JP4675126B2 - Curable composition, sealing agent and adhesive - Google Patents

Description

  The present invention relates to a curable composition that is crosslinked by moisture in an atmosphere to give a cured product having elasticity, and is preferably used for, for example, a sealing agent, an adhesive, a paint, a coating material, a sealant, a primer, and the like. Related to things. Furthermore, it is related with the sealing agent and adhesive agent using this curable composition.

  Conventionally, various curable compositions based on a (meth) acrylic polymer having an alkoxysilyl group have been proposed. (For example, the following patent documents 1 and 2). These curable compositions are crosslinked by moisture in the atmosphere, and give a cured product having excellent weather resistance and elasticity. Therefore, the said curable composition is used for various uses, such as a coating material, a coating agent, an adhesive agent, a pressure sensitive adhesive, a sealant, and a sealing agent.

Since the curable composition is cured by moisture in the atmosphere, the surface is easily cured. However, when the surface is cured, there is a problem that penetration of moisture into the deep portion is likely to be reduced and the deep portion curability is poor.
As a method of improving the deep part curability, a method of slowing the curing rate or lowering the crosslinking density can be considered. However, such a method has a problem in surface tackiness because the surface is not sufficiently cured. That is, even after the curing is completed, stickiness (hereinafter referred to as “tack”) remains on the surface of the cured product. For example, when it is used as a sealing material, it causes joint contamination due to adhesion of dust and the like, causing damage to the appearance of the building.
As a method for improving the deep-curability without problems in surface tackiness, an organic polymer having one or more hydrolyzable silicon groups in the molecule and 2.1 or more trialkylsilyloxy groups in the molecule And the curable composition containing the compound which can generate | occur | produce a silanol compound by hydrolysis is proposed (patent document 3). According to this proposal, the tack is improved and the deep curability is also improved. However, the higher the number of functional groups, the greater the influence on the stretch physical properties, which is not necessarily sufficient, and further the tack improvement and internal curability, and There was a need for a balance of elongation properties.

JP 57-179210 A JP 04-43512 A JP 11-2441029 A

  The object of the present invention is to provide a rubber-like cured product that is cured by moisture in the atmosphere in view of the current state of the prior art described above, and further has excellent weather resistance and deep-curability, no surface tackiness, and after curing. Another object of the present invention is to provide a curable composition excellent in high elongation and a sealing agent and an adhesive using the curable composition.

The invention according to claim 1 includes a (meth) acrylate polymer (a) containing a crosslinkable hydrolyzable silyl group and a crosslinkable hydrolyzable containing an alkyl side chain having 10 or more carbon atoms. This is a curable composition comprising a (meth) acrylate polymer (b) containing no silyl group.

According to a second aspect of the invention, (meth) acrylate polymer, the curable composition of claim 1 wherein the radical polymerization obtained (meth) acrylate-based polymer using a peroxide as a polymerization initiator It is a thing.

According to a third aspect of the invention, a curable composition according to claim 1 or 2 polyether polymer (c) it is formed by further blending with a cross-linking capable hydrolyzable silyl group.

Invention of Claim 4 is a curable composition of any one of Claims 1-3 which further mix | blends inorganic powder (d).

Invention of Claim 5 is a curable composition of Claim 4 whose inorganic powder (d) is calcium carbonate powder (d1).

Invention of Claim 6 is a sealing agent using the curable composition of any one of Claims 1-5 .

The invention of claim 7 wherein is an adhesive using the curable composition according to any one of claims 1-5.

  Details of the present invention will be described below.

(Organic polymer (a))
The organic polymer (a) used in the present invention is not particularly limited as long as it has a crosslinkable hydrolyzable silyl group. When the hydrolyzable silyl group is hydrolyzed to form a siloxane bond, the organic polymer is crosslinked to form a rubber-like cured product.

  The hydrolyzable silyl group is a group in which 1 to 3 hydrolyzable groups are bonded to a silicon atom. Examples of the hydrolyzable group include a hydrogen atom, a halogen atom, a methoxy group, and an ethoxy group. Preferred examples include alkoxy groups, acyl oxide groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyl oxide groups, which do not generate harmful by-products during the reaction. Alkoxy groups are particularly preferred.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, a tert-butoxy group, a phenoxy group, and a benzyloxy group. These alkoxy groups are the same type. It may be present or different types may be combined.
Examples of the alkoxysilyl group in which an alkoxy group is bonded to a silicon atom include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, triphenoxysilyl group; dimethoxymethylsilyl group, diethoxy Examples thereof include dimethoxysilyl groups such as methylsilyl group; monoalkoxysilyl groups such as methoxydimethoxysilyl group and ethoxydimethylsilyl group. A plurality of these may be used in combination, or a plurality of different alkoxy groups may be used in combination.

The main chain structure of organic polymer (a), strength after curing, the vinyl polymer main chain structure obtained by polymerizing a polymerizable unsaturated group from ease of manufacture and the like are preferable.

As the vinyl polymer main chain structure obtained by polymerizing a polymerizable unsaturated group, (meth) acrylate-based polymer is used, for example, a poly (meth) acrylates and. Among the above Symbol vinyl polymer, using the cohesion and adhesion, etc., the number average molecular weight of 8,000 or more (meth) acrylate polymer, (meth) is preferably a copolymer of acrylate monomers with other vinyl monomers It is done. Here, (meth) acrylate is an expression collectively showing methacrylate and acrylate.

Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) ) Acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Sundiol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, 2- Hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydro Cypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-3-methylbutyl ( (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-[(meth) acryloyloxy] ethyl 2-hydroxyethylphthalic acid, 2-[(meth) acryloyloxy ] Ethyl 2-hydroxypropylphthalic acid,
[Compound 1]
CH2 = CH-C (O) O-CH2CH2O-
[C (O) CH2CH2CH2CH2CH2O] n-H
(N = 1-10)
[Compound 2]
CH2 = C (CH3) -C (O) O-CH2CH2O-
[C (O) CH2CH2CH2CH2CH2O] n-H
(N = 1-10)
[Compound 3]
CH2 = CH-C (O) O- (CH2CH2O) n-H
(N = 1-12)
[Compound 4]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-H
(N = 1-12)
[Compound 5]
CH2 = CH-C (O) O- [CH2CH (CH3) O] n-H
(N = 1-12)
[Compound 6]
CH2 = C (CH3) -C (O) O- [CH2CH (CH3) O] n-H
(N = 1-12)
[Compound 7]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(N = 1-12)
(M = 1-12)
[Compound 8]
CH2 = CH-C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(N = 1-12)
(M = 1-12)
[Compound 9]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-
(CH2CH2CH2CH2O) mH
(N = 1-12)
(M = 1-12)
[Compound 10]
CH2 = CH-C (O) O- (CH2CH2O) n-
(CH2CH2CH2CH2O) mH
(N = 1-12)
(M = 1-12)
[Compound 11]
CH2 = CH-C (O) O- (CH2CH2O) n-CH3
(N = 1-10)
[Compound 12]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-CH3
(N = 1-30)
[Compound 13]
CH2 = CH-C (O) O- [CH2CH (CH3) O] n-CH3
(N = 1-10)
[Compound 14]
CH2 = C (CH3) -C (O) O- [CH2CH (CH3) O] n-CH3 (n = 1-10)
[Compound 15]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(N = 1-10)
(M = 1-10)
[Compound 16]
CH2 = CH-C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(N = 1-10)
(M = 1-10)
[Compound 17]
CH2 = CH-C (O) O- [CH2CH (CH3) O] n
-C (O) -CH = CH2
(N = 1-20)
[Compound 18]
CH2 = C (CH3) -C (O) O- [CH2CH (CH3) O] n
-C (O) -C (CH3) = CH2
(N = 1-20)
[Compound 19]
CH2 = CH-C (O) O- (CH2CH2O) n-C (O) -CH = CH2
(N = 1-20)
[Compound 20]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n
-C (O) -C (CH3) = CH2
(N = 1 to 20).

  Examples of the other vinyl monomers include styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, and divinylbenzene. Styrene derivatives; for example, compounds having vinyl ester groups such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate; maleic anhydride, N-vinylpyrrolidone, N-vinylmorpholine , (Meth) acrylonitrile, (meth) acrylamide, N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, N-benzylmaleimide, n-propylvinylether, n-butylvinylether, isobutylvinylether, ter -Butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether, ethylene glycol butyl vinyl ether, tritylene glycol methyl vinyl ether, benzoic acid (4-vinyloxy) butyl, ethylene Glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1,4-diol-divinyl ether, hexane-1,6-diol-divinyl ether, cyclohexane-1,4-dimethanol -Divinyl ether, di (4-vinyloxy) butyl isophthalate, glu Di (4-vinyloxy) butyl tartrate, di (4-vinyloxy) butyl trimethylolpropane trivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexane-1,4-di succinate Mention may be made of compounds having a vinyloxy group such as methanol-monovinyl ether, diethylene glycol monovinyl ether 3-aminopropyl vinyl ether, 2- (N, N-diethylamino) ethyl vinyl ether, urethane vinyl ether, polyester vinyl ether and the like.

  The vinyl polymer may contain a halogen element. For example, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, chlorinated polyethylene, chlorinated polypropylene, poly (meth) acrylic acid perfluoro Alkyl etc. are mentioned.

A known method can be used as a method for producing the vinyl polymer. For example, a free radical polymerization method, an anionic polymerization method, a cationic polymerization method, a UV radical polymerization method, a living anion polymerization method, a living cation polymerization method, a living radical polymerization method, etc. can be used, and depending on the polymerizable reaction of the monomer A polymerization method may be selected as appropriate, and among these polymerization methods, a free radical polymerization method is preferable because of easy production. As the free radical polymerization method, a free radical polymerization method using a peroxide initiator and an azo compound initiator as a polymerization initiator is preferred, and when used as an azo compound initiator, the polymer tends to yellow . Particularly preferred is a free radical polymerization method using a peroxide polymerization initiator.

As a method for introducing a crosslinkable hydrolyzable silyl group into a vinyl polymer, a (meth) acrylic acid ester having a crosslinkable hydrolyzable silyl group or a copolymer having a crosslinkable hydrolyzable silyl group can be used. A method of introducing a polymerizable monomer, an initiator having a crosslinkable hydrolyzable silyl group, a chain transfer agent having a crosslinkable hydrolyzable silyl group, etc. during polymerization of the polymer (for example, Japanese Patent Laid-Open No. Sho 54- No. 123192, JP-A-57-179210, JP-A-59-78220, JP-A-60-23405), synthesizing a polymer having an alkenyl group, and then hydrosilylating the alkoxysilyl group (For example, Japanese Patent Laid-Open Nos. 54-40893 and 11-80571).
The method for producing a vinyl polymer having a crosslinkable silyl group constituting the present invention is not particularly limited as long as a vinyl polymer having a crosslinkable silyl group is obtained. Technology can be used.

  Examples of the peroxide polymerization initiator include benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, di (3,5,5-trimethyl) Diacyl peroxides such as hexanoyl peroxide; diisopropyl purge carbonate, di-sec-butyl purge carbonate, di-2-ethylhexyl purge carbonate, di-1-methylheptyl purge carbonate, di-3-methoxybutyl purge carbonate, dicyclohexyl Peroxydicarbonates such as purge carbonate; tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoe , Peroxyesters such as tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl diperadipate, cumyl perneodecanoate; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide Dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane ; Hydroperoxides such as cumene hydroxy peroxide and tert-butyl hydroperoxide; 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane . In addition, only 1 type may be used for a peroxide and multiple types may be used together. Further, the peroxide may be added sequentially over a plurality of times.

  Examples of the chain transfer agent having a crosslinkable hydrolyzable silyl group include functional groups having high chain transfer properties such as mercaptomethyltrimethylsilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyldimethoxysilane. An alkoxysilane is mentioned. The amount of the chain transfer agent having a crosslinkable hydrolyzable silyl group is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts per 100 parts by weight of the vinyl polymerizable monomer. Parts by weight.

  Examples of the (meth) acrylic acid ester having a crosslinkable hydrolyzable silyl group include N- (3-acryloyloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane and 3-acryloyloxypropyldimethylmethoxysilane. 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropylmethylbis (trimethylsiloxy) silane, 3-methacryloyloxypropyldimethylmethoxysilane, 3-methacryloyloxypropyldimethylethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltrimethoxy Run, 3-methacryloyloxy-propenyl trimethoxy silane, and the like. These methacrylic acid esters may be used alone or in combination of two or more.

Examples of the copolymerizable monomer having a crosslinkable hydrolyzable silyl group include vinylmethyldiacetoxysilane, vinyltriacetoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, binletriisopropoxysilane, vinyltriphenoxysilane, vinyldimethylisopentenyloxysilane, vinyldimethyl-2-((2-ethoxyethoxy) ethoxy) silane, vinyltris (1-methylvinyloxy) silane, vinyltris (2-methoxyethoxy) silane, phenylvinyldiethoxysilane, diphenylvinylethoxysilane, 6-triethoxysilyl-2-norbornene, octa-7-enyltrimethoxysilane, Styryl ethyltrimethoxysilane, allyl triethoxysilane, allyl trimethoxysilane, and the alkoxysilane having a polymerizable unsaturated group such as 3-allyl-aminopropyltrimethoxysilane. These monomers may be used alone or in combination of two or more.
The amount of the (meth) acrylic acid ester or copolymerizable monomer having a crosslinkable hydrolyzable silyl group is preferably 0.01 to 20% by weight in 100% by weight of the vinyl polymerizable monomer, More preferably, it is 0.1 to 5% by weight.

The main chain structure of the organic polymer (b) is substantially the same as that of the organic polymer (a). When the main chain structures are different, the compatibility between the organic polymer (a) and the organic polymer (b) is lowered, and the above-mentioned addition effect is not recognized. Examples of the organic polymer (b), vinyl-based polymers are preferred, particularly preferably (meth) acrylate polymer. It does not specifically limit as a monomer which comprises the said methacrylate polymer, The (meth) acrylate monomer mentioned above may be used.

The polymer (b) is a polymer having an alkyl group having 10 or more carbon atoms in the side chain. When a polymer having an alkyl group having 10 or more carbon atoms in the side chain is used in combination, the curable composition has less surface tack when cured, and moisture permeability, that is, depth curable property is further improved. .
The alkyl group having 10 or more carbon atoms is not particularly limited, and at least one hydrogen atom of an alkyl group such as a linear alkyl group, a branched alkyl group, an aralkyl group, or a cycloalkyl group is a cyclic hydrocarbon group or the like. And a substituted alkyl group substituted with a hydrocarbon group. The preferable carbon number of the alkyl group is 10-30. When the number of carbon atoms is 10 or less, the above effect cannot be obtained.

  As the monomer having an alkyl group having 10 or more carbon atoms in the side chain, a (meth) acrylic acid alkyl ester monomer having an alkyl group having 10 or more carbon atoms is preferred, and the alkyl group has 10 carbon atoms. Examples of the above (meth) acrylic acid alkyl ester monomer include decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, and (meth) acrylic. Examples include octadecyl acid, eicosanyl (meth) acrylate, docosanyl (meth) acrylate, hexacosanyl (meth) acrylate, and the like.

  The other (meth) acrylate monomer constituting the polymer (b) is not particularly limited, and is the same (meth) acrylate as the (meth) acrylate monomer used in the polymer (a) described above. System monomers may be used. Moreover, the polymer (b) may be copolymerized with other monomers copolymerizable with (meth) acrylate monomers other than (meth) acrylic monomers.

  The amount of the (meth) acrylate monomer having 10 or more carbon atoms in the alkyl group in the polymer (b) is preferably 10 to 80% by weight, more preferably 30 to 50% by weight. When the amount of the (meth) acrylate monomer having 10 or more carbon atoms in the alkyl group is less than 10% by weight, the above effect is hardly recognized, and when it exceeds 80% by weight, the organic polymer (a) This is not preferable because the compatibility with is easily lowered.

  The molecular weight of the organic polymer (b) is preferably a number average molecular weight of 1500 to 10,000, more preferably 3000 to 5000. When the number average molecular weight of the organic polymer (b) is less than 1500, the control of the polymerization is complicated and economically disadvantageous, and when it exceeds 10,000, the viscosity of the curable composition increases and the workability is increased. It is not preferable because it tends to decrease.

  As the method for producing the organic polymer (b), the same method as the organic polymer (a) is used, and the production conditions, for example, the type and amount of the polymerization initiator to be used, the type and amount of the chain transfer agent, The molecular weight can be adjusted within a predetermined range by adjusting the type and amount of the polymerization medium, the polymerization temperature, and the like.

  The blending ratio of the organic polymer (a) and the organic polymer (b) is preferably 10 to 150 parts by weight of the organic polymer (b) with respect to 100 parts by weight of the organic polymer (a). When the amount of the organic polymer (b) is less than 10 parts by weight, the viscosity of the curable composition increases and the workability tends to deteriorate, and when the amount of the organic polymer (b) exceeds 150 parts by weight, it is cured. It is not preferable because the physical properties are likely to decrease.

  When a vinyl polymer is used as the organic polymer (a) used in the present invention, it is preferable to add at least a polyether polymer (c) having a hydrolyzable silyl group capable of crosslinking, Further, it is possible to further improve the depth curability, increase the water resistance of the cured product, and increase the rubber elasticity when a sealing agent is configured.

  The polyether-based polymer (c) containing the crosslinkable hydrolyzable silyl is essentially composed of a general formula — (R—O) n—, wherein R is a carbon number of 1 4 represents an alkylene group, which is a polymer containing a crosslinkable hydrolyzable silyl group containing a repeating unit represented by the following formula: O represents an oxygen atom, and n represents a natural number. A polymer (a) having an ether main chain structure may be used. The amount of the polyether polymer (c) is preferably 20 to 80 parts by weight relative to 100 parts by weight of the total of the organic polymer (a) and the organic polymer (b).

  The curable composition of the present invention preferably contains an inorganic powder (d), and examples of the inorganic powder (d) include silica, alumina, titanium oxide, magnesia, mica, talc and the like. Of the inorganic powder (d), calcium carbonate powder (d1) such as heavy calcium carbonate and fatty acid-treated calcium carbonate is preferable.

  The amount of the inorganic powder (d) is preferably 80 to 200 parts by weight with respect to 100 parts by weight of the resin component. When it is less than 80 parts by weight, the strength of the cured product is lowered, and when it exceeds 200 parts by weight, workability is remarkably lowered.

(Other additives)
As long as the effects and objects of the present invention are not impaired, the curable composition of the present invention is thickened to adjust the viscosity characteristics of the curing accelerator of the organic polymer (a) and the curable composition as necessary. Various additives having public functions such as an agent / thixotropic agent, a physical property modifier for improving tensile properties, a filler, a reinforcing agent, a plasticizer, a colorant, a flame retardant, and the like may be added.

  As said hardening accelerator, an organometallic compound part can be used, for example. As an organic metal compound that can be suitably used, an organic metal compound obtained by substituting a metal element such as germanium, tin, lead, boron, aluminum, gallium, indium, titanium, and zirconium with an organic group can be given. Also, for example, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis (dibutyltin laurate) oxide, dibutyltin bisacetylacetonate, dibutyltin bis (monoester malate), tin octylate In addition, tin compounds such as dibutyltin octoate and dioctyltin oxide, and titanate compounds such as tetra-n-butoxy titanate and tetraisopropoxy titanate can be used, and these can be used alone or in combination of two or more.

  The thickener is selected from, for example, a polymer compound having good compatibility with the organic polymer (a) and appropriately selected from compounds to be blended. For example, acrylic polymers, methacrylic polymers, polyvinyl alcohol derivatives, polyvinyl acetate, polystyrene derivatives, polyesters, polyethers, polyisobutene, polyolefins, polyalkylene oxides, polyurethanes, polyamides, natural rubber, polybutadiene , Polyisoprene, NBR, SBS, SIS, SEBS, hydrogenated NBR, hydrogenated SBS, hydrogenated SIS, hydrogenated SEBS, and the like. Moreover, these copolymers and functional group modified products can be mentioned, and these may be combined as appropriate.

  As the thixotropic agent, a curable composition is appropriately selected from substances that exhibit thixotropic properties. Examples thereof include colloidal silica, polyvinyl pyrrolidone, hydrophobized calcium carbonate, glass balloons, and glass beads. About selection of a thixotropic agent, it is preferable to have a surface with high affinity with the organic polymer (a).

  As the physical property adjusting agent for improving the above-mentioned tensile characteristics, various silane coupling agents are used. For example, vinyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N, N′-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (triethoxysilyl) Propyl] Examples include tylenediamine, N, N′-bis- [3- (trimethoxysilyl) propyl] hexaethylenediamine, N, N′-bis- [3- (triethoxysilyl) propyl] hexaethylenediamine, and the like. Or two or more kinds may be used in combination.

As the above extender, those which are added to the curable composition of the present invention and do not exhibit thixotropic properties can be suitably used. For example, talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrous silicon, calcium silicate , Titanium dioxide, carbon black and the like, and these may be used alone or in combination of two or more.

  Examples of the plasticizer include phosphate esters such as tributyl phosphate and tricresyl phosphate, phthalate esters such as dioctyl phthalate, fatty acid-basic acid esters such as glycerol monooleate, and dioctyl adipate. Examples thereof include fatty acid dibasic acid esters and polypropylene glycols, and these may be used alone or in combination of two or more.

  In addition, an anti-sagging agent, an antioxidant, an anti-aging agent, an ultraviolet absorber, a solvent, a fragrance, a pigment, a dye, and the like may be added as necessary.

  The adhesive and sealing agent of the present invention can be obtained by using the curable composition of the present invention as a main component, adding various additives such as a curing accelerator as necessary, kneading and defoaming.

In the compositions of the present invention, containing crosslinkable hydrolyzable silyl group-containing (meth) acrylate-based polymer (a), contains the alkyl side chain of 10 or more carbon atoms, and crosslinkable hydrolyzable silyl Since it contains a (meth) acrylate polymer (b) that does not contain a group, it is excellent in weather resistance and depth curability, and can be cured to obtain a highly extensible cured product with less surface tack after curing. It becomes possible to provide a sex composition. Moreover, the said effect can further be show | played by adding a polyether-type polymer (c). Moreover, the said effect can be show | played further by adding inorganic powder (d).

  Therefore, the curable composition of the present invention is excellent in weather resistance and depth curability, and when cured, a highly stretched cured product with little surface tack is obtained, and should be suitably used as a coating agent and adhesive. I can do it.

  Hereinafter, the present invention will be described in more detail by describing specific examples of the present invention. The present invention is not limited to the following examples.

(Reference Example 1 Preparation of vinyl polymer (a1) having hydrolyzable silyl group)
In a 2 L separable flask provided with a stirrer, a cooler, a thermometer, and a nitrogen gas inlet, n-butyl acrylate 90 g, 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-503) 0.5 g Monomer mixture by adding 0.2 g of 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-803), 0.1 g of lauryl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 g of ethyl acetate. It was set as the solution.

  The monomer mixture solution was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the mixture reached reflux with stirring. After refluxing, a solution prepared by diluting 0.024 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was added to the polymerization system. Further, after 2, 3 and 4 hours from the start of the polymerization, di (3,3,5-trimethylhexanoyl) peroxide 0.048 g, 0.12 g, and 0.36 g were diluted with 1 g of ethyl acetate, respectively. I put it in. Seven hours after the first polymerization initiator was charged, the mixture was cooled to room temperature, the polymerization was terminated, and a polymer (a1) was obtained.

(Reference Example 2 Preparation of vinyl polymer (a2) having hydrolyzable silyl group)
In a 2 L separable flask equipped with a stirrer, a cooler, a thermometer and a nitrogen gas inlet, n-butyl acrylate 90 g, 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-503) 1.1 g Then, 0.3 g of 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-803) and 100 g of ethyl acetate were added and mixed to obtain a monomer mixed solution.

  The monomer mixture solution was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the mixture reached reflux with stirring. After refluxing, a solution obtained by diluting 0.024 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was added to the polymerization system. Furthermore, after 2, 3 and 4 hours after the start of polymerization, di (3,3,5-trimethylhexanoyl) peroxide 0.048 g, 0.12 g, and 0.36 g were diluted with 1 g of ethyl acetate, respectively. I put it in. Seven hours after the first introduction of the polymerization initiator, the mixture was cooled to room temperature to complete the polymerization to obtain a polymer (a2).

(Reference Example 3 Preparation of vinyl polymer (a3) having hydrolyzable silyl group)
A 1 L three-necked round bottom flask equipped with a reflux tube was charged with cuprous bromide (6.25 g, 156 mmol), acetonitrile (50 mL), and pentamethyldiethylenetriamine (9.1 mL) and replaced with nitrogen gas. Acrylic acid-n-butyl (500 mL, 447 g, 3.9 mol) and diethyl-2,5-dibromoadipate (15.7 g, 43.6 mmol) were added, and the mixture was heated and stirred at 70 ° C. for 7 hours. The mixture was diluted with ethyl acetate and treated with activated alumina. Volatile components were distilled off under reduced pressure to obtain 350 g of poly (acrylic acid-n-butyl) having a halogen at the terminal (polymerization yield: 87%). The number average molecular weight of the polymer was 10700 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.15.

Next, in a 2 L three-necked round bottom flask equipped with a reflux tube, poly (acrylic acid-n-butyl) having halogen at the terminal obtained as described above (350 g), potassium salt of 4-pentenoic acid ( 22.3 g, 161 mmol) and dimethylacetamide (350 mL) were charged and reacted at 70 ° C. for 4 hours in a nitrogen atmosphere. The mixture was diluted with ethyl acetate and washed with 2% hydrochloric acid, brine. The organic layer was dried over Na ₂ SO ₄ and the polymer was isolated by removing the volatiles under reduced pressure. An equivalent amount of aluminum silicate (manufactured by Kyowa Chemical Co., Ltd .: Kyowaard 700PEL) was added to the polymer and stirred at 100 ° C. for 4 hours to obtain poly (butyl acrylate) having an alkenyl group at the terminal. According to ¹ H-NMR analysis, 1.82 alkenyl groups were introduced per oligomer-1 molecule.

Next, the polymer (150 g), dimethoxymethylhydrosilane (18 mL, 145 mmol), dimethyl orthoformate (2.6 mL, 24.2 mmol), and a platinum catalyst were charged into a 200 mL pressure-resistant glass reaction vessel. However, the amount of the platinum catalyst used was 2 × 10 ⁻⁴ equivalent in terms of molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 ° C. for 4 hours. The volatile component of the mixture was distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having a silyl group at the terminal. According to ¹ H-NMR analysis, the number of silyl groups introduced per oligomer-1 molecule was 1.46.

(Reference Example 4 Preparation of vinyl polymer (b1) having an alkyl group having 10 or more carbon atoms in the side chain)
To a 2 L separable flask equipped with a stirrer, a cooler, a thermometer and a nitrogen gas inlet, n-
60 g of butyl acrylate (Nippon Catalytic), 40 g of stearyl acrylate, 4 g of lauryl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 g of ethyl acetate were added and mixed. The obtained monomer mixed solution was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the reflux was reached while stirring.

  After the reflux, a solution obtained by diluting 0.024 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was added to the polymerization system. After 1 hour, a solution prepared by diluting 0.036 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. Further, 2, 3, and 4 hours after the start of polymerization, a solution prepared by diluting 0.048 g, 0.12 g, and 0.3 g of di (3,3,5-trimethylhexanoyl) peroxide with 1 g of ethyl acetate was added. As a result, a polymer (b1) was obtained.

(Reference Example 5 Preparation of vinyl polymer (b2) having an alkyl group having 10 or more carbon atoms in the side chain)
To a 2 L separable flask equipped with a stirrer, a cooler, a thermometer and a nitrogen gas inlet, n-
60 g of butyl acrylate (Nippon Catalytic), 40 g of lauryl acrylate, 4 g of lauryl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 g of ethyl acetate were added and mixed. The obtained monomer mixed solution was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the reflux was reached while stirring.

  After the reflux, a solution obtained by diluting 0.024 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was added to the polymerization system. After 1 hour, a solution prepared by diluting 0.036 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. Further, 2, 3, and 4 hours after the start of polymerization, a solution obtained by diluting 0.048 g, 0.12 g, and 0.3 g of di (3,3,5-trimethylhexanoyl) peroxide with 1 g of ethyl acetate was added. As a result, a polymer (b2) was obtained.

(Reference Example 6 Preparation of vinyl polymer (x) having an alkyl group having 10 or more carbon atoms in the side chain)
To a 2 L separable flask equipped with a stirrer, a cooler, a thermometer and a nitrogen gas inlet, n-
80 g of butyl acrylate (Nippon Catalytic), 10 g of stearyl acrylate, 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-503), 0.5 g, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., Product number: KBM-803) 0.2 g, lauryl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) 0.1 g and ethyl acetate 100 g were added and mixed. The obtained monomer mixed solution was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the reflux was reached while stirring.

  After the reflux, a solution obtained by diluting 0.024 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was added to the polymerization system. After 1 hour, a solution prepared by diluting 0.036 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. Further, 2, 3, and 4 hours after the start of polymerization, a solution prepared by diluting 0.048 g, 0.12 g, and 0.3 g of di (3,3,5-trimethylhexanoyl) peroxide with 1 g of ethyl acetate was added. As a result, a polymer (b3) was obtained.

(Reference Example 7 Preparation of low molecular weight vinyl polymer (y))
To a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas inlet, 100 g of n-butyl acrylate (Nippon Catalytic), 4 g of lauryl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 g of ethyl acetate are added. , Mixed. The obtained monomer mixed solution was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the reflux was reached while stirring.

  After the reflux, a solution obtained by diluting 0.024 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was added to the polymerization system. After 1 hour, a solution prepared by diluting 0.036 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. Further, 2, 3, and 4 hours after the start of polymerization, a solution obtained by diluting 0.048 g, 0.12 g, and 0.3 g of di (3,3,5-trimethylhexanoyl) peroxide with 1 g of ethyl acetate was added. As a result, a polymer (z) was obtained.

Example 1
160 g of the ethyl acetate solution of the polymer (a1) before removing the ethyl acetate obtained above and 40 g of the ethyl acetate solution of the polymer (b1) before removing the ethyl acetate were mixed, and then using a rotary evaporator. Ethyl acetate was removed to obtain a viscous liquid composition.
To the viscous liquid composition obtained as described above, 70 g of heavy calcium carbonate, 30 g of fatty acid-treated calcium carbonate, and 3 g of a curing accelerator (dibutyltin dilaurate) are further added until uniform with a sealed stirrer. After mixing, the mixture was defoamed under reduced pressure for 10 minutes to obtain a white paste-like curable composition.

(Examples 2-5, Comparative Examples 1-6)
It carried out similarly to Example 1 according to the compounding composition of Table 1, 2, and obtained the curable composition.

[Evaluation]
(Creation of test piece for curability test)
Furthermore, 3 g of aminosilane and 3 g of a curing accelerator were added to the curable composition obtained above, and a test piece was prepared by coating on a polyethylene plate so as to have a film thickness of 5 mm, and the following evaluation was performed. . The results are shown in Tables 1 and 2.
(Deep part curability)
After curing the obtained test piece for 24 hours in an environment of 20 ° C. and 50% relative humidity, the cross-section of the test piece was observed, and the distance from the surface of the portion where hardening was progressing was measured to obtain the cured thickness.
(Surface tackiness)
The obtained test piece was cured for 7 days in an environment of 20 ° C. and a relative humidity of 50%, and the tackiness of the surface of the test piece was observed by tentacle observation, and the surface tackiness was evaluated according to the following criteria.
○: Tack was not recognized.
X: Tack was recognized.
(Weatherability)
Further, 3 g of aminosilane and 3 g of a curing accelerator were added to the curable composition obtained above, and after coating on a stainless steel plate so that the film thickness was 0.5 mm, 20 ° C. and 60% RH. A test piece was prepared by curing for 7 days in an atmosphere. The obtained test piece was irradiated with light under the following conditions, and the presence or absence of surface cracks after 150 hours and 400 hours was visually observed to evaluate the weather resistance according to the following criteria. The results are shown in Tables 1 and 2.

Claims (7)

A (meth) acrylate polymer (a) containing a crosslinkable hydrolyzable silyl group and an alkyl side chain having 10 or more carbon atoms and no crosslinkable hydrolyzable silyl group (meth) A curable composition comprising an acrylate polymer (b). (Meth) acrylate polymers, curable composition according to claim 1, characterized in that the radical polymerization obtained (meth) acrylate-based polymer using a peroxide as a polymerization initiator. The curable composition according to claim 1 or 2 polyether polymer having a cross-linking capable hydrolyzable silyl group (c) is characterized by comprising the further compounded. Inorganic powder (d) is mix | blended further, The curable composition of any one of Claims 1-3 characterized by the above-mentioned. The curable composition according to claim 4 , wherein the inorganic powder (d) is a calcium carbonate powder (d1). A sealing agent using the curable composition according to any one of claims 1 to 5 . An adhesive comprising the curable composition according to any one of claims 1 to 5 .