Urethane-based adhesive composition

Abstract

An object of the present application is to provide a urethane-based adhesive composition which is excellent in bonding durability to an olefin resin. The present application is a urethane-based adhesive composition containing: a urethane prepolymer having an isocyanate group; an isocyanurate compound of 1,5-pentanediisocyanate and / or 1,6-hexanediisocyanate; and a secondary amino silane compound.

Description

TECHNICAL FIELD

[0001] The present application relates to a urethane-based adhesive composition. BACKGROUND

[0002] In recent years, from the viewpoint of weight reduction of automobiles, the material of a vehicle body (a vehicle body) is replaced from a steel sheet to a resin material (for example, a resin material containing at least an olefin-based resin).

[0003] On the other hand, as an adhesive composition which can be applied to an adherend formed of a material such as an olefin resin, for example, a two-component curing type urethane adhesive composition having a main agent containing a urethane prepolymer (A), a polyisocyanate containing an isocyanurate group (B), and an isocyanate silane (C), and a curing agent containing a compound (D) having two or more active hydrogen groups in one molecule, and an aromatic compound (E) represented by a specific formula is proposed (Patent Document 1).

[0004] Further, as an adhesive composition which can be applied to a substrate containing an olefin resin and the like, for example, a urethane-based adhesive composition containing a urethane prepolymer having an isocyanate group, an isocyanurate compound having an isocyanurate ring, and a terpene compound having an active hydrogen is proposed (Patent Document 2).

[0005] PRIOR ART DOCUMENTS

[0006] PATENT DOCUMENTS

[0007] Patent Document 1: Japanese Patent Application Publication No. 2017-218539

[0008] Patent Document 2: International Publication No. 2017 / 022666 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] Further, from the viewpoint of safety and the like of automobiles, the requirement for adhesion of resins is increasingly improved.

[0011] In this case, the present inventors and the like prepared a urethane-based adhesive composition containing a silane coupling agent with reference to Patent Documents 1 and 2 and evaluated it, and as a result, it was clarified that in the case where such a composition is applied to a substrate containing at least an olefin resin which has not been subjected to a primer treatment, sometimes the durability of adhesion of the adhesive composition does not necessarily satisfy the level required recently.

[0012] Therefore, an object of the present application is to provide a urethane-based adhesive composition which is excellent in adhesion durability to an olefin resin.

[0013] MEANS FOR SOLVING THE PROBLEMS

[0014] The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that the desired effects can be obtained by using a specific amino silane compound for a urethane-based adhesive composition, thereby completing the present application.

[0015] The present application is based on the above understanding, and specifically, the above problems are solved by the following configuration.

[0016] [1] A urethane-based adhesive composition, comprising:

[0017] a urethane prepolymer having an isocyanate group;

[0018] an isocyanurate compound which is an isocyanurate compound of 1,5-pentamethylene diisocyanate and / or 1,6-hexamethylene diisocyanate; and

[0019] a secondary amino silane compound.

[0020] [2] The urethane-based adhesive composition according to [1], wherein the secondary amino silane compound is a bis type.

[0021] [3] The urethane-based adhesive composition according to [1] or [2], wherein the secondary amino silane compound is a compound represented by the following formula (A).

[0022]

[0023] In formula (A), R 13 , R 23 each independently represents a divalent linking group, R 11 , R 12 , R 21 , R 22 each independently represents a monovalent hydrocarbon group, and m1, m2 each independently is 1 to 3.

[0024] [4] The urethane-based adhesive composition according to [3], wherein in formula (A), R 11 , R 21 each independently represents an aliphatic hydrocarbon group.

[0025] [5] The urethane-based adhesive composition according to [3] or [4], wherein in formula (A), R 13 , R 23 each independently represents a divalent hydrocarbon group having 2 to 10 carbon atoms.

[0026] [6] The urethane-based adhesive composition according to any one of [1] to [5], further comprising a terpene compound.

[0027] [7] The urethane-based adhesive composition according to [6], wherein the terpene compound contains at least an adduct of a compound represented by the following formula (X) and a phenol compound.

[0028]

[0029] In the formula (X), R 11 , R 12 each independently represents a hydrocarbon group.

[0030] [8] The urethane-based adhesive composition according to any one of [1] to [7], further containing an isocyanate silane compound.

[0031] [9] The urethane-based adhesive composition according to [8], wherein the isocyanate silane compound is a compound represented by the following formula (I).

[0032]

[0033] In the formula (I), R 1 , R 2 each independently represents a monovalent hydrocarbon group, R 3 represents a divalent linking group, and m is 1 to 3.

[0034]

[10] The urethane-based adhesive composition according to [9], wherein, in the formula (I), R 3 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and m is 2 to 3.

[0035]

[11] The urethane-based adhesive composition according to any one of [1] to

[10] , wherein the content of the secondary amino silane compound is less than 0.5 mass% relative to the total amount of the urethane-based adhesive composition.

[0036]

[12] The urethane-based adhesive composition according to any one of [1] to

[11] , wherein the isocyanurate compound is an isocyanurate compound of 1,5-pentamethylene diisocyanate.

[0037]

[13] The urethane-based adhesive composition according to any one of [1] to

[12] , which is used for bonding a substrate containing an olefin resin.

[0038] Effects of the Invention

[0039] The urethane-based adhesive composition of the present application is excellent in bonding durability to an olefin resin. DETAILED DESCRIPTION

[0040] The present application will be described in detail below.

[0041] Note that in the present specification, (meth)acrylate represents acrylate or methacrylate, (meth)acryloyl represents acryloyl or methacryloyl, and (meth)acrylic acid represents acrylic acid or methacrylic acid.

[0042] Further, in the present specification, a numerical range represented by "to" means a range including the lower limit value and the upper limit value recited before and after "to".

[0043] In the present specification, each component can be used individually or in combination of two or more kinds of substances equivalent to the component, as long as there is no particular indication. In the case where the component includes two or more kinds of substances, the content of the component means the total content of the two or more kinds of substances.

[0044] In the present application, the production method of each component is not particularly limited, as long as there is no particular indication. For example, a method publicly known heretofore can be cited.

[0045] In the present specification, sometimes the more excellent effect of the present application is referred to as "the more excellent effect of the present application" on the adhesion durability to an olefin resin. Further, sometimes the "adhesion durability to an olefin resin" is simply referred to as "adhesion durability".

[0046] [urethane-based adhesive composition]

[0047] The urethane-based adhesive composition of the present application (adhesive composition of the present application) contains:

[0048] a urethane prepolymer having an isocyanate group;

[0049] an isocyanurate compound which is an isocyanurate compound of 1,5-pentamethylene diisocyanate and / or 1,6-hexamethylene diisocyanate; and

[0050] a secondary amino silane compound.

[0051] In the present specification, sometimes the above-mentioned isocyanurate compound is referred to as "specific isocyanurate compound", and the above-mentioned secondary amino silane compound is referred to as "specific amino silane compound".

[0052] The adhesive composition of the present application can be considered to achieve such an effect (for example, durability of adhesion to water or heat) that the adhesion durability is excellent, since it adopts such a configuration.

[0053] The reason is that the specific amino silane compound can react with the urethane prepolymer and a part of the specific isocyanurate compound by having a secondary amino group, and thus the urethane prepolymer and the specific isocyanurate compound can be cured by two curing systems based on the reaction of the isocyanate group and the reaction of the hydrolyzable silyl group.

[0054] Further, the specific amino silane compound has a secondary amino group, and thus has lower polarity than an amino silane compound having a primary amino group, and thus it can be considered that the adhesive composition of the present application containing the specific amino silane compound is easily wetted to a substrate containing at least an olefin resin having low polarity.

[0055] Based on the above reasons, the present inventors et al. have speculated that the adhesive composition of the present application is excellent in durability of adhesion to a substrate when applied to a substrate containing at least an olefin resin, even if the above substrate is not subjected to primer treatment.

[0056] Note that the mechanism involved in the present application is not limited to the above. As long as it is within the scope of the present application, the mechanism can be other than the above.

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

[0058] [urethane-based adhesive composition]

[0059] <urethane prepolymer>

[0060] The urethane prepolymer contained in the adhesive composition of the present application is a compound having an isocyanate group.

[0061] The urethane prepolymer can be exemplified by one having a plurality of isocyanate groups (preferably 2 isocyanate groups) as one of the preferable modes.

[0062] The urethane prepolymer preferably has an isocyanate group at the molecular terminal.

[0063] As the urethane prepolymer, a substance conventionally known can be used. For example, a reaction product obtained by reacting a polyisocyanate compound with a compound having 2 or more active hydrogen-containing groups in 1 molecule (hereinafter, referred to as "active hydrogen compound" for short) in a manner that isocyanate groups are in excess to active hydrogen-containing groups, and the like can be used.

[0064] In the present application, the active hydrogen-containing group refers to a group containing active hydrogen. As the active hydrogen-containing group, for example, a hydroxyl group, an amino group, an imino group can be exemplified.

[0065] (polyisocyanate compound)

[0066] The polyisocyanate compound used at the time of production of the urethane prepolymer is not particularly limited as long as it is a compound having 2 or more isocyanate groups in the molecule.

[0067] As the polyisocyanate compound, for example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), dimethyl diphenyl diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), aromatic polyisocyanate compounds such as triphenylmethane triisocyanate;

[0068] 1,6-hexane 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), aliphatic polyisocyanates (the above aliphatic is a concept including linear, branched, and alicyclic) such as the above;

[0069] their carbodiimide-modified polyisocyanates.

[0070] The polyisocyanate compound can be used alone or in combination with two or more.

[0071] Among them, from the reason that the curability is excellent, an aromatic polyisocyanate is preferred, and MDI is more preferred.

[0072] (active hydrogen compound)

[0073] The compound having two or more active hydrogen-containing groups in one molecule (active hydrogen compound) used at the time of production of the urethane prepolymer is not particularly limited. As the active hydrogen-containing group, for example, a hydroxyl (OH) group, an amino group, an imino group can be mentioned.

[0074] As the above active hydrogen compound, for example, a polyol compound having two or more hydroxyl (OH) groups in one molecule, a polyamine compound having two or more amino groups and / or imino groups in one molecule, and the like can be suitably mentioned, of which a polyol compound is preferred.

[0075] The above polyol compound is not particularly limited as long as it is a compound having two or more OH groups. As specific examples of the polyol compound, a polyether polyol; a polyester polyol; an acrylic polyol; a polybutadiene polyol, a hydrogenated polybutadiene polyol; a low molecular polyol; a mixed polyol thereof can be mentioned. Among them, a polyether polyol can be mentioned as one of the preferred modes.

[0076] The polyether polyol is not particularly limited as long as it is a compound having a polyether as a main chain and having 2 or more hydroxyl groups. The polyether is a group having 2 or more ether bonds, and as specific examples thereof, a group having 2 or more structural units -O-R a -O-R b may be given. Here, in the above structural unit, R a and R b each independently represent a hydrocarbon group. The hydrocarbon group is not particularly limited. For example, a linear alkylene group having 1 to 10 carbon atoms can be given.

[0077] As the polyether polyol, for example, a polyoxyethylene glycol (polyethylene glycol), a polyoxypropylene glycol (polypropylene glycol: PPG), a polyoxypropylene triol, a polyol of an ethylene oxide / propylene oxide copolymer, a polytetramethylene ether glycol (PTMEG), a polytetraethylene glycol, a sorbitol-based polyol, and the like can be given.

[0078] From the viewpoint that the compatibility with the polyisocyanate compound is excellent, the polyether polyol is preferably a polypropylene glycol or a polyoxypropylene triol.

[0079] From the viewpoint that the viscosity of the urethane prepolymer obtained by the reaction with the isocyanate compound has moderate flowability at ordinary temperature, the weight average molecular weight of the polyether polyol is preferably 500 to 20,000. In the present application, the above weight average molecular weight is a polystyrene conversion value obtained by a GPC method (solvent: tetrahydrofuran (THF)).

[0080] The active hydrogen compound can be used alone or in combination with 2 or more kinds, respectively.

[0081] From the viewpoint that the effects of the present application are more excellent and the curability is excellent, the urethane prepolymer is preferably a urethane prepolymer obtained by reacting a polyether polyol with an aromatic polyisocyanate compound.

[0082] The urethane prepolymer can be used alone or in combination with 2 or more kinds, respectively.

[0083] The method for producing the urethane prepolymer is not particularly limited. For example, the urethane prepolymer can be produced by mixing and reacting them in such a manner that the polyisocyanate compound is used in an amount of 1.5 to 2.5 moles per 1 mole of the active hydrogen-containing group (for example, a hydroxyl group) possessed by the active hydrogen compound.

[0084] The urethane prepolymer can be used alone or in combination with 2 or more kinds, respectively.

[0085] <Isocyanurate compound>

[0086] The adhesive composition of the present application contains an isocyanurate compound of 1,5-pentamethylene diisocyanate and / or 1,6-hexamethylene diisocyanate (specific isocyanurate compound). The specific isocyanurate compound has an isocyanurate ring.

[0087] The isocyanurate ring is represented by the following formula (B1).

[0088]

[0089] The diisocyanate compound constituting the specific isocyanurate compound can be any one of 1,5-pentamethylene diisocyanate (PDI) alone, 1,6-hexamethylene diisocyanate (HDI) alone, and a combination of 1,5-pentamethylene diisocyanate and 1,6-hexamethylene diisocyanate.

[0090] As the specific isocyanurate compound, for example, a compound represented by the following formula (C1-1) as an isocyanurate body of 1,6-hexamethylene diisocyanate, a compound represented by the following formula (C1-2) as an isocyanurate body of 1,5-pentamethylene diisocyanate can be given.

[0091]

[0092] The specific isocyanurate compound is preferably a compound represented by the above formula (C1-2) for the reason that the adhesion durability is more excellent, the initial adhesion is excellent, and it is easy to add in the composition because of low viscosity.

[0093] • Content of the specific isocyanurate compound

[0094] The content of the specific isocyanurate compound is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, relative to the total amount of the adhesive composition of the present application, from the viewpoint that the adhesion durability is more excellent and the initial adhesion is excellent.

[0095] <Secondary amino silane compound>

[0096] The secondary amino silane compound contained in the adhesive composition of the present application (specific amino silane compound) is a compound having -NH- as a secondary amino group and a hydrolyzable silyl group.

[0097] The specific amino silane compound can be reacted with the above urethane prepolymer and the specific isocyanurate compound, respectively.

[0098] Further, the specific amino silane compound can also be reacted with the isocyanate silane compound described later.

[0099] (Secondary amino group)

[0100] As the nitrogen atom constituting -NH- which is a secondary amino group, one which is bonded to different two carbon atoms as a preferable mode can be exemplified.

[0101] The specific amino silane compound preferably has one secondary amino group in one molecule.

[0102] (hydrolyzable silyl group)

[0103] As the hydrolyzable silyl group which the secondary amino silane compound has, for example, -Si(OR 10 ) m R 20 3-m the group shown by the formula (1). m is 1 to 3.

[0104] In the -Si(OR 10 ) m R 3-m , R 10 , R 20 each independently is a monovalent hydrocarbon group.

[0105] As the above monovalent hydrocarbon group, for example, an aliphatic hydrocarbon group (any one of straight chain, branched chain, alicyclic, or a combination thereof can be, the same hereinafter), an aromatic hydrocarbon group, or a combination thereof can be exemplified. Among them, the aliphatic hydrocarbon group can be exemplified as one of preferable modes.

[0106] As the above aliphatic hydrocarbon group, for example, methyl group, ethyl group can be exemplified.

[0107] A part of the hydrolyzable silyl group can be hydrolyzed to form a silanol group.

[0108] • linking group

[0109] The above secondary amino group and the hydrolyzable silyl group can be bonded via a linking group. The above linking group can be exemplified as divalent as one of preferable modes.

[0110] As the above linking group, for example, a hydrocarbon group can be exemplified. The above hydrocarbon group can be exemplified as an aliphatic hydrocarbon group (any one of straight chain, branched chain, alicyclic, or a combination thereof can be, the same hereinafter), an aromatic hydrocarbon group, or a combination thereof.

[0111] Among the above linking groups, from the viewpoint that the adhesion durability is more excellent, the initial adhesion is excellent, an aliphatic hydrocarbon group is preferable, a straight chain or branched chain aliphatic hydrocarbon group is more preferable.

[0112] Among the above linking groups, from the viewpoint that the adhesion durability is more excellent, the initial adhesion is excellent, 1,3-propylene group, 1,2-propylene group is preferable, 1,3-propylene group is more preferable.

[0113] Further, from the viewpoint of more excellent adhesion durability and excellent initial adhesion, the number of carbon atoms of the linking group (particularly, aliphatic hydrocarbon group) is preferably 2 to 10, more preferably 2 to 5.

[0114] The above linking group is preferably formed only of carbon and hydrogen.

[0115] • Bis type

[0116] From the viewpoint of more excellent adhesion durability and excellent initial adhesion, the specific amino silane compound is preferably of bis type.

[0117] In the present application, the specific amino silane compound of bis type means that the specific amino silane compound has two hydrolyzable silyl groups per one molecule.

[0118] • Formula (A)

[0119] From the viewpoint of more excellent adhesion durability and excellent initial adhesion, the specific amino silane compound is preferably a compound represented by the following Formula (A).

[0120]

[0121] ··R 13 , R 23

[0122] In Formula (A), R 13 , R 23 each independently represents a divalent linking group. As the linking group of R 13 , R 23 , the same as the above linking group between secondary amino group and hydrolyzable silyl group.

[0123] R 13 , R 23 each independently preferably represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and is preferably 1,3-propylene group, 1,2-propylene group, more preferably 1,3-propylene group.

[0124] ··R 11 , R 12 , R 21 , R 22

[0125] R 11 , R 12 , R 21 , R 22 each independently represents a monovalent hydrocarbon group. As the monovalent hydrocarbon group of R 11 , R 12 , R 21 , R 22 , the same as the above R 10 , R20 a monovalent hydrocarbon group.

[0126] R 11 , R 21 Preferably, each independently represents a monovalent aliphatic hydrocarbon group, more preferably a methyl group, an ethyl group.

[0127] m1, m2

[0128] Each of m1 and m2 is independently 1 to 3. Each of m1 and m2 is preferably independently 2 to 3, and m1 and m2 are more preferably 3.

[0129] As the specific amino silane compound, specifically, for example, N,N-bis[(3-trimethoxysilyl)propyl]amine, N,N-bis[(3-triethoxysilyl)propyl]amine, N,N-bis[(3-tripropoxysilyl)propyl]amine, 3-(n-butylamino)propyltrimethoxysilane can be mentioned.

[0130] From the viewpoint that the adhesion durability is more excellent, and the initial adhesion is excellent, the specific amino silane compound is preferably N,N-bis[(3-trimethoxysilyl)propyl]amine.

[0131] • Content of the specific amino silane compound

[0132] From the viewpoint that the adhesion durability is more excellent, and the initial adhesion is excellent, the content of the specific amino silane compound is preferably less than 0.5 mass% relative to the total amount of the adhesive composition of the present application, and more preferably 0.01 to 0.4 mass%.

[0133] Further, from the viewpoint that the adhesion durability is more excellent, and the initial adhesion is excellent, the molar ratio of the secondary amino group to the total amount of the isocyanate group (NH / NCO molar ratio) in the adhesive composition of the present application is preferably 0.0005 to 0.05.

[0134] From the viewpoint that the adhesion durability is more excellent, and the initial adhesion is excellent, the molar ratio of the specific amino silane compound to the specific isocyanurate compound (specific amino silane compound / specific isocyanurate compound) is more preferably 0.0005 to 3.

[0135] (Terpenoid compound)

[0136] From the viewpoint that the adhesion durability is more excellent, and the initial adhesion is excellent, the adhesive composition of the present application preferably further contains a terpenoid compound.

[0137] In the present application, the above-mentioned terpenoid compound can function as a tackifier.

[0138] In the present application, the above-mentioned terpenoid compound refers to a terpene or a derivative thereof.

[0139] The above-mentioned terpenes generally refer to a structure in which a single isoprene unit (C5H8) or a plurality of isoprene units (C5H8) are connected, but the elements constituting the terpenes are not limited to carbon and hydrogen, and sometimes include oxygen in addition to carbon and hydrogen. In the case where the terpenes have oxygen, the above-mentioned oxygen can form, for example, a carbonyl group, a hydroxyl group in the terpenes. The above-mentioned terpenes having a carbonyl group or the like are also generally referred to as terpenoids.

[0140] In the present application, the derivative of the terpenes can include, in addition to the terpenoids, for example, a phenol derivative of the terpenes.

[0141] Further, in the present application, the terpenoid compound can further have, for example, an active hydrogen, an ether bond.

[0142] • Active hydrogen

[0143] In the case where the above-mentioned terpenoid compound further has an active hydrogen, the terpenoid compound having an active hydrogen can have, for example, a hydroxyl group as the active hydrogen (a group having an active hydrogen).

[0144] As the above-mentioned hydroxyl group, for example, a phenolic hydroxyl group (a hydroxyl group bonded to a benzene ring), an alcoholic hydroxyl group (a hydroxyl group bonded to an aliphatic hydrocarbon having a linear shape, a branched shape, a cyclic shape, or a combination thereof) can be mentioned.

[0145] The above-mentioned terpenoid compound having an active hydrogen can mention, as one of the preferred modes, a terpenoid compound having a phenolic hydroxyl group.

[0146] • Ether bond

[0147] In the case where the above-mentioned terpenoid compound further has an ether bond, as the above-mentioned terpenoid compound having an ether bond, for example, a terpenoid compound having an alkoxy group, a terpenoid compound having a phenoxy group can be mentioned.

[0148] The above-mentioned terpenoid compound having an ether bond can mention, as one of the preferred modes, a terpenoid compound having a phenoxy group.

[0149] Note that the oxygen atom constituting the above-mentioned alkoxy group can be bonded to two carbon atoms to constitute an ether bond. The same applies to the oxygen atom constituting the above-mentioned phenoxy group.

[0150] • Terpenes

[0151] The terpenes can be generally classified according to the number (the number of carbon atoms) of isoprene units. In the case where the terpenes are classified according to the number of isoprene units, as the above-mentioned terpenes, for example, a hemiterpene as a compound having 5 carbon atoms;

[0152] a monoterpene as a compound having 10 carbon atoms;

[0153] Sesquiterpenes are compounds with 15 carbon atoms;

[0154] Diterpenes are compounds with 20 carbon atoms;

[0155] A disesquiterpene, a compound with 25 carbon atoms;

[0156] Triterpenes are compounds with 30 carbon atoms;

[0157] Tetraterpenes, etc., are compounds with 40 carbon atoms.

[0158] The aforementioned terpenoids can also be hydrogenated. Hydrogenation can be either partial or complete.

[0159] From the viewpoint of superior adhesion durability and excellent initial adhesion, the terpenoids mentioned above as terpenoid compounds are preferably the monoterpenes mentioned above or their derivatives (e.g., phenolic derivatives of terpenoids or monoterpenes).

[0160] Monoterpenes or their derivatives

[0161] Examples of the above-mentioned monoterpenes or their derivatives include, for example, myrcene, linalool, nerol, and other chain-like monoterpenes and their derivatives.

[0162] The compound (limonene) shown in formula (3) below, 1-para Terpineol, carvone, compound (α-terpineol) shown in formula (5), compound (β-terpineol) shown in formula (6), compound (γ-terpineol) shown in formula (7), and other monocyclic monoterpenes and their derivatives such as terpineol (terpineol is a monocyclic monoterpene with hydroxyl groups).

[0163] Compounds such as α-pinene (shown by formula (1)), β-pinene (shown by formula (2)), camphor, dicyclic monoterpenes and their derivatives such as those shown by formula (X), etc.

[0164] Furthermore, examples of monoterpene derivatives include, for instance, phenolic derivatives of monoterpenes, such as adducts of compounds represented by formula (X) with phenolic compounds.

[0165]

[0166] In equation (X), R 11 R 12 Each can be represented independently as a hydrocarbon group.

[0167] From the perspective of superior adhesion durability and excellent initial adhesion, the aforementioned terpene compounds are preferably terpene compounds with active hydrogen or ether bonds.

[0168] More preferably, a derivative of a monoterpene having an active hydrogen or an ether bond,

[0169] Further preferably, a phenol derivative of a monoterpene,

[0170] Particularly preferably, an adduct of a compound represented by the following formula (X) and a phenol compound.

[0171] Note that, in the present specification, the adduct of a compound represented by the formula (X) and a phenol compound is sometimes simply referred to as "adduct".

[0172] • Adduct

[0173] The above-mentioned adduct is a reaction product obtained by the addition of a compound represented by the formula (X) to a phenol compound.

[0174] • Compound represented by the formula (X)

[0175] In the above-mentioned formula (X), as R 11 , R 12 The above-mentioned hydrocarbon group is not particularly limited. The above-mentioned hydrocarbon group can have a hetero atom. As one of preferable modes, a hydrocarbon group composed of only carbon atoms and hydrogen atoms can be mentioned.

[0176] The above-mentioned hydrocarbon group is not particularly limited, and specifically, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a combination thereof can be mentioned. Among them, an aliphatic hydrocarbon group is preferable.

[0177] The above-mentioned aliphatic hydrocarbon group can be any one of a straight chain, a branched chain, a ring, a combination thereof. As a specific example of the above-mentioned aliphatic hydrocarbon group, for example, a straight chain or branched chain aliphatic hydrocarbon group, and the like can be mentioned. From the viewpoint that the effect of the present application is more excellent, the above-mentioned aliphatic hydrocarbon group is preferably a straight chain aliphatic hydrocarbon group.

[0178] From the viewpoint that the effect of the present application is more excellent, the number of carbon atoms of the above-mentioned aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10.

[0179] From the viewpoint that the effect of the present application is more excellent, the above-mentioned aliphatic hydrocarbon group is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, more preferably a methyl group.

[0180] As the above-mentioned aromatic hydrocarbon group, for example, an aryl group, a naphthyl group, and the like can be mentioned. As the above-mentioned aryl group, for example, a phenyl group, a tolyl group, a xylyl group, and the like, an aryl group having 6 to 18 carbon atoms, and the like can be mentioned.

[0181] The heteroatom that the hydrocarbon group can have is not particularly limited, and examples include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), and the like. The heteroatom can be combined with another heteroatom, a carbon atom, or a hydrogen atom to form a functional group.

[0182] From the viewpoint of more excellent adhesion durability, the compound represented by the above formula (X) is preferably camphene. Camphene is a compound represented by the following formula (Xl).

[0183]

[0184] Phenolic compound

[0185] The phenolic compound that is another compound capable of forming the above addition product is not particularly limited as long as a hydroxyl group is bonded to a benzene ring.

[0186] The above phenolic compound can have one or more phenolic hydroxyl groups (hydroxyl groups directly bonded to a benzene ring) in one molecule, and preferably has one.

[0187] As the above phenolic compound, a compound represented by the following formula (Y) can be given, for example.

[0188]

[0189] In formula (Y), R 23 represents a substituent, and n2 represents 0 or 1 to 4.

[0190] As the substituent for R 23 in formula (Y), a hydrocarbon group, a hydroxyl group, and the like can be given.

[0191] n2 represents 0 or 1 to 4, and from the viewpoint of more excellent adhesion durability, 0 is preferable.

[0192] The above phenolic compound is preferably phenol from the viewpoints of more excellent adhesion durability, excellent initial adhesion, and the like.

[0193] From the viewpoints of more excellent adhesion durability, excellent initial adhesion, and less odor, the above terpene compound preferably contains at least an addition product of the compound represented by the above formula (X) and a phenolic compound, and more preferably a reaction product of one molecule of the compound represented by the above formula (X) and one molecule of the above phenolic compound.

[0194] From the viewpoints of more excellent effects of the present application and excellent initial adhesion, the above addition product preferably has a phenolic hydroxyl group or a phenoxy group (both can further have the above substituent on a benzene ring) derived from the above phenolic compound.

[0195] Note that the above addition product can include at least the above reaction product. The above addition product can further include a reaction by-product, an unreacted material, in addition to the above reaction product.

[0196] As the above addition product, a compound represented by any one of the following formulae (Z1) to (Z3) can be given.

[0197]

[0198] In formula (Z1), R 31 , R 32 each independently represents a hydrocarbon group, R 33 represents a substituent, and n3 represents 0 or 1 to 4.

[0199] In formula (Z1), as the hydrocarbon group of R 31 , R 32 is the same as the hydrocarbon group of R 11 , R 12 of formula (X).

[0200] As the substituent of R 33 is the same as the substituent of R 23 of formula (Y).

[0201] n3 represents 0 or 1 to 4, and is preferably 0.

[0202]

[0203] In formula (Z2), R 41 , R 42 each independently represents a hydrocarbon group, R 43 represents a substituent, and n4 represents 0 or 1 to 4.

[0204] In formula (Z2), as the hydrocarbon group of R 41 , R 42 is the same as the hydrocarbon group of R 11 , R 12 of formula (X).

[0205] As the substituent of R 43 is the same as the substituent of R 23 of formula (Y).

[0206] n4 represents 0 or 1 to 4, and is preferably 0.

[0207]

[0208] In formula (Z3), R 51 , R 52 each independently represents a hydrocarbon group, R 53represents a substituent, and n5 represents 0 or 1 to 4.

[0209] In formula (Z3), the hydrocarbon group of R 51 52 is the same as the hydrocarbon group of R 11 12 is the same as the hydrocarbon group of R 53 23 is the same as the substituent of R 1 2 is the same as the substituent of R 1 2 n5 represents 0 or 1 to 4, and is preferably 0. 1 2 From the viewpoint of more excellent effects of the present application, excellent initial adhesiveness, and less odor, the above addition product preferably contains at least one compound selected from the group consisting of Compound 1 represented by 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). 10 20 3 3 3 (Method for producing) 3 1 The method for producing the above terpene compound is not particularly limited. In the case where the above terpene compound is the above addition product, as the method for producing the above addition product, for example, a method in which the above compound represented by formula (X) is allowed to react with the above phenol compound can be mentioned. 2 The use amount of the above compound represented by formula (X) and the above phenol compound in the above reaction is not particularly limited.

[0001] The use amount of the above compound represented by formula (X) and the above phenol compound (molar ratio of the compound represented by formula (X) : the phenol compound) when the above compound represented by formula (X) is allowed to react with the above phenol compound can be, for example, 1 : 0.5 to 2, preferably 1 : 0.8 to 1.2, and more preferably 1 : 1.

[0002] The above compound represented by formula (X) can be allowed to react with the above phenol compound in the presence of a catalyst. As the above catalyst, for example, a boron trifluoride ether complex compound can be mentioned.

[0003] The above compound represented by formula (X) can be allowed to react with the above phenol compound in a solvent. As the above solvent, for example, an aromatic hydrocarbon such as benzene or toluene; an aliphatic hydrocarbon such as cyclohexane; a halogenated hydrocarbon such as carbon tetrachloride can be mentioned.

[0004] ​​​The reaction temperature when the compound represented by the above formula (X) is reacted with the above phenol compound can be, for example, 0 to 100°C.

[0221] The above terpene compound can be used alone or in combination with two or more.

[0222] In the case where the above terpene compound is used in combination, from the viewpoints of more excellent adhesion durability, excellent initial adhesion, and less odor, the combination of the above adduct and the above monocyclic monoterpene having a hydroxyl group (but the above adduct is excluded. The same applies hereinafter) is preferred, and the combination of the above adduct and terpineol is more preferred.

[0223] In the case where the above adduct is used in combination with the above monocyclic monoterpene having a hydroxyl group, and a two-component type adhesive composition is produced, for example, the above adduct can be incorporated into a main agent, and the above monocyclic monoterpene having a hydroxyl group can be incorporated into a curing agent.

[0224] From the viewpoints of more excellent adhesion durability and excellent initial adhesion, the content of the above terpene compound is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 3.0 parts by mass, and further preferably 0.5 to 2.0 parts by mass, relative to 100 parts by mass of the urethane prepolymer.

[0225] In the case where the above terpene compound is used in combination with the above adduct and a terpene compound other than the above adduct, from the viewpoints of more excellent adhesion durability and excellent initial adhesion, the mass ratio of the above adduct to the terpene compound other than the above adduct (adduct / terpene compound other than the adduct) is preferably 0.5 to 1.5, and more preferably 0.8 to 1.2.

[0226] (Mass ratio of isocyanurate compound / adduct)

[0227] In the case where the above terpene compound is the above adduct, from the viewpoints of more excellent effects of the present application and excellent initial adhesion, the mass ratio of the content of the above isocyanurate compound to the content of the above adduct (mass ratio of isocyanurate compound / adduct) is preferably 0.1 to 50, more preferably 2 to 15, and further preferably 2 to 10.

[0228] (Isocyanate silane compound)

[0229] From the viewpoints of more excellent adhesion durability and excellent initial adhesion, the adhesive composition of the present application preferably further contains an isocyanate silane compound.

[0230] The isocyanate silane compound that can be further contained in the adhesive composition of the present application is a compound having an isocyanate group and a hydrolyzable silyl group.

[0231] The isocyanate silane compound described above can be reacted with the urethane prepolymer and the specific isocyanurate compound described above, respectively.

[0232] Further, the isocyanate silane compound described above can also be reacted with the polyol compound described later.

[0233] • isocyanate group

[0234] The isocyanate silane compound described above preferably has one isocyanate group in one molecule.

[0235] (hydrolyzable silyl group)

[0236] The hydrolyzable silyl group possessed by the isocyanate silane compound described above is the same as the hydrolyzable silyl group possessed by the specific amino silane compound.

[0237] • linking group

[0238] The isocyanate group and the hydrolyzable silyl group described above can be combined via a linking group. The linking group described above can be exemplified by a divalent group as one of the preferable modes.

[0239] As the linking group described above, a hydrocarbon group can be exemplified, for example. The hydrocarbon group described above can be exemplified by an aliphatic hydrocarbon group (any one of a linear, branched, alicyclic group, or a combination thereof can be used. The same applies hereinafter), an aromatic hydrocarbon group, or a combination thereof.

[0240] Among the linking groups described above, from the viewpoint that the adhesion durability is more excellent, the initial adhesion is excellent, an aliphatic hydrocarbon group is preferable, and a linear or branched aliphatic hydrocarbon group is more preferable.

[0241] Among the linking groups described above, from the viewpoint that the adhesion durability is more excellent, a 1,3-propylene group, a 1,2-propylene group is preferable, and a 1,3-propylene group is more preferable.

[0242] Further, from the viewpoint that the adhesion durability is more excellent, the initial adhesion is excellent, the number of carbon atoms of the linking group (particularly, the aliphatic hydrocarbon group) is preferably 1 to 6, and more preferably 2 to 3.

[0243] The linking group described above is preferably formed only of carbon and hydrogen.

[0244] • formula (I)

[0245] From the viewpoint that the adhesion durability is more excellent, the initial adhesion is excellent, the isocyanate silane compound described above is preferably a compound represented by the following formula (I).

[0246]

[0247] ··R 1 , R 2

[0248] In formula (A), R 1 , R 2 each independently represents a monovalent hydrocarbon group. As the monovalent hydrocarbon group of R 1 , R 2 is the same as the monovalent hydrocarbon group of R 10 , R 20 .

[0249] ··R 3

[0250] R 3 represents a divalent linking group. As the linking group of R 3 is the same as the linking group between the isocyanate group and the hydrolyzable silyl group.

[0251] R 3 preferably represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and is preferably 1,3- propylene, 1,2-propylene, and more preferably 1,3-propylene.

[0252] ··m

[0253] m is 1 to 3, preferably 2 to 3, and more preferably 3.

[0254] As the isocyanate silane compound, specifically, for example, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyldiethoxysilane can be given.

[0255] From the viewpoint that the adhesion durability is more excellent and the initial adhesion is excellent, the isocyanate silane compound is preferably 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxysilane, and more preferably 3-isocyanatopropyltrimethoxysilane.

[0256] • Content of isocyanate silane compound

[0257] From the viewpoint that the adhesion durability is more excellent and the initial adhesion is excellent, the content of the isocyanate silane compound is preferably 0.01 to 5% by mass, and more preferably 0.05 to 1% by mass, with respect to the total amount of the adhesive composition of the present application.

[0258] The adhesive composition of the present application can be of a one-component type or a two-component type.

[0259] (Adhesive composition of a two-component type)

[0260] In the case where the adhesive composition of the present application is of a two-component type, the adhesive composition of a two-component type can have a main agent and a curing agent (broadly, a curing agent).

[0261] • Main agent

[0262] The above-mentioned main agent can cite, as one of the preferred ways, one including the above-mentioned urethane prepolymer, the specific isocyanurate compound, and the specific aminosilane compound.

[0263] The above-mentioned isocyanate silane compound can be added to the main agent.

[0264] The above-mentioned terpene compound can be added to either or both of the above-mentioned main agent and the above-mentioned curing agent.

[0265] • Curing agent

[0266] The above-mentioned (broad sense) curing agent can include a compound having multiple active hydrogen-containing groups in one molecule (narrow sense curing agent). The above-mentioned narrow sense curing agent refers to a compound that substantially reacts with the above-mentioned urethane prepolymer to cure the adhesive composition. The above-mentioned broad sense curing agent can include at least the above-mentioned narrow sense curing agent.

[0267] As the above-mentioned narrow sense curing agent, the same substances as the above-mentioned active hydrogen compound that can be used at the time of manufacturing the above-mentioned urethane prepolymer can be cited.

[0268] The narrow sense curing agent is preferably a polyether polyol, a polybutadiene polyol.

[0269] The polyether polyol is the same as the above-mentioned.

[0270] The polybutadiene polyol is a polymer having 2 or more hydroxyl groups, and a main chain of polybutadiene or a copolymer of butadiene.

[0271] As the main chain of the polybutadiene polyol, for example, a butadiene homopolymer, a copolymer of butadiene and another monomer component, and the like can be cited. As the monomer component that can be copolymerized with butadiene, for example, styrene, acrylonitrile can be cited. The above-mentioned monomer component can be used alone or 2 or more can be used in combination.

[0272] The polybutadiene polyol can be hydrogenated.

[0273] The number of hydroxyl groups that the polybutadiene polyol can have in one molecule can be 2 or more. Note that the number of hydroxyl groups that the polybutadiene polyol can have in one molecule can be an average value.

[0274] In the above-mentioned polybutadiene polyol, the position at which the hydroxyl group is bound is not particularly limited, but it is preferable that the hydroxyl group be bound to the terminal.

[0275] The above-mentioned polybutadiene polyol can cite, as one of the preferred ways, one that is liquid at room temperature.

[0276] As the above polybutadiene polyol, for example, R45HT, R15HT (both are manufactured by Showa Denko K.K.), and the like commercially available products can be used.

[0277] In the case of the two-component type, for example, the urethane prepolymer can be used in an amount such that the amount of isocyanate group becomes 1.5 to 2.5 moles per 1 mole of active hydrogen group (for example, hydroxyl group) possessed by the strict sense of the curing agent.

[0278] (Other optional components)

[0279] The adhesive composition of the present application can further contain, as needed, a filler (for example, carbon black, calcium carbonate), a curing catalyst, a plasticizer, an age resistor, an antioxidant, a silane coupling agent other than the specific amino silane compound and the isocyanate silane compound, a pigment (dye), a thixotropy imparting agent, an ultraviolet absorber, a flame retardant, a surfactant (including a leveling agent), a dispersant, a dehydrating agent, a tackifier other than the above terpene compound, an antistatic agent, and the like various additives, and the like, within a range not impairing the object of the present application.

[0280] Note that the above filler can be surface-treated with, for example, at least one treating agent selected from the group consisting of a fatty acid, a resin acid, a urethane compound, and a fatty acid ester.

[0281] Further, in the case where the adhesive composition of the present application is of the two-component type, to which of the main agent and the curing agent the above optional component is added can be appropriately selected.

[0282] • Carbon black

[0283] The adhesive composition of the present application preferably further contains carbon black.

[0284] The carbon black is not particularly limited. Examples thereof include SAF (Super Abrasion Furnace), ISAF (Intermediate Super Abrasion Furnace), HAF (High Abrasion Furnace), FEF (Fast Extruding Furnace), GPF (General Purpose Furnace), SRF (Semi-Reinforcing Furnace), FT (Fine Thermal), MT (Medium Thermal), and the like.

[0285] Specifically, as the above-mentioned SAF, Sioot 9 (manufactured by Tokai Carbon Co., Ltd.) can be exemplified, as the ISAF, Showa Black N220 (manufactured by Showa Denko K.K.) can be exemplified, as the HAF, Sioot 3 (manufactured by Tokai Carbon Co., Ltd.), Niteron #200 (manufactured by Shin Nittetsu Carbon Co., Ltd.) can be exemplified, as the FEF, HTC #100 (manufactured by Chubu Carbon Co., Ltd.) and the like can be exemplified. Further, as the GPF, Asahi #55 (manufactured by Asahi Carbon Co., Ltd.), Sioot 5 (manufactured by Tokai Carbon Co., Ltd.) can be exemplified, as the SRF, Asahi #50 (manufactured by Asahi Carbon Co., Ltd.), Mitsubishi #5 (manufactured by Mitsubishi Chemical Corporation) can be exemplified, as the FT, Asahi Thermal (manufactured by Asahi Carbon Co., Ltd.), HTC #20 (manufactured by Chubu Carbon Co., Ltd.) can be exemplified, as the MT, Asahi #15 (manufactured by Asahi Carbon Co., Ltd.) and the like can be exemplified.

[0286] The content of the carbon black is preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass, relative to 100 parts by mass of the urethane prepolymer.

[0287] • Calcium carbonate

[0288] The adhesive composition of the present application preferably further contains calcium carbonate.

[0289] The calcium carbonate is not particularly limited. Examples thereof include, for example, heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), colloidal calcium carbonate, and the like.

[0290] The content of the calcium carbonate is preferably 20 to 150 parts by mass, more preferably 20 to 120 parts by mass, further preferably 30 to 70 parts by mass, relative to 100 parts by mass of the urethane prepolymer or the curing agent.

[0291] As the filler other than the carbon black and the calcium carbonate, various kinds of fillers of organic or inorganic shapes can be exemplified. Specifically, examples thereof include, for example, silicon dioxide such as fumed silica, baked silica, precipitated silica, pulverized silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; magnesium carbonate, zinc carbonate; pyrophyllite clay, kaolin, baked clay; fatty acid-treated products, resin acid-treated products, urethane compound-treated products, fatty acid ester-treated products thereof; and the like.

[0292] • Curing catalyst

[0293] The above-mentioned curing catalyst is not particularly limited, and specifically, for example, carboxylic acids such as 2-ethylhexanoic acid, oleic acid, and the like; phosphoric acids such as polyphosphoric acid, ethyl acid phosphate, butyl acid phosphate, and the like; bismuth catalysts such as bismuth octoate; tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, and the like; tertiary amine catalysts such as 1,4-diazabicyclo[2.2.2]octane, 2,4,6-tris(dimethylaminomethyl)phenol (e.g., DMP-30), a compound containing a dimorpholinodiethyl ether structure, and the like can be given.

[0294] In the aspect where the adhesion is more excellent, the curing catalyst preferably contains a dimorpholinodiethyl ether structure.

[0295] The dimorpholinodiethyl ether structure is a structure having a dimorpholinodiethyl ether as a basic skeleton.

[0296] In the dimorpholinodiethyl ether structure, the hydrogen atoms possessed by the morpholine rings can be substituted with a substituent. The substituent is not particularly limited. For example, an alkyl group can be given. As the alkyl group, for example, a methyl group, an ethyl group can be given.

[0297] As the amine-based catalyst containing a dimorpholinodiethyl ether structure, for example, a compound represented by the following formula (9) can be given.

[0298]

[0299] In the above-mentioned formula (9), R 1 , R 2 each independently is an alkyl group, and m, n each independently is 0, 1, or 2.

[0300] As the amine-based catalyst containing a dimorpholinodiethyl ether structure, specifically, for example, dimorpholinodiethyl ether (DMDEE), di(methylmorpholinodiethyl ether), di(dimethylmorpholinodiethyl ether) can be given.

[0301] The curing catalyst can be used alone or in combination with two or more kinds, respectively.

[0302] The content of the curing catalyst is preferably 0.05 to 2.0 parts by mass, more preferably 0.1 to 0.5 parts by mass, with respect to 100 parts by mass of the urethane prepolymer or the curing agent in a narrow sense.

[0303] • Plasticizer

[0304] As the above-mentioned plasticizer, specifically, for example, diisononyl phthalate (DINP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate, butylene glycol adipate, and the like can be given, and one of them can be used alone, or two or more kinds thereof can be used in combination.

[0305] The content of the plasticizer is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, relative to 100 parts by mass of the urethane prepolymer.

[0306] (Method for producing)

[0307] In the case where the adhesive composition of the present application is of a one-component type, the method for producing the same is not particularly limited, and for example, the adhesive composition can be produced by a method in which the urethane prepolymer, the specific isocyanurate compound, the specific aminosilane compound, and other optional ingredients which can be used as necessary are mixed.

[0308] In the case where the adhesive composition of the present application is of a two-component type, the method for producing the same is not particularly limited, and for example, the adhesive composition can be produced by a method in which the above-mentioned main agent and the above-mentioned curing agent are respectively put into different containers, and the contents of the respective containers are mixed under a nitrogen atmosphere.

[0309] Further, as a method for using the adhesive composition of the present application, the above-mentioned main agent and the above-mentioned curing agent can be used by mixing them.

[0310] (Substrate)

[0311] As a substrate to which the adhesive composition of the present application can be applied, for example, plastics, glass, rubber, metal, and the like can be given.

[0312] The substrate is suitably a substrate containing an olefin resin.

[0313] The substrate containing an olefin resin can be a substrate obtained by mixing an olefin resin, and

[0314] For example, a substrate obtained by mixing carbon fibers, glass such as glass fillers, talc, calcium carbonate, or alumina, and a filler.

[0315] The plastics can be, for example, a homopolymer, a copolymer, a hydrogenated product. The same applies to rubber.

[0316] As a specific plastic, for example, an olefin resin such as polypropylene, polyethylene, an ethylene-propylene copolymer, COP (cyclic olefin polymer), COC (cyclic olefin copolymer);

[0317] a polyester resin such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT);

[0318] a polymethyl methacrylate resin (PMMA resin), a polycarbonate resin, a polystyrene resin, an acrylonitrile / styrene copolymer resin, a polyvinyl chloride resin, an acetate resin, an ABS resin (acrylonitrile butadiene styrene resin), a polyamide resin.

[0319] The above-mentioned COC refers to a cyclic olefin copolymer such as a copolymer of a cyclic olefin such as tetracyclododecene and an olefin such as ethylene.

[0320] Further, the above-mentioned COP refers to a cyclic olefin polymer such as a polymer obtained by ring-opening polymerization and hydrogenation of a norbornene-based compound.

[0321] The plastic can be a difficult-to-bond resin.

[0322] The substrate can be surface-treated. As the surface treatment, flame treatment, corona treatment, ITRO treatment, and the like can be given. The method of each of the above-mentioned surface treatments is not particularly limited. A method conventionally known can be given.

[0323] The method of applying the adhesive composition of the present application to a substrate is not particularly limited. A method conventionally known can be given.

[0324] In the case of using the adhesive composition of the present application, the adhesion durability can be exhibited at an excellent level even if a primer is not used for the substrate. Further, the adhesive composition of the present application is excellent in initial adhesion even if a primer is not used for the substrate.

[0325] The adhesive composition of the present application can be cured by moisture or the like. For example, the adhesive composition of the present application can be cured under conditions of 5 to 90°C and a relative humidity (RH) of 5 to 95%.

[0326] (Use)

[0327] As the use of the adhesive composition of the present application, window frameless mounting agents, automobile sealants, and building material sealants can be given.

[0328] Examples

[0329] The following examples specifically illustrate the present application. However, the present application is not limited thereto.

[0330] Manufacture of the adhesive composition of one-component type

[0331] Each component in the column of "Main agent of the adhesive composition of one-component type, or the adhesive composition of two-component type" in the following Table 1 was mixed using a blender at the composition (mass parts) shown in the table. The obtained mixture was used as the adhesive composition of one-component type.

[0332] Manufacture of the adhesive composition of two-component type

[0333] Each component in the following Table 1 was mixed using a blender at the composition (mass parts) shown in the table to manufacture each main agent and each curing agent, and the adhesive composition of two-component type was obtained.

[0334] Next, the main agent 100 g manufactured as described above and the curing agent manufactured as described above were mixed at the mass ratio shown in the "two-component type main agent / curing agent" column of Table 1, and a mixture of a two-component type adhesive composition was obtained.

[0335] <Production of Test Bodies>

[0336] (Initial Test Body)

[0337] Two pieces of a substrate on which flame treatment was performed (width: 25 mm, length: 120 mm, thickness: 3 mm) were prepared by molding using a composition containing a polypropylene resin and glass fibers (trade name: Funke Star, manufactured by Japan Polypro Corporation. Described as "PP-GF" in Table 1.) After the flame treatment, the wettability of the resin surface was confirmed to be 45.0 mN / m or more using a mixed solution for a wetting tension test (manufactured by Wako Pure Chemical Industries, Ltd.).

[0338] Next, the above-described one-component type adhesive composition or the mixture of the two-component type adhesive composition was applied to the surface on which flame treatment was performed of one of the substrates in such a manner as to have a width of 25 mm, a length of 10 mm, and a thickness of 5 mm, and then, the other substrate was bonded to the surface on which flame treatment was performed of the one substrate, pressure bonding was performed, and the initial test body was produced by leaving it under conditions of 23°C and 50% RH for 3 days.

[0339] (Water Immersion Aging Test Body)

[0340] • Water Immersion Aging Test

[0341] Each initial test body was subjected to a water immersion aging test in which it was immersed in warm water at 50°C for 2,000 hours, and a water immersion aging test body was obtained.

[0342] (Hot Aging Test Body)

[0343] Each initial test body was subjected to a hot aging test in which it was left under conditions of 90°C for 2,000 hours, and a hot aging test body was obtained.

[0344] <Evaluation>

[0345] With respect to each test body manufactured as described above, the adhesiveness was evaluated by the following method. The results are shown in Table 1.

[0346] (Tensile Test)

[0347] With respect to each test body produced as described above, a tensile test was performed in accordance with JIS K6850:1999 (tensile speed: 50 mm / minute, under an environment of 20°C), the shear strength (MPa) of each test body was measured, and the failure state of each test body was confirmed by visual observation.

[0348] As to the failure state of the initial test piece, the test piece after water immersion aging, or the test piece after heat aging after the tensile test, the case where cohesive failure of the adhesive occurs is evaluated as "CF", and the case where interfacial peeling between the adherend-adhesive interface occurs is evaluated as "AF". "CF / AF" indicates that cohesive failure and interfacial peeling exist in mixture.

[0349] • Evaluation criteria of the adhesive durability

[0350] In the present application, the case where the failure state after water immersion aging and heat aging is "CF" is evaluated as "the adhesive durability is most excellent".

[0351] The case where either of the failure states after water immersion aging and heat aging is "CF", and the remaining is "CF / AF" is evaluated as "the adhesive durability is very excellent".

[0352] The case where the failure state after water immersion aging and heat aging is "CF / AF" is evaluated as "the adhesive durability is slightly excellent".

[0353] The case where either of the failure states after water immersion aging and heat aging is "CF / AF", and the remaining is "AF" is evaluated as "the adhesive durability is slightly poor".

[0354] The case where both of the failure states after water immersion aging and heat aging are "AF" is evaluated as "the adhesive durability is very poor".

[0355] In the present application, in the case where the above evaluation is "the adhesive durability is most excellent", "the adhesive durability is very excellent", or "the adhesive durability is slightly excellent", it is set that the adhesive durability is excellent.

[0356] • Evaluation criteria of the shear strength

[0357] Note that, in the case where the evaluation results of the failure state of the test piece after water immersion aging are equal, the one having a higher shear strength therebetween is preferred. The same is true for the test piece after heat aging.

[0358] Further, the shear strength after water immersion aging is preferably 3.0 MPa or higher. The same is true for the shear strength after heat aging.

[0359] • Evaluation criteria of the initial test piece

[0360] • "Excellent initial adhesion"

[0361] In the present application, the case where the failure state of the initial test piece after the tensile test is "CF" and the initial shear strength is 3.0 MPa or higher is evaluated as "excellent initial adhesion".

[0362] "Initial adhesion is slightly poor"

[0363] The case where the above-mentioned failure state is "CF" and the initial shear strength is less than 3.0 MPa, or

[0364] The case where the above-mentioned failure state is "CF / AF" and the initial shear strength is 3.0 MPa or more is evaluated as "initial adhesion is slightly poor".

[0365] "Initial adhesion is very poor"

[0366] The case where the above-mentioned failure state is "CF / AF" and the initial shear strength is less than 3.0 MPa, or the case where the above-mentioned failure state is "AF" is evaluated as "initial adhesion is very poor".

[0367] Evaluation criteria for the shear strength of the initial test body

[0368] Note that, in the case where the evaluation results of the failure state of the initial test body are equivalent, the one having a higher shear strength is set to be more excellent in initial adhesion.

[0369] [Table 1]

[0370]

[0371] Details of each component shown in each table are described below.

[0372] (Main agent of the one-component type adhesive composition, or the two-component type adhesive composition)

[0373] • Urethane prepolymer: urethane prepolymer manufactured by mixing polypropylene oxide diol (trade name: Sunnice X PP2000, manufactured by Sanyo Chemical Industries, Co., Ltd., weight average molecular weight 2,000) 70 parts by mass with polypropylene oxide triol (trade name: Sunnice X GP3000, manufactured by Sanyo Chemical Industries, Co., Ltd., weight average molecular weight 3,000) and MDI (trade name: Sumidur 44S, manufactured by Sumika Bayer Urethane Co., Ltd.) in such a manner that the NCO / OH (molar ratio) becomes 2.0, and reacting the mixture at 80°C for 5 hours

[0374] • Isocyanurate compound 1 (PDI): isocyanurate of 1,5-pentamethylene diisocyanate represented by the above-mentioned formula (C1-2) (manufactured by Mitsui Chemicals, Inc.). Molecular weight 462

[0375] • Isocyanurate compound 2 (HDI): isocyanurate of 1,6-hexamethylene diisocyanate represented by the above-mentioned formula (C1-1) (manufactured by Mitsui Chemicals, Inc.). Molecular weight 504

[0376] • Secondary amino silane compound 1 (bis type): A compound represented by the following formula. N,N-[3-(trimethoxysilyl)propyl]amine. Trade name: Silquest A-1170 silane, manufactured by Momentive Performance Materials Inc. Molecular weight: 341.5

[0377]

[0378] • Secondary amino silane compound 2: N-phenyl-3-aminopropyltrimethoxysilane. Silquest Y-9669. Manufactured by Momentive Performance Materials Inc. Molecular weight: 255

[0379] • (Comparative) Primary amino silane compound: 3-aminopropyltrimethoxysilane. Manufactured by Shin-Etsu Chemical Co., Ltd.

[0380] • (Comparative) Tertiary amino silane compound: N,N-dimethyl-3-(trimethoxysilyl)propylamine. Manufactured by Tokyo Chemical Industry Co., Ltd.

[0381] • (Comparative) Mercapto silane: 3-mercaptopropyltrimethoxysilane. Manufactured by Momentive Performance Materials Inc.

[0382] • (Comparative) Sulfide silane: A compound represented by the following formula (2).

[0383]

[0384] • Terpene compound 1: An adduct of camphene and phenol. The above adduct contains at least one compound selected from the group consisting of a compound 1 represented by the following formula (Z1-1), a compound 2 represented by the following formula (Z1-2), a compound 3 represented by the following formula (Z2-1), a compound 4 represented by the following formula (Z2-2), and a compound 5 represented by the following formula (Z3-1). Manufactured by Yasuhara Chemical Co., Ltd.

[0385]

[0386] • Isocyanate silane compound: 3-isocyanatepropyltrimethoxysilane, manufactured by Momentive Performance Materials Inc.

[0387] • Carbon black: Trade name: Niteron #200, manufactured by Shinnippon Carbon Co., Ltd., HAF grade carbon black

[0388] • Calcium carbonate 1: Heavy calcium carbonate, trade name: Super S, manufactured by Maruo Calcium Co., Ltd.

[0389] • Plasticizer 1: Diisononyl phthalate, manufactured by Jayplas

[0390] • Curing catalyst 1: dimorpholinodiethylether, trade name UCAT-660M, manufactured by San-Apro Co., Ltd.

[0391] (Curing agent of the adhesive composition of the two-component type)

[0392] • Polyol compound 1: polyoxypropylene triol, weight average molecular weight 1,000, trade name EXCENOL 1030, manufactured by Asahi Glass Co., Ltd. Corresponds to the curing agent in the narrow sense.

[0393] • Polyol compound 2: liquid polybutadiene diol having a hydroxyl group at the terminal ("poly bd R-45HT", manufactured by Shin- Etsu Chemical Co., Ltd.). Corresponds to the curing agent in the narrow sense. Liquid at room temperature. About 2 hydroxyl groups in 1 molecule.

[0394] • Terpene compound 2: terpineol (manufactured by Yasuhara Chemical Co., Ltd.)

[0395] • Calcium carbonate 2: calcium carbonate subjected to surface treatment with a fatty acid, Calfine 200, manufactured by Marutani Calcium Co., Ltd.

[0396] • Curing catalyst 2 DMDEE: dimorpholinodiethylether, trade name UCAT-660M, manufactured by San-Apro Co., Ltd.

[0397] It is clear from the results shown in Table 1 that the adhesive durability of Comparative Example 1 (one-component type) and Comparative Example 4 (two-component type) which do not contain the specific isocyanurate compound and the specific amino silane compound is very poor.

[0398] The adhesive durability of Comparative Example 2 (one-component type) which does not contain the specific amino silane compound is very poor.

[0399] The adhesive durability of Comparative Example 3 (one-component type) which does not contain the specific isocyanurate compound is slightly poor.

[0400] The adhesive durability of Comparative Example 5 (one-component type) which does not contain the specific amino silane compound and instead contains a primary amino silane compound is very poor.

[0401] The adhesive durability of Comparative Example 6 (one-component type) which does not contain the specific amino silane compound and instead contains a tertiary amino silane compound is very poor.

[0402] The adhesive durability of Comparative Example 7 (one-component type) which does not contain the specific amino silane compound and instead contains a mercapto silane compound is slightly poor.

[0403] The adhesive durability of Comparative Example 8 (one-component type) which does not contain the specific amino silane compound and instead contains a sulfide silane compound is slightly poor.

[0404] On the other hand, the adhesive composition of the present application is excellent in the durability of adhesion to an olefin resin. Furthermore, the adhesive composition of the present application is excellent in the initial adhesion to an olefin resin.

Claims

1. A urethane-based adhesive composition, comprising: a urethane prepolymer having an isocyanate group; an isocyanurate compound which is an isocyanurate compound of 1,5-pentamethylene diisocyanate and / or 1,6-hexamethylene diisocyanate; and a secondary amino silane compound, the secondary amino silane compound is a compound represented by the following formula (A), 4. The urethane-based adhesive composition according to claim 1 or 2, further comprising a terpene compound.

5. The urethane-based adhesive composition according to claim 4, the terpene compound comprising at least an adduct of a compound represented by the following formula (X) and a phenol compound, 6. The urethane-based adhesive composition according to claim 1 or 2, further comprising an isocyanate silane compound. In formula (A), R 13 , R 23 each independently represents a divalent linking group, R 11 , R 12 , R 21 , R 22 each independently represents a monovalent hydrocarbon group, m1, m2 each independently is 1 to 3.

2. The urethane-based adhesive composition according to claim 1, in the formula (A), R 11 , R 21 each independently represents an aliphatic hydrocarbon group.

3. The urethane-based adhesive composition according to claim 1 or 2, in the formula (A), R 13 , R 23 each independently represents a divalent hydrocarbon group having 2 to 10 carbon atoms.

7. The urethane-based adhesive composition according to claim 6, the isocyanate silane compound being a compound represented by the following formula (I), 9. The urethane-based adhesive composition according to claim 1 or 2, the content of the secondary amino silane compound being less than 0.5 mass% relative to the total amount of the urethane-based adhesive composition. In formula (X), R 11 , R 12 each independently represents a hydrocarbon group.

10. The urethane-based adhesive composition according to claim 1 or 2, the isocyanurate compound being an isocyanurate compound of 1,5-pentamethylene diisocyanate.

11. The urethane-based adhesive composition according to claim 1 or 2, for use in bonding a substrate comprising an olefin resin. In formula (I), R 1 , R 2 each independently represents a monovalent hydrocarbon group, R 3 represents a divalent linking group, and m is 1 to 3.

8. The urethane-based adhesive composition according to claim 7, in the formula (I), R 3 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and m is 2 to 3. ​ ​ ​

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