JP2005336401A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition having good physical properties, capable of keeping performances, such as a pot life and curing characteristics, unchanged even after stored, when compared with those given immediately after produced, and therefore excellent in storage stability. <P>SOLUTION: This curable composition contains (A) at least one kind of polymer selected from a group consisting of a crosslinkable silyl group-containing polyoxyalkylene-based polymer having a number-average molecular weight of ≥15,000 and a crosslinkable silyl group-containing (meth)acylic polymer having a number-average molecular weight of ≥10,000, (B) an ethoxysilane compound expressed by the formula: R<SB>n</SB>-Si(OCH<SB>2</SB>CH<SB>3</SB>)<SB>4-n</SB>, and (C) a curing catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable composition, and more particularly to a curable composition having excellent storage stability, physical properties, and workability.

  Room temperature curable compositions based on polyoxyalkylene organic polymers having reactive silicon groups can be used, for example, in building sealants (called modified silicone sealants) and are inexpensive and have excellent performance have. Various properties are required for these, but in addition to mechanical properties such as modulus, elongation at break and strength at break, long-term weather resistance is an important property, and many studies have been conducted so far. As a result, mechanical properties such as modulus, elongation at break, and strength at break can be obtained by adding a phthalate ester, polyester, polyether plasticizer, or the like to the curable composition. Are known.

  In addition, the weather resistance is a moisture curable composition containing, as main components, a polyoxyalkylene organic polymer having a reactive silicon group and a vinyl polymer having a reactive silicon group, and a polyoxyalkylene having a reactive silicon group. Patent Documents 1 to 3 and the like disclose that it can be improved as compared with the case of using only an organic polymer. However, this composition has improved weather resistance, but may have a problem in storage stability.

  Usually, a curable composition such as a sealing material is often stored for a long time until it is used after production, and the performance immediately after production is maintained even when the user uses the curable composition. It is particularly problematic that performance such as pot life and curing properties change greatly after storage.

In recent years, the aesthetics of buildings have improved and the appearance has become even more important. Therefore, the touch drying time (tack-free time) and the curing speed are very important from the point of view of aesthetics in construction. When a sealant having a low touch drying time and a slow curing rate is applied, surface tack remains for a long time. In the state where the tack remains on the surface, contamination with dust is severely undesirable in appearance. Further, when a sealing material having a fast drying time and a fast curing speed is applied, the pot life required for a series of operations until the surface is smoothed with a spatula is shortened, which is not preferable.
JP 59-122541 A JP 60-31556 A JP 2001-354846 A Japanese Unexamined Patent Publication No. Sho 63-112642 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 Japanese Unexamined Patent Publication No. 60-6747 JP-A-61-233043 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 Japanese Patent Laid-Open No. 11-80250 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 JP 2004-51830 A JP 2004-59782 A JP 2001-329065 A JP 2001-271055 A WO96 / 30421 publication WO97 / 18247 WO98 / 01480 publication WO98 / 40415 publication JP-A-9-208616 Japanese Patent Laid-Open No. 8-41117 JP-A-4-132706 JP-A 61-271306 Japanese Patent No. 2594402 JP 54-47782 A J. Am. Chem. Soc., 1994, 116, 7943 Macromolecules, 1994, 27, 7228 J. Am. Chem. Soc., 1995, 117, 5614 Macromolecules, 1995, 28, 7901 Science, 1996, 272, 866 Macromolecules, 1995, 28, 1721 Macromolecules, 1999, 32, 2872

  An object of the present invention is to provide a curable composition having excellent physical properties and excellent storage stability in which performance such as pot life and curing characteristics does not change immediately after production and after storage.

  In order to solve the above problems, the curable composition of the present invention comprises (A) a crosslinkable silyl group-containing polyoxyalkylene polymer having a number average molecular weight of 15,000 or more and a crosslinkability having a number average molecular weight of 10,000 or more. Containing at least one polymer selected from the group consisting of silyl group-containing (meth) acrylic polymers, (B) an ethoxysilane compound represented by the following formula (1), and (C) a curing catalyst. Features. In the present invention, acryl and methacryl are collectively referred to as (meth) acryl.

_{R n -Si (OCH 2 CH 3} ) 4-n ··· (1)
(In Formula 1, R is a hydrogen atom or a C1-C20 monovalent organic group, and when a plurality of R are present, they may be the same or different, and n is 0-3. (It is an integer.)

  It is preferable that the curable composition of the present invention further contains (D) an organic polymer having less than one crosslinkable silyl group in one molecule.

  It is preferable that the curable composition of the present invention further contains (E1) an amine compound and (E2) a carbonyl compound.

  The curable composition of the present invention preferably further contains (E3) a compound that reacts with water to form an amine compound.

  The (meth) acrylic polymer preferably contains a crosslinkable silyl group at the molecular chain end. Although the manufacturing method of this crosslinkable silyl group containing (meth) acrylic-type polymer is not specifically limited, Control radical polymerization method is preferable, Living radical polymerization method is more preferable, Atom transfer radical polymerization method is further more preferable.

  It is preferable that the polymer (A) contains 1.5 to 6 crosslinkable silyl groups in one molecule.

  According to the present invention, it has excellent physical properties, has excellent storage stability that does not change performance such as pot life and curing characteristics immediately after production and after storage, and is suitably used as an adhesive or a sealing material. A composition can be provided.

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

The curable composition of the present invention contains the following components (A) to (C) as essential components.
(A) selected from the group consisting of a crosslinkable silyl group-containing polyoxyalkylene polymer having a number average molecular weight of 15,000 or more and a crosslinkable silyl group-containing (meth) acrylic polymer having a number average molecular weight of 10,000 or more. At least one polymer;
(B) an ethoxysilane compound represented by the following formula (1):
(C) A curable composition containing a curing catalyst.

_{R n -Si (OCH 2 CH 3} ) 4-n ··· (1)
(In Formula (1), R is a hydrogen atom or a C1-C20 monovalent organic group, and when two or more R exist, they may be the same or different. It is an integer of 3.)

  As the polymer (A), a crosslinkable silyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing (meth) acrylic polymer, and a mixture thereof are used. The number average molecular weight of the crosslinkable silyl group-containing polyoxyalkylene polymer is 15,000 or more, preferably 15,000 to 30,000. The number average molecular weight of the crosslinkable silyl group-containing (meth) acrylic polymer is 10,000 or more, preferably 10,000 to 20,000. These polymers having a narrow molecular weight distribution are easy to handle because of their low viscosity before curing, and physical properties such as strength, elongation and modulus after curing are suitable.

  In the polymer (A), the crosslinkable silyl group is a silicon-containing group having a hydroxyl group or hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. The crosslinkable silyl group is not particularly limited, but it is generally 1 to 6 in one molecule from the viewpoint of the curability of the composition and the physical properties after curing, and 1.5 to 6 More preferably. By using a polymer containing 1.5 to 6 crosslinkable silyl groups in one molecule, problems of bubble generation and deterioration of appearance can be prevented. Further, the crosslinkable silyl group is preferably one represented by the following general formula (2) which is easily crosslinked and easy to produce.

[In Formula (2), R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. An aralkyl group of ˜20 is preferred, and a methyl group is most preferred. When a plurality of R ¹ are present, they may be the same or different. X is a hydroxyl group or a hydrolyzable group, and is a group selected from a halogen atom, hydrogen atom, hydroxyl group, alkoxy group, acyloxy group, ketoximate group, amide group, acid amide group, mercapto group, alkenyloxy group and aminooxy group Are preferred, alkoxy groups are more preferred, and methoxy groups are most preferred. When a plurality of X are present, they may be the same or different. a is 1, 2 or 3, and 2 is most preferable. ]

  In the polymer (A), when there are a plurality of crosslinkable silyl groups, these may be the same or different, and further, the number of a in the formula (2) may be the same or different. May be. Two or more organic polymers having different crosslinkable silyl groups may be used. The position of the crosslinkable silyl group is not particularly limited, but the molecular chain terminal is preferred.

  Specifically, as the polymer (A), polyoxyalkylene polymers containing a crosslinkable silyl group as disclosed in Patent Documents 1 and 4 to 22, Patent Documents 2, 3 and 18 to (Meth) acrylic polymer containing a crosslinkable silyl group as disclosed in No. 42, and a mixture thereof, and a (meth) acrylic polymer having a crosslinkable silyl group at the terminal are preferred examples. Further, a mixture of the (meth) acrylic polymer having the crosslinkable silyl group and the polyoxyalkylene polymer having the crosslinkable silyl group is more preferable.

  The production method of the polymer (A) is not particularly limited, and a known synthesis method can be used. When the (meth) acrylic polymer containing a crosslinkable silyl group at the molecular end is used as the polymer (A), it is preferable to use a polymer synthesized by a radical polymerization method.

  The radical polymerization method uses a general radical polymerization method in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound, a peroxide, or the like as a polymerization initiator. The control radical polymerization method can introduce a specific functional group at a controlled position. In the present invention, a (meth) acrylic polymer synthesized by a controlled radical polymerization method is more effective.

  The controlled radical polymerization method further includes a chain transfer agent method in which a vinyl polymer having a functional group at the terminal is obtained by polymerization using a chain transfer agent having a specific functional group, and a polymerization growth terminal is terminated. It can be divided into the living radical polymerization method that grows without causing etc.

  The living radical polymerization method has an arbitrary molecular weight, a molecular weight distribution is narrow, a polymer having a low viscosity can be obtained, and a monomer having a specific functional group can be introduced at an arbitrary position. Is particularly preferred. In the present invention, in addition to the polymerization in which the terminal always has activity and the molecular chain grows, the terminal inactivated and the activated one are grown while in equilibrium. Living polymerization is also included in living polymerization.

  Examples of the living radical polymerization method include a method using a cobalt porphyrin complex as disclosed in Non-Patent Document 1, a method using a radical scavenger such as a nitroxide compound as disclosed in Non-Patent Document 2, and the like. Atom transfer radical polymerization (Atom Transfer) in which vinyl monomers are polymerized using an organic halogen compound or sulfonyl halide compound as disclosed in Patent Documents 3 to 6 and Patent Documents 43 to 48 as an initiator and a transition metal complex as a catalyst. Radical Polymerization (ATRP) method and the like. The living radical polymerization method is not particularly limited, but the atom transfer radical polymerization method is preferable. In the present invention, a reverse atom transfer radical polymerization method, that is, a high oxidation state when a normal atom transfer radical polymerization catalyst generates radicals, for example, Cu (II) when Cu (I) is used as a catalyst, is used. In addition, a method in which a general radical initiator such as a peroxide is allowed to act on, and as a result an equilibrium similar to that of atom transfer radical polymerization (see, for example, Non-Patent Document 7) is also used. Is included.

  Examples of the chain transfer agent method include a method of obtaining a halogen-terminated polymer using a halogenated hydrocarbon as disclosed in Patent Document 49 as a chain transfer agent, and Patent Documents 50 to 52. Examples thereof include a method for obtaining a hydroxyl-terminated polymer using such a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent.

  Hereinafter, the atom transfer radical polymerization method will be described. As an initiator of the atom transfer radical polymerization method, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position). Alternatively, a sulfonyl halide compound or the like is used.

  Further, as an initiator of atom transfer radical polymerization, an organic halide having a functional group other than a functional group for initiating polymerization, such as an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, an amide group, or the like Halogenated sulfonyl compounds can also be used. In this case, a vinyl polymer having a functional group at one end of the main chain and a growth terminal structure of atom transfer radical polymerization at the other main chain end is synthesized. In the present invention, it is preferable to use an organic halide or sulfonyl halide compound having a crosslinkable silyl group. In this case, a polymer having a crosslinkable silyl group at one end and a halogen end at the other end is obtained, and a polymer having a crosslinkable silyl group at both ends is obtained by substituting the halogen end. be able to.

  In the present invention, the vinyl monomer used in the polymerization is one or more acrylic monomers such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, and the like. It is more preferable that the main component is (meth) acrylic acid ester such as alkyl (meth) acrylate and alkoxyalkyl (meth) acrylate.

  Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylic acid Lauryl, alkyl (meth) acrylates such as tridecyl (meth) acrylate and stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and tricyclodecynyl (meth) acrylate ( (Meth) acrylic acid alicyclic alkyl, (meth) acrylic acid 2-methyl Examples include heteroatom-containing (meth) acrylic acid esters such as xylethyl, dimethylaminoethyl (meth) acrylate, chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. . Among these, methyl methacrylate, ethyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl acrylate, and cyclohexyl acrylate are particularly preferable in terms of balancing plasticity. Other than these (meth) acrylic acid esters, other copolymerizable monomers may be used as long as the physical properties are not impaired. Examples of such monomers include α-olefins such as ethylene, propylene and isobutylene; chloroethylenes such as vinyl chloride and vinylidene chloride; and alkyl vinyl ethers such as ethyl vinyl ether and butyl vinyl ether.

  Although there is no limitation in particular as a transition metal complex used as a polymerization catalyst, the metal complex complex which uses a 7th, 8th, 9th, 10th, or 11th group element of a periodic table as a central metal is preferable, and a zerovalent A complex of copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel is more preferred, and a copper complex is particularly preferred.

  Examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as a polyamine is added.

Further, tristriphenylphosphine complex of divalent ruthenium chloride [RuCl ₂ (PPh ₃ ) ₃ ], bistriphenylphosphine complex of divalent iron [FeCl ₂ (PPh ₃ ) ₂ ], bistriphenylphosphine of divalent nickel A complex [NiCl ₂ (PPh ₃ ) ₂ ] and a divalent nickel bistributylphosphine complex [NiBr ₂ (PBu ₃ ) ₂ ] are also suitable as the catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator.

  The polymerization can be carried out without solvent or in various solvents. The polymerization temperature is preferably in the range of 0 to 200 ° C, more preferably in the range of room temperature to 150 ° C.

  Acrylics having a halogen at the end by radical polymerization of vinyl monomers containing acrylic monomers as the main component, using organic halides or sulfonyl halides as initiators and transition metal complexes as catalysts. A polymer is produced. The (meth) acrylic polymer having a crosslinkable silyl group at the molecular chain end used in the present invention can be obtained by converting the halogen of the acrylic polymer having the halogen at the end to a crosslinkable silyl group. . The conversion method is not particularly limited, and a known method (for example, see Patent Documents 18 to 20, 39 to 42, etc.) can be used.

As said ethoxysilane compound (B), the compound shown by following formula (1) and its partial hydrolysis-condensation product are used.
_{R n -Si (OCH 2 CH 3} ) 4-n ··· (1)
(In Formula (1), R is a hydrogen atom or a C1-C20 monovalent organic group, a C1-C20 alkyl group, a C6-C20 aryl group, or C7-C20. Aralkyl groups are preferred, and when a plurality of R are present, they may be the same or different, and n is an integer of 0 to 3.)

  Specific examples of the ethoxysilane compound include tetraethoxysilane; alkyltriethoxysilane such as methyltriethoxysilane and octadecyltriethoxysilane; aryltriethoxysilane such as phenyltriethoxysilane; aminopropyltriethoxysilane, amino Aminosilanes such as propylethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylethyldiethoxysilane; glycidoxypropyltriethoxysilane, glycidoxy Epoxy silanes such as propylethyldiethoxysilane, β- (3,4-epoxycyclohexylpropyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexylpropyl) diethyldiethoxysilane Mercaptosilanes such as γ-mercaptopropyltriethoxysilane and γ-mercaptopropylethyldiethoxysilane; vinyltriethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylethyldi Vinyl type unsaturated group-containing silanes such as ethoxysilane; chlorine atom-containing silanes such as γ-chloropropyltriethoxysilane; isocyanate silanes such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropylethyltriethoxysilane; Examples include hydrosilanes such as methyldiethoxysilane and partial hydrolysis condensates of these ethoxysilane compounds.

  Examples of the partially hydrolyzed condensate of the ethoxysilane compound include those obtained by adding water to an ethoxysilane compound such as the tetraethoxysilane and triethoxysilane and condensing them by partial hydrolysis, and the tetraethoxysilane and the like. Examples include those obtained by hydrolyzing an ethoxysilane compound in an alcohol solvent in the presence of an acidic substance and water.

  The blending ratio of the component (B) is not particularly limited, but it is preferably blended so as to be 0.01 to 20 parts by weight, particularly 0.5 to 20 parts by weight with respect to 100 parts by weight of the component (A). . The said ethoxysilane compound and its hydrolysis condensate may be used independently and may be used together 2 or more types.

  The curing catalyst (C) is not particularly limited as long as it exhibits the action of a curing catalyst on the polymer (A). Examples thereof include organometallic compounds and amines, and particularly silanol condensation catalysts. Is preferably used. 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; Co tetra acetylacetonate, chelate compounds such as titanium tetraacetyl acetonate; lead octylate; silanol condensation catalyst as known other acidic catalysts and basic catalysts, and the like. Of these, dibutyltin diacetylacetonate is particularly preferred because it is a liquid having a high crosslinking rate, toxicity and relatively low luminescence.

  The blending ratio of the curing catalyst (C) is from 0.1 to 30 parts by weight, particularly from 0.5 to 20 parts by weight, based on 100 parts by weight of the polymer (A), from the viewpoints of crosslinking speed and physical properties of the cured product. It is preferable to use it. These curing catalysts may be used alone or in combination of two or more.

  It is preferable to further blend an organic polymer (D) containing less than one crosslinkable silyl group in one molecule into the curable composition of the present invention. As the polymer (D), an organic polymer in which the number of crosslinkable silyl groups contained in the molecule is 0 or more and less than 1 is used. The crosslinkable silyl group is preferably the one represented by the general formula (2). Specifically, the polyoxyalkylene polymer, which contains 0 to less than 1 crosslinkable silyl group on average in one molecule, and each main chain may contain an organosiloxane, (meta ) Acrylic polymers, vinyl-modified polyoxyalkylene polymers, vinyl polymers, polyester polymers, copolymers and mixtures thereof are preferred examples. In particular, from the viewpoint of physical properties such as tensile adhesiveness and modulus after curing, the main chain contains less than 1, preferably less than 0.7 crosslinkable silyl groups per molecule, and each main chain is an organosiloxane. A polyoxyalkylene polymer, a (meth) acrylic polymer, a (meth) acryl-modified polyoxypropylene polymer, and a copolymer or a mixture thereof are preferable.

  The method for producing the polymer (D) is not particularly limited. For example, in the method for producing a crosslinkable silyl group-containing organic polymer disclosed in Patent Documents 1 to 42, the crosslinkability existing in one molecule. It can be produced by making the number of silyl groups less than one. Specifically as a manufacturing method of the said polymer (D), the manufacturing method etc. which were used in the synthesis example 8 mentioned later can be mentioned.

  In the present invention, the polymer (D) has a number average molecular weight of 2,000 or more and 50,000 or less, more preferably 2,000 or more and 30,000 or less and a narrow molecular weight distribution because the viscosity before curing is low. It is easy to handle, and physical properties such as strength, elongation and modulus after curing are suitable. The said polymer (D) may be used only by 1 type, and may be used together 2 or more types.

  The blending ratio of the polymer (D) is not particularly limited, but it is preferable to use 1 to 400 parts by weight of the polymer (D) with respect to 100 parts by weight of the polymer (A). More preferably, parts by weight are used.

  In addition, it is preferable to further add (E1) an amine compound and (E2) a carbonyl compound to the curable composition of the present invention in order to improve non-staining properties.

  The amine compound (E1) is not particularly limited, and examples thereof include primary and / or secondary amines and amine compounds having at least one alkoxysilyl group in one molecule.

  Examples of the primary amine include monoamines such as butylamine, hexylamine, heptylamine, 2-ethylhexylamine, octylamine, 3-methoxypropylamine, tetradecylamine, pentadecylamine, cetylamine, stearylamine, and trimethylcyclohexylamine. , Benzylamine, aniline and the like. Examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 1,7-diaminoheptane, Trimethylhexamethylenediamine, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20- Diaminoeicosane, 1,2-diaminohenticosane, 1,2-diaminodocosane, 1,23-diaminotricosane, 1,24-diaminotetracosane, isophoronediamine, diaminodicyclohexylmethane, 3,9- Bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, xylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, polyoxyethylenediamine, polyoxypropylenediamine, etc. To mention It can, as a polyamine, such as hexane tri (methylamino) can be exemplified. Examples of secondary amines include monoamines such as dilaurylamine, distearylamine, and methyllaurylamine, N, N'-dilaurylpropylamine, N, N'-distearylbutylamine, and N-butyl-N'-. Examples thereof include diamines such as laurylethylamine, N-butyl-N′-laurylpropylamine, and N-lauryl-N′-stearylbutylamine. Examples of the primary and secondary mixed amines include N-lauryl propylene diamine and N-stearyl propylene diamine. Examples of the primary and secondary mixed polyamines include diethylenetriamine, triethylenetetramine, and methylaminopropylamine.

  Examples of the amine compound having at least one alkoxysilyl group in one molecule include those represented by the following general formula (3).

[In the formula (9), m = 0, 1 or 2, R ² and R ³ are the same or different and each is a hydrocarbon group having 1 to ⁴ carbon atoms, and R ⁴ is a hydrocarbon having 1 to 10 carbon atoms. The group Y represents a hydrogen atom or an aminoalkyl group having 1 to 4 carbon atoms. ]

Here, examples of R ² and R ³ include alkyl groups such as methyl, ethyl, propyl, and butyl, and alkenyl groups such as vinyl, allyl, propenyl, and butenyl, and alkyl groups are particularly preferable. Examples of R ⁴ include alkylene groups such as methylene, ethylene, propylene, and butylene, arylene groups such as phenylene, alkylene arylene groups, and the like, and alkylene groups are particularly preferable. m is preferably 0 or 1.

  Specific examples include compounds represented by the following formulas (4) to (11), N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyl. Examples include aminosilanes typified by methyldimethoxysilane. Among these, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and the like are adhesive. Is particularly preferable.

  Examples of the carbonyl compound (E2) include known compounds such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-amylaldehyde, isohexylaldehyde, diethylacetaldehyde, glyoxal, benzaldehyde, and phenylacetaldehyde. Aldehydes: Cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, methylcyclohexanone, trimethylcyclohexanone; acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone, diethyl ketone, Aliphatic keto such as dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone Aromatic ketones such as acetophenone, benzophenone, propiophenone; and the following general formula (12) such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, diethyl malonate, methyl ethyl malonate, dibenzoylmethane However, it is not limited to these. Of these, methyl isobutyl ketone, dipropyl ketone, phenylacetaldehyde, and β-dicarbonyl compounds having an active methylene group [compound represented by the following general formula (12)] are more preferred.

[In the formula (12), R ⁵ and R ⁶ are the same or different and each is an alkyl group having 1 to 16 carbon atoms (for example, methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl, decyl, undecyl). Hexadecyl, etc.), an aryl group having 6 to 12 carbon atoms (for example, phenyl, tolyl, hexyl, naphthyl, etc.), or an alkoxyl group having 1 to 4 carbon atoms (for example, methoxy, ethoxy, prooxy, putoxy, etc.). means. ]

  The component (E1) and the component (E2) cause a dehydration reaction in the blend. The dehydration reaction may be carried out by a reaction treatment such as a heat treatment as necessary, but can be progressed over time without performing a special step.

  The blending ratio of the components (E1) and (E2) is not particularly limited, but the components (E1) and (E2) are each 0.05 to 50 parts by weight, particularly 0. It is preferable to mix | blend so that it may become 1-20 weight part. Further, [molar amount of component (E1)] / [molar amount of component (E2)] is preferably in the range of 0.1 to 5.0, and preferably in the range of 0.5 to 2.0. Further preferred. The amine compound and the carbonyl compound may be used alone or in combination of two or more.

  It is preferable to further add (E3) a compound that reacts with water to form an amine compound in the curable composition of the present invention, since the non-staining property can be remarkably improved. Specific examples of the component (E3) include an amine compound ketimine compound, enamine compound, and / or aldimine compound from the viewpoint of easy availability of raw materials, storage stability, and reactivity with water. As mentioned.

  The ketimine compound, enamine compound and aldimine compound can be obtained by dehydration reaction of an amine compound and a carbonyl compound, respectively. As the amine compound and the carbonyl compound, the amine compound and the carbonyl compound mentioned in the description of the components (E1) and (E2) can be used in the same manner. The manufacturing method of the said component (E3) is not specifically limited, A well-known method can be used.

  The blending ratio of the component (E3) is not particularly limited, but it is preferably 0.05 to 50 parts by weight, particularly 0.1 to 20 parts by weight with respect to 100 parts by weight of the component (A). . The compound which reacts with water to produce an amine compound may be used alone or in combination of two or more.

  In order to improve the designability, it is preferable to further add a scaly or granular material to the curable composition of the present invention. In particular, a scaly substance colored in a predetermined color is suitable because of its high design. As the scale-like or granular substance, natural products such as silica sand and mica, synthetic rubber, synthetic resin, inorganic materials such as alumina and the like may be used, and may be colored in an appropriate color as necessary. The particle size is preferably about 0.01 to 5 mm, and in the case of a scaly substance, the thickness is preferably about 1/10 to 1/5 of the diameter.

  In addition to the above-described components, the curable composition of the present invention includes an adhesion-imparting agent, a physical property modifier, a filler, a plasticizer, a thixotropic agent, a dehydrating agent (storage stability improving agent), and an adhesive as necessary. Substances such as imparting agents, anti-sagging agents, 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.

  When a colorant such as a pigment is blended in the curable composition of the present invention, a colorant may be blended in advance in the composition, or the colorant is added at the stage of use after the curable composition is manufactured. You may mix | blend and a mixing | blending time is not specifically limited.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

(Synthesis Example 1) Synthesis of Acrylic Polymer A1 Having a Crosslinkable Silyl Group at the Terminal 1. Into a 500 mL flask, 1.80 g (12.6 mmol) of copper bromide and 21 mL of acetonitrile were charged, and heated and stirred at 70 ° C. for 20 minutes under a nitrogen stream. did. To this, 5.05 g (14.0 mmol) of diethyl 2,5-dibromoadipate, 60 mL (0.418 mol) of butyl acrylate, 84 mL (0.775 mol) of ethyl acrylate, 63 mL (0.489 mol) of 2-methoxyethyl acrylate ) Was added, and the mixture was further heated and stirred at 80 ° C. for 20 minutes. To this was added 0.262 mL (1.26 mmol) of pentamethyldiethylenetriamine (hereinafter referred to as triamine) to initiate the reaction. Further, 0.087 mL (0.42 mmol) of triamine was added. 240 minutes after the start of the reaction, 62 mL of acetonitrile, 62 mL (0.42 mol) of 1,7-octadiene, and 0.87 mL (4.18 mmol) of triamine were added, followed by continued heating and stirring at 80 ° C., followed by heating after 620 minutes from the start of the reaction. Stopped. The reaction solution was heated under reduced pressure to remove volatile components, diluted with toluene and filtered, and the filtrate was concentrated to obtain a polymer.

  The obtained polymer and Kyoward 500SH (manufactured by Kyowa Chemical: 2 parts by weight with respect to 100 parts by weight of the polymer) and Kyoward 700SL (manufactured by Kyowa Chemical: 2 parts by weight with respect to 100 parts by weight of the polymer) were converted into xylene ( 100 parts by weight with respect to 100 parts by weight of the polymer) and stirred at 130 ° C. After 3 hours, aluminum silicate was filtered, and the volatile matter in the filtrate was distilled off by heating under reduced pressure. The polymer was devolatilized at 180 ° C. for 12 hours (the degree of vacuum was 10 torr or less) to desorb the Br group from the copolymer.

  The obtained polymer and Kyoward 500SH (manufactured by Kyowa Chemical: 3 parts by weight with respect to 100 parts by weight of the polymer) and Kyoward 700SL (manufactured by Kyowa Chemical: 3 parts by weight with respect to 100 parts by weight of the polymer) were converted into xylene ( 100 parts by weight with respect to 100 parts by weight of the polymer) and stirred at 130 ° C. After 5 hours, aluminum silicate was filtered, and the volatile matter in the filtrate was distilled off by heating under reduced pressure to obtain an alkenyl-terminated polymer [1].

The number average molecular weight of the obtained polymer [1] was 19000 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.1. Moreover, the average number of alkenyl groups introduced per molecule of the oligomer was 1.9 from ¹ H NMR analysis.

Next, in a 200 mL pressure-resistant glass reaction vessel, the above polymer [1] (23.3 g), dimethoxymethylhydrosilane (2.55 mL, 20.7 mmol), dimethyl orthoformate (0.38 mL, 3.45 mmol), and A platinum catalyst was charged. However, the amount of the platinum catalyst used was 2 × 10 ⁻⁴ equivalent in terms of molar ratio with respect to the alkenyl group of the polymer [1]. The reaction mixture was heated at 100 ° C. for 3 hours. By distilling off the volatile components of the mixture under reduced pressure, a polymer A1 of poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) having a methyldimethoxysilyl group at the terminal was obtained.

The number average molecular weight of the obtained polymer A1 was 20000 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.2. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis, it was 1.9.

(Synthesis Example 2) Synthesis of Acrylic Polymer A2 Having a Crosslinkable Silyl Group at the Terminal In the same manner as in Synthesis Example 1, it has a methyldimethoxysilyl group at the terminal and the number average molecular weight is 18000 by GPC measurement (polystyrene conversion). The molecular weight distribution was 1.2. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis, 1.9 polymer A2 was obtained.

(Synthesis Example 3) Synthesis of Acrylic Polymer A3 Having a Crosslinkable Silyl Group at the Terminal In the same manner as in Synthesis Example 1, it has a methyldimethoxysilyl group at the terminal and the number average molecular weight is 16000 by GPC measurement (polystyrene conversion). The molecular weight distribution was 1.2. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis, 1.9 polymer A3 was obtained.

(Synthesis Example 4) Synthesis of Acrylic Polymer 4 Having a Crosslinkable Silyl Group at the Terminal In the same manner as in Synthesis Example 1, the terminal has a methyldimethoxysilyl group and the number average molecular weight is 8000 by GPC measurement (polystyrene conversion). The molecular weight distribution was 1.2. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis, 1.9 polymer 4 was obtained.

(Synthesis Example 5) Synthesis of polyoxyalkylene polymer A5 having a crosslinkable silyl group at the terminal Hydroxyl group obtained by reacting propylene oxide with propylene glycol as an initiator and in the presence of a zinc hexacyanocobaltate-glyme complex catalyst A polyoxypropylene having a valence converted molecular weight of 18,000 and Mw / Mn = 1.3 was obtained. The reaction product is reacted with methyldimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst, having a methyldimethoxysilyl group at the terminal and an average of 1.8 crosslinkable silyl groups in one molecule. A polymer A5 having a molecular weight of 18,000 was obtained.

(Synthesis Example 6) Synthesis of polyoxyalkylene polymer A6 having a crosslinkable silyl group at the terminal In the same manner as in Synthesis Example 5, the terminal has a methyldimethoxysilyl group at the terminal, and an average of 1.8 per molecule. A polymer A6 having a number average molecular weight of 16,000 and having one crosslinkable silyl group was obtained.

(Synthesis Example 7) Synthesis of polyoxyalkylene polymer 7 having a crosslinkable silyl group at the end In the same manner as in Synthesis Example 5, it has a methyldimethoxysilyl group at the end, and an average of 1.8 per molecule. A polymer 7 having a number average molecular weight of 12,000 having one crosslinkable silyl group was obtained.

(Synthesis Example 8) Synthesis of Acrylic Polymer D1 Having a Crosslinkable Silyl Group at the End In the same manner as in Synthesis Example 1, it has a methyldimethoxysilyl group at the end and an average of 0.4 per molecule. A polymer D1 having a number average molecular weight of 10,000 having a crosslinkable silyl group was obtained.

(Synthesis Example 9) Synthesis of Ketimine Compound After heating and dissolving stearylamine (Kao Co., Ltd., Farmin 80, amine value 207) 500 g in a heating apparatus and a stirring vessel with an ester tube, methyl isobutyl ketone was stirred. (Molecular weight: 100.2) 203 g was added. To this was further added 130 g of toluene, followed by heating and stirring at 110 to 150 ° C. for 3 hours to dehydrate the water through an ester tube. Subsequently, the pressure was reduced to remove excess methyl isobutyl ketone and toluene to obtain a ketimine compound.

(Example 1)
As shown in Table 1, the polymer (A1) obtained in Synthesis Example 1 as the component (A) crosslinkable silyl group-containing polymer, and polyoxypropylene glycol and calcium carbonate as the component (D) are respectively charged in predetermined amounts and heated. The mixture was stirred under reduced pressure at 110 ° C. for 2 hours to dehydrate the compounded material. Further, vinyltriethoxysilane as component (B), dibutyltin diacetylacetonate as component (C) curing catalyst, and aminosilane compound as silane coupling agent are added in predetermined amounts, and mixed with stirring to prepare a curable composition. did.

(Examples 2-11 and Comparative Examples 1-3)
As shown in Table 1, a curable composition was prepared in the same manner as in Example 1 except that the compounding material and the compounding ratio were changed.

The blending amount in Table 1 is indicated by (g), and (* 1 to * 20) is as follows.
* 1: Polymer A1 obtained in Synthesis Example 1
* 2: Polymer A2 obtained in Synthesis Example 2
* 3: Polymer A3 obtained in Synthesis Example 3
* 4: Polymer A5 obtained in Synthesis Example 5
* 5: Polymer A6 obtained in Synthesis Example 6
* 6: Polymer 4 obtained in Synthesis Example 4
* 7: Polymer 7 obtained in Synthesis Example 7
* 8: Vinyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE1003)
* 9: Tetraethoxysilane (manufactured by Colcoat Co., Ltd., trade name: ethyl silicate 28)
* 10: Vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM1003)
* 11: Dibutyltin diacetylacetonate (manufactured by Nitto Kasei Co., Ltd., trade name: U-220)
* 12: Asahi Glass Co., Ltd., trade name: PML3012
* 13 Product name: UP-1000, manufactured by Toagosei Co., Ltd.
* 14: Polymer D1 obtained in Synthesis Example 8 (number of crosslinkable silyl groups: 0.4)
* 15: Ketimine compound obtained in Synthesis Example 9 * 16: Stearylamine (trade name: Farmin 80, manufactured by Kao Corporation)
* 17: Methyl isobutyl ketone * 18: Shiraishi Calcium Industry Co., Ltd., trade name: Whiten SB
* 19: Maruo Calcium Co., Ltd., trade name: Calfine 200M
* 20: Aminosilane compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM603)

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

1) Tack-free time measurement test The tack-free time was measured immediately after production of the curable composition and after storage (50 ° C. × 1, 2, 4 weeks). It was constructed to a thickness of 5 mm under the conditions of 23 ° C. and 50% RH. The surface dry state by finger touch was confirmed, and the time during which the composition did not adhere to the finger was measured.

2) Physical property test It tested based on "4.21 tensile adhesiveness test" of JIS A1439: 1997 "Test method of sealing material for construction" (test temperature 23 degreeC). In addition, the test body was produced by curing the test body casted on anodized aluminum using the obtained curable composition as an adherend for 14 days at 23 ° C. and 50% relative humidity and for 14 days at 30 ° C. Evaluation was made as ○ when the elongation rate exceeded 350%, and x when the elongation rate was 350% or less.

3) Workability confirmation (scalar repair) test A spatula repairable time immediately after the production of the curable composition and after storage (50 ° C. × 4 weeks) was measured. The case where the spatula repairable time exceeded 40 minutes was evaluated as ◯, the case of 20 minutes to 40 minutes as Δ, and the case of 20 minutes or less as ×.

4) Surface contamination test The curable composition was formed into a sheet having a thickness of 10 mm, exposed outdoors at 45 ° south for 6 months, and visually checked for surface contamination. The case where the contamination was severe was evaluated as x, and the case where there was almost no contamination was evaluated as ○.

  As shown in Table 2, the curable compositions of Examples 1 to 11 can improve workability as a spatula repairable time while maintaining good tensile properties (particularly high elongation).

Claims (7)

(A) selected from the group consisting of a crosslinkable silyl group-containing polyoxyalkylene polymer having a number average molecular weight of 15,000 or more and a crosslinkable silyl group-containing (meth) acrylic polymer having a number average molecular weight of 10,000 or more. At least one polymer;
(B) A curable composition containing an ethoxysilane compound represented by the following formula (1) and (C) a curing catalyst.
_{R n -Si (OCH 2 CH 3} ) 4-n ··· (1)
(In Formula 1, R is a hydrogen atom or a C1-C20 monovalent organic group, and when a plurality of R are present, they may be the same or different, and n is 0-3. (It is an integer.) (D) The curable composition according to claim 1, further comprising an organic polymer having less than one crosslinkable silyl group in one molecule. The curable composition according to claim 1 or 2, further comprising (E1) an amine compound and (E2) a carbonyl compound. (E3) The curable composition according to any one of claims 1 to 3, further comprising a compound that reacts with water to produce an amine compound.   The curable composition according to any one of claims 1 to 4, wherein the (meth) acrylic polymer contains a crosslinkable silyl group at a molecular chain terminal.   The curable composition according to claim 1, wherein the (meth) acrylic polymer is a polymer synthesized by a living radical polymerization method.   The said polymer (A) contains 1.5-6 crosslinkable silyl groups in 1 molecule, The curable composition of any one of Claims 1-6 characterized by the above-mentioned. .