JPH06271833A - Adhesion-providing agent for polysulfide composition and curing type composition using the same - Google Patents

Abstract

PURPOSE:To obtain the subject agent consisting of a specific modified compound, capable of giving a sealing material exhibiting good adhesiveness without applying a primer to an adherend and not impairing rubber elasticity and storage stability. CONSTITUTION:This agent is obtained by modifying at least part of terminal groups of a compound having the formula R<1>O, R<2>COO (R<1> is 2-4C alkylene; R<2> is 1-10C alkylene) and/or polysulfide bond in the main chain and having SH, OH or NCO at the ends with an alkoxysilane of the formula [R<3> is 1-4C divalent hydrocarbon; R<4> and R<5> are each 1-4C monovalent hydrocarbon; A is NCO, methacryloxy, etc., when the terminal is SH or A is NCO or glycidoxy when the terminal is OH or A is mercapto or amino when the terminal is NCO; (a) is 0-2]. As its base compound, e.g. a mercaptan-terminated polysulfide compound is used and as the alkoxysilane of the formula, e.g. gamma- glycidoxypropylmethoxysilane is used.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an adhesion promoter for a polysulfide composition and a curable composition containing the same,
In particular, the present invention relates to an adhesion-imparting agent that gives a curable composition that adheres well without applying a primer to an adherend, and one-component and multi-component curable compositions containing the same.

[0002]

2. Description of the Related Art A polymer containing two or more thiol groups in one molecule easily reacts with an oxidant to form a high molecular weight product and becomes a cured product. Widely used as a sealing material.

As a method of improving the adhesiveness of the sealing material with such a thiol group-containing polymer, a method of adding a silane coupling agent such as epoxysilane or mercapton silane to the sealing material is generally used. Additives that improve the adhesiveness by blending with such a sealing material are called adhesion promoters. By adding this adhesion-imparting agent, the adhesive force between the adherend and the sealing material can be made strong without applying a primer to the adhesive surface of the adherend in advance.

However, the conventional adhesion promoters such as epoxy silane and mercapto silane are usually blended in an amount of about 0.03 to 1.0 part by weight with respect to 100 parts by weight of the sealing material. Even if compounded, there is a problem that a sufficient adhesive force cannot be imparted to the sealing material. Therefore, it is conceivable to increase the amount of the adhesion-imparting agent added in order to improve the adhesiveness, but this causes a problem that the modulus of the obtained sealing material is increased and the followability to the adherend is deteriorated. Further, since the added adhesion-imparting agent is not always introduced into the skeleton of the thiol group-containing polymer, there is a problem that the reproducibility of the adhesiveness is poor.

Therefore, an object of the present invention is to provide a sealing material having good adhesiveness without applying a primer to an adherend, and to retain the excellent rubber elasticity and storage stability of the sealing material. It is to provide an adhesion promoter.

Another object of the present invention is to have good adhesiveness without applying a primer to an adherend,
A curable composition having excellent storage stability is provided.

[0007]

DISCLOSURE OF THE INVENTION As a result of earnest research in view of the above object, the present inventors have found that two or more SHs per molecule.
A compound obtained by modifying a compound having an OH group, an OH group and / or an NCO group with a specific silane compound imparts strong adhesiveness to a sulfur-containing polymer even in a small amount, and has excellent rubber elasticity and excellent rubber elasticity of the sulfur-containing polymer. It has been found that it is suitable as an adhesion promoter without impairing storage stability. The present inventors have also disclosed a curable composition containing the above-mentioned adhesion-imparting agent and a sulfur-containing polymer having any one structural unit of a polyether bond, a polysulfide bond, a carbonyl structure, a urethane bond and a thiourethane bond. Is
It has been found that, even if the adherend is not coated with a primer, it has good adhesiveness and excellent storage stability. The present invention has been made based on the above findings.

That is, in the adhesion-imparting agent of the present invention, (a) the main chain is -R ¹ O- (provided that R ¹ represents an alkylene group having 2 to 4 carbon atoms), -R ² COO- (provided that: , R ² represents an alkylene group having 1 to 10 carbon atoms) and a polysulfide bond, and (b) has —SH, —OH or —NCO at the terminal, At least a part of the terminal group is AR ³ _a SiR ⁴ (OR ⁵ ) _3-a (wherein R ³ is a divalent hydrocarbon group having 1 to 4 carbon atoms, R ⁴ and R ⁵ are 1 to 4 carbon atoms). Represents a monovalent hydrocarbon group of, when A is --SH, an isocyanate group, a glycidoxy group or a methacryloxy group, and when the terminal is --OH,
Isocyanate group or glycidoxy group, the terminal-
In the case of NCO, it is a mercapto group or an amino group, and a is 0, 1 or 2. ) Is modified with an alkoxysilane.

Further, the curable composition of the present invention, (A) and adhesion promoter of claim 1, (B) _{^{(i) - (R 6 O) n}} - ( where, R ⁶ is the number of carbon atoms 2 to
4 is an alkylene group, and n is an integer of 6 to 200. ),
_{(B) - (C 2 H 4 OCH} 2 OC 2 H 4 S x) m -, -
_{(C 2 H 4 OC 2 H} 4 OC 2 H 4 S x) m -, and / or _{- (CH 2 CH (OH)} CH 2 S x) m - ( where
x represents an integer of 1 to 4 and m represents an integer of 6 to 50. ),
(C) -R ⁷ COO- (provided that, R ⁷ represents an alkylene group having 1 to 10 carbon atoms), containing (D) -NHCOO- and / or -NHCOS- 1 or two or more, and At least two ends have -CHR ⁸ SR ⁹ (provided that
R ⁸ represents —H, —CH ₃ or C ₂ H ₅ , and R ⁹ represents —
H or —SiR ¹⁰ R ¹¹ R ¹² (R ¹⁰ , R ¹¹ and R ¹² are each an alkyl group having 1 to 6 carbon atoms, a phenyl group or a haloalkyl group). ) Molecular weight 500 ~
It is characterized by containing 10,000 sulfur-containing liquid polymer.

The present invention will be described in detail below. [1] a tackifier based compound-based compounds, -R ¹ O in the main chain ^{(a) -, - R 2} CO
O- and / or polysulfide bonds (-S _x -) (provided that, R ¹ is an alkylene group having 2 to 4 carbon atoms, R ² is an alkylene group having 1 to 10 carbon atoms, x is an integer of 1 to 4. )
And (b) has -SH, -OH or -NCO at the end.

In this base compound, the content of the component (a) is preferably 30 to 97% by weight, and the content of the component (b) is preferably 3 to 70% by weight. The number average molecular weight (Mn) of this base compound is usually 200 to 10,000, preferably 200 to 5,000.

Examples of such base compounds include mercaptan-terminated polysulfide compounds, mercapto-terminated permapol P2, mercapto-terminated permapol P3, mercaptan-terminated polymers described in Japanese Patent Publication No. 47-48279, NCO-terminated prepolymers, Takeda (stock). ) Made D10
3N, D120N, D140N, etc. can be mentioned.

Alkoxysilane The alkoxysilane that modifies the above-mentioned base compound is represented by the following general formula (1). AR ³ _a SiR ⁴ (OR ⁵ ) _3-a (1) (In the formula, A represents any one of an isocyanate group, a glycidyloxy group and a methacryloxy group, and R ³ has 1 carbon atom.
~ 4 divalent hydrocarbon groups, R ⁴ and R ⁵ have 1 to 4 carbon atoms
Represents a monovalent hydrocarbon group, and a is 0, 1 or 2.

However, A is determined by the type of terminal of the above-mentioned base compound. When the terminal is --SH, it is an isocyanate group, glycidoxy group or methacryloxy group, and in the case of --OH, it is an isocyanate group or glycidoxy group. In the case of —NCO, it is a mercapto group or an amino group.

Examples of such alkoxysilanes include γ
-Glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- (2aminoethyl) aminopropyltrimethoxysilane, or these The ethoxysilane compound and the like can be mentioned.

The modification ratio with the above alkoxysilane is preferably 70 to 90 mol% with respect to 100 mol% of the base compound. If the modification ratio by the alkoxysilane is less than 70 mol%, the adhesiveness-improving effect of the obtained adhesion-imparting agent is not sufficient, whereas if it exceeds 90 mol%, the adhesion-imparting agent is not introduced into the polymer skeleton, resulting in good adhesion. It is not preferable because it does not show the property and it terminates at the end even if it is introduced.

Production Method In the modification of the base compound with the alkoxysilane, for example, the base compound and the alkoxysilane are mixed in an inert gas atmosphere, and a catalyst is added if necessary,
It can be performed by stirring at 30 to 90 ° C. for 0.5 to 5 hours. As the above catalyst, KOH, NaO
Hydroxides of alkali metals such as H and Ca (OH) ₂ , tin-based organometallic compounds such as dibutyltin laurate, 2, 4, 6
-Tris (dimethylamino / methyl) phenol, triethylamine, tributylamine, toeethylenediamine and the like can be mentioned. The alkali metal hydroxide catalyst component can be appropriately dissolved in an organic solvent such as polyethylene glycol or polypropylene glycol before use.

[2] Curable Composition The curable composition of the present invention comprises (A) the above-mentioned adhesion-imparting agent,
(B) contains a sulfur-containing polymer.

(A) Adhesion imparting agent As the adhesion imparting agent, the above-mentioned adhesion imparting agent can be used.

[0020] (B) a sulfur-containing polymeric sulfur-containing polymer is a polymer comprising the following (i) in the main chain - (d) _{^{(i) - (R 6 O) n}} - ( where, R ⁶ is alkylene of 2 to 4 carbon atoms Group, n represents an integer of 6 to 200), (b)
_{- (C 2 H 4 OCH 2} OC 2 H 4 S x) m -, - (C 2
_{H 4 OC 2 H 4 OC 2} H 4 S x) m -, and / or -
_{(CH 2 CH (OH) CH} 2 S x) m - (. Here, x is an integer from 1 to 4, m is indicating an integer of from 6 to 50), (c) -
R ⁷ COO- (However, R ¹³ represents an alkylene group having 1 to 10 carbon atoms), (d) -NHCOO- and / or -NH
Containing one or more COS-, and at least two terminal -CHR ⁸ SR ⁹ (provided that, R ⁸ is
Represents —H, —CH ₃ or C ₂ H ₅ , and R ⁹ represents —H or —
SiR ¹⁰ R ¹¹ R ¹² (R ¹⁰ , R ¹¹ and R ¹² have 1 to 6 carbon atoms.
Is an alkyl group, a phenyl group or a haloalkyl group). ) Is a polymer.

In the above sulfur-containing polymer, the terminal group-
CHR ⁸ SR ⁹ is —CHR ⁸ SSiR ¹⁰ R ¹¹ R ¹² (R ⁸
Represents —H, —CH ₃ or C ₂ H ₅ , and R ¹⁰ , R ¹¹ and R ¹² represent any of an alkyl group having 1 to 6 carbon atoms, a phenyl group and a haloalkyl group. ) Is suitable as a one-pack curable composition. This is the case
The following chemical reaction formula sulfur-containing polymer is reacted with moisture in the air ^{-SSiR 10 R 11 R 12 + H} 2 O → -SH + R 10 R 11 R
^{This is because 12} Si + OH progresses and active hydrogen reacts with the curing agent or NCO group in the system to be oxidized.

Further, when the adhesion-imparting agent (a) of the present invention is a one-pack type, in addition to NCO, OH and SH, SSiR ¹⁰ R ¹¹ R ¹²
Alternatively, the presence of OSiR ¹⁰ R ¹¹ R ¹² is preferable from the viewpoint of improving stability.

When -CHR ⁸ SR ⁹ is -CHR ⁸ SH, it is suitable as a two-component or three-component curable composition. That is, by mixing with a curing agent or a urethane prepolymer containing an NCO group, etc.
The HR ⁸ SH groups react and harden. In this case, the adhesion-imparting agent may be added to the polymer side or may be added at the time of mixing as long as there is no problem in storage stability.

The sulfur-containing polymer is 500 to 10,000,
It preferably has a molecular weight of 800 to 8,000. When the molecular weight of the sulfur-containing polymer is less than 500, the hydrolysis becomes extremely fast, which makes the compound difficult to handle, and further, the storage stability of the composition is deteriorated. The hydrolysis rate is too slow.

As such a sulfur-containing polymer, in particular, two or more trialkylsilylthio groups (-
^{SSiR 10 R 11 R 12 (R} 10, R 11 and represents an alkyl group having 1 to 6 carbon atoms.) The has terminated, -R ⁶ O- (R ⁶
Preferably those in the oxyalkylene group and / or -R ⁷ COO- (R ⁷ carbon atoms represented by an alkylene group) having from 2 to 4 containing an ester group carbon atoms represented by alkylene groups) of 1 to 10 For example, those represented by the following general formula (3) are preferable.

R ¹⁰ R ¹¹ R ¹² SiS (CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ S ₂ ) _q — —CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ SSiR ¹⁰ R ¹¹ R ¹² (3) ( (In the formula, q is an integer of 0 to 25.)

[0027] Especially the following formula among the above-mentioned compound _{(4): (CH 3)} 3 SiS (CH 2 CH 2 OCH 2 OCH 2 CH 2 S 2) r - -CH 2 CH 2 OCH 2 OCH 2 CH 2 S Si (CH ₃ ) ₃ (4) (wherein r is an integer of 0 to 10) are preferable.

In addition, those represented by the following general formulas (5) to (8) are also suitable. ^{R 10 R 11 R 12 SiS (} R 13 O) s R 14 SSiR 10 R 11 R 12 ··· (5) ( wherein, R ¹³ and R ¹⁴ is an alkylene group having 2 or 3 carbon atoms, S is . 0-50 is an integer ^{of) R 10 R 11 R 12 SiS} (CH 2) 6 SCH 2 CH 2 (OCHR 15 - -CH 2 SCH 2 CH 2) m (CH 2) 4 SSiR 10 R 11 R 12 · .. (6) (In the formula, R ¹⁵ is hydrogen or a methyl group, and m is 0 to 25.
Is an integer. ^{) R 10 R 11 R 12 SiSCH} 2 COOCH 2 C- - (CH 2 OCOCH 2 SSiR 10 R 11 R 12) 3 ··· (7) (R 10 R 11 R 12 SiSCH 2 CH 2 COOCH 2) 3 CC 2 H ₅ ··· (8)

Such a compound can be obtained by converting a thiol group of a compound having two or more thiol groups per molecule into a trialkyl (or phenyl) silylthio group.

Examples of the thiol group-containing compound used as a raw material here include liquid polysulfide polymers described in US Pat. No. 2,466,963, polyoxyalkylene polyols described in Japanese Patent Publication No. 47-48,279, and US Pat. No. 4,092,293. Polymercaptans described in U.S. Pat. No. 3,923,748, mercaptan-terminated liquid polymers described in U.S. Pat.No. 3,923,748, and poly (oxyalkylene) -polyester-polyls described in Japanese Patent Publication No. 52-34677.
(Monosulfide) -Polythiol, U.S. Pat.No. 3,282,9
Butadiene mercaptan polymer described in No. 01, mercaptan-containing polymer described in U.S. Pat. No. 3,523,985, and Japanese Patent Publication Nos. 55-39261 and 60-342.
1 and mercaptoorganopolysiloxanes described in JP-A-4-7331 and the like.

Examples of the method for converting the thiol group of the thiol group-containing compound as described above into a trialkylsilylthio group include the following methods (1) and (2).

(1) A compound containing a thiol group and a halosilane having a molar equivalent to that of the thiol group of the compound (a compound represented by the general formula: R ¹⁰ R ¹¹ R ¹² SiX, provided that R ¹⁰ , R ¹¹ and R ¹² is the same as above, and X represents a halogen group) in the presence of a tertiary amine such as trimethylamine or triethylamine to react the thiol group of the thiol group-containing compound with a trialkyl (or phenyl) group.
Convert to silylthio group.

Examples of the above-mentioned halosilanes include trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, etc., but from the viewpoint of reactivity with a thiol group, easy removal of by-products, economical efficiency, etc. Is particularly preferable.

(2) It is also possible to use a method in which a thiol group-containing compound is reacted with 1/2 mol or more, preferably equimolar to 3 times mol, of the thiol group, in the presence of a suitable reaction catalyst. . As the reaction catalyst, J. Org.
Although those described in Chem. 47 , 3966 (1982) and the like can be used, imidazole, saccharin and the like are particularly preferable. The amount used is about 0.01 to 0.1 equivalent with respect to the thiol group-containing compound.

(C) Blending Ratio The blending ratio of the (A) adhesion-imparting agent as described above and the (B) sulfur-containing polymer is (A) adhesion-imparting agent based on 100 parts by weight of the (A) sulfur-containing polymer. 0.1 to 50 parts by weight, especially 0.2
It is preferably from 10 to 10 parts by weight. (A) Adhesion imparting agent is 0.
If it is less than 1 part by weight, the adhesiveness of the obtained composition is not sufficient, and if it exceeds 50 parts by weight, the change in physical properties becomes large, which is not preferable.

(D) Two or more isocyanate groups in the molecule
The urethane prepolymer having a curable composition of the present invention, in the above (A) and (B) component
By blending (D) a urethane prepolymer having two or more isocyanate groups in the molecule, a one-pack curable composition can be obtained.

As the urethane prepolymer having two or more isocyanate groups in the molecule, commercially available polyester type urethane prepolymer, polyether type urethane prepolymer and the like can be used. Among them, the molecular weight of 800 to 800 is particularly preferable. 20,000 is preferred, especially 1,00
It is preferably from 0 to 8,000. If the molecular weight is less than 800,
It is not preferable because the reactivity of the isocyanate group is high, the storage stability of the composition becomes poor, and foaming easily occurs. On the other hand, if the molecular weight exceeds 20,000, the storage stability becomes poor, which is not preferable.

The urethane prepolymer containing two or more isocyanate groups in one molecule can be obtained as a reaction product of an organic polyisocyanate and an active hydrogen-containing compound.

Examples of organic polyisocyanates include 2,
4- or 2,6-tolylene diisocyanate (TDI), diphenylmethane-4,4'-diisocyanate (MDI),
4,4'-Dicyclohexylmethane diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPD
I), 1,5-naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), methylcyclohexylene diisocyanate (hydrogenated TDI), cyclohexylene diisocyanate (hydrogenated XDI) ) And the like. These may be used alone or in combination of two or more.

Examples of active hydrogen-containing compounds include high molecular weight polyols (eg, polyether polyols, polyester polyols, polybutadiene polyols, polyacrylate polyols, polyisoprene polyols).
And low molecular weight polyols.

The compounding ratio of the urethane prepolymer as described above is such that the SR of the sulfur-containing polymer is based on the NCO group.
It is preferred that the ratio of the groups is 0.3 to 2.0.

(E) Curing Agent In the curable composition of the present invention, instead of the component (D),
(E) A curing agent can be added. As a curing agent,
Examples thereof include oxidizing agents such as lead peroxide, manganese peroxide, zinc peroxide, sodium perborate, calcium peroxide, barium peroxide, strontium peroxide, antimony dioxide, cumene hydroperoxide, and oxygen.

The compounding amount of these curing agents varies depending on the kind, but is generally 1 to 20 parts by weight with respect to 100 parts by weight of the sulfur-containing polymer.

To the curable composition of the present invention, a filler such as calcium carbonate, talc, clay, titanium oxide or silica is added for the purpose of further improving the economical efficiency, workability and physical properties after curing. You can Further, a phthalic acid ester such as dioctyl phthalate (DOP) or butylbenzyl phthalate (BBP), or a plasticizer such as chlorinated paraffin or hydrogenated terphenyl may be added to the curable composition of the present invention.

[0045]

The adhesion-imparting agent of the present invention is obtained by modifying a compound having two or more SH groups, OH groups and / or NCO groups per molecule with a specific alkoxysilane.
It gives strong adhesion to the sulfur-containing polymer even in a small amount, and does not impair the excellent rubber elasticity and storage stability of the sealing material. Further, a curable composition containing the adhesion-imparting agent and a sulfur-containing compound having a structural unit of any one of a polyether bond, a polysulfide bond, a carbonyl structure, a urethane bond and a thiourethane bond is to be adhered to an adherend. Even without applying a primer, it has good adhesiveness and excellent storage stability.

Although the reason why such an effect is obtained is not necessarily clear, the portion of the alkoxysilane introduced into the adhesion promoter is hydrolyzed to a silanol group, and this silanol group is highly reactive. It is thought that this is because the surface of the non-adhesive is firmly bonded.

[0047]

The present invention will be described in more detail by the following examples. Synthesis Example 1 Production of adhesion-imparting agent a Mercaptan-terminated polysulfide polymer (“Thiocol LP3” manufactured by Toray Thiokol Ltd., ratio of SH groups 6.
(8 wt%) 200 g and 48.6 g of γ-glycidoxypropyltrimethoxysilane were placed in a flask and heated under a N ₂ stream while mixing, and after the temperature reached 80 ° C., 2% of KOH as a catalyst was used. % Polyethylene glycol solution% 2 g was added and mixed for 1.5 hours while maintaining the temperature at 80 ° C.

Then, the unreacted material was distilled off under reduced pressure with heating to obtain a product (hereinafter, this product is referred to as an adhesion promoter a). When the product thus obtained was subjected to IR measurement, the ratio of SH groups was halved.

Synthesis Example 2 Manufacture of adhesion promoter b Mercaptan-terminated polysulfide polymer ("Thiocol LP3" manufactured by Toray Thiokol Ltd., ratio of SH groups 6.
(8% by weight) 200 g and 42.2 g of 3 isocyanatopropyltrimethoxysilane were put in a flask and heated under a N ₂ stream while mixing, and after the temperature reached 80 ° C., 0.2 g of triethylamine was added as a catalyst. Then, the mixture was mixed for 0.5 hour while maintaining the temperature at 80 ° C.

Then, the unreacted material was distilled off under heating and reduced pressure to obtain a product (hereinafter, this product is referred to as an adhesion promoter b). When the product thus obtained was subjected to IR measurement, the ratio of SH groups was halved.

Synthesis Example 3 Production of Polysulfide Polymer C 100 parts by weight of a polymer obtained by adding epichlorohydrin to a bifunctional polypropylene glycol having a molecular weight of 700 and further SH-terminating the end with sodium hydrosulfide, and a mercaptan-terminated polysulfide polymer (Toray Thiokol Ltd.) Made "L
P55 ") 100 parts by weight, and 50 against this total
% Citric acid aqueous solution 0.1% is added to cause exchange reaction, and SH
A liquid polymer with a group content of 3.5% was obtained. Hereinafter, this liquid polymer is referred to as polysulfide polymer C.

Synthesis Example 4 Production of Adhesion-imparting Agent d Polysulfide polymer C (350 g) was added to SH.
1.3 times the molar amount of trimethylchlorosilane (56.2
g) and its equivalent to triethylamine (49.9 g) were mixed with toluene as a solvent, and the product was filtered to obtain a polymer. When IR measurement was performed on this polymer, the SH group disappeared, but the OH group remained.

An equimolar amount of 3 isocyanatopropyltrimethoxysilane with respect to the residual OH groups of this polymer and 0.1% by weight of dibutyltin laurate as a catalyst were added and reacted. The polymer thus obtained is hereinafter referred to as an adhesion imparting agent d.

Synthesis Example 5 Production of Adhesion Agent e Polysulfide polymer ("Thiocol LP70" manufactured by Toray Thiokol Co., Ltd., SH group ratio 13.9% by weight) 20
0 g and γ-glycidoxypropyltrimethoxysilane
99.4g was placed in a flask and heated under a N ₂ stream while mixing, and after the temperature reached 80 ° C., 2 g of 2% polyethylene glycol solution of KOH was added as a catalyst to keep the temperature at 80 ° C. While mixing for 1.5 hours.

Then, the unreacted material was distilled off under heating and reduced pressure to obtain a polymer product (hereinafter, this product is referred to as an adhesion promoter e). When the product thus obtained was subjected to IR measurement, the ratio of SH groups was halved.

Synthesis Example 6 Production of adhesion-imparting agent f Polysulfide polymer ("Thiocol LP70" manufactured by Toray Thiokol Ltd., SH group ratio 13.9% by weight) 20
0 g and 3 isocyanatopropyltrimethoxysilane
86.3 g was put in a flask and heated under a N ₂ stream while mixing, and after the temperature reached 80 ° C., 2,4 as a catalyst
0.05% by weight of 6-tris (dimethylaminomethyl) phenol was added, and the mixture was mixed for 0.5 hours while maintaining the temperature at 80 ° C.

Then, the unreacted material was distilled off under heating and reduced pressure to obtain a polymer product (hereinafter, this product is referred to as an adhesion-imparting agent f). When the product thus obtained was subjected to IR measurement, the ratio of SH groups was halved.

Synthesis Example 7 Production of Sulfur-Containing Polymer (I) Polysulfide polymer C (500 g) was added to SH.
2 times the molar amount of trimethylchlorosilane (123
g) and trimethylamine (109 g) were mixed with toluene as a solvent, and the product was filtered to obtain a polymer (hereinafter, this polymer is referred to as polymer (I)). When IR measurement was performed on this polymer, SH groups and OH groups were completely disappeared.

Synthesis Example 8 Production of Sulfur-Containing Polymer (II ) 500 g of polysulfide polymer (“LP3” manufactured by Toray Thiokol Ltd., SH group content 6.8% by weight), 161 g of hexamethyldisilazane, and 0.5 g of saccharin. And were placed in a 1-liter reaction vessel equipped with a cooler and a stirrer, immersed in a thermostat of 120 ° C., and reacted for 5 hours. Then, the pressure was reduced to remove excess hexamethyldisilazane to obtain a polymer represented by the following chemical formula (hereinafter, this polymer is referred to as polymer (II)). (CH ₃ ) ₃ Si (SCH ₂ CH ₂ OCH ₂ OCH ₂ CH
₂ S) ₆ Si (CH ₃ ) ₃

Synthesis Example 9 Production of Urethane Prepolymer Polyoxypropylene triol having an average molecular weight of 5000,
100 parts by weight of a mixture of polyoxypropylene having an average molecular weight of 4000 was reacted with 7.7 parts by weight of tolylene diisocyanate to give a urethane prepolymer (NCO group content ratio of 1.3.
(Wt%) was obtained (hereinafter, this polymer is referred to as polymer U).

Example 1 22 parts by weight of the polymer (I) was mixed with 100 parts by weight of the polymer U, and they were sufficiently mixed in a mixing container. 30 parts by weight of dioctyl phthalate which had been dehydrated in advance, 150 parts by weight of sufficiently dried calcium carbonate and 10 parts by weight of titanium oxide were added thereto and mixed sufficiently under reduced pressure, and after defoaming, 15 parts by weight of xylene and N, N, N ', N' tetramethyl 1,
0.05 parts by weight of 3 diaminopropene was added to obtain a one-component curing type sealant.

4 parts by weight of the adhesion-imparting agent d was added to 327 parts by weight of this one-component curing type sealant to obtain a curing type composition. Using the curable composition thus obtained as a sealing material, tensile properties, curability, and storage stability were measured. The results are shown in Table 1 together with the composition.

(1) Tensile properties 20 mm × 7 days + 30 ° C. Filling the gap (12 mm) between two 50 mm × 50 mm × 3.5 mm plate materials (alumite material: no primer) with a depth of 12 mm × After curing for 7 days and at 20 ℃
50% elongation strength, maximum tensile strength and maximum elongation after curing for 7 days + 20 ° C and 7 days (immersion in water) were measured using a tensile adhesion tester. Further, the peeled state when the plate material was peeled off after aging was visually observed and evaluated according to the following criteria. ◯: The sealant layer was cohesively broken. Δ: The sealant layer was cohesively broken on the adhesive surface. X: Peeled on the adhesive surface.

(2) Curability A single-sided bead having a width of 12 mm and a depth of 15 mm was prepared, and the temperature was 10 ° C for 7 days.
(RH 40%) After curing, the thickness of the cured part from the surface was measured.

(3) Storage stability The sealant is sealed in an aluminum tube and kept at 70 ° C.
The sample was stored in a constant temperature bath of No. 2 and measured for the period until it could not be extruded due to thickening or solidification in the tube.

Example 2 Instead of the polymer (I) in Example 1, the polymer (II) was used.
A one-component curing type sealant was manufactured in the same manner except that was used.

3 parts by weight of the adhesion-imparting agent a was added to 327 parts by weight of this one-component curing type sealant to obtain a curing type composition. Using the curable composition thus obtained as a sealing material, tensile properties, curability, and storage stability were measured in the same manner as in Example 1. The results are shown in Table 1 together with the composition.

Example 3 A one-component curable composition was produced in the same manner as in Example 2 except that the adhesion-imparting agent d was used instead of the adhesion-imparting agent a. Using the curable composition thus obtained as a sealing material, tensile properties, curability, and storage stability were measured in the same manner as in Example 1. The results are shown in Table 1 together with the composition.

Comparative Examples 1, 2 Tensile properties, curability, and storage stability were measured in the same manner as in Example 1 except that the adhesion promoter was not added in Examples 1 and 2. The results are shown in Table 1 together with the composition.

Table 1 Composition Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Polymer component (I) + U (II) + U (II) + U (I) + U (II) + U Adhesive type d ad − − Addition amount ⁽¹⁾ 4 3 3 − − Physical properties 20 ° C. × 7 days + 30 ° C. × 7 days 50% elongation after curing ⁽²⁾ 2.2 0.9 1.0 1.8 1.0 Maximum tensile strength ⁽³⁾ 9.2 2.3 2.6 5.5 2.2 Maximum elongation ⁽⁴⁾ 700 435 465 775 435 Peeling condition ○ × × △ × 20 ℃ × 7 days + 20 ℃ × 7 days (water immersion) 50% elongation strength after curing 2.0 1.0 1.0 1.6 0.9 Maximum tensile strength 7.8 3.4 2.9 3.3 1.8 Maximum elongation 685 655 565 565 330 Peeling condition △ △ △ × × Curability ⁽⁵⁾ 7.2 7.6 6.1 5.5 5.5 Storage stability ⁽⁶⁾ 8 1 10 10 10

Note) (1): Sealant material (polymer component)
327 Addition amount based on parts by weight (unit is parts by weight). (2): Unit is kg / cm ² (3): Unit is kg / cm ² (4): Unit is% (5): Unit is mm. (6): Unit is day.

Example 4 Tensile physical properties were the same as in Example 1 except that the adherend made of the sealing material was glass (without a primer).
Curability and storage stability were measured. The results are shown in Table 2 together with the composition.

Example 5 Tensile properties, curability, and storage stability were measured in the same manner as in Example 2 except that the adherend made of the sealing material was glass. The results are shown in Table 2 together with the composition.

Example 6 Tensile properties, curability, and storage stability were measured in the same manner as in Example 3, except that the adherend made of the sealing material was glass. The results are shown in Table 2 together with the composition.

Example 7 Commercially available polysulfide sealant (“SC-500” manufactured by Yokohama Rubber Co., Ltd .: three-component type consisting of a main agent, a curing agent and a coloring agent, hereinafter referred to as polymer (III)) Adhesive imparting agent a in parts by weight 0.5 part by weight was added to obtain a curable composition. Using the curable composition thus obtained as a sealing material, tensile properties were measured in the same manner as in Example 4. Also, the storage stability was evaluated. The results are shown in Table 2 together with the composition.

The storage stability was evaluated as follows. After storing the sealant at 50 ° C for 2 weeks, mix it with a curing agent to make two 50 mm x 50 mm x 3.5 mm plates (glass:
Fill the gap (12 mm) (without primer) with a depth of 12 mm, and after curing at 20 ° C x 7 days + 30 ° C x 7 days, and
Tensile physical properties after immersion in hot water at 50 ° C. for 7 days were measured, and those having good adhesion to the glass surface were evaluated as ◯, and those having poor adhesion were evaluated as x.

Example 8 A multi-part curable composition was produced in the same manner as in Example 7 except that the adhesion-imparting agent b was used instead of the adhesion-imparting agent a. The curable composition thus obtained was used as a sealing material to measure tensile properties and storage stability. The results are shown in Table 2 together with the composition.

Example 9 A multi-component curable composition was produced in the same manner as in Example 7 except that the adhesion imparting agent e was used instead of the adhesion imparting agent a. Using the curable composition thus obtained as a sealing material, tensile properties, curability, and storage stability were measured. The results are shown in Table 2 together with the composition.

Example 10 A multi-component curable composition was produced in the same manner as in Example 7 except that the adhesion-imparting agent f was used instead of the adhesion-imparting agent a. Using the curable composition thus obtained as a sealing material, tensile properties, curability, and storage stability were measured. The results are shown in Table 2 together with the composition.

Comparative Examples 3 to 5 Tensile physical properties, curability, and storage stability were measured in the same manner as in Example 4, except that the adhesion promoter was not added in Examples 4, 5 and 7. The results are shown in Table 2.

Comparative Examples 6 and 7 100 parts by weight of a commercially available polysulfide sealant (“SC-500” manufactured by Yokohama Rubber Co., Ltd .: a three-component type consisting of a main agent, a curing agent and a coloring agent) was used as an adhesion promoter. Methoxysilane (hereinafter referred to as adhesion promoter g)
0.1 and 0.3 parts by weight were added to obtain a curable composition. Using the curable composition thus obtained as a sealing material, tensile properties and storage stability were measured in the same manner as in Example 4. The results are shown in Table 2.

Comparative Example 8 A commercially available polysulfide sealant (“SC-500” manufactured by Yokohama Rubber Co., Ltd .: three-component type consisting of a main agent, a curing agent, and a coloring agent) was used alone as a sealing material on the glass surface to be adhered. Tensile properties were measured in the same manner as in Example 4 except that a primer (No. 18 manufactured by Yokohama Rubber Co., Ltd.) was applied.
The results are shown in Table 2.

Table 2 Composition Example 4 Example 5 Example 6 Example 7 Example 8 Polymer component (I) + U (II) + U (II) + U (III) (III) Kind of adhesion promoter d a d a b Addition amount 4 3 3 0.5 0.5 Physical properties 20 ℃ × 7 days + 30 ℃ × 7 days 50% elongation strength after curing 2.2 0.9 1.0 1.6 1.6 Maximum tensile strength 9.0 3.0 3.5 4.3 3.9 Maximum elongation 700 580 645 450 450 Peeling condition ○ ○ ○ ○ ○ 20 ℃ × 7 days + 20 ℃ × 7 days (water immersion) 50% elongation after curing 2.0 0.9 0.9 1.5 1.5 Maximum tensile strength 9.1 3.7 4.0 4.1 4.4 Maximum elongation 710 670 730 505 625 Peeling condition ○ ○ ○ ○ ○ Storage stability − − − ○ ○

Table 2 (continued) Composition Example 9 Example 10 Comparative Example 3 Comparative Example 4 Comparative Example 5 Polymer component (III) (III) (I) + U (II) + U (III) Adhesion imparting agent Type ef − − − Addition amount 0.5 0.5 − − − Physical properties 20 ℃ × 7 days + 30 ℃ × 7 days Elongation after curing 1.6 1.9 1.6 1.0 1.3 Maximum tensile strength 4.3 4.4 2.6 2.4 2.6 Maximum elongation 450 410 390 475 405 Peeling Condition ○ ○ × × × 20 ° C × 7 days + 20 ° C × 7 days (water immersion) Elongation after curing 1.7 1.9 1.5 0.9 1.3 Maximum tensile strength 4.2 4.4 1.8 2.2 2.2 Maximum elongation 460 460 180 455 410 Peeling condition ○ ○ × × × Storage stability ○ ○ − − ×

[0085]

As is clear from Tables 1 and 2, the curable compositions of the respective examples containing the adhesion-imparting agent of the present invention showed good adhesiveness even if the adherend was not coated with a primer. And has excellent curability and storage stability. On the other hand, each comparative example was inferior in adhesiveness to each corresponding example. In addition, the known adhesion-imparting agent markedly increased the modulus of cured physical properties when it was administered to the sealing agent until the adhesive effect was exhibited.

[0087]

The adhesion-imparting agent of the present invention contains 2 per molecule.
Since a compound having one or more SH group, OH group and / or NCO group is modified with a specific silane compound,
It gives strong adhesion to the sulfur-containing polymer even in a small amount, and does not impair the excellent rubber elasticity and storage stability of the sealing material. Further, a curable composition of the present invention containing the above-mentioned adhesion-imparting agent and a compound having one structural unit of a polyether bond, a polysulfide bond, a carbonyl bond, a urethane bond and a thiourethane bond is an adherend. It has good adhesiveness and excellent storage stability even if it is not coated with a primer.

The curable composition containing the adhesion-imparting agent of the present invention is extremely suitable as a sealing material.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tatsuro Matsui 2-3, Chikusaigan, Ichihara-shi, Chiba Torayachiol Co., Ltd. Chiba factory (72) Minoru Yabu 3-2, Chikusaigan, Ichihara-shi, Chiba Toletioco Chiba factory

Claims (4)

[Claims] 1. (a) The main chain of which is —R ¹ O— (wherein R ¹ represents an alkylene group having 2 to 4 carbon atoms), —R ² COO.
-(Provided that R ² represents an alkylene group having 1 to 10 carbon atoms) and a polysulfide bond, and (b) has -SH, -OH or -NC at the terminal.
O ^{3 and} at least a part of the end groups is AR ³ _a Si
R ⁴ (OR ⁵ ) _3-a (provided that R ³ has 2 to 4 carbon atoms)
Valent hydrocarbon group, R ⁴ and R ⁵ represent a monovalent hydrocarbon group having 1 to 4 carbon atoms, A is an isocyanate group, a glycidoxy group or a methacryloxy group when the terminal is -SH, and the terminal is- In the case of OH, it is an isocyanate group or a glycidoxy group, in the case of -NCO, it is a mercapto group or an amino group, and a is 0, 1 or 2. ) An adhesion-imparting agent characterized by being modified with an alkoxysilane. 2. A (A) adhesive imparting agent according to claim 1, (B) _{^{(i) - (R 6 O) n}} - ( where, R ⁶ is 2 carbon atoms
4 is an alkylene group, and n is an integer of 6 to 200. ),
_{(B) - (C 2 H 4 OCH} 2 OC 2 H 4 S x) m -, -
_{(C 2 H 4 OC 2 H} 4 OC 2 H 4 S x) m -, and / or _{- (CH 2 CH (OH)} CH 2 S x) m - ( where
x represents an integer of 1 to 4 and m represents an integer of 6 to 50. ),
(C) -R ⁷ COO- (provided that, R ⁷ represents an alkylene group having 1 to 10 carbon atoms), containing (D) -NHCOO- and / or -NHCOS- 1 or two or more, and At least two ends have -CHR ⁸ SR ⁹ (provided that
R ⁸ represents —H, —CH ₃ or C ₂ H ₅ , and R ⁹ represents —
H or —SiR ¹⁰ R ¹¹ R ¹² (R ¹⁰ , R ¹¹ and R ¹² are each an alkyl group having 1 to 6 carbon atoms, a phenyl group or a haloalkyl group). ) Molecular weight 500 ~
A curable composition containing 10,000 sulfur-containing liquid polymer. 3. The curable composition according to claim 2, wherein the composition further contains a urethane prepolymer having two or more isocyanate groups in the molecule. 4. The curable composition according to claim 2, wherein the composition further contains a curing agent.