JP6701670B2 - Two-component urethane adhesive composition - Google Patents

Description

  The present invention relates to a two-component urethane adhesive composition.

In recent years, resin materials (for example, olefin resin and matrix resin of fiber reinforced plastic (FRP)) have been used in place of steel plates for the body of automobiles from the viewpoint of weight reduction. There is.
It is known to use a one-component moisture-curable urethane composition as a direct glazing agent (hereinafter, also abbreviated as "DG agent") used for adhering such an automobile body and window glass (window glass). Has been.

  For example, in Patent Document 1, "2 to 32 parts by mass of carbon black (A) having a particle size of 20 to 25 nm is contained per 100 parts by mass of a urethane prepolymer, and a carbon black (B) having a particle size of 26 to 30 nm (B). 1-component moisture-curable urethane composition containing 8 to 38 parts by mass of ).

JP, 2006-176664, A

By the way, the conventionally known one-component moisture-curable urethane composition described in Patent Document 1 or the like has a problem that the curing speed is slow.
From the viewpoint of improving the curing speed, the present inventors changed the specification to a two-pack type using a main agent and a curing agent, and as the curing speed was improved, the base material (particularly a base material made of an olefin resin) was used. It has been clarified that the adhesiveness may be inferior and the heat resistance may be inferior depending on the structure of the urethane prepolymer.

  Therefore, it is an object of the present invention to provide a two-component urethane adhesive composition that retains an excellent curing rate as a two-component liquid and has good adhesiveness and heat resistance.

As a result of intensive studies to solve the above problems, the present inventors have added a compound having an isocyanurate ring to at least one of the main agent and the curing agent, and a fine particle having a predetermined particle size containing an organic substance. As a result, they have found that the excellent curing rate of the two liquids is maintained, and the adhesiveness and heat resistance are improved, and the present invention has been completed.
That is, it has been found that the above problems can be solved by the following configurations.

[1] Two-component urethane system having a main agent containing a urethane prepolymer (A) having an isocyanate group and a curing agent containing a compound (B) having two or more active hydrogen-containing groups in one molecule An adhesive composition,
A two-component urethane adhesive containing at least one of the main component and the curing agent, a compound (C) having an isocyanurate ring, and fine particles (D) containing an organic substance and having an average particle size of 0.1 to 10 μm. Composition.
[2] The compound (C) is an isocyanurate compound (C1) of an aliphatic diisocyanate, an isocyanurate compound (C2) of an aliphatic isocyanate silane, a (meth)acrylate compound having an isocyanurate ring (C3), an isocyanurate ring. The two-component urethane adhesive composition according to [1], which is at least one compound selected from the group consisting of a thiol compound (C4) having ##STR3## and a glycidyl compound (C5) having an isocyanurate ring.
[3] The two-component urethane adhesive according to [1] or [2], wherein the fine particles (D) are a polymer (D1) of a polymerizable unsaturated group-containing monomer dispersed in a polyoxyalkylene polyol. Composition.
[4] The two-component urethane adhesive composition according to [3], wherein the polymer (D1) has a glass transition temperature of 60° C. or higher.
[5] The two-component urethane adhesive composition according to any one of [1] to [4], which further contains a terpene compound (E) in at least one of the base material and the curing agent.

  As shown below, according to the present invention, it is possible to provide a two-component urethane-based adhesive composition that maintains an excellent curing rate as a two-component liquid and has good adhesiveness and heat resistance.

  The two-component urethane-based adhesive composition of the present invention (hereinafter, also simply referred to as “adhesive composition of the present invention”) comprises a main agent containing a urethane prepolymer (A) having an isocyanate group and one molecule. A two-component urethane adhesive composition comprising a curing agent containing a compound (B) having two or more active hydrogen-containing groups, wherein at least one of the main agent and the curing agent has an isocyanurate ring. A two-component urethane adhesive composition containing (C) and fine particles (D) containing an organic substance and having an average particle diameter of 0.1 to 10 μm.

In the present invention, as described above, the compound (C) having an isocyanurate ring and the fine particles (D) containing an organic substance and having an average particle diameter of 0.1 to 10 μm are blended with at least one of the main agent and the curing agent. As a result, the excellent curing rate of the two liquids is maintained, and the adhesiveness and heat resistance are improved.
Although this is not clear in detail, a resin skeleton having high heat resistance (isocyanurate ring derived from compound (C)) is incorporated into the crosslinked network after the curing reaction, and fine particles ( Due to the presence of D), the thermal mobility in a high temperature environment can be appropriately restrained, and the stress applied to the adhesive interface can be reduced as compared with the case where the compound (C) or the fine particles (D) are not present. Conceivable.
Therefore, the adhesive composition of the present invention is also useful as an adhesive composition for an olefin substrate.

[Main agent]
The main component of the adhesive composition of the present invention contains a urethane prepolymer (A) having an isocyanate group.

<Urethane prepolymer (A)>
The urethane prepolymer (A) contained in the main component of the adhesive composition of the present invention is a polymer containing a plurality of isocyanate groups in the molecule at the molecular end.
As such a urethane prepolymer (A), a conventionally known one can be used. For example, a polyisocyanate compound and a compound having two or more active hydrogen groups in one molecule (hereinafter, abbreviated as “active hydrogen compound”) are reacted so that the isocyanate groups are excessive with respect to the active hydrogen groups. The reaction product obtained by the reaction can be used.

(Polyisocyanate compound)
The polyisocyanate compound used in the production of the urethane prepolymer (A) is not particularly limited as long as it has two or more isocyanate groups in the molecule.
Specific examples of the isocyanate used in the polyisocyanate compound include TDI (for example, 2,4-tolylene diisocyanate (2,4-TDI) and 2,6-tolylene diisocyanate (2,6-TDI). )), MDI (eg, 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI)), 1,4-phenylene diisocyanate, polymethylene polyphenylene Aromatic polyisocyanates such as polyisocyanate, xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate; hexamethylene Aliphatic polyisocyanates such as diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(isocyanatomethyl)cyclohexane Alicyclic polyisocyanates such as (H ₆ XDI) and dicyclohexylmethane diisocyanate (H ₁₂ MDI); carbodiimide-modified polyisocyanates thereof; isocyanurate-modified polyisocyanates thereof; and the like.

Such polyisocyanate compounds may be used alone or in combination of two or more.
Of these, MDI is preferable because of its excellent curability.

(Active hydrogen compound)
The active hydrogen compound having two or more active hydrogen groups in one molecule used in the production of the urethane prepolymer (A) is not particularly limited.

  As the active hydrogen compound, for example, a polyol compound having two or more hydroxyl (OH) groups in one molecule and a polyamine compound having two or more amino groups and/or imino groups in one molecule are suitable. Among them, a polyol compound is preferable.

  The molecular weight and skeleton of the polyol compound are not particularly limited as long as it is a compound having two or more OH groups, and specific examples thereof include low molecular weight polyhydric alcohols, polyether polyols, polyester polyols, and the like. Examples thereof include polyols and mixed polyols thereof.

  Specific examples of the low molecular weight polyhydric alcohols include ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, (1,3- or 1,4-)butanediol, pentanediol. , Low-molecular polyols such as neopentyl glycol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, pentaerythritol; saccharides such as sorbitol; etc. Is mentioned.

Next, as the polyether polyol and the polyester polyol, those derived from the above-mentioned low molecular weight polyhydric alcohols are usually used. In the present invention, aromatic diols, amines and alkanolamines shown below are further used. Those derived from can also be suitably used.
Here, as the aromatic diols, specifically, for example, resorcin (m-dihydroxybenzene), xylylene glycol, 1,4-benzenedimethanol, styrene glycol, 4,4′-dihydroxyethylphenol; Bisphenol A structure (4,4'-dihydroxyphenylpropane) and bisphenol F structure (4,4'-
Dihydroxyphenyl methane), brominated bisphenol A structure, hydrogenated bisphenol A structure, bisphenol S structure, bisphenol AF structure having a bisphenol skeleton; and the like.

  Specific examples of the amines include ethylenediamine and hexamethylenediamine, and specific examples of the alkanolamines include ethanolamine and propanolamine.

Examples of the polyether polyol include, for example, at least one selected from the compounds exemplified as the low molecular weight polyhydric alcohols, the aromatic diols, the amines and the alkanolamines, ethylene oxide, propylene oxide, butylene oxide. (Tetramethylene oxide), polyols and the like obtained by adding at least one selected from alkylene oxides such as tetrahydrofuran and styrene oxide.
Specific examples of such polyether polyols include polyethylene glycol, polypropylene glycol (PPG), polypropylene triol, ethylene oxide/propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), polytetraethylene glycol, sorbitol-based polyol. Etc.

Similarly, as the polyester polyol, for example, a condensate of any one of the low molecular weight polyhydric alcohols, the aromatic diols, the amines and the alkanolamines with a polybasic carboxylic acid (condensed polyester polyol) is used. ); Lactone-based polyols; Polycarbonate polyols;
Here, as the polybasic carboxylic acid forming the condensed polyester polyol, specifically, for example, glutaric acid, adipic acid, azelaic acid, fumaric acid, maleic acid, pimelic acid, suberic acid, sebacic acid, Hydroxycarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, dimer acid, pyromellitic acid, other low molecular weight carboxylic acids, oligomeric acids, castor oil, reaction products of castor oil and ethylene glycol (or propylene glycol), etc. Is mentioned.
Further, as the lactone-based polyol, specifically, for example, lactone such as ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl-ε-caprolactone is subjected to ring-opening polymerization with a suitable polymerization initiator. Examples thereof include those having hydroxyl groups at both ends.

  Specific examples of the other polyols include acrylic polyols; polybutadiene diols; polymer polyols having a carbon-carbon bond in the main chain skeleton such as hydrogenated polybutadiene polyols; and the like.

In the present invention, the various polyol compounds exemplified above may be used alone or in combination of two or more.
Of these, polypropylene glycol is preferable because it is excellent in balance between hardness and elongation at break and cost of the adhesive composition of the present invention containing the resulting urethane prepolymer as a main component.

Specific examples of the polyamine compound include ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, and , 2-propanediamine, iminobispropylamine, methyliminobispropylamine, 1,5-diamino-2-methylpentane (MPMD, manufactured by DuPont Japan) and the like aliphatic polyamines; metaphenylenediamine, orthophenylenediamine, Aromatic polyamines such as paraphenylenediamine, m-xylylenediamine (MXDA), diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane; monoamines having an ether bond in the main chain such as N-aminoethylpiperazine; 3-butoxyisopropylamine A diamine having a polyether skeleton represented by Jeffamine EDR148 manufactured by San Techno Chemical Co.; isophorone diamine, 1,3-bisaminomethylcyclohexane (1,3BAC, manufactured by Mitsubishi Gas Chemical Co., Inc.), 1-cyclohexylamino-3-amino Alicyclic polyamines such as propane and 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine; norbornanediamines having norbornane skeletons such as norbornanediamine (NBDA, manufactured by Mitsui Chemicals, Inc.); Polyamidoamine; San Techno Chemical Co., which has 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis(2-amino-2-methylpropyl)piperazine, polypropylene glycol (PPG) as a skeleton Manufactured by Jefferson D230, Jeffamine D400; and the like. These may be used alone or in combination of two or more.
Among them, diamine having a polyether skeleton (Jeffamine) and hexamethylenediamine are preferable.

  In the present invention, the urethane prepolymer (A) uses an aromatic polyisocyanate as a polyisocyanate compound and a polyether polyol having a molecular weight of 500 to 20,000 as an active hydrogen compound, and these are added to 1 mol of hydroxyl groups of the polyether polyol. On the other hand, it is preferably a urethane prepolymer which is reacted so that the isocyanate group of the aromatic polyisocyanate is 1.5 to 2.5 mol.

[Curing agent]
The hardening|curing agent of the adhesive composition of this invention contains the compound (B) which has 2 or more active hydrogen groups in 1 molecule.

<Compound (B)>
The compound (B) contained in the curing agent of the adhesive composition of the present invention is a component (a curing agent component in a narrow sense) that cures the urethane prepolymer contained in the above-mentioned main component.
In the present invention, examples of the compound (B) include the same compounds as the active hydrogen compound used for producing the urethane prepolymer (A). Of these, a polyol compound is preferable.
In particular, it is preferable to use a polyol compound having a hydrophobic skeleton such as polybutadiene diol as the polyol compound, because the adhesiveness with the resin material becomes better and the water-resistant adhesiveness becomes particularly good, and the rosin diol is used in combination. It is preferable to do so from the reason that the adhesiveness with the resin material is further improved.

  In the present invention, the compounding ratio of the main agent and the curing agent in the adhesive composition of the present invention is such that the molar ratio (NCO/OH) of the isocyanate group in the main agent and the active hydrogen group in the curing agent is An amount of 0.5 to 10.0 is preferable, and an amount of 1.0 to 4.0 is more preferable.

[Compound (C) Having Isocyanurate Ring]
The adhesive composition of the present invention contains a compound (C) having an isocyanurate ring in at least one of the above-mentioned main agent and curing agent.
Here, the compound (C) is contained in at least one of the main agent and the curing agent described above, independently of the fine particles (D) described below, and is contained in both the main agent and the curing agent described above. Good.

In the present invention, as the compound (C), an isocyanurate compound (C1) of an aliphatic diisocyanate and an isocyanurate compound (C2 of an aliphatic isocyanate silane) are used because the adhesiveness with an olefin base material becomes better. ), a (meth)acrylate compound having an isocyanurate ring (C3), a thiol compound having an isocyanurate ring (C4), and a glycidyl compound having an isocyanurate ring (C5). A compound is mentioned suitably.
Here, the "(meth)acrylate compound" refers to a compound having an acryloyloxy group or a methacryloyloxy group, and the "(meth)acryloyloxy group" described below refers to an acryloyloxy group or a methacryloyloxy group. .

<Isocyanurate compound (C1)>
Examples of the isocyanurate compound (C1) include isocyanurate bodies of aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI). Be done.
Among these, a compound represented by the following formula (C1-1), which is an HDI isocyanurate body, and a compound represented by the following formula (C1-2), which is an isocyanurate body of pentamethylene diisocyanate, are preferable.

<Isocyanurate compound (C2)>
The isocyanurate compound (C2) is an isocyanurate compound of an aliphatic isocyanate silane.
Here, the aliphatic isocyanate silane is a compound having an isocyanate group derived from an aliphatic compound and a hydrolyzable silicon-containing group, for example, an isocyanate group-containing aliphatic compound, and a functional group capable of reacting with the isocyanate group. It can be obtained by reacting with a compound having a hydrolyzable silicon-containing group.
Preferable examples of the isocyanurate compound (C2) include, for example, compounds in which an aliphatic isocyanate silane such as isocyanate propyl triethoxy silane and isocyanate propyl trimethoxy silane is converted to isocyanurate.

<(Meth)acrylate compound (C3)>
The (meth)acrylate compound (C3) is not particularly limited as long as it is a compound having an isocyanurate ring and a (meth)acryloyloxy group.
Specific examples of the (meth)acrylate compound (C3) include ethoxylated isocyanuric acid triacrylate, ε-caprolactone-modified tris(2-acryloxyethyl)isocyanurate; hexamethylene diisocyanate (HDI), pentamethylene. By reacting an aliphatic diisocyanate such as diisocyanate, trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI) with a hydroxyl group-containing acrylamide monomer such as hydroxyethyl acrylamide or a hydroxyl group-containing acrylate such as 4-hydroxybutyl acrylate. And the like.

<Thiol compound (C4)>
The thiol compound (C4) is not particularly limited as long as it is a compound having an isocyanurate ring and a mercapto group.
Specific examples of the thiol compound (C4) include tris(ethyl-3-mercaptopropionate) isocyanurate and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3. , 5-triazine-2,4,6(1H,3H,5H)-trione and the like.

<Glycidyl compound (C5)>
The glycidyl compound (C5) is not particularly limited as long as it is a compound having an isocyanurate ring and an epoxy group.
Specific examples of the glycidyl compound (C5) include 1,3,5-tris(2,3-epoxypropyl)-1,3,5-triazine-2,4,6(1H,3H, 5H)-trione and the like.

  In the present invention, the content of the compound (C) is preferably 0.1 to 10% by mass based on the total mass of the main agent when blended in the above-mentioned main agent, and 0.3 to 2. It is more preferably 5% by mass. When compounded in the above-mentioned curing agent, it is preferably 0.3 to 20% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the curing agent.

[Fine particles (D) having an average particle size of 0.1 to 10 μm containing an organic substance]
The adhesive composition of the present invention contains fine particles (D) containing an organic substance and having an average particle diameter of 0.1 to 10 μm in at least one of the above-mentioned main agent and curing agent.
Here, the fine particles (D) are contained in at least one of the main agent and the curing agent described above independently of the compound (C) described above, and are contained in both the main agent and the curing agent described above. Good.
The average particle diameter means the average value of the particle diameters of the fine particles (D), and is the 50% volume cumulative diameter (D50) measured using a laser diffraction type particle size distribution measuring device. The particle size used as the basis for calculating the average value is the average value obtained by dividing the total value of the major axis and the minor axis by 2 when the fine particles (D) have an elliptical cross section, and when the particle is a perfect circle. Refers to its diameter.

  The average particle size of the fine particles (D) is preferably 0.2 to 7 μm, and more preferably 0.3 to 5 μm.

<Polymer (D1)>
In the present invention, from the viewpoint of dispersibility in the resin matrix containing the urethane prepolymer (A) and the compound (B) described above, the organic material forming the fine particles (D) is a polymer of the polymerizable unsaturated group-containing monomer. The polymer (D1) is preferable, and the polymer (D1) dispersed in the polyoxyalkylene polyol is more preferable.
Here, examples of the polymerizable unsaturated group include polymerizable functional groups such as a (meth)acryloyloxy group, a vinyl group, an allyl group, and a styryl group.
As the monomer having such a polymerizable unsaturated group, a conventionally known crosslinkable monomer can be used, and examples thereof include alkyl methacrylate such as methyl methacrylate (MMA), ethyl methacrylate and butyl methacrylate; ethyl acrylate and butyl acrylate. Alkyl acrylates; styrene, vinyltoluene, aromatic vinyl such as α-methylstyrene, vinylidene cyanide; acrylonitrile, methacrylonitrile, etc. vinyl cyanide and vinylidene cyanide; and the like, and the above polymer (D1) May be a homopolymer of these monomers or a copolymer of these monomers.
Among them, the polymer (D1) is preferably an MMA homopolymer, a copolymer of acrylonitrile and styrene, or a styrene homopolymer.

  Examples of the method for preparing the polymer (D1) include a method utilizing suspension polymerization. Specific examples include a method of polymerizing a monomer in a solvent such as water to form particles, then removing the solvent and extracting only the particles. More specifically, JP-A-2014-198797, The method described in Japanese Patent Laid-Open No. 2014-198804 can be used.

  Moreover, as a method of preparing the polymer (D1) dispersed in the polyoxyalkylene polyol, for example, a method of using a so-called polymer polyol can be mentioned. Specifically, a method of preparing a finely divided polymer (D1) in a polymer solution by using polypropylene glycol (PPG) having low volatility as a solvent and polymerizing a monomer in the solvent (polymer solution) Is mentioned. More specifically, the methods described in Examples of JP2012-241182A and JP2012-46613A can be mentioned.

In the present invention, the polymer (D1) dispersed in a polyoxyalkylene polyol is used as the fine particles (D), and when the polymer (D1) is blended in the main agent side, the polyoxyalkylene polyol is the above-mentioned urethane prepolymer. It may be used as a part of the active hydrogen compound for producing (A).
Similarly, when the polymer (D1) dispersed in a polyoxyalkylene polyol is used as the fine particles (D) and is blended on the curing agent side, two polyoxyalkylene polyols are included in one molecule. It may be used (used) as a part of the compound (B) having the active hydrogen-containing group.

In the present invention, the glass transition temperature of the polymer (D1) is preferably 60° C. or higher, and more preferably 80 to 250° C. for the reason that the heat resistance becomes better and the chemical resistance also improves. preferable.
Here, the glass transition temperature (Tg) is calculated by a midpoint method, which is measured with a differential scanning calorimeter (DSC) at a temperature rising rate of 20° C./min.

In the present invention, the organic substance forming the fine particles (D) may be a melamine-based resin in addition to the polymer (D1) described above.
Examples of the fine particles (D) having a melamine-based resin as an organic substance include spherical composite cured melamine resins described in JP-A-2002-327036 and JP-A-2005-171033.

  In the present invention, the content of the fine particles (D) is preferably 0.1 to 30% by mass, and 0.5 to 20% by mass, based on the total mass of the main agent when blended in the above-mentioned main agent. % Is more preferable. When compounded in the above-mentioned curing agent, it is preferably 0.5 to 50% by mass, more preferably 1 to 15% by mass, based on the total mass of the curing agent.

[Terpene compound]
The adhesive composition of the present invention preferably contains a terpene compound in at least one of the above-mentioned main agent and curing agent.

Examples of the terpene compound include a monoterpene, a hydrogenated monoterpene, a modified monoterpene obtained by modifying the above monoterpene or the above hydrogenated monoterpene with a hydroxyl group, and a repeating unit derived from the above monoterpene or the above modified monoterpene. There is at least one terpene compound selected from the group consisting of oligomers having 6 to 6.
Here, the terpene is a series of compounds based on the isoprene rule, that is, a molecular formula (C ₅
H ₈ ) _n is a general term for compounds represented by the formula, and of these, the monoterpene means a compound represented by the molecular formula (C ₅ H ₈ ) ₂ . An oligomer having 2 to 6 repeating units derived from a monoterpene or a modified monoterpene means a compound having 2 to 6 repeating units represented by a skeleton of a monoterpene and a molecular formula (C ₅ H ₈ ) _2. It may be a homopolymer (homo-oligomer) or a copolymer (co-oligomer).

<Monoterpene>
Examples of the monoterpene include a compound (α-pinene) represented by the following formula (1),
Examples thereof include compounds represented by the following formula (2) (β-pinene), compounds represented by the following formula (3) (limonene), myrcene, carvone, camphor, etc., and these may be used alone. You may use together 2 or more types.
Of these, compounds represented by the following formulas (1) to (3) are preferable.

<hydrogenated monoterpene>
The hydrogenated monoterpene is a terpene compound obtained by hydrogenating the monoterpene.
Examples of the hydrogenated monoterpene include a compound (p-menthane) represented by the following formula (4).

<Modified monoterpene>
The modified monoterpene is a monoterpene obtained by modifying the above monoterpene or the above hydrogenated monoterpene with a hydroxyl group.
Examples of the modified monoterpene include a compound represented by the following formula (5) (α-terpineol), a compound represented by the following formula (6) (β-terpineol), and a following formula (7). Examples thereof include compounds (γ-terpineol), and these may be used alone or in combination of two or more.

<Oligomer>
The oligomer is a compound having 2 to 6 repeating units derived from the monoterpene or the modified monoterpene (excluding the modified monoterpene obtained by modifying the hydrogenated monoterpene with a hydroxyl group).
Examples of the oligomer include a compound represented by the following formula (8) (terpene resin), a compound represented by the following formula (9) (aromatic modified terpene resin), a compound represented by the following formula (10) (Terpene phenol resin) and the like, and these may be used alone or in combination of two or more.

Here, in the above formulas (8) to (10), m represents a number of 2 to 6, n represents a number of 1 to 3, and m×n represents a number of 2 to 6.
Further, m and m×n are preferably numbers of 2 to 5, and more preferably numbers of 2 to 3.
On the other hand, in the above formula (9), R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
Further, R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

  In the present invention, the content of the terpene compound in the case of containing the terpene compound is preferably 0.05 to 25 mass% with respect to the total mass of the main agent, and 0.2 to It is more preferably 10% by mass. When compounded in the above-mentioned curing agent, it is preferably 0.05 to 30% by mass, more preferably 1 to 20% by mass, based on the total mass of the curing agent.

〔Carbon black〕
The adhesive composition of the present invention preferably contains carbon black in at least one of the above-mentioned main agent and curing agent.
As the carbon black, a conventionally known one can be used as in the case of a normal one-pack type polyurethane composition.
Examples of the carbon black include SAF (Super Abrasion Furnace) and ISAF (Intermediate Super Abrasion Fur).
NACE), HAF (High Abrasion Furnace), FEF (Fast)
Extending Furnace), GPF (General Purpose Furnace), SRF (Semi-Reinforcing Furnace), FT (
Fine Thermal), MT (Medium Thermal), and the like.
Specifically, SEAST 9 (manufactured by Tokai Carbon Co., Ltd.) as the SAF, SHOWA BLACK N220 (manufactured by Showa Cabot Co.) as the ISAF, SEIST 3 (manufactured by Tokai Carbon Co.) as the HAF, and HTC#100 (as the FEF). Chubu Carbon Co., Ltd.) and the like are exemplified. Also, Asahi #55 (made by Asahi Carbon Co., Ltd.), Seast 5 (made by Tokai Carbon Co., Ltd.) as GPF, Asahi #50 (made by Asahi Carbon Co., Ltd.) as SRF, Mitsubishi #5 (made by Mitsubishi Chemical Co.), and FT as Asahi Thermal (manufactured by Asahi Carbon Co., Ltd.), HTC#20 (manufactured by Chubu Carbon Co., Ltd.) and Asahi #15 (manufactured by Asahi Carbon Co.) are exemplified.

  In the present invention, the content when the above carbon black is contained is preferably 5 to 70% by mass, and 10 to 50% by mass based on the total mass of the main agent when blended in the above-mentioned main agent. It is more preferable. When blended with the above-mentioned curing agent, it is preferably 3 to 80% by mass, more preferably 10 to 50% by mass, based on the total mass of the curing agent.

[Calcium carbonate]
The adhesive composition of the present invention preferably contains calcium carbonate in at least one of the above-mentioned main agent and curing agent.
As the calcium carbonate, a conventionally known one can be used as in the case of a normal one-pack type polyurethane composition, and may be ground calcium carbonate, precipitated calcium carbonate (light calcium carbonate), colloidal calcium carbonate or the like. ..

  In the present invention, when the calcium carbonate is contained in the above-mentioned main agent, the content is preferably 3 to 80% by mass, and 5 to 50% by mass based on the total mass of the main agent. It is more preferable. When blended with the above-mentioned curing agent, it is preferably 3 to 90% by mass, more preferably 10 to 70% by mass, based on the total mass of the curing agent.

[Other optional ingredients]
The adhesive composition of the present invention is, if necessary, a filler other than carbon black and calcium carbonate, a curing catalyst, a plasticizer, an antioxidant, an antioxidant, a pigment (dye) as long as the object of the present invention is not impaired. ), a thixotropic agent, an ultraviolet absorber, a flame retardant, a surfactant (including a leveling agent), a dispersant, a dehydrating agent, an adhesion imparting agent, an antistatic agent, and various other additives.

  Examples of the filler include various shapes of organic or inorganic fillers. Specifically, for example, fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; magnesium carbonate, zinc carbonate; wax stone clay , Kaolin clay, calcined clay; carbon black; these fatty acid-treated products, resin acid-treated products, urethane compound-treated products, fatty acid ester-treated products; and the like. These may be used alone or in combination of two or more. You may.

The curing catalyst is not particularly limited, but specifically, for example, carboxylic acids such as 2-ethylhexanoic acid and oleic acid; phosphoric acids such as polyphosphoric acid, ethyl acid phosphate, butyl acid phosphate; bismuth octylate and the like. Catalyst; tin catalyst such as dibutyltin dilaurate, dioctyltin dilaurate; first catalyst such as 1,4-diazabicyclo[2.2.2]octane, 2,4,6-tris(dimethylaminomethyl)phenol (for example, DMP-30) Tertiary amine catalysts; and the like.

  Specific examples of the plasticizer include diisononyl phthalate (DINP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; tricresyl phosphate, phosphate Trioctyl; propylene glycol adipate polyester, butylene glycol adipate polyester, etc. may be mentioned, and these may be used alone or in combination of two or more.

Specific examples of the antiaging agent include compounds such as hindered phenols.
Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

  Specific examples of the pigment include inorganic pigments such as titanium oxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride and sulfate; azo pigments, phthalocyanine pigments, Quinacridone pigment, quinacridone quinone pigment, dioxazine pigment, anthrapyrimidine pigment, ansanthuron pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, perinone pigment, diketopyrrolopyrrole pigment, quinonaphthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazo Organic pigments such as ron pigment, isoindoline pigment, and carbon black; and the like.

Specific examples of the thixotropic agent include Aerosil (manufactured by Nippon Aerosil Co., Ltd.) and Disparon (manufactured by Kusumoto Kasei Co., Ltd.).
Specific examples of the adhesion-imparting agent include phenol resin, rosin resin, and xylene resin.

Specific examples of the flame retardant include chloroalkyl phosphate, dimethyl methylphosphonate, bromine/phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether and the like.
Specific examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycol and ethylene oxide derivatives.

The method for producing the adhesive composition of the present invention is not particularly limited, and examples thereof include a main agent containing a urethane prepolymer (A) and the like, and a compound (B) having two or more active hydrogen groups in one molecule. And a curing agent containing a can be prepared separately by a method of thoroughly mixing them under a nitrogen gas atmosphere.
Further, in the present invention, the prepared main agent can be stored in a container replaced with nitrogen gas or the like, and the prepared curing agent can be filled and stored in another container, respectively. It can also be prepared by mixing with.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

<Synthesis of Urethane Prepolymer A-1>
700 g of polyoxypropylene diol (average molecular weight 2000), 300 g of polyoxypropylene triol (average molecular weight 3000), and 499 g of 4,4′-diisocyanate phenylmethane (molecular weight 250) were mixed (NCO/OH=2.0 at this time) Further, 500 g of diisononyl phthalate was added, and the mixture was stirred at 80° C. for 12 hours in a nitrogen stream and reacted to synthesize urethane prepolymer A-1 containing 2.10% of isocyanate groups.

<Synthesis of urethane prepolymer A-2 containing fine particles D-1>
Polyoxypropylene glycol (average molecular weight 2000) 700 g, fine particles D-1 (organic substance: styrene-acrylonitrile copolymer, average particle diameter: 0.7 μm) dispersed in polyoxypropylene glycol (fine particle content: 42% by mass, hydroxyl group Value: 30.4 mg KOH/g, product name: FS-7301, manufactured by Sanyo Chemical Industries, Ltd., and 300 g of 4,4'-diisocyanate phenylmethane (molecular weight 250) 431 g are mixed (at this time, NCO/OH=2. 0) and 500 g of diisononyl phthalate were further added, and the mixture was stirred at 80° C. for 12 hours in a nitrogen stream and reacted to synthesize a urethane prepolymer A-2 containing 1.87% of isocyanate groups.

[Examples 1 to 11 and Comparative Examples 1 to 3]
The components shown in Table 1 below were mixed with a composition (parts by mass) shown in the same table using a stirrer to prepare a main agent shown in the upper part of the table and a curing agent shown in the lower part of the table.
Next, 100 g of the prepared main agent and 10 g of the curing agent were mixed to obtain an adhesive composition.
The adhesive properties of the obtained adhesive compositions were evaluated by the following methods. The results are shown in Table 1.

〔Adhesiveness〕
<Shear strength>
Two substrates to be frame-treated on one surface of an olefin resin substrate (width: 25 mm, length: 120 mm, thickness: 3 mm, short fiber GFPP K7000, manufactured by Prime Polymer Co., Ltd.) were prepared.
After the frame treatment, it was confirmed that the wettability of the resin surface was 45.0 mN/m or higher using a wet tension test mixture (manufactured by Wako Pure Chemical Industries, Ltd.).
Then, each adhesive composition immediately after preparation (mixing) is applied to the surface (frame-treated surface) of one adherend so as to have a thickness of 3 mm, and then the surface of the other adherend (frame). A test body was prepared by laminating it to the treated surface) and pressing it.
After leaving the produced test body in an environment of 23° C. and 50% relative humidity for 3 days, a tensile test according to JIS K6850:1999 is performed at 23° C. and a shear strength (MPa) is obtained at a pulling speed of 50 mm/min. It was measured.
As a result of the measurement, those having a shear strength of 3.1 MPa or more are evaluated as "⊚", those having a shear strength of 2.0 MPa or more and less than 3.1 MPa are evaluated as "○", and those having a shear strength of less than 2.0 MPa. Was evaluated as "x". The results are shown in Table 1 below.

<Destroyed state>
The fracture state of the test body whose shear strength was measured was visually confirmed.
Of the area adhered by the adhesive, a ratio of 90% or more of cohesive failure (CF) of the adhesive is evaluated as "A", and a ratio of cohesive failure is 75% or more and less than 90%. Those having a cohesive failure rate of less than 75% were evaluated as "x". The results are shown in Table 1 below.
In Table 1 below, "CF numerical value" indicates the rate of cohesive failure, "AF numerical value" indicates the rate of adhesive failure (interfacial peeling), and for example, "CF80AF20" indicates 80% cohesive failure. It shows that the adhesive failure is 20%.

〔Heat-resistant〕
A test body similar to the one used for evaluation of adhesiveness was prepared, and the prepared test body was allowed to stand in an environment of 23° C. and relative humidity of 50% for 3 days, and further left in an oven at 100° C. for 200 hours. The same evaluation as the adhesiveness was performed. The results are shown in Table 1 below.

Details of each component shown in Table 1 above are as follows.
-Urethane prepolymer A-1: Urethane prepolymer synthesized above-Particle D-1 containing urethane prepolymer A-2: Urethane prepolymer synthesized above-Particle D-2: Silica melamine composite particles (Product number: Optobeads 500 SL, manufactured by Nissan Kagaku Co., Ltd., fine particle concentration: 100% by mass, fine particle average particle diameter: 0.6 μm, fine particle glass transition temperature: 210° C., 15 parts by mass, and polyoxypropylene triol (molecular weight 5100) 100 parts by mass. Was homogenized using a paint mill (S-43/4X11, Inoue Seisakusho) Fine particles D-3: polymethacrylic acid particles (product number: XX-2851Z, manufactured by Sekisui Plastics Co., Ltd., fine particle concentration: 100% by mass) , Fine particles average particle diameter: 0.3 μm, fine particles glass transition temperature: 100° C.) 15 parts by mass and polyoxypropylene triol (molecular weight 5100) 100 parts by mass with a paint mill (S-43/4X11, Inoue Seisakusho). What was homogenized by using:-Particle D-4: PPG solution in which fine particles of a copolymer of acrylonitrile and styrene were dispersed (product number: FL-557, concentration of fine particles: 40% by mass, average particle diameter of fine particles: 1) 0.0 μm, glass transition temperature of fine particles: 100° C., manufactured by Sanyo Chemical Industry Co., Ltd.)
Fine particles D-5: PPG solution in which fine particles of a styrene homopolymer are dispersed (product number: Exenol 910, concentration of fine particles: 20% by mass, average particle diameter of fine particles: 1 μm, glass transition temperature of fine particles: 110° C., (Made by Asahi Glass Co., Ltd.)

-Isocyanurate compound C1-1: isocyanurate body of hexamethylene diisocyanate (Tolonate HDT, manufactured by Perstorp)
-Isocyanurate compound C1-2: isocyanurate body of pentamethylene diisocyanate-Isocyanurate compound C2-1: isocyanurate body of isocyanatopropyltrimethoxysilane (Y-19020, manufactured by Momentive Co.)
-Isocyanurate compound C2-2: Isocyanurate body of isocyanatopropyltriethoxysilane (A-1310, manufactured by Momentive Co.)
-(Meth)acrylate compound C3-1: ethoxylated isocyanuric acid triacrylate (A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
-(Meth)acrylate compound C3-2: ε-caprolactone-modified tris(2-acryloxyethyl) isocyanurate (A-9300-1CL, manufactured by Shin-Nakamura Chemical Co., Ltd.)
-Thiol compound C4-1: tris(ethyl-3-mercaptopropionate) isocyanurate body

Compound B-1: Exenol 1030 (manufactured by Asahi Glass Co., Ltd.)
・Terpene compound 1: YS resin CP (manufactured by Yasuhara Chemical Co.)
・Terpene compound 2: terpineol (manufactured by Yasuhara Chemical Co., Ltd.)
・Carbon black: #200MP (manufactured by Shin Nikka Carbon Co., Ltd.)
・Calcium carbonate 1: Super S (Maruo Calcium)
・Calcium carbonate 2: Calfine 200 (manufactured by Maruo Calcium Co., Ltd.)
・Plasticizer: diisononyl phthalate (made by J-Plus)
・Catalyst: Dimorpholino diethyl ether (manufactured by San-Apro)

From the results shown in Table 1 above, an adhesive composition prepared without compounding the compound (C) having an isocyanurate ring and the fine particles (D) containing an organic substance and having an average particle size of 0.1 to 10 μm It was found that the product had poor adhesiveness and heat resistance (Comparative Example 1).
In addition, the adhesive composition prepared without compounding any one of the compound (C) having an isocyanurate ring and the fine particles (D) having an average particle diameter of 0.1 to 10 μm containing an organic substance has an adhesive property. Was found to be insufficient and the heat resistance was poor (Comparative Examples 2 to 3).
On the other hand, the adhesive composition prepared by blending the compound (C) having an isocyanurate ring and the fine particles (D) having an average particle diameter of 0.1 to 10 μm containing an organic material has adhesiveness and heat resistance. Was found to be good (Examples 1 to 11). Although not shown in Table 1, regarding the curing speed, a bead (diameter 1 cm) was applied to the adhesive after mixing the main component/curing agent at room temperature and cut with a cutter knife after 12 hours. However, it was confirmed that all of the examples were cured from the surface layer of the bead to the inside thereof, and it was found that the excellent curing rate as a two-component solution could be sufficiently maintained.
Further, from the comparison between the examples, it was found that the adhesive composition prepared by blending the terpene compound had better adhesiveness and heat resistance than the example in which the terpene compound was not blended.

Claims (4)

Two-component urethane adhesive composition having a main agent containing a urethane prepolymer (A) having an isocyanate group and a curing agent containing a compound (B) having two or more active hydrogen-containing groups in one molecule A thing,
At least one of the main agent and the curing agent, a compound having an isocyanurate ring (C), and an average particle diameter containing organic substances contained 0.1~10μm microparticles (D),
The compound (C) is an isocyanurate compound (C2) of an aliphatic isocyanate silane, a (meth)acrylate compound (C3) having an isocyanurate ring, a thiol compound (C4) having an isocyanurate ring, and an isocyanurate ring. A two-component urethane adhesive composition , which is at least one compound selected from the group consisting of glycidyl compounds (C5) . The two-component urethane adhesive composition according to claim 1 , wherein the fine particles (D) are a polymer (D1) of a polymerizable unsaturated group-containing monomer dispersed in a polyoxyalkylene polyol. The two-component urethane adhesive composition according to claim 2 , wherein the glass transition temperature of the polymer (D1) is 60°C or higher. The main component and at least one of the curing agent, further contains a terpene compound (E), 2-component urethane adhesive composition according to any one of claims 1-3.