JP2005082750A - Curable composition with excellent adhesion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition which is excellent in workability, adhesive property, water-resistant adhesive property, shelf stability, in-depth curability, adhesion to a paint and antifouling property and has good initial adhesion. <P>SOLUTION: The curable composition contains (A) a (meth)acrylic polymer containing a crosslinkable silyl group, (B) an organic polymer which contains, on average, 0.5-1.5 crosslinkable silyl groups in a molecule and has a weight average molecular weight of 2,000-50,000 and (C) a curing catalyst. The component (A) is preferably an acrylic-modified polyoxyalkylene polymer containing a crosslinkable silyl group, and the component (B) is suitably a polyoxyalkylene polymer containing a crosslinkable silyl group and/or an acrylic-modified polyoxyalkylene polymer containing a crosslinkable silyl group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable composition, and more particularly to a curable composition excellent in adhesiveness.

  Conventionally, an oxyalkylene-based polymer having a crosslinkable silyl group is a polymer that is cured by moisture in the air at room temperature to give a rubber-like material, such as room temperature-cured silicone rubber. Since this cured product is excellent in heat resistance, water resistance, weather resistance and the like, it is used for sealing materials, adhesives and the like.

  In recent years, for the purpose of improving construction efficiency, an excellent expression of adhesiveness at an early stage is required for sealing materials and adhesives. Furthermore, strong adhesion with non-primers is being demanded for various adherends.

However, the above-mentioned oxyalkylene polymers having a crosslinkable silyl group have insufficient initial-stage adhesion or non-primer adhesion to various adherends due to the main chain skeleton, etc. It has a weak point in performance such as
Japanese Patent Publication No. 1-58219 Japanese Patent No. 3062625 JP-A-8-337713 JP 2003-138151 A Japanese Patent Laid-Open No. 11-12480 JP-A-52-73998 JP 55-9669 A JP 59-122541 A Japanese Unexamined Patent Publication No. 60-6747 JP-A-61-233043 Japanese Unexamined Patent Publication No. Sho 63-112642 JP-A-3-79627 JP-A-4-283259 JP-A-5-70531 JP-A-5-287186 Japanese Patent Laid-Open No. 11-80571 Japanese Patent Laid-Open No. 11-116763 JP-A-11-130931 Japanese Patent No. 3313360 JP 2003-155469 A Japanese Examined Patent Publication No. 3-14068 Japanese Patent Publication No. 5-72427 Japanese Patent Publication No. 4-55444 JP-A-6-221922 JP 2000-345136 A Japanese Patent Laid-Open No. 2003-48721 Japanese Patent Laid-Open No. 2001-40037 JP 2003-155469 A Japanese Patent Laid-Open No. 11-80250 JP 59-122541 A JP 60-31556 A JP 59-78223 A JP 59-168014 A JP-A-60-228516 Japanese Patent Publication No. 7-42376 Japanese Patent Publication No. 10-195151 Japanese Patent Publication No. 2-44845 Japanese Patent Publication No. 7-238143 JP 2000-17249 A

  The present invention has been made in view of the above-described problems of the prior art, and is excellent in workability, adhesiveness, water-resistant adhesiveness, storage stability, deep-curability, paint adhesion, and stain resistance. It aims at providing the curable composition which has initial adhesiveness.

  In order to solve the above problems, the curable composition of the present invention comprises (A) a crosslinkable silyl group-containing (meth) acrylic polymer, (B) 0.5 or more on average in one molecule. It contains a crosslinkable silyl group-containing organic polymer having a weight average molecular weight of 2,000 to 50,000 having 5 or less crosslinkable silyl groups, and (C) a curing catalyst.

  The component (A) is preferably a crosslinkable silyl group-containing (meth) acryl-modified polyoxyalkylene polymer.

  The component (B) is preferably a crosslinkable silyl group-containing polyoxyalkylene polymer and / or a crosslinkable silyl group-containing (meth) acryl-modified polyoxyalkylene polymer.

  The component (B) preferably has 0.7 to 1.5 crosslinkable silyl groups on average per molecule, and preferably 1.0 to 1.5 on average in one molecule. It is more preferable to have not more than one crosslinkable silyl group.

  It is preferable to further add (D) a silane coupling agent to the curable composition of the present invention.

  According to the present invention, it is possible to provide a curable composition having excellent initial adhesiveness as well as excellent workability, adhesiveness, water-resistant adhesiveness, storage stability, deep part curability, paint adhesion, and stain resistance. Can do.

  Embodiments of the present invention will be described below, but these embodiments are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

  The curable composition of the present invention comprises (A) a crosslinkable silyl group-containing (meth) acrylic polymer, (B) an average of 0.5 to 1.5 crosslinkable silyl groups per molecule. A crosslinkable silyl group-containing organic polymer having a weight average molecular weight of 2,000 to 50,000 and (C) a curing catalyst.

  Component (A) of the present invention includes a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond, that is, an acrylic polymer containing a crosslinkable silyl group. A methacrylic polymer containing a coalescence and / or a crosslinkable silyl group is used. In this specification, an acrylic polymer and a methacrylic polymer may be collectively referred to as a (meth) acrylic polymer. Examples of such a crosslinkable silyl group-containing (meth) acrylic polymer (A) include those disclosed in Patent Documents 20 to 39.

  The crosslinkable silyl group is preferably one represented by the following general formula (1) which is easy to crosslink and easy to produce. The crosslinkable silyl group is not particularly limited, but from the viewpoint of the curability of the sealing material and the physical properties after curing, it is preferably contained in an average of 0.5 or more, and contains 1 to 6 in one molecule. It is common.

Wherein R is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and most preferably a methyl group. The reactive group is a group selected from a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group, and an aminooxy group. In this case, X may be the same group or different groups, among which X is preferably an alkoxy group, most preferably a methoxy group, a is an integer of 0, 1 or 2, Most preferred.)

  Specifically, the crosslinkable silyl group-containing (meth) acrylic polymer (A) has a crosslinkable silyl group and each may contain an organosiloxane, and the main chain is essentially ( Compounds that are polymers obtained by (co) polymerizing one or more acrylic monomers such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, and mixtures thereof The composition which has as a main component is mentioned. Although it does not specifically limit as said acrylic monomer, (meth) acrylic acid ester is preferable.

  Examples of the acrylate ester include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (meth) acrylate-n-butyl, (Meth) acrylic acid isobutyl, (meth) acrylic acid s-butyl, (meth) acrylic acid t-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid-n- Hexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid Isodecyl, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate and (meth) Alkyl (meth) acrylates such as stearyl acrylate; alicyclic alkyl acrylates such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and tricyclodecynyl (meth) acrylate; phenyl (meth) acrylate , Aromatic acrylic esters such as toluyl (meth) acrylate and benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate and (meth) Hydroxyalkyl (meth) acrylate such as ε-caprolactone addition reaction product of hydroxyethyl acrylate; 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-aminoethyl (meth) acrylate , Dimethylamino (meth) acrylate Examples include heteroatom-containing acrylic esters such as ethyl, chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate, trifluoromethyl methyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. Not limited to these. Moreover, you may use together 1 type, or 2 or more types of these. Among the above (meth) acrylic acid esters, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, acrylic acid-n-butyl, acrylic acid 2-ethylhexyl, methyl methacrylate from the viewpoint of characteristics after curing. Ethyl methacrylate, methacrylic acid-n-propyl, methacrylic acid-n-butyl, and 2-ethylhexyl methacrylate are preferred.

  In addition, as the crosslinkable silyl group-containing (meth) acrylic polymer (A), in addition to the acrylic monomer, a monomer copolymerizable therewith can be copolymerized. The copolymerizable monomer is not particularly limited, and examples thereof include vinyl monomers such as fluoroolefins, α-olefins, vinyl esters and vinyl ethers.

  In addition, as the component (A), the crosslinkable silyl group-containing (meth) acrylic polymer and other polymers such as a crosslinkable silyl group-containing polyoxyalkylene polymer and a crosslinkable silyl group-containing vinyl-modified polyoxy It is also possible to use a mixture with an alkylene polymer or the like, and it is included in the present invention. When a mixture of a crosslinkable silyl group-containing (meth) acrylic polymer and another polymer is used, the blending ratio of the crosslinkable silyl group-containing (meth) acrylic polymer in the mixture is 10% by mass or more. Is preferred.

  In particular, it is preferable to use a (meth) acryl-modified polyoxyalkylene polymer having a crosslinkable silyl group as the component (A) from the viewpoint of adhesiveness and workability. Examples of such crosslinkable silyl group-containing (meth) acryl-modified polyoxyalkylene polymers include those disclosed in Patent Documents 30 to 39.

  In the present invention, the crosslinkable silyl group-containing (meth) acrylic polymer (A) has a weight average molecular weight of 500 or more, particularly 1,000 to 30,000, and a narrow molecular weight distribution, which is easy to handle because the viscosity before curing is low, Properties such as strength, elongation and modulus after curing are suitable. The said component (A) may be used only by 1 type, and may be used together 2 or more types.

  As the component (B) of the present invention, an organic polymer having 0.5 to 1.5 crosslinkable silyl groups on average in one molecule is used. As the crosslinkable silyl group of the component (B), crosslinkable silyl groups exemplified in the description of the component (A) can be used. The average number of crosslinkable silyl groups is 0.5 or more, preferably 0.7 or more, more preferably 1.0 or more, and 1.5 or less, more preferably 1.4 or more in one molecule. Contains no more.

  As such a crosslinkable silyl group-containing organic polymer (B), specifically, a main chain containing 0.5 to 1.5 crosslinkable silyl groups on average in one molecule. Each of which may contain an organosiloxane, a polyoxyalkylene polymer, a vinyl-modified polyoxyalkylene polymer, a vinyl polymer, a polyester polymer, a (meth) acrylic acid ester polymer, Examples include coalescence and mixtures. In particular, from the viewpoint of physical properties such as tensile adhesiveness and modulus after curing, 0.5 to 1.5, preferably 0.7 to 1.5, more preferably 1 on average per molecule. A polyoxyalkylene polymer, a (meth) acrylic polymer, a (meth) acrylic polymer containing 0 to 1.5 crosslinkable silyl groups, each main chain optionally containing an organosiloxane. Modified polyoxyalkylene polymers, polyisobutylene polymers, copolymers and mixtures thereof are preferred, and polyoxyalkylene polymers, (meth) acrylic, each of which may contain an organosiloxane. More preferred are polymer-based polymers, (meth) acryl-modified polyoxypropylene polymers, copolymers and mixtures thereof.

  The method for producing the component (B) is not particularly limited. For example, in the method for producing a crosslinkable silyl group-containing organic polymer disclosed in Patent Documents 1 to 39, a crosslinkable silyl present in one molecule. It can be produced by adjusting the number of groups to 0.5 to 1.5. Moreover, as a component (B), it obtained by mixing 2 or more types of organic polymers from which the number of crosslinkable silyl groups differs, and on average 0.5 or more and 1.5 or less crosslinkability in 1 molecule is obtained. An organic polymer having a silyl group can also be used. Specifically as a manufacturing method of a component (B), the manufacturing method etc. which were used in the synthesis examples 2-5 and the synthesis examples 8-11 mentioned later can be mentioned.

  In the present invention, the crosslinkable silyl group-containing organic polymer (B) has a weight average molecular weight of 2,000 to 50,000, preferably 2,000 to 30,000 and a narrow molecular weight distribution before curing. Since its viscosity is low, it is easy to handle, and physical properties such as strength, elongation and modulus after curing are suitable. Further, when an acrylic polymer containing a crosslinkable silyl group is used as the component (B), the weight average molecular weight of the crosslinkable silyl group-containing acrylic polymer may be 2,000 or more and 50,000 or less. Is preferably 5,000 or more and 50,000 or less, and more preferably 8,000 or more and 50,000 or less. The said component (B) may be used only by 1 type, and may be used together 2 or more types.

  The blending ratio of the component (B) is not particularly limited, but the component (B) is preferably used in an amount of 1 to 1000 parts by weight, and 10 to 500 parts by weight, based on 100 parts by weight of the component (A). It is more preferable.

  The component (C) curing catalyst is not particularly limited as long as it exhibits the effect of the curing catalyst on the component (A) and / or the component (B), and examples thereof include organometallic compounds and amines. In particular, it is preferable to use a silanol condensation catalyst. Examples of the silanol condensation catalyst include stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate. Organotin compounds such as dioctyltin dilaurate, dioctyltin diversate, tin octylate and tin naphthenate; reactants of dibutyltin oxide and phthalate; titanates such as tetrabutyl titanate and tetrapropyl titanate; aluminum Organoaluminum compounds such as trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; Chelate compounds such as Konium tetraacetylacetonate and Titanium tetraacetylacetonate; Leads of organic acids such as lead octylate and lead naphthenate; Bismuths of organic acids such as bismuth octylate, bismuth neodecanoate and bismuth rosinate; Silanol condensation Examples of the catalyst include other known acidic catalysts and basic catalysts.

  The blending ratio of the component (C) is 100 masses of the crosslinkable silyl group-containing (meth) acrylic polymer (A) and the crosslinkable silyl group-containing organic polymer (B) from the viewpoint of the crosslinking speed and the physical properties of the cured product. It is preferable to use 0.1 to 30 parts by mass, particularly 0.5 to 20 parts by mass with respect to parts. These curing catalysts may be used alone or in combination of two or more.

  It is preferable to further add (D) a silane coupling agent to the curable composition of the present invention in order to impart adhesion. As the silane coupling agent, conventionally known silane coupling agents can be widely used and are not particularly limited. For example, aminosilanes such as aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropylmethylmethoxysilane, and the like. , Epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane And isocyanate silanes.

  Although the compounding ratio of the said component (D) is not specifically limited, About 0.1-30 mass parts of component (D) is preferable with respect to 100 mass parts of components (A), and 0.3-15 mass parts is further preferable. These silane coupling agents may be used alone or in combination of two or more.

  In order to impart flexibility and workability to the curable composition of the present invention, it is preferable to further add an organic polymer (E) having a weight average molecular weight of 2,000 to 50,000. Specific examples of the component (E) include polyoxyalkylene polymers, vinyl-modified polyoxyalkylene polymers, vinyl polymers, polyester polymers, (meth) acrylic acid ester polymers, and copolymers of these. A polymer, a mixture, etc. can be mentioned. These organic polymers (E) may not contain a crosslinkable silyl group or may contain a crosslinkable silyl group, and those containing a crosslinkable silyl group are averaged in one molecule. It is preferable to use an organic polymer containing less than 0.5 crosslinkable silyl groups. In particular, it is preferable to use a polyoxyalkylene polymer, a (meth) acrylic polymer, a copolymer or a mixture thereof.

  The polyoxyalkylene-based polymer includes, for example, a monoepoxide such as an alkylene oxide in an initiator such as a hydroxy compound having at least one hydroxyl group in the presence of a catalyst such as an alkali metal catalyst, a double metal cyanide complex catalyst, or a metal porphyrin catalyst. Etc. can be made to react.

  Specific examples of the initiator include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, diglycerin. Sucrose and polyols having a lower molecular weight than the target product obtained by reacting these with alkylene oxide. These may be used alone or in combination of two or more. Also, unsaturated group-containing monohydroxy compounds such as allyl alcohol can be used.

  Particularly preferred polyoxyalkylene polymers are polyoxypropylene diol, polyoxyalkylene triol and polyoxytetraol.

  In addition, a polyoxyalkylene polymer obtained by converting a hydroxyl group of the polyoxyalkylene polymer into another group can also be used. As an example of a polymer in which a hydroxyl group is converted to another group, a polyoxyalkylene polymer having a terminal hydroxyl group such as oxypropylene glycol is bonded to a urethane bond, an ester bond, a urea bond, a carbonate bond, or the like. Through, alkyl groups such as methyl group, ethyl group, propyl group, chloromethyl group, benzyl group and glycidyl group, aryl groups such as phenyl group, toluyl group and chlorophenyl group, alkenyl groups such as vinyl group and allyl group, etc. Examples thereof include oxyalkylene polymers blocked with a substituted or unsubstituted hydrocarbon group, preferably a C1-C40 hydrocarbon group.

  Although the mixture ratio of the said component (E) is not specifically limited, About 1-400 mass parts of components (E) are preferable with respect to 100 mass parts of components (A), and 5-200 mass parts is more preferable. These organic polymers may be used alone or in combination of two or more.

  In addition to the above-described components, the curable composition of the present invention includes a physical property adjuster, a filler, a plasticizer, a thixotropic agent, a dehydrating agent (storage stability improving agent), a tackifier, and a sagging agent as necessary. Substances such as inhibitors, ultraviolet absorbers, antioxidants, flame retardants, colorants, radical polymerization initiators and various solvents such as toluene and alcohol may be blended, and other compatible polymers may be blended. May be.

  As the other compatible polymer, various polyethers are particularly preferable, and in particular, polyethers having a silicon functional group are exemplified.

  The physical property modifier is added for the purpose of improving the tensile physical properties. Examples of the physical property modifier include a silicon compound having one silanol group in one molecule, and examples thereof include triphenylsilanol, trialkylsilanol, dialkylphenylsilanol, diphenylalkylsilanol, and the like. Various silane coupling agents such as silicon compounds that can be decomposed to produce a compound having one silanol group in one molecule, such as triphenylmethoxysilane, trialkylmethoxysilane, dialkylphenylmethoxysilane, diphenylalkylmethoxy Silane, triphenylethoxysilane, trialkylethoxysilane, etc. are mentioned. The said physical property modifier may be used independently and may be used together 2 or more types.

  The filler is added for the purpose of reinforcing the cured product. Examples of the filler include calcium carbonate, magnesium carbonate, diatomaceous earth hydrous silicic acid, hydrous silicic acid, anhydrous silicic acid, calcium silicate, silica, titanium dioxide, clay, talc, carbon black, slate powder, mica, kaolin, and zeolite. Of these, calcium carbonate is preferable, and fatty acid-treated calcium carbonate is more preferable. In addition, glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloons, glass balloons, silica balloons, saran balloons, acrylic balloons, etc. can be used. Among them, an acrylic balloon is more preferable from the viewpoint that the decrease in elongation after curing of the composition is small. The fillers may be used alone or in combination of two or more.

  The plasticizer is added for the purpose of enhancing the elongation physical properties after curing or enabling low modulus. Examples of the plasticizer include phosphate esters such as tributyl phosphate and tricresyl phosphate; phthalate esters such as dioctyl phthalate (DOP), dibutyl phthalate and butyl benzyl phthalate; fatty acid monobases such as glycerin monooleate Acid esters; fatty acid dibasic acid esters such as dibutyl adipate and dioctyl adipate; glycol esters such as polypropylene glycol; aliphatic esters; epoxy plasticizers; polyester plasticizers; polyethers; Is mentioned. The plasticizers may be used alone or in combination of two or more.

  Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and asbestos powder, organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide, hydrogenated castor oil derivative, fatty acid amide wax, and aluminum stearylate. And barium stearylate. The thixotropic agent may be used alone or in combination of two or more.

  The dehydrating agent is added for the purpose of removing moisture during storage. Examples of the dehydrating agent include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane.

  The antioxidant is used to prevent oxidation of the cured sealant and improve weather resistance, and examples thereof include hindered amine-based and hindered phenol-based antioxidants. Examples of the hindered amine antioxidant include N, N ′, N ″, N ″ ′-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine- 4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N'-bis- (2,2,6 , 6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine · N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4- Peridyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, [bis (2,2,6,6-tetramethyl-decanedioic acid) 1 (octyloxy) -4-piperidyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane (70%)]-polypropylene (30%), bis (1,2,2,6,6- Pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl seba Kate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 1- [2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9- Examples include, but are not limited to, tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, etc. Examples of hindered phenol antioxidants include pentane. Erythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [3- (3,5-di-ter t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropioamide), benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4 -Dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ', 3 ", 5 5 ', 5 "-hexane-tert-butyl-4-a, a', a"-(mesitylene-2,4,6-tolyl) tri-p-cresol, calci Mudiethylbis [[[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) Bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 , 5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, N-phenylbenzenamine Product of 2,4,4-trimethylpentene with 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5 Triazin-2-ylamino) phenol and the like, but not limited thereto. The antioxidants may be used alone or in combination of two or more.

  The ultraviolet absorber is used to improve the weather resistance by preventing photodegradation of the cured sealant, for example, an ultraviolet absorber such as benzotriazole, triazine, benzophenone, or benzoate. Etc. Examples of the ultraviolet absorber include 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -4,6- Di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H-benzotriazole-2) -Yl) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4 -Benzotriazole ultraviolet absorbers such as methylphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(he Sil) oxy] -phenol and the like triazine ultraviolet absorbers, benzophenone ultraviolet absorbers such as octabenzone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. Examples include, but are not limited to, benzoate ultraviolet absorbers. The said ultraviolet absorber may be used independently or may use 2 or more types together.

  Examples of the present invention will be specifically described below, but it is needless to say that these examples are illustrative and should not be construed in a limited manner. In the following, “part” means “part by mass”, and “%” means “% by mass”.

(Synthesis Example 1) Synthesis of Polymer A2 In a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 10 parts by weight of normal butyl acrylate (hereinafter referred to as BA), 70 parts by weight of methyl acrylate, 20 parts by mass of stearyl acrylate, 20 parts by mass of γ-methacryloxypropyltrimethoxysilane, and 0.1 parts by mass of ruthenocene dichloride as a metal catalyst were charged, and the contents of the flask were heated to 80 ° C. while introducing nitrogen gas into the flask. did.

  Then, 20 parts by mass of 3-mercaptopropyltrimethoxysilane sufficiently substituted with nitrogen gas was added all at once to the flask with stirring. After adding 20 parts by mass of 3-mercaptopropyltrimethoxysilane, heating and cooling were performed for 4 hours so that the temperature of the contents in the stirring flask could be maintained at 80 ° C. Furthermore, 20 parts by mass of 3-mercaptopropyltrimethoxysilane sufficiently substituted with nitrogen gas was added to the flask over 5 minutes with stirring. After additional addition of 20 parts by mass of 3-mercaptopropyltrimethoxysilane, the reaction was carried out for 4 hours while further cooling and heating so that the temperature of the contents in the stirring flask could be maintained at 90 ° C. .

  Subsequently, the obtained reaction product was transferred to an evaporator, and THF, residual monomer, and residual thiol compound were removed while gradually heating to 80 ° C. under reduced pressure to obtain a crosslinkable silyl group-containing acrylic polymer A2.

(Synthesis Example 2) Synthesis of Polymer B1 Hydroxyl-converted molecular weight 7,000 obtained by reacting propylene oxide with propylene glycol as an initiator and in the presence of a zinc hexacyanocobaltate-glyme complex catalyst, and Mw / Mn = 1 .2 polyoxypropylene oxide was obtained. This reaction product was reacted with methyldimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst, having a methyldimethoxysilyl group at the end and an average of 1.2 silyl groups in one molecule. 1,000 crosslinkable silyl group-containing polyoxyalkylene polymer B1 was obtained.

(Synthesis Example 3) Synthesis of Polymer B2 In the same manner as in Synthesis Example 2, a weight average molecular weight of 7,000 having a methyldimethoxysilyl group at the terminal and an average of 1.5 silyl groups in one molecule. The crosslinkable silyl group-containing polyoxyalkylene polymer B2 was obtained.

(Synthesis Example 4) Synthesis of Polymer B3 In the same manner as in Synthesis Example 2, a weight average molecular weight of 7,000 having a methyldimethoxysilyl group at the terminal and an average of 0.8 silyl groups in one molecule. The crosslinkable silyl group-containing polyoxyalkylene polymer B3 was obtained.

(Synthesis Example 5) Synthesis of Polymer B4 A weight average molecular weight of 7,000 having a methyldimethoxysilyl group at the terminal and an average of 1.0 silyl group in one molecule in the same manner as in Synthesis Example 2. The crosslinkable silyl group-containing polyoxyalkylene polymer B4 was obtained.

(Synthesis Example 6) Synthesis of Polymer P1 In the same manner as in Synthesis Example 2, a weight average molecular weight of 7,000 having a methyldimethoxysilyl group at the terminal and an average of 1.7 silyl groups in one molecule. The crosslinkable silyl group-containing polyoxyalkylene polymer P1 was obtained.

(Synthesis Example 7) Synthesis of Polymer P2 In the same manner as in Synthesis Example 2, a weight-average molecular weight of 7,000 having a methyldimethoxysilyl group at the terminal and an average of 0.3 silyl groups in one molecule The crosslinkable silyl group-containing polyoxyalkylene polymer P2 was obtained.

(Synthesis Example 8) Synthesis of Polymer B5 In a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 80 parts by mass of ethyl acrylate (hereinafter referred to as EA), 20 parts by mass of stearyl acrylate, And 0.2 mass part of zirconocene dichloride was charged as a metal catalyst, and the contents were heated to 65 ° C. while introducing nitrogen gas into the flask.

  Next, 2.0 parts by mass of 3-mercaptopropyltrimethoxysilane sufficiently substituted with nitrogen gas was added all at once to the flask with stirring. After adding 2.0 parts by mass of 3-mercaptopropyltrimethoxysilane, heating and cooling were performed for 2 hours so that the temperature of the contents in the stirring flask could be maintained at 65 ° C. Thereafter, 3-mercaptopropyltrimethoxysilane sufficiently substituted with nitrogen was added all at once to the stirred flask. After additional addition of 1.4 parts by mass of 3-mercaptopropyltrimethoxysilane, the reaction was carried out for 2 hours while further cooling and heating so that the temperature of the contents in the stirring flask could be maintained at 75 ° C. . Then, it heated so that the temperature of the content in a flask could be maintained at 90 degreeC.

  After the reaction for 8 hours in total as described above, the temperature of the reaction product was returned to room temperature, and 20 parts by mass of a benzoquinone solution (95% THF solution) was added to the reaction product to stop the polymerization. The reaction product thus obtained was transferred to an evaporator, and THF, residual monomer, and residual thiol compound were removed while gradually heating to 80 ° C. under reduced pressure. On average, 1.0 crosslinkable silyl group per molecule was removed. A crosslinkable silyl group-containing acrylic polymer B5 was obtained. The weight average molecular weight of the obtained polymer was 12,000.

(Synthesis Example 9) Synthesis of Polymer B6 The polymer B1 obtained in Synthesis Example 2 and having 1.2 silyl groups per molecule on average and the polymer B6 obtained in Synthesis Example 8 on average 1 A polymer B5 having 1.0 crosslinkable silyl groups in the molecule is blended so as to have a solid content ratio of 60/40, and an average of 1.12 crosslinkable silyl groups in one molecule is crosslinked. The silyl group-containing acrylic modified polyoxyalkylene polymer B6 was obtained.

(Synthesis Example 10) Synthesis of Polymer B7 200 parts by mass of 2-propanol (hereinafter referred to as IPA) was charged into a 2 L pressure-resistant autoclave equipped with a stirrer. Next, degassing and nitrogen substitution were repeated three times, followed by degassing under reduced pressure and heating to 260 ° C. When the temperature rise is completed, 750 parts by weight of BA and 130 parts by weight of EA are used as an acrylate monomer, 120 parts by weight of γ-methacryloxypropyltrimethoxysilane, 200 parts by weight of IPA, and 10 parts by weight of ditertiary butyl peroxide. The mixture was fed into the autoclave at a constant rate to initiate the reaction. Added and reacted over 2 hours, cooled to 30 ° C. 10 minutes after completion of the addition, and averaged crosslinkable silyl group-containing acrylic polymer B7 having 0.72 crosslinkable silyl groups in one molecule. Obtained. The weight average molecular weight of the obtained polymer was 3,500.

(Synthesis Example 11) Synthesis of Polymer B8 Polymerization was conducted in the same manner as in Synthesis Example 10, except that the acrylic acid ester monomer in the mixed solution was BA840 parts by mass and γ-methacryloxypropyltrimethoxysilane was 160 parts by mass. And a crosslinkable silyl group-containing acrylic polymer B8 having 1.29 crosslinkable silyl groups in one molecule on average was obtained. The weight average molecular weight of the obtained polymer was 4800.

(Example 1)
As shown in Table 1, as a component (A), a crosslinkable silyl group-containing acrylic-modified polyoxyalkylene polymer A1, and as a component (B), an average of 1.2 in one molecule obtained in Synthesis Example 2. Each of the crosslinkable silyl group-containing polyoxyalkylene polymer B1 having a crosslinkable silyl group, a filler, and vinyltrimethoxysilane were charged in predetermined amounts, followed by heating under reduced pressure for 2 hours at 110 ° C. Dehydration was performed. Furthermore, a predetermined amount of an aminosilane compound was added as a component (C) curing catalyst and component (D), mixed and stirred to prepare a curable composition.

The compounding amounts of the compounding substances in Table 1 are shown in parts by mass, and * 1 to * 15 are as follows.
* 1: Product name: MA440, manufactured by Kaneka Chemical Co., Ltd.
* 2: Polymer A2 obtained in Synthesis Example 1
* 3: Polymer B1 obtained in Synthesis Example 2 (1.2 crosslinkable silyl groups)
* 4: Polymer B2 obtained in Synthesis Example 3 (1.5 crosslinkable silyl groups)
* 5: Polymer B3 obtained in Synthesis Example 4 (0.8 crosslinkable silyl groups)
* 6: Polymer B4 obtained in Synthesis Example 5 (1.0 crosslinkable silyl group)
* 7: Polymer B5 obtained in Synthesis Example 8 (1.0 crosslinkable silyl group)
* 8: Polymer B6 obtained in Synthesis Example 9 (1.12 crosslinkable silyl groups)
* 9: Polymer B7 obtained in Synthesis Example 10 (0.72 crosslinkable silyl groups)
* 10: Polymer B8 obtained in Synthesis Example 11 (1.29 crosslinkable silyl groups)
* 11: Polymer P1 obtained in Synthesis Example 6 (1.7 crosslinkable silyl groups)
* 12: Polymer P2 obtained in Synthesis Example 7 (0.3 crosslinkable silyl groups)
* 13: Dibutyltin diacetylacetonate (manufactured by Nitto Kasei Co., Ltd., trade name: U-220)
* 14: Nihon Unicar Co., Ltd., product name: A-1121
* 15: Calcium carbonate (Maruo Calcium Co., Ltd., trade name: Calfine 200M)

(Example 2)
As shown in Table 1, as a component (B), instead of the polymer B1 obtained in Synthesis Example 2, an average of 1.5 crosslinkable silyl groups obtained in Synthesis Example 3 per molecule is contained. A curable composition was prepared in the same manner as in Example 1 except that the crosslinkable silyl group-containing polyoxyalkylene polymer B2 was used.

(Example 3)
As shown in Table 1, as a component (B), instead of the polymer B1 obtained in Synthesis Example 2, 0.8 crosslinkable silyl groups on average per molecule obtained in Synthesis Example 4 were obtained. A curable composition was prepared in the same manner as in Example 1 except that the crosslinkable silyl group-containing polyoxyalkylene polymer B3 having the following formula was used.

Example 4
As shown in Table 1, as a component (B), instead of the polymer B1 obtained in Synthesis Example 2, 1.0 crosslinkable silyl group obtained in Synthesis Example 5 on average per molecule was obtained. A curable composition was prepared in the same manner as in Example 1 except that the crosslinkable silyl group-containing polyoxyalkylene polymer B4 was used.

(Example 5)
As shown in Table 1, as a component (A), a crosslinkable silyl group-containing acrylic polymer A2 obtained in Synthesis Example 1 and as a component (B) obtained in Synthesis Example 2 on average, one molecule A curable composition was prepared in the same manner as in Example 1 except that a predetermined amount of each of the crosslinkable silyl group-containing polyoxyalkylene polymer B1 having 1.2 crosslinkable silyl groups was blended therein.

(Example 6)
As shown in Table 1, as a component (B), instead of the polymer B1 obtained in Synthesis Example 2, 1.5 crosslinkable silyl groups on average per molecule obtained in Synthesis Example 3 were obtained. A curable composition was prepared in the same manner as in Example 5 except that the crosslinkable silyl group-containing polyoxyalkylene polymer B2 having the following formula was used.

(Example 7)
As shown in Table 1, as a component (B), instead of the polymer B1 obtained in Synthesis Example 2, 0.8 crosslinkable silyl groups on average per molecule obtained in Synthesis Example 4 were obtained. A curable composition was prepared in the same manner as in Example 5 except that the crosslinkable silyl group-containing polyoxyalkylene polymer B3 having the following formula was used.

(Example 8)
As shown in Table 1, as a component (B), instead of the polymer B1 obtained in Synthesis Example 2, an average of 1.0 crosslinkable silyl groups per molecule obtained in Synthesis Example 5 was obtained. A curable composition was prepared in the same manner as in Example 5 except that the crosslinkable silyl group-containing polyoxyalkylene polymer B4 having the following formula was used.

Example 9
As shown in Table 1, as the component (A), a crosslinkable silyl group-containing acrylic-modified polyoxyalkylene polymer A1, and as the component (B), 1. A curable composition was prepared in the same manner as in Example 1 except that a predetermined amount of each of the crosslinkable silyl group-containing acrylic polymer B5 having 0 crosslinkable silyl groups was blended.

(Example 10)
As shown in Table 1, as a component (A), the crosslinkable silyl group-containing acrylic polymer A2 obtained in Synthesis Example 1 and as a component (B) obtained in Synthesis Example 8 on average, one molecule A curable composition was prepared in the same manner as in Example 1 except that a predetermined amount of each of the crosslinkable silyl group-containing acrylic polymer B5 having 1.0 crosslinkable silyl groups was blended therein.

(Example 11)
As shown in Table 1, as the component (A), a crosslinkable silyl group-containing acrylic-modified polyoxyalkylene polymer A1 and as the component (B) were obtained in Synthesis Example 9 in an average of 1. A curable composition was prepared in the same manner as in Example 1 except that a predetermined amount of each of the crosslinkable silyl group-containing acrylic modified polyoxyalkylene polymer B6 having 12 crosslinkable silyl groups was blended.

(Example 12)
As shown in Table 1, as a component (A), the crosslinkable silyl group-containing acrylic polymer A2 obtained in Synthesis Example 1, and as a component (B), obtained in Synthesis Example 9 on average, one molecule A curable composition was prepared in the same manner as in Example 1 except that a predetermined amount of each of the crosslinkable silyl group-containing acrylic modified polyoxyalkylene polymer B6 having 1.12 crosslinkable silyl groups was blended therein. .

(Example 13)
As shown in Table 1, as the component (A), a crosslinkable silyl group-containing acrylic-modified polyoxyalkylene polymer A1 was obtained, and the component (B) obtained in Synthesis Example 10 was averaged in an amount of 0.001 per molecule. A curable composition was prepared in the same manner as in Example 1 except that a predetermined amount of each of the crosslinkable silyl group-containing acrylic polymer B7 having 72 crosslinkable silyl groups was blended.

(Example 14)
As shown in Table 1, as the component (A), a crosslinkable silyl group-containing acrylic-modified polyoxyalkylene polymer A1 and as the component (B) were obtained in Synthesis Example 11 in an average of 1. A curable composition was prepared in the same manner as in Example 1 except that a predetermined amount of each of 29 crosslinkable silyl groups-containing crosslinkable silyl group-containing acrylic polymer B8 was blended.

(Comparative Example 1)
As shown in Table 1, instead of the crosslinkable silyl group-containing polyoxyalkylene polymer B1, a crosslinkable silyl group having an average of 1.7 crosslinkable silyl groups in one molecule obtained in Synthesis Example 6 A curable composition was prepared in the same manner as in Example 1 except that the containing polyoxyalkylene polymer P1 was used.

(Comparative Example 2)
As shown in Table 1, instead of the crosslinkable silyl group-containing polyoxyalkylene polymer B1, a crosslinkable silyl group having an average of 0.3 crosslinkable silyl groups in one molecule obtained in Synthesis Example 7 A curable composition was prepared in the same manner as in Example 1 except that the containing polyoxyalkylene polymer P2 was used.

(Comparative Example 3)
As shown in Table 1, 100 parts by mass of the crosslinkable silyl group-containing acrylic modified polyoxyalkylene polymer A1 is blended as the component (A) and cured by the same method as in Example 1 except that the component (B) is not blended. A sex composition was prepared.

(Comparative Example 4)
As shown in Table 1, curing was performed in the same manner as in Example 1 except that 100 parts by mass of the crosslinkable silyl group-containing polyoxyalkylene polymer B1 was blended as the component (B) without blending the component (A). A sex composition was prepared.

  The following performance test was done about the obtained curable composition. The results are shown in Tables 2 and 3.

1) Adhesion test JIS A 1439: 1997 “Test method of sealing material for building” was performed according to “4.21 tensile adhesion test” (test temperature 23 ° C.). The test specimen was a test specimen placed on anodized aluminum, acrylic, or HIPS (High Impact Polystyrene) with the obtained curable composition as an adherend for 3 days or 14 days at 23 ° C. and 50% relative humidity. Cured and made. The fracture condition was evaluated as follows and indicated as initial adhesiveness. Moreover, after immersing the specimen prepared by curing at 23 ° C. and 50% relative humidity for 14 days in 50 ° C. water for 7 days or 14 days, a tensile test is performed to evaluate the breaking state and show the resistance to hot water. It was. The conditions and results are shown together in Table 2.
Judgment criteria for adhesion: A: Cohesive failure, O: When thin layer cohesive failure is confirmed, x: When interface fracture is confirmed.

2) Storage stability It evaluated as follows by the ratio of the viscosity after two-week progress at 50 degreeC, and an initial stage viscosity, and the result was shown in Table 3.
◎: Less than 1.2 times, ◯: 1.2 times to 1.4 times, ×: more than 1.4 times.

3) Deep Curability After blending each of the obtained curable compositions in a 50 cc PP pudding cup at 23 ° C. and 50% relative humidity in a pile, the surface was scraped off with a putty knife. did. After 24 hours, the cured part of the surface layer was peeled off so that the peeled surface was peeled off and the uncured adhered part was thoroughly wiped off, and the thickness was measured with five calipers. It is shown in Table 3.
Evaluation of deep-curing property: A: Deep-curing degree 2 mm or more, ○: Deep-curing degree 1.5 mm or more and less than 2 mm, x: Deep-curing degree 1.5 mm or less.

4) Paint adhesion The obtained composition was extended to a thickness of 3 mm, cured under conditions of 23 ° C. and 50% RH, and one day later, the paint shown in Table 2 was applied to the cured product surface with a brush. A grid pattern test (25 pieces) at intervals of 2 mm was performed using Nichiban cellophane tape after the day. The evaluation was based on the number of paints remaining on the surface, and the results are shown in Table 3.
Evaluation of paint adhesion: A: 20 or more, B: 10-19, X: 9 or less.

5) Contamination resistance A joint having a width of 20 mm, a depth of 5 mm, and a length of 5 mm was filled with the curable composition, cured at 23 ° C. and 50% relative humidity for 14 days, and then exposed outdoors. Outdoor exposure was conducted for 6 months at 45 ° C on the south side, and the contamination of the joints was examined. The results are shown in Table 3.
Contamination resistance evaluation: A: No contamination at all, X: Contamination is observed.

In Table 3, * 16 to * 22 are as follows.
* 16: Bildec; Solvent-based acrylic, manufactured by Dainippon Paint Co., Ltd. * 17: Buron; Water-based acrylic, manufactured by Dainippon Paint Co., Ltd. * 18: Odecoat G; Water-based acrylic, manufactured by Nippon Paint Co., Ltd. * 19: DAN UNI; water-based acrylic, manufactured by Nippon Paint Co., Ltd. * 20: Vinylose; solvent-based vinyl, manufactured by Dainippon Paint Co., Ltd. * 21: please coat; water-based acrylic, manufactured by SK Chemical Industries, Ltd. * 22: Tile rack EMA ; Solvent acrylic, manufactured by Nippon Paint Co., Ltd.

  As shown in Tables 2 and 3, all of the curable compositions of Examples 1 to 14 showed good storage stability, deep curability, paint adhesion, and stain resistance, and after curing for 3 days. Adhesiveness including initial adhesiveness and hot water resistant adhesiveness was very excellent. On the other hand, instead of Component (B), Comparative Example 1 using a crosslinkable silyl group-containing organic polymer having 1.7 crosslinkable silyl groups in the molecule and Crosslinkable silyl in the molecule instead of Component (B) In Comparative Example 2 using a crosslinkable silyl group-containing organic polymer having 0.3 groups, the initial adhesiveness, hot water resistant adhesiveness and paint adhesion were very poor, and Comparative Example 3 containing no component (B) Then, there existed a problem in initial adhesiveness, and in the comparative example 4 which does not contain a component (A), the problem had arisen in initial adhesiveness and warm water-resistant adhesiveness.

The curable composition of the present invention can be a one-component type or a two-component type as required, but can be suitably used particularly as a one-component type. The curable composition of the present invention is suitably used as a sealing material, an adhesive, a coating material, and the like. The curable composition of the present invention is excellent in workability, adhesion, water-resistant adhesion, storage stability, deep-curing property, paint adhesion, stain resistance and good initial adhesion without impairing basic performance. In particular, it is preferably used for adhesives and sealants for buildings, but can be used for various other automobiles, civil engineering, electric / electronic fields, and the like.

Claims (6)

(A) a crosslinkable silyl group-containing (meth) acrylic polymer,
(B) a crosslinkable silyl group-containing organic polymer having a weight average molecular weight of 2,000 to 50,000 having 0.5 to 1.5 crosslinkable silyl groups on average in one molecule, and (C ) A curable composition containing a curing catalyst.   The curable composition according to claim 1, wherein the component (A) is a crosslinkable silyl group-containing (meth) acryl-modified polyoxyalkylene polymer.   The component (B) is a crosslinkable silyl group-containing polyoxyalkylene polymer and / or a crosslinkable silyl group-containing (meth) acryl-modified polyoxyalkylene polymer. Curable composition.   The said component (B) has 0.7 or more and 1.5 or less crosslinkable silyl groups on the average in 1 molecule, Curability of any one of Claims 1-3 characterized by the above-mentioned. Composition.   The curable composition according to any one of claims 1 to 3, wherein the component (B) has 1.0 to 1.5 crosslinkable silyl groups on average in one molecule. Composition. (D) A silane coupling agent is further added, The curable composition of any one of Claims 1-4 characterized by the above-mentioned.