WO2018029938A1 - 2液混合型接着剤 - Google Patents
2液混合型接着剤 Download PDFInfo
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- WO2018029938A1 WO2018029938A1 PCT/JP2017/019077 JP2017019077W WO2018029938A1 WO 2018029938 A1 WO2018029938 A1 WO 2018029938A1 JP 2017019077 W JP2017019077 W JP 2017019077W WO 2018029938 A1 WO2018029938 A1 WO 2018029938A1
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone 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
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
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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
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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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
- C08K3/34—Silicon-containing compounds
Definitions
- the present invention relates to a two-component mixed adhesive.
- one composition contains a complex derived from a compound having an organoborane and a group that undergoes an addition reaction with an isocyanate group, and the other composition contains a compound having an isocyanate group and a polymerizable group. It is.
- this adhesive by mixing the two compositions at the time of bonding, a compound having a group that undergoes an addition reaction with an isocyanate group reacts with a compound having an isocyanate group and a polymerizable group, thereby producing a radical.
- the organoborane having the polymerization initiating ability is liberated, and the adhesive component can be cured and adhered.
- radicals generated from the liberated organoborane and oxygen molecules can modify the surface of difficult-to-adhere materials such as polypropylene, so that excellent adhesion can be achieved without plasma treatment or the like. Has been.
- the conventional adhesive is low in storage stability because the compound having an isocyanate group and a polymerizable group contained in the other composition disappears over time due to alteration or the like, and as a result, the adhesive strength is low. There is an inconvenience that it is still insufficient for market demand.
- the present invention has been made on the basis of the above circumstances, and an object thereof is to provide a two-component mixed adhesive having excellent storage stability and adhesive strength.
- composition (I) a first composition
- composition (II) a second composition
- composition (II) a second composition
- a two-component mixed adhesive wherein the composition (I) has a first group (hereinafter also referred to as “group (X)”) that undergoes an addition reaction with an organoborane and an isocyanate group (hereinafter referred to as “group (X)”).
- a complex derived from “compound (a)” (hereinafter also referred to as “[A] complex”) and a second compound having no polymerizable group as a diluent (hereinafter referred to as “[B] compound”)
- the composition (II) has an isocyanate group and a polymerizable group (hereinafter also referred to as “[C] compound”) and a dehydrating agent (hereinafter referred to as “[D]”). And a dehydrating agent ”)).
- the two-component mixed adhesive of the present invention high adhesive strength can be obtained while exhibiting excellent storage stability. Therefore, the two-component mixed adhesive can be suitably used for bonding various materials including difficult-to-adhere materials such as automobile outer plates.
- the two-component mixed adhesive includes a composition (I) and a composition (II).
- the [C] compound having an isocyanate group and a polymerizable group in the composition (II) is obtained by mixing the composition (I) and the composition (II). It reacts (deprotection reaction) with the compound (a) having a group (X) that undergoes an addition reaction with the isocyanate group constituting the [A] complex in (I), and as a result, the organoborane and the compounds (a) and [ C] A reaction product with the compound (hereinafter also referred to as “deprotection reaction product (p)”) is generated.
- This deprotection reaction product (p) has polymerizability, for example, it is polymerized using the produced organoborane as a polymerization initiator, and in addition, for example, a radical formed from the organoborane and the adherend. Bonding or the like is also formed, and adhesion proceeds.
- the two-component mixed adhesive includes a composition (I) containing a [A] complex and a [B] compound and a composition (II) containing a [C] compound and a [D] dehydrating agent. Excellent storage stability and adhesive strength.
- the reason why the two-component mixed adhesive has the above-described configuration provides the above-mentioned effect is not necessarily clear, but can be inferred as follows, for example. That is, in the conventional two-component mixed adhesive, it is considered that the isocyanate group of the [C] compound having an isocyanate group and a polymerizable group easily reacts with moisture coming from the air and disappears with time.
- the [A] complex is altered by the reaction of the polymerizable group or the like of the polymerizable compound with the group (X) of the compound (a). Disappears over time. As a result, the rate of formation of organoborane due to the reaction between the [C] compound and the compound (a) having a group (X) that undergoes an addition reaction with the isocyanate group constituting the [A] complex decreases with time. Therefore, it is considered that the storage stability is low.
- the disappearance of the isocyanate group is suppressed by allowing the [D] dehydrating agent to coexist in the composition (II), and the [A] complex is added to the polymerizable group in the composition (I).
- the [B] compound that does not have the above it is considered that these temporal alterations could be suppressed and the storage stability could be improved.
- the two-component mixed adhesive further includes, in addition to the composition (I) and the composition (II), another composition that does not contain the [A] complex or the [C] compound, and the three-component or more mixed adhesive. It is good.
- composition (I) and the composition (II) will be described.
- composition (I) contains a [A] complex and a [B] compound. Moreover, the composition (I) may contain components other than [A] component and [B] component in the range which does not impair the effect of this invention.
- the composition (I) contains a compound having one polymerizable group described below in the section of the composition (II) (hereinafter also referred to as “[E] polymerizable compound”), a [F] polymer component, and the like.
- the composition (I) substantially comprises a compound having a polymerizable group that reacts with the compound (a) constituting the [A] complex and reduces the storage stability of the two-component mixed adhesive. It is preferable not to contain.
- the polymerizable compound and the [F] polymer component have a polymerizable group and the like, and it is preferable that the composition (I) does not substantially contain these components.
- each component will be described.
- a complex is a complex derived from organoborane and compound (a).
- the compound (a) has a group (X) that undergoes an addition reaction with an isocyanate group.
- the complex is usually formed by organoborane and a group (X) of the compound (a) coordinated to the organoborane, and the compound (a) suppresses the polymerization initiation ability of the organoborane. Yes.
- Organoborane can form an [A] complex by interacting with one or more compounds (a).
- organoborane is a compound in which the hydrogen atom of borane is substituted with an organic group.
- Organic group refers to a group containing at least one carbon atom. Examples of the organoborane include compounds represented by the following formula (1).
- R 1 , R 2 and R 3 are each independently a monovalent organic group having 1 to 20 carbon atoms.
- Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R 1 , R 2 and R 3 include, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the carbon-carbon gap of the hydrocarbon group. And a group ( ⁇ ) having a divalent heteroatom-containing group, a group obtained by substituting a part or all of the hydrogen atoms of the hydrocarbon group and the group ( ⁇ ) with a monovalent heteroatom-containing group, and the like.
- Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include, for example, a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, Examples thereof include 6-20 monovalent aromatic hydrocarbon groups.
- Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; An alkenyl group such as an ethenyl group, a propenyl group, a butenyl group; Examples thereof include alkynyl groups such as ethynyl group, propynyl group and butynyl group.
- Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, and tricyclodecyl group; And cycloalkenyl groups such as a cyclopentenyl group, a cyclohexenyl group, a norbornenyl group, and a tricyclodecenyl group.
- Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, and anthryl group; Examples thereof include aralkyl groups such as benzyl group, phenethyl group, and naphthylmethyl group.
- hetero atom contained in the monovalent and divalent heteroatom-containing group examples include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.
- Examples of the divalent heteroatom-containing group include —O—, —CO—, —NR′—, —S—, —CS—, —SO—, —SO 2 —, —POR ′ 2 —, and —SiR. ' 2- , a group combining these and the like.
- R ′ is a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- Examples of the monovalent heteroatom-containing group include —OH, —COOH, —NH 2 , —CN, —NO 2 , —SH and the like.
- the organoborane is preferably a compound in which R 1 to R 3 in the above formula (1) are hydrocarbon groups from the viewpoint of high polymerization initiating ability, stability, and availability, more preferably trialkylborane, Borane, triethylborane, tripropylborane and tributylborane are more preferred, and triethylborane is particularly preferred.
- the compound (a) is a compound having a group (X).
- Group (X) is a group that undergoes an addition reaction with isocyanate.
- the compound (a) reacts with the isocyanate group of the [C] compound contained in the composition (II) when the composition (I) and the composition (II) are mixed.
- Examples of the group (X) include a group having active hydrogen bonded to a hetero atom (hereinafter also referred to as “group (X1)”).
- groups of such a hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.
- group (X1) for example, as a group having active hydrogen bonded to a nitrogen atom, an amino group (—NH 2 ), a monosubstituted amino group (one of hydrogen atoms of —NH 2 is substituted with a hydrocarbon group) ) Etc.
- group having active hydrogen bonded to the oxygen atom for example, a hydroxy group
- examples of the group having active hydrogen bonded to a sulfur atom include a sulfanyl group.
- Examples of the group having active hydrogen bonded to the phosphorus atom include a phosphino group (—PH 2 ), a mono-substituted phosphino group (one in which one hydrogen atom of —PH 2 is substituted with a hydrocarbon group), and the like.
- Examples of the compound having an amino group include monoamines such as methylamine, ethylamine, propylamine, butylamine, aniline, ethanolamine, cyclopentylamine, and cyclohexylamine; 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 , 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 2,2-bis (4-aminopheny
- Examples of the compound having a monosubstituted amino group include dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclopentylamine, dicyclohexylamine, N, N′-dimethyl-1,3-diaminopropane, N, N, N ′. , N′-tetramethyl-1,3-diaminopropane, diethanolamine and the like.
- Examples of the compound having a hydroxy group include monoalcohols such as methanol and ethanol; Diols such as ethylene glycol, 1,4-butanediol, 1,2-cyclohexanediol; Examples include triols such as glycerin and trimethylolpropane.
- Examples of the compound having a sulfanyl group include monothiols such as mercaptan and ethanethiol; And dithiols such as ethanedithiol and butanedithiol.
- Examples of the compound having a phosphino group include monophosphines such as ethylphosphine and butylphosphine; Examples include diphosphinoethane and diphosphinobutane.
- Examples of the compound having a monosubstituted phosphino group include diethyl phosphine and dibutyl phosphine.
- the number of the group (X) possessed by the compound (a) may be 1 or 2 or more, preferably 2 or more, more preferably 2 to 4, more preferably 2 or 3. Two are particularly preferred.
- the deprotection reaction product (p) having a plurality of polymerization sites is formed from the compound (a) and the [C] compound, and as a result, the curing rate is further increased.
- the adhesive strength can be further improved.
- the group (X) is preferably an amino group, a monosubstituted amino group, a sulfanyl group, a phosphino group, or a monosubstituted phosphino group from the viewpoint of facilitating the deprotection reaction and increasing the adhesive strength.
- a group is more preferable, and an amino group is more preferable.
- the compound (a) is preferably a compound containing an amino group, more preferably a diamine and a triamine, further preferably a diamine, from the viewpoint of further facilitating the deprotection reaction with the [C] compound and further increasing the adhesive strength.
- a diaminoalkane having a number of 2 to 4 is more particularly preferred, and 1,3-aminopropane is most preferred.
- the lower limit of the molar ratio of the compound (a) to the organoborane in the [A] complex is preferably 0.5, more preferably 0.7, still more preferably 0.9, particularly preferably 1, and 1.8 More particularly preferred, 2.5 is even more preferred, and 3.5 is most preferred.
- the upper limit of the molar ratio is preferably 8, more preferably 7, still more preferably 6, and particularly preferably 5.5.
- the lower limit of the molar ratio of the compound (a) to the organoborane used in the preparation of the composition (I) is preferably 0.5, more preferably 0.7, still more preferably 0.9, and particularly preferably 1. 1.8 is more particularly preferable, 2.5 is further particularly preferable, and 3.5 is most preferable.
- the upper limit of the molar ratio is preferably 8, more preferably 7, still more preferably 6, and particularly preferably 5.5.
- the lower limit of the content of the [A] complex in the composition (I) is preferably 0.1% by mass, more preferably 1% by mass, from the viewpoint of further increasing the adhesive strength of the two-component mixed adhesive. More preferably, it is more preferably 10% by weight.
- the upper limit of the content is preferably 70% by mass, more preferably 50% by mass, further preferably 40% by mass, and particularly preferably 30% by mass from the viewpoint of easy handling of the two-component mixed adhesive.
- a complex may use 1 type (s) or 2 or more types.
- [[B] Compound] [B] A compound is a compound which does not have a polymeric group as a diluent. That is, the [B] compound is a component for diluting the [A] complex in the composition (I). [B] Since the compound does not have a polymerizable group, reaction with the compound (a) in the [A] complex is suppressed, and as a result, the storage stability in the composition (I) can be maintained. it can.
- [B] compound in composition (I) As a minimum of content of [B] compound in composition (I), 30 mass% is preferred, 50 mass% is more preferred, 60 mass% is still more preferred, and 70 mass% is especially preferred. As an upper limit of the said content, 99.9 mass% is preferable, 99 mass% is more preferable, 95 mass% is further more preferable, 90 mass% is especially preferable.
- the lower limit of the mass ratio of the [B] compound to the [A] complex is preferably 0.5, more preferably 1, more preferably 1.5, and even more preferably 2.
- the upper limit of the mass ratio is preferably 100, more preferably 10, and even more preferably 5.
- the compound can be used as long as it does not have a polymerizable group, and is not particularly limited. Examples thereof include hydrocarbon compounds and compounds having a polar group.
- the compound may be any of a low molecular weight compound, an oligomer and a polymer.
- hydrocarbon compounds examples include alkanes, olefin oligomers, and polyolefins.
- Examples of the compound having a polar group include a compound having a polar group between one or more carbons of the hydrocarbon compound, a compound in which one or more hydrogen atoms of the hydrocarbon compound are substituted with a polar group, and the like. .
- Examples of the polar group include a group having a hetero atom.
- Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and a halogen atom.
- Examples of the polar group having a hetero atom include oxygen atom-containing groups such as a hydroxy group, an alkoxy group, an acyl group, an ether group, and a carbonyl group; Nitrogen atom-containing groups such as amino groups, substituted amino groups, imino groups; Sulfur atom-containing groups such as sulfanyl groups, alkylsulfanyl groups, sulfanediyl groups; Phosphorus atom-containing groups such as phosphino groups and substituted phosphino groups; Silicon atom-containing groups such as silyl groups and substituted silyl groups; And halogen atom-containing groups such as fluorine atom, chlorine atom, bromine atom and iodine atom.
- oxygen atom-containing groups such as a hydroxy group, an alkoxy group, an acyl group, an ether group, and a carbonyl group
- Nitrogen atom-containing groups such as amino groups, substituted amino groups, im
- the compound [B] is preferably a compound having a polar group, more preferably a compound having an oxygen atom-containing group, and a compound having a hydroxy group from the viewpoints of solubility of the [A] complex and stabilization of the [A] complex. Is more preferable.
- the compound When the compound is a compound having a hydroxy group, when the composition (I) and the composition (II) are mixed, the [B] compound undergoes an addition reaction with the isocyanate group of the [C] compound, B] The compound can be incorporated into the polymer of the adhesive layer, and as a result, the strength of the adhesive layer can be further improved and the adhesive strength can be further increased. In this case, the [B] compound undergoes an addition reaction with the isocyanate group of the [C] compound to form a carbamate group (—NH—CO—O—), thereby improving the flexibility of the adhesive layer. Can do.
- the number of hydroxy groups in the compound having a hydroxy group may be a monool compound which is 1 or a polyol compound which is 2 or more, but the [B] compound is taken into the main chain of the polymer of the adhesive layer.
- a polyol compound is preferable from the viewpoint of further improving the strength of the adhesive layer and further increasing the adhesive strength.
- the upper limit of the number of hydroxy groups is 20, for example.
- polyol compound examples include alkane diols such as ethylene glycol, propylene glycol, 2-butyl-2-ethyl-1,3-propanediol; Alkanetriols such as 1,2,4-butanetriol, trimethylolpropane; Alkanetetraols such as pentaerythritol; Polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol; Polyalkylene glycol-containing polyols such as both end ethylene glycol adducts of polypropylene glycol represented by the following formula (B-1) and both ends ethylene glycol adducts of polytetramethylene glycol; Bisphenol-containing polyols such as propylene glycol adducts of bisphenol A and ethylene glycol adducts of bisphenol A represented by the following formula (B-2); Polyester polyols such as polycaprolactone diol and polycaprolactone
- a, b and c are each independently an integer of 1 to 200.
- p and q are each independently an integer of 1 to 200.
- Examples of commercially available propylene glycol adducts of bisphenol A include Newpol BP-2P, BP-23P, BP-3P, and BP-5P (Sanyo Chemical Industries, Ltd.).
- Commercially available products of bisphenol A ethylene glycol adduct include, for example, Newpol BPR-20NK, BPE-20T, BPE-40, BPE-60, BPE-100, BPE-180 (above, Sanyo Chemical Industries) Company).
- [B] When the compound is a compound having a hydroxy group and the compound (a) is a compound having an amino group, [C] [C] relative to the total number of moles of the hydroxy group of the compound and the amino group of the compound (a)
- a minimum of the ratio of the number of moles of an isocyanate group of a compound 0.5 is preferred, 1 is more preferred, and 1.5 is still more preferred.
- the upper limit of the ratio is, for example, 10.
- the lower limit of the molecular weight of the [B] compound is preferably 100, more preferably 300, still more preferably 500, and particularly preferably 1,000 from the viewpoint of further increasing the strength of the adhesive layer.
- the upper limit of the molecular weight is preferably 10,000, more preferably 8,000, more preferably 6,000, and still more preferably 5,000.
- the molecular weight is, for example, a number average molecular weight.
- a compound may use 1 type (s) or 2 or more types.
- composition (I) may contain, for example, a plasticizer, an inorganic filler, a colorant, a metal salt, a polymerization inhibitor and the like as components other than the above [A] and [B] components.
- a plasticizer for example, a plasticizer, an inorganic filler, a colorant, a metal salt, a polymerization inhibitor and the like as components other than the above [A] and [B] components.
- Each of these other components may contain one kind or two or more kinds.
- plasticizer examples include phthalic acid esters such as dibutyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate; dipropylene glycol dibenzoate, triethylene Examples thereof include benzoic acid esters such as glycol dibenzoate.
- examples of the inorganic filler include alumina, silica, titanium dioxide, calcium carbonate, talc and the like.
- Examples of the colorant include carbon black.
- the metal salt can be contained for adjusting the pot life of the two-component mixed adhesive.
- the metal salt include copper (II) bromide, copper (II) chloride, copper (II) 2-ethylhexanoate and the like.
- polymerization inhibitor examples include hydroquinone and hydroquinone monomethyl ether.
- composition (II) contains a [C] compound and [D] a dehydrating agent.
- the composition (II) preferably contains the [E] polymerizable compound and / or the [F] polymer component, and other components other than the [C] to [F] components, as long as the effects of the present invention are not impaired. It may contain components. Hereinafter, each component will be described.
- a compound is a compound which has an isocyanate group and a polymeric group.
- the compound [C] is a compound that forms a deprotection reaction product (p) by deprotecting with the compound (a) constituting the [A] complex of the composition (I), and this deprotection reaction product (P) has polymerizability.
- the composition (I) and the composition (II) are mixed, whereby the [A] complex compound (a) is added to the isocyanate group of the [C] compound.
- Examples of the polymerizable group include a carbon-carbon double bond-containing group such as a vinyl group, an allyl group, a styryl group, and a (meth) acryloyl group; And carbon-carbon triple bond-containing groups such as an ethynyl group and a propargyl group.
- a carbon-carbon double bond-containing group is preferable and a (meth) acrylolyl group is more preferable from the viewpoint of high polymerizability and a higher curing rate.
- the number of isocyanate groups possessed by the [C] compound is preferably 1 to 3, more preferably 1 and 2, and even more preferably 1 from the viewpoint of facilitating the deprotection reaction.
- the number of polymerizable groups possessed by the compound is preferably 1 to 3, more preferably 1 and 2, more preferably 1 from the viewpoint of further increasing the polymerization rate of the deprotection reaction product (p) to be formed. preferable.
- the number of isocyanate groups is preferably 1 and 2, and the number of polymerizable groups is preferably 1 and 2, and the number of isocyanate groups and polymerizable groups. Is preferably 1.
- Examples of the [C] compound include aliphatic isocyanates such as isocyanatoalkyl (meth) acrylates such as isocyanatoethyl (meth) acrylate and isocyanatopropyl (meth) acrylate; Alicyclic isocyanates such as isocyanato cycloalkyl (meth) acrylates such as isocyanatocyclohexyl (meth) acrylate and isocyanato norbornyl (meth) acrylate; Aromatic isocyanates such as styryl isocyanate and isocyanatophenyl (meth) acrylate; (Meth) acrylate having an isocyanate group such as an adduct of diisocyanate and hydroxyalkyl (meth) acrylate; Examples thereof include alkenes having an isocyanate group such as isocyanatobutene, isocyanatopentene, and isocyanatohexene.
- the isocyanate group easily undergoes an addition reaction due to the group (X) of the compound (a).
- the two-component mixed adhesive does not require the use of an addition reaction catalyst such as an organotin compound.
- an addition reaction catalyst such as an organotin compound.
- Examples of such a [C] compound include aliphatic isocyanate and aromatic isocyanate.
- aliphatic isocyanate and aromatic isocyanate are preferable, aliphatic isocyanate is more preferable, (meth) acrylate having an isocyanate group is further preferable, isocyanatoalkyl (meth) acrylate is particularly preferable, and isocyanatoethyl. (Meth) acrylate is more particularly preferred.
- the lower limit of the content of the [C] compound in the composition (II) is preferably 0.1% by mass, more preferably 1% by mass, further preferably 3% by mass, and particularly preferably 5% by mass.
- 40 mass% is preferable, 20 mass% is more preferable, 15 mass% is further more preferable, 10 mass% is especially preferable.
- the lower limit of the molar ratio of the isocyanate group of the compound [C] to the group (X) of the compound (a) is preferably 0.5, more preferably 0.7, still more preferably 1, and particularly preferably 1.5.
- the upper limit of the molar ratio is preferably 6, more preferably 4, more preferably 3, and particularly preferably 2.5.
- the lower limit of the molar ratio of the isocyanate group to the diamine is preferably 1, more preferably 1.3, still more preferably 1.5, and particularly preferably 1.7.
- the upper limit of the molar ratio is preferably 3, more preferably 2.7, even more preferably 2.5, and particularly preferably 2.3.
- composition (II) contains [D] dehydrating agent, so that moisture mixed from outside the system during storage can be removed.
- Examples of the dehydrating agent include inorganic dehydrating agents and organic dehydrating agents.
- Examples of the inorganic dehydrating agent include zeolites such as zeolite 3A, zeolite 4A, and zeolite 5A;
- Anhydrous inorganic salts such as anhydrous calcium chloride, anhydrous sodium sulfate, anhydrous calcium sulfate, anhydrous magnesium chloride, anhydrous magnesium sulfate, anhydrous potassium carbonate, anhydrous potassium sulfide, anhydrous potassium sulfite, anhydrous sodium sulfite, anhydrous copper sulfate;
- Examples include silica gel, alumina, silica alumina, activated clay and the like.
- organic dehydrating agents examples include orthoformates such as methyl orthoformate, ethyl orthoformate, and propyl orthoformate; Orthoacetic esters such as methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate; Carboxylic acid orthoesters such as orthopropionate such as methyl orthopropionate and ethyl orthopropionate; Benzaldehyde dimethyl acetal, acetaldehyde dimethyl acetal, formaldehyde dimethyl acetal, acetone dimethyl acetal, acetone dibenzyl acetal, diethyl ketone dimethyl acetal, benzophenone dimethyl acetal, benzyl phenyl ketone dimethyl acetal, cyclohexanone dimethyl acetal, acetophenone dimethyl acetal, 2,2-dimethoxy- Acetal compounds such as 2-phenylacetophenone, 4,4-dimethoxy-2,5-cyclohex
- an inorganic dehydrating agent is preferable, and zeolite is more preferable from the viewpoint that the strength of the adhesive layer can be further increased, and as a result, the adhesive strength can be further increased.
- zeolites zeolite 3A and zeolite 5A are preferable, and zeolite 3A is more preferable from the viewpoint of further improving the storage stability.
- [D] dehydrating agent in composition (II) As a minimum of content of [D] dehydrating agent in composition (II), 0.1 mass% is preferable, 0.4 mass% is more preferable, 0.8 mass% is further more preferable, 2 mass% is Particularly preferred is 2.5% by mass, even more preferred. As an upper limit of the said content, 15 mass% is preferable, 11 mass% is more preferable, 8 mass% is further more preferable, and 6 mass% is especially preferable. [D] By making content of a dehydrating agent into the said range, storage stability and adhesive strength can be made compatible with balance.
- the lower limit of the mass ratio of the dehydrating agent to the [C] compound is preferably 0.05, more preferably 0.1, still more preferably 0.3, and particularly preferably 0.5.
- the upper limit of the mass ratio is preferably 2, more preferably 1.5, still more preferably 1, and particularly preferably 0.8.
- [D] By making the mass ratio of the dehydrating agent to the [C] compound within the above range, it is possible to achieve both storage stability and adhesive strength in a balanced manner.
- [D] 1 type (s) or 2 or more types may be used for a dehydrating agent.
- the polymerizable compound is a compound having one polymerizable group and no isocyanate group.
- the composition (II) contains the [E] polymerizable compound, whereby the strength of the adhesive layer can be further improved, and as a result, the adhesive strength can be further improved. it can.
- Examples of the polymerizable group include a carbon-carbon double bond-containing group such as a vinyl group, an allyl group, a styryl group, and a (meth) acryloyl group; And carbon-carbon triple bond-containing groups such as an ethynyl group and a propargyl group.
- a carbon-carbon double bond-containing group is preferable and a (meth) acrylolyl group is more preferable from the viewpoint of superior polymerizability.
- Examples of the polymerizable compound include olefins such as butene, pentene, hexene, octene, decene, and dodecene; Styrene compounds such as styrene, ⁇ -methylstyrene and methylstyrene; Vinyl carboxylates such as vinyl acetate, vinyl propionate and vinyl laurate; Halogenated olefins such as vinyl chloride and vinylidene chloride; Vinyl compounds such as methyl vinyl ketone and methyl vinyl ether; Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate ; Cyclopentyl (meth) acrylate,
- a (meth) acrylate compound is preferred from the viewpoint of superior polymerizability.
- a heteroatom-containing (meth) acrylate is preferable, and tetrahydrofurfuryl (meth) acrylate is more preferable.
- alkyl (meth) acrylate is preferable, and 2-ethylhexyl (meth) acrylate is more preferable.
- One or two or more polymerizable compounds may be used.
- the lower limit of the content of the [E] polymerizable compound in the composition (II) is preferably 10% by mass, more preferably 30% by mass, 40 mass% is further more preferable and 50 mass% is especially preferable.
- the upper limit of the said content 90 mass% is preferable, 80 mass% is more preferable, 75 mass% is further more preferable, 70 mass% is especially preferable.
- composition (II) preferably contains a [F] polymer component from the viewpoints of improving the initial adhesive strength and adjusting the viscosity of the two-component mixed adhesive and suppressing the curing shrinkage of the adhesive layer.
- the polymer component is not particularly limited as long as it is a polymer, and examples thereof include polyolefin, polystyrene, styrene copolymer, poly (meth) acrylate, polydiene, acrylic copolymer, and thermoplastic elastomer. Further, ethylene-vinyl acetate copolymer, epoxy resin, phenol resin, silicone resin, polyester resin, urethane resin, and the like can be used. Furthermore, as a [F] polymer component, the copolymer containing the structure of these polymers can also be used suitably.
- polystyrene resin examples include polyethylene, polypropylene, and ethylene- ⁇ -olefin copolymers.
- polystyrene examples include polystyrene and poly ( ⁇ -methylstyrene).
- styrene copolymer examples include styrene-methyl methacrylate copolymer, styrene-acrylic acid copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, ABS (acrylonitrile-butadiene-styrene copolymer). Polymer) and the like.
- poly (meth) acrylate include polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate and the like.
- polydiene examples include polybutadiene and polyisoprene.
- acrylic copolymer examples include polymers having plural types of (meth) acrylic acid ester units, butyl (meth) acrylate-acrylonitrile copolymers, and the like.
- thermoplastic elastomer examples include SBS (styrene-butadiene-styrene block copolymer), SEBS (styrene-ethylene-butadiene-styrene block copolymer), SIS (styrene-isoprene-styrene block copolymer), and SEPS.
- conjugated diene copolymers such as (styrene-ethylene-propylene-styrene block copolymer), and hydrogenated products thereof.
- thermoplastic elastomers and poly (meth) acrylates are preferable, and thermoplastic elastomers are more preferable.
- the polymer component preferably has a polymerization site. Since the [F] polymer component has a polymerization site, the [F] polymer component and the deprotection reaction product (p) and the like are copolymerized. Suppression can be performed more effectively.
- the polymerization site include a carbon-carbon double bond in the polymer main chain, a polymerizable group in the side chain or terminal of the polymer, and the like.
- Examples of the [F] polymer component having a polymerization site include an unhydrogenated product of a conjugated diene copolymer. Among these, SBS is preferable from the viewpoint of having a more appropriate viscosity.
- the polymer component may be polymer particles or a polymer that does not form particles.
- the composition (II) preferably contains polymer particles as the [F] polymer component.
- the two-component mixed adhesive can further improve the flexibility of the adhesive layer.
- the composition (II) contains polymer particles and a polymer not forming particles as the [F] polymer component.
- the composition (II) contains both the polymer particles and the polymer not forming the particles, the two-component mixed adhesive can further improve the flexibility of the adhesive layer.
- the [F] polymer component forming the polymer particles is preferably a polyolefin, polystyrene, styrene copolymer, poly (meth) acrylate, polydiene acrylic copolymer, or a copolymer containing the structure of these polymers, and polystyrene.
- Poly (meth) acrylates, polydienes and copolymers comprising the structures of these polymers are more preferred.
- the lower limit of the average particle diameter of the polymer particles is preferably 0.005 ⁇ m, more preferably 0.01 ⁇ m, further preferably 0.05 ⁇ m, and particularly preferably 0.1 ⁇ m.
- the upper limit of the average particle diameter is preferably 1 ⁇ m, more preferably 0.8 ⁇ m, further preferably 0.6 ⁇ m, and particularly preferably 0.4 ⁇ m.
- polymer particles examples include single particles and particles having a core-shell structure (core-shell particles). Of these, core-shell particles are preferred.
- core-shell particles are preferred.
- the two-component mixed adhesive can further improve the flexibility of the adhesive layer. Examples of such commercially available core-shell particles include “Kane Ace M-511”, “M-521”, “M-570”, “M-711” of Kaneka Corporation, “FX602P” of JSR Corporation. ”,“ FX501 ”,“ Zeon F351 ”manufactured by Nippon Zeon Co., Ltd., and the like.
- the lower limit of the content of the polymer particles in the [F] polymer component is preferably 10% by mass, more preferably 15% by mass, and 20% by mass. Further preferred is 25% by mass.
- 70 mass% is preferable, 60 mass% is more preferable, 50 mass% is further more preferable, 45 mass% is especially preferable.
- polystyrene copolymer As the [F] polymer component not forming the particles, styrene copolymer, poly (meth) acrylate, polydiene, thermoplastic elastomer, silicone resin, polyester resin and urethane resin are preferable, and thermoplastic elastomer is more preferable. SBS is more preferred.
- composition (II) contains a [F] polymer component
- a [F] polymer component As a minimum of content of [F] polymer component in composition (II), 1 mass% is preferable, 5 mass% is more preferable, 8 mass % Is more preferable, and 10% by mass is particularly preferable.
- As an upper limit of the said content 60 mass% is preferable, 45 mass% is more preferable, 35 mass% is further more preferable, 30 mass% is especially preferable.
- [F] By making content of a polymer component into the said range, improvement of initial adhesive strength, viscosity adjustment, hardening shrinkage
- composition (II) contains, for example, a crosslinkable compound, a plasticizer, an inorganic filler, a colorant, a metal salt, a polymerization inhibitor, etc. as other components other than the above [C] to [F] components. Also good. These other components may contain 1 type (s) or 2 or more types, respectively.
- the crosslinkable compound is a compound having two or more polymerizable groups and no isocyanate group.
- a crosslinkable compound in the composition (II) By including a crosslinkable compound in the composition (II), the elongation percentage of the adhesive layer can be further increased.
- Examples of the polymerizable group possessed by the crosslinkable compound include those exemplified as the polymerizable group possessed by the [E] polymerizable compound. Among these, a (meth) acryloyl group is preferable from the viewpoint of further improving the adhesive strength.
- the number of polymerizable groups possessed by the crosslinkable compound is preferably 2 to 4, more preferably 2 and 3, and even more preferably 2 from the viewpoint of further improving the adhesive strength.
- crosslinkable compounds examples include chain glycol crosslinkable compounds such as ethylene glycol di (meth) acrylate and triethylene glycol di (meth) acrylate; Alicyclic glycol-based crosslinkable compounds such as tricyclodecanediyl di (meth) acrylate; Trimethylolpropane-based crosslinkable compounds such as trimethylolpropane tri (meth) acrylate; Bisphenol crosslinkable compounds such as bisphenol A bis (polyethylene glycol (meth) acrylate); Imido isocyanurate crosslinkable compounds such as tri (N-hydroxyethyl) isocyanurate di (meth) acrylate; Urethane-based crosslinkable compounds such as compounds represented by the following formula (2); Examples thereof include terminal bismaleimide-modified polyimide crosslinkable compounds such as a compound represented by the following formula (3).
- chain glycol crosslinkable compounds such as ethylene glycol di (meth) acrylate and triethylene glycol di (meth) acrylate
- n is an integer of 1-20.
- R 4 and R 5 are each independently an alkylene group having 1 to 20 carbon atoms.
- Ar 1 is an arylene group having 6 to 20 carbon atoms.
- n is 2 or more, the plurality of R 4 may be the same or different, and the plurality of Ar 1 may be the same or different.
- crosslinkable compound an alicyclic glycol-based crosslinkable compound is preferable, and tricyclodecanediyl di (meth) acrylate is more preferable.
- the content of the crosslinkable compound in the composition (II) is preferably 0.1% by mass, more preferably 0.5% from the viewpoint of further improving the adhesive strength. % Is more preferable, and 2% by mass is more preferable. As an upper limit of the said content, 20 mass% is preferable, 15 mass% is more preferable, 12 mass% is further more preferable, and 10 mass% is especially preferable.
- the two-component mixed adhesive is prepared by, for example, preparing the composition (I) by mixing the [A] complex, the [B] compound and other components as necessary, and separately preparing the [C] compound, [ D] It can be obtained by preparing the composition (II) by mixing the dehydrating agent and, if necessary, the [E] polymerizable compound, the [F] polymer component and other components.
- the two-component mixed adhesive can be used by a known method. In the bonding operation, first, the composition (I) and the composition (II) are mixed.
- the mass ratio of the usage-amount of composition (II) with respect to composition (I) 1 is preferable, 3 is more preferable, 5 is further more preferable, and 9 is especially preferable.
- As an upper limit of the mass ratio 30 is preferable, 20 is more preferable, 15 is further preferable, and 12 is particularly preferable.
- the other adherend can be adhered to the applied mixture so as to adhere to each other.
- PP polypropylene
- PE polyethylene
- PPS polyphenylene sulfide
- PA6 polyamide 6
- PA66 polyamide 66
- SUS stainless steel
- SUS hot dip galvanized steel
- ED electrodeposited steel
- the upper limit of the thickness is preferably 5 mm, more preferably 3 mm, and even more preferably 1 mm.
- composition (I) ⁇ Preparation of two-component mixed adhesive>
- composition (II) ⁇ Preparation of two-component mixed adhesive>
- TEB-DAP “TEB-DAP” from BASF Japan (complex derived from tetraethylborane and diaminopropane)
- THFMA “Light Ester THF” from Kyoeisha Chemical Co., Ltd. 2EHMA: Kyoeisha Chemical Company's “Light Ester EH”
- composition (I) [A] 2.5 parts by mass of TEB-DAP as a complex and BP5P7.5 parts by mass of a [B] compound were placed in a plastic container and mixed to prepare a composition (I-1).
- composition (II) In a separable flask equipped with a stirrer, 50.5 parts by mass of THFMA as the [E] polymerizable compound and 16.8 parts by mass of SBS as the polymer component and 9.9 parts by mass of M521 in an oil bath at 40 ° C. For 3 hours to completely dissolve SBS and to disperse M521 uniformly. Next, 7.6 parts by mass of MOI as a [C] compound, 0.5 part by mass of zeolite 5A as a [D] dehydrating agent, and 14.7 parts by mass of 2EHMA as a [E] polymerizable compound were added and further stirred for 1 hour. After mixing, the mixture was degassed under reduced pressure for 2 hours to prepare a composition (II-1).
- compositions (II) to (II-8) and (II-8) were prepared in the same manner as in the preparation of the composition (II-1) of Example 1, except that the components having the types and contents shown in Table 1 were used. (CII-1) was prepared. “-” In Table 1 indicates that the corresponding component was not used.
- composition (I) [A] 2.5 parts by mass of TEB-DAP as the complex and 7.5 parts by mass of THFMA as the polymerizable compound [E] were mixed in a plastic container to prepare a composition (CI-1). .
- composition (II) As the composition (II), the composition (II-7) prepared in Example 7 was used.
- the storage temperatures were 5 ° C, 25 ° C and 40 ° C, respectively, and the storage days were 0 days (immediately after preparation of the composition) , 14 days, 30 days, 60 days, and 90 days, and as the adherend, glass fiber reinforced polypropylene / glass fiber reinforced polypropylene (GFPP / GFPP) or electrodeposited steel / electrodeposited steel (ED / ED)
- GFPP / GFPP glass fiber reinforced polypropylene
- ED / ED electrodeposited steel
- the adhesive strength was measured.
- the fracture mode was evaluated visually.
- the fracture modes indicate A: interface fracture, B: substrate fracture, and C: cohesive fracture, respectively.
- the evaluation results are shown in Tables 2 to 11, respectively.
- the storage stability of the two-component mixed adhesive is evaluated to be better as the decrease in the adhesive strength when the storage days are long is smaller even when the storage temperature is high. “Uncured” in the tables of Example 1, Example 5 and Comparative Example 1 does not cure even when the composition (I) and the composition (II) are mixed, and the storage stability is poor. Indicates. In addition, “CI-1 curing” in the table of Comparative Example 2 indicates that the composition (CI-1) is cured alone during storage and storage stability is poor.
- composition (I) contains the [B] compound in addition to the [A] complex
- composition (II) contains the [D] dehydrating agent in addition to the [C] compound.
- the two-component mixed adhesive of the present invention is excellent in storage stability and adhesive strength.
- the two-component mixed adhesive of the present invention high adhesive strength can be obtained while exhibiting excellent storage stability. Therefore, the two-component mixed adhesive can be suitably used for bonding various materials including difficult-to-adhere materials such as automobile outer plates.
Abstract
Description
当該2液混合型接着剤は、組成物(I)と組成物(II)とを備える。当該2液混合型接着剤は、組成物(I)と組成物(II)とを混合することで、組成物(II)中のイソシアネート基及び重合性基を有する[C]化合物が、組成物(I)中の[A]錯体を構成するイソシアネート基に付加反応する基(X)を有する化合物(a)と反応(脱保護反応)し、その結果、オルガノボラン、及び化合物(a)と[C]化合物との反応生成物(以下、「脱保護反応生成物(p)」ともいう)が生じる。この脱保護反応生成物(p)は重合性を有しており、例えば生成したオルガノボランを重合開始剤として重合するものであり、加えて、例えばオルガノボランから形成されたラジカルにより被着材との結合等も形成されて接着が進行する。
組成物(I)は、[A]錯体と[B]化合物とを含有する。また、組成物(I)は、本発明の効果を損なわない範囲において、[A]成分及び[B]成分以外の他の成分を含有していてもよい。組成物(I)は、組成物(II)の項で後述する1の重合性基を有する化合物(以下、「[E]重合性化合物」ともいう)、[F]ポリマー成分等を含有してもよいが、組成物(I)は、[A]錯体を構成する化合物(a)と反応し、当該2液混合型接着剤の保存安定性を低下させる重合性基を有する化合物を実質的に含有しないことが好ましい。[E]重合性化合物及び[F]ポリマー成分は、重合性基等を有しており、組成物(I)は、これらの成分を実質的に含有しないことが好ましい。以下、各成分について説明する。
[A]錯体は、オルガノボラン及び化合物(a)に由来する錯体である。化合物(a)は、イソシアネート基に付加反応する基(X)を有する。[A]錯体は、通常オルガノボランと、このオルガノボランに化合物(a)の基(X)が配位結合等して形成され、化合物(a)は、オルガノボランの重合開始能を抑制している。オルガノボランは、1又は複数の化合物(a)と相互作用することにより[A]錯体を形成することができる。
上記オルガノボランは、ボランの水素原子を有機基で置換した化合物である。「有機基」とは、少なくとも1個の炭素原子を含む基をいう。上記オルガノボランとしては、例えば下記式(1)で表される化合物等が挙げられる。
メチル基、エチル基、プロピル基、ブチル基等のアルキル基;
エテニル基、プロペニル基、ブテニル基等のアルケニル基;
エチニル基、プロピニル基、ブチニル基等のアルキニル基などが挙げられる。
シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、ノルボルニル基、アダマンチル基、トリシクロデシル基等のシクロアルキル基;
シクロペンテニル基、シクロヘキセニル基、ノルボルネニル基、トリシクロデセニル基等のシクロアルケニル基などが挙げられる。
フェニル基、トリル基、キシリル基、ナフチル基、アントリル基等のアリール基;
ベンジル基、フェネチル基、ナフチルメチル基等のアラルキル基などが挙げられる。
化合物(a)は、基(X)を有する化合物である。基(X)は、イソシアネートに付加反応する基である。化合物(a)は、組成物(I)と組成物(II)を混合した時点で、組成物(II)が含有する[C]化合物が有するイソシアネート基と反応する。
窒素原子に結合する活性水素を有する基として、アミノ基(-NH2)、一置換アミノ基(-NH2の水素原子の1つを炭化水素基で置換したもの)等が、
酸素原子に結合する活性水素を有する基として、例えばヒドロキシ基等が、
硫黄原子に結合する活性水素を有する基として、例えばスルファニル基等が、
リン原子に結合する活性水素を有する基として、例えばホスフィノ基(-PH2)、一置換ホスフィノ基(-PH2の水素原子の1つを炭化水素基で置換したもの)等が挙げられる。
メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、アニリン、エタノールアミン、シクロペンチルアミン、シクロヘキシルアミン等のモノアミン;
1,2-ジアミノエタン、1,2-ジアミノプロパン、1,3-ジアミノプロパン、1,4-ジアミノブタン、1,5-ジアミノペンタン、1,6-ジアミノヘキサン、1,7-ジアミノヘプタン、1,8-ジアミノオクタン、1,9-ジアミノノナン、1,10-ジアミノデカン、1,12-ジアミノドデカン、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルエーテル、4,4’-ジアミノベンゾフェノン、2,2-ビス(4-アミノフェニル)プロパン、2-(3-アミノフェニル)-2-(4-アミノフェニル)プロパン、1,4-ビス[1-(4-アミノフェニル)-1-メチルエチル]ベンゼン、1,3-ビス[1-(4-アミノフェニル)-1-メチルエチル]ベンゼン、4,7,10-トリオキサトリデカン-1,13-ジアミン、4,9-ジオキサドデカン-1,12-ジアミン、3,6,9-トリオキサウンデカン-1,11-ジアミン等のジアミン;
1,2,3-トリアミノプロパン、1,2,4-トリアミノブタン、1,3,5-トリアミノシクロヘキサン、1,3,5-トリアミノベンゼン等のトリアミンなどが挙げられる。
メタノール、エタノール等のモノアルコール;
エチレングリコール、1,4-ブタンジオール、1,2-シクロヘキサンジオール等のジオール;
グリセリン、トリメチロールプロパン等のトリオールなどが挙げられる。
エタンジチオール、ブタンジチオール等のジチオールなどが挙げられる。
ジホスフィノエタン、ジホスフィノブタン等のジホスフィンなどが挙げられる。
[B]化合物は、希釈剤としての重合性基を有さない化合物である。すなわち、[B]化合物は、組成物(I)における[A]錯体を希釈するための成分である。[B]化合物は、重合性基を有さないことで、[A]錯体における化合物(a)と反応することが抑制され、その結果、組成物(I)における保存安定性を維持することができる。
ヒドロキシ基、アルコキシ基、アシル基、エーテル基、カルボニル基等の酸素原子含有基;
アミノ基、置換アミノ基、イミノ基等の窒素原子含有基;
スルファニル基、アルキルスルファニル基、スルファンジイル基等の硫黄原子含有基;
ホスフィノ基、置換ホスフィノ基等のリン原子含有基;
シリル基、置換シリル基等のケイ素原子含有基;
フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子含有基などが挙げられる。
エチレングリコール、プロピレングリコール、2-ブチル-2-エチル-1,3-プロパンジオール等のアルカンジオール;
1,2,4-ブタントリオール、トリメチロールプロパン等のアルカントリオール;
ペンタエリスリトール等のアルカンテトラオール;
ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリアルキレングリコール;
下記式(B-1)で表されるポリプロピレングリコールの両末端エチレングリコール付加物、ポリテトラメチレングリコールの両末端エチレングリコール付加物等のポリアルキレングリコール含有ポリオール;
下記式(B-2)で表されるビスフェノールAのプロピレングリコール付加物、ビスフェノールAのエチレングリコール付加物等のビスフェノール含有ポリオール;
ポリカプロラクトンジオール、ポリカプロラクトントリオール等のポリエステルポリオール;
ポリカーボネートジオール、ポリカーボネートポリオール等のポリカーボネートポリオールなどが挙げられる。
組成物(I)は、上記[A]及び[B]成分以外の他の成分として、例えば可塑剤、無機充填剤、着色剤、金属塩、重合禁止剤等を含有していてもよい。これらの他の成分は、それぞれ1種又は2種以上を含有していてもよい。
組成物(II)は、[C]化合物と、[D]脱水剤とを含有する。組成物(II)は、[E]重合性化合物及び/又は[F]ポリマー成分を含有することが好ましく、本発明の効果を損なわない範囲において、[C]~[F]成分以外のその他の成分を含有していてもよい。以下、各成分について説明する。
[C]化合物は、イソシアネート基及び重合性基を有する化合物である。[C]化合物は、組成物(I)の[A]錯体を構成する化合物(a)と脱保護反応して脱保護反応生成物(p)を形成する化合物であり、この脱保護反応生成物(p)は重合性を有する。上述したように、当該2液混合型接着剤の使用時に、組成物(I)と組成物(II)を混合することで、[C]化合物のイソシアネート基に、[A]錯体の化合物(a)のイソシアネート基に付加反応する基(X)が反応して、脱保護反応生成物(p)とオルガノボランとが生じ、このオルガノボランの重合開始能により、脱保護反応生成物(p)が重合することにより接着が進行する。
ビニル基、アリル基、スチリル基、(メタ)アクリロイル基等の炭素-炭素二重結合含有基;
エチニル基、プロパギル基等の炭素-炭素三重結合含有基などが挙げられる。これらの中で、重合性が高く、硬化速度をより高めることができる観点から、炭素-炭素二重結合含有基が好ましく、(メタ)アクリロリル基がより好ましい。
イソシアナトエチル(メタ)アクリレート、イソシアナトプロピル(メタ)アクリレート等のイソシアナトアルキル(メタ)アクリレートなどの脂肪族イソシアネート;
イソシアナトシクロヘキシル(メタ)アクリレート、イソシアナトノルボルニル(メタ)アクリレート等のイソシアナトシクロアルキル(メタ)アクリレート等などの脂環族イソシアネート;
スチリルイソシアネート、イソシアナトフェニル(メタ)アクリレート等の芳香族イソシアネート;
ジイソシアネートと、ヒドロキシアルキル(メタ)アクリレートの付加物などのイソシアネート基を有する(メタ)アクリレート;
イソシアナトブテン、イソシアナトペンテン、イソシアナトヘキセン等のイソシアネート基を有するアルケンなどが挙げられる。
[D]脱水剤は、物質中に存在する水分を除去することができる物質をいう。従って、組成物(II)は[D]脱水剤を含有することにより、貯蔵中に系外から混入する水分を除去することができる。
ゼオライト3A、ゼオライト4A、ゼオライト5A等のゼオライト;
無水塩化カルシウム、無水硫酸ナトリウム、無水硫酸カルシウム、無水塩化マグネシウム、無水硫酸マグネシウム、無水炭酸カリウム、無水硫化カリウム、無水亜硫化カリウム、無水亜硫酸ナトリウム、無水硫酸銅等の無水無機塩;
シリカゲル、アルミナ、シリカアルミナ、活性白土等が挙げられる。
オルトギ酸メチル、オルトギ酸エチル、オルトギ酸プロピル等のオルトギ酸エステル;
オルト酢酸メチル、オルト酢酸エチル、オルト酢酸プロピル等のオルト酢酸エステル;
オルトプロピオン酸メチル、オルトプロピオン酸エチル等のオルトプロピオン酸エステル等のカルボン酸オルトエステル;
ベンズアルデヒドジメチルアセタール、アセトアルデヒドジメチルアセタール、ホルムアルデヒドジメチルアセタール、アセトンジメチルアセタール、アセトンジベンジルアセタール、ジエチルケトンジメチルアセタール、ベンゾフェノンジメチルアセタール、ベンジルフェニルケトンジメチルアセタール、シクロヘキサノンジメチルアセタール、アセトフェノンジメチルアセタール、2,2-ジメトキシ-2-フェニルアセトフェノン、4,4-ジメトキシ-2,5-シクロヘキサジエン-1-オンアセタール、ジメチルアセトアミドジエチルアセタール等のアセタール化合物;
ジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド等のカルボジイミド化合物;
メチルシリケート、エチルシリケート等のシリケート化合物などが挙げられる。
[E]重合性化合物は、1の重合性基を有しかつイソシアネート基を有さない化合物である。当該2液混合型接着剤は、組成物(II)が[E]重合性化合物を含有することで、接着層の強度をより向上することができ、その結果、接着強度をより向上させることができる。
ビニル基、アリル基、スチリル基、(メタ)アクリロイル基等の炭素-炭素二重結合含有基;
エチニル基、プロパギル基等の炭素-炭素三重結合含有基などが挙げられる。これらの中で、重合性により優れる観点から、炭素-炭素二重結合含有基が好ましく、(メタ)アクリロリル基がより好ましい。
ブテン、ペンテン、ヘキセン、オクテン、デセン、ドデセン等のオレフィン;
スチレン、α-メチルスチレン、メチルスチレン等のスチレン化合物;
酢酸ビニル、プロピオン酸ビニル、ラウリル酸ビニル等のカルボン酸ビニル;
塩化ビニル、塩化ビニリデン等のハロゲン化オレフィン;
メチルビニルケトン、メチルビニルエーテル等のビニル化合物;
メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-ブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート等のアルキル(メタ)アクリレート;
シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、4-ブチルシクロヘキシル(メタ)アクリレート、ボルニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、トリシクロデカン-イル(メタ)アクリレート、テトラシクロドデカン-イル(メタ)アクリレート等のシクロアルキル(メタ)アクリレート、シクロペンテニル(メタ)アクリレート、シクロヘキセニル(メタ)アクリレート、トリシクロデセン-イル(メタ)アクリレート等のシクロアルケニル(メタ)アクリレートなどの脂環を有する(メタ)アクリレート;
フェニル(メタ)アクリレート、トリル(メタ)アクリレート等のアリール(メタ)アクリレート;ベンジル(メタ)アクリレート等のアラルキル(メタ)アクリレート;フェノキシエチル(メタ)アクリレート等のアリールオキシアルキル(メタ)アクリレートなどの芳香環を有する(メタ)アクリレート;
ヒドロキシエチル(メタ)アクリレート、グリシジル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート等のヘテロ原子含有(メタ)アクリレートなどの(メタ)アクリレート化合物;
(メタ)アクリルアミド、N-メチル(メタ)アクリルアミド等の(メタ)アクリルアミド化合物;
(メタ)アクリロニトリルなどが挙げられる。
組成物(II)は、当該2液混合型接着剤の初期接着強度の向上及び粘度調整、接着層の硬化収縮抑制等の観点から、[F]ポリマー成分を含有することが好ましい。
上記ポリ(メタ)アクリレートとしては、ポリメチル(メタ)アクリレート、ポリエチル(メタ)アクリレート、ポリブチル(メタ)アクリレート等が挙げられる。
上記熱可塑性エラストマーとしては、例えばSBS(スチレン-ブタジエン-スチレンブロック共重合体)、SEBS(スチレン-エチレン-ブタジエン-スチレンブロック共重合体)、SIS(スチレン-イソプレン-スチレンブロック共重合体)、SEPS(スチレン-エチレン-プロピレン-スチレンブロック共重合体)等の共役ジエン系共重合体の未水素添加体、これらの水素添加体などが挙げられる。
組成物(II)は、上記[C]~[F]成分以外のその他の成分として、例えば架橋性化合物、可塑剤、無機充填剤、着色剤、金属塩、重合禁止剤等を含有していてもよい。これらのその他の成分は、それぞれ1種又は2種以上を含有していてもよい。
上記架橋性化合物は、2以上の重合性基を有しかつイソシアネート基を有さない化合物である。組成物(II)に架橋性化合物を含有させることで、接着層の伸び率をより高めることができる。
エチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート等の鎖状グリコール系架橋性化合物;
トリシクロデカンジイルジ(メタ)アクリレート等の脂環式グリコール系架橋性化合物;
トリメチロールプロパントリ(メタ)アクリレート等のトリメチロールプロパン系架橋性化合物;
ビスフェノールAビス(ポリエチレングリコール(メタ)アクリレート)等のビスフェノール系架橋性化合物;
トリ(N-ヒドロキシエチル)イソシアヌレートジ(メタ)アクリレート等のイミド系イソシアヌレート系架橋性化合物;
下記式(2)で表される化合物等のウレタン系架橋性化合物;
下記式(3)で表される化合物等の末端ビスマレイミド変性のポリイミド系架橋性化合物などが挙げられる。
上記式(3)中、nは、1~20の整数である。R4及びR5は、それぞれ独立して、炭素数1~20のアルキレン基である。Ar1は、炭素数6~20のアリーレン基である。nが2以上の場合、複数のR4は同一でも異なっていてもよく、複数のAr1は同一でも異なっていてもよい。
当該2液混合型接着剤は、例えば[A]錯体、[B]化合物及び必要に応じて他の成分を混合することにより組成物(I)を調製し、また別途、[C]化合物、[D]脱水剤並びに必要に応じて[E]重合性化合物、[F]ポリマー成分及びその他の成分を混合することにより組成物(II)を調製することにより得ることができる。
当該2液混合型接着剤は、公知の方法により使用することができる。接着操作の際に、まず、組成物(I)と組成物(II)とを混合する。
2液混合型接着剤の組成物(I)及び組成物(II)の調製に用いた各成分を以下に示す。
TEB-DAP:BASFジャパン社の「TEB-DAP」(テトラエチルボランと、ジアミノプロパンとに由来する錯体)
BP5P:三洋化成工業社の「ニューポールBP-5P」(水酸基価:211)
MOI:昭和電工社の「カレンズMOI」(2-イソシアナトエチルメタクリレート)
ゼオライト5A:ユニオン昭和社の「モレキュラーシーブ5A」
ゼオライト3A:ユニオン昭和社の「モレキュラーシーブ3A」
THFMA:共栄社化学社の「ライトエステルTHF」
2EHMA:共栄社化学社の「ライトエステルEH」
SBS:JSR社の「TR2787」
M521:カネカ社の「カネエースM-521」(コア-シェル粒子)
[A]錯体としてのTEB-DAP2.5質量部と、[B]化合物としてのBP5P7.5質量部とをプラスチック製容器中に入れて混合させ、組成物(I-1)を調製した。
攪拌機を備えたセパラブルフラスコに、[E]重合性化合物としてのTHFMA50.5質量部並びに[F]ポリマー成分としてのSBS16.8質量部及び9.9質量部のM521を40℃のオイルバス中で3時間撹拌し、SBSを完全に溶解させ、M521を均一に分散させた。次いで、[C]化合物としてのMOI7.6質量部、[D]脱水剤としてのゼオライト5A0.5質量部及び[E]重合性化合物としての2EHMA14.7質量部を加えてさらに1時間撹拌して混合した後、2時間減圧脱泡して組成物(II-1)を調製した。
(組成物(I))
組成物(I)としては、実施例1で調製した組成物(I-1)を用いた。
下記表1に示す種類及び含有量の各成分を用いた以外は、実施例1の組成物(II-1)の調製と同様にして、組成物(II-2)~(II-8)及び(CII-1)を調製した。表1中の「-」は、該当する成分を用いなかったことを示す。
(組成物(I))
[A]錯体としてのTEB-DAP2.5質量部と、[E]重合性化合物としてのTHFMA7.5質量部とをプラスチック製容器中に入れて混合させ、組成物(CI-1)を調製した。
組成物(II)としては、実施例7で調製した組成物(II-7)を用いた。
上記調製した各2液混合型接着剤を用い、下記方法に従って、接着強度測定用試験片を作製し、下記剪断試験により接着強度(剪断強度)を測定し、評価した。
(試験片作製方法)
2枚の被着材(それぞれ縦2.5cm×横10cm)を準備し、それぞれ接着剤を塗布する直前に、アセトンを含んだ紙ワイパー(日本製紙クレシア社の「キムワイプ」)で表面の汚れを除去した。次に、組成物(I)と組成物(II)とをバッグ混合法により混合した。すなわち、ポリエチレン製の袋に、組成物(I)と組成物(II)とを(I):(II)=1:10の質量比になるようそれぞれ秤量し、袋を封じた後、均一に混合するため、手のひらの上で転動させることにより、1分間混合した。次いで、袋の隅をハサミでカットし、混合された接着剤を、被着材の一方の1.25cm四方の部分に均一に塗布した。接着剤の厚みを一定にするため、直径0.25mmのガラスビーズを挟んでから、他方の被着材を上に重ねて、試験片を作製した。
上記作製した試験片について、接着部の引張剪断強度を、引張試験機(島津製作所社の「オ-トグラフAG5000B」)を使用してJIS-K6850に準拠して測定した。測定条件は、温度:23℃、チャック間距離:110mm、テストスピード:5mm/分とした。
上記調製した実施例1~8並びに比較例1及び2の2液混合型接着剤について、貯蔵温度を5℃、25℃及び40℃のそれぞれとし、貯蔵日数が0日(組成物の調製直後)、14日、30日、60日及び90日のそれぞれにおいて、また、被着材として、ガラス繊維補強ポリプロピレン/ガラス繊維補強ポリプロピレン(GFPP/GFPP)又は電着鋼/電着鋼(ED/ED)の場合の接着強度(剪断強度)の測定を行った。また、破壊モードを目視により評価した。破壊モードは、A:界面破壊、B:基材破壊、C:凝集破壊であったことをそれぞれ示す。評価結果を表2~11にそれぞれ示す。
Claims (11)
- 第1組成物と第2組成物とを備える2液混合型接着剤であって、
上記第1組成物が、オルガノボラン及びイソシアネート基に付加反応する第1基を有する第1化合物に由来する錯体と、希釈剤としての重合性基を有さない第2化合物とを含有し、
上記第2組成物が、イソシアネート基及び重合性基を有する第3化合物と、脱水剤とを含有することを特徴とする2液混合型接着剤。 - 上記第1組成物が、重合性基を有する化合物を実質的に含有しない請求項1に記載の2液混合型接着剤。
- 上記脱水剤が、ゼオライトである請求項1又は請求項2に記載の2液混合型接着剤。
- 上記第2組成物における上記脱水剤の含有量が0.1質量%以上15質量%以下である請求項1、請求項2又は請求項3に記載の2液混合型接着剤。
- 上記第1組成物における上記第2化合物の上記錯体に対する質量比が0.5以上である請求項1から請求項4のいずれか1項に記載の2液混合型接着剤。
- 上記第1組成物が、上記第2化合物として、ヒドロキシ基を有する化合物を含有する請求項1から請求項5のいずれか1項に記載の2液混合型接着剤。
- 上記ヒドロキシ基を有する化合物が、ポリオール化合物である請求項6に記載の2液混合型接着剤。
- 上記第1化合物の上記第1基がアミノ基である請求項1から請求項7のいずれか1項に記載の2液混合型接着剤。
- 上記第2組成物が、1の重合性基を有しかつイソシアネート基を有さない化合物、ポリマー成分又はこれらの組み合わせをさらに含有する請求項1から請求項8のいずれか1項に記載の2液混合型接着剤。
- 上記第3化合物の重合性基が(メタ)アクリロイル基である請求項1から請求項9のいずれか1項に記載の2液混合型接着剤。
- 上記第3化合物のイソシアネート基のモル数の上記第2化合物のヒドロキシ基及び第1化合物のアミノ基の合計モル数に対する比が1以上である請求項8、請求項9又は請求項10に記載の2液混合型接着剤。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/321,561 US11274233B2 (en) | 2016-08-09 | 2017-05-22 | Two-component adhesive |
JP2018533430A JP6851380B2 (ja) | 2016-08-09 | 2017-05-22 | 2液混合型接着剤 |
KR1020197003466A KR102265579B1 (ko) | 2016-08-09 | 2017-05-22 | 2액 혼합형 접착제 |
CN201780047811.9A CN109563376B (zh) | 2016-08-09 | 2017-05-22 | 双液混合型粘合剂 |
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WO2020110911A1 (ja) * | 2018-11-27 | 2020-06-04 | 株式会社イーテック | 2液混合型接着剤 |
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WO2012160452A1 (en) * | 2011-05-26 | 2012-11-29 | Henkel Ireland Limited | Two-part polymerisable compositions |
WO2014140138A1 (en) * | 2013-03-14 | 2014-09-18 | Henkel IP & Holding GmbH | Curable acrylate or methacrylate compositions |
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DE4412759A1 (de) * | 1994-04-13 | 1995-10-19 | Beiersdorf Ag | Polyurethan-Klebstoff für tragende Holzbauteile |
US5686544A (en) * | 1995-08-11 | 1997-11-11 | Minnesota Mining And Manufacturing Company | Organoborane polyamine complex initiator systems and polymerizable compositions made therewith |
EP1411066B1 (en) * | 2001-07-18 | 2011-05-11 | Asahi Kasei Chemicals Corporation | Modified block copolymer |
US8846809B2 (en) * | 2007-10-12 | 2014-09-30 | Emulsion Technology Co., Ltd. | Urethane adhesive composition |
US8742050B2 (en) * | 2008-03-28 | 2014-06-03 | Henkel US IP LLC | Two part hybrid adhesive |
US20110104508A1 (en) * | 2008-08-29 | 2011-05-05 | Dow Global Technologies Inc. | Adhesive for bonding to flexible polymer surfaces |
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JPH11512123A (ja) * | 1995-08-11 | 1999-10-19 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | 開始剤系および該開始剤を使用して製造された接着組成物 |
WO2012160452A1 (en) * | 2011-05-26 | 2012-11-29 | Henkel Ireland Limited | Two-part polymerisable compositions |
WO2014140138A1 (en) * | 2013-03-14 | 2014-09-18 | Henkel IP & Holding GmbH | Curable acrylate or methacrylate compositions |
Cited By (4)
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WO2020110911A1 (ja) * | 2018-11-27 | 2020-06-04 | 株式会社イーテック | 2液混合型接着剤 |
CN113039253A (zh) * | 2018-11-27 | 2021-06-25 | 株式会社E-Tec | 双液混合型粘合剂 |
CN113039253B (zh) * | 2018-11-27 | 2023-05-12 | 株式会社E-Tec | 双液混合型粘合剂 |
JP7433241B2 (ja) | 2018-11-27 | 2024-02-19 | 株式会社イーテック | 2液混合型接着剤 |
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KR20190038823A (ko) | 2019-04-09 |
KR102265579B1 (ko) | 2021-06-17 |
CN109563376B (zh) | 2022-07-05 |
CN109563376A (zh) | 2019-04-02 |
US11274233B2 (en) | 2022-03-15 |
JP6851380B2 (ja) | 2021-03-31 |
US20200347275A1 (en) | 2020-11-05 |
JPWO2018029938A1 (ja) | 2019-06-06 |
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