JP2832459B2 - Curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a curable resin composition containing a curable resin,
More specifically, it relates to a curable resin composition capable of obtaining a cured product exhibiting excellent mechanical properties, weather resistance, heat resistance and the like.

[Problems to be Solved by Conventional Techniques and Inventions] Conventionally, various kinds of resin compositions curable at room temperature have been developed. In recent years, there has been a demand for a curable resin composition capable of exhibiting excellent mechanical properties, weather resistance, heat resistance, and the like after curing, and a resin composition containing a polyoxytetramethylene polymer as having such properties. Attention has been paid.

However, the polyoxytetramethylene polymer is crystalline, and its resin composition cannot be used for applications requiring rubber-like elasticity after curing (for example, sealants for high-rise buildings).

An object of the present invention is to provide a curable resin composition in which the cured product can exhibit excellent mechanical properties, weather resistance, and heat resistance and does not lose elasticity.

[Means and Actions for Solving the Problems] The curable resin composition of the present invention comprises: (A) a silicon atom-containing group containing a silicon atom to which a hydroxyl group or a hydrolyzable group is bonded (hereinafter referred to as “reactive silicon group”); (B) a polyoxytetramethylene-based polymer which has at least one and which can be crosslinked by forming a siloxane bond, (B) an aromatic hydrocarbon-based compound represented by the following general formula (1), (Wherein, R ¹ and R ² are each a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. R ³ and R ⁴ are each a hydrocarbon group having 1 to 5 carbon atoms. And q each represent 0 or an integer of 1 to 5.) and (C) a silanol condensation catalyst.

In the present invention, the component (A) is a polyoxytetramethylene-based polymer having at least one reactive silicon group.

The reactive silicon group referred to here is not particularly limited, but typical examples include a group represented by the following general formula (2).

Wherein R ⁵ and R ⁶ are each represented by an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO— It represents a triorganosiloxy group, and when two or more R ⁵ or R ⁶ are present, they may be the same or different. Here, R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same or different. a represents 0, 1, 2 or 3, b represents 0,
1 or 2 is shown, respectively. In addition, m B in may be different. m is 0 or 1 to 19
Indicates an integer. However, it is assumed that a + Σb ≧ 1 is satisfied. The hydrolyzable group represented by X is not particularly limited, and may be any conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Of 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 preferred, but an alkoxy group is preferred from the viewpoint of gentle hydrolysis and easy handling. Is particularly preferred.

This hydrolyzable group or hydroxyl group is one to one silicon atom.
Three can be bonded, and (a + Δb) is preferably 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are present in the reactive silicon group, they may be the same or different.

The reactive silicon group may have one silicon atom or two or more silicon atoms. In the case of a reactive silicon group in which silicon atoms are linked by a siloxane bond or the like,
There may be about one.

In addition, a reactive silicon group represented by the following general formula (3) is preferable from the viewpoint of easy availability.

(In the formula, X ⁶ , X and a are the same as described above.) Further, specific examples of R ⁵ and R ⁶ in the general formula (2) include, for example, an alkyl group such as a methyl group and an ethyl group, and a cyclohexyl group. Such as a cycloalkyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ′ being a methyl group or a phenyl group (R ′) ₃ S
and a triorganosiloxy group represented by iO-. R ⁶ is particularly preferably a methyl group.

It is preferable that at least one, preferably 1.1 to 5 reactive silicon groups exist in one molecule of the polyoxytetramethylene-based polymer. When the number of reactive silicon groups contained in one molecule of the polymer is less than one, the curability becomes insufficient and it becomes difficult to exhibit good rubber elasticity behavior.

The reactive silicon group may be present at the end of the molecular chain of the polyoxytetramethylene-based polymer, may be present inside, or may be present at both. In particular, when the reactive silicon group is present at the end of the molecular chain, the effective network chain amount of the polyoxytetramethylene-based polymer component contained in the finally formed cured product increases, so that high strength is obtained. This is preferable because it has an advantage that a rubber-like cured product exhibiting high elongation (low elastic modulus) is easily obtained.

The polymer constituting the skeleton of the polyoxytetramethylene-based polymer having a reactive silicon group used as the component (A) in the present invention is easily produced according to a method such as cationic ring-opening polymerization of tetrahydrofuran. The number average molecular weight of this polymer is preferably about 500 to 30,000, and particularly preferably about 1,000 to 15,000.
Further, other monomer units may be contained in the polymerization main chain.

The introduction of the reactive silicon group into the polymer may be performed by a known method. That is, for example, a polyoxytetramethylene glycol-based polymer having a functional group such as a hydroxyl group at a terminal or main chain is reacted with an organic compound having an active group and an unsaturated group which are reactive with the functional group. Then, a hydrosilane having a hydrolyzable group is allowed to act on the obtained reaction product to perform hydrosilylation.

The reactive silicon group-containing polyoxytetramethylene-based polymer used as the component (A) in the present invention may be used alone or in combination of two or more.

The aromatic hydrocarbon compound as the component (B) used in the present invention acts as a plasticizer for the reactive silicon group-containing polyoxytetramethylene polymer as the component (A). Generally, polyoxytetramethylene has high crystallinity and has a melting point near room temperature. Therefore, the introduction of the reactive silicon group alone does not make the cured product a good rubber elastic body. Therefore, by adding an aromatic hydrocarbon compound represented by the following general formula (1), crystallization of polyoxytetramethylene can be suppressed, and a rubber-like elastic body having excellent mechanical properties can be obtained. it can.

(Wherein, R ¹ and R ² are each a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. R ³ and R ⁴ are each a hydrocarbon group having 1 to 5 carbon atoms. And q each represent 0 or an integer of 1 to 5.) The above compound acts as a plasticizer that is particularly superior to a generally known plasticizer for a polyoxytetramethylene-based polymer. When a commonly known plasticizer is used, the cured product crystallizes, and a rubber-like elastic body cannot be obtained.

Specific examples of such aromatic hydrocarbon compounds are as follows.

The mixing ratio of the above components (A) and (B) is not particularly limited and can be appropriately selected in a wide range. Usually, 100 parts by weight of the component (A) (hereinafter simply referred to as “parts”). )
The component (B) is preferably added in an amount of 10 to 1,000 parts, more preferably 30 to 300 parts.

As the silanol condensation catalyst (curing catalyst) as the component (C) in the present invention, conventionally known ones can be widely used. Specific examples thereof include titanates such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate,
Tin carboxylates such as tin naphthenate; reaction products of dibutyltin oxide and phthalic acid esters; dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate Chelating compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; butylamine, octylamine, dibutylamine;
Monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylamino Amine compounds such as methyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicyclo (5.4.0) undecene-7 (DBU), or carboxylic acids of these amine compounds A low molecular weight polyamide resin obtained from an excess of a polyamine and a polybasic acid; a reaction product of an excess of a polyamine with an epoxy compound; γ-aminopropyltrimethoxysilane, N- (β- Minoechiru) a silane coupling agent having an amino group such as aminopropyl methyl dimethoxy silane; silanol condensation catalyst such as news include known silanol condensation catalysts such as such as other acidic catalysts, basic catalysts. These catalysts may be used alone or in combination of two or more.

The compounding amount of the component (C) in the resin composition of the present invention is as follows:
(A) The amount is preferably about 0.1 to 20 parts with respect to 100 parts of the component.
About 10 parts is more preferable. (C) for component (A)
If the amount of the components is too small, the curing rate is slowed down, and the curing reaction does not easily proceed sufficiently. On the other hand, if the amount of the component (C) is too large relative to the component (A), local heat generation or foaming occurs during curing, and it becomes difficult to obtain a favorable cured product, which is not preferable.

The composition of the present invention may further contain, if necessary, an adhesion improver, a physical property modifier, a storage stability improver, other plasticizers, a filler, an antioxidant, an ultraviolet absorber, and a metal deactivator. Various additives such as an agent, an ozone deterioration inhibitor, a light stabilizer, an amine radical chain inhibitor, a phosphorus peroxide decomposer, a lubricant, a pigment, and a foaming agent can be appropriately added.

[Effect of the Invention] A cured product obtained by curing the curable resin composition of the present invention does not crystallize at room temperature and has excellent mechanical properties, weather resistance, heat resistance and the like as an elastic body. .

[Examples] In order to further clarify the present invention, examples will be given below.

Example 1 The following formula is added to 100 parts of a polyoxytetramethylene-based polymer having a silyl group (reactive silicon group) at a terminal having a number average molecular weight of about 4,000 represented by the above formula. Aromatic hydrocarbon compounds represented by
SAS-296, manufactured by Nippon Petrochemical Co.) was added, 50 parts of which were added, 3 parts of tin octylate and 0.75 part of laurylamine were added to produce a resin composition, and the composition was cured to a thickness of 3 mm.
Was obtained.

Example 2 The same polyoxytetramethylene-based polymer 10 as in Example 1
To 0 parts, 100 parts of the same aromatic hydrocarbon compound as in Example 1 was added, and a cured product was obtained under the same conditions as in Example 1.

Example 3 The same polyoxytetramethylene-based polymer 10 as in Example 1
0 parts, 50 parts of the same aromatic hydrocarbon compound as in Example 1,
120 parts of calcium carbonate (CCR), 5 parts of titanium oxide, Irganox 1010 (Antioxidant, manufactured by Ciba-Geigy Japan)
Parts, 3 parts of tin octylate and 0.75 part of laurylamine were added to prepare a resin composition, and this composition was cured to obtain a cured product having a thickness of 3 mm.

Comparative Example 1 Same polyoxytetramethylene-based polymer 10 as in Example 1.
To 0 parts, only 3 parts of tin octylate and 0.75 part of laurylamine were added to prepare a cured product, which was crystallized at room temperature.

Comparative Example 2 Same polyoxytetramethylene-based polymer 10 as in Example 1.
To 0 parts, 50 parts of dioctyl phthalate (DOP), 3 parts of tin octylate and 0.75 part of laurylamine were added to prepare a cured product, which was crystallized at room temperature.

Comparative Example 3 Same polyoxytetramethylene-based polymer 10 as in Example 1.
To 0 parts, 50 parts of dioctyl adipate (DOA), 3 parts of tin octylate and 0.75 part of laurylamine were added to produce a cured product, which was crystallized at room temperature.

The tensile properties of the cured products obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured. Table 1 shows the results.

As is clear from Table 1, the cured products obtained in Examples 1 to 3 had a small modulus at 50% elongation and exhibited rubber-like elasticity.

On the other hand, the cured products obtained in Comparative Examples 1 to 3 were plastically denatured and did not show rubber-like elasticity.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-1-198661 (JP, A) JP-A-1-254739 (JP, A) JP-A-52-73998 (JP, A) JP-A-58-1983 126184 (JP, A) Patent 2557444 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 71/00-71/14 C08K 5/00-5/59 CAS (STN)

Claims (1)

(57) [Claims] (A) a polyoxytetramethylene-based polymer having at least one silicon atom-containing group containing a silicon atom to which a hydroxyl group or a hydrolyzable group is bonded and which can be crosslinked by forming a siloxane bond; (B) an aromatic hydrocarbon compound represented by the following general formula (1), (Wherein, R ¹ and R ² are each a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. R ³ and R ⁴ are each a hydrocarbon group having 1 to 5 carbon atoms. And q each represent 0 or an integer of 1 to 5.) and (C) a curable resin composition comprising a silanol condensation catalyst.