JP2002363189A - Silane coupling agent and polymer composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new silane coupling agent of a low molecular weight (a monomer), capable of making an adherend (an organic material) recycable and capable of exhibiting high adhesion. SOLUTION: This silane coupling agent has a nitrogen-containing heterocyclic ring, an organic group containing at least one of linkage selected from a group comprising a urethane, thiourethane, urea, thiourea, amide, thioamide, ester, thioester, amino, and thioether (sulfide) linkage, and a hydrolyzable silyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel silane coupling agent capable of recycling an adherend (organic material), and more particularly to a silane coupling agent having a hydrogen-bondable silyl group and a nitrogen-containing heterocyclic ring. The present invention also relates to a silane coupling agent which is bonded by an organic group and which exhibits a strong adhesive force capable of recycling a new adherend (organic material).

[0002]

2. Description of the Related Art A silane coupling agent has an organic functional group having a substituent which bonds to an organic material in the same molecule, and a hydrolyzable group which reacts with and bonds to an inorganic material. The silane coupling agent is present at the interface between the organic material and the inorganic material and plays a bridging role of bonding the two, and has effects such as improvement in mechanical strength, heat resistance, water resistance, and adhesiveness. Widely used for.

[0003] However, in these silane coupling agents, the substituent binding to the organic material is a vinyl group, an epoxy group, an amino group, or the like. It serves as a bridge that connects Therefore, even in today's demand for recycling of used organic and / or inorganic materials from the standpoints of environmental protection and resource saving, they have not been recycled.

The formation of hydrogen bonds between a carbonyl group and an amino group is a well-known fact found in biomolecules and the like. The immobilization of functional groups using hydrogen bonds is widely used in the field of supramolecular chemistry to develop new functional molecules such as ion channels, and patents utilizing this have been published in the field of resins. I have. For example, the present applicant discloses in Japanese Patent Application Laid-Open No. 11-209524, a heat-resistant, recyclable elastomer containing a carboxyl-modified elastomer and a compound such as pyridine or triazole capable of forming a hydrogen bond with the carbonyl group. A composition is described. In addition, the present applicant discloses in Japanese Patent Application Laid-Open No. 2000-169527 that a polymer having a carbonyl group-containing group and a nitrogen-containing heterocyclic group in a side chain exhibits rubber properties and mechanical strength by forming hydrogen bonds. Describes thermoplastic elastomers and thermoplastics which are flowable and recyclable by hydrogen bond cleavage.

However, there is no known low-molecular-weight (monomer) silane coupling agent that is recyclable by heat and plays a role of linking an organic material and an inorganic material.

On the other hand, silane compounds having a divalent substituent which binds a hydrolyzable silyl group to a nitrogen-containing heterocyclic ring are known as metal surface treating agents. For example, an alkyl group (Japanese Unexamined Patent Publication No.
-287198), a urethane group having a fluorinated hydrocarbon having 2 to 16 carbon atoms (JP-A-7-309846), an ether group (JP-A-9-3770 and the like), and the like. As a whole, hydrogen bonding is difficult. Further, even when the organic group uses a functional group capable of hydrogen bonding, the substituent bonding to the organic material is not a nitrogen-containing heterocyclic ring, but a tertiary alkyl group which cannot hydrogen bond (Japanese Patent Application Laid-Open No. 6-340677). ) Or a polyoxyalkylene polymer that hardly undergoes hydrogen bonding (JP-A-7-18
No. 171) is only known.

[0007]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a strong adhesive force capable of forming a hydrogen bond with an organic material, having a silyl group, an organic group, and a nitrogen-containing heterocyclic ring and capable of recycling an adherend (organic material). It is an object of the present invention to provide a low-molecular-weight (monomer) novel silane coupling agent exhibiting the following.

Further, a second object of the present invention is to provide an adhesive force between an organic material and glass or a metal or the like containing a silane coupling agent, a carbonyl-containing group, a nitrogen-containing heterocyclic ring and an elastomer contained in the molecule. It is an object of the present invention to provide a composition which further enhances heat resistance and maintains heat recyclability.

[0009]

Means for Solving the Problems As a result of researches on silane coupling agents for many years, the present inventors have used a nitrogen-containing heterocyclic ring capable of hydrogen bonding to a substituent of a silane coupling agent bonded to an organic material, and By using an organic group capable of hydrogen bonding to form a higher-order cross-link of hydrogen bonding, a low molecular weight (single amount) which expresses strong adhesion and enables recycling of an adherend (organic material) The present inventors have found a silane coupling agent of the present invention, and have completed the present invention.

[0010] That is, the first aspect of the present invention is that 1) a nitrogen-containing heterocycle, a urethane bond, a thiourethane bond, a urea bond, a thiourea bond, an amide bond, a thioamide bond, an ester bond, a thioester bond, an amino bond Provided is a silane coupling agent having an organic group containing at least one selected from the group consisting of thioether (sulfide) bonds and a hydrolyzable silyl group. Here, the organic group is a divalent hydrocarbon group containing a functional group such as the urethane bond and the thiourethane bond. According to the present invention, the first object can be achieved.

Further, the present invention provides the following inventions. 2) A silane coupling agent represented by the following general formula (1).

Embedded image (R ¹ and R ² may be the same or different;
12 hydrocarbon groups which may contain oxygen; n is an integer of 0 to 2; X is a nitrogen-containing heterocyclic ring which may have a substituent; Y is a urethane bond, a thiourethane bond, a urea bond, a thiourea bond A substituent containing at least one selected from the group consisting of amide bond, thioamide bond, ester bond, thioester bond, amino bond and thioether (sulfide) bond;
Or an aralkylene group having 6 to 12 carbon atoms. )

3) The second aspect of the present invention is a method according to 1) or 2).
And a polymer composition comprising the silane coupling agent described in (1). According to the present invention, the second object can be achieved.

The present invention also provides the polymer composition according to 3), wherein the polymer is an elastomer having a carbonyl-containing group and a nitrogen-containing heterocycle in a molecule.

[0014] 4) The third aspect of the present invention relates to 1) or 2).
And a primer for bonding glass or metal and rubber, comprising the silane coupling agent described in (1).

Further, the present invention provides the adhesive primer according to 5), which contains an elastomer having a carbonyl-containing group and a nitrogen-containing heterocyclic ring in the molecule.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The silane coupling agent according to the first aspect of the present invention will be described in detail below. The first aspect of the present invention is a nitrogen-containing heterocyclic ring, a specific organic group capable of hydrogen bonding to bond the nitrogen-containing heterocyclic ring and a hydrolyzable silyl group,
It is a silane coupling agent having a hydrolyzable silyl group.

First, the nitrogen-containing heterocycle will be described. The nitrogen-containing heterocycle needs to have a structure capable of hydrogen bonding. Such a nitrogen-containing heterocyclic ring is not particularly limited,
As long as the heterocycle contains a nitrogen atom, a heterocycle other than a nitrogen atom in the heterocycle, such as a sulfur atom, an oxygen atom, a phosphorus atom, or the like can be used.
The reason for using a heterocyclic compound capable of hydrogen bonding is that the presence of a heterocyclic structure increases the hydrogen bonding power described later. Further, the heterocyclic ring may have a substituent, and examples of the substituent include a methyl group, an ethyl group, an (iso) propyl group,
Alkyl group such as hexyl group, methoxy group, ethoxy group,
Examples include alkoxy groups such as (iso) propoxy groups, groups consisting of halogen atoms such as fluorine, iodine, and chlorine, cyano groups, amino groups, aromatic hydrocarbon groups, ester groups, ether groups, acyl groups, thioether groups, and the like. , Can be used in combination. These substitution positions are not particularly limited, and the number of substituents is not limited. These substituents preferably have a site capable of hydrogen bonding.

Examples of such a nitrogen-containing heterocyclic ring include, for example, pyrrololine, pyrrolidone, oxindole (2-
Oxindole), indoxyl (3-oxindole), dioxindole, isatin, indolyl,
Phthalimidine, β-isoindigo, monoporphyrin, diporphyrin, triporphyrin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, phyroerythrin, imidazole,
Pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole, imidazoline, imidazolone, imidazolidone, hydantoin, pyrazoline, pyrazolone, pyrazolidone, indazole, pyridoindole, purine, cinnoline, pyrrole, pyrroline, indole, indolin, oxylindole, Carbazole, phenothiazine, indolenine, isoindole, oxazoles, thiazoles,
Isoxazoles, isothiazole, oxadiazole, thiadiazole, oxatriazole, thiatriazole, phenanthroline, oxazine, benzoxazine, phthalazine, pteridine, pyrazine, phenazine, tetrazine, benzoxazole, benzoisoxazole, anthranyl, benzothiazole, benzofurazan, Pyridine, quinoline, isoquinoline, acridine, phenanthridine, anthrazolin, naphthyridine, thiazine, pyridazine, pyrimidine, quinazoline,
Quinoxaline, triazine, adenine, guanine, thymine, cytosine and the like.

The nitrogen-containing heterocyclic ring is preferably a 5- or 6-membered ring, and more preferably a 5-membered ring. This is because the dipole moment is large and electrostatic interaction is added in addition to hydrogen bonding. As typical examples of the nitrogen-containing 5-membered cyclic heterocycle, the following compounds are preferably exemplified. Those having various substituents can also be used.

Embedded image

Further, a cycloalkyl group, an aromatic ring and the like, for example, a condensed benzene ring and a condensed monocyclic heterocycle may be used. For example, the following condensed rings can be mentioned.

Embedded image The heterocyclic ring can be used with or without aromaticity, but is preferably used because it has a high π-π interaction.

The nitrogen-containing heterocyclic ring needs to be capable of hydrogen bonding as described above, but preferably has two or more ring-constituting nitrogen atoms. This is because if there are two or more ring-constituting nitrogen atoms, the crosslinking density due to hydrogen bonding increases, and a strong adhesive force can be exhibited. More preferably, it is a nitrogen-containing heterocycle having at least one nitrogen to which hydrogen is bonded and at least one nitrogen having no hydrogen. That is, it is a nitrogen-containing heterocycle having hydrogen capable of hydrogen bonding (donor) and nitrogen capable of acting as an acceptor of hydrogen. Here, the donor and the acceptor will be described later. Representative examples of such more preferred nitrogen-containing heterocycles include, for example, pyridine, pyrazole, imidazole, triazole, tetrazole, thiadiazole and the like. Among them,
1,2,4-triazole is particularly preferred.

The position at which the nitrogen-containing heterocycle is bonded to a specific organic group described below is not particularly limited, but is preferably 4-position for a 6-membered ring, 1-position, 3-position or 4-position for a 5-membered ring.
The position is preferred, and the first and third positions are particularly preferred. This is because hydrogen bonding between molecules can be prioritized over intramolecular.

Next, an organic group that bonds a nitrogen-containing heterocyclic ring to a hydrolyzable silyl group will be described. This organic group must contain at least one substituent capable of hydrogen bonding. This is because an organic group and an organic material form a hydrogen bond, the crosslink density of the hydrogen bond is increased, and a strong adhesive force is developed. Specific examples of such a hydrogen bondable substituent include a urethane bond, a thiourethane bond,
It is a urea bond, a thiourea bond, an amide bond, a thioamide bond, an ester bond, a thioester bond, an amino bond or a thioether (sulfide) bond. The organic group is
One or more such substituents may be contained, and the following organic groups may be mentioned.

Embedded image

Among these substituents, urethane bond, thiourethane bond, urea bond, thiourea bond, amide bond,
Since the thioamide bond has an acceptor (such as carbonyl oxygen) capable of hydrogen bonding and a donor (hydrogen) in its group, the crosslink density due to hydrogen bonding increases, which is preferable. Among these, a urethane bond, a urea bond, and an amide bond are particularly preferable because a strong hydrogen bond is developed.

The organic group may be an organic group consisting of only a substituent capable of hydrogen bonding as exemplified above, or may contain an organic group other than these substituents. That is,
The nitrogen-containing heterocyclic ring and / or the hydrolyzable silyl group and the hydrogen-bondable substituent may be directly bonded, and the nitrogen-containing heterocyclic ring and / or the hydrolyzable silyl group and It may be bonded to the substituent capable of hydrogen bonding via another organic group.

The organic group other than the hydrogen-bondable substituent is not particularly limited, but includes, for example, an alkylene group such as a methylene group, an ethylene group and a propylene group; an alkenylene group such as a vinylene group and a propenylene group; Groups, alkynylene groups such as propynylene groups; phenylene groups; aralkylene groups such as xylylene groups.
From the viewpoints of compatibility between the polymer which is an organic material and the silane coupling agent containing the organic group and availability of raw materials, these organic groups may be alkylene groups having 1 to 10 carbon atoms or carbon atoms. 6-12 aralkylene groups are preferred. Ethylene groups and propylene groups are particularly preferred from the viewpoint of formation of hydrogen bonds and compatibility between the organic material and the silane coupling agent.

These groups can be introduced in advance into the nitrogen-containing heterocyclic ring and the silane compound described later, or can be introduced separately and separately.

Next, the hydrolyzable silyl group will be described. The silyl group used in the present invention needs to have hydrolyzability. This is because adhesiveness is developed by a covalent bond generated by a dehydration condensation reaction between a silanol group of glass or a hydroxyl group on a metal surface and a silyl group. The substituent on this silyl group is not particularly limited, for example,
An alkoxyl group, a halogen group and the like, and a silyl group having hydrolyzability, for example, a trichlorosilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group,
Examples include a trimethoxysilyl group, an ethyldiethoxysilyl group, a diethylethoxysilyl group, a triethoxysilyl group, a tris (2-methoxyethoxy) silyl group, an ethyldimethoxysilyl group, and a methyldiethoxysilyl group.

The number of these groups is not particularly limited, but it is preferable to have two or more. This is because the covalent bond generated by the condensation reaction has a high-order cross-linking structure, and the bonding force between the glass or metal surface and the silicon of the silyl group becomes strong, thereby increasing the adhesive force. A silyl group having three of these groups, such as a trimethoxysilyl group, a triethoxysilyl group, and a trichlorosilyl group, is more preferred. In particular, an alkoxy group is preferable as the hydrolyzing group, and specifically, a trimethoxysilyl group and a triethoxysilyl group are preferable in terms of moderate reactivity and safety of the eliminated product.

The method for producing the silane coupling agent of the present invention is as follows:
For example, it can be produced by reacting three components of a nitrogen-containing heterocyclic ring, a silyl group, and an organic group bonding these, or a precursor that becomes a part of a specific bonding group of the organic group. By reacting a nitrogen-containing heterocyclic compound or silane compound having a substituent (for example, an isocyanate group or an amino group) as a substituent with a silane compound or nitrogen-containing heterocyclic compound having a substituent corresponding to the precursor. You can also. Specifically, in a silane coupling agent having a urea bond as an organic group, a nitrogen-containing heterocyclic compound having an amino group and a silane compound having an isocyanate group are reacted in an anhydrous solvent. As a method for producing a silane coupling agent having another bond, isocyanate silane,
Nitrogen containing one or more silane compounds selected from epoxy silane, vinyl silane, acryl silane (methacryl silane) or chloro silane and one or more groups selected from amino group, hydroxyl group or thiol group A method of reacting a heterocyclic compound in an anhydrous solvent may be used.

In the silane coupling agent of the present invention, the hydrogen-bondable group of the organic material and the nitrogen-containing heterocyclic ring are hydrogen-bonded, and the organic group is also hydrogen-bonded. And a bond between the nitrogen-containing heterocycle and the organic material occurs. Also, silyl groups are hydrolyzed, which forms covalent bonds with glass and metal surfaces. Therefore, the silane coupling agent of the present invention is bonded to glass or the like by a covalent bond, and is bonded to an organic material by a higher-order cross-linking hydrogen bond. Also, hydrogen bonds are thermotropic,
When used at room temperature, a crosslinked structure is formed, and when heated, the bond is broken. In other words, one hydrogen bond itself is a weaker bond than a covalent bond.
Expresses strength comparable to covalent bonds. This hydrogen bond forms a bond at room temperature, but the bond is broken when heated, and the formation and cleavage reaction of the hydrogen bond can be repeatedly reproduced. Therefore, in the bonding between glass and the like and an organic material using the silane coupling agent of the present invention, the hydrogen bond is broken by heating, the organic material and the silane compound are easily separated, and the organic material can be recycled.

The use of the silane coupling agent of the present invention is as follows.
It is not particularly limited, and is suitably used for, for example, a hot melt adhesive, a sealing agent, and a sealant. In particular,
When included in the polymer, especially around the car, for example, tire tread, carcass; exterior radiator grille, side molding, garnish (pillar, rear, cowl top), aero parts (air dam, spoiler), wheel cover, weather strip, Cow belt grill, air outlet louver, air scoop, food bulge, ventilation port parts, anti-fouling parts (over fender,
Side seal panels, moldings (windows, hoods, door belts)), marks; doors, lights, parts for interior window frames such as wiper weatherstrips, glass runs, glass run channels; air duct hoses, radiator hoses, brake hoses; crankshaft seals , Valve stem seal, head cover gasket, A / T oil cooler hose, transmission oil seal, P / S hose, lubricating oil system parts such as P / S oil seal; fuel hose, emission control hose, inlet filler hose, tire flams Fuel-related parts such as; anti-vibration parts such as engine mount and in-tank pump mount;
Boots such as CVJ boots, rack and pinion boots;
Air conditioning components such as A / C hoses and A / C seals; Belt components such as timing belts and accessory belts; Sealers such as windshield sealers, vinyl plastisol sealers, anaerobic sealers, body sealers, and spot weld sealers And the like. Further, when the resin or rubber which causes cold flow at room temperature is contained as a rubber modifier, for example, as a flow-preventing agent, flow during extrusion and cold flow can be prevented.

The preferred silane coupling agent of the present invention is represented by the following formula (1).

Embedded image (R ¹ and R ² may be the same or different;
12 hydrocarbon groups which may contain oxygen; n is an integer of 0 to 2; X is a nitrogen-containing heterocyclic ring which may have a substituent; Y is a urethane bond, a thiourethane bond, a urea bond, a thiourea bond A substituent containing at least one selected from the group consisting of amide bond, thioamide bond, ester bond, thioester bond, amino bond and thioether (sulfide) bond;
Or an aralkylene group having 6 to 12 carbon atoms. That is, when the nitrogen-containing heterocycle X and the silyl group form an organic group -A
-Y-B-. Where R ₁ ,
The hydrocarbon group of R ₂ which may contain oxygen having 1 to 12 carbon atoms is not particularly limited, and includes, for example, a hydrocarbon group having 1 to 12 carbon atoms or an ether group, a carbonyl group, a hydroxyl group and the like therein. be able to. Specifically, a methyl group, an ethyl group, an alkyl group such as a propyl group, a methoxymethyl group,
Examples thereof include an ether group-containing group such as a 2-ethoxyethyl group, a methoxyethyl group, and an ethoxymethyl group, and a carbonyl group-containing group such as an acetyl group.

As the nitrogen-containing heterocyclic ring, any of those described above can be used, but those having a substituent (for example, an amino group, a hydroxyl group, etc.) which is a precursor of a specific bonding group Y capable of hydrogen bonding are to be used. Can be. The nitrogen-containing heterocycle containing such a substituent is not particularly limited, and specifically, ethylene dipyridyl, trimethylene dipyridyl, dipyridylamine, 2-benzimidazole urea, pyrrole-2-
Carboxylic acid, 4 (or 2) -hydroxymethylpyridine,
2 (or 4)-(β-hydroxyethyl) -pyridine, 2
(or 4)-(2-aminoethyl) -pyridine, 2 (or
4) -aminopyridine, 2,6-diaminopyridine, 2
-Amino-6-hydroxypyridine, acetoguanamine, citrazic acid, 1,2,4-triazole, 3-amino-1,2,4-triazole, 3-aminomethyl-
1,2,4-triazole, 3-methylamino-1,
2,4-triazole, 3-methylol-1,2,4-
Triazole, 3-hydroxy-1,2,4-triazole, 2-hydroxytriazine, 2-aminotriazine, 2-hydroxy-5-methyltriazine, 2-amino-5-methyltriazine, 2-hydroxypyrimidine, 2-amino Pyrimidine, 2-aminopyrazine, 2-
Hydroxypyrazine, 6-aminopurine, 6-hydroxypurine and the like. Among them, 3-amino-
1,2,4-triazole, 3-aminomethyl-1,
2,4-triazole, 3-methylamino-1,2,4
-Triazole, 3-methylol-1,2,4-triazole, 3-hydroxy-1,2,4-triazole and the like are preferred. 3-Amino-1,2,4-triazole is particularly preferred.

In the formula (1), the organic group is -AY
It is a group represented by -B-. This organic group is a direct bond, that is, a specific substituent Y such as a urethane bond and a nitrogen-containing heterocyclic ring and / or a silyl group are bonded via no other organic group, or an alkyl group having 1 to 10 carbon atoms. Alternatively, it is necessary to bond through an aralkyl group having 6 to 12 carbon atoms.

As the silyl group, any of those described above can be used, but a substituent (for example, an amino group, an isocyanate group, etc.) which is a precursor of a specific bonding group Y capable of hydrogen bonding can be used.
Can be used. The silane compound containing such a substituent is not particularly limited, and specifically,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane,
N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-
Aminopropyltriethoxysilane, N-phenyl-γ
Amino-containing silane compounds such as aminopropyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ
-Mercapto group-containing silane compounds such as mercaptopropylmethyldimethoxysilane and γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyl Epoxy group-containing silane compounds such as dimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane;
-Carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-
Carboxysilane compounds such as aminopropyltrimethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanateethyltrimethoxy Silane, γ
-Isocyanate group-containing silane compounds such as isocyanate ethyltriethoxysilane, γ-isocyanateethylmethyldiethoxysilane, γ-isocyanateethylmethyldimethoxysilane; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane,
Vinyl group-containing silane compounds such as vinyl tris (β-methoxyethoxy) silane; γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane Methacryloxy group-containing silane compounds such as silane; γ
Halogen-containing silane compounds such as -chloropropyltrimethoxysilane. Among them, γ
-Isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatoethyltrimethoxysilane, γ-isocyanatoethyltriethoxysilane, γ- Isocyanate group-containing silane compounds such as isocyanate ethylmethyldiethoxysilane and γ-isocyanateethylmethyldimethoxysilane, and γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyl Epoxy groups such as dimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane Yes silane compounds are preferred.

The polymer composition according to the second embodiment of the present invention will be described in detail below. A second aspect of the present invention is a polymer composition containing the above silane coupling agent.

In the composition of the present invention, one or more of the above silane coupling agents can be used.
When two or more kinds are used, the mixing ratio of the silane coupling agent is not particularly limited, and any mixing ratio can be used. The content of the silane coupling agent in the composition is 0.1 to 100 parts by mass of the polymer described below.
50 parts by mass. Within this range, only the adhesion can be improved without impairing the physical properties of the polymer. It is preferably from 1 to 30 parts by mass, particularly preferably from 10 to 30 parts by mass.

The polymer in the composition of the present invention is not particularly limited, but specifically, a phenol resin which is a thermosetting resin such as a thermoplastic resin such as polyethylene (PE), polypropylene (PP) and polystyrene (PS). , Epoxy resins, polyurethane resins, etc., thermoplastic elastomers such as styrene, vinyl chloride, urethane, etc., thermosetting elastomers such as silicone, urethane, etc., natural rubber, isoprene rubber (IR) which is a synthetic rubber, butadiene rubber (BR), styrene-butadiene rubber (SB
R), butyl rubber (IIR), chloroprene rubber (C
R), ethylene propylene rubber (EPM, EPDM) and the like, and acrylonitrile-butadiene rubber (NBR) which is a special rubber, and the like. These polymers are 1
Species or two or more can be used. When two or more kinds are used, the mixing ratio of the polymer is not particularly limited, and any mixing ratio can be used.

The polymer is preferably a polymer or an elastomer having a site capable of hydrogen bonding in the molecule. In particular, polymers or elastomers having both hydrogen bond donor and acceptor reaction sites are more preferred.
This is because the affinity between the silane coupling agent and the polymer in the composition becomes good, and a higher-order structure of hydrogen bonding is formed, so that the bonding strength becomes strong. Specifically, a polymer having a site capable of hydrogen bonding to the main chain, such as an epoxy resin or a polyurethane resin, or a polymer or an elastomer having a side chain in which a carboxyl group, an amino group, an epoxy group, or the like is grafted is used. No.

The composition according to the second aspect of the present invention comprises a reinforcing agent (filler), an antioxidant, an antioxidant, a pigment and a tackifier (tackifier) as long as the object of the present invention is not impaired. ) And the like. The content of these additives and the like is 10% of the polymer in the present composition.
The amount is preferably from 0.1 to 100 parts by mass, particularly preferably from 1 to 70 parts by mass, based on 0 parts by mass.
If the amount is less than 0.1 part by mass, the effect of the reinforcing material or the like cannot be expected, and if it exceeds 100 parts by mass, the composition becomes too hard.

Examples of the reinforcing agent (filler) include carbon black, fumed silica, calcined silica, precipitated silica, crushed silica, fused silica, diatomaceous earth, iron oxide,
Examples include zinc oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, pyrite clay, kaolin clay and calcined clay. Examples of the anti-aging agent include hindered phenol compounds, aliphatic and aromatic hindered amine compounds, and the like. Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA). As a pigment,
Titanium dioxide, zinc oxide, ultramarine, redwood, lithopone,
Examples include inorganic pigments such as lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate, and organic pigments such as azo pigments and copper phthalocyanine pigments. Examples of the tackifier include rosins, terpene-based resins, aliphatic hydrocarbon resins, aromatic hydrocarbon resins, phenol-based resins, and chromanindene-based resins for the purpose of improving adhesiveness and adjusting viscosity.

The method for producing the composition is not particularly limited. For example, the composition can be produced by mixing with a roll, a kneader, an extruder, a universal stirrer, or the like.

The hydrogen bonds in the composition are formed from a donor and an acceptor. In the composition of the present invention, either the polymer or the silane coupling agent may be a donor or an acceptor.

The term “donor” as used herein means a hydrogen that forms a hydrogen bond and a negative atom or a substituent containing a negative atom that serves as a proton donor (proton donor) that forms a partially ionic covalent bond. Say. Examples of the negative atom include an oxygen atom and a nitrogen atom. Substituents containing these negative atoms, i.e., donors include -OH, -NH-,
Specific examples include —NH ₂ and —SH, and specifically, preferably include an alcoholic hydroxyl group, a phenolic hydroxyl group, a hydroxyl group in a carboxyl group of a carboxylic acid (including a fatty acid), an amino group, an amide group, and a mercapto group. be able to.

An acceptor is a proton acceptor (proton acceptor) that forms a hydrogen bond with hydrogen.
A negative atom or a substituent containing a negative atom.
Negative atoms in the acceptor include a nitrogen atom, an oxygen atom, and a sulfur atom. Substituents containing these negative atoms, that is, acceptors include -CO-, -N
—NR ¹ R ² (R ¹ and R ² are each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), —COO
H, —COOR ³ (R ³ is an alkyl group or an aryl group having 1 to 20 carbon atoms), —C≡N, —SCN, ＮＯNOH,
_{-NHCONH 2, -CONH -, = SO} , -CSS
_{H, -CSNH 2, -COSH, -CSOH} , -SC
N, -OP (= O) (OR ⁴ ) ₂ (R ⁴ is a hydrogen atom, a phenyl group or an alkyl group having 1 to 20 carbon atoms), a 5-membered ring containing a nitrogen atom as an isomer atom or 6
And the like. Including a nitrogen atom as an isomer 5
Specific examples of the six-membered or six-membered ring include pyridine,
Examples include imidazole, triazole, triazine, pyrimidine, pyrazine, quinoline and the like.

Such hydrogen bonds are thermotropic, and form a crosslinked structure when used at normal temperature, and are broken when heated. In other words, one hydrogen bond itself is a weak bond as compared with a covalent bond, but by assembling a large number, a strength comparable to a covalent bond is exhibited. This hydrogen bond forms a bond at room temperature, but the bond is broken when heated, and the formation and cleavage reaction of the hydrogen bond can be repeatedly reproduced. Therefore, in the composition of the present invention, the hydrogen bond is cleaved by heating, and the composition can be easily separated from the silane compound, and the polymer can be recycled.

The use of the composition is not particularly limited. For example, if a polymer having rubber elasticity is used, it can be used for various rubber applications, and if it is used as an adhesive with glass or metal, a strong adhesive force is obtained. Obtained and heat recyclable. Specifically, it is particularly suitably used for everything around the automobile. In addition, when incorporated in a sealing agent, a sealant, or a rubber modifier, for example, a resin or rubber that causes a cold flow at room temperature, it can be used as a flow inhibitor capable of preventing the flow during extrusion and the cold flow.

As the polymer used in the composition of the present invention,
Particularly preferred are elastomers having a carbonyl-containing group and a nitrogen-containing heterocycle in the molecule. When an elastomer having both a hydrogen bond donor and an acceptor reactive site is used, the affinity between the silane coupling agent and the polymer in the composition becomes good, and a higher-order structure of the hydrogen bond is formed. This is because the bonding strength becomes strong. Here, the thermoplastic elastomer having a reactive site capable of forming a hydrogen bond is a natural polymer or a synthetic polymer elastomeric polymer having a carbonyl-containing group and a nitrogen-containing heterocyclic ring in a side chain independently or in common. It is introduced into the side chain in a branched manner, and the formation and collapse of hydrogen bonds can be caused reversibly by heat due to temperature changes,
It is a recyclable elastomer with improved heat cohesion.

The thermoplastic elastomer which is particularly preferable as the polymer used in the composition will be described. A particularly preferred thermoplastic elastomer is an elastomer obtained by introducing a carbonyl-containing group and a nitrogen-containing heterocyclic ring into a side chain of a natural polymer or a synthetic polymer elastomeric polymer.
The elastomeric polymer serving as the main chain is a natural polymer or a synthetic polymer generally known as a rubber elastic material for vulcanization (crosslinking, curing). Specific examples of such an elastomeric polymer include, for example, natural rubber, isoprene rubber, butadiene rubber, 1,2-butadiene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, butyl rubber, ethylene-propylene diene rubber ( Diene rubbers such as EPDM), ethylene-propylene rubber (EPM), ethylene-butene rubber (EBM), chlorosulfonated polyethylene, olefin rubbers such as acrylic rubber and fluororubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber , Urethane rubber and the like. In addition, a thermoplastic elastomer containing a resin component (TP
E), for example, polystyrene-based elastomeric polymers (SBS, SIS,
SEBS), a polyolefin-based elastomeric polymer, a polyvinyl chloride-based elastomeric polymer, a polyurethane-based elastomeric polymer, a polyester-based elastomeric polymer or a polyamide-based elastomeric polymer. The elastomeric polymer as described above may be either liquid or solid. The molecular weight is not particularly limited and can be appropriately selected depending on the purpose of use, crosslink density, and the like. However, when importance is placed on fluidity during heating (decrosslinking) of the thermoplastic elastomer, liquid rubber is preferable. For example, in diene rubbers such as isoprene rubber and butadiene rubber, the weight average molecular weight is preferably 1,000 to 100,000,
About 50,000 is particularly preferable. On the other hand, when importance is placed on strength, solid rubber is preferred. For example, in the case of diene rubbers such as isoprene rubber and butadiene rubber, the weight average molecular weight is preferably 100,000 to 2,000,000, and
It is particularly preferably from 10,000 to 1.5 million. As the elastomer, a polymer or an elastomer having no hydrogen bondable site in the molecule is preferable, and it is preferable that the hydrogen bond cross-linking site is involved in cross-linking at a pinpoint and the main chain has no interaction. This is because the rubber elasticity is excellent.

The carbonyl-containing group to be introduced into the side chain of the elastomer is not particularly restricted but includes, for example, amide, ester, imide and carboxyl groups. Further, the compound into which such a group can be introduced is not particularly limited, and examples thereof include a carboxylic acid compound and a derivative thereof. Examples of the carboxylic acid compound include an organic acid having a saturated or unsaturated hydrocarbon group. As the hydrocarbon group, any of aliphatic, alicyclic, and aromatic carboxylic acids can be used. Examples of the carboxylic acid derivative include carboxylic anhydride, ester, ketone, amino acid, amide, imide, thiocarboxylic acid (mercapto group-containing carboxylic acid) and the like.

Specifically, acrylic acid, malonic acid, maleic acid, which are carboxylic acids and carboxylic acids having a substituent,
Succinic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, p-phenylenediacetic acid, p-hydroxybenzoic acid, p-aminobenzoic acid, mercaptoacetic acid and the like; succinic anhydride, maleic anhydride which is an acid anhydride; Glutaric anhydride, phthalic anhydride, propionic anhydride, benzoic anhydride, etc., aliphatic esters such as acrylic esters, maleic esters, malonic esters, succinic esters,
Glutaric acid ester, ethyl acetate and the like, phthalic acid ester which is an aromatic ester, isophthalic acid ester, terephthalic acid ester, ethyl-m-aminobenzoate, methyl-p-hydroxybenzoate and the like, ketone quinone, anthraquinone, naphthoquinone and the like, Amino acids such as glycine, tricine, bicine, alanine, valine, leucine, serine, threonine, lysine, aspartic acid, glutamic acid, cysteine, methionine, proline, and N- (p-aminobenzoyl) -β-alanine;
Amides such as maleamide, maleamic acid (maleic monoamide), succinic monoamide, 5-hydroxyvaleramide, N-acetylethanolamine, N,
N'-hexamethylenebis (acetamido), malonamide, cycloserine, 4-acetamidophenol, p
Imides such as maleimide and succinimide (succinimide) such as acetamidobenzoic acid; Among these, the carbonyl-containing group used in the thermoplastic elastomer is preferably derived from a cyclic acid anhydride such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride, and is particularly preferably derived from maleic anhydride. It is more preferable that it is removed.

The nitrogen-containing heterocycle to be introduced into the side chain of the elastomer is not particularly limited, and any of the above-mentioned nitrogen-containing heterocycles can be used. The nitrogen-containing heterocyclic ring may be bonded to the main chain of the elastomer by direct covalent bonding, but preferably has a bonding group between the heterocyclic ring and the elastomer constituting the main chain, It is preferable that they are chemically bonded (covalently bonded) to the main chain via the bonding group. For example, a nitrogen-containing 5-membered cyclic heterocyclic ring containing the nitrogen-containing 5-membered cyclic heterocycle and a group capable of covalently bonding to an elastomer constituting a main chain.
It can be introduced by a membered heterocyclic compound. Examples of such a functional group include an amino group, a hydroxyl group, a carboxyl group, and a thiol group. As a bonding group between these functional groups and the main chain of the elastomer,
Preferable examples include a sulfide group, an amide group, an ester group, a methylene group, and an ethylene group. Among these, an amide group is preferable because a complementary hydrogen bond is formed. The bonding position between the nitrogen-containing heterocyclic ring and the bonding group is not particularly limited, and the heterocyclic ring and the bonding group may be directly bonded to each other. They may be combined. When covalently bonded to the side chain of the elastomer, these may be bonded to the main chain as side chains independent of each other, or the carbonyl group and the nitrogen-containing heterocyclic ring may be branched into the same side chain. You may have. In particular, from the viewpoint of synthesis, it is preferable to have them in the same side chain, and examples thereof include those having the structures represented by the following formulas (2), (3) and (4).

[0054]

Embedded image Here, R represents a nitrogen-containing heterocyclic ring, and includes all the heterocyclic rings exemplified above. The structures represented by the formulas (2) to (4) are preferably bonded to the main chain of the elastomer at the α-position or the β-position in the formula.

The side chain portion composed of these groups is based on 100 mol% of the main chain portion per mole of monomer unit.
It is preferable to have it at a rate of 0.1 to 50 mol%, and more preferably at a rate of 1 to 35 mol%. Within this range, the interaction between these side chains is well-balanced between molecules or within the molecule, a higher-order hydrogen bond with the silane coupling agent can be formed, and a strong bond can be achieved. The ratio between the carbonyl-containing group and the nitrogen-containing heterocyclic group is not particularly limited.

The method for producing the thermoplastic polymer is not particularly limited, and it can be synthesized by an ordinary method. Among the thermoplastic polymers, those having a carbonyl-containing group and a nitrogen-containing heterocyclic ring in the same side chain, for example, by reacting an elastomer modified with a carbonyl-containing group with a compound capable of introducing a nitrogen-containing heterocyclic ring, It is obtained by covalently bonding the carbonyl-containing group and the nitrogen-containing heterocycle.
Specifically, a toluene solution containing a diene-based rubber such as butadiene rubber and maleic anhydride or mercaptoacetic acid is stirred at room temperature or under a nitrogen atmosphere for 5 hours under a nitrogen atmosphere to precipitate the reaction mixture in methanol, and Obtained by drying. As such a modified elastomer, a commercially available product can be used. For example, LIR-4
03 (manufactured by Kuraray), maleic anhydride-modified isoprene rubber such as LIR-410A (prototype of Kuraray), LIR-
Modified isoprene rubber such as 410 (manufactured by Kuraray), carboxyl-modified nitrile rubber such as Clinac 110, 221 and 231 (manufactured by Policer), CPIB (manufactured by Nisseki Chemical), HRPIB (produced by Nisseki Chemical Lab) Examples thereof include carboxyl-modified polybutene, Nucrel (manufactured by Mitsui DuPont Polychemicals), and Yucalon (manufactured by Mitsubishi Chemical Corporation). Alternatively, the compounds capable of introducing a carbonyl-containing group and a nitrogen-containing heterocycle may be bonded in advance, and then bonded to a side chain of the elastomer.

When synthesizing a thermoplastic polymer having a carbonyl-containing group and a nitrogen-containing heterocycle independently in the side chain, a monomer capable of forming the main chain of the polymer is used during the production of the elastomer. The above-mentioned thermoplastic polymer can also be directly produced by copolymerizing with a monomer capable of introducing the above group, and a main chain (elastomer) is formed in advance by polymerization or the like, and then a compound capable of introducing the above group is used. Graft modification can also be performed. In each of the above production methods, whether each group of the side chain of the elastomer is independently bonded or bonded to each other is determined by N
It can be confirmed by commonly used analytical means such as MR and IR spectra.

Among the elastomers used in the present invention, the carbonyl-containing group and the nitrogen-containing 5-membered heterocyclic ring-containing group are preferably bonded to the same side chain of the preformed elastomer. The modified elastomer having an anhydride in the side chain is bonded to the nitrogen-containing heterocyclic ring at a temperature at which the nitrogen-containing heterocyclic ring can be chemically bonded (eg, covalently or ionically) with the cyclic acid anhydride group. Is preferred. (The acid anhydride opens the ring by this reaction.) The temperature at which the nitrogen-containing heterocyclic ring can chemically bond to the cyclic acid anhydride group varies depending on the type of the compound, but is usually about room temperature to about 150 ° C. The reaction time is usually about 1 to 5 hours.

One or more thermoplastic elastomers having a reactive site capable of forming a hydrogen bond can be used. When two or more kinds are used, the mixing ratio of the thermoplastic elastomer is not particularly limited, and any mixing ratio can be used.

The composition has a specific functional group capable of forming a hydrogen bond between the thermoplastic elastomer and the silane coupling agent, and both the elastomer and the silane coupling agent can form a hydrogen bond by themselves. In order to achieve the object, it is preferable to form a hydrogen bond between the elastomer and the silane coupling agent. In this case, the proton source of the substituent capable of hydrogen bonding is hydrogen bonded to the nitrogen of the nitrogen-containing heterocycle, hydrogen bonded to the carbonyl-containing group, or the like in the case of the elastomer. Examples of the silane coupling agent include hydrogen of an organic group such as a urea bond and hydrogen bonded to the ring-constituting nitrogen of a nitrogen-containing heterocycle. On the other hand, the proton accepting portion is a tertiary nitrogen of a nitrogen-containing heterocyclic ring in an elastomer, a carbonyl oxygen in a carbonyl-containing group, and a silane coupling agent is a carbonyl oxygen in an organic group such as a urea bond.
And tertiary nitrogen of a nitrogen-containing heterocycle. These hydrogen bonds are not specified, and may be bonded at any position. Further, the main chain may be involved in hydrogen bonding, and any of them may be a proton source.

As described above, when a thermoplastic elastomer having a reactive site capable of forming a hydrogen bond is used in the polymer of the composition, cross-linking by a higher-order hydrogen bond becomes possible, so that a stronger bonding force is obtained. Can be expected.

The adhesive primer according to the third embodiment of the present invention will be described in detail. A third aspect of the present invention is a glass and rubber bonding primer containing the silane coupling agent.

In the primer of the present invention, one or more of the above-mentioned silane coupling agents and a solvent can be used. When two or more kinds are used, the mixing ratio of the silane coupling agent is not particularly limited, and any mixing ratio can be used. The silane coupling agent is 1 to 100% by mass of the total solid content of the primer.
It is contained in the primer in a proportion of 50% by mass, preferably 5 to 30% by mass. If the amount is less than 1% by mass, the effect of the silane coupling agent is weak, and if it exceeds 50% by mass, storage stability and workability are adversely affected.

The solvent used in the present invention is not particularly limited, and a solvent having appropriate volatility is preferable. For example,
Examples include ethyl acetate, butyl acetate, cellosolve acetate, mineral spirit, toluene, xylene, dimethylacetamide, methyl ethyl ketone, acetone, n-hexane, methylene chloride, tetrahydrofuran, ethyl ether, dioxane and the like. These organic solvents can be used alone or in combination of two or more. The total solid content in the primer is 0.5 to 30% by mass, preferably 1 to 15% by mass. It is preferable to add a solvent so that the total solid content in the primer falls within this range, from the viewpoint of viscosity (ease of application) and adhesiveness.

The primer of the present invention can contain a polymer if necessary, and any of the above-mentioned polymers can be used as the polymer to be contained. A polymer having a main chain having rubber elasticity at room temperature is preferable. This is because the compatibility with the rubber of the adherend is good and the adhesive strength is improved. Specific examples include urethane-based thermoplastic elastomers and the like. In particular, a thermoplastic elastomer having a reaction site capable of forming a hydrogen bond is preferable. This is because the affinity with the silane coupling agent is improved, and cross-linking by higher-order hydrogen bonding becomes possible, so that stronger adhesive strength can be expected. Specific examples include a polymer having a site capable of hydrogen bonding to the main chain, such as an epoxy resin and a polyurethane resin, and a polymer having a side chain on which a carboxyl group, an amino group, an epoxy group, or the like is grafted. The content of the polymer is 0.5 to 5 when the total mass of the solid content of the primer is 100% by mass.
It is preferably 0% by mass, and particularly preferably 1 to 30% by mass. If the amount is less than 0.5% by mass, the effect is low, and if it exceeds 50% by mass, the viscosity becomes too high and the workability deteriorates.

The primer according to the third aspect of the present invention comprises:
Contains additives such as an adhesion promoter or all the above-mentioned reinforcing agents (fillers), an antioxidant, an antioxidant, a dehydrating agent (zeolite), and a pigment within a range not to impair the object of the present invention. Can be. The content of these additives and the like is 1 to 5 when the total mass of the solid content of the primer is 100% by mass.
It is preferably 0% by mass, particularly preferably 5 to 30% by mass. If it is less than 1% by mass, the reinforcing effect and the anti-aging effect cannot be expected, and if it exceeds 50% by mass, it becomes too hard and the fluidity deteriorates.

The method for producing the primer is not particularly limited.
Any of various known methods capable of sufficiently mixing the components can be applied, and examples thereof include mixing with a ball mill.

When the primer of the present invention contains a polymer, either the polymer or the silane coupling agent may be a hydrogen bond donor or an acceptor. Specific examples of the donor and the acceptor include all those described above.

The rubber as the adherend of the present invention is not particularly limited, and a natural polymer or a synthetic polymer generally known as a rubber elastic material for vulcanization (crosslinking, curing) can be used. Specifically, all of the above-mentioned diene rubber, olefin rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, urethane rubber, and the like, or thermoplastic elastomer containing a resin component (TPE) can be used. . As the adherend glass and metal,
It is not particularly limited, and can be used for various glasses and metals. The primer of the present invention is suitably used as a urethane-based adhesive, silicone-based, modified silicone-based, or polysulfide-based primer. Specifically, WS-100 (manufactured by Yokohama Rubber Co., Ltd.), WS-100H (manufactured by Yokohama Rubber Co., Ltd.), UH-30, and the like are preferably exemplified as the urethane-based adhesive, but are not limited thereto. . The silicone type is SS-310, silicone 7
0, etc., and the modified silicone type is preferably exemplified by Super II, and the polysulfide type is preferably exemplified by SC-500, but is not limited thereto.

The primer is used as a primer for bonding glass or metal and rubber. Specifically, it is particularly suitably used for everything around the automobile. As other uses, it is suitably used as a sealing agent for civil engineering and construction.

Particularly preferred as the polymer used for the primer of the present invention is an elastomer having a carbonyl-containing group and a nitrogen-containing heterocycle in the molecule. When an elastomer having both the hydrogen bond donor and acceptor reaction sites is used, the affinity between the silane coupling agent and the polymer in the primer becomes good, and a higher-order structure of hydrogen bonds is formed. This is because the bonding force becomes strong. Here, as the thermoplastic elastomer having a reactive site capable of forming a hydrogen bond, any of the above-mentioned thermoplastic elastomers can be used. More preferred are elastomers in which a carbonyl-containing group and a nitrogen-containing heterocycle are introduced into the side chain of a natural polymer or a synthetic polymer elastomeric polymer, all of which are described above.

The thermoplastic elastomer having a reactive site capable of forming a hydrogen bond can be used alone or in combination of two or more. When two or more kinds are used, the mixing ratio of the thermoplastic elastomer is not particularly limited, and any mixing ratio can be used.

[0073]

EXAMPLES The present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Γ-isocyanatopropyltrimethoxysilane (Y-5187, manufactured by Nippon Unicar) 41.10 g
(0.2 mol) dissolved in anhydrous acetone solution (58.
To 87 g), 16.82 g (0.2 mol) of 3-aminotriazole (manufactured by Nippon Carbide) was added.
Stir for 2 hours. After acetone was distilled off under reduced pressure, the residue was dried under reduced pressure to obtain the following alkoxysilane compound TS-1. The disappearance of the isocyanate group was confirmed by a reverse titration method using an amine. Also, generation of urea bond from IR (18
Absorption around 00 cm ^-1 ). Except that 4-aminopyridine was used instead of 3-aminotriazole,
In a similar manner, the following alkoxysilane compound TS
-2 was synthesized. Imidazole silane (IS) is a commercially available product (manufactured by Japan Energy, product number IS-100)
0) was used.

Embedded image

In a pressure kneader heated to 80 ° C., 350.0 g (6.07 mol; butyl unit) of butyl rubber under bromine was put, and after mastication for a short time, N- (1,3-dimethylbutyl) -N ′ was obtained. -Phenyl-p-phenylenediamine 3.5 g (1.0 phr), maleic anhydride 35.1
g (0.358 mol) and 38.0 g of xylene
(0.358 mol) was added and mixed for 10 minutes. Once the mixture was removed, the pressure kneader was set at 190 ° C. The removed mixture was placed in a kneader and kneaded for 40 minutes. Part of the obtained rubber is dissolved in toluene,
Purification was performed by performing a reprecipitation operation. By conducting IR analysis and ¹ H-NMR analysis using the purified product, the introduction of the acid anhydride skeleton was confirmed.
It was 0 mol%. This anhydrous maleated butyl rubber 3
57.7 g (0.113 mol; amount of acid anhydride), 3-
9.51 g of amino-1,2,4-triazole (0.1
13 mol) and N- (1,3-dimethylbutyl)
-N'-phenyl-p-phenylenediamine 3.54 g
(1.0 phr) was kneaded in a pressure kneader at a temperature of 100 ° C. for 20 minutes. IR analysis confirmed the introduction of the triazole ring.

A mixture of 600 g of polypropylene diol having a number average molecular weight of 2,000, 400 g of polypropylene triol having a number average molecular weight of 4,000, and 180 g of 4,4'-diphenylmethane diisocyanate (NCO / O
H = 1.6), and 630 g of dioctyl phthalate was further added thereto, and the mixture was stirred at 80 ° C. in a stream of N ₂ and reacted to synthesize a urethane prepolymer having 1.2% by mass of isocyanate groups.

<Example 1> Anhydrous maleated butyl rubber 1
00 parts by mass and 5 parts by mass of the silane coupling agent TS-1 were kneaded to obtain a composition. Float glass plate (5 × 25 × 140 mm) whose surface has been wiped with isopropanol
A band-shaped adhesive composition (5 × 15 × 100 mm) was brought into close contact with the substrate, and heated and pressed by a press machine (180 ° C. × 10 minutes, 4.9 MPa) so that the thickness of the composition became 3 mm. <Example 2> A silane coupling agent T was added to the above glass plate.
A 10% by mass toluene solution of S-1 was applied in the same manner as the primer. After the solution was applied, the solution was air-dried for about one hour, and adhered in the same manner as in Example 1. <Example 3> Thermocompression bonding was performed in the same manner as in Example 1 except that a urethane prepolymer was used instead of the anhydrous maleated butyl rubber. <Example 4> Adhesion was performed in the same manner as in Example 2 except that a urethane prepolymer was used instead of the anhydrous maleated butyl rubber. <Example 5> Thermocompression bonding was performed in the same manner as in Example 1, except that a silane coupling agent TS-2 was used instead of the silane coupling agent TS-1. <Example 6> Adhesion was performed in the same manner as in Example 2, except that a silane coupling agent TS-2 was used instead of the silane coupling agent TS-1. <Example 7> Thermocompression bonding was performed in the same manner as in Example 3, except that a silane coupling agent TS-2 was used instead of the silane coupling agent TS-1. <Example 8> Adhesion was performed in the same manner as in Example 4 except that a silane coupling agent TS-2 was used instead of the silane coupling agent TS-1.

<Comparative Example 1> Only an anhydrous maleated butyl rubber was kneaded in the same manner as in Example 1, and then heat-pressed in the same manner. <Comparative Example 2> Example 1 was repeated except that imidazole silane IS was used instead of the silane coupling agent TS-1.
Thermocompression bonding was performed in the same manner as described above. <Comparative Example 3> Adhesion was performed in the same manner as in Example 2 except that IS was used instead of the silane coupling agent TS-1. <Comparative Example 4> Thermocompression bonding was performed in the same manner as in Example 3, except that IS was used instead of the silane coupling agent TS-1. <Comparative Example 5> Adhesion was performed in the same manner as in Example 4 except that IS was used instead of the silane coupling agent TS-1.

Table 1 shows the results of various tests of the composition and the primer thus obtained.

[Table 1]

[Table 2]

The state of the rubber during kneading was evaluated by visually observing the rubber in the kneader, setting the uniform state to “good”, and gelling or bleeding the surface to “poor”.
And The evaluation of the sheet skin was evaluated as "good" when the rubber was formed into a belt shape and the surface was smooth, and "poor" when the other conditions were not obtained. The adhesiveness was evaluated by a peel test. In the test method, a cut of about 30 to 50 mm was made along the bonding interface in the test sample bonded by the method described above. This sample was fixed with a vice or the like, and a sharp cut was made at an angle of about 60 degrees with a knife while strongly pulling the end of the rubber at an angle of 90 degrees or more so as not to break with pliers or the like. At this time, the cut with the knife was made to reach the surface of the adherend (glass). The cut interval was set to about 3 to 5 mm, and this operation was repeated 10 times or more. Depending on the state of the cut rubber, thin-layer cohesive failure, cohesive failure and adhesion occurred. The term "adhesion" refers to a state in which the adherends only adhered but not adhered.
Regarding the recyclability of the rubber, the rubber which was peeled off by heating after bonding was mixed with a silane coupling agent again, and the case where bonding was possible in the same manner was evaluated as “Yes”, and the other cases were evaluated as “No”.

[0081]

According to the present invention, a novel low-molecular-weight (monomer) silane cup having both an organic group for bonding a hydrolyzable silyl group and a nitrogen-containing heterocycle and a nitrogen-containing heterocycle is provided. A silane coupling agent that is a ring agent, which forms a strong bond with the silane coupling agent, which forms a hydrogen bond with an organic material and the like, breaks the hydrogen bond by heating, and enables recycling of the adherend (organic material). Can be provided.
In addition, by mixing a silane coupling agent, a carbonyl-containing group, a nitrogen-containing heterocyclic ring, and an elastomer contained in the molecule, a complementary high-dimensional cross-linking hydrogen bond is formed, and glass and a metal or the like and an organic material are mixed. It is possible to provide a composition having higher adhesive strength and maintaining heat recyclability.

Continued on front page F-term (reference) 4H049 VN01 VP01 VQ59 VQ70 VR21 VR43 VU22 VW02 4J038 CA011 CA021 CA071 CA131 CB021 CB101 CB131 CC021 CD021 CQ011 DA051 DB001 DG001 DL031 DL06 DL09 GA03 GA06 GA08 GA09 GA03 PA11 PA19 PB07 PC02 PC03 PC07

Claims (6)

[Claims] (1) a nitrogen-containing heterocyclic ring; selected from the group consisting of a urethane bond, a thiourethane bond, a urea bond, a thiourea bond, an amide bond, a thioamide bond, an ester bond, a thioester bond, an amino bond and a thioether (sulfide) bond. A silane coupling agent comprising: an organic group containing at least one of the following; and a hydrolyzable silyl group. Here, the organic group is a divalent hydrocarbon group containing a functional group such as the urethane bond and the thiourethane bond. 2. A silane coupling agent represented by the following general formula (1). Embedded image (R ¹ and R ² may be the same or different;
12 hydrocarbon groups which may contain oxygen; n is an integer of 0 to 2; X is a nitrogen-containing heterocyclic ring which may have a substituent; Y is a urethane bond, a thiourethane bond, a urea bond, a thiourea bond A substituent containing at least one selected from the group consisting of amide bond, thioamide bond, ester bond, thioester bond, amino bond and oether (sulfide) bond; A and B are a direct bond or an alkylene having 1 to 10 carbon atoms Or an aralkylene group having 6 to 12 carbon atoms. ) 3. A polymer composition comprising the silane coupling agent according to claim 1 or 2. 4. The polymer according to claim 3, wherein the polymer has a carbonyl-containing group and a nitrogen-containing heterocycle in the molecule.
A polymer composition according to claim 1. 5. A primer for bonding glass or metal and rubber, comprising the silane coupling agent according to claim 1 or 2. 6. The adhesive primer according to claim 5, further comprising an elastomer having a carbonyl-containing group and a nitrogen-containing heterocycle in the molecule.