JPH02132151A - Hardening resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition giving cured material having excellent curing properties in deep part, weatherability and heat resistance, etc., by mixing specific polyethylene oxide, silicon compound and silanol condensation catalyst. CONSTITUTION:(A) Polyethylene oxide having hydroxyl group or hydrolyzable group bonded to silicon atom and having at least one silicon atom-containing group crosslinking by formation of siloxane bonding is blended with (B) silicon compound having at least two silanol groups and (C) silanol condensation catalyst. Mixing ratio of the component A and B is preferably 0.1-8, especially 0.3-4 hydroxyl groups bonding to silicon atom in the component B to one hydroxyl group or hydrolyzable group in the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a curable resin composition, more particularly a curable resin composition which has excellent deep curability and which can impart excellent weather resistance, heat resistance, etc. to the cured product. The present invention relates to a resin composition.

Conventional technology and its problems Various types of room temperature curable resin compositions have been developed, but these have excellent deep curability and can impart excellent weather resistance, heat resistance, etc. to the cured product. Hardly any curable resin compositions have been developed.

Means for Solving the Problems An object of the present invention is to provide a curable resin composition that has excellent deep curability and can impart excellent weather resistance, heat resistance, etc. to the cured product.

That is, the present invention provides at least (A) a silicon atom-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond (hereinafter referred to as a "reactive silicon group"). (B) a silicon compound having two or more diranol groups;
and (C) a curable resin composition containing a silanol condensation catalyst.

In the present invention, component (A) is polyethylene oxide having at least one reactive silicon group.

Here, the reactive silicon group is not particularly limited, but representative examples include, for example, general formula (1) [wherein, R represents an organic group having 1 to 20 carbon atoms, R When two or more are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group,
When two or more Xs exist, they may be the same or different. a is 0, 1, 2 or 3, b
represents 0, 1 or 2, respectively. Further, b in m pieces of --Si-0-Xb does not need to be the same. m is O or 1-1
Indicates an integer of 9. However, it is assumed that a+(sum of b)≧1 is satisfied. ] Examples include groups represented by the following.

Examples of the organic group having 1 to 20 carbon atoms represented by R above include 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, (R')
3 SiO (R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same,
Examples include triorganosiloxy groups represented by (which may be different). More specifically, for example, an alkyl group such as a methyl group or 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, or where R' is a methyl group, a phenyl group, etc. Examples include a triorganosiloxy group represented by (R')3SiO-. Among these, methyl group is particularly preferred.

The hydrolyzable group represented by X above is not particularly limited, and includes conventionally known hydrolyzable groups, specifically,
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, ketoximeryl groups, amino groups, amido groups, aminooxy groups, mercapto groups, and alkenyloxy groups are preferred. From this point of view, an alkoxy group is particularly preferred.

The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in a range of 1 to 3, and (sum of a+b) is preferably in a range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to a reactive silicon group, they may be the same or different.

The number of silicon atoms forming the reactive silicon group may be one,
The number may be two or more, but in the case of silicon atoms connected by siloxane bonds or the like, the number may be up to about 20. In particular, a reactive silicon group represented by the general formula (2) S iXa [wherein R, X and a are the same as above] is preferred from the viewpoint of easy availability.

At least one reactive silicon group, preferably 1.1 to 5 reactive silicon groups, should be present in one molecule of polyethylene oxide.

When the number of reactive silicon groups contained in the molecule is less than 1, curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior.

The reactive silicon group may be present at the end of the polyethylene oxide molecular chain, may be present within the polyethylene oxide molecular chain, or may be present on both sides. In particular, when a reactive silicon group is present at the end of the molecular chain, the effective network chain amount of the polyethylene oquindo component contained in the finally formed cured product increases.
This is preferable because it makes it easier to obtain a rubber-like cured product with high strength and high elasticity (low elastic modulus).

Typical polyethylene oxides having reactive silicon groups used as component (A) in the present invention include those shown in the following formula.

CH3 [In the above formula, n and m each represent an integer of 1 to 500. ] In the present invention, the polyethylene oxide may contain units other than ethylene oxide units.

In the present invention, the number average molecular weight of the polyethylene oxide is preferably about 500 to 30,000, and 10
It is particularly preferable that it is about 00 to 15,000.

The reactive silicon group may be introduced into the above polymer by a known method. For example, polyethylene oxide having a functional group such as a hydroxyl group at the end or in the main chain is added with an active silicon group that is reactive with the above functional group. An organic compound having a group and an unsaturated group may be reacted, and then a hydrosilane having a hydrolyzable group may be applied to the resulting reaction product for hydrosilylation.

In the present invention, the polyethylene oxide having a reactive silicon group used as the component (A) may be used alone or in combination of two or more.

The silicon compound that is the component (B) used in the present invention acts as a crosslinking agent for the reactive silicon group-containing polyethylene oxide that is the component (A), and in order to form a network structure, the silicon compound that is the component (B) is It is necessary that two or more numbers exist in one molecule. As such a silicon compound, a wide range of commercially available silicon compounds can be used, but if it is particularly compatible with the above component (A), a cured product with more stable performance can be obtained. It is desirable to use a material with a relatively low molecular weight, that is, a material having 50 or less silicon atoms in one molecule. Specific examples of such silicon compounds are as follows.

(c+d=1-50) [In each of the above formulas, Me is a methyl group and ph is a phenyl group, and the same applies to the following examples. ] Among such silicon compounds, polysiloxane is particularly suitable in the present invention.

The blending ratio of component (A) and component (B) is not particularly limited and can be appropriately selected within a wide range, but usually, for one hydroxyl group or hydrolyzable group of component (A), (B) The number of hydroxyl groups bonded to the gay element atoms of component is 0.
The proportion is preferably about 1 to 8, preferably about 0.3 to 4. If the amount of component (B) relative to component (A) is too small, a resin composition with insufficient deep curability will be obtained, and the resulting cured product will also have poor weather resistance and heat resistance. , undesirable.

On the other hand, if the blending amount of component (B) relative to component (A) is too large, the tensile properties of the cured product will deteriorate, which is not preferable.

pH 10 Me As the silanol condensation catalyst which is component (C) of the present invention, a wide variety of conventionally known catalysts can be used. Specific examples thereof include titanic acid esters such as tetrabutyl titanate and tetrabutyl titanate; tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, and tin naphthenate; dibutyltin Reaction product of oxide and phthalate ester; dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoquine aluminum ethylacetoacetate: zirconium tetraacetylacetonate, titanium Chelate compounds such as tetraacetylacetonate; lead octylate; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, penzylamine, diethylaminopropyl Amine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4.6-
Amine compounds such as tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo(5,4.0)undecene-7 (DBU), Or salts with these carboxylic acids, etc.: low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products between excess polyamines and epoxy compounds; γ-aminobrobyltrimethoxysilane, If-( Examples include silane coupling agents having an amino group such as β-aminoethyl)aminopropylmethyldimethoxysilane, and other known silanol condensation catalysts such as other acidic catalysts and basic catalysts. These catalysts may be used alone or in combination of two or more. When a curing catalyst is used, the amount thereof is usually about 0.1 to 20 parts, preferably about 1 to 10 parts, per 100 parts by weight of component (A) (hereinafter simply referred to as "parts"). If the blending amount of component (C) relative to component (A) is too small, the curing speed will be slow and the curing reaction will be difficult to proceed sufficiently, which is not preferable. On the other hand, if the ratio of component (C) to component (A) is too large, 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 an adhesion improver, if necessary.
Physical property modifier, storage stability improver, plasticizer, filler, anti-aging agent, ultraviolet absorber, metal deactivator, ozone deterioration inhibitor, light stabilizer, amine radical chain inhibitor, phosphorus peroxide Various additives such as a substance decomposer, a lubricant, a pigment, and a foaming agent can be added as appropriate.

Effects of the Invention The curable resin composition of the present invention has excellent deep curability and can impart excellent weather resistance, heat resistance, etc. to the cured product.

EXAMPLES In order to further clarify the present invention, examples are given below.

In Examples 1 and 2, 100 parts of polyethylene oxide having a silyl group at the end and having a molecular weight of about 2000 were added with 80 parts of silanol-terminated hydrosiloxane having an average molecular formula of In No. 2, 90 parts were added, and 3 parts of tin octylate and 0.75 parts of laurylamine were added thereto and stirred to prepare a 5 cm square cube sample. The curing time was defined as the point at which the stickiness in the center of the sample disappeared. In addition, a cured product with a thickness of 3 mm was prepared, and the tensile properties, weather resistance, and heat resistance of this cured product were examined. The results are shown in Table 1 below.

Comparative Example 1 3 parts of tin octylate and 0.75 parts of laurylamine were added to 100 parts of the same polymer as in the above example, and the curing time, tensile properties, and weather resistance of the cured product were determined in the same manner as in the above example. The properties and heat resistance were investigated. The results are also shown in Table 1 below.

Claims (1)

[Scope of Claims] [1] (A) A polyethylene oxide having at least one silicon atom-containing group that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond, ( B) a silicon compound having two or more silanol groups,
and (C) a curable resin composition containing a silanol condensation catalyst.