JPH02185565A - Curable resin composition - Google Patents

Abstract

PURPOSE:To prepare a curable resin compsn. which is excellent in curability in the depth and which gives a cured product with excellent weathering and heat resistances by compounding a satd. hydrocarbon polymer contg. a reactive silicon-contg. group, a hydrate of a metal salt and a silanol condensation catalyst. CONSTITUTION:A satd. hydrocarbon polymer having a hydroxyl or hydrolyzable group attached to a silicon atom and at least one silicon-contg. group crosslinkable by forming a siloxane linkage [e.g. a hydrogenated polyisoprene polymer of the formula, having an MW of about 2800, a viscosity at 20 deg.C of 520 P, and a terminal silyl group) is compounded with a hydrate of a metal salt (e.g. Na2SO4.10H2O) and a silanol condensation catalyst (e.g. stannous octoate) to give a curable resin compsn. The resulting compsn. is excellent in curability in the depth, gives a cured product with excellent weathering and heat resistances, and is suitably used for an adhesive, pressure-sensitive adhesive, coating, sealant compsn. for, e.g. a multilayered glass, waterproofing agent, spraying material, mold material, casting rubber, etc.

Description

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

Conventional techniques and their problems Oxyalkylene having a silicon atom-containing group (hereinafter referred to as "reactive silicon group") that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond BACKGROUND OF THE INVENTION BACKGROUND ART Polymers are already known and are used in large quantities because they have the interesting property of being cured by moisture even at room temperature and producing a rubber-like cured product. However, the oxyalkylene polymer has a problem in that the cured product obtained by curing the polymer has insufficient properties such as heat resistance, water resistance, and weather resistance.

In order to improve these problems, for example, isobutylene polymers having reactive silicon groups have been studied (see Japanese Patent Laid-Open No. 63-6041, etc.).

However, the properties of cured products made from such isobutylene polymers, such as heat resistance, water resistance, weather resistance, and moisture barrier properties, are
Although this is significantly improved compared to the cured product made from the above-mentioned oxyalkylene polymer, the moisture barrier properties of the cured product are good, so when curing with moisture in the air, the moisture required for curing is If the supply is insufficient, curing from the surface is inevitable, and therefore thick cured products have the disadvantage that it takes about a week to completely cure.

Means for Solving the Problems The purpose of the present invention is to solve the problems of the conventional curable resin compositions as described above, to cure quickly at room temperature, and to have deep curability (to obtain a thick cured product). Curing that can give a rubber-like cured product with excellent heat resistance, water resistance, weather resistance, etc., and high strength and high elongation (low elastic modulus). An object of the present invention is to provide a synthetic resin composition.

The above object of the present invention can be achieved by blending a hydrate of a specific metal salt as component (B) with component (A) below, and further blending component (C).

That is, the present invention provides a curable resin containing (A) a saturated hydrocarbon polymer having at least one reactive silicon group, (B) a hydrate of a metal salt, and (C) a silanol condensation catalyst. It concerns a composition.

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

Here, the reactive silicon group is not particularly limited, but representative examples include -Funenin (1) [In the formula, R1 and R2 both have 1 to 20 carbon atoms] Alkyl group, aryl group having 6 to 20 carbon atoms, 7 to 2 carbon atoms
0 aralkyl group or (R') 3 SiO-(R'
is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and 3 R
' may be the same or different), and when two or more R1 or R2 are present, they may be the same,
May be different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X's are present, they may be the same or different. a represents 0.1.2 or 3, and b represents 0.1 or 2, respectively. Moreover, b in m pieces does not need to be the same. m represents 0 or an integer of 1 to 19. However, it is assumed that the sum of shima and b≧1 is satisfied. ] Groups represented by these can be mentioned.

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 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, and from the viewpoint of mild hydrolyzability and easy handling, alkoxy groups is particularly preferred.

The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and (the sum of a and b) is 1 to 5.
A range of is preferred. 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, general formula (2) [wherein R2, X and a are the same as above. A reactive silicon group represented by the following is preferred from the viewpoint of easy availability.

Further, specific examples of R1 and R2 in the above general formula (1) include alkyl groups such as methyl group and ethyl group,
Examples include cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, and triorganosiloxy groups represented by (R')3sio- where R' is a methyl group, phenyl group, etc. It will be done. 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 one molecule of the saturated hydrocarbon polymer.

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 saturated hydrocarbon polymer molecular chain, may be present inside, 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 saturated hydrocarbon polymer component contained in the finally formed cured product increases.
This is preferable from the viewpoint that it becomes easier to obtain a rubber-like cured product with high strength and high elongation.

The polymer forming the skeleton of the saturated hydrocarbon polymer having a reactive silicon group used as component (A) in the present invention is produced, for example, according to the method shown in (1) or (2) below.

(1) Ethylene, propylene, 1-butene, isobutylene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene,
An olefinic compound having 1 to 6 carbon atoms, such as hexene or vinylcyclohexane, is polymerized as a raw monomer. Here, the monomers may all be formed from the above-mentioned olefin compounds, and preferably 5 of the monomers include other monomers that are copolymerizable with the olefin compounds.
The content may be in the range of 0% by weight (hereinafter simply referred to as "%") or less, more preferably 30% or less, particularly preferably 10% or less. Examples of other monomers copolymerizable with olefin compounds include vinyl ethers, aromatic vinyl compounds, vinylsilanes, allylsilanes, and the like. Specific examples of such monomers include methyl vinyl ether, ethyl vinyl ether,
Examples include styrene, α-methylstyrene, vinyltrichlorosilane, vinylmethyldichlorosilane, allyltrichlorosilane, allyldimethylchlorosilane, and the like.

(2) Hydrogenating homopolymers of diene compounds such as butadiene and imbutylene, and copolymers of the above-mentioned olefin compounds and diene compounds.

Even in the case of a polymer obtained by this method, monomer units derived from the other monomers may be present in the same proportion in the polymer.

In particular, ethylene-propylene copolymers, hydrogenated polyisoprene, and isobutylene-based polymers are preferred from the viewpoint of easy availability of raw materials and ease of handling.

The introduction of reactive silicon groups into the above saturated hydrocarbon polymer is as follows:
This may be carried out using a known method, for example, adding active groups and unsaturated groups that are reactive with the functional groups to a saturated hydrocarbon polymer having a functional group such as a hydroxyl group or an anhydride group at the end or in the main chain. The reaction product may be reacted with an organic compound having the following, and then the resulting reaction product may be hydrosilylated by acting on a hydrosilane having a hydrolyzable group. Among the above-mentioned isobutylene polymers having a reactive silicon group, isobutylene polymers having a reactive silicon group at the end of the molecular chain are produced by a polymerization method called the Vinifer method (using both an initiator and a chain transfer agent called Inifer). It can be produced using a terminally functional type, preferably all terminally functional type isobutylene polymer obtained by a cationic polymerization method using a specific compound. Such a manufacturing method is described, for example, in Japanese Patent Application Laid-Open Nos. 63-6041 and 63-6003.

The number average molecular weight of the saturated hydrocarbon polymer having reactive silicon groups is preferably about 500 to 30,000, particularly preferably about 1,000 to 15,000. In the present invention, such saturated hydrocarbon polymers may be used alone or in combination of two or more.

The hydrate of the metal salt, which is the component (B) used in the present invention, acts as a source of moisture necessary for crosslinking the saturated hydrocarbon polymer having reactive silicon groups, which is the component (A). ,
It helps form a network structure. As such hydrates of metal salts, commercially available products can be widely used, such as hydrates of alkali metal salts, hydrates of alkali metal salts, hydrates of other metal salts, etc. It will be done. Specifically, 1!203 ΦH20, AQ203 ・3H20, A
Q2 (804)3 ・18H20, AQ2 (C
204) 3・4H20・AQ Na (so4)
2 ” 12H20, AQK (Sol) 2 ・12H
20, BaCQ2 *2H20, Ba (OH)2 ・8H20S CaO2・8H
20, CaSO3e2H20, Ca5Ot” 2H
20, Ca52 03 φ6H20, Ca (NO3) 2 φ4H20%CaHPO4
φ2H20, Ca (C204)・C20, Co (NO3)2 φ6H20゜co (CH
3C00) 2 Conflict 4H201CuCQ2 ・2H2
0, CuSO4” 5H20%FeCQ2 ψ4H20
S FeCQ6 ・6H20, FeSO4* 7H20
, F e (NHa) (SO4) 2 ・12
H20゜C2CO3・1.5H20゜KNaC03・6H20, L t B r ・2 H2
05Li2SO4・C20, MgSO4・C20, Mg
SO4・7H20, MgHPO4・7H20゜Mg3
(POa)2 ・8H20・MgCO3・3H20
゜Mga (CO3)3 (OH)2 ・3H20
1MoO3112H201NaBr ・2H20, Na
2 SO3' 7H20% Na2 S04 φ10H20% N C28203" 5H20゜N C28206・2H20゜NaHPHO3112,5H20s Na 3 P 04 " 12 C20xN a
C2P 04 ” 2 C20, Na2 CO3
H20S Na2 CO3' 7H20゜Na2
CO3・10H20, Na CH3COO” 3 H20%NaHC204
・C201NiSO4・6H20, N i C204φ
2H20,5n02 ・nH20゜Sn (SO4
)2 Φ2H20゜ZnS03 ・2H20, Zn5
Oa” 7H20sZn3 (PO4)2 ・4H
Examples include, but are not limited to, 20S Z n (CH3Coo)2 .2H20.

Among these, hydrates of alkali metal salts and hydrates of alkaline earth metal salts are preferred, specifically CaO2" 8H20, CaSO4" 2H2OsMg
Examples include SO4 7H20, Na2 SO4・10H20°Na2 CO3φ10H20, and so on.

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), The number of water molecules in the hydrate of the metal salt of component (B) is 0. 1
It is preferable to set the ratio to about 100 pieces, more preferably about 0.3 to 10 pieces. (B) for (A) component
If the blending amount of the components is too small, a resin composition with insufficient deep curability will be obtained, which is not preferable.

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

As the silanol condensation catalyst used as component (C) in the present invention, a wide variety of conventionally known catalysts can be used. Specific examples include titanate esters such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, and tin naphthenate; dibutyltin oxide and phthalic acid. Reactant with ester; dibutyltin diacetylacetonate; aluminum trisacetylacetonate,
Organoaluminum compounds such as aluminum trisethyl acetoacetate and diisopropoxyaluminum ethylacetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; butylamine, octylamine, dibutylamine, mono Ethanolamine, jetanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine,
2.4.6-) Lis(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-
4-methylimidazole, 1,8-diazabicyclo(5
, 4, O) Amine compounds such as undecene-7 (DBU), or salts thereof with carboxylic acids, etc.; Low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; Excess polyamines and epoxy compounds. reaction product;
Silane coupling agents having amino groups, such as silanol condensation catalysts such as γ-aminopropyltrimethoxysilane and N-(β-aminoethyl)aminopropylmethyldimethoxysilane, as well as other known acidic catalysts, basic catalysts, etc. Examples include silanol condensation catalysts.

These catalysts may be used alone or in combination of two or more. The blending amount of component (C) is preferably about 0.1 to 20 parts, more preferably about 1 to 10 parts, per 100 parts by weight (hereinafter simply referred to as "parts") of component (A). (A)
If the amount of the silanol condensation catalyst blended with respect to the components is too small, the curing speed of the resulting resin composition will be slow (on the other hand, if it is too large, the physical properties such as tensile properties of the obtained cured product will deteriorate, so both are undesirable). .

Incorporation of plasticizers into the compositions of the present invention further improves the deep effectiveness of the resulting compositions. The plasticizer to be used is not particularly limited, and any commonly used plasticizer can be used, but those having good compatibility with the various components contained in the composition of the present invention are preferred. Specific examples of such plasticizers include polybutene,
Hydrogenated polybutene, ethylene-α-olefin oligomer α-methylstyrene oligomer, biphenyl, triphenyl, triaryl dimethane, alkylene triphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyldiphenyl, partially hydrogenated terphenyl, paraffin oil, Hydrocarbon compounds such as naphthenic oil and atactic polypropylene; Chlorinated paraffins; Dibutyl phthalate, dibutyl phthalate, di(2-ethylhexyl)
Phthalate esters such as phthalate, butyl benzyl phthalate, butyl phthalyl butyl glycolate; non-aromatic 2 such as dioctyl adipate and dioctyl sebacate
Basic acid esters; esters of polyalkylene glycol such as diethylene glycol benzoate and triethylene glycol dibenzoate; phosphoric acid esters such as tricresyl phosphate and tributyl phosphate; and the like. These may be used alone or in combination of two or more. Among these, hydrocarbon compounds that do not have unsaturated groups (specifically, hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthenic oil, atactic polypropylene, etc.) are blended into the composition of the present invention. It is preferable because it has good compatibility with various components, the resulting cured product has good weather resistance, and it is inexpensive.

The composition of the present invention further includes an adhesion improver, a physical property regulator,
Storage stability improvers, fillers, sulfur-based anti-aging agents, ultraviolet absorbers, metal deactivators, ozone deterioration inhibitors, light stabilizers, amine-based radical chain inhibitors, phosphorus-based peroxide decomposers , lubricants, pigments, foaming agents, and other various additives may be added as appropriate.

Effects of the Invention The curable resin composition of the present invention has remarkable weather resistance, heat resistance, water resistance, moisture barrier properties, strength, elongation properties, etc., and can provide a cured product with particularly excellent deep curability. . Furthermore, since the polymer used as component (A) in the present invention contains a reactive silicon group, it can be applied to various adherends, such as glass,
Aluminum, natural rubber, butyl rubber, epoxy resin,
It can be adhered to various base materials such as acrylic resin, vinyl chloride resin, nylon, and galvanized iron, and can have good water-resistant adhesiveness, heat-resistant adhesiveness, etc. Therefore, the composition of the present invention is suitable as an adhesive, a pressure-sensitive adhesive, a paint, a sealant composition such as a sealant for double-glazed glass, a waterproofing agent, a spray agent, a molding material, a casting rubber material, etc. can be used.

EXAMPLES In order to further clarify the present invention, Examples and Comparative Examples are given below.

Examples 1 to 5 The molecular weight represented by the molecular formula is approximately 2800, and the viscosity is approximately 520.
To 100 parts of a hydrogenated polyisoprene polymer having a silyl group at the end of Poise (20°C), hydrated metal salts, fillers, and plasticizers were added as shown in Table 1, and the mixture was applied to three paint rolls. , and kneaded three times. Further, 3 parts of tin di-n-octylate and 0.75 parts of laurylamine were added to this, stirred, and poured into a mold with a thickness of 20 mm.
and aged at 50°C. The thickness thus obtained was 40 m.
The deep curability was evaluated by inserting a needle into the composition of m and observing the curing situation over time, and the results are shown in Table 1 below.

Comparative Example 1 The same procedure as Example 1 was carried out except that the metal salt hydrate was not blended, and the results are shown in Table 1.

Examples 6 to 10 10 parts of the hydrogenated polyisoprene polymer of Example 1 was converted into a polymer having a molecular formula of about 5400, a viscosity of about 610
The same procedures as in Examples 1 to 5 were carried out except that 100 parts of polyisobutylene having a silyl group at the terminal and having a temperature of 0 poise (20 DEG C.) was used, and the results are shown in Table 2.

Comparative Example 2 The same procedure as in Example 6 was carried out except that the metal salt hydrate was not blended, and the results are shown in Table 2.

Claims (4)

[Claims] (1) (A) A saturated hydrocarbon polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon atom-containing group that can be crosslinked by forming a siloxane bond, (B) A curable resin composition comprising a hydrate of a metal salt and (C) a silanol condensation catalyst. (2) The composition according to claim 1, wherein the saturated hydrocarbon polymer as component (A) has a number average molecular weight of 1,000 to 15,000. (3) Claim (1) wherein the hydrate of the metal salt as component (B) is at least one selected from the group consisting of hydrates of alkali metal salts and hydrates of alkaline earth metal salts. Compositions as described. (4) The number of water molecules in the hydrate of the metal salt of component (B) is 0.3 to 1 per hydroxyl group or hydrolyzable group of component (A).
Claim (1): The above two components are blended in an amount of 10.
Compositions as described.