JP2634629B2 - Curable composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a curable composition. More specifically, an improved deep curability, which contains a (meth) acrylic acid alkyl ester-based copolymer and a curable oxyalkylene-based copolymer having curable properties, and further contains a filler. Curable composition having mechanical properties and weather resistance.

The alkyl (meth) acrylate means alkyl acrylate and / or alkyl methacrylate.

[Prior Art / Problems to be Solved by the Invention] The present inventors have developed a (meth) acrylic acid alkyl ester polymer having a reactive silicon group which can be cured by forming a siloxane bond at a terminal or a side chain. However, it has been found that it cures at room temperature due to moisture, especially atmospheric moisture, and forms a dense network structure, resulting in excellent cured products such as weather resistance, high hardness, and water resistance. (JP-A-54-36395).

On the other hand, oxyalkylene polymers having a reactive silicon group, for example, JP-B-45-36319, JP-B-46-12154,
JP-A-49-32673, JP-A-50-156599, JP-A-51-73561,
No. 54-6096, No. 55-82123, No. 55-123620, No. 55
-125121, 55-131022, 55-135135, 55-
It is proposed in various publications such as 137129.

The (meth) acrylic acid alkyl ester-based polymer having a reactive silicon group has excellent performance, but when the surface is hardened, the inside hardly hardens (deep curability is not good) and has a long time. Even when cured inside, the cured product is brittle, even if the resin composition has a low glass transition point,
It has the drawback that the tensile elongation is low, and at the same time, the strength is significantly reduced and the tensile properties are inferior.

On the other hand, the cured product of the oxyalkylene polymer having a reactive silicon group has excellent tensile properties, but has poor weather resistance and insufficient adhesion to various adherends. Also have performance weaknesses due to the main chain structure and the like.

In order to improve the drawbacks of the (meth) acrylic acid alkyl ester-based polymer having a reactive silicon group and the oxyalkylene-based polymer having a reactive silicon group, the present inventors have also proposed a method of blending these polymers. Attempts have been made to improve many of the above disadvantages (JP-A-60-31556, JP-A-63-112642, etc.)
It is the actual situation that the deep curing property has not been sufficiently improved.

[Means for Solving the Problems] As a result of further studies, the present inventors have found that a (meth) acrylic acid alkyl ester-based copolymer having a characteristic having a reactive silicon group and an oxyalkylene having a reactive silicon group The inventors have found that a curable composition in which a filler is further added to a system polymer can improve the deep curability of the composition which the present inventors have already applied for, and have reached the half invention.

That is, the present invention provides: (A) a molecular chain having a reactive silicon group having substantially (1) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms; A (meth) acrylic acid alkyl ester-based copolymer comprising (meth) acrylic acid alkyl ester monomer units having at least 10 alkyl groups, (B) an oxyalkylene-based polymer having a reactive silicon group, and (C) The present invention relates to a curable composition comprising a filler.

In the composition of the present invention, the molecular chain having a reactive silicon group is substantially composed of (1) an alkyl (meth) acrylate monomer unit having an alkyl group having 1 to 8 carbon atoms, and Compared with (meth) acrylic acid alkyl ester-based copolymers comprising the above alkyl group-containing (meth) acrylic acid alkyl ester monomer units and oxyalkylene-based polymers having reactive silicon groups, and blends of both This shows that the deep part curability is significantly improved as compared with the product.

[Examples] In the present invention, as a component of the curable composition, a molecular chain having a reactive silicon group is substantially (1) an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms. (Meth) acrylic acid alkyl ester-based copolymer comprising a monomer unit and (2) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms (hereinafter referred to as a reactive silicon group-containing ( (Meth) alkyl acrylate-based polymer or polymer (A)) is used.

The above-mentioned reactive silicon group-containing (meth) acrylic acid alkyl ester-based polymer means that 50% (% by weight, the same applies hereinafter) or more, preferably 70% or more of the molecular chain is composed of alkyl (meth) acrylate units. Wherein the (meth) acrylic acid alkyl ester unit includes (1) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms and (2) an alkyl group having 10 or more carbon atoms. (Meth) acrylic acid alkyl ester monomer units.

Further, the polymer (A) has a number average molecular weight of 500 to 100,000.
Are preferred in terms of ease of handling, and 1,000 to 75,
000 is more preferred.

When 50% or more of the molecular chain of the polymer (A) does not consist of (meth) acrylic acid alkyl ester units,
The compatibility with the oxyalkylene-based polymer having a reactive silicon group is poor, and a problem is likely to occur in practical use.

The alkyl group constituting the (meth) acrylic acid alkyl ester unit is an alkyl group having 1 to 8 carbon atoms or 10 or more carbon atoms, and may be a branched alkyl group or a non-branched alkyl group. There may be. Specific examples of such an alkyl group include, for example, methyl, ethyl, propyl, n-butyl, isobutyl, 1-ethylpropyl, 1-methylpentyl, 2-methylpentyl,
-Methylpentyl, 1-ethylbutyl, 2-ethylbutyl, isooctyl, 3,5,5-trimethylhexyl, 2-
Examples include alkyl groups such as ethylhexyl, decyl, lauryl, tridecyl, cetyl, stearyl, alkyl having 22 carbon atoms, and behenyl.

Among the molecular chains, general formula (III): (Wherein, R ⁴ represents an alkyl group having 1 to 8 carbon atoms, and R ⁵ represents a hydrogen atom or a methyl group) An alkyl (meth) acrylate monomer having an alkyl group having 1 to 8 carbon atoms represented by the following formula: Unit and general formula (IV): (Wherein, R ⁵ is the same as above, and R ⁶ represents an alkyl group having 10 or more carbon atoms) containing a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms The molecular chain is preferred in that compatibility with the oxyalkylene polymer having a reactive silicon group is improved.

The ratio of the monomer unit represented by the general formula (III) / the monomer unit represented by the general formula (IV) is from 95/5 by weight.
40/60 is preferred, and 90/10 to 60/40 is more preferred.

R ⁴ in the general formula (III) is, for example, a group having 1 to 8, preferably 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group and a 2-ethylhexyl group. And more preferably 1 to 2 alkyl groups. R ⁴ in the polymer (A) does not need to be a single kind. Further, as ⁶ in the general formula (IV),
Examples thereof include long-chain alkyl groups having 10 or more carbon atoms, usually 10 to 30, preferably 10 to 20, such as lauryl group, tridecyl group, cetyl group, stearyl group, alkyl group having 22 carbon atoms, and behenyl group. Note that R ⁶ in the polymer (A) is R ⁷
As in the case of the above, it is not necessary to use a single species, and for example, it may be a mixture of C12 and C13.

Specific examples of the unsaturated monomer copolymerizable with the alkyl (meth) acrylate which can be contained in the polymer (A) in a range of 50% or less include acrylic monomers such as acrylic acid and methacrylic acid. Acid monomers: ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, di (meth) acrylic acid-1,3
-Multifunctional (meth) acrylate monomers such as butylene glycol and trimethylolpropane tri (meth) acrylate; acrylamide, methacrylamide, N-
Monomers containing an amide group such as methylol acrylamide and N-methylol methacrylamide, an epoxy group such as glycidyl acrylate and glycidyl methacrylate, and an amino group such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate and aminoethyl vinyl ether; other acrylonitrile and iminol methacrylate Styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

The reactive silicon group that can be crosslinked and / or polymerized by forming a siloxane bond contained in the polymer (A) is a well-known functional group, and has a feature that it can be crosslinked even at room temperature. As a typical example of the reactive silicon group, general formula (V): (Wherein R ⁷ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms or a triorganosiloxy group, and when R ⁷ is 2 or more, they may be different. X ′ is a hydroxyl group or Are hydrolyzable groups, and when X ′ is 2 or more, they may be different, a is 0, 1, 2 or 3, b is 0, 1 or 2, and a + mb ≧ 1, m is 0 To an integer of to 19). Among the reactive silicon groups represented by the general formula (V), the general formula (VI): Wherein R ⁷ and X ′ are the same as above, and 1 is 1, 2 or 3.
The group represented by is preferred.

The number of reactive silicon groups in the polymer (A) is preferably 1 to 20 on average, more preferably 1.1 or more, especially 1.5 or more, from the viewpoint of obtaining sufficient curability. The number average molecular weight per group is apparently 300 to 8,000
It is preferably present to be 0, preferably 500-5,000.

Specific examples of the hydrolyzable group which is one kind of X ′ in the general formula (V) include, for example, a halogen atom, a hydrogen atom,
Examples thereof include 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, the methoxy group, in that the hydrolyzability is mild,
Alkoxy groups such as ethoxy groups are preferred.

Specific examples of R ⁷ in the general formula (V) include, for example, an alkyl group such as a methyl group and an ethyl group; a cycloalkyl group such as a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; An aralkyl group or a general formula: (R ′) ₃ SiO— (R ′ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and three R ′s need not be the same) And the like, and the like. Of these, a methyl group is particularly preferred.

The polymer (A) used in the present invention is an unsaturated unsaturated copolymerizable with an alkyl (meth) acrylate and, if necessary, an alkyl (meth) acrylate used by vinyl polymerization, for example, vinyl polymerization by a radical reaction. It can be obtained by an ordinary solution polymerization method or a bulk polymerization method in which a monomer is polymerized with, for example, a compound having a polymerizable unsaturated bond and a reactive silicon group.

The reaction is carried out at 50 to 150 ° C. by adding the above-mentioned monomer and, if necessary, a radical initiator and the like and, if necessary for adjusting the molecular weight, a chain transfer agent such as n-dodecyl mercaptan or t-dodecyl mercaptan. At this time, a solvent may or may not be used, but if used, a non-reactive solvent such as ethers, hydrocarbons and acetates is preferably used.

As the compound having a polymerizable unsaturated bond and a reactive silicon group, a compound represented by the general formula (VII): (Wherein, R ⁸ is an organic residue having a polymerizable unsaturated bond, R ⁷ ,
X ', a, b and m are the same as defined above). Among the compounds represented by formula (VII), preferred are compounds represented by formula (VIII): (Wherein R ⁵ , X ′ and l are the same as above, and Q is —COOR ⁹
- (R ⁹ is _{-CH 2 -, - CH 2 CH} 2 - 2 of 1 to 6 carbon atoms, such as
Valent alkylene _{group), - CH 2 C 6 H} 4 CH 2 CH 2 -, - CH 2 OCOC 6 H
₄ Divalent organic group such as COO (CH ₂ ) _3- or direct bond)
It is a compound represented by these.

Specific examples of the compound represented by the general formula (VII) or (VIII) include, for example, CH ₂ CHCHSi (OCH ₃ ) ₃ , CH ₂ CHCHSiCl ₃ , CH ₂ = CHCOO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CH ₂ = CHCOO (CH ₂ ) ₂ SiCl ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ SiCl ₃ , And so on.

These silane compounds are synthesized by various methods.For example, they are produced by reacting acetylene, allyl acrylate, allyl methacrylate, diallyl phthalate, etc. with methyldimethoxysilane, methyldichlorosilane, etc. in the presence of a Group VIII transition metal catalyst. can do. Such transition metal complex catalysts include platinum,
A Group VIII transition metal complex compound selected from rhodium, cobalt, palladium and nickel is effectively used.
In particular, platinum compounds such as platinum black, chloroplatinic acid, platinum alcohol compounds, platinum olphin complexes, platinum aldehyde complexes, and platinum ketone complexes are effective.

The polymer (A) used in the present invention can also be produced by producing a polymer having no reactive silicon group and then introducing a reactive silicon group. For example, a compound (for example, acrylic acid) having a polymerizable unsaturated bond and a reactive functional group (hereinafter, referred to as a Y group) is represented by the general formula (III)
And copolymerization by adding the monomer represented by (IV) to a monomer which gives a unit represented by formula (IV), and then forming the resulting copolymer with a functional group capable of reacting with a reactive silicon group and a Y group (hereinafter referred to as a Y 'functional group). ) it can also be produced by compounds (e.g. isocyanate groups and -Si (OCH ₃₎ a method of reacting a compound having a ₃ group) with.

Examples of the Y group and the 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 Y'.
The Y group and the Y 'group can be bonded by a hydrosilylation reaction. 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, and 1,5-pentanediol Acrylate,
1,5-pentanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol acrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, divinylbenzene, butadiene And so on.

As a typical example of a compound having a silicon hydride group as the Y ′ group and further having a reactive silicon group, a compound represented by the general formula (I
X): (Wherein, R ⁷ , X ′, a, b and m are the same as described above).

Specific examples of the hydrosilane compound represented by the general formula (IX) include trichlorosilane, methyldichlorosilane,
Halogenated silanes such as dimethylchlorosilane and trimethylsiloxydichlorosilane; trimethoxysilane,
Triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1,3,3,5,5,7,7-heptamethyl-
Alkoxysilanes such as 1,1-dimethoxytetrasiloxane; acyloxysilanes such as methyldiacetoxysilane and trimethylsiloxymethylacetoxysilane; bis (dimethylketoxime) methylsilane, bis (cyclohexylketoxime) methylsilane, and bis ( Ketoxime silanes such as diethylketoxime) trimethylsiloxysilane; hydrosilanes such as dimethylsilane, trimethylsiloxymethylsilane and 1,1-dimethyl-2,2-dimethyldisiloxane; methyldi (isopropenyloxy) silane And the like, but are not limited thereto.

The amount of the hydrosilane compound used for reacting the hydrosilane compound with the C ＝ C bond may be an arbitrary amount with respect to the C ＝ C bond, but is preferably 0.5 to 2 moles. However, this does not hinder the use of a larger amount of silane, and even if it is used more, it is only recovered as unreacted hydrosilane.

In addition, the catalyst of the Group VIII transition metal complex is used in the step of reacting the hydrosilane compound with a C ＝ C bond. This hydrosilylation reaction is accomplished at any temperature between 50 and 130 ° C., and the reaction time is on the order of 1 to 10 hours.

Further, as the hydrosilane compound, a highly reactive halogenated silane can be easily used with an inexpensive basic material.

When halogenated silanes are used, the resulting polymer (A) cures rapidly at room temperature while generating hydrogen chloride when exposed to air, but has a problem of irritating odor and corrosion due to hydrogen chloride. Since it can be practically used only for limited uses, it is preferable to further convert the bonded halogen atom to another hydrolyzable group or hydroxyl group.
Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group,
And an amino group.

Methods for converting a halogen atom into an alkoxy group include methanol, ethanol, 2-methoxyethanol,
A method of converting a halogen atom using an alcohol or phenol such as sec-butanol, tert-butanol or phenol, an alkali metal salt of alcohol or phenol, an alkyl orthoformate such as methyl orthoformate or ethyl orthoformate, or the like. And the like.

Specific examples of the method for converting to an acyloxy group include a method for converting a halogen atom using a carboxylic acid such as acetic acid, propionic acid, or benzoic acid, or an alkali metal salt of a carboxylic acid.

Examples of the method of converting to an aminoxy group include hydroxylamines such as N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine, N, N-methylphenylhydroxylamine or N-hydroxypyrrolidine, and alkalis of hydroxylamines. A specific method includes a method of converting a halogen atom using a metal salt or the like.

As a method for converting to an amino group, primary or secondary amines such as N, N-dimethylamine, N, N-methylphenylamine and pyrrolidine, and alkali metal salts of primary or secondary amines are used. Specific examples include a method of converting a halogen atom.

Examples of the method for converting to a thioalkoxy group include a method for converting a halogen atom using a thioalcohol or thiophenol such as ethyl mercaptan or thiophenol, or an alkali metal salt of thioalcohol or thiophenol. As

Regarding the silyl group introduced into the C = C bond by the hydrosilylation reaction, instead of converting only the halogen atom to another hydrolyzable group, other groups such as an alkoxy group and an acyloxy group may be optionally substituted with an amino group, It can be converted to a hydrolyzable group such as an aminoxy group or a hydroxyl group.

Thus, the temperature at which the hydrolyzable group on the silyl group directly introduced by the hydrosilylation reaction is converted into another hydrolyzable group is suitably from 50 to 150 ° C. These conversion reactions can be achieved with or without the use of a solvent, but when a solvent is used, an inert solvent such as ethers, hydrocarbons, and acetates is suitable. is there.

The oxyalkylene polymer having a reactive silicon group in the molecule used in the present invention (hereinafter referred to as a reactive silicon group-containing oxyalkylene polymer or polymer (B)) is described in JP-B-45-36319. Nos. 46-12154, 49-
No. 32673, JP-A-50-156599, JP-A-51-73561, JP-A-54-15661
No. 6096, No. 55-82123, No. 55-123620, No. 55-12512
No. 1, No. 55-131022, No. 55-135135, No. 55-137129
It is proposed in each gazette of the issue.

The molecular chain of the polymer (B) has essentially the general formula: —R ¹⁰ —O— (wherein R ¹⁰ is a divalent organic group, most of which are hydrocarbons having 3 or 4 carbon atoms) Group is most preferred)
Those having a repeating unit represented by are preferred. Specific examples of R ¹⁰ include: —CH ₂ CH ₂ CH ₂ CH ₂ — and the like. The molecular chain of the polymer (B) may be composed of only one type of repeating unit or may be composed of two or more types of repeating units.
Especially for ¹⁰ Is preferred.

The repeating unit represented by —R ¹⁰ —O— is a polymer (B)
Preferably, the content is 50% or more, more preferably 70% or more, and particularly preferably 80% or more.

The reactive silicon group in the polymer (B) is the same as the reactive silicon group.

The number of reactive silicon groups in the polymer (B) is preferably 1 to 5 on average, more preferably 1.1 or more, particularly preferably 1.5 to 4 from the viewpoint of obtaining sufficient curability. Further, the reactive silicon group is preferably present at the terminal of the molecular chain of the polymer (B).

The number average molecular weight of the polymer (B) is preferably from 500 to 30,000, more preferably from 3,000 to 15,000. The polymer (B) may be used alone or in combination of two or more.

The polymer (B) is, for example, a hydrosilane compound represented by the general formula (IX) and a general formula (X): (Wherein, R ¹¹ is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, R ¹² is a divalent organic group having 1 to 20 carbon atoms, and c is 0 or 1). It is produced by a method such as an addition reaction of a polyether with a group VIII transition metal compound such as the platinum compound as a catalyst.

As a method for producing the polymer (B) other than the above, a polyisocyanate compound such as toluene diisocyanate is reacted with a hydroxyl group-terminated polyoxyalkylene polymer to obtain an isocyanate group-terminated alkylene oxide polymer, and then the isocyanate Based on the general formula (X
I): Wherein W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary), and l, R ⁷ , R ¹² and X ′ are the same as those described above. A method of reacting a W group of a silicon compound, a method of reacting a silicon compound represented by the general formula (XI) wherein W is a mercapto group with an olefin group of a polyoxyalkylene polymer having an olefin group represented by the general formula (X) A method of adding a mercapto group and a method of adding a hydroxyl group of a hydroxyl-terminated polyoxyalkylene polymer to a compound represented by the general formula (XII): (Wherein, R ⁷ , R ¹² , X ′ and 1 are the same as above), and the like. Specific examples thereof include, but are not limited to, these methods in the present invention.

In the method of reacting the hydrosilyl compound represented by the general formula (IX) with the polyoxyalkylene polymer having an olefin group represented by the general formula (X), after reacting them, a part or all of X The 'group may be further converted to other hydrolysable or hydroxyl groups. For example, when the X ′ group is a halogen atom or a hydrogen atom, an alkoxy group, an acyloxy group, an aminooxy group,
It is preferable to use it after converting it to an alkenyloxy group, a hydroxyl group or the like. In the general formula (X), R ¹¹ is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, but is preferably a hydrogen atom or a hydrocarbon group, particularly a hydrogen atom. Is preferred. R ¹²
Although is a divalent organic group having 1 to 20 carbon atoms, -R ¹³ -, - R
¹³ OR ¹³ −, (R ¹³ is a divalent hydrocarbon group having 1 to 10 carbon atoms), and particularly preferably a methylene group.

As a specific method for producing an alkylene oxide polymer having an olefin group represented by the general formula (X),
No. 54-6097, or when polymerizing an epoxy compound such as ethylene oxide or propylene oxide, an olefin group-containing epoxy compound such as allyl glycidyl ether is added and copolymerized. A method for introducing a group can be exemplified.

The filler as the component (C) used in the present invention is a component used for the purpose of improving the deep curing property. Depending on the type of the filler, the curing property such as the mechanical strength and the elongation property is also different depending on the type of the filler. It can improve the properties of physical properties.

Specific examples of the filler include, for example, an average particle size of 0.03
~ 0.30μm colloidal calcium carbonate, average particle size 0.5 ~
3.0 μm light calcium carbonate, average particle size 1-5 μm
Heavy calcium carbonate, carbon black, synthetic silicic acid, talc, zeolite, calcined clay, kaolin, bentonite, aluminum hydroxide, precipitated barium sulfate and other reinforcing fillers, wood powder, glass balloons,
Examples include ordinary fillers such as organic polymer powder having an average particle size of 1 to 500 μm. Among the above-mentioned fillers, it is preferable to use a reinforcing filler having a large effect of improving the mechanical strength and elongation characteristics of the cured product.

Polymer (A) and polymer (B) in the composition of the present invention
Is used in the range of 5 to 5000 parts of the polymer (A) based on 100 parts of the polymer (B) (parts by weight, the same applies hereinafter),
(B) It is preferable from the viewpoint that the effect of improving the properties of each polymer becomes remarkable, more preferably in the range of 5 to 2,000 parts, and is usually selected according to the intended use and performance.

The amount of the component (C) used is preferably 5 to 300 parts with respect to 100 parts of the total amount of the polymer (A) and the polymer (B),
Further, 10 to 200 parts is preferable. (C) The amount of the component used is 5
When the amount is less than 300 parts, the effect of the present invention is not sufficient, and when it exceeds 300 parts, the mechanical properties tend to decrease.

If necessary, the following components (component (D)) for improving the properties of the cured product such as strength and adhesiveness, the viscosity stability of the composition, and the storage stability are added to the composition of the present invention. You may.

The component (D) is (i) a general formula (I): R ¹⁴ _-n SiX _n (I) (wherein X is a hydrolyzable group, and R ¹ is a monovalent organic group having 1 to 18 carbon atoms) , N is an integer of 1 to 4, (4-n) R ¹ , and n Xs need not be the same.) (Ii) a general formula (ii) And (iii) a general formula (II): R ² C (OR ³ ) ₃ (II) wherein R ² is a hydrogen atom or a methyl group, R ³ has 1 to 1 carbon atoms
8 monovalent organic group, a 3 R ³ is at least one compound selected from ortho organic acid ester represented by it need not) the same, significantly improves the properties of the cured product Not only the viscosity stability of the composition,
It also improves storage stability.

Specific examples of the organic silane monomer represented by the general formula (I) include, for example, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, ethylsilicate, methyltriethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane , Phenyltrimethoxysilane, diphenyldimethoxysilane, triphenylmethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyl Dimethoxysilane, methyltriacetoxysilane, γ-aminopropyltriethoxysilane, γ-
Examples include, but are not limited to, mercaptopropylmethoxysilane and γ-glycidoxypropyltrimethoxysilane.

Further, any of the above-mentioned partially hydrolyzed condensates of the organic silane monomer can be used as the component (D).

Specific examples of the ortho organic acid ester represented by the general formula (II) include, for example, ortho formate and ortho acetate, but are not limited thereto.

The amount of the component (D) used is preferably 0.1 to 100 parts, more preferably 0.5 to 20 parts, based on 100 parts of the total amount of the polymer (A) and the polymer (B). When the amount of the component (D) is less than 0.1 part, the effect of improving mechanical properties, adhesiveness, viscosity stability, storage stability and the like tends to be insufficient, and when the amount exceeds 100 parts. Is not desirable from the economical point of view.

A curing accelerator may be added to the composition of the present invention.

As the curing accelerator, for example, an organotin compound,
Examples include acidic phosphoric acid esters, reactants of acidic phosphoric acid esters with amines, saturated or unsaturated polycarboxylic acids or acid anhydrides thereof, and organic titanate compounds.

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

In addition, the acidic phosphate ester, Phosphate ester containing moieties, such as (Wherein, d represents 1 or 2, and R represents an organic residue). [(CH ₂ OH) (CHOH) C ₂ H ₄ O] And so on.

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

The composition of the present invention may further include a plasticizer and other additives.

Examples of the plasticizer include dioctyl phthalate, butylbenzyl phthalate, chlorinated paraffin, and epoxidized soybean oil.

Examples of the other additives include an anti-sagging agent such as hydrogenated castor oil and organic bentonite, a coloring agent, an antiaging agent, and the like.

The composition of the present invention improves the respective deep defects by using the polymer (A) and the polymer (B) in combination and improves the deep curability by using a filler. The material has excellent properties such as mechanical properties such as strength and elongation properties, weather resistance, water resistance, and adhesive strength, and sufficiently cures not only on the surface but also on the inside at room temperature.

In addition, the polymer (A) has the general formula (III) and the general formula (I
V) is a molecular chain having a monomer unit represented by
The compatibility between the polymer (A) and the polymer (B) is improved, and the polymer (A) is easily solubilized. When the component (D) is further added to this system, the compatibility between the polymer (A) and the polymer (B) is further improved, and the viscosity stability and storage stability of the blend are also improved. In this way, the reactive silicon groups react in a homogeneously compatible state to form a three-dimensional network. At that time, when the filler is present and the moisture easily reaches a deep part, the properties and composition ratio of each polymer are reduced. A cured product exhibiting properties superior to those expected from, for example, elongation, tensile properties such as tensile strength, adhesive strength, impact resistance, weather resistance, water resistance, solvent resistance, etc. is quickly formed. In particular, the effect of improving tensile properties and adhesive strength becomes very remarkable. Compared with a conventional composition comprising a reactive silicon group-containing (meth) acrylate polymer and a reactive silicon group-containing oxyalkylene polymer. Excellent in transparency, viscosity stability and storage stability (especially turbidity during storage, two-phase separation is improved). Also, since the compatibility of each polymer is good, it is necessary to select hardness. Free choice of blend ratio Ri, with a cured product having excellent performance such as that the design of materials with a wide range of performance is possible, resulting remarkable effects such as rapidly cured deep.

The composition of the present invention thus obtained comprises an adhesive,
It can be usefully used as a pressure-sensitive adhesive, a paint, a coating film waterproofing agent, a sealant composition, a molding material, a cast rubber material, a foam material, and the like.

For example, when used as an adhesive, it exhibits excellent adhesive strength in a short time due to its good deep curability, and is particularly suitable as an adhesive with a good balance between peel adhesive strength and shear adhesive strength. Application is expected.

In addition, when used as a sealing material, if the curing catalyst and the compound are kneaded and stored in a sealed state in the absence of moisture, a stable composition for a long time, by exposing to moisture in the air. A one-component elastic sealing material that cures quickly to a deep part and provides a good rubber elastic body,
Moreover, the cured product exhibits good weather resistance, transparency, and tensile elongation.

When used as a paint, it gives a cured product with much higher tensile elongation and weatherability than generally thought, and has excellent properties as a high elastic paint for construction, a primer for concrete structures, a waterproofing agent, etc. .

In addition, when used as a coating film waterproofing agent, the balance between breaking strength and elongation is excellent, and the durability and water resistance are good, so that deterioration such as blistering and peeling is improved as compared with those obtained by existing techniques.

Next, the composition of the present invention will be specifically described based on examples.

Synthesis Examples 1 to 7 A solution prepared by dissolving azobisisobutyronitrile as a polymerization initiator in a monomer mixture shown in Table 1 in xylene heated to 110 ° C. in the amount shown in Table 1 was dropped over 6 hours. After 2 hours, polymerization was carried out to obtain a copolymer as shown in Table 1.

Synthesis Example 8 800 g of a polyoxypropylene polymer having an average molecular weight of about 8000 in which an allyl ether group was introduced to 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 _{(H 2 PtCl 6 · 6H 2} O in
8.9 g was dissolved in 18 ml of isopropyl alcohol and 160 ml of tetrahydrofuran).
The reaction was carried out at 6 ° C. for 6 hours.

When the amount of the remaining silicon hydride groups in the reaction solution was quantified by IR spectroscopy, almost no remaining silicon hydride groups remained. When the silicon group was quantified by NMR,
At the end of the molecule Of a polyoxypropylene-based polymer having about 1.7 molecules per molecule.

Examples 1 to 5 and Comparative Examples 1 to 9 The polymer (A) obtained in Synthesis Examples 1 to 7 was replaced with 50 parts of a solid component and the reactive silicon group having an average molecular weight of about 8200 obtained in Synthesis Example 8. A polyoxypropylene polymer having a terminal
After blending 50 parts, 100 parts of heavy calcium carbonate (Whiteton SB manufactured by Shiraishi Industry Co., Ltd.) was blended, and the mixture was kneaded well with three paint rolls. Next, an organotin compound No.918 (manufactured by Sankyokisei Co., Ltd.) was used as a curing accelerator.
After deep kneading and kneading well, fill in a soft can with a depth of 8 mm and leave it at 23 ° C for 3 days. Deep curability (cut the cured product and measure the thickness from the surface of the cured part visually. ) Was evaluated. The results are shown in Table 2.

Table 2 shows the evaluation results of the deep-side curability when no heavy calcium carbonate was blended as Comparative Examples 3 to 9.

Examples 6 to 14 and Comparative Examples 10 to 11 Deep curability was evaluated in the same manner as in Examples 1 to 5, using the composition shown in Table 3. The results are shown in Table 3.
The results of the storage stability test of these formulations are also shown. The storage stability is shown by the ratio of the initial viscosity (measured with a B-type viscometer) to the viscosity after storage at 50 ° C. for one month.

As is clear from the results in Tables 2 and 3,
It can be seen that the deep curability of the composition is significantly improved by the presence of the component (C).

[Effect of the Invention] When the composition of the present invention is used, the deep part curability is good, and the tensile properties such as tensile strength and elongation, the adhesive strength, the weather resistance and the like are higher than those expected from the performance of each polymer. A cured product showing excellent properties and dramatically improved as compared with the conventional compositions can be obtained.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C08L 71/02 LQC C08L 71/02 LQC LQE LQE (56) References JP-A-60-31556 (JP) JP-A-61-225205 (JP, A) JP-A-58-19361 (JP, A)

Claims (3)

(57) [Claims] (A) a molecular chain having a reactive silicon group is substantially (1) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms; A (meth) acrylic acid alkyl ester-based copolymer consisting of (meth) acrylic acid alkyl ester monomer units having 10 or more alkyl groups, (B) an oxyalkylene-based polymer having a reactive silicon group, and (C) A curable composition comprising a filler. 2. The composition according to claim 1, wherein the filler as the component (C) is a reinforcing filler. 3. The curable composition further comprises (i) a compound represented by the general formula (I): R ¹⁴ _-n SiX _n (I) (wherein X is a hydrolyzable group, and R ¹ is A monovalent organic group of 18; n is an integer of 1 to 4; (4-n) R ^{1 s} and n Xs need not be the same). (Ii) a partially hydrolyzed condensate of an organosilane monomer represented by the general formula (I); and (iii) a general formula (II): R ² C (OR ³ ) ₃ (II) wherein R ² Is a hydrogen atom or a methyl group, and R ³ has 1 to 1 carbon atoms.
8 monovalent organic group, three R ³ is Claims first made is contained at least one compound selected from ortho organic acid ester represented by it need not) the same The composition according to Item.