素基はR4、R5としての2価の脂肪族炭化水素基と同様である。)N-ヒドロキシ基含有アルキル(メタ)アクリルアミドとしては具体的には例えば、N-ヒドロキシエチルアクリルアミド(HEAA)、N-ヒドロキシエチルメタクリルアミドが挙げられる。;
脂肪族ポリイソシアネートの変性体は、1分子中イソシアネート基を2個以上有するのが好ましい態様の1つとして挙げられ、イソシアネート基の数が2個であるのが好ましい。
脂肪族ポリイソシアネートの変性体としては、例えば、脂肪族ポリイソシアネートのアロファネート変性体が挙げられ、具体的には例えば、ヘキサメチレンジイソシアネート(HDI)のアロファネート変性体が挙げられる。
N-ヒドロキシ基含有アルキル(メタ)アクリルアミドは、少なくとも1個のヒドロキシ基を有するアルキル基を有する(メタ)アクリルアミドであるのが好ましい態様の1つとして挙げられる。当該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。
N-ヒドロキシ基含有アルキル(メタ)アクリルアミドとしては、例えば、N-ヒドロキシエチル(メタ)アクリルアミド(HEAA)が挙げられる。
式(3)で表されるN-ヒドロキシ基含有アルキル(メタ)アクリルアミド、式(2)で表されるN-エーテル結合含有アルキル(メタ)アクリルアミドがより好ましく、
DMAA、DEAA、HEAA、ACMOが更に好ましい。
ヒドロキシ基を有するN-アルキル(メタ)アクリルアミド、N-エーテル結合含有アルキル(メタ)アクリルアミドがより好ましく、
式(3)で表されるN-ヒドロキシ基含有アルキル(メタ)アクリルアミド、式(2)で表されるN-エーテル結合含有アルキル(メタ)アクリルアミドが更に好ましく、
HEAA、ACMOが特に好ましい。
本発明において、カーボンブラックの含有量は、2液ウレタン系接着剤組成物100質量部中、10~80質量部であるのが好ましく、15~60質量部であるのがより好ましい。
本発明の接着剤組成物は、必要に応じて本発明の目的を損なわない範囲で、カーボンブラック、炭酸カルシウム以外の充填剤、硬化触媒、可塑剤、老化防止剤、酸化防止剤、顔料(染料)、揺変性付与剤、紫外線吸収剤、難燃剤、界面活性剤(レベリング剤を含む)、分散剤、脱水剤、接着付与剤、帯電防止剤などの各種添加剤等を含有することができる。添加剤の量は特に制限されない。例えば従来公知と同様とすることができる。
本発明において、主剤と硬化剤のうちの一方又は両方が、(メタ)アクリルアミド化合物を含有する。主剤と硬化剤のうちの一方が(メタ)アクリルアミド化合物を含有するのが好ましい態様の1つとして挙げられる。
少なくとも硬化剤が(メタ)アクリルアミド化合物を含有する場合、接着性(特に耐温水接着性)に優れ、貯蔵安定性に優れるので好ましい。
少なくとも主剤が(メタ)アクリルアミド化合物を含有する場合、接着性(特に初期接着性)に優れるので好ましい。
本発明の接着剤組成物を使用する際、主剤と硬化剤とを混合して使用すればよい。混合の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。
プラスチックとしては、例えば、プロピレン、エチレンやシクロオレフィン系モノマーの重合体が挙げられる。上記の重合体は単独重合体、共重合体、水素添加物であってもよい。
具体的な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、COP、COC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(アクリロニトリル・ブタジエンゴム・スチレン共重合体)、ポリアミド樹脂のような難接着性樹脂が挙げられる。
ここで、COCは、例えば、テトラシクロドデセンとエチレン等のオレフィンとの共重合体のようなシクロオレフィンコポリマーを意味する。
また、COPは、例えば、ノルボルネン類を開環重合し、水素添加して得られる重合体のようなシクロオレフィンポリマーを意味する。
基材は表面処理がなされていてもよい。表面処理としては例えば、フレーム処理やコロナ処理やイトロ処理が挙げられる。これらの処理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。
本発明の接着剤組成物を基材に適用する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接着剤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。
次に、上記のとおり製造された主剤100gと、上記のとおり製造された硬化剤とを第1表に示す主剤/硬化剤混合比で混合し、接着剤組成物を得た。
製造された各接着剤組成物について、下記の方法により接着性を評価した。結果を第1表に示す。
ポリプロピレン樹脂(商品名ノーブレン、住友化学社製)からなる基板(幅:25mm、長さ:120mm、厚さ:3mm)の片面にフレーム処理を施した被着体を2枚用意した。
被着体をフレーム処理後、ぬれ張力試験用混合液(和光純薬工業社製)を用いて樹脂表面の濡れ性が45.0mN/m以上であることを確認した。
次いで、一方の被着体の表面(フレーム処理を施した面)に、調製(混合)直後の各接着剤組成物を幅25mm、長さ10mm、厚さ5mmとなるように塗布した後、他方の被着体の表面(フレーム処理を施した面)と張り合わせ、圧着させることで試験体を作製した。
作製した試験体を以下の条件で放置した後に、JIS K6850:1999に準じた引張試験(引っ張り速度50mm/分、20℃の環境下)を行い、剪断強度(MPa)を測定した。結果を下記第1表に示す。
・条件1:23℃、50%RHの条件下で3日間放置(初期)
・条件2:23℃、50%RHの条件下で3日間放置後、更にその後60℃の温水に3日間浸漬
剪断強度が2.5MPa以上である場合、接着強度に優れるといえる。
剪断強度を測定した試験体について、破壊状態を目視で確認し、接着剤が凝集破壊しているものを「CF」と評価し、被着体-接着剤間で界面剥離しているものを「AF」と評価した。「CF」「AF」の後ろの数値は、接着面において各破壊状態が占めるおおよその面積(%)である。結果を下記第1表に示す。
CFが占める面積が80%以上である場合、接着性に優れるといえる。
・ウレタンプレポリマー:ポリオキシプロピレンジオール(商品名サンニックスPP2000、三洋化成工業社製、重量平均分子量2,000)70質量部とポリオキシプロピレントリオール(商品名サンニックスGP3000、三洋化成工業社製、重量平均分子量3,000)とMDI(商品名スミジュール44S、住化バイエルウレタン社製)とをNCO/OH(モル比)が2.0となるように混合し、混合物を80℃の条件下で5時間反応させて製造したウレタンプレポリマー
・アクリルアミド:CH2=CH-CONH2
・DMAA:N,N-ジメチルアクリルアミド
・DEAA:N,N-ジエチルアクリルアミド
・HEAA:N-(2-ヒドロキシエチル)アクリルアミド
・DMAPAA:N-(ジメチルアミノプロピル)アクリルアミド
・ACMO:アクリロイルモルホリン
・HEAAのイソシアネート付加物:HEAA9.4gとイソアネート化合物(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9時間反応させ、反応生成物を得た。得られた反応生成物は、上記イソシアネート化合物が有する2つのイソシアネート基のうち1つがHEAAの水酸基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、アロファネート結合の他、ウレタン結合、イソシアネート基を有する。)と、上記イソシアネート化合物が有する2つのイソシアネート基の両方がHEAAの水酸基と反応して生成した化合物と、未反応のイソシアネート化合物とを少なくとも含む混合物である。上記のとおりにして製造された反応物をHEAAのイソシアネート付加物として使用した。
・カーボンブラック:商品名#200MP、新日化カーボン社製
・炭酸カルシウム1:重質炭酸カルシウム、商品名スーパーS、丸尾カルシウム社製
・炭酸カルシウム2:脂肪酸で表面処理された炭酸カルシウム、カルファイン200、丸尾カルシウム社製
・ポリエーテルポリオール:ポリオキシエチレンを少量含有するポリオキシプロピレントリオール、重量平均分子量6,000、商品名プレミノール7001K、旭硝子社製
・可塑剤 DINP:ジイソノニルフタレート、ジェイプラス社製
・触媒 DMDEE:化合物名ジモルフォリノジエチルエーテル、商品名UCAT-660M、サンアプロ社製
・(メタ)アクリレート化合物1:アクリル酸ブチル(BA)
・(メタ)アクリレート化合物2:ヒドロキシエチルアクリレート(HEA)
・(メタ)アクリルアミド化合物の重合物:冷却管、窒素導入管、温度計と攪拌装置を備えた500mlの反応容器に、ジメチルアクリルアミド2.0g、アクリル酸ブチル23.0gをエタノール200mlに溶解し、室温で30分間攪拌しながら、窒素置換した後に、AIBN(アゾビスイソブチロニトリル)0.162gを重合開始剤として加え、60℃で6時間重合反応を行なった後、反応後の混合液からエバポレーターでエタノールを除去して、ジメチルアクリルアミド-アクリル酸ブチルコポリマーを得た。得られたジメチルアクリルアミド-アクリル酸ブチルコポリマーは室温で液状であった。上記のとおり得られたポリマーを(メタ)アクリルアミド化合物の重合物とする。(メタ)アクリルアミド化合物の重合物は二重結合を有さない。
また、(メタ)アクリレート(比較例2、4)や(メタ)アクリルアミド化合物の重合物(比較例3、5)をして調製した接着剤組成物は、接着性が劣ることが分かった。
実施例1~12の結果から、(メタ)アクリルアミド化合物は主剤及び/又は硬化剤に添加することができることが分かった。
(メタ)アクリルアミド化合物が有するアミド結合の窒素原子に、ヘテロ原子を有してもよいアルキル基が少なくとも1個結合する場合(実施例1~6、8~12)、上記窒素原子に水素原子が2個結合する場合(実施例7)より、剪断強度がより高く、接着性により優れた。
主剤中のイソシアネート基と硬化剤中のヒドロキシ基の比の等しい実施例1、2を比較すると、(メタ)アクリルアミド化合物が有する窒素原子に置換するアルキル基がエチル基である場合、メチル基より剪断強度に優れた。実施例5、6の結果も同様であった。
実施例3、9の結果(温水浸漬後に評価された引張試験後の破壊状態がCF100%)から、(メタ)アクリルアミド化合物がヒドロキシ基を有する場合、耐温水接着性により優れた。
詳細には、(メタ)アクリルアミド化合物が硬化剤に含有される、実施例11と実施例1、2、4、7とを耐温水接着性について比較すると、(メタ)アクリルアミド化合物がエーテル結合を有する実施例11は、エーテル結合を有さない実施例1、2、4、7よりも破壊状態が良く耐温水接着性に優れた。
また、(メタ)アクリルアミド化合物が主剤に含有される、実施例12と実施例5、6、8とを初期接着性について比較すると、(メタ)アクリルアミド化合物がエーテル結合を有する実施例12は、エーテル結合を有さない実施例5、6、8よりも破壊状態が良く初期水接着性に優れた。
Claims (9)
- イソシアネート基を有するウレタンプレポリマーを含有する主剤と、1分子中に2個以上の活性水素含有基を有する化合物を含有する硬化剤と、を有する2液ウレタン系接着剤組成物であって、
前記主剤と前記硬化剤のうちの一方又は両方が、(メタ)アクリルアミド化合物を含有する、2液ウレタン系接着剤組成物。 - 前記(メタ)アクリルアミド化合物が有するアミド結合の窒素原子に、ヘテロ原子を有してもよいアルキル基が少なくとも1個結合する、請求項1に記載の2液ウレタン系接着剤組成物。
- 前記イソシアネート基と前記活性水素含有基のモル比(イソシアネート基/活性水素含有基)が、0.8~20.0である、請求項1又は2に記載の2液ウレタン系接着剤組成物。
- 前記ウレタンプレポリマーが、ポリエーテルポリオールと芳香族ポリイソシアネートとを反応させてなるウレタンプレポリマーである、請求項1~3のいずれか1項に記載の2液ウレタン系接着剤組成物。
- 前記主剤及び/又は前記硬化剤が、更にカーボンブラック及び/又は炭酸カルシウムを含有する、請求項1~4のいずれか1項に記載の2液ウレタン系接着剤組成物。
- 前記(メタ)アクリルアミド化合物の含有量が、当該2液ウレタン系接着剤組成物中の0.01~30質量%である、請求項1~5のいずれか1項に記載の2液ウレタン系接着剤組成物。
- 湿気によって硬化する、請求項1~6のいずれか1項に記載の2液ウレタン系接着剤組成物。
- オレフィン基材を接着するために使用される、請求項1~7のいずれか1項に記載の2液ウレタン系接着剤組成物。
- 前記(メタ)アクリルアミド化合物が、ヒドロキシ基を有するN-アルキル(メタ)アクリルアミド及びエーテル結合を有するN-アルキル(メタ)アクリルアミドからなる群から選ばれる少なくとも1種である、請求項1~8のいずれか1項に記載の2液ウレタン系接着剤組成物。
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WO2022153761A1 (ja) * | 2021-01-14 | 2022-07-21 | シーカ・ハマタイト株式会社 | 2液ウレタン系接着剤 |
JP2022108817A (ja) * | 2021-01-14 | 2022-07-27 | シーカ・ハマタイト株式会社 | 2液ウレタン系接着剤 |
JP7273076B2 (ja) | 2021-01-14 | 2023-05-12 | シーカ・ハマタイト株式会社 | 2液ウレタン系接着剤 |
Also Published As
Publication number | Publication date |
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JP6572888B2 (ja) | 2019-09-11 |
CN106459721A (zh) | 2017-02-22 |
JPWO2015186555A1 (ja) | 2017-04-20 |
CN106459721B (zh) | 2020-04-14 |
US10793758B2 (en) | 2020-10-06 |
US20170204311A1 (en) | 2017-07-20 |
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