JP6950616B2 - Organosilicon compounds and compositions containing them - Google Patents

Description

The present invention relates to an organosilicon compound and a composition containing the same, and more specifically, to an organosilicon compound having a ketimine structure and a composition containing the same.

A silane coupling agent is a compound having a part having reactivity with an inorganic substance (a hydrolyzable group bonded to a Si atom) and a part having a high reactivity and solubility with an organic substance in one molecule, and is an inorganic substance and an organic substance. Since it acts as an adhesion aid at the interface with, it is widely used as a composite resin modifier.

Among them, the aminoalkylsilane compound is known to be useful as a surface treatment agent, a fiber treatment agent, an adhesive, a paint additive, etc., and in particular, when added to a urethane prepolymer or an epoxy compound, the aminoalkylsilane compound is used as a base material. It is known that the adhesion is improved.
Further, in order to obtain a one-component moisture-curable composition, an organosilicon compound having a ketimine structure in which an amino group is protected by a reaction with a carbonyl compound such as methyl isobutyl ketone is used.

However, the organic silicon compound having a ketimine structure has poor storage stability, and the viscosity of the polymer material increases when it is mixed with a polymer material having an isocyanate group, an epoxy group, or an acid anhydride, or when it is stored after mixing. Problems such as hardening occur.
Therefore, it is required to improve the storage stability of the organosilicon compound having a ketimine structure.

Japanese Unexamined Patent Publication No. 2014-77094

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an organosilicon compound that provides a composition having a ketimine structure, good storage stability, and excellent adhesion to a substrate. And.

As a result of diligent studies to solve the above problems, the present inventors have found that an organosilicon compound having a ketimine structure having a double bond between α carbon and β carbon is excellent in storage stability, and the organosilicon is excellent in storage stability. The present invention has been completed by finding that the composition containing a silicon compound has excellent adhesion to a substrate.

（式中、Ｒ¹は、それぞれ独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、Ｒ²は、それぞれ独立して、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶は、それぞれ独立して、水素原子、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表し、ｎは、１〜３の整数、ｍは１〜１２の整数を表す。）
２． 前記Ｒ⁶が、水素原子である１の有機ケイ素化合物、
３． ウレタンプレポリマー１００質量部に対し、１または２の有機ケイ素化合物を０．０１〜１０質量部含有する組成物、
４． エポキシ化合物１００質量部に対し、１または２の有機ケイ素化合物を０．０１〜１０質量部含有する組成物、
５． ３または４の組成物の硬化物
を提供する。 That is, the present invention
1. 1. An organosilicon compound represented by the following formula (1).

(In the formula, R ¹ independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² independently represents an alkyl group having 1 to 10 carbon atoms. Alternatively, it represents an aryl group having 6 to 10 carbon atoms, and R ³ , R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. , N is an integer of 1 to 3, and m is an integer of 1 to 12.)
2. 1 organosilicon compound in which R ^{6 is a hydrogen atom,}
3. 3. A composition containing 0.01 to 10 parts by mass of 1 or 2 organosilicon compounds with respect to 100 parts by mass of urethane prepolymer.
4. A composition containing 0.01 to 10 parts by mass of 1 or 2 organosilicon compounds with respect to 100 parts by mass of the epoxy compound.
5. A cured product of the composition of 3 or 4 is provided.

The organosilicon compound of the present invention has a ketimine structure having a double bond between a hydrolyzable silyl group and α-carbon-β-carbon in one molecule, and when mixed with a compound having an isocyanate group or an epoxy group. Excellent storage stability.
Further, the modified resin surface-treated with the composition of the present invention has excellent adhesion to various inorganic materials such as glass.

Hereinafter, the present invention will be specifically described. In the present invention, the "silane coupling agent" is included in the "organosilicon compound".
The organosilicon compound according to the present invention has (i) a hydrolyzable silyl group and (ii) a ketimine structure having a double bond between α-carbon and β-carbon, and specifically, the following formula (1). Examples thereof include an organosilicon compound having a ketimine structure represented by.

In the formula (1), R ¹ independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² independently represents 1 to 10 carbon atoms. Represents an alkyl group or an aryl group having 6 to 10 carbon atoms, and R ³ , R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkyl group having 6 to 10 carbon atoms, respectively. Represents an aryl group.

The alkyl group having 1 to 10 carbon atoms may be linear, cyclic or branched, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl and s. -Butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl group, etc. Can be mentioned.
Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl, α-naphthyl, β-naphthyl group and the like.
Among these, as R ¹ and R ² , a linear alkyl group is preferable, and a methyl group and an ethyl group are more preferable.
Further, as R ³ , R ⁴ , R ⁵ , and R ⁶ , a hydrogen atom and an alkyl group having 1 to 6 carbon atoms are preferable, a hydrogen atom, a methyl group, an ethyl group, and an n-propyl group are more preferable, and further, R It is preferable that the total number of carbon atoms of ³ , R ⁴ , R ⁵ and R ^{6 is 5 or less.}

In the formula (1), n represents an integer of 1 to 3, but 2 or 3 is preferable, and 3 is more preferable.
Although m represents an integer of 1 to 12, 2 or 3 is preferable, and 3 is more preferable.

In particular, in the present invention, the ^{organosilicon compound represented by the following formula (2) in which R 6} is a hydrogen atom is preferable, and further, the organosilicon compounds represented by the following formulas (3) to (5) are used. More preferred.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、ｍ、ｎは、上記と同じ意味を表す。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , m, n have the same meanings as above.)

（式中、Ｒ¹、Ｒ²、ｍ、ｎは、上記と同じ意味を表す。）

(In the formula, R ¹ , R ² , m, n have the same meanings as above.)

Examples of the organosilicon compound having a suitable ketimine structure include those represented by the following formulas (6) to (8), but are not limited thereto.

（式中、Ｅｔは、エチル基を意味する。）

(In the formula, Et means an ethyl group.)

In the organosilicon compound of the present invention, an alkoxysilyl group-containing amine compound represented by the following formula (9) and a carbonyl group-containing alkylene compound represented by the following formula (10) are dehydrated by a known method. Obtainable.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、ｍ、ｎは、上記と同じ意味を表す。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , m, n have the same meanings as above.)

Specific examples of the amine compound represented by the above formula (9) include 3-trimethoxysilylpropylamine, 3-triethoxysilylpropylamine, 3-dimethoxymethylsilylpropylamine and the like. Specific examples of the carbonyl group-containing alkylene compound represented by the above formula (10) include 2-ethyl-2-hexenal, 2-hexenal, 3-methyl-2-butenal and the like.

Generally, ketimine compounds form an enamine structure in equilibrium due to imine-enamine tautomerism. Therefore, when mixed with an isocyanate compound or an epoxy compound, the amine compound forming an enamine structure reacts with the isocyanate group or the epoxy group, which may deteriorate the storage stability.
In this respect, the organosilicon compound represented by the formula (1) of the present invention has a structure in which imine-enamine tautomerization does not occur, so that the reaction does not proceed even when mixed with an isocyanate compound or an epoxy compound, and storage stability is stable. The property becomes good.

By adding the organosilicon compound of the present invention to the urethane prepolymer, stable and excellent adhesiveness can be imparted to the adherend without using a primer composition, and in particular, the organosilicon of the present invention can be imparted. The composition containing the compound and the urethane prepolymer exhibits excellent adhesiveness to an adherend made of a material such as an olefin resin such as glass or polypropylene resin.
That is, the hydrolyzable silyl group (Si-OR group) contained in the organic silicon compound of the present invention is hydrolyzed by the moisture in the air to become a silanol group (Si-OH group), which reacts with the OH group contained in glass or the like. , Si—O—Si bond is formed, high adhesiveness is imparted, and the amino group (-NH ₂ group) generated by deprotecting the ketimine structure by the moisture in the air and the NCO group in the urethane prepolymer Reacts to form a urea bond, imparting high adhesiveness.

In this case, the content of the organosilicon compound is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the urethane prepolymer as the main agent, and is 0.5 to 0.5 to 100 parts by mass from the viewpoint of achieving both improvement in adhesiveness and cost. 8 parts by mass is more preferable.

The urethane prepolymer contains a polyol having two or more hydroxyl groups (OH) and a polyisocyanate compound having two or more isocyanate groups (NCO) so that the isocyanate group becomes excessive, that is, the molar ratio of NCO / OH. Can be obtained by reacting so that is greater than 1.
The reaction conditions include, for example, an NCO / OH equivalent ratio of 2.0 to 15.0, more preferably 2.0 to 8.0, at 70 to 100 ° C. in a nitrogen or dry air stream. Conditions for time reaction can be mentioned. The NCO content of the obtained NCO-containing prepolymer is preferably in the range of 5 to 25% by mass.

The polyisocyanate compound is not particularly limited as long as it has two or more isocyanate groups in the molecule, and is, for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tri. Range isocyanate (2,6-TDI), 4,4′-diphenylmethanediisocyanate (4,4′-MDI), 2,2′-diphenylmethanediisocyanate (2,2′-MDI), 2,4′-diphenylmethanediisocyanate (2,4′-diphenylmethanediisocyanate) 2,4'-MDI), 1,4-phenylenediocyanate, polymethylene polyphenylene polyisocyanate, trizine diisocyanate (TODI), 1,5-naphthalenediocyanate (NDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate ( Aromatic polyisocyanates such as TMXDI) and triphenylmethane triisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate and norbornan diisocyanate (NBDI); transcyclohexane-1, Alicyclic polyisocyanates such as 4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanate methyl) cyclohexane (H ₆ XDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI); polyisocyanate compounds such as polymethylene polyphenylene polyisocyanate; Carbodiimide-modified polyisocyanates of isocyanate compounds; isocyanurate-modified polyisocyanates of these isocyanate compounds; urethane prepolymers obtained by reacting these isocyanate compounds with polyol compounds described later. These polyisocyanate compounds may be used alone or in combination of two or more.

On the other hand, the polyol compound is not particularly limited, and can be appropriately selected from conventionally known polyols such as polyether polyols, polyester polyols, acrylic polyols, and polycarbonate polyols, and these polyols are used alone. Alternatively, two or more types may be used in combination.
Specific examples of the polyol compound include polypropylene ether diol, polyethylene ether diol, polypropylene ether triol, polytetramethylene glycol, polyethylene glycol (PEG), polypropylene glycol (PPG), polyoxyethylene glycol, polyoxypropylene glycol, and polyoxypropylene. Triol, polyoxybutylene glycol, polytetramethylene ether glycol (PTMG), polymer polyol, poly (ethylene adipate), poly (diethylene adipate), poly (propylene adipate), poly (tetramethylene adipate), poly (hexamethylene adipate) , Poly (neopentylene adipate), poly-ε-caprolactone, poly (hexamethylene carbonate) and the like, and natural polyol compounds such as castor oil.

In this case, the polyol compound preferably has a polystyrene-equivalent number average molecular weight in the range of 1,000 to 20,000, particularly 2,000 to 10,000, by gel permeation chromatography (GPC).

Further, by adding the organosilicon compound of the present invention to the epoxy compound, stable and excellent adhesiveness can be imparted to the adherend without using a primer composition, and in particular, the organosilicon of the present invention can be imparted. The composition containing the silicon compound and the epoxy compound exhibits excellent adhesiveness to an adherend made of glass or an adherend made of metal such as a SUS plate.
That is, the hydrolyzable silyl group (Si-OR group) of the organic silicon compound of the present invention is hydrolyzed by the moisture in the air to become a silanol group (Si-OH group), which reacts with the OH group of glass or the like to form Si. -O-Si bond is formed to impart high adhesiveness, and the amino group (-NH ₂ group) generated by deprotecting the ketimine structure by the moisture in the air reacts with the epoxy group in the epoxy compound. As a result, high adhesiveness is exhibited.

In this case, the content of the organosilicon compound is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the epoxy compound as the main agent, and is 0.5 to 8 parts by mass from the viewpoint of both improving adhesiveness and cost. Part is more preferable.

The epoxy resin is generally not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, and is, for example, epichlorohydrin, polyphenols such as bisphenols, and polyalcohols. The one obtained by the condensation of is mentioned.
Specific examples thereof include bisphenol A type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, novolac type, phenol novolac type, Examples thereof include glycidyl ether type epoxy resins such as orthocresol novolak type, tris (hydroxyphenyl) methane type and tetraphenylol ethane type.
In addition, a glycidyl ester type epoxy resin obtained by condensing epichlorohydrin with a carboxylic acid such as a phthalic acid derivative or a fatty acid; a glycidyl amine type epoxy resin obtained by reacting epichlorohydrin with amines, cyanulic acids or hydranthins; Examples include, but are not limited to, epoxy resins modified by various methods.
Each of the above epoxy resins may be used alone or in combination of two or more.

Among these, bisphenol A type and bisphenol F type epoxy resins are preferable in consideration of price.
Bisphenol A type and bisphenol F type epoxy resins can also be obtained as commercial products, and as commercially available bisphenol A type epoxy resins, jER828 manufactured by Mitsubishi Chemical Co., Ltd., DER331 manufactured by Dow Chemical Co., Ltd., etc. Examples of commercially available bisphenol F type epoxy resins include jER807 and jER1750 manufactured by Mitsubishi Chemical Corporation.

In addition to the above-mentioned components, the composition of the present invention contains, if necessary, a curing catalyst, an adhesion-imparting agent, a physical property adjusting agent, a filler, a plasticizer, a shaking agent, and a dehydrating agent (storage stability improving agent). , Various additives such as tackifiers, anti-dripping agents, ultraviolet absorbers, antioxidants, flame retardants, colorants, radical polymerization initiators, and various solvents such as toluene and alcohol may be blended.

The filler is not particularly limited, and for example, calcium carbonate, aluminum hydroxide, carbon black, white carbon, silica, glass, kaolin, talc (magnesium silicate), fumed silica, precipitated silica, and silicic anhydride. , Hydrous silicic acid, clay, calcined clay, bentonite, glass fiber, asbestos, glass filament, crushed quartz, silica soil, aluminum silicate, zinc oxide, magnesium oxide, titanium oxide, and inorganic fillers such as surface-treated products thereof. Carbonates, organic bentonite, high styrene resin, kumaron-inden resin, phenol resin, formaldehyde resin, modified melamine resin, cyclized rubber, lignin, ebonite powder, cellac, cork powder, bone powder, wood powder, cellulose powder, coconut palm Organic fillers such as shavings and wood pulp; inorganic pigments such as lamp black, titanium white, red iron oxide, titanium yellow, zinc flower, lead tan, cobalt blue, iron black, aluminum powder; neozabon black RE, neoblack RE, ora Examples thereof include organic pigments such as Zol Black CN, Orazole Black Ba (all manufactured by Ciba Geigy Co., Ltd.), and Spiron Blue 2BH (manufactured by Hodogaya Chemical Industry Co., Ltd.).
These fillers may be used alone or in combination of two or more. The blending amount is preferably 0.1 to 100 parts by mass, more preferably 1 to 70 parts by mass, based on 100 parts by mass of the composition of the present invention.

Among these, it is preferable to use at least one selected from carbon black and calcium carbonate in order to impart desired properties.
The carbon black and calcium carbonate are not particularly limited, and commercially available ones can be used. For example, carbon black includes N110, N220, N330, N550, N770, and mixtures thereof according to the standards of the American Materials Testing Association, and calcium carbonate includes heavy calcium carbonate, precipitated calcium carbonate, and the like.

The catalyst used in the urethane composition is not particularly limited as long as it can react with the main agent.
Specific examples thereof include divalent organic tin compounds such as tin octanate, tin octylate, tin butanoate, tin naphthenate, tin caprylate, tin oleate, and tin laurate; dibutyltin dioctate, dibutyltin dilaurate, and the like. Dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dibutyltin dioleate, dibutyltin benzoate, dioctyltin dilaurate, dioctyltin diversate, diphenyltin diacetate, dibutyltin dimethoxydo, dibutyltin oxide, dibutyltin bis (triethoxysilicate) , A tetravalent organic tin compound such as a reaction product of dibutyltin oxide and phthalate ester; a metal catalyst such as bismuth octylate; Primary amines; Secondary amines such as dibutylamine; Polyamines such as diethylenetriamine, triethylenetetramine, guanidine, diphenylguanidine, xylylene diamine; triethylenediamine and its derivatives, 2-methyltriethylenediamine, morpholin, N-methylmorpholin, Cyclic amines such as 2-ethyl-4-methylimidazole, 1,8-diazabicyclo [5.4.0] -7-undecene; amino alcohol compounds such as monoethanolamine, diethanolamine, triethanolamine; 2,4,6 -Amine compounds such as aminophenol compounds such as tris (dimethylaminomethyl) phenol and their carboxylates; quaternary ammonium salts such as benzyltriethylammonium acetate; low molecular weight amides obtained from excess polyamines and polybasic acids Resins: Reaction products of excess polyamines and epoxy compounds. These catalysts may be used alone or in combination of two or more.
The blending amount is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the composition of the present invention.
Among these, tin-based catalysts (divalent or tetravalent organic tin compounds) and amine-based catalysts are preferable from the viewpoint of having a large catalytic ability in a small amount.

The catalyst used in the epoxy composition is not particularly limited as long as it can react with the main agent.
Specific examples thereof include aliphatic amines such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, and oleylamine; mensendiamine, Isophoronediamine, norbornandiamine, piperidine, N, N'-dimethylpiperazin, N-aminoethylpiperazin, 1,2-diaminocyclohexane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane , Polycyclohexylpolyamines, alicyclic amines such as 1,8-diazabicyclo [5,4,0] undecene-7 (DBU); 3,9-bis (3-aminopropyl) -2,4,8,10 -Tetraoxaspiro [5,5] amines having ether bonds such as undecane (ATU), morpholin, N-methylmorpholin, polyoxypropylenediamine, polyoxypropylenetriamine, polyoxyethylenediamine; diethanolamine, triethanolamine, etc. Hydroxyl group-containing amines; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-( 2-Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyl Diethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6-aminohexyl) aminopropyltri Methoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, γ -Ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenylaminomethyltrimethoxysilane, N-benzyl- γ-Aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N-cyclohexylaminomethyltriethoxysilane, N- Aminosilanes such as cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine Ketimine-type silanes such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propaneamine; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydroanhydrogen Acid anhydrides such as phthalic acid and dodecyl anhydride succinic acid; polyamides obtained by reacting dimer acid with polyamines such as diethylenetriamine and triethylenetetramine, and polyamideamines such as polyamides using polycarboxylic acids other than dimer acid; Imidazoles such as 2-ethyl-4-methylimidazole; dicyandiamide; epoxy-modified amines obtained by reacting the above amines with epoxy compounds, Mannig-modified amines obtained by reacting the above amines with formalin and phenols, Michael Examples thereof include modified amines such as addition-modified amines and ketimine. These curing agents may be used alone or in combination of two or more.
The blending amount is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the composition of the present invention.

Since the composition of the present invention described above has excellent adhesion, it is suitably used as an adhesive for vehicles such as automobiles and trains, ships, aircraft, construction / civil engineering, electronics, the space industry, and other industrial products. be able to.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.
In the following, the viscosity was measured based on JIS Z 8803. The analysis by gas chromatography was performed under the following conditions.
Gas Chromatography Analysis GC Equipment: HP7890B manufactured by Agilent Technologies, Inc.
Detector: Thermal conductivity detector (TCD)
Column: DB-5 (length 30 m x inner diameter 0.530 mm x film thickness 1.50 μm)
Column temperature: 100 ° C → temperature rise 15 ° C / min → 300 ° C (hold for 10 minutes)
Measurement time Total 23.3 minutes Inlet temperature: 250 ° C
Detector temperature: 300 ° C
Carrier gas: He
Carrier gas flow rate: 3.0 mL / min

[1] Synthesis of urethane prepolymer [Synthesis example 1]
600 g of polypropylene ether triol with a number average molecular weight of 5000 (G-5000, trade name "EXCENOL5030", manufactured by Asahi Glass Co., Ltd.) and 300 g of polypropylene ether diol with a number average molecular weight of 2000 (D-2000, trade name "EXCENOL2020", Asahi Glass ( (Manufactured by Co., Ltd.) was put into a flask, heated to 100 to 130 ° C., stirred while degassing, and dehydrated until the water content became 0.01% or less.
Then, it is cooled to 90 ° C., and diphenylmethane diisocyanate (MDI, trade name "Sumijour 44S", manufactured by Sumitomo Bayer Japan Co., Ltd.) has an equivalent ratio of NCO group / OH group (NCOmol / OHmol) of 1.70. After the addition in an amount, the reaction proceeded in a nitrogen atmosphere for about 24 hours to prepare a urethane prepolymer.

[2] Synthesis of organosilicon compounds [Example 1]
In a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 425 g (3.37 mol) of 2-ethyl-2-hexenal and 700 g of toluene were placed, and 186 g of 3-triethoxysilylpropylamine (186 g). 0.84 mol) was added dropwise at an internal temperature of 120 to 125 ° C. over 1 hour. Then, the mixture was stirred at 130 ° C. for 4 hours and analyzed by gas chromatography. As a result, the peak of 2-ethyl-2-hexenal disappeared. During dropping and aging, the produced water was extracted by refluxing it together with toluene. The obtained solution was distilled and purified under the conditions of 9 mmHg and 170 ° C. to obtain 145 g of a pale yellow transparent liquid. ¹ It was confirmed by 1 H-NMR that it was an organosilicon compound represented by the above formula (6).

[Example 2]
In a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 331 g (3.37 mol) of 2-hexenal and 670 g of toluene were placed, and 186 g (0.84 mol) of 3-triethoxysilylpropylamine was placed. ) Was added dropwise at an internal temperature of 120 to 125 ° C. over 1 hour. Then, the mixture was stirred at 130 ° C. for 4 hours and analyzed by gas chromatography. As a result, the peak of 2-hexenal disappeared. During dropping and aging, the produced water was extracted by refluxing it together with toluene. The obtained solution was distilled and purified under the conditions of 9 mmHg and 164 ° C. to obtain 135 g of a pale yellow transparent liquid. ¹ It was confirmed by 1 H-NMR that it was an organosilicon compound represented by the above formula (7).

[Example 3]
In a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 283 g (3.37 mol) of 3-methyl-2-butenal and 650 g of toluene were placed, and 186 g of 3-triethoxysilylpropylamine (186 g). 0.84 mol) was added dropwise at an internal temperature of 120 to 125 ° C. over 1 hour. Then, the mixture was stirred at 130 ° C. for 4 hours and analyzed by gas chromatography. As a result, the peak of 3-methyl-2-butenal disappeared. During dropping and aging, the produced water was extracted by refluxing it together with toluene. The obtained solution was distilled and purified under the conditions of 9 mmHg and 160 ° C. to obtain 132 g of a pale yellow transparent liquid. ¹ It was confirmed by 1 H-NMR that it was an organosilicon compound represented by the above formula (8).

[3] Evaluation of storage stability of the composition [Examples 4 to 9, Comparative Examples 1 and 2]
As shown in Table 1 below, each component was mixed to prepare a composition. Table 1 also shows the change in viscosity when stored at a constant temperature of 25 ° C.

イソシアネート化合物：コスモネートＭ−２００（三井化学（株）製）
エポキシ化合物：ｊＥＲ８２８（三菱ケミカル（株）製）
有機ケイ素化合物（１１）：３−トリエトキシシリル−Ｎ−（１，３−ジメチル−ブチリデン）プロピルアミン（ＫＢＥ−９１０３、信越化学工業（株）製）

Isocyanate compound: Cosmonate M-200 (manufactured by Mitsui Chemicals, Inc.)
Epoxy compound: jER828 (manufactured by Mitsubishi Chemical Corporation)
Organosilicon compound (11): 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (KBE-9103, manufactured by Shin-Etsu Chemical Co., Ltd.)

As shown in Table 1, it can be seen that the organosilicon compounds of the present invention prepared in Examples 1 to 3 are excellent in storage stability when blended with an isocyanate compound and an epoxy compound.

[4] Preparation of urethane composition and preparation of cured product [Examples 10 to 18, Comparative Examples 3 and 4]
As shown in Table 2 below, each component was mixed to prepare a urethane composition.
Each of the prepared compositions is applied onto a glass plate (50 mm × 50 mm × 5 mm thick) which is an adherend, and then heat-dried at 120 ° C. for 10 minutes to form an adhesive layer on the adherend. The composite material was prepared.
Further, each composition prepared under the same conditions is placed on an aluminum oxide plate (50 mm × 50 mm × 3 mm thickness), an acrylic resin plate (50 mm × 50 mm × 3 mm thickness) and a polyester plate (50 mm × 50 mm × 3 mm thickness). Each was applied and dried to prepare a composite material in which an adhesive layer was formed on the adherend.
The adhesion of each of the obtained composite materials was measured by the following method. The results are also shown in Table 2.
[Adhesion]
After curing each of the produced composite materials by leaving them at 23 ° C. and 55% RH for 3 days, the adhesive layer was cut with a knife, and a hand peeling test was conducted in which the cut portion was peeled off by hand. The state of the interface between the adhesive layer and the adhesive layer was visually observed.

硬化触媒：ジブチルスズジラウレート
有機ケイ素化合物（１２）：３−イソシアネートプロピルトリエトキシシラン（ＫＢＥ−９００７、信越化学工業（株）製）

Curing catalyst: Dibutyltin dilaurate organosilicon compound (12): 3-Isocyanatepropyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Examples 19 to 21, Comparative Examples 5 to 7]
As shown in Table 3 below, each component was mixed to prepare an epoxy composition.
Adhesion and shear strength of the obtained composition were measured and evaluated by the following methods.
[Adhesion]
Each composition was applied to a glass plate (150 mm × 50 mm × 5 mm thickness) as an adherend, and allowed to stand for 5 days under the conditions of 23 ° C. and 55% RH to cure to prepare a test piece. The adhesion of the obtained test piece was evaluated by the following method.
Grid peeling test: Performed in accordance with JIS K 5400.
Adhesion after water resistance test: After impregnating the test piece with water at room temperature for 24 hours, a grid peeling test was performed.
Adhesion after boiling test: After impregnating the test piece in boiling water at 100 ° C. for 2 hours, a grid peeling test was performed.
[Shear strength]
The ends of the two SUS substrates (manufactured by KDS Co., Ltd., width 25 mm) were overlapped by 10 mm, and the obtained composition was sandwiched between them with a thickness of 0.01 mm, and allowed to stand at room temperature for 5 days. It was cured. As a result, a test piece composed of two SUS substrates bonded with the epoxy resin composition (bonding area 25 mm × 10 mm = 250 mm ^{2) was produced.}
Each end of this test piece was pulled in the opposite direction using a tensile tester (manufactured by Shimadzu Corporation, Autograph) at a tensile speed of 50 mm / min, and the adhesive strength (MPa) per unit area was determined. .. The shear strength (relative ratio) in Table 3 is obtained by dividing each measured value by the value of Comparative Example 5.

エポキシ樹脂：ｊＥＲ８２８（三菱ケミカル（株）製）
触媒：Ｈ３（湿気硬化型エポキシ硬化剤、三菱ケミカル（株）製）
有機ケイ素化合物（１３）：３−グリシドキシプロピルトリメトキシシラン（ＫＢＭ−４０３、信越化学工業（株）製）

Epoxy resin: jER828 (manufactured by Mitsubishi Chemical Corporation)
Catalyst: H3 (moisture-curable epoxy hardener, manufactured by Mitsubishi Chemical Corporation)
Organosilicon compound (13): 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

As shown in Tables 2 and 3, it can be seen that the urethane composition and the epoxy composition containing the organosilicon compound of the present invention have high adhesion.

Claims (5)

An organosilicon compound represented by the following formula (3), formula (4) or formula (5).

(In the formula, R ¹ independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
R ² independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
n represents an integer of 1 to 3 and m represents an integer of 1 to 12. ) The organosilicon compound according to claim 1, wherein m is 2 or 3. A composition containing 0.01 to 10 parts by mass of the organosilicon compound according to claim 1 or 2 with respect to 100 parts by mass of the urethane prepolymer. A composition containing 0.01 to 10 parts by mass of the organosilicon compound according to claim 1 or 2 with respect to 100 parts by mass of the epoxy compound. A cured product of the composition according to claim 3 or 4.