JP2018108935A - Silane compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silane compound that has high reactivity and affinity with organic polymer material such as rubber and also high reactivity with inorganic material such as silica and glass, and is useful as a silane coupling agent or an adhesion aid.SOLUTION: The present invention provides a silane compound represented by formula (I) (Ris H or an alkyl group; Ris an alkoxy group or an amino group substituted with one or more alkyl groups; n is an integer of 0-2; p is an integer of 1-10; q is an integer of 0-5; r is an integer of 0-5; s is an integer of 0-30; if p is 2 or more, each q is independently selected).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a silane compound. More specifically, the present invention relates to a silane compound having a low-polar reactive functional group and a hydrolyzable group.

  Conventionally, a silane compound having a reactive functional group and a hydrolyzable group is a silane coupling agent for improving the dispersibility between an organic polymer material such as rubber and an inorganic material such as silica in a rubber composition. Has been used. In addition, such silane compounds have been used as adhesive aids for improving adhesion to inorganic materials such as glass in adhesive compositions and sealant compositions.

  Usually, such a silane compound has a substituent such as a mercapto group, a polysulfide group, an amino group or an epoxy group as a reactive functional group highly reactive with an organic polymer material such as rubber, and silica or As a hydrolyzable group having high reactivity with an inorganic material such as glass, it has a substituent such as an alkoxysilyl group. For example, JP-A-8-259736 (Patent Document 1) discloses a polysulfide-based silane coupling agent. JP-A-11-335381 (Patent Document 2) discloses a silane compound having an amino group as a reactive functional group and a methoxy group as a hydrolyzable group.

JP-A-8-259736 JP 11-335381 A

  However, when a silane compound having a high-polar reactive functional group such as an amino group or an epoxy group is mixed with a low-polarity polymer material, the affinity between the silane compound and the organic polymer material decreases, resulting in poor dispersion or There was a tendency for poor mixing. In addition, when such a silane compound is added to an adhesive or a sealing agent, the affinity between the silane compound and the organic polymer material tends to decrease, and the adhesiveness to the inorganic material tends to decrease. On the other hand, when a silane compound having a reactive functional group with low polarity is added in order to increase the affinity with the organic polymer material, the reactivity with the organic polymer material is low, and the silane coupling agent or adhesion aid As the performance was insufficient.

  The present invention has been made in view of the above problems. The main object of the present invention is to have a high reactivity with organic polymer materials such as rubber, a low-polarity reactive functional group, and a hydrolyzable group with high reactivity with inorganic materials such as silica and glass. It is to provide a silane compound.

The silane compound according to the present invention is represented by the following general formula (I).
(In the above formula,
R ¹ is hydrogen or an alkyl group,
R ² is an alkoxy group or an amino group substituted with one or more alkyl groups,
n is an integer from 0 to 2,
p is an integer of 1 to 10,
q is an integer of 0 to 5;
r is an integer of 0 to 5;
s is an integer from 0 to 30,
When p is 2 or more, q is independently selected. )

In the embodiment of the present invention, R ² is preferably an amino group substituted with an alkoxy group having 1 to 30 carbon atoms or one or more alkyl groups having 1 to 30 carbon atoms.

In the embodiment of the present invention, R ² is preferably a methoxy group or an ethoxy group.

  According to the present invention, a silane coupling agent composition and an adhesion assistant composition that have high reactivity and affinity with organic polymer materials such as rubber and high reactivity with inorganic materials such as silica and glass. As a useful silane compound, it can be provided.

FIG. 1 shows a ¹ H-NMR chart of the silane compound synthesized in Reference Example 1. FIG. 2 shows a ¹³ C-NMR chart of the silane compound synthesized in Reference Example 1. FIG. 3 shows a chromatogram of the silane compound synthesized in Reference Example 1.

  In the present specification, “parts”, “%”, etc. indicating the blending are based on mass unless otherwise specified.

<Silane compound>
The silane compound according to the present invention is represented by the following general formula (I). Such a silane compound has a reactive functional group having a low active polarity and a high active site, and a hydrolyzable group. Therefore, the silane compound is used in combination with a polymer material having no polar group or the like. Even if it has excellent affinity (dispersibility), the reactivity with the polymer material can be maintained, and it can be suitably used as a silane coupling agent or an adhesion aid. Hereinafter, the reactive functional group and the hydrolyzable group in the silane compound according to the present invention will be described in detail.

(Reactive functional group)
The reactive functional group in the silane compound according to the present invention is a substituent containing the alicyclic hydrocarbon in the general formula (I). This substituent has a high active site (allylic hydrogen) while having low polarity as a whole reactive functional group, and has high reactivity with organic polymer materials such as rubber.

(Hydrolyzable group)
The hydrolyzable group in the silane compound according to the present invention is the substituent R ² in the general formula (I). The substituent R ² is highly reactive with inorganic materials such as silica and glass, and can form a bond between the silane compound and the inorganic material by a hydrolysis reaction.

In the general formula (I), R ¹ is hydrogen or an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, still more preferably an alkyl group having 1 to 20 carbon atoms, specifically, methyl Group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group and cyclohexyl group. Among them, methyl group and ethyl group Is preferred.

In the general formula (I), R ² is an alkoxy group, more preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 20 carbon atoms, or an amino group substituted with one or more alkyl groups. More preferably, it is an amino group substituted with one or more alkyl groups having 1 to 30 carbon atoms, more preferably an amino group substituted with one or more alkyl groups having 1 to 20 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group, and among these, a methoxy group or an ethoxy group is preferable. Examples of the amino group substituted with one or more alkyl groups include N-methylamino group, N, N-dimethylamino group, N-ethylamino group, N, N-diethylamino group, and N-isopropylamino group. Among these, an N-methylamino group or an N-ethylamino group is preferable. Note that the alkoxy group and the amino group may be bonded to silicon (Si) through a linking group such as a hydrocarbon group.

  In general formula (I), n is an integer of 0 to 2, p is an integer of 1 to 10, more preferably an integer of 1 to 5, and q is an integer of 0 to 5. More preferably, it is an integer of 0-3, r is an integer of 0-5, More preferably, it is an integer of 0-3, s is an integer of 0-30, Preferably it is 1-30 More preferably, it is an integer of 2-30, Most preferably, it is an integer of 2-10. When p is 2 or more, q is independently selected from integers of 0 to 5.

Examples of the compound satisfying the general formula (I) include the following compounds.

Among the above-mentioned compounds, the following compounds have a norbornene skeleton, so that they are highly reactive with organic materials and can eliminate ethanol that is not a health problem when condensed with a surface such as silica. Therefore, it is particularly preferable.

<Synthesis method of silane compound>
In one embodiment, the silane compound according to the present invention can be obtained by subjecting an alicyclic hydrocarbon compound having an unsaturated group and a silane compound to a hydrosilylation reaction in the presence of a hydrosilylation catalyst.

  The alicyclic hydrocarbon compound having an unsaturated group can be obtained, for example, by the formation of vinyl norbornene by the Diels-Alder reaction of 1,4-butadiene and cyclopentadiene, and further the reaction of cyclopentadiene. A silane compound to be reacted with an alicyclic hydrocarbon compound having an unsaturated group can be obtained by reacting a corresponding halosilane with an alcohol or an amine.

(Hydrosilylation catalyst)
The hydrosilylation catalyst is a catalyst that causes an addition reaction between an aliphatic unsaturated group (alkenyl group, diene group, etc.) in one raw material compound and a silicon-bonded hydrogen atom (that is, SiH group) in the other raw material compound. . Examples of the hydrosilylation catalyst include a platinum group metal catalyst such as a platinum group metal simple substance or a compound thereof. As the platinum group metal-based catalyst, conventionally known ones can be used. Specific examples thereof include finely divided platinum metal adsorbed on a support such as silica, alumina or silica gel, platinous chloride, chloroplatinic acid, chlorination. Examples thereof include an alcohol solution of platinic acid hexahydrate, a palladium catalyst, and a rhodium catalyst. For example, Speier catalyst (H ₂ PtCl ₆ · H ₂ O), Karstedt catalyst (Pt ₂ {[(CH ₂ = CH) Me ₂ Si] ₂ O} ₃ , RhCl (PPh ₃ ) ₃ and RhH (PPh ₃ ) ₄ Known catalysts such as Rh catalysts, etc., are preferred, but those containing platinum as the platinum group metal are preferred, and the hydrosilylation catalyst may be used alone or in combination of two or more.

  The addition amount of the hydrosilylation catalyst may be an effective amount that can promote the above addition reaction, and is usually 1 ppm (mass basis, hereinafter the same) to 1 mass in terms of the total amount of raw material compounds in terms of platinum group metal amount. % Is preferable, and a range of 10 to 500 ppm is more preferable. If the addition amount is within this range, the addition reaction is likely to be sufficiently promoted, and the addition reaction rate is likely to increase with an increase in the addition amount, which is economically advantageous.

  Hereinafter, an embodiment of a method for synthesizing a silane compound according to the present invention will be described in detail. First, 2-ethenyl-1,2,3,4,4a, 5,8,8a-octahydro-1,4-methanonaphthalene (hereinafter sometimes referred to as “VNBB”) is 5-vinyl-2- It can be obtained by reacting norbornene (VNB) and 1,4-butadiene with a Diels-Alder reaction. VNB can be obtained by a Diels-Alder reaction of 1,4-butadiene and cyclopentadiene.

  A solvent such as toluene is put into a flask in an atmospheric pressure nitrogen atmosphere, and a transition metal catalyst solution such as chloroplatinic acid IPA solution is injected. Next, VNBB obtained as described above is put, immersed in an oil bath, heated (for example, the bath temperature is about 50 ° C.), and a silane compound such as triethoxysilane is dropped therein.

The bath temperature is preferably 20 to 120 ° C. After 3-12 hours, remove the oil bath from the flask and leave to room temperature. In some cases, after washing with water and drying, the solvent is distilled off under reduced pressure, followed by drying using a vacuum dryer or the like, whereby a silane compound satisfying the above general formula (I) can be obtained. When the purity is low, it is preferable to purify by distillation or column.

  Another embodiment of the method for synthesizing a silane compound according to the present invention will be specifically described. First, the compound 2-ethenyl-1,2,3,4,4a, 5,8,8a-octahydro-1,4,5,8-dimethananaphthalene (hereinafter sometimes referred to as “VDMON”). Can be obtained by reacting VNB and cyclopentadiene with a Diels-Alder reaction.

  A solvent such as toluene is put into a flask in an atmospheric pressure nitrogen atmosphere, and a transition metal catalyst solution such as chloroplatinic acid IPA solution is injected. Next, the VGMON obtained as described above is put, immersed in an oil bath, heated (for example, the bath temperature is about 50 ° C.), and a silane compound such as triethoxysilane is dropped therein.

The bath temperature is preferably 20 to 120 ° C. After 3-12 hours, remove the oil bath from the flask and leave to room temperature. In some cases, after washing with water and drying, the solvent is distilled off under reduced pressure, followed by drying using a vacuum dryer or the like, whereby a silane compound satisfying the above general formula (I) can be obtained. When the purity is low, it is preferable to purify by distillation or column.

In one embodiment, the silane compound satisfying the general formula (I) can be obtained by utilizing the following two-stage Diels-Alder reaction.

<Silane coupling agent>
Since the silane compound of the present invention has a reactive functional group having a high active site while having low polarity and a hydrolyzable group, it is used in combination with a polymer material having no polar group or the like. Even if it has excellent affinity (dispersibility), since it can maintain the reactivity with the polymer material, it can be suitably used as a silane coupling agent.

<Sealing agent composition>
The silane compound of this invention can be used suitably as a structural component of a sealing agent composition.

  The sealing agent composition can comprise the silane compound of the present invention and a sealing agent (sealing polymer). The sealing agent may be a one-component curing type (moisture curing, oxygen curing, dry curing, non-curing type) or a two-component curing type (reaction curing type).

  The content of the silane compound is preferably 0.1 to 30% by mass, and more preferably 1 to 20% by mass.

  The sealing agent (sealing polymer) is not particularly limited, and an acrylic polymer, an acrylic urethane polymer, a polyurethane polymer, a silicon polymer, a modified silicon polymer, a polysulfide polymer, an SBR polymer, a butyl rubber polymer, Examples thereof include oil-based caulking polymers, and among these, one-component curable polyurethane-based polymers, silicon-based polymers, modified silicon-based polymers, polysulfide-based polymers, and butyl rubber-based polymers are preferable. The sealing agent composition may contain one or two or more of the sealing agents described above.

  The weight average molecular weight of the sealing agent is preferably 300 to 500,000, more preferably 1000 to 300,000. In the present invention, the weight average molecular weight is a weight average molecular weight (in terms of polystyrene) measured by gel permeation chromatography (GPC). For the measurement, tetrahydrofuran (THF), N, N-dimethylformamide (DMF), or chloroform is preferably used as a solvent.

  Moreover, the sealing agent composition may contain additives such as an anti-aging agent, an antistatic agent, a heat stabilizer, and a light stabilizer as long as the effect is not impaired.

<Adhesive composition>
The silane compound of the present invention can be suitably used as a constituent component of an adhesive composition.

  The adhesive composition can comprise the silane compound of the present invention and an adhesive (adhesive polymer). The adhesive may be a one-component curable type or a two-component curable type.

  The content of the silane compound is preferably 0.1 to 30% by mass, and more preferably 1 to 20% by mass.

  Adhesive (adhesive polymer) is not particularly limited, water-soluble adhesive (vinyl acetate emulsion), rubber adhesive (nitrile rubber resin, synthetic rubber resin), epoxy adhesive, cyanoacrylic Adhesives, vinyl adhesives, silicone rubber adhesives, plastic adhesives, hot melt adhesives, etc., among these, rubber adhesives or epoxy adhesives from the viewpoint of compatibility and stability Is preferred. The adhesive composition may contain one or more of the above-described adhesives.

  The weight average molecular weight of the adhesive is preferably 300 to 500,000, and more preferably 1000 to 300,000.

  Adhesive composition is antioxidant, anti-aging agent, anti-static agent, heat stabilizer, UV absorber, light stabilizer, flame retardant, nucleating agent, clearing agent, processability, as long as its effect is not impaired. Additives such as improvers and lubricants may be included.

<Rubber composition>
The silane compound of this invention can be used suitably as a structural component of a rubber composition. When the rubber composition contains the silane compound, the tan δ balance (= tan δ (0 ° C.) / Tan δ (60 ° C.)) of the rubber composition can be improved, and good viscoelasticity can be imparted. it can. Tan δ (60 ° C.) and tan δ (0 ° C.) can be measured in accordance with JIS K 6394.

  The rubber composition can comprise the above-described silane compound, elastomeric polymer, and inorganic material.

  It is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of elastomeric polymers, and, as for content of a silane compound, it is more preferable that it is 1-20 mass parts.

(Elastomeric polymer)
The elastomeric polymer is a generally known natural polymer or synthetic polymer, and is not particularly limited as long as it has a glass transition point of room temperature (25 ° C.) or lower, that is, an elastomer. There may be.

  As the elastomeric polymer used in the rubber composition of the present invention, any rubber generally used conventionally can be used. Specifically, natural rubber, isoprene rubber, butadiene rubber, 1, 2-butadiene rubber, styrene-butadiene rubber, isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, ethylene-propylene-diene rubber, halogenated butyl rubber, halogenated isoprene rubber, halogenated isobutylene copolymer, chloroprene rubber, butyl rubber and halogenated isobutylene -Diene rubbers such as p-methylstyrene rubber, nitrile rubber, chloroprene rubber, butyl rubber, ethylene-propylene rubber (EPDM, EPM), ethylene-butene rubber (BBM), chlorosulfonated polyethylene, acrylic Olefin rubber such as rubber, fluorine rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, urethane rubber, and the like, and polystyrene elastomeric polymers (SBS, SIS, It may be a thermoplastic elastomer such as SEBS), polyolefin-based elastomeric polymer, polyvinyl chloride-based elastomeric polymer, polyurethane-based elastomeric polymer, polyester-based elastomeric polymer or polyamide-based elastomeric polymer. In addition, these can be used individually or as arbitrary blends. Preferred elastomeric polymers are diene rubbers such as natural rubber, butyl rubber, isoprene rubber, styrene butadiene rubber and butadiene rubber.

  The weight average molecular weight of the elastomeric polymer is preferably 1000 to 3000,000, more preferably 10,000 to 1,000,000.

  As described above, the glass transition temperature (Tg) of the elastomeric polymer is preferably 25 ° C. or less, and more preferably 0 ° C. or less. When the Tg of the elastomeric polymer is within this range, it is preferable because the rubber composition exhibits rubber-like elasticity at room temperature. In the present invention, Tg is a glass transition point measured by differential scanning calorimetry (DSC-Differential Scanning Calorimetry). The temperature raising rate is preferably 10 ° C./min.

  Examples of the inorganic material include silica, carbon black, calcium carbonate, titanium oxide clay, clay and talc. Among these, since the mechanical properties and heat resistance can be further improved, silica and / or It is preferable to use carbon black.

  The addition amount of the inorganic material is preferably 0.1 to 500 parts by mass, and more preferably 1 to 300 parts by mass with respect to 100 parts by mass of the elastomeric polymer.

  The rubber composition is a silica reinforcing agent, a reinforcing agent such as carbon black, a silane coupling agent, a vulcanizing agent such as sulfur and zinc oxide, a crosslinking agent, a vulcanization accelerator, and a crosslinking accelerator as long as the effect is not impaired. Further, it may contain additives such as a vulcanization acceleration aid, an anti-aging agent, a softening agent, various oils, an antioxidant, an anti-aging agent, a filler and a plasticizer.

The silica reinforcing agent is not particularly limited, and examples thereof include dry method white carbon, wet method white carbon, colloidal silica, and precipitated silica. Among these, wet method white carbon mainly containing hydrous silicic acid is preferable. These silicas can be used alone or in combination of two or more in an amount of 10 to 200 parts by weight. The specific surface area of these silica is not particularly limited, usually a nitrogen adsorption specific surface area (BET method) 50 to 400 m ² / g, preferably from 100 to 250 m ² / g, more preferably in the range of 120~190m ² / g In some cases, improvements in reinforcement, wear resistance, heat generation and the like are sufficiently achieved and suitable. Here, the nitrogen adsorption specific surface area is a value measured by the BET method according to ASTM D3037-81.

  The carbon black is appropriately selected and used depending on the application. Generally, carbon black is classified into hard carbon and soft carbon based on the particle diameter. Soft carbon has low reinforcement to rubber, and hard carbon has strong reinforcement to rubber. In the rubber composition of the present invention, it is preferable to use hard carbon having particularly strong reinforcement. It is good to contain 10-70 weight part with respect to 100 weight part of elastomeric polymers, Preferably it is 20-60 weight part, More preferably, it is 30-50 weight part.

  Examples of the anti-aging agent include hindered phenol compounds, aliphatic and aromatic hindered amine compounds, and 0.1 to 10 parts by weight, more preferably 1 part per 100 parts by weight of the elastomeric polymer. It is better to add ~ 5 parts by weight. Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA). It is good to add 0.1-10 weight part with respect to 100 weight part of elastomeric polymers, More preferably, 1-5 weight part is added.

  Examples of the colorant include titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, and other inorganic pigments, azo pigments, copper phthalocyanine pigments, and the like. It is good to add 0.1-10 weight part with respect to 100 weight part of elastomeric polymers, More preferably, 1-5 weight part is added.

  Examples of the vulcanizing agent include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, and other sulfur-based vulcanizing agents, zinc white, magnesium oxide, resurge, Examples include p-quinonedioxam, p-dibenzoylquinonedioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene, and methylenedianiline.

  Examples of the vulcanization aid include fatty acids such as acetyl acid, propionic acid, butanoic acid, stearic acid, acrylic acid, and maleic acid, zinc acetylate, zinc propionate, zinc butanoate, zinc stearate, zinc acrylate, maleic acid. And fatty acid zinc such as zinc acid.

  Examples of the vulcanization accelerator include thiurams such as tetramethylthiuram disulfide (TMTD) and tetraethylthiuram disulfide (TETD), aldehydes / ammonias such as hexamethylenetetramine, guanidines such as diphenylguanidine, dibenzothiazyl disulfide ( DM) and the like, and cyclohexylbenzothiazylsulfenamide type.

  In the present invention, the compounding agent and additive can be used as a rubber composition by kneading with a known rubber kneader, for example, a roll, a Banbury mixer, a kneader, etc., and vulcanizing under any conditions. The addition amounts of these compounding agents and additives can be set to conventional general compounding amounts as long as the object of the present invention is not violated.

<Tire>
A tire can be produced by a conventionally known method using the rubber composition. For example, a tire can be produced by extruding the rubber composition and then molding it using a tire molding machine, followed by heating and pressurizing using a vulcanizer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

(Example 1-1)
Synthesis of Silane Compound 1 A 100 mL two-necked flask is filled with a ball stopper, a three-way cock with a vacuum line, and a stirrer bar, and the system is degassed and replaced with nitrogen while heating with a dryer using the vacuum line. This was repeated several times to obtain a normal pressure nitrogen atmosphere.

  Into the flask, 11.37 g of toluene solvent dried with molecular sieves was added, and then 0.5 g (2.55 μmol) of chloroplatinic acid 0.267% isopropanol solution was injected to give 2-ethenyl-1,2 , 3,4,4a, 5,8,8a-1.838 g (10.54 mmol) of octahydro-1,4-methanonaphthalene (VNBB) was injected using a syringe.

  Then, it was stirred and dissolved using a stirrer. Next, the flask was immersed in an oil bath, and the bath temperature was gradually raised to 50 ° C. for reaction. Using a syringe, 2.00 g (12.22 mmol) of triethoxysilane was added dropwise.

After 6 hours, the oil bath was removed from the flask and allowed to stand at room temperature. Next, toluene was removed under reduced pressure, followed by drying at 1 mmHg for 12 hours at room temperature in a vacuum dryer to obtain 3.39 g of a compound (yield 95%). When the structure of the obtained compound was confirmed by ¹ H-NMR, ¹³ C-NMR measurement, and GC-MS measurement, the introduction rate of silane was 100%, and the target silane compound 1 was obtained. confirmed. Respective NMR charts are shown in FIGS. Moreover, the chromatogram of the obtained silane compound 1 is shown in FIG.

Preparation of sealing agent composition Silane compound 1 is mixed with a one-component urethane-based sealing agent (urethane seal S700NB, manufactured by Cemedine Co., Ltd.) in the amounts shown in Table 1, degassed with a vacuum dryer, and a sealing agent. A composition was obtained. The obtained sealing agent composition was applied to a glass plate (Matsunami Glass Industrial Co., Ltd., 76 mm × 26 mm × 1.0 mm microslide glass), allowed to stand at room temperature for 1 week and cured. Next, the adhesive strength (N / m) of the cured sealant composition was measured by a 90 ° peel test (tensile speed 300 mm / min, room temperature) in accordance with JIS K6854-1. The results are shown in Table 1.

(Comparative Example 1-1)
A one-component urethane sealant (urethane seal S700NB, manufactured by Cemedine Co., Ltd.) is applied to a glass plate (Matsunami Glass Industrial Co., Ltd., micro-slide glass 76 mm × 26 mm × 1.0 mm), left to stand at room temperature for 1 week, and cured. I let you. Next, the adhesive strength of the cured sealing agent was measured by a 90 ° peel test as in Example 1. The results are shown in Table 1.

(Comparative Example 1-2)
Table 1 shows one-component urethane sealant (urethane seal S700NB, manufactured by Cemedine Co., Ltd.), 3-glycidoxypropyltriethoxysilane (KBE-403, Shin-Etsu Chemical Co., Ltd., chemical formula (II) below) The mixture was mixed in the indicated amount and degassed with a vacuum dryer to obtain a sealing agent composition. The obtained sealing agent was applied to a glass plate (Matsunami Glass Industrial Co., Ltd., micro slide glass 76 mm × 26 mm × 1.0 mm) and allowed to stand at room temperature for 1 week to be cured. Next, the adhesive strength of the cured sealant composition was measured by a 90 ° peel test as in Example 1. The results are shown in Table 1.

(Example 2-1)

Preparation of rubber composition The following components were kneaded using a 100 mL kneader (Laboplast Mill manufactured by Toyo Seiki Co., Ltd.) to obtain a rubber composition. This rubber composition was subjected to press vulcanization at 160 ° for 15 minutes to obtain a rubber sheet having a thickness of 1 mm made of the rubber composition.
-Natural rubber (RSS # 3) 100 parts by mass-Silane compound 1 1.19 parts by mass-Silane coupling agent (trade name: Si69, manufactured by Evonik) 3.2 parts by mass-Silica AQ (trade name, manufactured by Tosoh Corporation) : Nip seal AQ) 40 parts by mass / Zinc oxide No. 3 (manufactured by Toho Zinc Co., Ltd., trade name: Gin R) 3 parts by mass / stearic acid (manufactured by Nihon Rika, trade name: stearic acid 300) 1 part by mass / anti-aging agent (Nouchi 224, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 2 parts by mass, sulfur (manufactured by Hosoi Chemical Co., Ltd., oil-treated sulfur) 2 parts by mass, vulcanization accelerator (manufactured by Ouchi Emerging Chemist, trade name: Non-seller CZ) Part, vulcanization accelerator (manufactured by Ouchi Shinsei Chemist, trade name: Non-seller D)

(Example 2-2)
A rubber composition and a rubber sheet were obtained in the same manner as in Example 2-1, except that the content of the silane coupling agent was changed to 2.2 parts by mass.

(Example 2-3)
A rubber composition and a rubber sheet were prepared in the same manner as in Example 2-1, except that natural rubber was changed to styrene butadiene rubber (manufactured by Zeon Corporation, trade name: Pole 1502), and the vulcanization time was changed to 20 minutes. Obtained.

(Comparative Example 2-1)
A rubber composition and a rubber sheet were obtained in the same manner as in Example 2-1, except that the silane compound 1 was not contained.

(Comparative Example 2-2)
A rubber composition and a rubber sheet were obtained in the same manner as in Example 2-3 except that the silane compound 1 was not contained.

<Physical property evaluation>
The physical properties of the rubber sheets obtained in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-2 were evaluated by the following methods.

(JIS-A hardness)
Six rubber sheets obtained in Example 2-1 were stacked, and JIS-A hardness was measured according to JIS K6353 (issued in 2012). It measured similarly about the rubber sheet obtained in Examples 2-2 to 2-3 and Comparative Examples 2-1 to 2-2. The measurement results are shown in Table 2.

(Tensile properties)
A No. 3 dumbbell-shaped test piece was punched from the rubber sheet obtained in Example 2-1, and a tensile test at a tensile speed of 500 mm / min was performed in accordance with JIS K6251 (issued in 2010) to obtain a 100% modulus (100 % Mod) [MPa], 300% modulus (300% Mod) [MPa], breaking strength (TB) [MPa], and elongation at break (EB) [%] were measured at room temperature (25 ° C.). It measured similarly about the rubber sheet obtained in Examples 2-2 to 2-3 and Comparative Examples 2-1 to 2-2. The measurement results are shown in Table 2.

(Viscoelasticity)
A rubber obtained in Example 2-1 using a viscoelasticity measuring apparatus (REOGEL E-4000 manufactured by UBM) in accordance with JIS K 6394 under the conditions of a strain of 20 μm, about 0.1%, and a frequency of 10 Hz. The tan δ at the measurement temperatures of 0 ° C. and 60 ° C. of the sheet was determined, and the tan δ balance (= tan δ (0 ° C.) / Tan δ (60 ° C.)) was calculated from this value. It measured similarly about the rubber sheet obtained in Examples 2-2 to 2-3 and Comparative Examples 2-1 to 2-2. The measurement results are shown in Table 2.

  When comparing the rubber sheet obtained in Example 2-1 and 2-2 with the rubber sheet obtained in Comparative Example 2-1, the tan δ balance is higher in the rubber sheet obtained in Example 2-1, It turns out that it is excellent in viscoelasticity.

  Further, when the rubber sheet obtained in Example 2-3 and the rubber sheet obtained in Comparative Example 2-2 are compared, the tan δ balance is higher in the rubber sheet obtained in Example 2-3 and the viscoelasticity is higher. It is understood that it is excellent.

Claims (3)

A silane compound represented by the following general formula (I).
(In the above formula,
R ¹ is hydrogen or an alkyl group,
R ² is an alkoxy group or an amino group substituted with one or more alkyl groups,
n is an integer from 0 to 2,
p is an integer of 1 to 10,
q is an integer of 0 to 5;
r is an integer of 0 to 5;
s is an integer from 0 to 30,
When p is 2 or more, q is independently selected. ) The silane compound according to claim 1, wherein R ² is an amino group substituted with an alkoxy group having 1 to 30 carbon atoms or one or more alkyl groups having 1 to 30 carbon atoms. The silane compound according to claim 1 or 2, wherein R ² is a methoxy group or an ethoxy group.