JPH0322905B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a reactive emulsion made of polyether or polyester containing reactive silicon groups in the molecule. The present inventors have already reported that polyethers or polyesters containing reactive silicon groups, for example, at the terminals, are useful as room-temperature-curable elastic sealing materials when used in liquid form. The inventors,
When this reactive polyether or polyester was dispersed with water using a surfactant to form an emulsion, it was discovered that the emulsion was highly stable and could be used for various purposes, and the present invention was achieved. That is, the present invention is a reactive emulsion in which a polyether or polyester having at least one side chain or terminal reactive silicon group per molecule is dispersed in water using a surfactant. In the polyether or polyester having a reactive silicon group according to the present invention, it is necessary that at least one reactive silicon group exists at the terminal or side chain of the molecule. As the reactive silicon group, the following general formula (1) is used. [In the formula, m is an integer of 0 to 18, a is 0, 1, 2 or 3, and b is 0, 1 or 2. However, there is only m ( )
Each of the siloxy groups within may take on a different value. X is a hydride group, a hydroxyl group, or an alkoxy group (-OR: R is a hydrocarbon group having 1 to 20 carbon atoms).
However, the groups represented by X, which are equal to a+m×b, may be different from each other. However, it is necessary that at least one group represented by X be present in this formula. R ^I is a hydrocarbon group having 1 to 20 carbon atoms or a triorganosiloxy group. However, (3-a)+m
The groups represented by R ^I in (2-b) may be different from each other. ] It is a group represented by Among these, m is preferably 0, and one of X is preferably an alkoxy group. The main chain of the polyether used in the present invention essentially has repeating units represented by the formula -(R〓-0)-. Here, R is a divalent organic group, preferably a hydrocarbon group having 1 to 4 carbon atoms. Preferred examples of R〓 include −CH ₂ −, −CH ₂ CH ₂ −,

【formula】

[Formula] −CH ₂ CH ₂ CH ₂ CH ₂ −

【formula】 was given,

The formula is most preferred. These may be used alone or in combination. The molecular weight of the polyether used in the present invention is 500
~15000 is preferred. Other polyethers or polyesters containing reactive silicon groups in the molecule used in the present invention include:
Special Publication 1977-36319, Special Publication 12154, Special Publication 1977-
30711, Special Publication No. 48-36960, No. 49-32673, No. 129247 No. 53-129247, No. 6097 No. 54-6097, No. 55-
82123, JP 55-123620, JP 55-125121,
This is shown in Japanese Patent Application Laid-Open Nos. 55-135135, 1982-137129, etc. As the surfactant used in the present invention, anionic, cationic, nonionic, or amphoteric surfactants may be used alone or in combination. Specifically, these surfactants include fatty acid soap, higher alcohol sulfate ester salt, higher alcohol phosphate ester salt, alkyl sulfonate, alkylbenzene sulfonate, dinaphthylrethane disulfonate, N-methyl alkyl taurate, Alkyl sulfosuccinate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenol ether sulfate, N-acyl sarcosinate, alkylamine salt, trimethylalkylammonium salt, alkyldimethylbenzylammonium salt, alkylpyridinium salt, polyoxy Ethylene alkylamino ether, alkylimidazoline, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty acid ester, polyoxyethylene alkyl thioether, alkylolamide, polyoxyethylene/polyoxypropylene block copolymer,
Fatty acid sorbitan ester, polyoxyethylene sorbitan alkyl late, alkyl betaine,
Examples include, but are not limited to, N-alkyl(aminoethyl)glycine. In the present invention, the amount of surfactant is usually in the range of 1 to 30 parts by weight per 100 parts by weight of the polymer whose main component is polyether or polyester having at least one reactive silicon group in one molecule. However, preferably 2 to 15 parts by weight. In the present invention, an emulsion can be prepared by adding water and thoroughly dispersing both components. By appropriately selecting the amount of water and the type of surfactant, W/O type and O/W type emulsions can be made. The emulsion of the present invention can volatilize water,
If it is absorbed into something, the emulsion will be destroyed and become a solid-liquid fused substance. Further, the fused product is cured by chain extension and crosslinking due to the presence of reactive silicon groups. Utilizing this property, the emulsion of the present invention can be used as a sealant, adhesive, pressure-sensitive adhesive, paint, packaging material, spraying material, molding material, modifying material for various rubber and synthetic resin emulsions, surface treatment agent, binder, etc. It can be usefully used as The emulsion of the present invention has room-temperature curability compared to conventional reactive emulsions, and while the emulsion particles of ordinary reactive emulsions are solid, the emulsion of the present invention has liquid particles. Therefore, when the emulsion is broken, the particles have good fusion properties, and in normal reactive emulsions, a solvent is added in advance to increase the fusion properties of the particles when the emulsion is broken. However, in the emulsion of the present invention, this is not necessary and can be carried out without a solvent.
Moreover, because of this, it is excellent in that the concentration of the polymer itself can be increased. Furthermore, since the emulsion of the present invention is reactive, polymerization due to chain extension and crosslinking occurs when the emulsion is broken (in most cases, during coating formation).
This is its most important feature, and as a result, it can be used conveniently and easily for the various purposes mentioned above. In the present invention, various additives, modifiers, curing catalysts, and reinforcing agents are further added to stabilize the emulsion, accelerate the curing of the solid-liquid fused product, and improve the properties of the cured product. , fillers, etc. may be used in combination, especially in the aqueous phase. For example, to stabilize emulsions, cationic systems derived from sodium carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, polymaleic acid, copolymers of maleic acid or acrylic acid with various monomers such as vinyl acetate, vinylpyridine, etc. Synthetic polymer dispersants and thickeners such as polysoap, polyacrylpyrrolidone, polyacrylamide, and polyethylene glycol;
Natural polymers such as rubber, sodium alginate, glue, casein, egg white, lecithin, starch, starch derivatives, and methylated cellulose; inorganic materials such as bentonite and activated clay can be used. Since the emulsion of the present invention has a reactive silicon functional group, it can be used as a reactive emulsion, but the mechanism is that after the emulsion is broken, the silicon functional group causes a silanol condensation reaction, resulting in polymerization or tertiary formation. It will become original,
In order to allow this condensation reaction to proceed smoothly even at low temperatures, it is more preferable to use a silanol condensation catalyst in combination. Examples of the condensation catalyst include alkyl titanates; organosilicon titanates; metal salts of carboxylic acids such as tin octylate, dibutyltin dilaurate, dibutyltin maleate; and amine salts such as dibutylamine-2-ethylhexoate. Silanol condensation catalysts such as; and other acidic and basic catalysts are effectively used. It is preferable that these condensation catalysts are separately emulsionized and added. The amount of the condensation catalyst used is 0.01 to 10% by weight based on the reactive silicon group-containing polyether or polyester of the present invention.
It is appropriate to use. Various additives may be used in combination with the emulsion of the present invention in order to improve its properties after curing. For example, ultraviolet absorbers, antioxidants, etc. are used to improve weather resistance, and phenolic resins, epoxy resins, modified rosins, terpene resins, and reactive silicone compounds are used to improve adhesiveness (see, for example, JP-A-129247-1988). ), 1,2-polybutadiene, 1,4-polybutadiene, etc. to improve water resistance and mechanical properties.
Modified and unmodified polymers such as polybutadiene, polyisobutylene, polyester, polyisoprene, and polydimethylsiloxane, reinforcing agents such as white carbon, plasticizers, various fillers, etc. are added depending on the purpose. These additives are effective if they are directly added to polyether or polyester having at least one reactive silicon group in each molecule. The emulsion in the present invention is a sealant,
It can be usefully used as an adhesive, a pressure-sensitive adhesive, a paint, a packaging material, a spraying material, a molding material, a modifier for various rubber and synthetic resin emulsions, a surface treatment agent, etc. Examples will be specifically described below. Reference Example 1 800 g of polypropylene oxide (manufactured using polypropylene glycol as a starting material) with an average molecular weight of 8000 containing 97% allyl ether groups at the terminals was placed in a pressure-resistant reaction vessel equipped with a stirrer, and methyl dimethoxy Add 15 g of silane, followed by a catalyst solution of chloroplatinic acid (H ₂ PtCl ₆ .
After adding 0.34 ml of a solution of 8.9 g of 6H ₂ O dissolved in 18 ml of isopropyl alcohol and 160 ml of tetrahydrofuran, the mixture was reacted at 80° C. for 6 hours. As a result of quantifying the residual hydrosilyl group from the IR spectrum, it was found that most of it had reacted.

A polypropylene oxide terminated with the group [Formula] was obtained. Reference Example 2 800 g of polypropylene oxide with an average molecular weight of 8000 containing 97% allyl ether groups at the terminals was placed in a pressure-resistant reaction vessel equipped with a stirrer.

60 g of a silicon hydride compound having the structure of [Formula] was added, followed by 0.34 ml of a chloroplatinic acid catalyst solution (same as in Reference Example 1), and the mixture was reacted at 80° C. for 6 hours. IR analysis shows that there is no residual hydroxyl group at the end. It was found that polypropylene oxide having groups was obtained. Reference Example 3 600 g of polypropylene oxide with an average molecular weight of 6000 containing 96% of allyl ether groups at the ends was placed in a pressure-resistant reaction vessel equipped with a stirrer.

27 g of a silicon hydride compound having the structure of [Formula] was added, followed by 0.34 ml of a chloroplatinic acid catalyst solution (same as in Reference Example 1), and the mixture was reacted at 80° C. for 6 hours. Thereafter, 500 ml of toluene was added, further 18 g of triethylamine was added, and 4 g of water was added dropwise while stirring while maintaining the temperature at 30°C. Hydrolysis was carried out by stirring at 40°C for 3 hours. The generated triethylamine hydrochloride was separated and toluene etc. was distilled off at 60°C under reduced pressure.

The structure of [Formula] A polypropylene oxide with ends was obtained. Reference example 4 at one end

100 g of polycaprolactone having a molecular weight of 1000 and having a HO group at the other end is dissolved in 100 ml of toluene and placed in a pressure-resistant reaction vessel equipped with a stirrer. Furthermore, 11 g of triethylamine was added and mixed uniformly, and then 10.2 g of terephthalic acid chloride was added to toluene while stirring.
Add 100 ml of the mixed solution dropwise at 30°C. After stirring at 30°C for 5 hours, the mixture was heated to 60°C and reacted for 5 hours. If the triethylamine salt formed is separated and the toluene is distilled off at 80°C under reduced pressure, it will form a chain extension unit in the molecular chain.

[Formula] 1 group own and end

A polycaprolactone having an average molecular weight of about 2000 is obtained. 100 g of the polycaprolactone was placed in a reaction vessel equipped with a stirrer, and 50 ml of toluene was added to dissolve it uniformly. Then, 11 g of trimethoxysilane was added, followed by 0.25 g of a chloroplatinic acid catalyst solution (same as in Reference Example 1).
ml was added and reacted at 80°C for 6 hours. As a result of quantifying the residual hydroxyl groups from the IR spectrum, it was found that most of them had reacted.

A polycaprolactone terminated with the group [Formula] was obtained. Example 1 1 g of polyoxyethylene nonyl phenol ether (Nitsun Nonion NS-206), which is a nonionic surfactant, was thoroughly dissolved in 10 g of the polymer of Reference Example 1, then 10 g of H ₂ O was added, and the mixture was heated in a homogenizer for 10 minutes. An emulsion is obtained by dispersing at 10000 rpm. Even when observed after being left at room temperature for one day, the emulsion did not aggregate and was stable. Meanwhile, 0.5 g of polyoxyethylene nonylphenol ether (Nitsuntonion NS-210) was dissolved in 5 g of dibutyltin dilaurate, and then
Add 5g of H ₂ O and homogenize for 10 minutes
An emulsion of the dispersed catalyst is prepared at 10000 rpm. When 0.42 g of catalyst emulsion is mixed with 21 g of the above polymer emulsion and coated on paper, H ₂ O evaporates and a sticky coating is obtained.
After two days at room temperature, a cured coating film with rubber elasticity was obtained, indicating that the emulsion was reactive at room temperature. Example 2 A polymer emulsion and a catalyst emulsion were prepared in exactly the same manner as in Example 1, except that the polymer of Reference Example 2 was used instead of the polymer of Reference Example 1. Mix 21g of the polymer emulsion with 0.42g of the catalyst emulsion and coat it on paper.
Although a sticky coating film was obtained due to the volatilization of H ₂ O, a cured coating film with rubber elasticity was obtained after 3 days at room temperature. Example 3 A polymer emulsion and a catalyst emulsion were prepared in the same manner as in Example 1, except that instead of using the polymer of Reference Example 1, 10 g of the polymer of Reference Example 3 and 1 g of ethyl silicate were used together. . When 0.42 g of the same catalyst emulsion as in Example 1 is mixed with 22 g of the polymer emulsion and coated on paper, H ₂ O evaporates and a sticky coating is obtained, but after 5 days at room temperature, the rubber hardens. A coating film with elasticity was obtained. Example 4 A polymer emulsion and a catalyst emulsion were prepared in exactly the same manner as in Example 1 except that 1 g of sodium dodecylbenzenesulfonate was used instead of the nonionic surfactant. Mix 21g of the polymer emulsion with 0.42g of the catalyst emulsion and coat it on paper.
Although a sticky coating film was obtained due to the volatilization of H ₂ O, a cured coating film with rubber elasticity was obtained after 3 days at room temperature. Example 5 After dissolving 10 g of the polymer of Reference Example 4 in 2 g of toluene, sodium dodecylbenzenesulfonate was added.
Thoroughly dissolve 1.2 g, then add 12 g of H ₂ O, and disperse with a homogenizer at 10,000 rpm for 10 minutes to obtain an emulsion. Even when the emulsion was observed after being left at room temperature for one day, there was no aggregation of the emulsion and it was stable. When 25.2 g of the polymer emulsion was coated on paper, H ₂ O was volatilized and a soft coating film was obtained, but the coating gradually progressed to harden and became a hard coating film after 20 days at room temperature. Further, for 25.2 g of the polymer emulsion, 0.21 g of the catalyst emulsion prepared by the method of Example 1 was added.
When mixed and coated on paper, the H ₂ O evaporated and a soft coating was obtained, but after two days at room temperature it hardened and became a hard coating.

Claims (1)

[Claims] 1. [In the formula, m is an integer of 0 to 18, a is 0, 1, 2 or 3, and b is 0, 1 or 2. However, there is only m ( )
Each of the siloxy groups within may have different values. X is a hydride group, a hydroxyl group, or an alkoxy group (-OR: R is a hydrocarbon group having 1 to 20 carbon atoms). However, the groups represented by X, which are equal to a+m×b, may be different from each other. However, it is necessary that at least one group represented by X be present in this formula. R ¹ is a hydrocarbon group having 1 to 20 carbon atoms or a triorganosiloxy group. however,
The groups represented by R ¹ which are (3-a)+m(2-b) may be different from each other. ] A reactive emulsion in which a polyether or polyester having at least one reactive silicon group in one molecule in a side chain or terminal is dispersed in water using a surfactant.