Two-component urethane adhesive composition

Abstract

An object of the present invention is to provide a two-component urethane adhesive composition having excellent adhesiveness. The two-component urethane adhesive composition comprises a main agent containing a polyisocyanate component (A) and a curing agent containing water and an active hydrogen-containing compound (B). (B) contains a compound represented by formula (4). (A) contains a urethane prepolymer (A-3) of an active hydrogen-containing compound (A-1) and a polyisocyanate compound (A-2) having two or more functional groups. The ratio (NCO / H) of the number of isocyanate groups of (A-2) to the number of active hydrogens of (A-1) is 1.5 to 10. The average active hydrogen concentration of (B) is 0.50 to 3.50 mol / kg. The average active hydrogen concentration of (B) and water is 2.00 to 8.00 mol / kg. The mixing amounts of the main agent and the curing agent satisfy that the ratio (NCO / H) of the number of isocyanate groups of (A) to the number of active hydrogens of (B) is 1 to 5, and the ratio (NCO / H) of the number of isocyanate groups of (A) to the total number of active hydrogens of (B) and water is 0.5 to 2.5.

Description

Technical Field

[0001] The present invention relates to a two-component urethane adhesive composition. Background Art

[0002] Conventionally, two-component urethane adhesive compositions have been used, for example, in automotive applications (e.g., Patent Document 1).

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Patent No. 6621847 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] Under such circumstances, the present inventors prepared a two-component urethane adhesive composition with reference to Patent Document 1 and evaluated it. As a result, it was clarified that the adhesiveness obtained from such a composition sometimes fails to meet the currently required level.

[0008] Therefore, an object of the present invention is to provide a two-component urethane adhesive composition having excellent adhesiveness.

[0009] Means for Solving the Problems

[0010] The present inventors conducted intensive studies to solve the above problems and found that by having a main agent and a curing agent, the curing agent containing water and an active hydrogen-containing compound (B) having a plurality of active hydrogens, and the average active hydrogen concentration of the active hydrogen-containing compound (B) and water being within a specific range, etc., desired effects can be obtained, thereby completing the present invention.

[0011] The present invention has been completed based on the above insights, etc., and specifically, the above problems are solved by the following constitution.

[0012] [1] A two-component urethane adhesive composition, comprising:

[0013] A main agent containing a polyisocyanate component (A), and

[0014] A curing agent containing water and an active hydrogen-containing compound (B) having a plurality of active hydrogens;

[0015] The active hydrogen-containing compound (B) contains a nitrogen-containing compound represented by the following formula (4);

[0016] In the main agent, the polyisocyanate component (A) contains a urethane prepolymer (A-3) formed from an active hydrogen-containing compound (A-1) having a plurality of active hydrogens and a polyfunctional isocyanate compound (A-2), and the ratio R1 (NCO / H) of the number of isocyanate groups of the isocyanate compound (A-2) to the number of active hydrogens (A1-H) of the active hydrogen-containing compound (A-1) is 1.5 to 10;

[0017] In the curing agent, the average active hydrogen concentration (BH-c) of the active hydrogen-containing compound (B) is 0.50 to 3.50 mol / kg, and the average active hydrogen concentration (BWH-c) of the active hydrogen-containing compound (B) and the water is 2.00 to 8.00 mol / kg;

[0018] The mixing amounts of the main agent and the curing agent satisfy: the ratio R2 (NCO / H) of the number of isocyanate groups of the polyisocyanate component (A) to the number of active hydrogens (B-H) of the active hydrogen-containing compound (B) is 1 to 5, and the ratio R3 (NCO / H) of the number of isocyanate groups of the polyisocyanate component (A) to the total number of active hydrogens of the active hydrogen-containing compound (B) and the water is 0.5 to 2.5, wherein the active hydrogen-containing compound (B) does not contain silicon.

[0019]

[0020] In formula (4), R6 to R9 each independently represent an alkylene group, and R 10 represents an alkylene group or a polyoxyalkylene group, and a to d each independently represent 0 to 10.

[0021] The two-component urethane-based adhesive composition according to [2][1], wherein the urethane prepolymer (A-3) contains an unreacted polyfunctional isocyanate compound (A-2').

[0022] The two-component urethane-based adhesive composition according to [3][1] or [2], wherein the main agent further contains a silane coupling agent (F).

[0023] The silane coupling agent (F) includes a silane coupling agent (F-1) and / or a monothioether-containing silane coupling agent (F-2), and the silane coupling agent (F-1) is a silane coupling agent having a skeleton from the modifier and an isocyanate group obtained by reacting a modifier of an aliphatic polyisocyanate with an aminosilane coupling agent.

[0024] The two-component urethane-based adhesive composition according to [4][3], wherein the silane coupling agent (F) includes the silane coupling agent (F-1).

[0025] The two-component urethane adhesive composition described in [5][3] or [4], wherein the modified product of the aliphatic polyisocyanate contains a biuret body of HDI.

[0026] [6][3] The two-component urethane adhesive composition described in any one of [5], wherein the aminosilane coupling agent has an NH2 group or an NH group. In the aminosilane coupling agent, the number of the NH2 groups is 0 or 1 per molecule of the aminosilane coupling agent, and the total of the NH2 groups and the NH groups is 1 or more.

[0027] [7][1] The two-component urethane adhesive composition described in any one of [6], wherein the main agent further contains an aliphatic diisocyanate derivative (C), and the aliphatic diisocyanate derivative (C) is at least one selected from the group consisting of an isocyanurate body, a biuret body, and a urethane body of an aliphatic diisocyanate, and wherein the aliphatic diisocyanate derivative (C) does not contain silicon;

[0028] The content of the aliphatic diisocyanate derivative (C) is 0.1 to 10% by mass of the total amount of the main agent.

[0029] [8][1] The two-component urethane adhesive composition described in any one of [7], wherein the curing agent contains at least one selected from the group consisting of the following compounds:

[0030] Nitrogen-containing compound 1, which is represented by the formula (4), R6 to R9 each independently represent a propylene group and / or an ethylene group, R 10 represents an alkylene group having 2 to 10 carbon atoms, a to d each independently represent 1 to 10, and at least one of a to d is 3 or more,

[0031] Nitrogen-containing compound 2 represented by the following formula (5), and

[0032] Nitrogen-containing compound 3, which is represented by the formula (4), R6 to R9 each independently represent an alkylene group, R 10 represents a polyoxyalkylene group, a to d each independently represent 0,

[0033]

[0034] In formula (5), R 56 to R 59 each independently represent a propylene group and / or an ethylene group, R 50 represents an alkylene group having 2 to 10 carbon atoms, a to d each independently represent 1 to 2, and at least one of a to d is 2.

[0035] The two-component urethane-based adhesive composition described in [9][8], wherein the curing agent contains the nitrogen-containing compound 1, and the nitrogen-containing compound 2 and / or the nitrogen-containing compound 3.

[0036] The two-component urethane-based adhesive composition described in any one of

[10] [1] to [9], wherein the curing agent further contains a compound (D) having an alkoxysilyl group and / or a silanol group.

[0037] The content of the compound (D) contained in the curing agent is 0.002 to 5% by mass of the total amount of the composition.

[0038] The two-component urethane-based adhesive composition described in

[11]

[10] , wherein the compound (D) contains an amino silane coupling agent having a plurality of amino groups.

[0039] The two-component urethane-based adhesive composition described in

[12]

[11] , wherein the amino silane coupling agent having a plurality of amino groups has an organic chain or a siloxane skeleton as a skeleton.

[0040] Advantages of the Invention

[0041] The two-component urethane-based adhesive composition of the present invention has excellent adhesiveness. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 It is a side view schematic diagram of the creep test conducted in the examples of the present invention.

[0043] Figure 2 It is a side view schematic diagram showing a part of Sample 1 after applying a load. DETAILED DESCRIPTION

[0044] The present invention will be described in detail below.

[0045] It should be noted that in this specification, the numerical range indicated by "~" means the range including the numerical values described before and after "~".

[0046] In this specification, unless otherwise specified, each component may be used alone or in combination of two or more of the substances corresponding to the component. When the component contains two or more substances, the content of the component means the total content of the two or more substances.

[0047] In this specification, sometimes the more excellent adhesiveness is referred to as the more excellent effect of the present invention.

[0048] In this specification, sometimes the polyisocyanate component (A) is simply referred to as "(A)". The same applies to other components.

[0049] [Two-component urethane adhesive composition]

[0050] The two-component urethane adhesive composition (the adhesive composition of the present invention) of the present invention comprises:

[0051] A main agent containing a polyisocyanate component (A), and

[0052] A curing agent containing water and an active hydrogen-containing compound (B) having a plurality of active hydrogens;

[0053] The active hydrogen-containing compound (B) contains a nitrogen-containing compound represented by the following formula (4);

[0054] In the main agent, the polyisocyanate component (A) comprises a urethane prepolymer (A-3) formed from an active hydrogen-containing compound (A-1) having a plurality of active hydrogens and a polyisocyanate compound (A-2) having two or more functional groups. The ratio R1 (NCO / H) of the number of isocyanate groups of the polyisocyanate compound (A-2) to the number of active hydrogens (A1-H) of the active hydrogen-containing compound (A-1) is 1.5 to 10;

[0055] In the curing agent, the average active hydrogen concentration (BH-c) of the active hydrogen-containing compound (B) is 0.50 to 3.50 mol / kg, and the average active hydrogen concentration (BWH-c) of the active hydrogen-containing compound (B) and the water is 2.00 to 8.00 mol / kg;

[0056] The mixing amount of the main agent and the curing agent satisfies: the ratio R2 (NCO / H) of the number of isocyanate groups of the polyisocyanate component (A) to the number of active hydrogens (B-H) of the active hydrogen-containing compound (B) is 1 to 5, and the ratio R3 (NCO / H) of the number of isocyanate groups of the polyisocyanate component (A) to the total number of active hydrogens of the active hydrogen-containing compound (B) and the water is 0.5 to 2.5, wherein the active hydrogen-containing compound (B) does not contain silicon.

[0057] Hereinafter, each component contained in the adhesive composition of the present invention will be described in detail.

[0058] The adhesive composition of the present invention is a two-component urethane adhesive composition containing a main agent and a curing agent (a curing agent in a broad sense).

[0059] [Main agent]

[0060] In the present invention, the main agent contains a polyisocyanate component (A).

[0061] [Polyisocyanate component (A)]

[0062] In the present invention, the polyisocyanate component (A) contained in the main agent includes a urethane prepolymer (A-3) formed from an active hydrogen-containing compound (A-1) having a plurality of active hydrogens and a polyfunctional isocyanate compound (A-2) having two or more functional groups.

[0063] [Urethane prepolymer (A-3)]

[0064] In the present invention, the urethane prepolymer (A-3) preferably has a plurality of isocyanate groups. (A-3) preferably has an isocyanate group at the terminal.

[0065] [Active hydrogen-containing compound (A-1)]

[0066] In the present invention, the active hydrogen-containing compound (A-1) having a plurality of active hydrogens used to form the urethane prepolymer (A-3) is a compound having two or more active hydrogens per molecule.

[0067] [Active hydrogen (A1-H)]

[0068] The active hydrogen (A1-H) possessed by (A-1) can form functional groups such as, for example, a hydroxyl group, an amino group, an imino group, a mercapto group, and a carboxyl group.

[0069] From the perspective of more excellent effects of the present invention, it is preferred that the active hydrogen (A1-H) possessed by (A-1) forms a hydroxyl group.

[0070] From the perspective of more excellent effects of the present invention, it is preferred that (A-1) has 2 to 3 active hydrogens (A1-H) per molecule.

[0071] · Main chain skeleton of (A-1)

[0072] The main chain skeleton of (A-1) is not particularly limited. For example, hydrocarbons, polyethers, polyesters, and combinations thereof can be cited.

[0073] · Specific examples of (A-1)

[0074] As (A-1), for example, polyether polyols, polyester polyols, and polyamines can be cited.

[0075] From the perspective of more excellent effects of the present invention, it is preferred that (A-1) contains polyether polyols.

[0076] As polyether polyols, for example, polyoxyethylene polyols, polyoxypropylene polyols, and polyoxyethylene polyoxypropylene polyols can be cited.

[0077] [Isocyanate compound (A-2)]

[0078] In the polyisocyanate component (A), the polyisocyanate compound (A-2) having two or more functional groups used to form the urethane prepolymer (A-3) is a compound having multiple (two or more) isocyanate groups per molecule.

[0079] [Isocyanate group]

[0080] From the perspective of more excellent effects of the present invention, it is preferred that (A-2) has 2 to 3 isocyanate groups per molecule.

[0081] · Main chain skeleton of (A-2)

[0082] The main chain skeleton of (A-2) is not particularly limited. For example, hydrocarbon groups such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof can be cited.

[0083] · Specific examples of (A-2)

[0084] As (A-2), for example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (unsubstituted MDI, also called pure MDI, monomer MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), dimethylbiphenyl diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate, polymeric MDI (a compound obtained by polymerizing diphenylmethane diisocyanate (pure MDI)), modified MDI, etc. can be cited;

[0085] Pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(isocyanatomethyl)cyclohexane (H6XDI), dicyclohexylmethane diisocyanate (H 12 MDI), etc. can be cited;

[0086] As the aliphatic hydrocarbon group of the aliphatic polyisocyanate (a compound in which multiple isocyanate groups are bonded to an aliphatic hydrocarbon), for example, linear, branched, cyclic, or combinations thereof can be cited.

[0087] It is preferred that (A-2) contains an aromatic polyisocyanate (a compound in which multiple isocyanate groups are bonded to an aromatic hydrocarbon), and more preferably contains diphenylmethane diisocyanate.

[0088] [Ratio R1 (NCO / H)]

[0089] In the present invention, the ratio R1(NCO / H) of the number of isocyanate groups of (A-2) to the number of active hydrogens (A1-H) of (A-1) is 1.5 to 10.

[0090] From the perspective of more excellent effects of the present invention, the ratio R1(NCO / H) is preferably 1.6 to 8.5, and more preferably 1.6 to 7.0.

[0091] (Isocyanate compound (A-2'))

[0092] As described above, in the present invention, the ratio R1(NCO / H) is 1.5 to 10, and in the polyisocyanate component (A), the isocyanate groups are in excess relative to the active hydrogens (A1-H). Therefore, in addition to the urethane prepolymer as the reaction product, the urethane prepolymer (A-3) may further contain unreacted polyisocyanate compounds (A-2') having two or more functional groups.

[0093] From the perspective of more excellent effects of the present invention, it is preferred that the urethane prepolymer (A-3) contains unreacted polyisocyanate compounds (A-2') having two or more functional groups.

[0094] (Aliphatic diisocyanate derivative (C))

[0095] From the perspective of more excellent effects of the present invention, it is preferred that the main agent further contains at least one aliphatic diisocyanate derivative (C) selected from the group consisting of isocyanurate, biuret, and urethane forms of aliphatic diisocyanates. Among them, the aliphatic diisocyanate derivative (C) does not contain silicon. The main idea of the annotation is to exclude the silane coupling agent (F) and compound (D) described below from (C).

[0096] As the aliphatic hydrocarbon group of the aliphatic diisocyanate (a compound in which two isocyanate groups are bonded to an aliphatic hydrocarbon), for example, a linear, branched, cyclic, or a combination thereof can be cited.

[0097] As the aliphatic diisocyanate for forming the aliphatic diisocyanate derivative (C), for example, the aliphatic polyisocyanates exemplified as (A-2) can be cited.

[0098] From the perspective of more excellent effects of the present invention, the aliphatic diisocyanate derivative (C) preferably contains an isocyanurate form of pentamethylene diisocyanate and / or a urethane form of pentamethylene diisocyanate, and more preferably contains an isocyanurate form of pentamethylene diisocyanate and a urethane form of pentamethylene diisocyanate.

[0099] · Content of aliphatic diisocyanate derivative (C)

[0100] From the viewpoint of more excellent effects of the present invention, the content of the aliphatic diisocyanate derivative (C) is preferably 0.1 to 10% by mass, more preferably 0.5 to 5.0% by mass, based on the total amount of the main agent.

[0101] (Silane coupling agent (F))

[0102] From the viewpoint of more excellent effects of the present invention, it is preferable that the main agent further contains a silane coupling agent (F).

[0103] A silane coupling agent is a compound having a hydrolyzable silyl group and a functional group other than the hydrolyzable silyl group.

[0104] Examples of the hydrolyzable silyl group include an alkoxysilyl group and a silanol group.

[0105] ·Alkoxysilyl group

[0106] The alkoxysilyl group that the silane coupling agent (F) may have is a group in which 1 to 3 alkoxy groups are bonded to silicon.

[0107] Examples of the alkoxy group include a methoxy group and an ethoxy group.

[0108] ·Group other than alkoxy

[0109] When the number of alkoxy groups in the alkoxysilyl group is 1 to 2, the remaining group bonded to the silicon atom is not particularly limited. Examples of the remaining group include a hydrocarbon group that may have a hetero atom, and specifically, an unsubstituted hydrocarbon group, for example, may be mentioned.

[0110] Examples of the alkoxysilyl group include a methoxysilyl group and an ethoxysilyl group.

[0111] ·Silanol group

[0112] The silanol group that the silane coupling agent (F) may have is a group in which 1 to 3 OH groups are bonded to silicon.

[0113] Examples of the silanol group include a silanol group formed by partial or complete hydrolysis of the alkoxy group of the alkoxysilyl group.

[0114] When the main agent further contains a silane coupling agent (F), from the viewpoint of more excellent effects of the present invention, it is preferable that the silane coupling agent (F) has an alkoxysilyl group.

[0115] From the perspective of more excellent effects of the present invention, the functional groups other than the hydrolyzable silyl groups in the silane coupling agent (F) are preferably isocyanate groups, mercapto groups, monothioether groups (such as -C-S-Si bonds), and amino groups (the amino groups include the concepts of primary amino groups, secondary amino groups, and tertiary amino groups).

[0116] The hydrolyzable silyl group and the functional group other than the hydrolyzable silyl group can be bonded through an organic group. The organic group is not particularly limited. For example, hydrocarbon groups such as aliphatic hydrocarbon groups can be cited.

[0117] It should be noted that the hydrolyzable silyl group and the hydrocarbon group as an organic group can be bonded through a monothioether bond (-S-).

[0118] From the perspective of more excellent effects of the present invention, the silane coupling agent (F) preferably contains an isocyanate group-containing silane coupling agent (such as the silane coupling agent (F-1) described later), a monothioether-containing silane coupling agent (F-2), more preferably contains a silane coupling agent (F-1) having a skeleton from the modified body and an isocyanate group obtained by reacting a modified body of an aliphatic polyisocyanate with an amino silane coupling agent, and / or a monothioether-containing silane coupling agent (F-2), and further preferably contains the silane coupling agent (F-1).

[0119] Examples of the modified body of the aliphatic polyisocyanate as a raw material of the silane coupling agent (F-1) include isocyanurate bodies, biuret bodies, and urethane-formate bodies of hydrocarbon compounds having a plurality of isocyanate groups.

[0120] From the perspective of more excellent effects of the present invention, the modified body of the aliphatic polyisocyanate preferably contains a biuret body of an aliphatic diisocyanate, and more preferably contains a biuret body of HDI.

[0121] Examples of the amino silane coupling agent as a raw material of the silane coupling agent (F-1) include silane coupling agents having an NH2 group and / or an NH group.

[0122] From the perspective of more excellent effects of the present invention, the amino silane coupling agent preferably has an NH2 group or an NH group. For each molecule of the amino silane coupling agent, the number of NH2 groups is 0 or 1, and the total of NH2 groups and NH groups is 1 or more.

[0123] From the perspective of more excellent effects of the present invention, the amino silane coupling agent preferably contains (N-phenyl)aminopropyltrialkoxysilane, and more preferably contains (N-phenyl)aminopropyltrimethoxysilane.

[0124] The reaction between the modified aliphatic polyisocyanate and the aminosilane coupling agent is preferably carried out with an excess amount of the molar number of the isocyanate groups in the modified body compared to the molar number of the amino groups in the aminosilane coupling agent.

[0125] · Silane coupling agent containing monothioether (F-2)

[0126] The silane coupling agent containing monothioether (F-2) has a monothio bond and a hydrolyzable silyl group, and is a monothioether compound in which the monothio bond is directly bonded to the silicon atom of the hydrolyzable silyl group.

[0127] Regarding the silane coupling agent containing monothioether (F-2), from the perspective of more excellent effects of the present invention, one of the preferred embodiments is that in addition to the hydrolyzable silyl group bonded to the monothioether bond, it further has a second hydrolyzable silyl group.

[0128] As the second hydrolyzable silyl group, the hydrolyzable silyl group similar to the hydrolyzable silyl group bonded to the monothioether bond can be cited, and it can be the same as or different from the hydrolyzable silyl group bonded to the monothioether bond.

[0129] The second hydrolyzable silyl group can be bonded to the above-mentioned monothioether bond through a hydrocarbon group. The hydrocarbon group is not particularly limited.

[0130] As the hydrocarbon group, for example, an alkylene group (e.g., an alkylene group having 1 to 10 carbon atoms), a cycloalkylene group, an arylene group, or a combination thereof can be cited. The hydrocarbon group can be either linear or branched.

[0131] From the perspective of more excellent adhesiveness, the silane coupling agent containing monothioether (F-2) preferably contains a compound represented by the following formula (11).

[0132]

[0133] In the formula, R 1 , R 2 are each independently a hydrocarbon group that may have a heteroatom, n is each independently an integer from 1 to 3, and R 3 is a hydrocarbon group.

[0134] As the hydrocarbon group that may have a heteroatom for R 1 , there is no particular limitation. For example, the hydrocarbon group similar to the hydrocarbon group of the alkoxy in the above-mentioned alkoxysilyl group can be cited.

[0135] As the hydrocarbon group that may have a heteroatom for R 2 , when the number of alkoxy groups in the 1 hydrolyzable silyl group is 1 to 2, it is the same as the hydrocarbon group that can be bonded to the silicon atom of the hydrolyzable silyl group and may have a heteroatom.

[0136] Preferably, each n is independently 3.

[0137] As R 3 The hydrocarbon group is the same as the above-mentioned hydrocarbon group between the second hydrolyzable silyl group and the monothioether bond. As such a hydrocarbon group, for example, -C m H 2m - may be mentioned. m is preferably an integer of 1 to 5.

[0138] From the viewpoint of more excellent adhesiveness, the silane coupling agent (F-2) containing a monothioether preferably contains a compound represented by the following formula (12) (triethoxysilylpropyltrimethoxysilane).

[0139]

[0140] · Content of silane coupling agent (F)

[0141] When the main agent further contains the silane coupling agent (F), the content of the silane coupling agent (F) is preferably 0.02 to 5% by mass based on the total amount of the adhesive composition of the present invention. It should be noted that when the curing agent further contains the compound (D), the content of the silane coupling agent (F) contained in the main agent may be the same as above.

[0142] [Curing agent]

[0143] In the present invention, the curing agent (in a broad sense) contains water and an active hydrogen-containing compound (B) having a plurality of active hydrogens, and the active hydrogen-containing compound (B) includes a nitrogen-containing compound represented by the following formula (4).

[0144] Water and the active hydrogen-containing compound (B) having a plurality of active hydrogens can function as a curing agent (in a narrow sense) capable of reacting with the polyisocyanate component (A) to cure the adhesive composition of the present invention.

[0145] [Water]

[0146] The water contained in the curing agent (in a broad sense) is not particularly limited. For example, purified water can be mentioned.

[0147] [Active hydrogen-containing compound (B)]

[0148] The active hydrogen-containing compound (B) contained in the curing agent (in a broad sense) is a compound having 2 or more active hydrogens per molecule. Among them, in the present invention, the active hydrogen-containing compound (B) does not contain silicon.

[0149] [Active hydrogen (B-H)]

[0150] The active hydrogen (B-H) of the compound (B) containing active hydrogen can form functional groups such as hydroxyl group, amino group, imino group, mercapto group, carboxyl group, etc.

[0151] From the perspective of more excellent effects of the present invention, the active hydrogen (B-H) of (B) preferably forms a hydroxyl group or an amino group.

[0152] From the perspective of more excellent effects of the present invention, it is preferred that each molecule of (B) has 2 to 4 active hydrogens (B-H).

[0153] · The main chain skeleton of (B)

[0154] The main chain skeleton of (B) is not particularly limited. For example, hydrocarbons, polyethers, polyesters, and combinations thereof can be cited.

[0155] The nitrogen-containing compound represented by formula (4)

[0156] In the present invention, the compound (B) containing active hydrogen includes the nitrogen-containing compound represented by the following formula (4) (the compound represented by formula (4)).

[0157]

[0158] In formula (4), R6 to R9 each independently represent an alkylene group, and R 10 represents an alkylene group or a polyoxyalkylene group, and a to d each independently represent 0 to 10.

[0159] In formula (4), as the alkylene group of R6 to R9, for example, ethylene group, propylene group can be cited.

[0160] As for R 10 The alkylene group having 2 to 10 carbon atoms, for example, ethylene group, tetramethylene group, pentylene group, hexylene group, octylene group, decylene group can be cited. The alkylene group having 2 to 10 carbon atoms is preferably an ethylene group. R 10 can be a part of the skeleton of (B).

[0161] Regarding the polyether which can be the skeleton of (B), for example, when a in formula (4) is 3 or more, H-(O-R6) a - becomes a polyether having a hydroxyl group at the end. The same applies to b to d.

[0162] As the compound represented by formula (4), for example, the nitrogen-containing compound 1, nitrogen-containing compound 2, nitrogen-containing compound 3 described later can be cited.

[0163] · Nitrogen-containing compound 1

[0164] Nitrogen-containing compound 1 is represented by the above formula (4), and R6 to R9 each independently represent a propylene group and / or an ethylene group, and R10 An alkylene group having 2 to 10 carbon atoms, a to d each independently represent 1 to 10, and at least one of a to d is a tetrafunctional hydroxy compound having 3 or more.

[0165] From the perspective of more excellent effects of the present invention, the weight average molecular weight of the nitrogen-containing compound 1 is preferably 200 to 2,000, more preferably 400 to 800.

[0166] · Nitrogen-containing compound 2

[0167] The nitrogen-containing compound 2 is a compound represented by the formula (5). The nitrogen-containing compound 2 is a tetrafunctional hydroxy compound.

[0168]

[0169] In the formula (5), R 56 ~R 59 each independently represent propylene group and / or ethylene group, R 50 represents an alkylene group having 2 to 10 carbon atoms, a to d each independently represent 1 to 2, and at least one of a to d is 2.

[0170] In the formula (5), the alkylene group having 2 to 10 carbon atoms of R 50 is the same as R 10 in the formula (4).

[0171] From the perspective of more excellent effects of the present invention, the weight average molecular weight of the nitrogen-containing compound 2 is preferably 100 to 1,000, more preferably 200 to 500.

[0172] · Nitrogen-containing compound 3

[0173] The nitrogen-containing compound 3 is a diamine compound represented by the above formula (4), in which R6 to R9 each independently represent an alkylene group, R 10 represents a polyoxyalkylene group, and a to d each represent 0.

[0174] From the perspective of more excellent effects of the present invention, the curing agent preferably contains at least one selected from the nitrogen-containing compounds 1 to 3, and more preferably contains the nitrogen-containing compound 1.

[0175] When the curing agent contains the nitrogen-containing compound 1, from the perspective of more excellent effects of the present invention, it preferably further contains the nitrogen-containing compound 2 and / or the nitrogen-containing compound 3, and more preferably contains the nitrogen-containing compound 2.

[0176] The compound (B) containing active hydrogen may further contain a compound containing active hydrogen other than the compound represented by the formula (4) (other compounds containing active hydrogen).

[0177] As other active hydrogen-containing compounds, polyether polyols, polybutadiene polyols, polyester polyols, sugar-based polyols, etc., which do not contain nitrogen atoms, can be cited; amine compounds other than the compounds in which at least one of a to d in the formula (4) is 0.

[0178] From the viewpoint that the effects of the present invention are more excellent (especially excellent in the evaluation of the creep test 5 described later), it is preferable that the active hydrogen-containing compound (B) contains a polyether polyol having three or more hydroxyl groups in addition to the compound represented by the formula (4).

[0179] From the viewpoint that the effects of the present invention are more excellent (especially excellent in shear strength), it is preferable that the active hydrogen-containing compound (B) contains at least one selected from the group consisting of polybutadiene polyol, polyester polyol, and polyether polyol having two hydroxyl groups in addition to the compound represented by the formula (4).

[0180] In the present invention, the weight average molecular weight of the active hydrogen compound can be set as a polystyrene conversion value based on gel permeation chromatography using the solvent THF (tetrahydrofuran). The measurement method and measurement conditions of the weight average molecular weight of the active hydrogen compound in the present invention are as described below.

[0181] (Measurement method and measurement conditions of the weight average molecular weight of the active hydrogen compound)

[0182] GPC: LC Solution (manufactured by SHIMAZU)

[0183] Detector: SPD-20A (manufactured by SHIMAZU)

[0184] Column: Two columns with the trade name Shim-pack GPC-801 (manufactured by SHIMAZU) are connected in series. Solvent: Tetrahydrofuran

[0185] Temperature: 40 °C

[0186] Flow rate: 0.5 ml / min

[0187] Concentration: 2 mg / ml

[0188] Standard sample: Polystyrene

[0189] [(Average active hydrogen concentration (BH-c) of (B))]

[0190] In the present invention, the average active hydrogen concentration (BH-c) of the active hydrogen-containing compound (B) is 0.50 to 3.50 mol / kg.

[0191] The average active hydrogen concentration (BH-c) of the active hydrogen-containing compound (B) is expressed as the number of moles of all active hydrogens possessed by the active hydrogen-containing compound (B) relative to the total amount (kg) of the active hydrogen-containing compound (B).

[0192] From the perspective of more excellent effects of the present invention, (BH-c) is preferably 0.7 to 3.5 mol / kg, more preferably 1.5 to 2.9 mol / kg.

[0193] In the present invention, the average active hydrogen concentration (BH-c) of the active hydrogen-containing compound (B) can be calculated from the active hydrogen concentration and content (mass) of each active hydrogen-containing compound (B).

[0194] The active hydrogen concentration of the active hydrogen-containing compound (B) can be calculated from the hydroxyl value of the active hydrogen-containing compound (B). That is, divide the hydroxyl value of each active hydrogen-containing compound (B) by the molecular weight of KOH.

[0195] The hydroxyl value of the active hydrogen-containing compound (B) can be measured according to JIS K1557.

[0196] · Content of the active hydrogen-containing compound (B)

[0197] From the perspective of more excellent effects of the present invention, the content of the active hydrogen-containing compound (B) (when there are two or more active hydrogen-containing compounds (B), it is their total content) is preferably 50 to 90% by mass of the total amount of the curing agent, more preferably 55 to 80% by mass, and further preferably 60 to 70% by mass.

[0198] [Average active hydrogen concentration (BWH-c)]

[0199] In the present invention, the average active hydrogen concentration (BWH-c) of the active hydrogen-containing compound (B) and water is 2.00 to 8.00 mol / kg.

[0200] The average active hydrogen concentration (BWH-c) of the active hydrogen-containing compound (B) and water is expressed as the sum of the number of moles of the active hydrogens possessed by the active hydrogen-containing compound (B) and the number of moles of the active hydrogens possessed by the water relative to the total amount (kg) of the active hydrogen-containing compound (B) and water.

[0201] From the perspective of more excellent effects of the present invention, (BWH-c) is preferably 2.50 to 6.50 mol / kg, more preferably 3.20 to 5.50 mol / kg, further preferably 3.7 to 5.50 mol / kg, and even more preferably 4.20 to 5.20 mol / kg.

[0202] In the present invention, the average active hydrogen concentration (BWH-c) of the active hydrogen-containing compound (B) and water can be calculated from the active hydrogen concentrations and contents (by mass) of the respective active hydrogen-containing compounds (B) and water.

[0203] The active hydrogen concentration and content of the active hydrogen-containing compound (B) are the same as described above.

[0204] (Active hydrogen concentration of water)

[0205] In the present invention, the active hydrogen concentration of water is set to 111.1 mol / kg. This value is obtained by setting the hydroxyl value of water to 6233 mg KOH / g and dividing it by the molecular weight of KOH.

[0206] It should be noted that the hydroxyl value of water is calculated to be 6233 mg KOH / g, for example, as described in JP-A-2005-249957

[0043] , JP-A-2009-156944

[0050] , and JP-A-2011-68719

[0103] .

[0207] · Content of water

[0208] From the viewpoint of more excellent effects of the present invention, the content of water is preferably 0.1 to 5% by mass, more preferably 1.1 to 2.5% by mass, and still more preferably 1.2 to 1.5% by mass of the total amount of the curing agent.

[0209] [Compound (D)]

[0210] From the viewpoint of more excellent effects of the present invention, the curing agent preferably further contains a compound (D) having an alkoxysilyl group and / or a silanol group. When the curing agent further contains the compound (D), the compound (D) preferably has a silanol group.

[0211] · Alkoxysilyl group, silanol group

[0212] The alkoxysilyl group and silanol group that the compound (D) can have are the same as those that the above-mentioned silane coupling agent (F) can have.

[0213] From the viewpoint of more excellent effects of the present invention, the compound (D) can have functional groups other than the alkoxysilyl group and the silanol group. The functional group is preferably an amino group and / or an imino group.

[0214] From the viewpoint of more excellent effects of the present invention, the compound (D) preferably contains a compound having an alkoxysilyl group and / or a silanol group, and an amino group (the amino group includes the concepts of primary amino group, secondary amino group, and tertiary amino group), and more preferably contains an amino silane coupling agent having an alkoxysilyl group and / or a silanol group and multiple amino groups.

[0215] From the perspective of more excellent effects of the present invention, as the amino silane coupling agent having multiple amino groups of compound (D), it preferably has an organic chain or a siloxane skeleton as the skeleton, and more preferably has an organic chain as the skeleton.

[0216] The organic chain as the skeleton is not particularly limited.

[0217] The siloxane skeleton as the skeleton is not particularly limited. For example, a siloxane skeleton represented by -Si-(O-Si) n -O-Si- and n is 0 or more can be cited.

[0218] As the amino silane coupling agent having multiple amino groups, for example, an amino silane coupling agent at the monomer level or its oligomer can be cited.

[0219] As the amino silane coupling agent at the monomer level, for example, N-(aminoalkyl)-aminoalkyltrialkoxysilane such as N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (having one primary amino group and one secondary amino group) can be cited.

[0220] As the amino silane coupling agent having multiple amino groups, one of the preferred embodiments can be an oligomer of an amino silane coupling agent.

[0221] · Oligomer of amino silane coupling agent

[0222] The oligomer of the amino silane coupling agent is not particularly limited as long as it is a compound formed by oligomerizing the amino silane coupling agent. In the above case, the amino silane coupling agent capable of forming an oligomer only needs to have one or more amino groups. The amino silane coupling agent capable of forming an oligomer can further have a reactive group for oligomerization.

[0223] The degree of polymerization of the oligomer is not particularly limited, preferably 3 to 10, more preferably 3 to 8, and further preferably 4 to 8.

[0224] As the oligomer of the amino silane coupling agent of compound (D), for example, a compound in which the skeleton of the oligomer obtained by oligomerizing the amino silane coupling agent has an organic chain or a siloxane skeleton can be cited. When the skeleton of the oligomer is an organic chain, an alkoxysilyl group and / or a silanol group, and multiple amino groups can be bonded to the skeleton. When the skeleton of the oligomer is a siloxane skeleton, the silicon forming the siloxane skeleton can be bonded to a hydrocarbon group, an OH group or an alkoxy group, and multiple amino groups can be bonded to the skeleton.

[0225] · Content of compound (D)

[0226] When the curing agent further contains compound (D), from the perspective of more excellent effects of the present invention, the content of compound (D) is preferably 0.002 to 5% by mass of the total amount of the adhesive composition of the present invention.

[0227] · Total content of silane coupling agent (F) and compound (D)

[0228] When the main agent further contains silane coupling agent (F) and the curing agent further contains compound (D), from the perspective of more excellent effects of the present invention, the total content of silane coupling agent (F) and compound (D) is preferably 0.03 to 5% by mass of the total amount of the adhesive composition of the present invention.

[0229] [Mixing amount of main agent and curing agent]

[0230] In the present invention, the mixing amount of the main agent and the curing agent satisfies that the ratio R2 (NCO / H) of the number of isocyanate groups of the polyisocyanate component (A) to the number of active hydrogens (B-H) of the active hydrogen compound (B) is 1 to 5, and the ratio R3 (NCO / H) of the number of isocyanate groups of the polyisocyanate component (A) to the total number of active hydrogens of the active hydrogen compound (B) and water is 0.5 to 2.5.

[0231] [Ratio R2 (NCO / H)]

[0232] From the perspective of more excellent effects of the present invention, the ratio R2 (NCO / H) of the number of isocyanate groups of the polyisocyanate component (A) to the number of active hydrogens (B-H) of the active hydrogen compound (B) is preferably 1.5 to 4.5.

[0233] [Ratio R3 (NCO / H)]

[0234] From the perspective of more excellent effects of the present invention, the ratio R3 (NCO / H) of the number of isocyanate groups of the polyisocyanate component (A) to the total number of active hydrogens of the active hydrogen compound (B) and the water is preferably 1.0 to 1.8.

[0235] (Additive)

[0236] The adhesive composition of the present invention can further contain additives as needed within the range not impairing the object of the present invention. As additives, for example, fillers such as carbon black and calcium carbonate; plasticizers such as diisononyl phthalate; catalysts such as metal catalysts and amine catalysts; compound (E) having a skeleton derived from terpenes, antioxidants, anti-aging agents, and thixotropy imparting agents can be cited. The types and contents of the additives can be appropriately selected.

[0237] Each of the above additives can be added to either one or both of the main agent and the curing agent.

[0238] · Content of filler

[0239] When the adhesive composition of the present invention further contains a filler, the content of the filler is preferably 20 to 80% by mass based on the total amount of the adhesive composition of the present invention.

[0240] · Content of plasticizer

[0241] When the adhesive composition of the present invention further contains a plasticizer, the content of the plasticizer is preferably 2 to 50% by mass based on the total amount of the adhesive composition of the present invention.

[0242] · Compound (E) having a skeleton derived from terpene

[0243] From the viewpoint of more excellent effects of the present invention, the main agent and / or curing agent of the adhesive composition of the present invention preferably further contains a compound (E) having a skeleton derived from terpene.

[0244] Examples of the compound (E) having a skeleton derived from terpene include compounds having a skeleton derived from monoterpene. Specifically, examples include an adduct of camphene and phenol.

[0245] Examples of the adduct of camphene and phenol include an adduct containing at least one compound selected from the group consisting of compound 1 represented by the following formula (Z1-1), compound 2 represented by formula (Z1-2), compound 3 represented by formula (Z2-1), compound 4 represented by formula (Z2-2), and compound 5 represented by formula (Z3-1).

[0246]

[0247]

[0248] When the adhesive composition of the present invention further contains a compound (E) having a skeleton derived from terpene, from the viewpoint of more excellent effects of the present invention, the content of (E) is preferably 0.2 to 10% by mass based on the total amount of the adhesive composition of the present invention.

[0249] · Metal catalyst

[0250] The metal catalyst is not particularly limited as long as it is a metal-containing compound capable of activating the reaction of isocyanate groups. Examples of the metal catalyst include bismuth catalysts and tin catalysts. Specifically, examples include bismuth catalysts such as bismuth trioctoate and tetravalent tin catalysts such as dioctyltin(IV) dilaurate.

[0251] When the adhesive composition of the present invention further contains a metal catalyst, the content of the metal catalyst is preferably 0.001 to 0.1% by mass based on the total amount of the adhesive composition of the present invention.

[0252] · Amine catalysts

[0253] The amine catalysts are not particularly limited as long as they are compounds having an amino group, an imino group, or a tertiary amino group that can activate the reaction of isocyanate groups. Examples of the amine catalysts include catalysts having a tertiary amino group. Specifically, examples include monomorpholine compounds such as dimethylaminoethyl morpholine, dimorpholine compounds such as dimorpholinodiethyl ether, chain ether compounds such as bis(dimethylaminoethyl) ether, and 1,4-diazabicyclo[2,2,2]octane.

[0254] When the adhesive composition of the present invention further contains an amine catalyst, the content of the amine catalyst is preferably 0.1 to 2.0% by mass based on the total amount of the adhesive composition of the present invention.

[0255] [Manufacturing method]

[0256] For the adhesive composition of the present invention, its manufacturing method is not particularly limited. For example, the main agent can be prepared by fully mixing a polyisocyanate component (A), an aliphatic diisocyanate derivative (C), a silane coupling agent (F), a filler, a metal catalyst, an amine catalyst, a compound (E) having a skeleton derived from terpenes, etc. in a nitrogen atmosphere.

[0257] In addition, the curing agent can be prepared by fully mixing water, the compound represented by formula (4), other active hydrogen-containing compounds (B), compound (D), a filler, a metal catalyst, an amine catalyst, a compound (E) having a skeleton derived from terpenes, etc.

[0258] (Usage method)

[0259] When using the adhesive composition of the present invention, the main agent and the curing agent can be mixed in the above-mentioned mixing amounts, and the resulting mixture can be used as the adhesive composition of the present invention.

[0260] The adhesive composition of the present invention can be cured, for example, under the conditions of -20 to +50 °C.

[0261] In the present invention, the "urethane-based adhesive composition" refers to a cured product obtained from the adhesive composition of the present invention, which forms a urethane-based polymer in a broad sense, that is, a compound of a polymer class (urethane-based) derived from isocyanate groups.

[0262] The composition of the present invention can be used as an adhesive.

[0263] The adherend (substrate) to which the adhesive composition of the present invention can be applied is not particularly limited. For example, metals (including coated plates, electrodeposited steel sheets), plastics, rubbers, and glasses can be mentioned.

[0264] For the adherend, a primer can be used as needed. The primer is not particularly limited. For example, a composition containing a compound having an isocyanate group and / or a hydrolyzable silyl group such as an alkoxysilyl group can be mentioned.

[0265] The adhesive composition of the present invention can be used, for example, as an adhesive for bonding a vehicle body and a window glass; an adhesive for bonding components such as rocket pins and hinges to a window glass.

[0266] Examples

[0267] Hereinafter, the present invention will be specifically described by listing examples. However, the present invention is not limited to these examples. In the examples, "%" means "mass%" unless otherwise specified.

[0268] <Preparation of Polyisocyanate Component (A)>

[0269] 1. Polyisocyanate Component (A1)

[0270] A polyisocyanate component (A1) containing a urethane prepolymer (A-3-1) was prepared by reacting a mixture containing the following components at 80 °C for 5 hours. In the following, F represents the number of functional groups, Mw represents the weight average molecular weight, and OHV represents the hydroxyl value (unit: mgKOH / g).

[0271] (Details of Each Component, Blending Amount, and Obtained Polyisocyanate Component (A1))

[0272] · Active Hydrogen-Containing Compound (A-1)

[0273] ·· Sannix PL-2100 (polyoxyethylene polyoxypropylene glycol, F = 2, Mw = 2400, OHV: 44, manufactured by Sanyo Chemical Industries, Ltd.) 198 parts by mass

[0274] ··· Excenol 1020 (polyoxypropylene polyol, F = 2, Mw = 1000, OHV: 112, manufactured by AGC Inc.) 71 parts by mass

[0275] ·· Excenol 837 (ethylene oxide-added polyoxypropylene polyol, F = 3, Mw = 6000, OHV: 28, manufactured by AGC Inc., the same below) 443 parts by mass

[0276] · Isocyanate Compound (A-2)

[0277] ··MDI (Millionate MT) (NCO bifunctional, manufactured by Tosoh Corporation. The same applies hereinafter) 109 parts by mass

[0278] · Total: 821 parts by mass

[0279] · Ratio R1 (NCO / H) = 1.68

[0280] · NCO% of the polyisocyanate component (A1): 1.80%

[0281] · Residual MDI monomer in the polyisocyanate component (A1): 2%

[0282] 2. Polyisocyanate component (A2)

[0283] React a mixture containing the following components at 80 °C for 5 hours to prepare a polyisocyanate component (A2) containing a urethane prepolymer (A-3-2). F represents the functionality number.

[0284] (Details of each component, compounding amount, and the obtained polyisocyanate component (A2))

[0285] · Active hydrogen-containing compound (A-1)

[0286] ·· Excenol 2020 (F = 2, Mw = 2000, OHV: 56, manufactured by AGC Inc.) 230 parts by mass

[0287] ·· Excenol 837 (the same as above) 690 parts by mass

[0288] · Isocyanate compound (A-2)

[0289] ·· MDI (the same as above) 574 parts by mass

[0290] · Total: 1494 parts by mass

[0291] · Ratio R1 (NCO / H) = 8.00

[0292] · NCO% of the polyisocyanate component (A2): 11.73%

[0293] · Residual MDI monomer in the polyisocyanate component (A2): 29%

[0294] <Preparation of silane coupling agent (F-1-1)>

[0295] React a mixture containing the following components at 40 °C for 8 hours to prepare a silane coupling agent (F-1-1) having an alkoxysilyl group and / or a silanol group, and an isocyanate group.

[0296] (Details of each component, compounding quantity, and the obtained silane coupling agent [F-1-1])

[0297] ·Biuret body of HDI (D-165N, manufactured by Mitsui Chemicals, Inc.) 100 g

[0298] ·3-(N-Phenyl)aminopropyltrimethoxysilane (Y-9669, manufactured by Momentive Performance Materials Inc. The same applies hereinafter) 47.2 g

[0299] ·NCO% of silane coupling agent (F-1-1): 10.55%

[0300] The silane coupling agent (F-1-1) has an average of 2 isocyanate groups and 1 trimethoxysilyl group per molecule.

[0301] <Preparation of silane coupling agent (F-1-2)>

[0302] React a mixture containing the following components at 40 °C for 8 hours to prepare a silane coupling agent (F-1-2) having an alkoxysilyl group and / or silanol group and an isocyanate group.

[0303] (Details of each component, compounding quantity, and the obtained silane coupling agent (F-1-2))

[0304] React the isocyanurate body of HDI (D-170N, manufactured by Mitsui Chemicals, Inc.) with 3-(N-phenyl)aminopropyltrimethoxysilane (the same as above) at a molar ratio of 3:1.

[0305] ·NCO% of silane coupling agent (F-1-2): 10.36%

[0306] The silane coupling agent (F-1-2) has an average of 2 isocyanate groups and 1 trimethoxysilyl group per molecule.

[0307] <Manufacture of adhesive composition>

[0308] ·Base agent

[0309] Use the components in the following Tables 1 to 3 according to the composition (parts by mass) shown in the tables to prepare base agents respectively.

[0310] Table 1

[0311]

[0312] Table 2

[0313]

[0314] Table 3

[0315]

[0316] The details of each component shown in the (main agent) column of Tables 1 to 3 are as follows.

[0317] <Polyisocyanate component (A)>

[0318] · Polyisocyanate component (A1): The polyisocyanate component (A1) prepared as described above

[0319] · Polyisocyanate component (A2): The polyisocyanate component (A2) prepared as described above

[0320] · Plasticizer: DINP. Diisononyl phthalate, manufactured by Jayplas Co., Ltd.

[0321] · Aliphatic diisocyanate derivative (C): A mixture of the isocyanurate of pentamethylene diisocyanate and the urethane formate of pentamethylene diisocyanate. Trade name D-376N, manufactured by Mitsui Chemicals, Inc. NCO% = 23.6%

[0322] (Silane coupling agent (F))

[0323] · Silane coupling agent (F-2-1): A silane coupling agent containing a monothioether (structure of the following formula (12)). Trade name X-12-1056ES, manufactured by Shin-Etsu Chemical Co., Ltd.

[0324]

[0325] · Silane coupling agent (F-1-1): The silane coupling agent (F-1-1) prepared as described above, NCO% = 10.55%

[0326] · Silane coupling agent (F-1-2): The silane coupling agent (F-1-2) prepared as described above, NCO% = 10.36%

[0327] · Compound (E1) having a skeleton derived from monoterpene: An adduct of camphene and phenol. The adduct contains at least one compound selected from the group consisting of compound 1 represented by the following formula (Z1-1), compound 2 represented by the formula (Z1-2), compound 3 represented by the formula (Z2-1), compound 4 represented by the formula (Z2-2), and compound 5 represented by the formula (Z3-1). Manufactured by Yasuhara Chemical Co., Ltd.

[0328]

[0329]

[0330] (Filler)

[0331] · Filler 1 (carbon): Trade name Nitron #200, manufactured by Shin Nippon Carbon Co., Ltd., HAF grade carbon black

[0332] · Filler 2 (calcium carbonate): Heavy calcium carbonate. Trade name Super S, manufactured by Maruo Calcium Co., Ltd.

[0333] (Metal catalysts)

[0334] · Metal catalyst 1: Bismuth trioctanoate. Trade name Neostann U-600, manufactured by Nitto Kasei Co., Ltd.

[0335] · Metal catalyst 2: DOTL. Dioctyltin(IV) dilaurate. Neostann U-810 manufactured by Nitto Kasei Co., Ltd.

[0336] (Amine catalysts)

[0337] · Amine catalyst 1: Dimethylaminoethyl morpholine. Trade name X-DM, manufactured by Evonik

[0338] · Amine catalyst 2: Bis(dimethylaminoethyl) ether. Trade name BL-19, manufactured by Evonik

[0339] · Amine catalyst 3: DMDEE. Dimorpholinodiethyl ether (manufactured by San-Apro). The following structure

[0340]

[0341] · Curing agent

[0342] Use each component in the (curing agent) column of the following Table 1 to Table 3 in the composition (parts by mass) shown in the table to prepare a curing agent respectively.

[0343] Table 4

[0344]

[0345] Table 5

[0346]

[0347] Table 6

[0348]

[0349] Details of each component shown in the (curing agent) column of Table 1 to Table 3 are as follows.

[0350] (Compound (B) containing active hydrogen)

[0351] · Compound (B1) containing active hydrogen: Polyether polyol. Trade name: Excenol 837, manufactured by AGC Inc. Active hydrogen concentration: 0.50 mol / kg, hydroxyl value: 28 mg KOH / g. F (F is the average number of hydroxyl groups per molecule of polyol) = 3. Weight-average molecular weight: 6000

[0352] · Compound (B2) containing active hydrogen: Polyether tetrol. Trade name: Excenol 450ED, manufactured by AGC Inc. Active hydrogen concentration: 8.02 mol / kg, hydroxyl value: 450 mg KOH / g. A compound represented by the following formula (4) having 4 hydroxyl groups in each molecule. Nitrogen-containing compound 1 corresponding to the compound represented by the formula (4). Weight-average molecular weight: 550. Liquid at room temperature (23 °C).

[0353]

[0354] In formula (4), R6 to R9 each independently represent a propylene group, and R 10 represents an ethylene group, and a to d each independently represent 1 to 10. At least one of a to d is 3 or more.

[0355] · Compound (B3) containing active hydrogen: N - polyoxyalkylene polyalkylene polyamine. Trade name: Adeka Polyether BM-34, manufactured by Adeka Corporation. Active hydrogen concentration: 14.74 mol / kg, hydroxyl value: 827 mg KOH / g. A compound represented by the following formula (5) having 4 hydroxyl groups in each molecule. Nitrogen-containing compound 2 corresponding to the compound represented by the formula (4). Weight-average molecular weight: 280. Liquid at room temperature (23 °C).

[0356]

[0357] In formula (5), R 56 ~R 59 each independently represent a propylene group and / or an ethylene group, and R 50 represents an ethylene group, and a to d each independently represent 1 to 2. At least one of a to d is 2.

[0358] · Compound (B4) containing active hydrogen: Polyol having a polybutadiene backbone. Trade name: Poly bd R15HT, manufactured by Idemitsu Kosan Co., Ltd. Active hydrogen concentration: 1.83 mol / kg, hydroxyl value: 103 mg KOH / g. F = 2

[0359] · Compound (B5) containing active hydrogen: Polyol having a polybutadiene backbone. Trade name: Poly bd R45HT, manufactured by Idemitsu Kosan Co., Ltd. Active hydrogen concentration: 0.83 mol / kg, hydroxyl value: 47 mg KOH / g. F = 2

[0360] · Compound containing active hydrogen (B6): Polyether polyol. Trade name: Excenol 1020, manufactured by AGC Inc. Active hydrogen concentration: 2.00 mol / kg, hydroxyl value: 112 mgKOH / g. F = 2

[0361] · Compound containing active hydrogen (B7): Polyester polyol formed from 2,4 - diethyl - 1,5 - pentanediol and phthalic anhydride. Trade name: HS 2N - 226P, manufactured by Toyokoku Oil Co., Ltd. Active hydrogen concentration: 0.94 mol / kg, hydroxyl value: 53 mgKOH / g. F = 2

[0362] · Compound containing active hydrogen (B8): Amine having polypropylene glycol (PPG) as the backbone and having 2 amino groups (4 active hydrogens). Corresponds to nitrogen - containing compound 3 in the compound represented by the formula (4). Trade name: JEFFAMINE D - 400, manufactured by Santech Chemical Co., Ltd. Active hydrogen concentration: 9.30 mol / kg

[0363] · Comparative compound containing active hydrogen: Glycosyl polyol. Trade name: Excenol 450SN, manufactured by AGC Inc. Active hydrogen concentration: 8.0 mol / kg, hydroxyl value: 450 mgKOH / g. F ≥ 4

[0364] · Water: Purified water

[0365] · Compound having a backbone derived from monoterpene (E2): The same as (E1) contained in the main agent

[0366] [Compound containing alkoxysilyl and / or silanol group (D)]

[0367] · Compound (D - 1 - 1): Oligomer containing an amino - silane coupling agent. Trade name: KBP90, manufactured by Shin - Etsu Chemical Co., Ltd. Solids concentration: 30%. Solvent: Water

[0368] · Compound (D - 1 - 2): Oligomer containing an amino - silane coupling agent. Trade name: X - 12 - 972F, manufactured by Shin - Etsu Chemical Co., Ltd. Solids concentration: 15%, solvent: Alcohol

[0369] · Compound (D - 1 - 3): N - 2 - (aminoethyl) - 3 - aminopropyltrimethoxysilane. Trade name: KBM - 603, manufactured by Shin - Etsu Chemical Co., Ltd.

[0370] · Filler 3 (calcium carbonate): Calcium carbonate. Trade name: Calfine 200, manufactured by Maruo Calcium Co., Ltd

[0371] · Amine catalyst 4: TEDA. 1,4 - diazabicyclo[2,2,2]octane

[0372] · Metal catalyst 4: Dibutyltin bis(acetylacetonate). Trade name U-220H, manufactured by Nitto Kasei Co., Ltd.

[0373] · Metal catalyst 2: The same as the metal catalyst 2 used in the main agent

[0374] <Mixing of main agent and curing agent>

[0375] Mix the main agent and the curing agent in the mass ratios shown in the (Mixing of main agent and curing agent) column of Tables 1 to 3 below to obtain each mixture. At the same time, record the ratio R2 (NCO / H) and the ratio R3 (NCO / H) at this time.

[0376] Table 7

[0377]

[0378] Table 8

[0379]

[0380] Table 9

[0381]

[0382] <Evaluation>

[0383] Use each mixture manufactured as described above for the following evaluation. Show the results in the (Evaluation results) column of Tables 1 to 3. The evaluation method is as described later.

[0384] Table 10

[0385]

[0386] Table 11

[0387]

[0388] Table 12

[0389]

[0390] <Evaluation method>

[0391] (Production of test pieces)

[0392] · Surface treatment of resin substrate

[0393] ·· Plasma treatment

[0394] Using FG3001 (Generator) and RD1004 (Nozzle-Jet) (manufactured by Plasmatreat), the resin substrate [talc-PP (TSOP5)] was surface-treated by plasma treatment so that the wetting index became 52 mN / m.

[0395] ·· Primer treatment

[0396] For each resin substrate that had been subjected to plasma treatment as described above, a resin substrate that had been subjected to primer treatment using a primer (trade name RC-50E, manufactured by Yokohama Rubber Co., Ltd.) and a resin substrate that had not been subjected to primer treatment were prepared respectively.

[0397] · Preparation of test pieces

[0398] On the resin substrate that had been surface-treated as described above, each mixture of the two-component adhesive composition manufactured as described above was coated, and a cationic electrodeposited steel sheet (ED sheet) was stacked thereon. The resin substrate and the cationic electrodeposited steel sheet were pressed together so that the adhesive layer became 25 mm in length × 10 mm in width × 3 mm in thickness to form a laminate.

[0399] · Curing conditions

[0400] Curing condition 1: The laminate was allowed to cure by being placed at 20°C and a relative humidity of 65% for 30 minutes to obtain an initial sample.

[0401] Curing condition 2: The laminate was allowed to cure by being placed at 20°C and a relative humidity of 65% for 24 hours to obtain a post-cured sample (after 24 hours).

[0402] Curing condition 3: The laminate was allowed to cure by being placed at 20°C and a relative humidity of 65% for 1 week to obtain a sample after 1 week of curing.

[0403] · Creep test

[0404] Using each of the initial or post-cured samples obtained as described above, a creep test was conducted.

[0405] Figure 1 is a side view schematic diagram of the creep test conducted in the examples of the present invention.

[0406] Figure 1 In, in the creep test, sample 1 (the initial sample under curing condition 1, the post-cured sample under curing condition 2) was used vertically. In sample 1, the resin substrate 2 and the cationic electrodeposited steel sheet 4 were bonded by the adhesive layer 3. The thickness t of the adhesive layer 3 (the distance between the resin substrate 2 and the cationic electrodeposited steel sheet 4) was 3 mm. The bonding area between the resin substrate 2 and the adhesive layer 3 was the length of the adhesive layer 3 (Figure 1 (corresponding to the depth of the adhesive layer 3) 25 mm × the width L1 of the adhesive layer 3 is 10 mm. The bonding area between the cationic electrodeposited steel sheet 4 and the adhesive layer 3 is also the same.

[0407] After curing the laminate under the above-mentioned curing (hardening) conditions in the preparation of the test piece, immediately stand the sample 1 vertically as Figure 1 shown, apply a heavy object 5 to the cationic electrodeposited steel sheet 4, and conduct a creep test under the following conditions to measure the holding time from when the heavy object 5 is applied to the cationic electrodeposited steel sheet 4 until the cationic electrodeposited steel sheet 4 falls and the displacement amount (the offset of the upper end position of the cationic electrodeposited steel sheet 4 before and after applying the load).

[0408] Figure 2 is a side view schematic diagram of a part of the sample 1 after applying the load.

[0409] Figure 2 In, position 6 represents the position of the upper end of the cationic electrodeposited steel sheet 4 before applying the load. Position 7 represents the position of the upper end of the cationic electrodeposited steel sheet 4 after applying the load. The displacement amount L2 refers to the distance between position 6 and position 7.

[0410] · Conditions of the creep test

[0411] In this experiment, creep tests were conducted in the following 5 modes.

[0412] (1) Creep test 1: Under the conditions of a test temperature of 20 °C and a relative humidity of 65%, apply a heavy object (0.77 Kg. The same below) that causes a creep stress of 30 kPa to the initial sample with a primer (loading time: maximum 1 hour). (Curing conditions: 1)

[0413] (2) Creep test 2: Under the condition of a test temperature of 80 °C, apply a heavy object (0.13 Kg. The same below) that causes a creep stress of 5 kPa to the cured sample with a primer (loading time: maximum 48 hours).

[0414] (3) Creep test 3: Under the conditions of a test temperature of 20 °C and a relative humidity of 65%, apply a heavy object (0.77 Kg. The same below) that causes a creep stress of 30 kPa to the initial sample without a primer (loading time: maximum 1 hour).

[0415] (4) Creep test 4: Under the condition of a test temperature of 80 °C, apply a heavy object that causes a creep stress of 5 kPa to the cured sample without a primer (loading time: maximum 48 hours).

[0416] (5) Creep test 5: In creep test 3, instead of the weight of the heavy object, during the 1 hour period after the start of the creep test, evaluate the weight of the heavy object when a part of the sample falls off the sample along with the heavy object.

[0417] (Evaluation criteria for each creep test)

[0418] In the present invention, the adhesiveness is evaluated by comprehensively considering the evaluation results of creep tests 1 to 5 and the adhesive force. The evaluation criteria for each creep test are as described below.

[0419] · Creep test 1 (with primer, initial), creep test 3 (without primer, initial)

[0420] ◎: When the holding time (the time when the heavy object does not fall. The same applies hereinafter) is 1 hour or more and the displacement is less than 1 mm

[0421] Since the application load time for initial creep is 1 hour, a holding time of 1 hour or more means that the heavy object remains suspended on the sample for 1 hour or more from the start of the creep test.

[0422] ○: When the holding time is 1 hour or more and the displacement is 1 mm or more

[0423] △: When the holding time is more than 20 minutes and less than 1 hour (during the period of more than 20 minutes and less than 1 hour, the heavy object falls off the sample along with a part of the sample. Regarding the fall, the same applies hereinafter)

[0424] ×: When the holding time is less than 20 minutes

[0425] · Creep test 2 (with primer, after curing), creep test 4 (without primer, after curing)

[0426] ◎: When the holding time is 48 hours or more

[0427] Since the application load time for creep after curing is 48 hours, a holding time of 48 hours or more means that the heavy object remains suspended on the sample for 48 hours or more from the start of the creep test.

[0428] ○: When the holding time is more than 24 hours and less than 48 hours (during the period of more than 24 hours and less than 48 hours, the heavy object falls off the sample along with a part of the sample. Regarding the fall, the same applies hereinafter)

[0429] △: When the holding time is more than 12 hours and less than 24 hours

[0430] ×: When the holding time is less than 12 hours

[0431] · Creep test 5

[0432] ◎: In the creep test 3 (without primer, initial), during the period of 1 hour after applying the load, when using a weight of 2.5 kg, the weight remained suspended on the sample.

[0433] ○: When using a weight of 2.5 kg, part of the weight fell off with the sample, but when using a weight of 1.0 kg, the weight remained suspended on the sample.

[0434] △: When using a weight of 1.0 kg, part of the weight fell off with the sample, but when using a weight of 0.5 kg, the weight remained suspended on the sample.

[0435] ×: When using a weight of 0.5 kg, part of the weight fell off with the sample, but when using a weight of 0.1 kg, the weight remained suspended on the sample.

[0436] ××: When using a weight of 0.1 kg, part of the weight fell off with the sample.

[0437] · Shear test

[0438] For the samples cured for 1 week under the curing condition 3, a shear test (at 23°C, tensile speed 5.1 cm / min) was carried out in accordance with JIS K6850 - 1999 to measure the shear strength. The results of the shear strength are shown in the "Adhesive force" column of Tables 1 - 3 (evaluation results).

[0439] · Evaluation criteria for adhesive force

[0440] The evaluation criteria for adhesive force based on the shear strength are as follows.

[0441] When the shear strength is 3.0 MPa or more, the adhesive force is evaluated as high.

[0442] On the other hand, when the shear strength is less than 3.0 MPa, the adhesive force is evaluated as low.

[0443] [Evaluation criteria for adhesiveness] (Creep tests 1 - 5 and comprehensive evaluation criteria for adhesiveness based on adhesive force)

[0444] In the present invention, when at least 3 of the evaluation results in the creep tests 1 - 4 are ○ or more (only 1 can be △ or ×), the evaluation result of the creep test 5 is × or more, and the shear strength is 3.0 MPa or more, the adhesiveness is evaluated as excellent.

[0445] In the above cases, when at least one of the evaluation results of creep tests 1 to 4 is ◎, when all of the evaluation results of creep tests 1 to 4 are ○ or higher, when the evaluation result of creep test 5 is △ or higher, or when the shear strength is greater than 3.0 MPa, it is evaluated that the adhesiveness is more excellent.

[0446] On the other hand, in the case where two or more of the evaluation results of creep tests 1 to 4 are △ or lower, in the case where the evaluation result of creep test 5 is ××, or in the case where the shear strength is less than 3.0 MPa, it is evaluated that the adhesiveness is poor.

[0447] From the results shown in Tables 1 to 3, compared with Example 1, Comparative Example 1 in which the curing agent does not contain water, the average active hydrogen concentration (BWH-c), and the ratio R3 in the mixing of the main agent and the curing agent deviate from the specified range has poor adhesiveness due to the poor results of creep tests 3, 4, 5 and the adhesive strength.

[0448] In Comparative Example 2 where the ratios R2 and R3 in the mixing of the main agent and the curing agent deviate from the specified range, the adhesiveness is poor due to the poor results of creep tests 1, 3 and 5.

[0449] In Comparative Example 9 where the curing agent does not contain the compound represented by formula (4), the adhesiveness is poor due to the poor results of creep tests 1, 3 and 5.

[0450] Compared with Example 6, in Comparative Example 3 where the curing agent does not contain the compound represented by formula (4) and instead contains a compound containing active hydrogen for comparison, the adhesiveness is poor due to the poor results of creep tests 3, 4 and the adhesive strength.

[0451] In Comparative Example 4 where the curing agent does not contain water, the adhesiveness is poor due to the poor results of creep test 5 and the adhesive strength.

[0452] In Comparative Example 10 where the curing agent does not contain the compound represented by formula (4), the adhesiveness is poor due to the poor results of creep tests 1, 3 and 5.

[0453] Compared with Example 12, in Comparative Example 5 where the curing agent does not contain water, the average active hydrogen concentration (BWH-c), and the ratio R3 deviates from the specified range, the adhesiveness is poor due to the poor results of creep tests 1 to 5 and the adhesive strength.

[0454] In Comparative Example 6 where the curing agent does not contain water, the average active hydrogen concentration (BWH-c), and the ratio R3 deviates from the specified range, the adhesiveness is poor due to the poor results of creep tests 3 to 5 and the adhesive strength.

[0455] In Comparative Example 7 where the curing agent does not contain water and the ratio R3 deviates from the specified range, the adhesiveness is poor due to the poor results of creep test 5 and the adhesive strength.

[0456] In Comparative Example 8 where the curing agent does not contain the compound represented by the formula (4) but instead contains a compound having an active hydrogen for comparison, the adhesiveness is poor due to the difference in the results of Creep Tests 3 and 4 and the adhesive strength.

[0457] In Comparative Example 11 where, in addition to the conditions of Comparative Example 8, the water content is less than that of Comparative Example 8 and the ratio R3 deviates from the specified range, the adhesiveness is poor due to the difference in the results of Creep Tests 3 to 5 and the adhesive strength. The results of Creep Tests 3 and 5 and the adhesion of Comparative Example 11 are worse than those of Comparative Example 8.

[0458] In contrast, the two-component urethane adhesive composition of the present invention has excellent adhesiveness.

[0459] Symbol Explanation

[0460] 1 Creep Test

[0461] 2 Resin Substrate

[0462] 3 Adhesive Layer

[0463] 4 Cathodic Electrodeposition Steel Sheet

[0464] 5 Heavy Object

[0465] 6, 7 Positions

[0466] L1 Width

[0467] L2 Displacement

Claims

1. A two - component urethane - type adhesive composition, which comprises: a main agent containing a polyisocyanate component (A), and a curing agent containing water and an active - hydrogen - containing compound (B) having multiple active hydrogens; the active - hydrogen - containing compound (B) contains a nitrogen - containing compound represented by the following formula (4); In the main agent, the polyisocyanate component (A) contains a urethane prepolymer (A - 3) formed from an active - hydrogen - containing compound (A - 1) having multiple active hydrogens and a polyisocyanate compound (A - 2) having two or more functional groups. The ratio R1 (NCO / H) of the number of isocyanate groups of the isocyanate compound (A - 2) to the number of active hydrogens (A1 - H) of the active - hydrogen - containing compound (A - 1) is 1.5 to 10; In the curing agent, the average active - hydrogen concentration (BH - c) of the active - hydrogen - containing compound (B) is more than 0.96 mol / kg and less than 1.75 mol / kg, and the average active - hydrogen concentration (BWH - c) of the active - hydrogen - containing compound (B) and the water is 2.00 to 8.00 mol / kg; The mixing amounts of the main agent and the curing agent satisfy: the ratio R2 (NCO / H) of the number of isocyanate groups of the polyisocyanate component (A) to the number of active hydrogens (B - H) of the active - hydrogen - containing compound (B) is 1 to 5, and the ratio R3 (NCO / H) of the number of isocyanate groups of the polyisocyanate component (A) to the total number of active hydrogens of the active - hydrogen - containing compound (B) and the water is 0.5 to 1.8; Among them, the active - hydrogen - containing compound (B) does not contain silicon, In formula (4), R6 to R9 each independently represent an alkylene group, and R 10 represents an alkylene group or a polyoxyalkylene group, and a to d each independently represent 0 to 10. the curing agent further contains a compound (D) having an alkoxysilyl group and / or a silanol group, the content of the compound (D) contained in the curing agent is 0.002 to 5% by mass of the total amount of the composition, the compound (D) contains an amino - silane coupling agent having multiple amino groups, the amino - silane coupling agent having multiple amino groups is an oligomer containing an amino - silane coupling agent.

2. The two - component urethane - type adhesive composition according to claim 1, wherein the urethane prepolymer (A - 3) contains an unreacted polyisocyanate compound (A - 2') having two or more functional groups.

3. The two - component urethane - type adhesive composition according to claim 1 or 2, wherein the main agent further contains a silane coupling agent (F), the silane coupling agent (F) contains a silane coupling agent (F - 1) and / or a silane coupling agent containing a monothioether (F - 2). The silane coupling agent (F - 1) is a silane coupling agent obtained by reacting a modified product of an aliphatic polyisocyanate with an amino - silane coupling agent and having a skeleton from the modified product and an isocyanate group.

4. The two - component urethane - type adhesive composition according to claim 3, wherein the silane coupling agent (F) contains the silane coupling agent (F - 1).

5. The two - component urethane - type adhesive composition according to claim 3, wherein the modified product of the aliphatic polyisocyanate contains a biuret body of HDI.

6. The two-component urethane-based adhesive composition according to claim 3, wherein the aminosilane coupling agent has an NH2 group or an NH group, and in the aminosilane coupling agent, the number of NH2 groups is 0 or 1 per molecule of the aminosilane coupling agent, and the total of the NH2 group and the NH group is 1 or more.

7. The two-component urethane adhesive composition according to claim 1 or 2, wherein the main agent further contains an aliphatic diisocyanate derivative (C), and the aliphatic diisocyanate derivative (C) is at least one selected from the group consisting of isocyanurate bodies, biuret bodies, and urethane bodies of aliphatic diisocyanates. Among them, The aliphatic diisocyanate derivative (C) does not contain silicon; The content of the aliphatic diisocyanate derivative (C) is 0.1 to 10% by mass of the total amount of the main agent.

8. The two-component urethane-based adhesive composition according to claim 1 or 2, wherein the curing agent contains at least one selected from the group consisting of the following compounds: A nitrogen-containing compound 1, which is represented by the formula (4), wherein R6 to R9 each independently represent a propylene group and / or an ethylene group, and R 10 represents an alkylene group having 2 to 10 carbon atoms, a to d each independently represent 1 to 10, and at least one of a to d is 3 or more. The nitrogen-containing compound 2 represented by the following formula (5), and Nitrogen-containing compound 3, represented by the formula (4), wherein R6 to R9 each independently represent an alkylene group, R 10 represents a polyoxyalkylene group, and a to d each independently represent 0, In formula (5), R 56 ~R 59 each independently represents a propylene group and / or an ethylene group, and R 50 represents an alkylene group having 2 to 10 carbon atoms, a to d each independently represent 1 to 2, and at least one of a to d is 2.

9. The two-component urethane-based adhesive composition according to claim 8, wherein the curing agent contains the nitrogen-containing compound 1, and the nitrogen-containing compound 2 and / or the nitrogen-containing compound 3.

10. The two-component urethane-based adhesive composition according to claim 1, wherein the aminosilane coupling agent having a plurality of amino groups has an organic chain or a siloxane skeleton as a skeleton.

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