JPH0415251A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain a curable resin composition excellent in weather-resistant adhesion to glass by mixing a specified propylene glycol polymer with a specified oxytetra-methylene polymer and a silanol condensation catalyst. CONSTITUTION:A curable resin composition comprising 100 pts.wt. propylene glycol polymer (A) which has at least one group containing an Si atom to which a hydroxyl group or a hydrolyzable group is bonded and can be crosslinked by forming a siloxane bond, 5-120 pts.wt. oxytetramethylene polymer (B) which has at least one group having an Si atoms to which a hydroxyl group or a hydrolyzable group is bonded and can be crosslinked by forming a siloxane bond, and 0.1-20 pts.wt. silanol condensation catalyst. When the polymer component A or B contains below one reactive Si group per molecule, the composition has insufficient curability and can hardly exhibit good rubber elasticity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a curable resin composition containing a curable resin, and more particularly to a curable resin composition suitable for use as a sealant.

[Prior art and problems to be solved by the invention] Conventionally,
As a room temperature curable sealant, a composition containing as an active ingredient an organic polymer whose main chain is made of polypropylene glycol and has a methoxysilyl group bonded to the end (trade name: MSS Polymer, manufactured by Fuchi Kagaku Kogyo ■) is known. .

Although this composition contains a silane coupling agent to improve weather-resistant adhesion to glass, it still does not have sufficient weather-resistant adhesion to glass, and its use as a sealant is limited. .

An object of the present invention is to provide a curable resin composition that has excellent weather-resistant adhesive properties, particularly excellent weather-resistant adhesive properties to glass.

[Means and effects for solving the problems] The curable resin composition of the present invention has the following features: 1. (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 (B) 100 parts by weight of a polypropylene glycol polymer having at least one reactive silicon group and capable of crosslinking by forming a siloxane bond; It contains 5 to 120 parts by weight of a crosslinked polyoxytetramethylene polymer and 0.1 to 20 parts by weight of (C) a silanol condensation catalyst.

The reactive silicon groups present in component (A) and component (B) are not particularly limited, but typical examples include groups represented by the following general formula (1).

[In the formula, R and R2 are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 7 to 2 carbon atoms.
0 aralkyl group or a triorganosiloxy group represented by (R") 3S s O-, R1 or R2
When two or more 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, When two or more of X exist, they may be the same or different. a is 0.1.2
or 3, and b represents 0.1 or 2, respectively. Moreover, b in m pieces may be different. m is 0 or 1-1
Indicates an integer of 9. However, it is assumed that a+Σb≧1 is satisfied. The hydrolyzable group represented by X above 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. Among these, hydrogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amido groups, aminooxy groups, mercapto groups, and alkenyloxy groups are preferred, but alkoxy groups are preferable from the viewpoint of mild hydrolysis and ease of handling. is particularly preferred.

This hydrolyzable group or hydroxyl group has 1 to 3 per silicon atom.
It is preferable that (a+Σb) is 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.

There may be one silicon atom in the reactive silicon group,
There may be two or more, but in the case of a reactive silicon group in which silicon atoms are linked through a siloxane bond or the like, there may be about 20.

Incidentally, a reactive silicon group represented by the following general formula (2) is preferable from the viewpoint of easy handling.

R3-a ...... (2) iX a (In the formula, RX and a are the same as above.) Also, specific examples of R1 and R2 in the above formula (1) include, for example, a methyl group, an alkyl group such as an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group;

Examples include a triorganosiloxy group represented by (R') 3S i O-, where is a methyl group, a phenyl group, or the like. Among these, methyl group is particularly preferred.

At least one reactive silicon group, preferably 1.1 to 5 reactive silicon groups, should be present in each molecule of the component (A) and (B). When the number of reactive silicon groups contained in one polymer molecule is less than one, the curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior.

1. The reactive silicon groups present in component (A) and component (B) may be of the same type or may be of different types.

Further, the reactive silicon group may be present at the end of the polymer molecular chain, may be present inside the polymer chain, or may be present at both ends. In particular, when a reactive silicon group is present at the end of a molecular chain, the effective network chain amount of the polymer component contained in the finally formed cured product increases, resulting in high strength and high elongation (
It is preferable because it has the advantage that it becomes easier to obtain a rubber-like cured product exhibiting a low elastic modulus.

The reactive silicon group may be introduced by a known method. That is, for example, a polymer having a functional group such as a hydroxyl group at the end or in the main chain is reacted with an organic compound having an active group and an unsaturated group that is reactive with this functional group, and then the obtained polymer is The reaction product may be hydrosilylated by acting with a hydrosilane having a hydrolyzable group.

The polypropylene glycol polymer used as component (A) in the present invention has a number average molecular weight of 1,000.
It is preferable that it is 50,000. Number average molecular weight is 1
．． If it is less than 000, sufficient elongation will not be obtained when the composition of the present invention is made into a cured product, and breakage will occur before sufficient strength is exhibited. Therefore, in order to obtain sufficient mechanical strength, the number average molecular weight is preferably 1°000 or more. However, if the molecular weight is too large, curing will be insufficient and sufficient mechanical strength will not be obtained.

The polyoxytetramethylene polymer used as component (B) in the present invention has a number average molecular weight of 500 to 2.
Preferably it is 0,000. Number average molecular weight is 500
If it is less than that, sufficient elongation will not be obtained when the composition of the present invention is made into a cured product, and breakage will occur before sufficient strength is developed. Therefore, in order to obtain sufficient mechanical strength, the number average molecular weight is preferably 500 or more. However, if the molecular weight is too large, curing will be insufficient and sufficient mechanical strength will not be obtained. In particular, component (B) not only imparts weather-resistant adhesion to glass to component (A), but can also be used to adjust the mechanical strength of the cured product. That is, when component (B) having a relatively small molecular weight is used, the elastic modulus increases and elongation decreases. Furthermore, when component (B) having a large molecular weight is used, the strength and elongation become large.

Add 5 parts of component (B) to 100 parts by weight of component (A) above.
By adding ~120 parts by weight, the weathering adhesion to glass is dramatically improved. This is because the polyoxytetramethylene polymer of component (B) has excellent weather resistance and water resistance, so these characteristics are imparted to component (A) as well, resulting in improved glass weather resistance. This is because it results in an excellent composition. If the amount of component (B) is less than 5 parts by weight, such effects will not be effectively exhibited. On the other hand, component (B) is 1
If it exceeds 20 parts by weight, the elasticity will be poor when cured,
Does not work effectively as a sealant. Therefore, the composition having the blending ratio of the present invention can be used as an excellent sealing material in places where glass is used. The preferred blending ratio is (B) to 100 parts by weight of component (A).
) component is 10 to 100 parts by weight.

The silanol condensation catalyst (C) component in the present invention (
As the curing agent I), a wide variety of conventionally known materials can be used. Specific examples include titanate esters such as tetrabutyl titanenite and tetrapropyl titanate; tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, and tin naphthenate; Reactants with phthalate esters; dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate, titanium tetraacetylacetonate Chelate compounds such as lead octylate-nibutylamine, octylamine, dibutylamine, monoethanolamine, jetanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylene Diamine, triethylenediamine, guanidine, diphenylguanidine, 2.4.6-)lis(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1.8-diazabicyclo(5, 4,0) Undecene-7 (DBU)
amine compounds such as, or salts of these amine compounds with carboxylic acids; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products between excess polyamines and epoxy compounds; γ-amino Silanol condensation catalysts such as propyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane and other amino group-containing silane coupling agents; and other known silanol catalysts such as acidic and basic catalysts. Examples include condensation catalysts. These catalysts may be used alone or in combination of two or more.

The blending amount of component (C) in the resin composition of the present invention is (
The amount is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of component A). If the amount of component (C) blended is too small relative to component (A), the curing speed will be slow and the curing reaction will be difficult to proceed sufficiently.
Undesirable. On the other hand, if the blending amount of component (C) is too large relative to component (A), local heat generation and foaming will occur during curing, making it difficult to obtain a good cured product, which is not preferable.

The composition of the present invention further includes, if necessary, an adhesion improver, a physical property adjuster, a storage stability improver, a plasticizer, a filler,
Various additives such as anti-aging agents, ultraviolet absorbers, metal deactivators, anti-ozonants, light stabilizers, amine-based radical chain inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, foaming agents, etc. It can be added as appropriate.

〔Effect of the invention〕

The cured product obtained by curing the curable resin composition of the present invention has excellent weather-resistant adhesion, particularly weather-resistant adhesion to glass, and has excellent mechanical properties as an elastic body.

[Examples] In order to further clarify the present invention, Examples are given below.

Examples 1 to 4, Comparative Examples 1 to 3 1. The following polymers were used as component (A) and component (B).

(A) Number average molecular weight expressed by component quadratic formula: 8°000
Polypropylene glycol-based polymer (abbreviated as P-1) (B) component has a number average molecular weight of 2°000 expressed by the quadratic formula
Polyoxytetramethylene polymer (abbreviated as T-1) (B) Component 2 A polyoxytetramethylene polymer (abbreviated as T-2) with a number average molecular weight of 4,000 expressed by the same formula as T-1 above. (Omitted) The above polymers P-1, T-1, T-2 and other additives were blended as shown in Table 1 to obtain a curable resin composition. Using this composition and a glass plate, J l5-A5
A specimen for a tensile test was prepared in accordance with 757, and cured at room temperature for 4 days and at 50° C. for 4 days.

This test specimen was measured using a Sunshine Weather Meter (
Black panel temperature 63℃, watering 18mfn/2hr)
, and the tensile properties (glass weather resistance adhesion) were measured after a predetermined period of time. The results are shown in Table-2.

Table 1 aCOa: Filler TjO: Pigment tin-based compound didibutyltin acetylacetonate As is clear from Table 2, the composition of the present invention exhibited excellent weathering adhesion to glass.

Claims (1)

[Scope of Claims] 1. (A) A polypropylene glycol 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. 100 parts by weight, (B) Polyoxytetramethylene-based polymers 5 to 5, which have 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. 120 parts by weight, and (C) 0.1 to 20 parts by weight of a silanol condensation catalyst. 2. The number average molecular weight of component (A) is 1,000 to 50,0
The resin composition according to claim 1, wherein the resin composition has a molecular weight of 0.00. 3. The number average molecular weight of component (B) is 500 to 20,000
The resin composition according to claim 1 or 2, characterized in that: