JPH04309519A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a curable composition which can give a cured product improved in weathering resistance, toughness, adhesive strength, etc., by mixing a specified alkyl (meth)-acrylate with an oxyalkylene polymer and an epoxy resin. CONSTITUTION:Monomers which can give monomer units of formula I (wherein R<1> is 1-8C alkyl and R<2> is H or CH3) and formula II (wherein R<3> is 10C or higher alkyl), together with optionally a monomer copolymerizable therewith, are copolymerized with a compound having a polymerizable unsaturated bond and a reactive silicon group to obtain an alkyl (meth)acrylate (A) having an Si-bonded OH or hydrolyzable group (i) and at least one Si-containing group (ii) which can be crosslinked by forming siloxane bonds. Component A is mixed with an oxyalkylene polymer having component (i) and at least one component (ii) and an epoxy resin to obtain the title composition.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to curable compositions. More specifically, the present invention relates to a curable composition that can provide a cured product with improved toughness, strength, weather resistance, and the like.

0002

[Prior Art and Problems to be Solved by the Invention] Epoxy resins are used in various molding materials, including paints and adhesives, due to their excellent properties such as adhesion, abrasion resistance, chemical resistance, and moisture resistance. Epoxy resins are used in a wide range of applications such as plywood and laminates, but they have the disadvantage that the cured product is brittle. For example, when an epoxy resin is blended into an adhesive, an adhesive with only poor peel strength is obtained.

[0003] In order to solve these drawbacks of epoxy resins, silicon atom-containing groups (hereinafter referred to as “reactive A composition containing an oxyalkylene polymer having silicon groups (referred to as "silicon group") and an epoxy resin has been developed (Japanese Patent Application Laid-Open No. 61-268720).
Publication No.). The composition has excellent toughness and therefore can provide excellent shear adhesive strength and peel adhesive strength when used as an adhesive; however, the composition has poor weather resistance. It has the following drawbacks. Therefore, it is currently desired to develop a curable composition that has excellent weather resistance and can provide a cured product with even better shear adhesive strength and peel adhesive strength.

0004

[Means for Solving the Problems] An object of the present invention is to provide an epoxy resin and a reactive silicon group-containing oxysilane which can provide a cured product having excellent weather resistance, even better toughness, various adhesive strengths, etc. An object of the present invention is to provide a curable composition containing an alkylene polymer. The above object of the present invention is achieved by blending a specific (meth)acrylic acid alkyl ester polymer, which is the component (A) below, into an epoxy resin and an oxyalkylene polymer having a reactive silicon group.

That is, the present invention provides (A) a (meth)acrylic acid alkyl ester polymer having at least one reactive silicon group, (B) an oxyalkylene polymer having at least one reactive silicon group, and (C) a curable composition containing an epoxy resin. The cured product obtained from the curable composition of the present invention has excellent adhesive properties, as well as
It also has excellent weather resistance, which is important for civil engineering adhesives.

In the present invention, component (A) is a (meth)acrylic acid alkyl ester polymer having at least one reactive silicon group (hereinafter referred to as "reactive silicon group-containing (meth)acrylic acid alkyl ester polymer"). ). In the reactive silicon group-containing (meth)acrylic acid alkyl ester polymer, 50% by weight (hereinafter simply referred to as "%") or more, preferably 70% or more of the molecular chain consists of (meth)acrylic acid alkyl ester units. Preferably, the molecular chain of the polymer may be composed of a single (meth)acrylic acid alkyl ester unit, or may be composed of two or more types of (meth)acrylic acid alkyl ester units. Further, as the molecular chain of the above polymer, a single molecular chain may be used, or two or more types of molecular chains may be used in combination. If 50% or more of the molecular chain of the above polymer is not composed of (meth)acrylic acid alkyl ester units, the compatibility with the oxyalkylene polymer used as component (B) will be poor, causing a practical problem. becomes more likely to occur.

The alkyl group constituting the (meth)acrylic acid alkyl ester unit preferably has 1 to 3 carbon atoms.
0 alkyl group, which may be a linear alkyl group or a branched alkyl group. Specific examples of such alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, 1-
Ethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, isooctyl group, 3,5,5
Examples include -trimethylhexyl group, 2-ethylhexyl group, decyl group, lauryl group, tridecyl group, cetyl group, stearyl group, docosanyl group, and behenyl group.

Among the above molecular chains, general formula (1)

[Chemical 1
] [In the formula, R1 represents an alkyl group having 1 to 8 carbon atoms, and R2 represents a hydrogen atom or a methyl group. ] Carbon number 1~
Acrylic monomer unit having 8 alkyl groups and general formula (2)

embedded image [In the formula, R2 is the same as above. R3 represents an alkyl group having 10 or more carbon atoms. ] The molecular chain containing the acrylic monomer unit having an alkyl group having 10 or more carbon atoms can further improve the compatibility with the oxyalkylene polymer as component (B), preferable. The ratio of the monomer units of the general formula (1) and the monomer units of the general formula (2) is the former: the latter = 95:5 to 40:6 by weight.
0 is preferable, and the former:latter=90:10 to 60:40 is more preferable.

In the above general formula (1), R1 is, for example, a methyl group, an ethyl group, an n-propyl group, an n-
Butyl group, t-butyl group, 2-ethylhexyl group, etc. having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms
Examples include alkyl groups. Incidentally, the alkyl group for R1 may be used alone or in a mixture of two or more types. In the above general formula (2), R3 has 10 or more carbon atoms, usually 10 to 3 carbon atoms, such as lauryl group, tridecyl group, cetyl group, stearyl group, docosanyl group, behenyl group, etc.
0, preferably 10 to 20 long chain alkyl groups. As with the alkyl group R1, the alkyl group R3 may be used alone, or it may be a mixture of two or more, such as a mixture of 12 and 13 carbon atoms.

[0010] The formula (which may be contained in the reactive silicon group-containing (meth)acrylic acid alkyl ester polymer)
Examples of monomer units other than 1) and (2) include acrylic acids such as acrylic acid and methacrylic acid; ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and di(meth)acrylic acid. Polyfunctional group (meth)acrylic acid esters such as tetraethylene glycol acid, 1,3-butylene glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate;
Amide compounds such as acrylamide, methacrylamide, N-methylol acrylamide, and N-methylol methacrylamide; epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; amino compounds such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and aminoethyl vinyl ether;
Other examples include monomer units based on acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, and the like.

The reactive silicon group contained in the above-mentioned (meth)acrylic acid alkyl ester polymer is not particularly limited, but typical ones include, for example, those represented by the general formula (3).

[In the formula, R4 and R5 both have 1 to 20 carbon atoms]
Alkyl group, aryl group having 6 to 20 carbon atoms, 7 carbon atoms
~20 aralkyl groups or (R')3SiO-(R
' is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and R4 or R5 is When two or more are present, they may be the same or 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 is 0, 1, 2
or 3, and b represents 0, 1 or 2, respectively. Also, m

The b's in [Image Omitted] do not need to be the same. m is 0 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.

The hydrolyzable group represented by X above is
Although not particularly limited, conventionally known hydrolyzable groups are included,
Specifically, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group,
Examples include amide group, aminooxy group, mercapto group, and alkenyloxy group. Among these, hydrogen atoms, alkoxy groups, acyloxy groups, ketoximate groups,
An amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferable, and an alkoxy group is particularly preferable from the viewpoint of mild hydrolyzability and easy handling. The hydrolyzable group or hydroxyl group is 1 per silicon atom.
~3 can be combined, and (sum of a+b) is preferably in the 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.

[0013] The number of silicon atoms forming the reactive silicon group is 1
The number may be 2 or more, but in the case of silicon atoms connected by siloxane bonds or the like, the number may be up to about 20. Especially general formula (4)

embedded image [In the formula, R5, 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 R4 and R5 in the above 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, benzyl group, etc. an aralkyl group, R' is a methyl group, a phenyl group, etc. (R'
) A triorganosiloxy group represented by 3SiO- and the like. Among these, a methyl group is particularly preferred as R4 and R5.

At least one reactive silicon group, preferably 1.1 to 20 reactive silicon groups, should be present in one molecule of the (meth)acrylic acid alkyl ester polymer. When the number of reactive silicon groups contained in the molecule is less than one, the strength of the resulting cured product tends to decrease, which is not preferable. The reactive silicon group may be present at the end of the (meth)acrylic acid alkyl ester 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 (meth)acrylic acid alkyl ester polymer component contained in the finally formed cured product increases, resulting in high strength. This is preferable from the viewpoint that it becomes easier to obtain a rubber-like cured product with high elongation.

The above-mentioned (meth)acrylic acid alkyl ester polymer contains monomers capable of providing the monomer units of formulas (1) and (2) by vinyl polymerization, for example, vinyl polymerization by radical reaction, and if necessary, Depending on the situation, a monomer copolymerizable with these monomers can be obtained, for example, by a conventional solution polymerization method or bulk polymerization method in which the monomer is polymerized together with a compound having a polymerizable unsaturated bond and a reactive silicon group. This polymerization reaction is
The above monomers and, if necessary, a radical initiator, etc. are added, preferably a chain transfer agent is added as necessary to obtain the polymer having a desired number average molecular weight, and the reaction is carried out at about 50 to 150°C. The chain transfer agent is not particularly limited, but mercaptan is preferred from the viewpoint of chain transfer efficiency, cost, etc. Mercaptans that can be used are not particularly limited, and for example, n
-dodecylmercaptan, t-dodecylmercaptan,
Examples include benzyl mercaptan and mercaptans having functional groups such as olefin groups and reactive silicon groups (for example, mercaptosilane). Even if the solvent is used,
Although it is not necessary to use a solvent, if a solvent is used, a non-reactive solvent such as ethers, hydrocarbons, acetic esters, etc. is preferable.

Examples of the compound having the above-mentioned polymerizable unsaturated bond and a reactive silicon group include those represented by the general formula (5).

embedded image [In the formula, R6 represents an organic residue having a polymerizable unsaturated bond. R4, R5, X, a, b and m are the same as above. ] Compounds represented by the following can be mentioned. Among the compounds represented by the above general formula (5), particularly preferred compounds are those represented by the general formula (6).

[In the formula, A is -COOR7 (R7 is -CH2 -,
divalent alkylene group having 1 to 6 carbon atoms such as CH2 CH2 -, -CH2 C6 H4 CH2 CH2 , C
Indicates a divalent organic group such as H2 OCOC6 H4 COO(CH2 )3 - or a direct bond. R2, X and a
is the same as above. ] This is a compound represented by

Specific examples of the compound represented by the above general formula (6) are as follows.

[Chemical formula 8] etc. can be mentioned. Among these, especially

[C9
] is preferred.

The above-mentioned reactive silicon group-containing (meth)acrylic acid alkyl ester polymer used in the present invention can be obtained by producing a polymer having no reactive silicon groups and then introducing reactive silicon groups. can also be produced. Such a method includes, for example, polymerizable unsaturated bonds and reactive functional groups (
A compound (for example, acrylic acid) having a "Y group" (hereinafter referred to as "Y group") is added to a monomer capable of providing units represented by formulas (1) and (2) above and copolymerized, and then the resulting copolymer to react with a compound having a functional group (hereinafter referred to as "Y' functional group") that can react with a reactive silicon group and a Y group (for example, a compound having an isocyanate group and a -Si(OCH3)3 group). Can be done. Examples of the Y group and Y' group include various combinations of groups, and examples include a vinyl group as the Y group and a silicon hydride group (H-Si) as the Y' group. The Y group and the Y' group can be bonded by a hydrosilylation reaction.

Examples of compounds having a vinyl group as the Y group and further having a polymerizable unsaturated bond include allyl acrylate, allyl methacrylate, diallyl phthalate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1, 5-pentanediol diacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,
Examples include 6-hexanediol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, divinylbenzene, and butadiene.

Compounds having a silicon hydride group as the Y' group and further having a reactive silicon group include, for example, the compound represented by the general formula (
7)

embedded image [In the formula, R4, R5, X, a, b and m are the same as above. ] Hydrosilane compounds represented by the following can be mentioned.

Specific examples of the hydrosilane compound of the general formula (7) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethyldichlorosilane, and trimethylsiloxydichlorosilane; trimethoxysilane, triethoxysilane, and methyl. Dimethoxysilane, phenyldimethoxysilane, 1,3,3,5,5
, 7,7-heptamethyl-1,1-dimethoxytetrasiloxane; acyloxysilanes such as methyldiacetoxysilane, trimethylsiloxymethylacetoxysilane; bis(dimethylketoximate)methylsilane, bis(cyclohexylketoxymate); Ketoximate silanes such as methylsilane, bis(diethylketoximate)trimethylsiloxysilane; dimethylsilane, trimethylsiloxymethylsilane, 1,
Examples include hydrosilanes such as 1-dimethyl-2,2-dimethylsiloxane; alkenyloxysilanes such as methyldi(isopropenyloxy)silane; however, the present invention is not limited to these. When halogenated silanes are used as the above-mentioned hydrosilane compound, a halogen atom is introduced, but this halogen atom can be replaced by other hydrolyzable groups such as alkoxy groups, aminoxy groups, amino groups, thioalkoxy groups, etc. can be converted into

The above reactive silicon group-containing (meth)acrylic acid alkyl ester polymer has a number average molecular weight of 500 to 500.
A number of about 100,000 is preferable from the viewpoint of ease of handling, and a number of about 1,000 to 75,000 is more preferable. In the present invention, such polymers may be used alone or in combination of two or more.

In the present invention, component (B) is an oxyalkylene polymer having at least one reactive silicon group (
(hereinafter referred to as "reactive silicon group-containing oxyalkylene polymer").

The molecular chain of the reactive silicon group-containing oxyalkylene polymer essentially has the general formula: -R7 -O- [wherein R7 represents a divalent organic group]. ] is preferable. As a specific example of R7,

[Image Omitted] and the like. The molecular chain of the above oxyalkylene polymer may consist of only one type of repeating unit, or may consist of two types of repeating units.
It may consist of more than one type of repeating unit. Especially as R7

embedded image is preferred. The repeating unit represented by -R7-O- is preferably contained in the oxyalkylene polymer in an amount of 50% or more, more preferably 70% or more, particularly 80% or more.

The reactive silicon group in the oxyalkylene polymer is the same as the reactive silicon group in the (meth)acrylic acid alkyl ester polymer. From the point of view of obtaining sufficient curability, the number of reactive silicon groups in the oxyalkylene polymer is on average 1 to 5, more preferably 1.1 to 4, particularly 1.5 to 4. Preferably. Further, the reactive silicon group may be present at the end of the molecular chain of the oxyalkylene polymer, or may be present at both ends, but it is preferably present at the end of the molecular chain. The number average molecular weight of the oxyalkylene polymer is 500 to 30,000.
It is preferably about 3,000 to 15,000, and more preferably about 3,000 to 15,000. In the present invention, such polymers may be used alone or in combination of two or more.

[0027] The oxyalkylene polymer is, for example, a hydrosilane compound represented by the general formula (7) and a compound represented by the general formula (8).

embedded image In the formula, R8 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, R9 is a divalent organic group having 1 to 20 carbon atoms, and c is 0 or 1. VIII, such as a platinum compound, and an oxyalkylene polymer having an olefin group represented by
It is produced by a method such as an addition reaction using a group transition metal compound or the like as a catalyst.

As a method for producing an oxyalkylene polymer other than the above, (1) a hydroxyl group-terminated oxyalkylene polymer is reacted with a polyisocyanate compound such as toluene diisocyanate to form an isocyanate group-terminated alkylene oxide polymer; General formula (9) for the isocyanate group

embedded image [In the formula, W represents an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group, and an amino group (primary or secondary). R5, R9, X and a are the same as above. ]
A method of reacting the W group of a silicon compound represented by
(iii) A method of adding a mercapto group of a silicon compound represented by the general formula (9) in which W is a mercapto group to an olefin group of an oxyalkylene polymer having an olefin group represented by the above general formula (8), and ■
The general formula (10) is applied to the hydroxyl group of the hydroxyl group-terminated oxyalkylene polymer.

embedded image [In the formula, R5, R9, X and a are the same as above. ], but the present invention is not limited to these methods.

In the method of reacting the hydrosilyl compound represented by the general formula (7) with the olefin group-containing oxyalkylene polymer represented by the general formula (8), after the reaction, a part or all of the hydrosilyl compound represented by the general formula (7) is reacted. The X group may be further converted into another hydrolyzable group or a hydroxyl group. For example, when the X group is a halogen atom or a hydrogen atom, it is preferable to use these after converting them into an alkoxy group, an acyloxy group, an aminooxy group, an alkenyloxy group, a hydroxyl group, or the like. In general formula (8), R8 is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group,
Particularly preferred is a hydrogen atom. R9 has 1 or more carbon atoms
20 divalent organic groups,

embedded image (R10 is a divalent hydrocarbon group having 1 to 10 carbon atoms) is preferable, and a methylene group is particularly preferable.

Specific methods for producing the oxyalkylene polymer having an olefin group represented by the general formula (8) include, for example, the method disclosed in JP-A-54-6097, or the method using ethylene oxide, propylene oxide, etc. When polymerizing the epoxy compound, an olefin group-containing epoxy compound such as allyl glycidyl ether is added and copolymerized, thereby introducing an olefin group into the side chain. Such polymers are disclosed in, for example, Japanese Patent Publications No. 45-36319, No. 46-12154, No. 49-
No. 32673, JP-A-50-156599, JP-A No. 51-
No. 73561, No. 54-6096, No. 55-8212
No. 3, No. 55-123620, No. 55-125121
No. 55-131022, No. 55-135135, and No. 55-137129. In the present invention, such polymers may be used alone or in combination of two or more.

As the epoxy resin which is component (C) used in the present invention, a wide variety of conventionally known ones can be used, such as epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, and tetrabromobisphenol A type epoxy resin. Flame-retardant epoxy resins such as glycidyl ether, novolak epoxy resins, hydrogenated bisphenol A epoxy resins, glycidyl ether epoxy resins of bisphenol A propylene oxide adducts, p-oxybenzoic acid glycidyl ether ester epoxy resins, m- Aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether,
Glycidyl ether of polyhydric alcohol such as glycerin,
Examples include hydantoin type epoxy resins and epoxidized products of unsaturated polymers such as petroleum resins. Among these, especially the expression

Those containing at least two epoxy groups represented by the following formula in the molecule are preferred from the viewpoints of high reactivity during curing and the ability to easily form a three-dimensional network in the cured product. In the present invention, bisphenol A type epoxy resins and novolac type epoxy resins are most preferred. In the present invention, such epoxy resins may be used alone or in combination of two or more.

In the present invention, there is no particular restriction on the blending ratio of component (A) and component (B), and it may be selected as appropriate depending on the intended use, performance, etc., but the amount of component (A) The range of about 5 to 5,000 parts per 100 parts by weight of component (B) (hereinafter simply referred to as "parts") is preferable because the effect of improving properties is remarkable, and the range of about 5 to 2,000 parts is more preferable. Furthermore, the amount of component (C) to be blended is not particularly limited and can be appropriately selected depending on the intended use and performance. In the present invention, when the total amount of component (A) and component (B) is 100 parts, 0.1 to 10000
The amount is preferably in the range of about 0.5 to 2000 parts, as the effect of improving properties is remarkable, and the range of about 0.5 to 2000 parts is more preferable.

The composition of the present invention may contain a silicon compound containing in its molecule a functional group capable of reacting with an epoxy group and the above-mentioned reactive silicon group. The functional groups that can react with the epoxy group in the silicon compound are as follows:
Specific examples include primary, secondary, and tertiary amino groups; mercapto groups; epoxy groups; and carboxyl groups. Also,
As the reactive silicon group, the same hydrolyzable silicon group or silanol group as used in the above component (A) can be optionally used, but an alkoxysilyl group is particularly preferred from the viewpoint of ease of handling. .

Specific examples of such silicon compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane,
-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ
-(2-aminoethyl)aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-
Amino group-containing silanes such as β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane and γ-anilinopropyltrimethoxysilane: γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane , mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-
Epoxy group-containing silanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; β-carboxylethyltriethoxysilane, β-carboxylethylphenylbis(
Examples include carboxysilanes such as 2-methoxyethoxy)silane and N-β-(N-carboxylmethylaminoethyl)-γ-aminopropyltrimethoxysilane. In the present invention, these silicon compounds may be used alone or in combination of two or more. Such a silicon compound usually has a content in the range of about 0.1 to 20, preferably in the range of about 0.2 to 10, when the total amount of components (A), (B), and (C) is 100 parts. It is best to mix it with

The curable composition of the present invention may optionally contain a silanol condensation catalyst, an epoxy resin curing agent, etc. in order to improve the curability of the composition. Examples of silanol condensation catalysts include organic tin compounds, acidic phosphoric esters, reaction products of acidic phosphoric esters and amines,
Examples include saturated or unsaturated polycarboxylic acids or their acid anhydrides, organic titanate compounds, and the like.

Specific examples of the organic tin compounds include dibutyltin dilaurate, dioctyltin dimalate,
Examples include dibutyltin phthalate, tin octylate, dibutyltin methoxide, and the like. The acidic phosphate ester is

It refers to a phosphoric acid ester containing the following moiety, and includes acidic phosphoric acid esters as shown below. Examples of organic acidic phosphate esters include the general formula

embedded image [In the formula, d is 1 or 2, and R11 represents an organic residue. ], specifically, phosphate esters represented by

[C20] etc. can be exemplified.

The amine that can be reacted with the acidic phosphoric acid ester is not particularly limited, and includes, for example, methylamine, ethylamine, butylamine, hexylamine, laurylamine, hexamethylene diamine,

[Chemical Formula 21] Primary amines such as monoethanolamine and aniline; Secondary amines such as diethylamine, dibutylamine, piperidine, and diethanolamine; triethylamine, tributylamine, N,N-diethylhexylamine, N,
N-dimethyldecylamine, N,N-dimethyldodecylamine, N,N-dimethylbenzylamine, N,N,N
',N'-Tetramethyl-1,6-hexanediamine, triethylenediamine, triethanolamine, pyridine, and other tertiary amines; diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and other primary and secondary amines Examples include adducts of and epoxy compounds. The reaction product of the acidic phosphoric acid ester and the amine includes the acidic phosphoric acid ester (a) and the amine (b) in an equivalent ratio (b)/(a) of 0.05-20, preferably 0. It is obtained by mixing in the range of 1 to 10.

Examples of organic titanate compounds include titanate esters such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate. The amount of silanol condensation catalyst used is (A
) and (B) for a total of 100 parts.
1 to 20 parts is preferable, and 0.5 to 10 parts is more preferable.

Furthermore, as the epoxy resin curing agent, a wide variety of conventionally known epoxy resin curing agents can be used. Examples of such curing agents include triethylenetetramine,
Tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 2,4,6-tris(dimethylaminomethyl)phenol, etc. amines; tertiary amine salts; polyamide resins; imidazoles; dicyandiamide; boron trifluoride complex compounds; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecynyl Examples include carboxylic anhydrides such as succinic anhydride, pyromellitic anhydride, and chlorenic anhydride; alcohols; phenols; and carboxylic acids. In the present invention, such curing agents may be used alone or in combination of two or more.

[0040] Furthermore, by using ketimines,
It is possible to make one-part formulations. Such ketimines include 1,2-ethylenebis(isopentylideneimine), 1,2-hexylenebis(isopentylideneimine), 1,2-propylenebis(isopentylidene)imine, p,p'- Examples include biphenylene bis(isopentylideneimine), 1,2-ethylenebis(isopropylideneimine), 1,3-propylenebis(isopropylideneimine), and p-phenylenebis(isopentylideneimine). When blending the above-mentioned epoxy resin curing agent, the amount to be blended varies depending on the type of epoxy resin and the curing agent, and cannot be stated unconditionally, but (C)
The curing agent may be blended in an amount of about 0.1 to 300 parts per 100 parts of the components.

[0041] When preparing the curable composition of the present invention, there is no particular limitation, and for example, component (A), component (B),
(C) Components, etc. are blended and kneaded using a mixer, roll, kneader, etc. at room temperature or under heating, or by using a small amount of an appropriate solvent to dissolve and mix the above components, etc. by a normal method. may be adopted. In addition, by appropriately combining these components, one-component or two-component formulations can be created.
You can also use

The composition of the present invention further includes various fillers,
Plasticizers, additives, etc. may also be added. As a filler,
For example, heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, kaolin, talc, silica, titanium oxide, aluminum silicate, magnesium oxide, zinc oxide,
Examples include carbon black. Examples of the plasticizer include dioctyl phthalate, butylbenzyl phthalate, chlorinated paraffin, and epoxidized soybean oil. Examples of additives include anti-sagging agents such as hydrogenated castor oil and organic bentonite, colorants, and anti-aging agents.

The curable composition of the present invention can be suitably used as an adhesive, a pressure-sensitive adhesive, a paint, a coating film waterproofing agent, a sealing material, a molding material, a cast rubber material, a foaming material, and the like. For example, when used as an adhesive or sealant, it has excellent adhesion and toughness to various base materials, and as a material with excellent weather resistance, it can be applied to high-strength sealants and structural adhesives. . When used as a paint or waterproofing agent, it can exhibit excellent properties as a highly elastic architectural paint that requires excellent paint adhesion, elasticity, weather resistance, etc., or as a primer or waterproofing agent for concrete structures.

[0044]

[Effects of the Invention] The cured product produced from the curable composition of the present invention has excellent physical properties such as toughness and various adhesive strengths, as well as excellent weather resistance, and eliminates the drawbacks of conventional epoxy resins. It's something you get.

[0045]

EXAMPLES Next, the curable composition of the present invention will be explained based on examples. Synthesis Example 1 800 g of a polyoxypropylene polymer with an average molecular weight of approximately 8,000 in which allyl ether groups have been introduced into 97% of all terminals.
was placed in a pressure-resistant reaction vessel equipped with a stirrer, and 19 g of methyldimethoxysilane was added. Then the chloroplatinic acid catalyst solution (H2
After adding 0.34 ml of a solution of 8.9 g of PtCl6 .6H2 O dissolved in 18 ml of isopropyl alcohol and 180 ml of tetrahydrofuran, the mixture was reacted at 80° C. for 6 hours. The amount of silicon hydride groups remaining in the reaction solution is I
When quantified by R spectrum analysis, almost no residue remained. In addition, when we quantified the silicon group by NMR method, we found that at the end of the molecule,

A polyoxypropylene polymer having about 1.7 compounds per molecule was obtained.

Synthesis Example 2 To 570.0 g of toluene heated to 105°C, 947.9 g of methyl methacrylate, 84.7 g of butyl acrylate,
To a monomer mixture consisting of 189.2 g of stearyl methacrylate and 79.2 g of γ-methacryloxypropylmethyldimethoxysilane, 32.5 g of azobisisobutyronitrile as a polymerization initiator and γ-mercaptopropylmethyldimethoxysilane as a chain transfer agent. A solution containing 104.0 g was added dropwise over 5 hours to obtain a colorless and transparent liquid. The resin solid content concentration of this liquid was determined by heating at 120°C and was found to be 70.0%. Further, the number average molecular weight was determined to be 2,500 by GPC using styrene as a standard.

Experimental Method Adhesive properties were shown by tensile shear adhesive strength and 180° peel adhesive strength. Tensile shear adhesive strength is JIS H
4000 aluminum plate A-1050P (100×2
After thoroughly cleaning the surface of a test piece (5 x 2 mm) with acetone, various curable compositions shown below were applied with a spatula, and the test sample, which was pressed by hand, was measured based on JIS K6850. Peel adhesion strength is JIS as a rigid material.
A 5403 asbestos slate board (100 x 25 x 3 m
m) as a flexible material according to JIS H400.
0 aluminum plate A1050P (200 x 50 x 0.
Using a 1 mm) test piece whose surface was thoroughly washed with acetone, the above composition was applied to a thickness of about 0.5 mm with a spatula and bonded together, using a 5 kg hand roller.
Pressure bonding was performed five times without reciprocating in the length direction, and the 180° peel adhesive strength was measured. These adhesion test samples were 23
After hardening and curing at 50°C for 1 day and 7 days at 50°C, a tensile test was conducted. However, the tensile speed is 5mm/in case of tensile shear adhesion test.
min, and in the case of the 180° peel adhesion test, it was set at 200 mm/min. Regarding weather resistance, a sheet with a thickness of approximately 3 mm was obtained by degassing the well-mixed composition using a centrifuge, pouring it into a polyethylene mold, and curing it at 23°C for 7 days and at 50°C for 7 days. The change in surface condition was shown when the cured product was irradiated with ultraviolet rays for 500 hours and 1000 hours using a sunshine weather meter.

Examples 1 to 8 and Comparative Examples 1 to 5 The polymer obtained in Synthesis Example 1 as component (B), the polymer obtained in Synthesis Example 2 as component (A), and Epicoat as component (C) 828 (manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin) so that the solid content ratio becomes the ratio shown in Table 1, and after mixing well, Synthesis Example 2
At 110℃ for 3 hours to remove volatile components contained in
The mixture was devolatilized under reduced pressure using a rotary evaporator to obtain a colorless to pale yellow transparent liquid composition with viscosity. Furthermore, an amino group capable of reacting with an epoxy group and a reactive silicon group are added to this composition, based on 100 parts of the total amount of the polymer obtained in Synthesis Example 1 and the polymer obtained in Synthesis Example 2. As a silicon compound contained in the molecule, 1 part of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, as an antioxidant 1 part of Nocrac SP (manufactured by Ouchi Shinko Kagaku Co., Ltd., phenolic antioxidant) 1 part, #918 (organotin compound manufactured by Sankyo Co., Ltd.) as a silanol condensation catalyst and 0.4 part of water;
8100 parts, 2.4 parts as epoxy resin curing agent
, 10 parts of 6-tris(dimethylaminomethyl)phenol (hereinafter referred to as "DMP-30") were added and mixed, and the tensile shear adhesive strength and peel adhesive strength were evaluated, and the results are shown in Tables 1- 2 and Figures 1-2.

[Table 1]

[Table 2] From the results in Table 1 and FIG. 1, the composition of the present invention has sufficiently high peel adhesion strength compared to the conventional epoxy resin (Comparative Example 2), and the composition of the (B) component Compared to the cured product made only of Synthesis Example 1 (Comparative Example 1) and the cured product made only of components (A) and (B) (Comparative Example 3), it has a high shear adhesive strength and a balance of adhesive physical properties. It turns out. Also Table 2
From the results shown in FIG. 2 and FIG. It was found that it had a better balance of adhesive properties than Example 5).

Example 9 and Comparative Example 6 The polymer obtained in Synthesis Example 1 as component (B) and (A)
The polymer obtained in Synthesis Example 2 as a component and Epicoat 828 as component (C) were mixed well so that the solid content ratio was as shown in Table 3, and then the mixture was prepared in the same manner as in Examples 1 to 8. A pale yellow, transparent, viscous liquid composition was obtained. This composition further contains N-(β-aminoethyl)-γ-aminopropyltrimethoxy, based on 100 parts of the total amount of the polymer obtained in Synthesis Example 1 and the polymer obtained in Synthesis Example 2 contained therein. 1 part of silane, 0.1 part of Tinuvin 327 (manufactured by Nippon Ciba Geigy Co., Ltd., ultraviolet absorber) as an ultraviolet absorber, 1 part of Nocrac SP, 1 part of #918 and 0.4 part of water, and 100 parts of Epicote 828. Then, 10 parts of DMP was added and mixed, and the weather resistance was evaluated by the above method. The results are also shown in Table 3.

[Table 3] From the results in Table 3, the composition of the present invention is superior to the conventional composition consisting of an epoxy resin and an oxyalkylene polymer (Comparative Example 6).
), it was found that the weather resistance was significantly improved.

Example 10 50 parts of the polymer obtained in Synthesis Example 1 as component (B),
(A) Component 50 parts of the polymer obtained in Synthesis Example 2,
A liquid composition was obtained in the same manner as in Examples 1 to 8 by adding 50 parts of Epicoat 828 as the component (C). This composition contains 1 part of NOCRAC SP, 10 parts of ketimine-based epoxy resin curing agent H-3 (ketimine compound manufactured by Yuka Shell Epoxy Co., Ltd.), 4 parts of vinyltrimethoxysilane as a dehydrating agent, and #918 as a silanol condensation catalyst.
2 parts were added and mixed, and 4 parts were added and mixed at 23°C and 60%RH.
After being left for 8 hours, a strong elastic body was obtained.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between adhesive strength and the number of parts of Epikote 828 per 60 parts of the polymer obtained in Synthesis Example 1 and 40 parts of the polymer obtained in Synthesis Example 2.

FIG. 2 is a graph showing the relationship between the adhesion strength and the ratio of parts of the polymer obtained in Synthesis Example 1 and the polymer obtained in Synthesis Example 2 per 100 parts of Epicoat 828.

Claims (3)

[Claims] Claim 1: (A) A (meth)acrylic acid alkyl ester system 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) an oxyalkylene 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;
and (C) a curable composition containing an epoxy resin. 2. A (meth)acrylic acid alkyl ester monomer in which the molecular chain of the (meth)acrylic acid alkyl ester polymer that is component (A) substantially has (1) an alkyl group having 1 to 8 carbon atoms; 2. The composition according to claim 1, which is a copolymer consisting of (2) a (meth)acrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms. 3. The composition according to claim 1, further comprising a silicon compound containing in its molecule a functional group capable of reacting with an epoxy group and the silicon atom-containing group.