JPH01318066A - Aqueous polyether emulsion composition - Google Patents

Abstract

PURPOSE:To make it possible to form an aqueous polyether emulsion composition which, even after a long-term storage, can cure easily at room temperature into an elastomer of excellent rubber properties and good weather resistance by the removal of the water and has good adhesiveness to a substrate by mixing a specified polyether with an emulsifier and water. CONSTITUTION:This composition is prepared by mixing 100 pts.wt. polyether end-blocked with a hydrolyzable silyl group, represented by formula I (wherein R<1>, R<2>, R<3> and R<4> are each a bivalent hydrocarbon group, R<5> is a monovalent hydrocarbon group, X is a hydrolyzable group, a is a number of 1-3; A is -NH-Z- NH- or a group of formula II, wherein Z is a bivalent aromatic group; R<7> and R<8> are each a bivalent hydrocarbon group; m is a number of 10-500; and n is a number >=1) and having an MW of 500-50000 with 1-20 pts.wt. emulsifier and an arbitrary amount of water.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a polyether aqueous emulsion, which has particularly good storage stability, is easily cured at room temperature by removing water, has excellent rubber physical properties, and has good heat resistance. The present invention relates to an emulsion composition that transforms into an elastomer having good properties and weather resistance, and further exhibits good adhesion to various substrates.

[Technical background of the invention and its problems] A polymer whose main chain is polyether and which hardens at room temperature and turns into an elastic body has a low viscosity relative to the degree of polymerization and is excellent in workability. Due to its excellent rubber properties, it is widely used as a pace polymer for architectural sealants. In particular, a polymer whose main chain is polyether and has a hydrolyzable silyl group at the end of the molecular chain, as disclosed in JP-A-50-156599, has been gaining popularity in recent years because of its relatively excellent weather resistance. The amount used is increasing. The present inventor previously considered using this type of polyether as a coating material.

Coating materials currently mainly used for construction are mainly aqueous emulsions of acrylic ester polymers. These acrylic water-based emulsions do not use organic solvents, so there is no risk of poisoning or ignition, and they have the advantage of being able to be applied to substrates that contain some moisture, such as concrete, but they have the disadvantage of inferior rubber properties. Ta.

The present inventor was able to obtain good rubber properties by using the above-mentioned polymer whose main chain is polyether as the base polymer of the coating material. There were problems in that it was not only difficult to form an emulsion but also poor weather resistance.

[Purpose of the invention]

The present invention is intended to solve these problems, and even after long-term storage, it can be easily cured at room temperature by removing water and transformed into an elastomer with excellent rubber physical properties and good weather resistance. Furthermore, it is an object of the present invention to provide a polyether aqueous emulsion composition that has good adhesion to various substrates.

[Structure of the invention]

That is, the present invention is based on the general formula (^); A group represented by, where Z is a divalent aromatic group, R7, R@
is a divalent hydrocarbon group, m is a number from 10 to 500, and n is each a number from 1 to 1), and the molecular weight is from 500 to
50,000, polyether whose molecular chain ends are blocked with hydrolyzable silyl groups (B) 1 to 20 parts by weight (C) An aqueous polyether emulsion composition obtained from any amount of water. .

(^) General formula used in the present invention; % formula % (wherein, R', R'', R3, R', R', X,
In the polymer represented by (a, m, n, and ^ are as described above), the oxyalkylene unit represented by R10 is preferably an oxypropylene unit or a combination system of oxyethylene units and oxypropylene units, and it is easy to use raw materials and polymerize easily. An oxypropylene unit is particularly preferred because it can easily maintain a liquid state even at a high degree of polymerization.

The degree of polymerization m of the oxyalkylene unit is selected from the range of 10 to 500. When m is less than 10, it becomes difficult to obtain an emulsion that provides a rubber-like cured product with a viscosity that provides practical workability and a sufficient elongation rate.

On the other hand, if m is larger than 500, the storage stability, which is a feature of the present invention, decreases.

Examples of the divalent hydrocarbon group for R2 include methylene group, ethylene group, trimethylene group, tetramethylene group, phenylene group, and cyclohexylene tyrant. Among these, a methylene group is preferred due to ease of raw material availability.

Examples of R3 and R4 include the same ones as R2, but R3 is preferably a methylene group from the viewpoint of ease of handling raw materials. Moreover, R4 is preferably an ethylene group, a trimethylene group, or a tetramethylene group from the viewpoint of ease of synthesis and availability of raw materials, and a trimethylene group is particularly preferable.

The monovalent hydrocarbon group for R5 can be selected from alkyl groups, aryl groups, aralkyl groups, etc., but a methyl group is recommended from the viewpoint of ease of synthesis and raw material availability.

The hydrolyzable group of X is an alkoxy group, an alkoxyalkoxy group, an acyloxy group, an N,N-dialkylamino group,
N-alkylamino group, N,N-dialkylamino group,
Examples include N-alkylamide group, NjJ-dialkylaminoxy group, ketoxime group, and alkenoxy group,
Alkoxy groups with 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, and hexyloxy groups and 2 A -methoxyethoxy group and a 2-ethoxyethoxy group are suitable, and a methoxy group and an ethoxy group are particularly preferred because of their good hydrolyzability.

The number a of hydrolyzable groups is selected within the range of 1 to 3, but it is preferable that a is 2 for the purpose of obtaining an emulsion that provides a rubber-like cured product with a high elongation rate.

(The group represented by 8 in A> is -NH-Z-NH- or Z is a divalent aromatic group, R1, +p is a divalent hydrocarbon group. These (^) components are , the previously mentioned Japanese Patent Application Publication No. 50-1565
Unlike the polymers shown in Japanese Patent Application No. 9, etc., even those with a relatively high degree of polymerization are stable as an aqueous emulsion, so they are advantageous in obtaining a rubber-like cured product with a high elongation rate.

Furthermore, the resulting film has excellent heat resistance and weather resistance, and exhibits good adhesion to various substrates.

The molecular weight of (^) is selected from the range of 500 to 50,000, preferably from the range of 1,000 to 10,000. (^
) If the molecular weight is less than 500, the elongation rate of the rubber-like elastic body obtained will be low, and if it is more than 50,000, the storage stability of the aqueous emulsion will be lowered, which is not preferable.

The polyethylene of <A) used in the present invention is, for example, a polyethylene having the general formula (I); A polyoxyalkylene (II) having the general formula: )12N-Z-NH2 (wherein 2 is a) as described above, or an aromatic diamine represented by the general formula: Heterocyclic compound (III) having two imino groups in the molecule General formula: (In the formula, R', R', R', X and a are as described above.) Epoxy group and hydrolysis It can be synthesized by reacting an organic silicon compound with a functional group.

A typical example of (I) is one obtained by adding epichlorohydrin to polyoxyethylene or polyoxypropylene, both ends of which are blocked with hydroxyl groups, in the presence of a basic catalyst or the like.

Specific examples of component (H) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, γ-glycidoxybutyltriethoxysilane, methyl(γ-glycidoxypropyl)dimethoxysilane, methyl(γ-glycidoxypropyl)jethoxysilane, methyl(r-glycidoxybutyl)jet Toxysilane, phenyl (γ-glycitoxyprobyl) dimethoxysilane, phenyl (r-glycidoxybutyl)
Dimethoxysilane, dimethyl (γ-glycidoxypropylene) methoxysilane, dimethyl (γ-glycidoxybutyl) methoxysilane and these alkoxy groups can be converted into alkoxyalkoxy groups, acyloxy groups, N,N-dialkylaminoxy groups, ketoxime Examples include compounds substituted with groups, alkenoxy groups, etc.

Component (A) is the component (I) and (III) described above.
It is obtained by the reaction between the epoxy group of ) and the amino group or imino group of (■).

The reactions (1), (n) and (I) are preferably carried out at a temperature higher than the ambient temperature, for example 50 to 150°C. At that time, methanol, ethanol, phenonovesalicylic acid and tris(dimethylaminomethyl)
Preferably, compounds such as phenol are used as reaction accelerators. Methanol is one of the preferred ones. Although it is not necessary to use a solvent when carrying out this reaction, a hydrocarbon-based, ether-based, or ester-based solvent may be used.

The amounts of (1), (II) and (III) to be blended are theoretically such that the molar ratio is (I):(I[):(III>=
n: (n+112. However, actually (I
I) and (III) may be used in slightly higher than stoichiometric amounts.

As for the reaction procedure, (1), (If) and (II[) may be added and reacted at the same time, but first (
After reacting I) and (I[) to elongate the chain, (I
It is easier to control the degree of polymerization by adding II) and reacting.
Furthermore, a hydrolyzable group can be reliably introduced at the end of the molecular chain.

Further, n is a number of 1 or more, and may be 1, but for the above-mentioned reason, it is necessary to select it so that the molecular weight of the polyether, which is the component (^) of the present invention, is in the range of 500 to 50,000. There is.

The emulsifier (B) is a nonionic surfactant, an anionic surfactant, a cationic surfactant, or an amphoteric surfactant, such as glycerin higher fatty acid ester,
Examples thereof include polyethylene glycol higher fatty acid ester, polypropylene glycol higher fatty acid ester, ethenopesorubicun higher fatty acid ester, polyethylene glycol alkyl phenylethenope higher alcohol sulfate ester salt, alkylbenzene sulfonate, and higher alkyl quaternary ammonium salt.

The emulsion of the present invention can be obtained by adding an arbitrary amount of water (C) to the components (A> and (B)) described above, and uniformly mixing and stirring the mixture.

Although any method can be used for mixing and stirring, it is advantageous to use a homomixer or a homogenizer in order to obtain a stable emulsion.

Fillers such as colloidal silica, color pigments, dyes, preservatives, antioxidants, ultraviolet absorbers, and the like can be added to the emulsions of the present invention. It is not necessary to add an emulsion stabilizer, but it may be added.

Further, a catalyst, such as an organic tin compound, which promotes the hydrolysis of the hydrolyzable groups of the polyether may be added to the emulsion of the present invention.

〔Effect of the invention〕

The emulsion of the present invention has good storage stability, and when water is removed, it easily hardens at room temperature and transforms into an elastomer with excellent rubber physical properties and good heat resistance and weather resistance. It is suitable as a coating material for construction because it shows good adhesion.

〔Example〕

The present invention will be explained in more detail with reference to Examples below. In addition, in Examples, Comparative Examples, and Reference Examples, all parts are parts by weight, and % is weight %.

Reference Example 1 For 5 moles [10 (epoxy) equivalent] of glycidyl-based cylinder-end-capped polyoxypropylene having an average degree of polymerization of 15 and a molecular weight of about 1000.25°C and a viscosity of 270 cSt,
6 mmoles of piperazine represented by HNN)I and methanol in an amount equivalent to 10% of the polyoxypropylene were added, and heating and stirring at 60° C. under a nitrogen atmosphere was started. 8 Ha after the start of heating and stirring, CLCtl-CH-0-fCH-'r
2.2 mol of methyl(γ-glycidoxyprobyl)dimethoxysilane represented by T-S+ (QC)la) 2\0/ was added, and heating and stirring was continued under the same conditions. After adding the above silane and heating and stirring for 8 hours, methanol was distilled off and the viscosity at 25°C was 1.
A polyether (hereinafter referred to as P-1) whose molecular chain ends were blocked with a hydrolyzable silyl group represented by the following formula was obtained as a pale yellow viscous liquid having a molecular weight of 500 QcSt and a number average molecular weight of 6,000.

CI(.

fCII□辷3 S+ (OCH3) - Reference Example 2 5 moles of glycidyl-length double-end-capped polyoxypropylene [10 (epoxy) equivalent] clopentane with an average degree of polymerization of 32 and a molecular weight of approximately 2000.25°C and a viscosity of 55 QcSt. Then, ethanol in an amount equivalent to 10% of polyoxypropylene was added, and heating and stirring was started at 80° C. under a nitrogen atmosphere. Eight hours after the start of heating and stirring, CH1 was added, and heating and stirring was continued under the same conditions. After adding the above silane and heating and stirring for 8 hours, methanol was distilled off to form a pale yellow viscous liquid with a viscosity of 26,000 cSt at 25°C and a number average molecular weight of 11,000. A polyether (hereinafter referred to as P-2) whose molecular chain terminals were blocked with a decomposable silyl group was obtained.

C1l.

■ -[”)1.C)11”)12-0([)1 Tsujicho S+
(OCLC) l-) z 0 days Reference Example 3 3 moles of glycidyl-length double-end-capped polyoxypropylene [6 (epoxy) equivalents] having an average degree of polymerization of 50 and a molecular weight of 3000.25°C viscosity of 970 cSt [6 (epoxy) equivalents] ■ 4 moles of phenazine and 10 of polyoxypropylene
% methanol was added thereto, and heating and stirring was started at 60° C. under a nitrogen atmosphere. Heating and stirring was continued under intermaxillary conditions. After adding the above silane and heating and stirring for 8 hours, methanol was distilled off and the viscosity at 25°C was 22,000 cSt.

A polyether (hereinafter referred to as P-3) whose molecular chain ends were blocked with a hydrolyzable silyl group represented by the following formula was obtained as a pale yellow viscous liquid with a number average molecular weight of too many.

Reference Example 4 For 5 moles [10 (epoxy) equivalents] of glycidyl group-end-blocked polyoxypropylene having an average degree of polymerization of 15 and a molecular weight of about 1000.25°C and a viscosity of 270 cSt,
If2N tatami CH, = (2t 6 moles of NH2 and an amount of methanol corresponding to 10% of polyoxypropylene were added, and heating and stirring was started at 60°C under a nitrogen atmosphere. 12 hours after the start of heating and stirring CH.

In C112C)I-C)1. -0go CH2 catty S
2.2\0' mol of i (OCL) z was added, and heating and stirring was continued under the same conditions. After adding the above silane and heating and stirring for 12 hours, methanol was distilled off and the viscosity at 25°C was 19,000 cSt.
A polyether (hereinafter referred to as P-4) whose molecular chain ends were blocked with a hydrolyzable silyl group represented by the following formula was obtained as a pale yellow viscous liquid with a number average molecular weight of 6,500.

CH.

-NHC112C) ICII2-0-eCH Tsuji35i (
DC) I-)2 Reference Example 5 C1l.

Molecular weight 8000, as terminal group (CH30) zsi
The polyoxypropylene having -'ecH Tsujicho- is hereinafter referred to as P-5.

Examples 1 to 5 and Comparative Example 1 5100 parts of polyether P-1 shown in Reference Examples 1 to 5 were mixed with the emulsifier shown in Table 1, water, and colloidal silica (40% active ingredient). Samples 11 to 16 were obtained by emulsifying with a homomixer and passing through a homogenizer twice at a pressure of 3000 psi.

Note that the organic tin catalysts shown in Table 1 were added to Samples 12 and 16 at the time of sample preparation. Among these samples, sample 1G is
This is a comparative example using a polyether different from the polyether of the present invention.

These samples were cured on a Teflon plate into a sheet with a thickness of about Q, 5 mm, and after drying and curing at room temperature for 14 days, JI3
A No. 2 dumbbell was punched out and its physical properties were measured. A part of the dumbbell punched out at this time was placed in a weather meter and
It was placed in a 0°C dryer, and its physical properties were measured after irradiation with ultraviolet rays and after heating.

In addition, Samples 11 to 16 were sealed in a glass bottle and stored in a dryer at 50°C, and their properties were observed one week and one month after storage, and the physical properties of dumbbells were measured by curing them into a sheet in the same manner as above. did. The results are also shown in Table 1.

Examples 6 to 10 and Comparative Example 2 5100 parts of polyether P-1 to P-1 shown in Reference Examples 1 to 5 were mixed with the emulsifier shown in Table 2, water, and colloidal silica (40% active ingredient) to make a homogeneous Samples 21 to 26 were obtained by emulsifying with a mixer and passing through a homogenizer twice at a pressure of 3000 psi.

To Samples 22 and 26 on the right, the organotin catalysts shown in Table 2 were added at the time of sample preparation. Among these samples, Sample 26 is a comparative example using a polyether different from the polyether of the present invention.

These samples were applied to the surface of each base material shown in Table 2 so that the film thickness after drying was approximately Q, 5 mm, and after curing at room temperature for 14 days, the test specimen shown in Figure 1 was created. After curing for 14 days at room temperature, a tensile test was conducted to measure the adhesive strength and observe the state of destruction. The results are also shown in Table 2.

[Brief explanation of the drawing]

FIG. 1 shows a perspective view of a test piece subjected to an adhesion test. The unit in the diagram is combat. Further, Q indicates the tensile direction. 1... Test cured film 2... Base material 3... Silicone sealant <Toshiba Silicone@ manufactured Tosseal 381> 4... Aluminum metal fittings

Claims (1)

[Claims] 1 (A) General formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1, R^2, R^3, R^4 are divalent hydrocarbon groups, R^5 is a monovalent hydrocarbon group, X is a hydrolyzable group,
a is a number from 1 to 3, A is -NH-Z-NH- or a group represented by ▲Numerical formula, chemical formula, table, etc.▼, where Z is a divalent aromatic group, R^7, R ^8 is a divalent hydrocarbon group, m is a number of 10 to 500, and n is a number of 1 or more), and the molecular weight is a hydrolyzable silyl group with a molecular weight of 500 to 50,000, and the molecular chain terminal is a hydrolyzable silyl group. Polyether aqueous emulsion composition obtained from 100 parts by weight of occluded polyether (B) 1 to 20 parts by weight of emulsifier (C) any amount of water. 2. The composition according to claim 1, wherein (A) has a molecular weight of 1,000 to 10,000. 3. The composition according to claim 1, wherein ▲ in (A), which has a numerical formula, chemical formula, table, etc., is a polyoxypropylene unit. 4. The composition according to claim 1, wherein the hydrolyzable group X in (A) is an alkoxy group or an alkoxyalkoxy group. 5. The composition according to claim 1, wherein the hydrolyzable group X in (A) is a methoxy group or an ethoxy group. 6 A in (A) is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
The composition according to claim 1, which is a group selected from , ▲ includes a mathematical formula, a chemical formula, a table, etc. ▼, and ▲ includes a mathematical formula, a chemical formula, a table, etc. ▼.