JPH02214759A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition giving cured material having improved toughness, adhesive strength or weatherability, etc., containing specific alkyl (meta)acrylate-based polymer, oxyalkylene-based polymer and epoxy resin. CONSTITUTION:(A) Alkyl (meta)acrylate-based polymer having hydroxyl group or hydrolyzable group and at least one silicon atom-containing group crosslinkable by forming siloxane bonding [preferably copolymer composed of alkyl (meta)acrylate monomer unit having 1-8C alkyl group and alkyl (meta) acrylate monomer unit having >=10C alkyl group] is mixed with (B) oxyalkylene- based polymer having hydroxyl group or hydrolyzable group and silicon atom- containing crosslinkable by forming siloxane bonding and (C) epoxy resin and contained in the aimed composition.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present 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.

Conventional technologies and their problems Epoxy resins are used in a wide range of applications, including paints and adhesives, various molding materials, plywood, and laminates due to their excellent properties such as adhesion, abrasion resistance, chemical resistance, and moisture resistance. Although used for various purposes, epoxy resins 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.

In order to solve these drawbacks of epoxy resins, silicon atom-containing groups (hereinafter referred to as "reactive silicon groups") have a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond. A composition containing an oxyalkylene polymer and an epoxy resin has been developed (Japanese Unexamined Patent Publication No. 61-268720). 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.

Means for Solving the Problems The object of the present invention is to provide a cured product having excellent weather resistance, extremely superior toughness, various adhesive strengths, etc., and having an epoxy resin and a reactive silicon group. An object of the present invention is to provide a curable composition containing an oxyalkylene polymer.

The above object of the present invention is achieved by blending a specific (meth)acrylic acid alkyl ester polymer, which is the following component (A), 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 not only excellent adhesive properties but also excellent weather resistance, which is important in civil engineering adhesives and the like.

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"). be.

In the reactive silicon group-containing (meth)acrylic acid alkyl ester polymer, 50% by weight (hereinafter simply referred to as "r%") 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) becomes poor, which tends to cause practical problems.

The alkyl group constituting the above (meth)acrylic acid alkyl ester unit is preferably an alkyl group having 1 to 30 carbon atoms, and may be a linear alkyl group or a branched alkyl group. Good too.

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-trimethylhexyl group, 2-ethylhexyl group, decyl group, lauryl group, tridecyl group, cetyl group, stearyl group, docosanyl group, behenyl group, etc. Can be done.

In the above molecular chain, the general formula (1) R2 % formula % (1) [wherein R1 represents an alkyl group having 1 to 8 carbon atoms, and R2 represents a hydrogen atom or a methyl group]. ] An acrylic monomer unit having an alkyl group having 1 to 8 carbon atoms represented by the general formula (2) % formula % (2) [wherein R2 is the same as above. R3 represents an alkyl group having 10 or more carbon atoms. ] Since the molecular chain containing the acrylic monomer unit having an alkyl group having 10 or more carbon atoms represented by can further improve the compatibility with the oxyalkylene polymer which is the 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 by weight.
: 60 is preferable, former: latter = 90: 10-60
: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, a t-
Examples include alkyl groups having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms, such as a butyl group and a 2-ethylhexyl group. In addition, the alkyl group of R1 may be used alone,
Two or more types may be mixed.

In the above general formula (2), R3 has 10 or more carbon atoms, usually 10 carbon atoms, such as lauryl group, tridecyl group, cetyl group, stearyl group, docosanyl group, behenyl group, etc.
-30, preferably 10-20 long chain alkyl groups. Note that the alkyl group for R3 may be used alone, as in the case of the alkyl group for R1, or may be a mixture of two or more types, such as a mixture of 12 and 13 carbon atoms.

Formulas (1) and (2) which may be contained in the reactive silicon group-containing (meth)acrylic acid alkyl ester polymer
) Examples of monomer units other than acrylic acids such as acrylic acid and methacrylic acid; ethylene glycol di(meth)acrylate, triethylene glycol di(meth)°acrylate, and tetraethylene glycol di(meth)acrylate. , polyfunctional (meth)acrylic acid esters such as 1,3-butylene glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate: acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylate Amide compounds such as amides, epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, amino compounds such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; other acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, chloride Examples include monomer units derived from vinyl, vinyl acetate, vinyl propionate, ethylene, and the like.

The reactive silicon group contained in the above (meth)acrylic acid alkyl ester polymer is not particularly limited, but representative ones include, for example, the general formula (3
) (In the formula, R4 and R5 are both an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 2 carbon atoms.
0 aralkyl group or (R' ) 3 S i O(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
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
, 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 a+(sum of b)≧1 is satisfied. ] Examples include groups represented by the following.

The hydrolyzable group represented by X above is not particularly limited, and includes conventionally known hydrolyzable groups, specifically,
For example, hydrogen atom, hydrogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide group,
Examples include aminooxy group, mercapto group, alkenyloxy group and the like. Among these, hydrogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups,
An amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferred, and an alkoxy group is particularly preferred from the viewpoint of mild hydrolysis and easy handling.

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, general formula (4) [wherein 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,
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 (R')3 SiO where R/ is a methyl group, a phenyl group, etc.
Examples include triorganosiloxy groups represented by -.

Among these, a methyl group is particularly preferred as R4 and R5.

The number of reactive silicon groups is at least 1, preferably 1.1, in one molecule of the (meth)acrylic acid alkyl ester polymer.
It is preferable that there be ~20 pieces. 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, reactive silicon groups are present at the ends of the molecular chain.

In this case, the effective network chain amount of the (meth)acrylic acid alkyl ester polymer component contained in the final cured product increases, making it easier to obtain a rubber-like cured product with high strength and high elongation. This is preferable because of the following.

The above (meth)acrylic acid alkyl ester polymer is
Monomers that can give the monomer units of formulas (1) and (2) by vinyl polymerization, for example, vinyl polymerization by radical reaction, and monomers that can be copolymerized with these monomers as necessary, For example, it can be obtained by a conventional solution polymerization method or bulk polymerization method in which a compound having a polymerizable unsaturated phase bond and a reactive silicon group is polymerized together. This polymerization reaction is carried out using the above monomers and, if necessary, a radical initiator, etc., preferably at about 50 to 150°C, with the addition of a chain transfer agent as necessary to obtain the polymer with the desired number average molecular weight. It is done. 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 examples include n-dodecylmercaptan, t-dodecylmercaptan, benzylmercaptan, and mercaptans having functional groups such as olefin groups and reactive silicon groups (e.g., mercaptosilane). Can be done. A solvent may or may not be used, but when a solvent is used, non-reactive solvents such as ethers, hydrocarbons, and acetic esters are desirable.

The compound having a polymerizable unsaturated bond and a reactive silicon group is, for example, a compound represented by the general formula (5) [wherein R6 represents an organic residue having a polymerizable unsaturated bond]. R', R5, X, a
, b and m are the same as above. ] Compounds represented by these can be mentioned. Among the compounds represented by the above formula (5), particularly preferred compounds are those represented by the general formula (6) [wherein A is -COOR7 (R7 is =CH2-, CH2
divalent alkylene group having 1 to 6 carbon atoms such as CH2-),
CH2C6H4CH2CH2, CH20COCs
Indicates a divalent organic group such as H4Coo (CH2)3 - or a direct bond. R2X and a are the same as above. ] It is a compound represented by

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

CH3 CH2-CH31 (OCHa) 2.

CH3 CH2-CH5I CQ 2- CH2=CH3i (OCH3) 3.

CH2=CH8I CQ 3゜ CH2=CHC0(CH2) 231 CQ 3.

CH2-C-Co (CH2) 281(OCH3)
2.

C) 12-C-Co (CH2) 281 (OCft3
) 3.

CH2=CCO(CH2) 331(OCH3) 2
.

CH2-CCO(CH2) a 81(OCH3) 3
.

C)+2 = CCo (CH2) 281 CQ 2
.

CH2-CHCo (CH2) 25i(OCHa)
3゜CH2-CHCo (CHz) 2 Si C
Q2.

CH2-CCO(C)12 ) 2 St CQ a
.

-81 (OCH3) 2.

O -5t (OCh) 3.

-Si　CQ　2　.

-81C93 etc. can be mentioned. Among these, these are particularly preferred.

The above-mentioned reactive silicon group-containing (meth)acrylic acid alkyl ester polymer used in the present invention can also be produced by a method in which a reactive silicon group is introduced after producing a polymer having no reactive silicon groups. obtain.

As such a method, for example, a compound (for example, acrylic acid) having a polymerizable unsaturated bond and a reactive functional group (hereinafter referred to as "Y group") is combined with units represented by the above formulas (1) and (2). A compound having a reactive silicon group and a functional group (hereinafter referred to as "Y' functional group") that can react with a reactive silicon group and a Y group (for example, an isocyanate group) and -8E (OCH3) 3
A method of reacting with a compound having a group) can be mentioned.

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-8t) 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 diacrylate-bentanediol diacrylate, 1,5-bentanediol dimethacrylate, 1,6-hexanethiol diacrylate), 1,6-hexanethiol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, divinyl Examples include benzene and butadiene.

As a compound having a silicon hydride group as the Y' group and further having a reactive silicon group, for example, the compound having the general formula [wherein R',
R', X, a, b and m are the same as above. ] Hydrosilane compounds represented by these can be mentioned.

Specific examples of the hydrosilane compound of the above general formula (7) include trichlorosilane, methyldichlorosilane,
Halogenated silanes such as dimethyldichlorosilane, trimethylsiloxydichlorosilane, nitrimethoxysilane,
Triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1.3.3. 5.5.7.7-
Alkoxysilanes such as hebutamethyl-1,1-dimethoxytetrasiloxane; acyloxysilanes such as methyldiacetoxysilane, trimethylsiloxymethylacetoxysilane; bis(dimethylketoximate)methylsilane, bis(cyclohexylketoximate) ) Ketoximate silanes such as methylsilane, bis(diethylketoximate)trimethylsiloxysilane; hydrosilanes such as dimethylsilane, trimethylsiloxymethylsilane, 1,1-dimethyl-2゜2-dimethyldisiloxane; methyldi( Examples include alkenyloxysilanes such as isobrobenyloxy)silane, but the present invention is not limited thereto.

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 reactive silicon group-containing (meth)acrylic acid alkyl ester polymer has a number average molecular weight of 500 to 100,000.
100% is preferable from the point of view of ease of handling.
More preferably, it is about 0 to 75,000. 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: % formula % [wherein R7 represents a divalent organic group]. ] is preferable.

As a specific example of R7, -CHCH2- -CHCH2- H3 -C-CH2- H3 -CH2CH2CH2CH2- and the like.

The molecular chain of the oxyalkylene polymer may consist of only one type of repeating unit, or may consist of two or more types of repeating units. As R7, H3 is particularly preferably -CHCH2-.

The repeating unit represented by -R7-0- 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 above oxyalkylene polymer should be 1 on average.
5 or more, more preferably 1.1 or more, especially 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.
~30000 is preferable, and 3000~150
A value of about 00 is more preferable.

In the present invention, such polymers may be used alone or in combination of two or more.

The above-mentioned oxyalkylene polymer is, for example, the above-mentioned formula (
7) and the general formula (8) [wherein, 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 Indicates 0 or 1. ] It is produced by a method such as an addition reaction between an oxyalkylene polymer having an olefin group represented by the following and the like using a group Ⅰ transition metal compound such as a platinum compound as a catalyst.

Methods for producing oxyalkylene polymers other than those mentioned above include: (1) Reacting a hydroxyl group-terminated oxyalkylene polymer with a polyisocyanate compound such as toluene diisonanate to form an isocyanate group-terminated alkylene oxide polymer; The isocyanate group has the general formula (9) [where 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, R9X and a are the same as above. ] A method of reacting a W group of a silicon compound represented by (1) a reaction with an olefin group of an oxyalkylene polymer having an olefin group represented by the above general formula (8), in which W is a mercapto group; A method of addition-reacting a mercapto group of a silicon compound represented by the formula, and
General formula (10) [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 reacting them, some or all of the X groups are may be further converted into other hydrolyzable groups or hydroxyl groups. 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 has 1 to 1 carbon atoms.
The 20 substituted or unsubstituted monovalent organic groups are preferably a hydrogen atom or a hydrocarbon group, and particularly preferably a hydrogen atom. R9 is a divalent organic group having 1 to 20 carbon atoms, but R9 is a divalent organic group having 1 to 20 carbon atoms. Preferably, methylene group is particularly preferable.

Specific methods for producing the oxyalkylene polymer having an olefin group represented by general formula (8) include, for example, the method disclosed in JP-A-54-6097, or the method using epoxy compounds such as ethylene oxide and propylene oxide. When polymerizing, 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 Publication No. 45-36319, Japanese Patent Publication No. 46-12154, Japanese Patent Publication No. 49-326.
No. 73, JP-A-50-156599, JP-A No. 51-735
No. 61, No. 54-6096, No. 55-82123,
No. 55-123620, No. 55-125121, No. 55-131022, No. 55-135135, No. 5
It is disclosed in various publications such as No. 5-137129. 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, tetrapro, glycidyl ether of mobisphenol A. Flame-retardant epoxy resins such as, novolak epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol A
Glycidyl ether type epoxy resin of propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N ,
N-diglycidylaniline, N,N-diglycidyl-
Examples include 0-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ethers of polyhydric alcohols such as glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, and petroleum resins. Products containing at least two of these intermediate groups in the molecule have high reactivity during curing, and the cured product can easily form a three-dimensional network.
suitable. 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, the blending ratio of component (A) and component (B) is not particularly limited and may be selected appropriately depending on the intended use, performance, etc.
5 parts per 100 parts by weight of ingredients (hereinafter simply referred to as "parts")
The range of about 5,000 parts is preferable because the effect of improving properties is significant, 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, the total amount of component (A) and component (B) is 10
When it is set as 0 parts, it is preferable in the range of about 0.1 to 10,000 parts because the effect of improving properties is remarkable, and 0.5 to 20 parts.
A range of about 0.00 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.

Specific examples of the functional group that can react with the epoxy group in the silicon compound include primary, secondary, and tertiary 1-mino groups; mercapto groups; epoxy groups; and carboxyl groups. In addition, as the reactive silicon group, the same hydrolyzable silicon group or silanol group as used in the component (A) may be optionally used, but in particular, from the viewpoint of ease of handling, an alkoxysilyl group is preferred.

Specific examples of such silicon compounds include, for example, γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane , γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane Amino group-containing silanes such as methoxysilane: mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyljethoxysilane; Epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3°4-epoxycyclohexyl)ethyltrimethoxysilane, etc. Containing silanes; carboxysilanes such as β-carboxylethyltriethoxysilane, β-carboxylethylphenylbis(2-methoxyethoxy)silane, N-β-(N-carboxylmethylaminoethyl)-γ-aminopropyltrimethoxysilane etc.

In the present invention, these silicon compounds may be used alone or in combination of two or more.

Such a silicon compound usually contains 0.1 parts when the total amount of components (A), (B) and (C) is 100 parts.
It is preferable to mix the amount in the range of about 20 to 20, preferably about 0.2 to 10.

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,
Examples include acidic phosphoric acid esters, reaction products of acidic phosphoric acid esters and amines, saturated or unsaturated polyhydric carboxylic acids or their acid anhydrides, and organic titanate compounds.

Specific examples of the organic tin compound include dibutyltin dilaurate, dioctyltin simalate, dibutyltin phthalate, tin octylate, dibutyltin methoxide, and the like.

The acidic phosphoric acid ester is a phosphoric acid ester containing a moiety of 10-P (OH), and includes the acidic phosphoric acid esters shown below. Examples of the organic acidic phosphoric acid ester include the following formula: [where d is 1 or 2 and R11 represents an organic residue]. ], specifically phosphoric acid esters represented by (Ca 11170 )P (OH) 2, (C10H
210)2PO)i.

(CIo H210) P(OB) 2, (C1a II
2 y O) 2 POII s(C13H270)P
(OR)2, (HO-C8HIsO)2POH.

(HO-C8H+ s 0)P(OH) 2, (HO-
Cs Hl 20)2 POH.

(HO-Cs H120)P(OH)2, [(CH2
0H)(CHO)I)O12POH.

[(CH20H)(CHO)l) 0]P(OH) 2
．． [(CH20H)(CHOH) C4H401P(O
H) 2 etc. can be exemplified.

Examples of amines that can be reacted with acidic phosphate esters include:
There are no particular limitations, such as methylamine, ethylamine,
Primary amines such as butylamine, hexylamine, laurylamine, hexamethylenediamine, H2NCH2+cH2NH2, monoethanolamine, aniline; Secondary amines such as diethylamine, dibutylamine, piperidine, jetanolamine; triethylamine, tributylamine, N, N-diethylhexylamine, N,
N-dimethyldecylamine, N, N-dimethyldodecylamine, N, N-dimethylbenzylamine, N, N,
N'N'-tetramethyl-1,6-hexanediamine, triethylenediamine, triethanolamine,
Tertiary amines such as bilysine; diethylenetriamine,
Examples include adducts of primary and secondary amines such as triethylenetetramine and tetraethylenepentamine and epoxy compounds.

The reaction product of the acidic phosphoric acid ester and the amine contains the acidic phosphoric acid ester (a) and the amine (b) in an equivalent ratio (b)/(a) of 0.05 to 20, preferably 0. 1
It is obtained by mixing in the range of 10 to 10.

Examples of the organic titanate compound include titanate esters such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate.

The amount of the silanol condensation catalyst used is preferably 0.1 to 20 parts, and 0.1 to 20 parts, based on 100 parts of the total amount of components (A) and (B). More preferably 5 to 10 parts.

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゜Amines such as 6-tris(dimethylaminomethyl)phenol; tertiary amine salts; polyamide resins; imidazoles; dicyandiamides: boron trifluoride complex compounds: phthalic anhydride, hexahydrophthalic anhydride, tetrahydro Examples include carboxylic anhydrides such as phthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecynylsuccinic 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.
Used as a mixture of more than one species.

When blending the above-mentioned epoxy resin curing agent, the amount of the above-mentioned curing agent varies depending on the type of epoxy resin and the curing agent, and cannot be generalized, but it is approximately 0.1 to 300 parts of the above-mentioned curing agent per 100 parts of component (C). It is sufficient to mix within the range of .

When preparing the curable composition of the present invention, there is no particular limitation. For example, components (A), (B), and (C) are blended, and the composition is prepared at room temperature or at room temperature using a mixer, roll, kneader, etc. Conventional methods such as kneading under heat or using a small amount of an appropriate solvent to dissolve and mix the above components may be employed. Furthermore, by appropriately combining these components, one-pack type or two-pack type formulations can be prepared and used.

Various fillers, plasticizers, additives, etc. may be further added to the composition of the present invention.

Examples of fillers include heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, kaolin, talc,
Examples include silica, titanium oxide, aluminum silicate, magnesium oxide, zinc oxide, and 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 includes adhesives, pressure-sensitive adhesives, paints, coating film waterproofing agents, sealants, molding materials, cast rubber materials,
It can be suitably used as a foam material or 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. . In addition, 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., a brimmer for concrete structures, or a waterproofing agent.

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 can overcome the drawbacks of conventional epoxy resins. It is.

Example 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 8000 in which allyl ether groups were 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 chloroplatinic acid catalyst solution (H2P
t A solution of 8.9 g of CQ6.6H20 dissolved in isopropyl alcohol 18 and tetrahydrofuran 1801112) After adding 0, 3411Q, 6 at 80 ° C.
Allowed time to react.

When the amount of silicon hydride groups remaining in the reaction solution was determined by IR spectroscopy, it was found that almost no silicon hydride groups remained. Further, when silicon groups were quantified by NMR method, a polyoxypropylene polymer having about 1.7 (CH30)25ICH2CH2CH20- groups per molecule at the molecular terminal 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 2500 by GPC using styrene as a standard.

Experimental Method Adhesive properties were shown by tensile shear adhesive strength and 180° peel adhesive strength.

The tensile shear adhesive strength was determined by thoroughly cleaning the surface of a test piece of JIS H4000 aluminum plate A-1050P (100 x 25 x 21 Im) with acetone, applying various curable compositions shown below with a spatula, and pressing it by hand. The test sample was measured based on JIS K6850. Peel adhesion strength is JIS A 5403 for rigid materials.
Using a test piece of asbestos slate board (100 x 25 x 3 mm), and a JIS H4000 aluminum plate A1050P (200 x 50 x 0.1 mm) as a flexible material, the surface of which had been thoroughly cleaned with acetone, the above composition was mixed with a spatula. 0. 51101 and bonded together, and using a 5 kg hand roller, the adhesive was pressed 5 times without moving back and forth in the length direction, and the 180° peel adhesive strength was measured. These adhesion test samples were tested at 23°C.
After further hardening and curing at 50° C. for 7 days, a tensile test was conducted. However, the tensile speed is 5 for the tensile shear adhesion test.
ml! l/min, 200m for 180° peel adhesion test
m/min.

Regarding weather resistance, after degassing the well-mixed composition using a centrifuge, it was poured into a polyethylene mold, and
Changes in the surface condition were shown when a sheet-like cured product with a thickness of approximately 3 mm obtained by curing at ℃ for 7 days and 50 ℃ for 7 days 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) and (A)
The solid content ratio of the polymer obtained in Synthesis Example 2 as a component and Epicoat 828 (manufactured by Yuka Shell Epoxy ■, bisphenol A type epoxy resin) as the component (C) is as shown in Table 1 below. After mixing well, heat at 110°C to remove volatile components contained in Synthesis Example 2.
The mixture was devolatilized under reduced pressure using a rotary evaporator for 3 hours to obtain a colorless to light yellow transparent liquid composition with viscosity.

This composition further contains a total ff110 of the polymer obtained in Synthesis Example 1 and the polymer obtained in Synthesis Example 2.
As a silicon compound containing an amino group that can react with an epoxy group and a reactive silicon group in the molecule,
1 part of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, Tsukrac SP (as an antioxidant)
1 part of phenolic antioxidant manufactured by Iriuchi Shinko Kagaku ■, 1 part of #918 (organotin compound manufactured by Sankyo ■) as a silanol condensation catalyst and 0.41 part of water, and 100 parts of Epicote 828. Tensile shear adhesive strength and peel adhesive strength were evaluated for compositions in which 10 parts of 2.4.6-tris(dimethylaminomethyl)phenol (hereinafter referred to as rDMP-30J) were added and mixed as an epoxy resin curing agent. The results are shown in Tables 1-2 and 1-2.
It is shown in Figure 2.

From the results shown in Table 1 and FIG. Compared to the cured product consisting only of 1 (Comparative Example 1) and the cured product consisting only of components (A) and (B) (Comparative Example 3), it was found that it has a high shear adhesive strength and a good balance of adhesive properties. Ta.

Furthermore, from the results in Table 2 and FIG. 2, it is clear that the composition of the present invention
Cured product consisting only of components (A) and (C) (Comparative Example 4)
) and a cured product consisting only of components (B) and (C) (Comparative Example 5), it was found that the cured product had a high balance of adhesive properties.

Example 9 and Comparative Example 6 The polymer obtained in Synthesis Example 1 as component (B) and (A)
After thoroughly mixing the polymer obtained in Synthesis Example 2 as a component and Epicoat 828 as component (C) so that the solid content ratio was as shown in Table 3 below, Examples 1 to 8 were prepared.
In the same manner as above, a pale yellow, transparent, viscous liquid composition was obtained. The total amount of the polymer obtained in Synthesis Example 1 and the polymer obtained in Synthesis Example 2 contained in this composition is 10
0 part, 1 part of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, 0.1 part of Tinuvin 327 (manufactured by Nippon Ciba Geigy, UV absorber) as an ultraviolet absorber, and 1 part of Tsukrak SP. , #918 and 0.4 parts of water were added and mixed with 10 parts of DMP-100 parts of Epicoat 828, and the weather resistance was evaluated using the above method. The results are shown in Table 3. It is also shown in .

From the results shown in Table 3, it was found that the composition of the present invention had significantly improved weather resistance compared to the conventional composition comprising an epoxy resin and an oxyalkylene polymer (Comparative Example 6).

[Brief explanation of the drawing]

FIG. 1 shows Epikote 828 parts per 60 parts of the polymer obtained in Synthesis Example 1 and 40 parts of the polymer obtained in Synthesis Example 2.
It is a graph showing the relationship between the number of copies and adhesive strength. FIG. 2 is a graph showing the relationship between the adhesion strength and the proportion of the polymer obtained in Synthesis Example 1 and the polymer obtained in Synthesis Example 2 per 100 parts of Epicoat 828. (Above) Diagram Epicoat 828 (f!15) Diagram Synthesis Example 2 Rod 5 8ta Polymer (Static)

Claims (1)

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