JP3506269B2 - Curable composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-like curable composition which is cured at an appropriate curing rate in the presence of moisture, has excellent tensile properties and has a non-adhesive surface.

[0002]

2. Description of the Related Art Reactive silicon groups are condensed after being hydrolyzed in the presence of water. This polymer having a reactive silicon group is crosslinked and cured in the presence of moisture and can be used as a curable composition. Among these polymers, those whose main chain skeleton is polyoxyalkylene are generally known as modified silicones. A curable composition using this is liquid at room temperature and has a property of becoming a rubber elastic body when cured, and is widely used for a sealant for construction and the like. It is desirable that these have an appropriate curing rate when cured,
Further, it is desirable that the rubber-like cured product has non-adhesiveness on the surface, great elongation properties as tensile properties, and rubber elasticity with high flexibility. Many proposals have been made regarding a method for producing an organic polymer having a reactive silicon group in the molecule,
Some have already been industrially produced. For example, it is an organic polymer (trade name: MS polymer) manufactured and sold by Kanegafuchi Chemical Industry Co., Ltd., whose main chain is polyoxypropylene and a methoxysilyl group is bonded to the terminal. This polymer has an appropriate curing rate during curing, but when the elongation of the cured product and the residual tack (tackiness) of the surface are not sufficient under certain compounding compositions and use conditions. However, improvement has been desired depending on the application. On the other hand, the present inventors have already proposed a method of adding or reacting a silicon compound to the organic polymer in order to improve tensile properties (high elongation) and residual tack improvement (low tackiness). (See Japanese Patent Application Laid-Open No. 64-9268).

[0003]

However, the use of the silicon compound disclosed in JP-A-64-9268 tends to slow the internal curability (deep curing rate). This invention improves tensile properties (higher elongation)
It is made to provide a curable composition in which the improvement of residual tack (reduction of tackiness) is achieved and the internal curability (depth curing rate) is not reduced.

[0004]

Means for Solving the Problems The inventors of the present invention have made earnest studies to solve these problems, and as a result, by using a specific silicon compound, the internal curing rate is not lowered,
Moreover, they have found that it is possible to improve tensile physical properties (higher elongation) and residual tack (lower adhesiveness), and have completed the present invention based on this finding. The present invention relates to (a) at least one silanol in one molecule.
And an oxyalkylene polymer containing a reactive silicon group that can be crosslinked by a condensation reaction , and (b) the general formula (1):

[0005]

[Chemical 2]

(Wherein R ¹ is the same or different, and is a substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom, R 1
² is a divalent hydrocarbon group having 1 to 8 carbon atoms, m and n are positive integers (excluding n ≧ 15) , m is 1, m × n is 5 or more, and X is an alkyl group) has the structure shown, to produce a R ¹ ₃ SiOH by hydrolysis Mw (molecular weight)
Is a curable composition containing 300 or more and 3000 or less of a silicon compound. (A) 1 contained in the present invention
The main chain skeleton of the oxyalkylene polymer containing a reactive silicon group capable of being crosslinked by at least one silanol condensation reaction in the molecule is essentially one having a repeating unit represented by the general formula (2).

[0007]

[Chemical 3]

(In the formula, R ³ is a divalent organic group, preferably a linear or branched alkylene group having 1 to 14 carbon atoms.) Specific examples of the general formula (2) include

[0009]

[Chemical 4]

And the like. The main chain skeleton of the oxyalkylene polymer may be composed of only one type of repeating unit or may be composed of two or more types of repeating units, but an oxypropylene polymer is particularly preferable. The reactive silicon group contained in the component (a) is a group containing a silicon atom to which a hydrolyzable group or a hydroxyl group is bonded and crosslinkable by a silanol condensation reaction, and is not particularly limited. Is a general formula (3)

[0011]

[Chemical 5]

(Wherein R ⁴ and R ⁵ are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 2 to 6 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and Y is a hydrolyzable group. Or a hydroxyl group, a is 0, 1, 2 or 3, b is 0,
1 or 2 is shown. When two or more R ⁴ , R ⁵ or Y are present, they may be the same or different. ) Represents a triorganosiloxy group. In addition, a general formula (4) that constitutes p repeating units

[0013]

[Chemical 6]

B in does not have to be the same. p represents 0 or an integer of 1 to 19. However, it is assumed that a + (sum of b) ≧ 1 is satisfied. The hydrolyzable group represented by Y is not particularly limited and includes conventionally known hydrolyzable groups, and specifically, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group. Group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group and the like. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferable, and an alkoxy group is preferable from the viewpoint of mild hydrolyzability and easy handling. Particularly preferred.

The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and a + (the sum of b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different. The number of silicon atoms forming the reactive silicon group may be one,
It may be two or more, but may be up to about 20 in the case of silicon atoms connected by a siloxane bond or the like. Especially the general formula (5)

[0016]

[Chemical 7]

A reactive silicon group represented by the formula (wherein R ⁵ , Y and a are the same as above) is preferred from the viewpoint of easy availability. Specific examples of R ⁴ and R ⁵ in the general formula (3) include alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and aralkyl such as benzyl group. Groups and the like. Of these, a methyl group is particularly preferable.

The introduction of the reactive silicon group may be carried out by a known method. That is, for example, the following method can be used. (1) An oxyalkylene polymer having a functional group such as a hydroxyl group in a molecule is reacted with an organic compound having an active group and an unsaturated group reactive with the functional group to form an oxy-containing unsaturated group. An alkylene polymer is obtained. Alternatively, an unsaturated group-containing oxyalkylene polymer is obtained by copolymerization with an unsaturated group-containing epoxy compound. Then, the obtained reaction product is subjected to hydrosilylation by reacting hydrosilane having a reactive silicon group. (2) A compound having a mercapto group and a reactive silicon group is reacted with the unsaturated group-containing oxyalkylene polymer obtained in the same manner as in the method (1). (3) An oxyalkylene polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group (hereinafter referred to as a Z functional group) in the molecule is provided with a functional group and a reactive silicon group showing reactivity with the Z functional group. The compound having is reacted. Among the above methods, the method (1) or the method (3) of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group is preferable.

The component (a) may be linear or branched, and its molecular weight is about 500 to 50,000, more preferably 1,000 to 30,000. At least one reactive silicon group is preferably present in one molecule of the polymer, and preferably 1.1 to 5 reactive silicon groups are present. If the number of reactive silicon groups contained in the molecule is less than 1, the curability will be insufficient, and if it is too large, the network structure will be too dense and good mechanical properties will not be exhibited. Specific examples of the component (a) include JP-B-45-36319 and JP-B-46-
12154, JP-A-50-156599, JP-A-5
4-6096, JP-A-55-13767, JP-A-5-
5-13468, JP-A-57-164123, JP-A-4-283260, JP-B-3-2450, USP.
3,632,557, USP 4,345,053,
USP 4,366,307, USP 4,960,8
44 and the like, and those used effectively can be used, but the invention is not particularly limited thereto. As the silicon compound used as the component (b) of the present invention,

[0020]

[Chemical 8]

(In the formula, R ¹ is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom;
² is a divalent hydrocarbon group having 1 to 8 carbon atoms, m and n are positive integers (excluding n ≧ 15) , m is 1, m × n is 5 or more, and X is an alkyl group) the structure shown having one or more in one molecule, a silicon compound that produces R ¹ ₃ SiOH by hydrolysis. As the repeating unit represented by the above-mentioned —R ² O—, for example,

[0022]

[Chemical 9]

Specific examples include: The repeating unit represented by —R ² O— may be composed of only one kind of repeating unit or may be composed of two or more kinds of repeating units, but an oxypropylene polymer is particularly preferable . Specific examples in the following <br/>, is not limited by this silicone compound as component (b).

[0024]

[Chemical 10]

[0025]

[Chemical 11]

Among the above silicon compounds, R ¹
But a methyl group, the repeating unit represented by -R ² O-is those having a basic structure oxypropylene particularly preferred.
Regarding the molecular weight of these silicon compounds (b) , the Mw (molecular weight) is 300 or more and 3000 or more in order to minimize the influence of non-silicon residues remaining in the cured product (surface bleeding, etc.).
It is the following. The amount of the silicon compound (b), 0 to Oh Kishiarukiren polymer 100 parts by weight.
Ru is added 1-30 parts by weight.

The method of mixing the polymer (a) of the present invention with the organosilicon compound (b) is roughly classified into three methods. The first method is to simply add the organosilicon compound (b) to the polymer (a). Heating and stirring conditions may be adjusted according to the properties of the organosilicon compound (b) to uniformly disperse and dissolve. In this case, it is not necessary to make it completely uniform, and even if it is opaque, the object can be sufficiently achieved if it is dispersed. If necessary, a dispersion improver such as a surfactant may be used in combination. The second is a method of mixing a predetermined amount of the compound when the final product is used. For example, when it is used as a two-pack type sealing material, the compound can be mixed and used as a third component in addition to the base and the curing agent. The third method is to react the compound with an organic polymer in advance. If necessary, a tin-based compound, a titanic acid ester-based compound, an acid or a basic catalyst are used in combination, and a necessary amount of water is added, The object can be achieved by heating and devolatilizing under reduced pressure.

The composition of the present invention may contain a silanol condensation catalyst that accelerates the reaction of the reactive silicon group. Such silanol condensation catalysts include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, naphthenic acid tin, dibutyltin oxide and phthalic acid. Reaction products with esters, organotin compounds such as dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminumethylacetoacetate; zirconium tetraacetylacetonate Chelate compounds such as titanium tetraacetylacetonate; organic lead compounds such as lead octylate; organic vanadium compounds; butylamine, octylamine, Butylamine, monoethanolamine, diethanolamine, triethanolamine,
Diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine,
Diethylaminopropylamine, xylylenediamine,
Triethylenediamine, guanidine, diphenylguanidine, 2,4,5-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5.4.0) Amine compounds such as undecene-7 (DBU) or salts thereof with carboxylic acids; low molecular weight polyamide resins obtained from excess polyamine and polybasic acid; reaction products of excess polyamine and epoxy compound, etc. Although exemplified, the condensation catalyst is not limited thereto, and a commonly used condensation catalyst can be used. These silanol catalysts may be used alone or in combination of two or more. Among these silanol condensation catalysts, organometallic compounds or a combined system of organometallic compounds and an amine compound is preferable from the viewpoint of curability.

The composition of the present invention may further contain, if necessary, a dehydrating agent, a compatibilizing agent, an adhesion improving agent, a physical property adjusting agent, a storage stability improving agent, a filler, an antiaging agent, an ultraviolet absorbing agent, a metal. Deactivator, antiozonant, light stabilizer, amine radical chain inhibitor, phosphorus peroxide decomposer, lubricant, pigment,
Various additives such as a foaming agent can be appropriately added. For example, when using a filler as an additive, wood powder, walnut shell powder, chaff powder, pulp, cotton chips, mica, graphite, diatomaceous earth, clay, kaolin, clay, talc, fumed silica, precipitated silica, Silica anhydride, quartz powder, glass beads, calcium carbonate, magnesium carbonate, titanium oxide, aluminum powder, zinc powder, asbestos, glass fiber, carbon fiber and the like can be used. These fillers may be used alone or in combination of two or more.

In addition to (a) an oxyalkylene polymer containing at least one reactive silicon group in one molecule, another polymer having a reactive silicon group, such as polydimethylsiloxane, may be added. Good. The method for preparing the curable composition of the present invention is not particularly limited, and for example, the above-mentioned components are mixed and kneaded at room temperature or under heating using a mixer, roll, kneader, or the like, or a suitable solvent is used in a small amount. Conventional methods such as dissolving the components and mixing can be adopted. Further, by appropriately combining these components, a one-pack type or a two-pack type compound can be prepared and used. When exposed to the atmosphere, the curable composition of the present invention forms a three-dimensional network structure by the action of water and cures into a solid having rubber-like elasticity.

[0031]

EFFECTS OF THE INVENTION The curable composition of the present invention can improve tensile properties (high elongation) and residual tack (low tack) while maintaining an appropriate curing rate. The curable composition of the present invention is particularly useful as an elastic sealant and can be used as a sealant for buildings, ships, automobiles, roads and the like. Further, it can be adhered to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings alone or with the aid of a primer, and thus it can be used as various types of sealing compositions and adhesive compositions. In addition, adhesives, paints, waterproof coatings, food packaging materials, cast rubber materials,
It is also useful as a molding material and a foam material.

[0032]

EXAMPLES The present invention will be described more specifically based on examples, but the present invention is not limited to these examples. Example 1, Reference Examples 1 to 3 and Comparative Examples 1 to 2 Average of 2 methyldimethoxysilyl groups per molecule

[0033]

[Chemical 12]

To 100 parts by weight of a propylene oxide polymer having an average molecular weight of 10500 (hereinafter referred to as a methyldimethoxysilyl group-containing propylene oxide polymer) containing 100 parts by weight (the same applies hereinafter), the organosilicon compounds shown in the table and the colloidal carbonate 120 parts of calcium (Shiroishi Industry Co., Ltd.),
Add 20 parts of heavy calcium carbonate (Shiraishi Industry Co., Ltd.),
Add 50 parts of dioctyl phthalate (Kyowa Fermentation) and 2 parts of anti-aging agent, knead thoroughly, pass through 3 small paint rolls 3 times, then add 3 parts of tin octylate and 0.65 part of lauryl amine and homogenize. To obtain a curable composition. Using the obtained composition, tensile properties were measured according to JIS A 5758. Also, by touching the finger,
The residual tack (surface tackiness) after curing at 23 ° C. for 7 days was evaluated. The cured state of the interior was evaluated by the acupressure method after curing at 5 ° C. for 24 hours.

As a comparative example, a case where 2.5 parts of a silicon compound C ₆ H ₅ O Si (CH ₃ ) ₃ disclosed in JP-A-64-9268 is added instead of the organosilicon compound, and a silicon compound Evaluation was performed in the same manner as in the case of not adding. The results are shown in Table 1.
In Table 1, M ₅₀ is the modulus at 50% tension, E
B indicates the elongation at break, and A in the evaluation of residual tack
Indicates that the case is comparable to that of Comparative Example 2 in which no silicon compound is added, and B indicates that the stickiness is larger than that. In addition, the evaluation standard of the curability of the inside is ◎ when it is completely cured up to the inside, ○ when there is some uncured portion inside but almost completely cured, and uncured inside. The case where a large number of parts are recognized is indicated by Δ, and the case where only the surface is hardened by skin and the inside is not cured is indicated by ×.

[0036]

[Table 1]

From the results in Table 1, the silicon compound shown in Example 1 exhibits the same level of tensile properties and residual tack as compared with the case of using C ₆ H ₅ OSi (CH ₃ ) ₃ , but the internal hardenability. It turns out that is excellent.

─────────────────────────────────────────────────── ─── Continuation of front page (72) Fumio Kawakubo 6-21-17 Kitaochiai, Suma-ku, Kobe City, Hyogo Prefecture (56) References JP-A-6-57122 (JP, A) JP-A-5-117521 ( (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 71/02-71/03 C08K 5/54-5/549

Claims (5)

(57) [Claims] 1. (a) With respect to 100 parts by weight of an oxyalkylene polymer containing a reactive silicon group crosslinkable by at least one silanol condensation reaction in one molecule,
0.1 to 30 parts by weight of (b) general formula (1): (In the formula, R ¹ is the same or different, a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, R ² is C 1 -C
~ 8 divalent hydrocarbon group, m, n is a positive integer (provided that n
≧ 15) , m is 1, m × n is 5 or more, and X is
Has a structure represented by the Kill group), R ¹ ₃ Mw (molecular weight of generating SiOH) curable composition containing 300 to 3000 of silicon compounds by hydrolysis. 2. The curable composition according to claim 1, wherein the reactive silicon group (a) is an alkoxysilyl group. 3. The curable composition according to claim 1, wherein the main chain of (a) is an oxypropylene polymer. 4. The curable composition according to claim 1, wherein R ¹ bonded to a silicon atom in the formula (b) is a methyl group. 5. The curable composition according to claim 1, wherein the repeating unit represented by —R ² O— in the formula (b) is oxypropylene.