JP2010059397A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition causing no deterioration in initial curability and mechanical properties, exhibiting excellent storage stability of curability and viscosity, and giving a cured product with improved surface discoloration. <P>SOLUTION: The curable composition comprises a vinyl polymer (I) having at least one crosslinkable silyl group on the average, a guanidine compound (II), and a carboxylic acid (III). In the curable composition, a content of the carboxylic acid (III) is 1-10 equivalents by molar ratio based on a content of the guanidine compound (II). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curable composition comprising a vinyl polymer (I) having an average of at least one crosslinkable silyl group, a guanidine compound (II), and a carboxylic acid (III). It is related with the curable composition whose content of carboxylic acid (III) contained in a thing is 1-10 equivalent in molar ratio with respect to content of guanidine compound (II).

  Various vinyl polymers having a crosslinkable functional group are known. For example, a synthesis method of a (meth) acrylic polymer having an alkenyl group at the terminal using an alkenyl group-containing disulfide as a chain transfer agent (see Patent Document 1 and Patent Document 2 below), or using a disulfide having a hydroxyl group A method for obtaining a (meth) acrylic polymer having an alkenyl group at the terminal by synthesizing a vinyl polymer having a hydroxyl group at both ends and further utilizing the reactivity of the hydroxyl group (see Patent Document 3 below) In addition, a vinyl polymer having hydroxyl groups at both ends is synthesized using polysulfide having hydroxyl groups, and further, a (meth) acrylic polymer having a silyl group at the ends by utilizing the reactivity of hydroxyl groups. A method for obtaining coalescence (see Patent Document 4 below) has already been disclosed.

  On the other hand, an acrylic rubber polymer into which an active chlorine group or an epoxy group has been used has conventionally been used for an acrylic rubber composition for molding, and a molded product having good heat resistance and oil resistance has been obtained. In order to cope with the need to improve heat resistance, a technique for introducing a vinyl group-containing organosilicon group has been proposed (see Patent Document 5 and Patent Document 6 below).

  A curable composition containing a polymer having an alkenyl group or a crosslinkable silyl group in the side chain obtained by these methods is used for highly weather-resistant paints and the like.

  However, although these methods can easily produce a polymer, it is difficult to reliably introduce silicon groups at both ends of the polymer, and the cured product has insufficient rubber properties such as elongation. Thus, a curable composition having satisfactory characteristics could not be obtained. In order to reliably introduce functional groups at both ends, a large amount of chain transfer agent had to be used, which was a problem in the production process. In these methods, since ordinary radical polymerization is used, it is difficult to control the molecular weight and molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) of the obtained polymer.

  If a vinyl polymer having a crosslinkable silyl group at the molecular chain end can be obtained by a simple method, it is possible to obtain a cured product having excellent cured product properties compared to those having a crosslinkable group in the side chain. it can. Therefore, many researchers have studied the production method so far, but it is not easy to produce them industrially.

  Therefore, in order to solve this problem, a method for producing a (meth) acrylic polymer having a functional group at the terminal has been developed. In particular, polymers synthesized using living radical polymerization can arbitrarily control the molecular weight and molecular weight distribution, and can quantitatively introduce functional groups at the ends. As a result, weather resistance, heat resistance, oil resistance And can be used for curable compositions having good mechanical properties that cannot be obtained with the above polyether polymers, hydrocarbon polymers, or polyester polymers (Patent Documents 7 to 17 listed below). reference).

  On the other hand, an organic polymer containing at least one crosslinkable silyl group in the molecule is crosslinked at the room temperature by the formation of a siloxane bond accompanied by hydrolysis reaction of the crosslinkable silyl group by moisture or the like, and rubbery cured It is known that it has the property that a product is obtained. Among these polymers having a crosslinkable silyl group, polyoxyalkylene polymers and polyisobutylene polymers having a main chain skeleton have been disclosed (see Patent Document 18 and Patent Document 19 below), which have already been industrially used. Is widely used in applications such as sealing materials, adhesives, and paints. Various properties such as curability, adhesiveness, mechanical properties, and storage stability are required for curable compositions used for sealing materials, adhesives, paints, and the like, and rubber-like cured products obtained by curing.

  Since the curable composition containing the organic polymer having a crosslinkable silyl group is cured with moisture in the air, there is a large difference between the curability (deep curability) inside the composition and the surface curability. Is likely to occur. In particular, in the case of a one-component composition obtained by dehydrating the composition, a noticeable difference is likely to occur between deep part curability and surface curability. In general, a curable composition having both fast surface curable property and deep curable property is desired.

  A curable composition containing an organic polymer having such a crosslinkable silyl group is cured using a silanol condensation catalyst, and usually has a carbon-tin bond such as dibutyltin bis (acetylacetonate). Organotin-based catalysts that are possessed are widely used. However, in recent years, toxicity of organotin compounds has been pointed out, and development of non-organotin catalysts has been demanded.

  As non-organotin catalysts, many studies have been made on carboxylic acid metal salts, metal alkoxides, etc. Among them, carboxylic acids and amine compounds are metal-free catalyst systems and have relatively little impact on the environment. There is expected. However, none of them has been able to obtain sufficient curability as a silanol condensation catalyst of an organic polymer having a reactive silicon group.

  In the following Patent Documents 20 to 23, carboxylic acid tin salts and other carboxylic acid metal salts are disclosed as silanol condensation catalysts, and the curability is improved by adding an amine compound as a co-catalyst. Is disclosed. Further, in consideration of environmental load, a curing catalyst that does not substantially contain a metal is promising. In the following Patent Document 24, curability is dramatically improved by using a carboxylic acid and an amine compound in combination. Is disclosed. Thus, although it is known that curability can be improved by using an amine compound in combination with another silanol condensation catalyst, most catalyst systems using an amine compound alone as a silanol condensation catalyst have been disclosed. Absent. Patent Document 25 below discloses a technique in which an aryl group-containing biguanide compound such as 1- (o-tolyl) biguanide, which is a conventionally known amine compound, is used as a silanol condensation catalyst. However, as can be seen from the examples of such patent documents in which an example of curing for a long time of 1 week is described, a catalyst system using an amine compound alone provides practical curability. It was difficult. Further, when the non-organotin-based catalyst described in the above patent is used, there is a problem that the adhesiveness tends to be inferior compared with the case where the organotin-based catalyst is used.

  Furthermore, in a vinyl polymer having at least one crosslinkable silyl group and having a main chain produced by a living radical polymerization method, the curability after storage may be reduced by the addition of an amine compound (Patent Document 26 below). reference).

  Examples of the invention relating to a curable composition using an organic polymer having a crosslinkable silyl group similar to the present invention, a curing catalyst and a carboxylic acid compound include those described in Patent Documents 27 to 30 below. . However, in these patent documents, an organotin catalyst is used as a curing catalyst, and there is no mention of a non-organotin catalyst system.

  In addition, in the following Patent Document 31, a curable composition using an organic polymer having a crosslinkable silyl group, a non-organotin catalyst, and a carboxylic acid is disclosed. It is intended to improve curability and is not mentioned in terms of improving storage stability.

Japanese Patent Laid-Open No. 01-247403 JP 05-255415 A Japanese Patent Laid-Open No. 05-262808 JP 05-211922 A JP-A 61-127711 Japanese Examined Patent Publication No. 02-001859 JP 09-272714 A JP-A-11-005815 Japanese Patent Laid-Open No. 11-043512 Japanese Patent Laid-Open No. 11-080571 JP-A-11-116617 JP-A-11-130931 Japanese Patent Laid-Open No. 12-086999 JP-A-12-191912 JP 2000-038404 A JP 2000-044626 A JP 2000-072804 A JP-A-52-73998 JP-A 63-6041 Japanese Patent No. 2993778 Japanese Patent No. 3145011 JP 2000-345054 A JP 2003-206410 A Japanese Patent No. 312775 JP 2005-248175 A JP 2006-131651 A JP 05-117518 A Japanese Patent Laid-Open No. 09-12860 JP 2002-37953 A JP 2007-308692 A WO07 / 094273

  The present invention is a curable composition containing a vinyl polymer having a crosslinkable silyl group as a component and using a guanidine compound as a non-organotin-based silanol condensation catalyst, which has initial curability and mechanical properties. An object of the present invention is to provide a curable composition that is not impaired, has excellent curability and storage stability of viscosity, and has improved surface coloring of the cured product.

  As a result of intensive studies to solve such problems, the present inventors have found that, on average, a vinyl polymer (I) having at least one crosslinkable silyl group, a guanidine compound (II), and a carboxylic acid ( When the content of carboxylic acid (III) contained in the curable composition is 1 to 10 equivalents in terms of molar ratio with respect to the content of guanidine compound (II) As a result, the present invention has been completed.

That is, the present invention is a curable composition containing a vinyl polymer (I) having an average of at least one crosslinkable silyl group, a guanidine compound (II), and a carboxylic acid (III), It is related with the curable composition whose content of the said carboxylic acid (III) contained in a curable composition is 1-10 equivalent in molar ratio with respect to content of the said guanidine compound (II). In the curable composition, the guanidine compound (II) is represented by the general formula (1):
R ¹ N═C (NR ¹ ₂ ) ₂ (1)
(Wherein ^one of five R ¹ is an aryl group and the remaining four are each independently a hydrogen atom or a hydrocarbon group in which the carbon atom at the 1-position is saturated). It is preferable that it is at least one of 1-phenylguanidine and 1- (2-methylphenyl) guanidine. In the curable composition, the carboxylic acid compound (III) is preferably an aliphatic monocarboxylic acid having 10 to 20 carbon atoms or an aliphatic polycarboxylic acid.

  The vinyl polymer (I) having at least one crosslinkable silyl group on average (hereinafter sometimes simply referred to as “vinyl polymer (I)”) has a molecular weight distribution of less than 1.8. The crosslinkable silyl group is preferably represented by the general formula (2).

^{_{- [Si (R 2) 2}} -b (Y) b O] m -Si (R 3) 3-a (Y) a (2)
(In the formula, R ² and R ³ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ² or When two or more R ³ are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0, 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1. Satisfaction with something)

  The vinyl polymer (I) has at least a main chain selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferable that it is produced mainly by polymerizing one monomer. More preferably, the main chain is a vinyl polymer that is a polymer composed of (meth) acrylic monomers, more preferably a polymer composed of acrylic monomers, and most preferably a polymer composed of acrylic acid ester monomers. It is a coalescence.

  The main chain of the vinyl polymer (I) is preferably produced by a living radical polymerization method, and more preferably produced by an atom transfer radical polymerization method.

  The crosslinkable silyl group of the vinyl polymer (I) is preferably at the end of the molecular chain.

  The curable composition of the present invention can further contain a polyether polymer (IV), and the main chain of the polyether polymer (IV) is preferably essentially polypropylene oxide. The polyether polymer (IV) is preferably a polymer having an average of at least one crosslinkable silyl group. Moreover, this invention relates to the sealing material which uses the said curable composition.

  The present invention is a curable composition containing a vinyl polymer having a crosslinkable silyl group as a component and using a guanidine compound as a non-organotin silanol condensation catalyst, and is contained in the curable composition. By adjusting the content ratio of the guanidine compound and the content of the carboxylic acid used in combination, the initial curability and mechanical properties are not impaired, and the curability and viscosity storage stability are excellent. It is possible to provide a curable composition with improved surface coloring of the product.

  As described above, the curable composition according to the present invention is very useful as a one-component curable composition because it has excellent curability and viscosity storage stability, particularly surface curability and viscosity storage stability. .

  The method for producing the vinyl polymer (I) used in the present invention will be described in detail below, focusing on an atom transfer radical polymerization method using a transition metal catalyst as an example.

<Main chain of vinyl polymer>
The vinyl polymer (I) having a crosslinkable silyl group in the present invention is a vinyl polymer containing at least one alkenyl group capable of hydrosilylation reaction in the molecule, and constituting the main chain of the vinyl polymer. It does not specifically limit as a monomer, A various thing can be used. Specifically, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl , (Meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (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 dodecyl, (meth) acrylic Acid phenyl, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth ) -3-methoxybutyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, ( (Meth) acrylic acid 2-perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl ethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, ( (Meth) acrylic acid diperfluoromethylmethyl, (meth) a 2-perfluoromethyl-2-perfluoroethylmethyl crylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecyl (meth) acrylate (Meth) acrylic acid monomers such as ethyl; aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Fluorine-containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; monoalkyl esters of fumaric acid and fumaric acid And Dialkyl esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene And conjugated dienes such as isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of these may be copolymerized.

  The main chain of the vinyl polymer (I) having a crosslinkable silyl group used in the curable composition of the present invention is a (meth) acrylic monomer, an acrylonitrile monomer, an aromatic vinyl monomer, or a fluorine-containing vinyl polymer. It is preferable that it is produced mainly by polymerizing at least one monomer selected from the group consisting of a monomer and a silicon-containing vinyl monomer. Here, “mainly” means that 50 mol% or more of the monomer units constituting the vinyl polymer (I) having a crosslinkable silyl group is the above monomer, preferably 70 mol% or more. is there.

  Of these, aromatic vinyl-based monomers and / or (meth) acrylic acid-based monomers are preferable, acrylic acid ester monomers and / or methacrylic acid ester monomers are more preferable, and acrylic acid ester monomers are more preferable in view of physical properties of the product. . Particularly preferred acrylic ester monomers include alkyl acrylate monomers, specifically ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid. 2-methoxybutyl is mentioned.

  In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, these preferred monomers may be contained in a weight ratio of 40% by weight or more. preferable.

  The molecular weight distribution of the vinyl polymer (I) having a crosslinkable silyl group in the present invention, that is, the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) (Mw / Mn) is not particularly limited, but is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, even more preferably 1.5 or less, Particularly preferred is 1.4 or less, and most preferred is 1.3 or less. If the molecular weight distribution is too large, the viscosity at the molecular weight between the same cross-linking points increases and the handling tends to be difficult. In the GPC measurement in the present invention, chloroform is used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  The number average molecular weight of the vinyl polymer (I) having a crosslinkable silyl group in the present invention is not particularly limited, but when measured by GPC, a range of 500 to 1,000,000 is preferable, and 1,000 to 100,000 is more preferred, 5,000-80,000 is more preferred, and 8,000-50,000 is even more preferred. If the molecular weight is too low, the original characteristics of the vinyl polymer (b) tend to be difficult to be expressed. On the other hand, if the molecular weight is too high, handling tends to be difficult.

<Synthesis of vinyl polymer>
The vinyl polymer (I) having a crosslinkable silyl group used in the present invention can be obtained by various polymerization methods, and is not particularly limited. However, radical weight is considered from the viewpoint of versatility of the monomer and ease of control. Legal methods are preferred, and controlled radical polymerization is more preferred among radical polymerizations. This controlled radical polymerization method can be classified into a “chain transfer agent method” and a “living radical polymerization method”. Living radical polymerization that allows easy control of the molecular weight and molecular weight distribution of the resulting vinyl-based polymer (I) having a crosslinkable silyl group is more preferred, because of the availability of raw materials and the ease of introduction of functional groups at the polymer ends. Atom transfer radical polymerization is particularly preferred. The radical polymerization, controlled radical polymerization, chain transfer agent method, living radical polymerization method, and atom transfer radical polymerization are known polymerization methods. For example, JP-A-2005-232419 and JP-A-2005-234419 The description of 2006-291073 gazette etc. can be referred to.

  The atom transfer radical polymerization, which is one of the preferred methods for synthesizing the vinyl polymer (I) having a crosslinkable silyl group in the present invention, will be briefly described below.

  In atom transfer radical polymerization, 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), or a sulfonyl halide. A compound or the like is preferably used as an initiator. Specific examples include compounds described in paragraphs [0040] to [0064] of JP-A-2005-232419.

  In order to obtain a vinyl polymer having two or more alkenyl groups capable of hydrosilylation in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. preferable.

  There is no restriction | limiting in particular as a vinyl-type monomer used in atom transfer radical polymerization, All the illustrated vinyl-type monomers mentioned above can be used suitably.

  Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which has a periodic table group 7, 8, 9, 10, or 11 element as a central metal, More preferably, it is 0. Examples thereof include transition metal complexes having valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal, particularly preferably a copper complex. Specific examples of the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. When a copper compound is used, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine or the like is used in order to increase the catalytic activity. These polyamines are added as ligands.

The polymerization reaction can be carried out without solvent, but can also be carried out in various solvents. It does not specifically limit as a kind of solvent, The solvent of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0067] is mentioned. These may be used alone or in combination of two or more. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO ₂ as a medium.

  Although superposition | polymerization temperature is not limited, It can carry out in the range of 0-200 degreeC, Preferably, it is the range of room temperature-150 degreeC.

<Crosslinkable silyl group>
The crosslinkable silyl group of the present invention includes a general formula (2);
^{_{- [Si (R 2) 2}} -b (Y) b O] m -Si (R 3) 3-a (Y) a (2)
(In the formula, R ² and R ³ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ² or When two or more R ³ are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0, 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1. A group represented by the above formula).

  Examples of the hydrolyzable group include commonly used groups such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group, an amide group, and an aminooxy group are preferable, but an alkoxy group is particularly preferable in terms of mild hydrolyzability and easy handling. Among the alkoxy groups, those having a smaller number of carbon atoms have higher reactivity, and the reactivity decreases in the order of methoxy group> ethoxy group> propoxy group, and can be selected according to the purpose and application.

Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (a + Σb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming the crosslinkable silyl group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less. In particular, the general formula (3):
-Si (R ³ ) _3-a (Y) _a (3)
A crosslinkable silyl group represented by the formula (wherein R ³ and Y are the same as described above, and a is an integer of 1 to 3) is preferable because it is easily available.

  Although not particularly limited, a is preferably 2 or more in consideration of curability.

  As such a vinyl polymer having a crosslinkable silyl group, a polymer having a hydrolyzable silicon group formed by bonding two hydrolyzable groups per silicon atom is often used. When using a very fast curing rate, such as when used at low temperatures, etc., the curing rate is not sufficient, and if you want to give flexibility after curing, it is necessary to reduce the crosslinking density For this reason, the crosslink density is not sufficient, and stickiness (surface tack) may occur. In that case, it is preferable that a is 3 (for example, trimethoxy functional group).

  Further, those having a of 3 (for example, trimethoxy functional group) cure faster than those having 2 (for example, dimethoxy functional group), but those having 2 are superior in terms of storage stability and mechanical properties (elongation, etc.). There is a case. In order to balance the curability and physical properties, two (for example, dimethoxy functional group) and three (for example, trimethoxy functional group) may be used in combination.

  For example, when Y is the same, the greater the a, the higher the reactivity of Y. Therefore, by variously selecting Y and a, it is possible to control the curability and mechanical properties of the cured product. And can be selected according to the application. A compound having a of 1 is used as a chain extender mixed with a polymer having a crosslinkable silyl group, specifically, at least one polymer comprising a polysiloxane, polyoxypropylene or polyisobutylene. it can. It is possible to obtain a composition having low viscosity before curing, high elongation at break after curing, low bleeding, low surface contamination, and excellent paint adhesion.

  The number of crosslinkable silyl groups in the vinyl polymer (I) having a crosslinkable silyl group is preferably 1 or more on average in the molecule from the viewpoint of the curability of the composition and the physical properties of the cured product. Is 1.1 or more and 4.0 or less, more preferably 1.2 or more and 3.5 or less.

  When a rubber-like property is particularly required for a cured product obtained by curing the one-component curable composition of the present invention, a molecular weight between crosslinking points that greatly affects rubber elasticity can be increased. At least one of the groups is preferably at the end of the molecular chain. More preferably, it has all crosslinkable functional groups at the molecular chain ends.

  Methods for producing vinyl polymers having a crosslinkable silyl group at the molecular chain terminal, in particular, (meth) acrylic polymers, are disclosed in Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, and Japanese Patent Laid-Open No. Hei 6-1994. No. 211922 and the like. However, since these methods are free radical polymerization methods using the above-mentioned “chain transfer agent method”, the resulting polymer has a relatively high proportion of crosslinkable silyl groups at the molecular chain ends, while Mw / Mn The value of the molecular weight distribution represented by is generally as large as 2 or more, and the viscosity is increased. Therefore, in order to obtain a vinyl polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable silyl group at the molecular chain terminal at a high ratio, the above “living radical polymerization method” is used. However, it is not limited to a polymer having a narrow molecular weight distribution.

<Introduction method of crosslinkable silyl group>
As a method for introducing a crosslinkable silyl group into the obtained vinyl polymer, a known method can be used. Examples thereof include the methods described in paragraphs [0083] to [117] of JP2007-302749A. Among these methods, the method of adding a hydrosilane compound having a crosslinkable silyl group to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst is preferable because it is easier to control. .

  Here, a method for adding a hydrosilane compound having a crosslinkable silyl group to a vinyl polymer having at least one alkenyl group, which is one of preferable introduction methods, in the presence of a hydrosilylation catalyst will be briefly described below. . In this method, a vinyl polymer obtained by living radical polymerization of a vinyl monomer is reacted with a compound having at least two alkenyl groups having low polymerizability (hereinafter referred to as “diene compound”) to obtain the alkenyl obtained. A hydrosilane compound having a crosslinkable silyl group is added to a vinyl polymer having at least one group in the presence of a hydrosilylation catalyst.

  The vinyl polymer having at least one alkenyl group used in the method (A) can be obtained by various methods. Although the synthesis method is illustrated below, it is not necessarily limited to these.

(Aa) When synthesizing a vinyl polymer by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula (4) To react as a second monomer.
_{^{H 2 C = C (R 4}} ) -R 5 -R 6 -C (R 7) = CH 2 (4)
(Wherein R ⁴ represents hydrogen or a methyl group, R ⁵ represents —C (O) O—, or o-, m-, p-phenylene group, and R ⁶ represents a direct bond, 20 represents a divalent organic group having 20 and may contain one or more ether bonds, R ⁷ represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. Represents -20 aralkyl groups).

  There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule. However, particularly in the case of living radical polymerization, when a rubber-like property is expected, a polymerization reaction is performed. It is preferable to react as the second monomer at the end of the reaction or after completion of the reaction of the predetermined monomer.

  (Ab) When synthesizing a vinyl polymer by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. A method of reacting a compound having at least two alkenyl groups having low polymerizability, such as

  (Ac) Various organometallic compounds having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin on a vinyl polymer having at least one highly reactive carbon-halogen bond A method of replacing halogen by reaction.

(Ad) A method of substituting a halogen by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having an alkenyl group as shown in the general formula (5). .
^{M + C - (R 8)} (R 9) -R 10 -C (R 7) = CH 2 (5)
(Wherein, R ⁷ is the same, R ^8, R ⁹ are both carbanion C ^- or an electron withdrawing group stabilizing, or one of the other is hydrogen or a 1 to 10 carbon atoms in the electron-withdrawing group Represents an alkyl group or a phenyl group, R ¹⁰ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms, and may contain one or more ether bonds, M ⁺ represents an alkali metal ion, Or a quaternary ammonium ion).

As the electron-withdrawing group for R ⁸ and R ⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

  (Ae) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with, for example, a single metal such as zinc or an organometallic compound. A method of reacting with an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group .

(Af) An oxyanion or carboxylate anion having an alkenyl group as represented by the general formula (6) or (7) is added to a vinyl polymer having at least one highly reactive carbon-halogen bond. A method of replacing halogen by reaction.
_{^{H 2 C = C (R 7}} ) -R 11 -O - M + (6)
(Wherein R ⁷ and M ⁺ are the same as above. R ¹¹ is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds),
_{^{H 2 C = C (R 7}} ) -R 12 -C (O) O - M + (7)
(Wherein R ⁷ and M ⁺ are the same as above. R ¹² may be a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds).
Etc.

  The method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond is an atom transfer radical polymerization method using an organic halide as described above as an initiator and a transition metal complex as a catalyst. For example, but not limited to.

  Further, the vinyl polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below can be used, but are not limited thereto. . A method of reacting a hydroxyl group of a vinyl polymer having at least one hydroxyl group with a base such as (Ag) sodium methoxide and reacting with an alkenyl group-containing halide such as allyl chloride.

  (Ah) A method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate.

  (Ai) A method in which an alkenyl group-containing acid halide such as (meth) acrylic acid chloride is reacted in the presence of a base such as pyridine.

  (Aj) A method in which an alkenyl group-containing carboxylic acid such as acrylic acid is reacted in the presence of an acid catalyst;

  In the present invention, when halogen is not directly involved in the method of introducing an alkenyl group such as (Aa) and (Ab), it is preferable to synthesize a vinyl polymer using a living radical polymerization method. . The method (Ab) is more preferable from the viewpoint of easier control.

  An organic halide having at least one highly reactive carbon-halogen bond in the case of introducing an alkenyl group by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond; Alternatively, a vinyl compound having at least one highly reactive carbon-halogen bond at the terminal, obtained by radical polymerization of a vinyl monomer using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst (atom transfer radical polymerization method) It is preferable to use a polymer. In view of easier control, the method (Af) is more preferable.

Moreover, there is no restriction | limiting in particular as a hydrosilane compound which has a crosslinkable silyl group, If a typical thing is shown, the compound shown by General formula (8) will be illustrated.
^{_{H- [Si (R 13) 2}} -b (Y) b O] m -Si (R 14) 3-a (Y) a (8)
(In the formula, each of R ¹³ and R ¹⁴ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ¹³ or When two or more R ¹⁴ are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0, 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1. Satisfaction with something)

Among these hydrosilane compounds, in particular, the general formula (9):
H-Si (R ¹⁴ ) _3-a (Y) _a (9)
(Wherein R ¹⁴ and Y are the same as defined above, a is an integer of 1 to 3),
The compound which has a crosslinkable group shown by is preferable from a point with easy acquisition.

When the hydrosilane compound having a crosslinkable silyl group is added to an alkenyl group, a transition metal catalyst is usually used. Examples of the transition metal catalyst include platinum simple substance, alumina, silica, carbon black and the like in which a platinum solid is dispersed, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum-olefin. Complex, platinum (0) -divinyltetramethyldisiloxane complex is mentioned. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2, TiCl 4 , and the like.

<Guanidine Compound (II)>
The content of the guanidine compound (II) contained in the composition using the guanidine compound (II) of the present invention and the carboxylic acid (III) and the content of the carboxylic acid (III) contained in the composition Even if it is used as a silanol condensation catalyst for vinyl polymer (I) having a crosslinkable silyl group when it is in a molar ratio of 1 to 10 equivalents to the initial curing, it is a non-organic tin catalyst, Thus, it is possible to obtain a one-component curable composition that is excellent in curability and storage stability of viscosity, and that can suppress surface coloring of the cured product.

As the guanidine compound (II), a known guanidine compound can be used, but a guanidine compound represented by the general formula (1) is preferable because of high activity and good curability.
R ¹ N═C (NR ¹ ₂ ) ₂ (1)
(In the formula, one of five R ¹ is an aryl group, and the remaining four are each independently a hydrogen atom or a hydrocarbon group in which the carbon atom at the 1-position is saturated).

To satisfy both the adhesiveness and good curability, it is essential that a five one R ¹ is an aryl group of R ¹ in the general formula (1). There is no limitation in particular as an aryl group, What is necessary is just a well-known aryl group. Specific examples of the aryl group include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,6-dimethylphenyl group, 2,4,4 6-trimethylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 2,4-dichlorophenyl group, 2,6-dichlorophenyl group, 2-hydroxyphenyl group, 4-hydroxyphenyl group, 2-aminophenyl group, 4- Aminophenyl group, 2,4-diaminophenyl group, 4- (dimethylamino) phenyl group, 4-nitrophenyl group, 4-cyanophenyl group, 4-sulfonic acid phenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl Group, 4-benzyloxyphenyl group, 4-phenoxyphenyl group, 4-carboxyphenyl group, 4-acetate Xiphenyl group, 4-benzoylphenyl group, 4- (ethoxycarbonyl) phenyl group, 4- (phenoxycarbonyl) phenyl group, 4-guanidinophenyl group, 2,4-diguanidinophenyl group, 4- (acetylamino) phenyl group 4- (benzoylamino) phenyl group, 4- (dimethylaminosulfonyl) phenyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-4-nitrophenyl group, 2-methoxy-4-guanidinophenyl group, Examples include 2-methoxy-4- (acetylamino) phenyl group, naphthyl group, biphenyl group and the like. Of these, a phenyl group, a 2-methylphenyl group, a 4-aminophenyl group, and a 4-guanidinophenyl group are preferable, and a phenyl group and a 4-guanidinophenyl group are more preferable because good curability and adhesiveness can be obtained. Preferred is a phenyl group.

To satisfy both adhesion and good curability, one of R ¹ of the five R ¹ in the general formula (1) is essential to be an aryl group, the four remaining R ¹ is hydrogen It is essential that the atom or a hydrocarbon group in which the carbon atom at the 1-position is saturated. When R ¹ is a hydrocarbon group in which the carbon atom at the 1-position is saturated, the hydrocarbon group is not particularly limited as long as the carbon atom at the 1-position is saturated, and is saturated or unsaturated consisting of only a hydrogen atom and a carbon atom. A saturated hydrocarbon group may be sufficient and the hydrocarbon group which has a substituent which consists of 1 or more selected from a hydrogen atom, a carbon atom, and an oxygen atom may be sufficient. In view of availability, when R ¹ is a hydrocarbon group in which the carbon atom at the 1-position is saturated, the number of carbon atoms is preferably 1 to 50, more preferably 1 to 20, and particularly preferably 1 to 10. Moreover, since favorable sclerosis | hardenability is obtained, four R < ¹ > other than an aryl group has a hydrogen atom or the saturated hydrocarbon group which consists only of a hydrogen atom and a carbon atom, and a hydrogen atom is more preferable. When R ¹ is a hydrocarbon group in which the carbon atom at the 1-position as represented by an aryl group, —C (═NH) —NH ₂ or the like is unsaturated, it is not preferable because curability is lowered.

  The guanidine compound (II) represented by the general formula (1) is preferably a guanidine compound represented by the general formula (10) from the viewpoint of curability and adhesiveness, and is represented by the general formula (11). The guanidine compound is more preferable, and 1-phenylguanidine is particularly preferable.

（４つのＲ^１は、それぞれ独立に水素原子、または１位の炭素原子が飽和である炭化水素基であり、Ｒ^２は水素原子、ハロゲン原子、ヒドロキシ基、アミノ基、ニトロ基、シアノ基、スルホン酸基、または有機基である）。

(Four R ^{1 s} are each independently a hydrogen atom or a hydrocarbon group in which the carbon atom at the 1-position is saturated; R ² is a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, A sulfonic acid group or an organic group).

（Ｒ^２は水素原子、ハロゲン原子、ヒドロキシ基、アミノ基、ニトロ基、シアノ基、スルホン酸基、または有機基である）。

(R ² is a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, a sulfonic acid group, or an organic group).

In order to satisfy both good curability and adhesiveness, it is essential that the four R ¹ in the general formula (10) are a hydrogen atom or a hydrocarbon group in which the carbon atom at the 1-position is saturated. is there. When R ¹ in the general formula (11) is a hydrocarbon group in which the carbon atom at the 1-position is saturated, the same hydrocarbon group as R ¹ in the general formula (1) is exemplified.

R ² in the general formula (10) or (11) includes a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, a sulfonic acid group, or an organic group. When R ² in the general formula (10) or (11) is an organic group, the organic group is not particularly limited, and may be a saturated or unsaturated hydrocarbon group composed of only a hydrogen atom and a carbon atom, It may be a hydrocarbon group having a substituent composed of one or more selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. In addition, as R ² , a functional group such as an alkoxy group, a carboxy group, an acyl group, a carbonyl group, an imino group, or a sulfonyl group may be bonded to the aryl group in the general formula (10) or (11). When R ² is an organic group, the upper limit of the number of carbon atoms need not be specified, but a general numerical range includes 10,000 or less. However, from the viewpoint of availability, the number of carbon atoms is preferably 1 to 50, more preferably 1 to 20, and particularly preferably 1 to 10. Moreover, since favorable curability is obtained, R ² is preferably a hydrogen atom, an amino group, or a hydrocarbon group, and a hydrogen atom, an amino group, or a saturated hydrocarbon group consisting of only a hydrogen atom and a carbon atom. More preferred is a hydrogen atom.

Further, from the viewpoint of curability it is preferably a guanidine compound to form a cyclic structure of any two or more of the five R ¹ in the general formula (1) are bonded to the general formula (12), and / Or it is more preferable that it is a cyclic guanidine compound represented by General formula (13).

（Ｒ^１５はグアニジノ基に結合した炭素原子が飽和である２価の炭化水素基であり、３つのＲ^１のうち１つはアリール基であり、残り２つはそれぞれ独立に水素原子、または１位の炭素原子が飽和である炭化水素基である。３つのＲ^１のうち任意の２つが結合して環状構造を形成していても良い）。

(R ¹⁵ is a divalent hydrocarbon group in which the carbon atom bonded to the guanidino group is saturated, one of the three R ¹ is an aryl group, and the remaining two are each independently a hydrogen atom, or 1 A hydrocarbon group in which the carbon atom at the position is saturated, and any two of the three R ¹ may combine to form a cyclic structure).

（Ｒ^１６はグアニジノ基に結合した炭素原子が飽和である２価の炭化水素基であり、３つのＲ^１のうち１つはアリール基であり、残り２つはそれぞれ独立に水素原子、または１位の炭素原子が飽和である炭化水素基である。３つのＲ^１のうち任意の２つが結合して環状構造を形成していても良い）。

(R ¹⁶ is a divalent hydrocarbon group in which the carbon atom bonded to the guanidino group is saturated, one of the three R ¹ is an aryl group, and the other two are independently a hydrogen atom, or 1 A hydrocarbon group in which the carbon atom at the position is saturated, and any two of the three R ¹ may combine to form a cyclic structure).

In order to satisfy both good curability and adhesiveness, it is essential that one of the three R ^{1 s in} the general formula (12) or (13) is an aryl group. Formula (12) or (13) each of the three ^{R 1} in one ^{R 1} is an aryl group include the same aryl group as ^{R 1} in the general formula (1). Formula (12) or (13) each of the three R ¹ in the two R ¹ other than an aryl group, it is essential hydrogen atom or a carbon atom in position 1, is a hydrocarbon group which is saturated is there. When R ¹ in the general formula (12) or (13) is a hydrocarbon group in which the carbon atom at the 1-position is saturated, the same hydrocarbon group as R ¹ in the general formula (1) is exemplified. Further, from the viewpoint of availability, it is preferable that any two of the three R ^{1 s in} the general formula (12) or (13) are bonded to each other to form a cyclic structure. It is preferable that two R ¹ are bonded to form a cyclic structure.

It is essential that R ¹² in the general formula (12) or R ¹³ in the general formula (13) is a divalent hydrocarbon group in which the carbon atom bonded to the guanidino group is saturated. From the viewpoint of curability and availability, a divalent hydrocarbon group having 1 to 10 carbon atoms is preferred, a divalent hydrocarbon group having 1 to 5 carbon atoms is more preferred, and 2 having 2 or 3 carbon atoms. Divalent hydrocarbon groups are particularly preferred.

  Specific examples of the guanidine compound (II) include 1-phenylguanidine, 1-phenyl-3-methylguanidine, 1-phenyl-1,3,3-trimethylguanidine, 1-phenyl-3-aminoguanidine, 2-phenyl. Guanidine, 2-phenyl-1,1,3,3-tetramethylguanidine, 1- (2-methylphenyl) guanidine, 1- (4-methylphenyl) guanidine, 1- (4-octylphenyl) guanidine, 1- (2,6-dimethylphenyl) guanidine, 4-guanidinophenol, 1- (4-methoxyphenyl) guanidine, 1- (3,4-dimethoxyphenyl) guanidine, 1- (4-chlorophenyl) guanidine, 1- (3 , 4-Dichlorophenyl) guanidine, 1-methyl-3-phenylguanidine, 1-methyl- -Phenylguanidine, 1-cyclohexyl-3- (3-methylphenyl) guanidine, 1- (4-aminophenyl) guanidine, 1- (4-dimethylaminophenyl) guanidine, 1- (4-guanidinophenyl) guanidine, 1 -(2-guanidinophenyl) guanidine, 1- (guanidinophenyl) -3-hexylguanidine, 4-guanidinobenzoic acid, 3-amino-5-guanidinobenzoic acid, 4-tert-butylphenyl 4-guanidinobenzoic acid, benzoic acid Acid 4-guanidinophenyl, 4-phenylbutanoic acid 4-guanidinophenyl, 4-guanidinobenzamide, N, N-dioctadecyl-4-guanidinobenzamide, 1- (4-nitrophenyl) guanidine, 1- (3-nitrophenyl ) Guanidine, 1- (2-naphthyl) Anidine, 1- [3- (trifluoromethyl) phenyl] guanidine, N- (2-imidazolin-2-yl) -1-naphthalenamine, N- (2-imidazolin-2-yl) -2,3-xylidine 2-[(5,6,7,8-tetrahydronaphthalen-1-yl) amino] -2-imidazoline, 7-phenyl-1,5,7-triazabicyclo [4.4.0] -5 Decene, 1,1 ′-[4- (dodecyloxy) -m-phenylene] bisguanidine, 1,1 ′-[methylenebis (p-phenylene)] bisguanidine, 1,3-bis (3-guanidinophenyl) guanidine 1,8-bis (1,1,3,3-tetramethylguanidin-2-yl) naphthalene, N- (tert-butoxycarbonyl) -β-alanine 6-guanidino-1-naphthyl And the like. These guanidine compounds (II) may be used alone or in combination of two or more.

  Among the guanidine compounds, 1-phenylguanidine, 1- (2-methylphenyl) guanidine, 1- (4-methylphenyl) guanidine, 1- (2,6-dimethylphenyl) are preferable from the viewpoint of curability and adhesiveness. Guanidine, 1- (4-aminophenyl) guanidine, 1- (4-dimethylaminophenyl) guanidine and 1- (4-guanidinophenyl) guanidine are preferred, 1-phenylguanidine, 1- (2-methylphenyl) guanidine, 1- (4-guanidinophenyl) guanidine is more preferable, and 1-phenylguanidine and 1- (4-guanidinophenyl) guanidine are particularly preferable. From the viewpoint of availability, 1-phenylguanidine and 1- (2-methylphenyl) guanidine are preferable, and 1-phenylguanidine is more preferable.

  The amount of the guanidine compound (II) used is preferably 0.001 to 20 parts by weight, and 0.01 to 15 parts by weight with respect to 100 parts by weight of the vinyl polymer (II) having a crosslinkable silyl group. Parts are more preferred, and 0.1 to 10 parts by weight are particularly preferred. If the blending amount of the guanidine compound (II) is below this range, a practical curing rate may not be obtained, and the curing reaction may not be sufficiently advanced. On the other hand, when the blending amount of the guanidine compound (II) exceeds this range, the pot life tends to be too short and the workability tends to deteriorate.

<Carboxylic acid (III)>
In the present invention, carboxylic acid (III) is used in combination. By containing carboxylic acid (III), the initial curability and mechanical properties are not impaired, the curability and the storage stability of the viscosity are excellent, and the one-component curability that can suppress the surface coloring of the cured product. A composition can be obtained.

  Specific examples of carboxylic acid (III) include monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, Pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid , Linear saturated fatty acids such as laccellic acid; undecylenic acid, lindelic acid, tuzuic acid, fizeteric acid, myristoleic acid, 2-hexadecenoic acid, 6-hexadecenoic acid, 7-hexadecenoic acid, palmitoleic acid, petrothelic acid, olein Acid, elaidic acid, asclepic acid, vaccenic acid, Mono-unsaturated fatty acids such as drain acid, gondoic acid, celetic acid, erucic acid, brassic acid, ceracolic acid, ximenoic acid, lumenic acid, acrylic acid, methacrylic acid, angelic acid, crotonic acid, isocrotonic acid, 10-undecenoic acid Linoelaidic acid, linoleic acid, 10,12-octadecadienoic acid, hiragoic acid, α-eleostearic acid, β-eleostearic acid, punicic acid, linolenic acid, 8,11,14-eicosatrienoic acid 7,10,13-docosatrienoic acid, 4,8,11,14-hexadecatetraenoic acid, moloctic acid, stearidonic acid, arachidonic acid, 8,12,16,19-docosatetraenoic acid, 4,8, 12,15,18-eicosapentaenoic acid, sardine acid, nisinic acid, docosahexaenoic acid and other polyenes Fatty acids: 1-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid, isovaleric acid, tuberculostearic acid, pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2-diethylbutyric acid 2,2-dimethylvaleric acid, 2-ethyl-2-methylvaleric acid, 2,2-diethylvaleric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid Branched fatty acids such as 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, and versatic acid; triple bonds such as propiolic acid, talylic acid, stearolic acid, crepenic acid, xymenic acid, and 7-hexadesinic acid Fatty acids having: acetoacetic acid, ethoxyacetic acid, glyoxylic acid, glycolic acid, gluconic acid, sabinic acid, 2-hydroxytetradecanoic acid, iprolic acid 2,2-dimethyl-3-hydroxypropionic acid, 2-hydroxyhexadecanoic acid, yalapinolic acid, uniperic acid, ambretoleic acid, alluritic acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid 9,10-dihydroxyoctadecanoic acid, ricinoleic acid, camlorenic acid, ricanoic acid, ferronic acid, cerebronic acid, 2-methyl-7-oxabicyclo [2.2.1] -5-heptene-2-carboxylic acid, etc. And oxygenated fatty acids. Examples of alicyclic carboxylic acids include naphthenic acid, malvalic acid, sterlic acid, hydonocarbic acid, sorghumulinic acid, gollulinic acid, 1-methylcyclopentanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2-methylbicyclo [2.2. .1] -5-heptene-2-carboxylic acid, 1-adamantanecarboxylic acid, bicyclo [2.2.1] heptane-1-carboxylic acid, bicyclo [2.2.2] octane-1-carboxylic acid. It is done. Examples of polycarboxylic acids include tricarboxylic acids such as aconitic acid, 4,4-dimethylaconitic acid, citric acid, isocitric acid, and 3-methylisocitric acid; ethylenediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, and the like Tetracarboxylic acids of the above; pentacarboxylic acids such as diethylenetetraminepentaacetic acid; hexacarboxylic acids such as triethylenetetraminehexaacetic acid. Aromatic carboxylic acids include aromatic monocarboxylic acids such as benzoic acid, 9-anthracenecarboxylic acid, atrolactic acid, anisic acid, isopropylbenzoic acid, salicylic acid, toluic acid; phthalic acid, isophthalic acid, terephthalic acid, carboxyphenyl Examples thereof include aromatic polycarboxylic acids such as acetic acid, pyromellitic acid, trimellitic acid, and trimesic acid. The carboxylic acid (III) used in combination with the guanidine compound (II) may be used alone or in combination of two or more.

  Among these, a monocarboxylic acid is more preferable and an aliphatic monocarboxylic acid is more preferable from the viewpoint of good compatibility with the vinyl polymer (I) having a crosslinkable silyl group.

  Moreover, when the melting point of carboxylic acid is high (crystallinity is high), handling becomes difficult (workability deteriorates). Therefore, the melting point of the carboxylic acid (III) used together with the amidine compound as the silanol condensation catalyst is preferably 65 ° C. or less, more preferably −50 to 50 ° C., and −40 to 35 ° C. Particularly preferred.

  Further, the carboxylic acid (III) preferably has 5 to 20 carbon atoms, more preferably 6 to 20, and particularly preferably 10 to 20. When the number of carbon atoms exceeds this range, it tends to become solid and becomes difficult to be compatible with the vinyl polymer (I) having a crosslinkable silyl group, and there is a tendency that the activity cannot be obtained. On the other hand, when the number of carbon atoms is small, the volatility of the carboxylic acid increases and the odor tends to increase.

  As described above, from the viewpoint of availability and workability, 2-ethylhexanoic acid, octylic acid, oleic acid, naphthenic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecane Acid, versatic acid and the like are preferable. On the other hand, when polycarboxylic acid is used, aliphatic polycarboxylic acid is preferable, the number of carboxyl groups is more preferably 2 to 6, and particularly preferably 3 to 5. Specifically, tetracarboxylic acids such as ethylenediaminetetraacetic acid and 1,3-diamino-2-hydroxypropanetetraacetic acid are preferred.

  In the present invention, it is essential that the content of carboxylic acid (III) contained in the composition is 1 to 10 equivalents in terms of molar ratio with respect to the content of guanidine compound (II) contained in the composition. It is. From the viewpoint of curability and storage stability, the content of carboxylic acid (III) is preferably 1 to 8 equivalents and more preferably 2 to 6 equivalents in terms of molar ratio with respect to the content of guanidine compound (II). When the content is less than 1 in molar ratio to the content of the guanidine compound (II) or greater than 10, the curability and the storage stability of the viscosity tend to decrease.

<Polyether polymer (IV)>
In the present invention, it is also possible to use a polyether polymer (IV) as necessary.

  The main chain of the polyether polymer (IV) is not particularly limited, and examples thereof include polyethylene oxide, polypropylene oxide, polybutylene oxide, polyphenylene oxide and the like. Among these, it is preferable that it is essentially polyoxyalkylene, and it is more preferable that it is essentially polypropylene oxide, and this may contain ethylene oxide, butylene oxide, phenylene oxide, etc. in addition to propylene oxide. The polyether polymer (IV) may or may not contain a urethane bond in the main chain. Here, “the main chain is essentially polypropylene oxide” means that the propylene oxide unit accounts for 50% or more of the repeating units constituting the main chain, preferably 70% or more, more preferably 90%. % Or more. The lower the viscosity, the better the handleability, so that the molecular weight distribution (Mw / Mn) of the polypropylene oxide polymer is more preferably 1.5 or less.

<Crosslinkable functional group>
The crosslinkable functional group in the polyether polymer (IV) is not particularly limited, and is preferably a crosslinkable silyl group, an alkenyl group, a hydroxyl group, an amino group, or a group having a polymerizable carbon-carbon double bond. And an epoxy group. In particular, a crosslinkable silyl group is preferable. The number of crosslinkable functional groups possessed by the polyether polymer (IV) is preferably at least one, but may be less than one. From the viewpoint of curability of the composition, it is preferably more than 1, more preferably 1.1 to 4.0 on average, and even more preferably 1.5 to 2.5 on average. Moreover, it is preferable from a viewpoint of rubber elasticity of hardened | cured material that a crosslinkable functional group exists in the terminal of polyether type polymer (IV). More preferably, there are functional groups at both ends of the polymer.

<Molecular weight>
The polyether polymer (IV) having at least one crosslinkable functional group preferably has a number average molecular weight of 7500 or more, but may be less than 7500. In particular, it is more preferable to use an organic polymer having a number average molecular weight of 7500 to 25000. When the number average molecular weight of the polyether polymer (IV) is smaller than 7500, the cured product tends to be hard and the elongation tends to be low. When the number average molecular weight exceeds 25,000, the flexibility and elongation of the cured product are There is no problem, but the adhesiveness of the polymer itself tends to be low, and the practicality tends to be low. However, even if the molecular weight is low, flexibility and elongation may be improved if the number of crosslinkable functional groups is small, and adhesion may be improved if the number of crosslinkable functional groups is large even if the molecular weight is high. There is. The number average molecular weight is particularly preferably 8000 to 20000 from the viewpoint of viscosity, but it may be 8000 or less, or 20000 or more.

<Use amount of polyether polymer (IV)>
The amount used when adding the polyether polymer (IV) may be any amount, but the weight ratio ((IV) / (I) with respect to the vinyl polymer (I) having a crosslinkable silyl group. )) Is preferably in the range of 100/1 to 1/100, more preferably in the range of 100/5 to 5/100, and even more preferably in the range of 100/10 to 10/100. The addition amount can be set according to each application and purpose. However, if the addition amount is too large, the excellent heat resistance and weather resistance, which are one of the effects of the present invention, may be lowered.

  In the above-mentioned polyether polymer (IV), (meth) acrylic polymer produced by a general radical polymerization method, or high-temperature continuous bulk polymer (for example, SGO oligomer manufactured by Toa Gosei Co., Ltd.) or those A product obtained by previously mixing the silylated product may be used for mixing with the vinyl polymer.

<Polyether polymer having a crosslinkable silyl group>
The polyether polymer having a crosslinkable silyl group will be described below.

  The main chain structure of the polyether polymer having a crosslinkable silyl group is the same as described above. The main chain may be linear or branched, or a mixture thereof. Of these, a main chain derived from polyoxypropylene diol, polyoxypropylene triol or a mixture thereof is particularly preferable. Further, other monomer units and the like may be contained, but the monomer unit represented by the above formula is preferably present in the polymer in an amount of 50% by weight or more, preferably 80% by weight or more. The main chain may or may not contain a urethane bond or urea bond.

  The molecular structure of the polyether-based polymer varies depending on the intended use and intended properties, and those described in JP-A-63-112642 can be used. Such polyoxyalkylenes can be obtained by conventional polymerization methods (anionic polymerization methods using caustic), cesium metal catalysts, JP-A 61-197631, JP-A 61-215622, JP-A 61-215623, and Porphyrin / aluminum complex catalysts exemplified in JP-A-61-218632 and the like, composite metal cyanide complex catalysts exemplified in JP-B-46-27250 and JP-B-59-15336, etc. It can be obtained by a method using a catalyst comprising a polyphosphazene salt exemplified in Kaihei 10-273512. In a method using a porphyrin / aluminum complex catalyst, a double metal cyanide complex catalyst or a catalyst comprising a polyphosphazene salt, the molecular weight distribution (Mw / Mn) is 1.6 or less, and further a small value such as 1.5 or less. When an oxyalkylene polymer can be obtained and the molecular weight distribution is small, there is an advantage that the viscosity of the composition can be reduced while maintaining the low modulus and high elongation of the cured product.

<Crosslinkable silyl group>
As the crosslinkable silyl group, a group represented by the general formula (2) can be used as in the vinyl polymer, and a group represented by the general formula (3) is preferable. The explanation about the group represented by the general formula (2) or the general formula (3) is similarly applied to the polyether polymer having a crosslinkable silyl group. The crosslinkable silyl group in the polyether polymer may have the same structure as the crosslinkable silyl group in the vinyl polymer having a crosslinkable silyl group, or may have a different structure.

  Since the bond between the crosslinkable silyl group and the polyether moiety is resistant to hydrolysis, there are at least three carbon atoms between the silicon atom of the silyl group and the ether oxygen atom of the polyether moiety. As it exists, it is preferably an alkylene group such as trimethylene and tetramethylene.

  From the viewpoint of the curability of the composition, the number of crosslinkable silyl groups is preferably at least one on average in one molecule of the polymer, preferably at least 1.2, and preferably 1.2 The number is more preferably 4.0 or less, and still more preferably 1.5 or more and 2.5 or less. Moreover, it is preferable that the crosslinkable silyl group of a polyether-type polymer exists in the terminal of a molecular chain from a viewpoint of the rubber elasticity of hardened | cured material, More preferably, it has a functional group in the both ends of a polymer.

  A polyether polymer having an average of less than 1.2 crosslinkable silyl groups can also be used. In this case, a cured product having high elongation at break, low bleeding, low surface contamination, and excellent paint adhesion can be obtained. Moreover, the viscosity of a composition can be reduced by setting the molecular weight of this polymer smaller. The lower limit of the number of crosslinkable silyl groups is preferably at least 0.1, more preferably 0.3 or more, and even more preferably 0.5 or more. The crosslinkable silyl group is preferably at the end of the molecular chain. Further, the crosslinkable silyl group of this polyether polymer is preferably only at one end in the main chain and not at the other end, but if it is less than 1.2 on average It is not particularly limited. In the case of reducing the viscosity by using a polyether polymer having an average of less than 1.2 crosslinkable silyl groups, the preferred molecular weight is less than 10,000, and further less than 5,000.

<Introduction method of crosslinkable silyl group>
The introduction of the crosslinkable silyl group may be performed by a known method. That is, for example, the following method can be mentioned. For example, an oxyalkylene polymer obtained using a double metal cyanide complex catalyst is disclosed in JP-A-3-72527, and an oxyalkylene polymer obtained using a polyphosphazene salt and active hydrogen as a catalyst is disclosed in -60723.

  (1) An oxyalkylene polymer having a functional group such as a hydroxyl group at the terminal is reacted with an organic compound having an active group and an unsaturated group that are reactive with the functional group, or an unsaturated group-containing epoxy compound To obtain an unsaturated group-containing oxyalkylene polymer. Next, hydrosilylation is performed by allowing hydrosilane having a crosslinkable silyl group to act on the obtained reaction product.

  (2) An unsaturated group-containing oxyalkylene polymer obtained in the same manner as in the method (1) is reacted with a compound having a mercapto group and a crosslinkable silyl group.

  (3) An oxyalkylene polymer having a functional group (hereinafter referred to as Y functional group) such as a hydroxyl group, an epoxy group or an isocyanate group at the terminal (hereinafter referred to as Y ′) And a compound having a crosslinkable silyl group). Examples of the silicon compound having a Y ′ functional group include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, 3- Amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyltrimethoxysilane, 4-amino-3-methylpropyltrimethoxysilane, 4-amino-3-methylpropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and amino group-containing silanes such as partial Michael addition reaction products of various amino group-containing silanes with maleic esters and acrylate compounds; γ-mercaptopropyltrimethoxysilane Γ-mercaptopropylmethyldi Mercapto group-containing silanes such as methoxysilane; epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; vinyltriethoxysilane, γ -Vinyl type unsaturated group-containing silanes such as methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, etc .; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; γ-isocyanatopropyl Isocyanate-containing silanes such as triethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltrimethoxysilane, etc .; methyldimethoxysilane, trimethoxysilane, methyldiethoxysilane, tri Specific examples include hydrosilanes such as ethoxysilane, but are not limited thereto.

  In addition, when producing a polymer having an average number of crosslinkable silyl groups of less than 1.2, when introducing a crosslinkable silyl group, a polyether-based polymer having only one functional group in the molecule is used. A method of obtaining a polyether polymer having an average of less than 1.2 crosslinkable silyl groups by reacting a compound having a crosslinkable silyl group with an equivalent amount or a smaller amount of the functional group. And, on the average, using a polyether polymer having one or more functional groups in the molecule and reacting with a compound having a crosslinkable silyl group that is smaller than the functional group, resulting in a crosslinkable silyl group. There is a method of obtaining a polyether polymer having an average of less than 1.2 groups.

<Amount of polyether polymer having a crosslinkable silyl group>
The amount used in the case of using the polyether polymer (IV) having a crosslinkable silyl group may be any amount, but for the vinyl polymer (I) having at least one crosslinkable silyl group, The weight ratio is preferably in the range of 100/1 to 1/100, more preferably in the range of 100/5 to 5/100, and still more preferably in the range of 100/10 to 10/100. The addition amount can be set according to each application and purpose. However, if the addition amount is too large, the excellent heat resistance and weather resistance, which are one of the effects of the present invention, may be lowered. When using a polyether polymer having an average of less than 1.2 crosslinkable silyl groups, the amount used is 1 part by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the vinyl polymer. It is preferably 3 parts by weight or more and 100 parts by weight or less, more preferably 5 parts by weight or more and 80 parts by weight or less. If it is less than 1 part by weight, the effect of addition is difficult to obtain, and if it exceeds 200 parts by weight, the physical properties of the cured product tend to become unstable.

  As an aspect to be used as a mixture, i) a vinyl polymer having a crosslinkable silyl group represented by the general formula (2), a polyether polymer having a crosslinkable silyl group, and an average of 1.2 polymers A polyether polymer having less than a crosslinkable silyl group, ii) a polyether polymer having a crosslinkable silyl group, and a vinyl polymer having a crosslinkable silyl group at one end; Iii) When adding a polyether polymer having a crosslinkable silyl group and a vinyl polymer having a crosslinkable functional group and a molecular weight distribution of 1.8 or more, the average is added. Adding a polyether polymer having less than 1.2 crosslinkable silyl groups and a vinyl polymer having a crosslinkable silyl group at one end, and iv) an average of 1.2 Less crosslinkable silyl groups A polyether polymer of a crosslinkable have a functional group molecular weight distribution is 1.8 or more of the vinyl polymer, it like the addition can be mentioned but not limited thereto.

<Arbitrary polymer components having various crosslinkable functional groups>
In the curable composition of the present invention, polymers having various crosslinkable functional groups may be added as optional components. Examples of the polymer having a crosslinkable functional group include (i) a polyisobutylene polymer having a crosslinkable functional group, particularly a polyisobutylene polymer having a crosslinkable silyl group, and (ii) polysiloxane. . These polymers can be added using 1 type (s) or 2 or more types. When these polymer optional components are added to the vinyl polymer having a crosslinkable silyl group of the present invention, the polymer has a hydrolyzable silicon group formed by bonding two hydrolyzable groups per silicon atom. A vinyl polymer and a polymer arbitrary component formed by bonding three hydrolyzable groups per crosslinkable functional group may be combined. Conversely, three hydrolyzable groups per silicon atom are combined. You may combine the vinyl polymer which has a hydrolysable silicon group formed by combining, and the polymer arbitrary component formed by combining two hydrolyzable groups per crosslinkable functional group. Also, any polymer may be a combination having a crosslinkable functional group formed by bonding three hydrolyzable groups, or a combination having a crosslinkable functional group formed by bonding two hydrolyzable groups. . Furthermore, one to three things may be mixed.

<Curable composition>
As described above, the curable composition of the present invention contains a vinyl polymer (I) having an average of at least one crosslinkable silyl group, a guanidine compound (II), and a carboxylic acid (III). A curable composition, wherein the content of carboxylic acid (III) contained in the curable composition is 1 to 10 equivalents in molar ratio to the content of guanidine compound (II). It is a composition.

  As described above, the curable composition according to the present invention is very useful as a one-component curable composition because it has excellent curability and viscosity storage stability, particularly surface curability and viscosity storage stability. . In addition, a polyether polymer (IV) can be contained as needed.

  Furthermore, in the curable composition of this invention, you may add various compounding agents according to the target physical property.

  In the present invention, the guanidine compound (II) is used as the silanol condensation catalyst, but other silanol condensation catalysts may be used in combination so as not to reduce the effects of the present invention. Specific examples include tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate, carboxyl Carboxylic acid metal salts such as iron oxide, cobalt carboxylate, nickel carboxylate, cerium carboxylate; tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diiso Titanium compounds such as propoxy titanium bis (ethylacetocetate); dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexyl) Noate), dibutyltin bis (methyl maleate), dibutyltin bis (ethyl maleate), dibutyltin bis (butylmaleate), dibutyltin bis (octylmaleate), dibutyltin bis (tridecylmaleate), dibutyl Tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (ethyl maleate), dioctyl tin bis (octyl maleate), dibutyl tin dimethoxide, dibutyl tin bis (nonyl phenoxide), dibutenyl tin oxide, dibutyl tin Organic tin compounds such as oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester; aluminum G Aluminum compounds such as tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate; zirconium compounds such as zirconium tetrakis (acetylacetonate); various metal alkoxides such as tetrabutoxyhafnium Organic organic phosphoric acid esters; organic sulfonic acids such as trifluoromethanesulfonic acid; and inorganic acids such as hydrochloric acid, phosphoric acid and boronic acid. By using these curing catalysts in combination, the catalytic activity is increased, and improvement in deep part curability, thin layer curability, adhesion and the like is expected. However, from the viewpoint of toxicity, it is preferable that the amount of the organic tin compound added is small. The non-organotin-based curable composition referred to in the present invention defines that the addition amount of the organic tin compound is 50% by weight or less in the compound component that acts as a silanol condensation catalyst. It is preferably 10% by weight or less, more preferably 1% by weight or less, and particularly preferably not contained. Furthermore, when the burden on the environment is taken into consideration, it is preferable that the addition amount of the metal compound other than the organotin compound is small.

  The curable composition of the present invention is a non-organic tin-based curable composition, but substantially contains a tin compound such as an organic tin-based compound or tin carboxylate from the viewpoint of toxicity or environmental load. Non-tin-based curable compositions are preferred, non-organic tin and non-carboxylic acid metal salt-based curable compositions substantially free of organic tin compounds and various carboxylic acid metal salts are more preferred, carboxylic acid metal salts Particularly preferred are non-metallic catalyst-based curable compositions that substantially do not contain the metal element-containing curing catalyst such as titanium compounds, organotin compounds, organoaluminum compounds, and zirconium compounds.

<Adhesive material>
An adhesiveness imparting agent can be used in the curable composition of the present invention. The adhesion imparting agent here is a compound having a hydrolyzable silicon group and other functional groups in the molecule, and various adherends, that is, inorganic materials such as glass, aluminum, stainless steel, zinc, copper, and mortar. When used for a base material or an organic base material such as vinyl chloride, acrylic, polyester, polyethylene, polypropylene, polycarbonate, etc., it shows a remarkable adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. In addition, it is a compound that can function as a physical property modifier, an inorganic filler dispersibility improver, and the like.

  Specific examples of the hydrolyzable silicon group of the adhesion-imparting agent include the groups already exemplified, but a methoxy group, an ethoxy group, and the like are preferable from the viewpoint of hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly 3 or more.

  Examples of functional groups other than hydrolyzable silicon groups include amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, and halogens. Of these, amino groups, epoxy groups, isocyanate groups, isocyanurates and the like are preferable because of their high effect of improving adhesiveness, and amino groups are particularly preferable.

  Specific examples of the adhesion-imparting agent include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and (isocyanatemethyl) trimethoxysilane. And isocyanate silanes such as (isocyanate methyl) dimethoxymethylsilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-amino Propylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2- Minoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) amino Ethyl) aminopropyltrimethoxysilane, γ- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, N -Cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Aminomethyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N -Cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N'-bis [3- (tri Aminosilanes such as methoxysilyl) propyl] ethylenediamine; ketimine silanes such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine; γ-mercaptopropyltrimethoxysilane; γ-mercaptopropi Mercaptosilanes such as triethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ- Epoxy such as glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Silanes: β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane Carboxysilanes; vinyl type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxysilane; Halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (3-trimethoxysilylpropyl) isocyanurate, and the like. The reaction product of aminosilane and epoxysilane, the reaction product of aminosilane and isocyanate silane, or the like can also be used. Condensates obtained by partially condensing the silanes can also be used. Furthermore, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives obtained by modifying these, can also be used as an adhesion-imparting agent.

  The adhesiveness-imparting agent may be used alone or in combination of two or more.

  The amount of the adhesion-imparting agent used is preferably about 0.01 to 20 parts by weight and more preferably about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group. About 1 to 7 parts by weight is preferable. If the blending amount of the adhesiveness-imparting agent is below this range, sufficient adhesion may not be obtained. On the other hand, if the blending amount of the adhesion-imparting agent exceeds this range, practical deep curability may not be obtained.

  As the adhesiveness imparting agent, in addition to the adhesiveness imparting agent, the adhesiveness imparting agent is not particularly limited. For example, epoxy resins, phenol resins, sulfur, alkyl titanates, aromatic polyisocyanates, and the like can be used. The adhesiveness-imparting agent may be used alone or in combination of two or more. However, since the epoxy resin may reduce the catalytic activity of the guanidine compound (II) depending on the addition amount, it is preferable that the addition amount of the epoxy resin is small in the curable composition of the present invention. The amount of the epoxy resin used is preferably 5 parts by weight or less, more preferably 0.5 parts by weight or less, and substantially contains 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group. It is particularly preferred not to.

<Filler>
A filler can be added to the composition of the present invention. Fillers include reinforcing silica such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate Diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenolic resin and vinylidene chloride Examples thereof include fillers such as resin powders such as resin organic microballoons, PVC powder, and PMMA powders; and fibrous fillers such as glass fibers and filaments. When using a filler, the amount of use is 1-250 weight part with respect to 100 weight part of vinyl-type polymer (I) which has a crosslinkable silyl group, Preferably it is 10-200 weight part.

  When you want to obtain a hardened product with high strength by using these fillers, mainly fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment fine A filler selected from calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable, and used in the range of 1 to 200 parts by weight with respect to 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group. Favorable results are obtained. In addition, when it is desired to obtain a cured product having low strength and high elongation at break, mainly calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon When a filler selected from the above is used in a range of 5 to 200 parts by weight with respect to 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group, preferable results are obtained. In general, calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases. Of course, these fillers may be used alone or in combination of two or more. When calcium carbonate is used, it is desirable to use a combination of surface treated fine calcium carbonate and heavy calcium carbonate such as heavy calcium carbonate. The particle diameter of the surface-treated fine calcium carbonate is preferably 0.5 μm or less, and the surface treatment is preferably treated with a fatty acid or a fatty acid salt. Moreover, the particle size of calcium carbonate having a large particle size is preferably 1 μm or more, and an untreated surface can be used.

  In order to improve the workability (such as sharpness) of the composition and to make the surface of the cured product matt, it is preferable to add an organic balloon or an inorganic balloon. These fillers can be surface-treated, and may be used alone or in combination of two or more. In order to improve workability (such as sharpness), the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, 5-300 μm is preferable.

  The composition of the present invention is an adhesive for exterior wall joints, exterior wall tiles, and exterior wall tiles such as sizing boards, especially ceramic sizing boards, due to the good chemical resistance of the cured product. However, it is desirable that the design of the outer wall and the design of the sealing material are harmonized. In particular, high-quality outer walls are used as outer walls due to the mixture of spatter coating, colored aggregates, and the like. When a scaly or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5.0 mm, is blended in the composition of the present invention, the cured product is in harmony with such a high-quality outer wall. However, since the chemical resistance is excellent, the appearance of the cured product is an excellent composition that lasts for a long time. When a granular material is used, the surface becomes sandy or sandstone-like rough, and when a scaly material is used, the surface becomes uneven.

  As described in JP-A-9-53063, preferable diameters, blending amounts, materials, and the like of the scaly or granular substance are as follows.

  The diameter is 0.1 mm or more, preferably about 0.1 to 5.0 mm, and a material having an appropriate size is used according to the material and pattern of the outer wall. The thing of about 0.2 mm-5.0 mm and about 0.5 mm-5.0 mm can also be used. In the case of a scaly substance, the thickness is about 1/10 to 1/5 of the diameter (about 0.01 to 1.00 mm). The scale-like or granular substance is mixed in advance in the main sealing material and transported to the construction site as a sealing material, or mixed in the main sealing material at the construction site when used.

  The scale-like or granular substance is blended in an amount of about 1 to 200 parts by weight with respect to 100 parts by weight of a composition such as a sealing material composition or an adhesive composition. The blending amount is appropriately selected depending on the size of each scale-like or granular substance, the material of the outer wall, the pattern, and the like.

  As the scale-like or granular substance, natural substances such as silica sand and mica, synthetic rubber, synthetic resin, and inorganic substances such as alumina are used. In order to enhance the designability when filling the joint, it is colored in an appropriate color according to the material and pattern of the outer wall. A preferable finishing method and the like are described in JP-A-9-53063.

  Further, if a balloon (preferably having an average particle size of 0.1 mm or more) is used for the same purpose, the surface becomes sandy or sandstone-like, and the weight can be reduced. As described in JP-A-10-251618, preferred diameters, blending amounts, materials, and the like of the balloon are as follows.

  The balloon is a spherical filler with a hollow inside. Examples of the balloon material include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran, but are not limited thereto. An inorganic material and an organic material can be combined or laminated to form a plurality of layers. An inorganic or organic balloon or a combination of these can be used. The balloons used may be the same balloon or a mixture of different types of balloons. Furthermore, the balloon can be used by processing or coating the surface thereof, or can be used by treating the surface with various surface treatment agents. For example, an organic balloon may be coated with calcium carbonate, talc, titanium oxide, or the like, or an inorganic balloon may be surface treated with an adhesion-imparting agent.

  The balloon preferably has a particle size of 0.1 mm or more in order to obtain a surface having a sandy or sandstone texture. The thing of about 0.2 mm-5.0 mm and about 0.5 mm-5.0 mm can also be used. If it is less than 0.1 mm, even if it is blended in a large amount, it may only increase the viscosity of the composition and the rough feeling may not be exhibited. The blending amount of the balloon can be easily determined according to the desired degree of sanding tone or sandstone tone. In general, it is desirable to blend those having a particle size of 0.1 mm or more in a ratio of 5 to 25 vol% in terms of volume concentration in the composition. When the volume concentration of the balloon is less than 5 vol%, there is no feeling of roughness, and when it exceeds 25 vol%, the viscosity of the sealing material and the adhesive becomes high, the workability is poor, the modulus of the cured product is also high, and the sealing material and bonding The basic performance of the agent tends to be impaired. The volume concentration with a particularly preferable balance with the basic performance of the sealing material is 8 to 22 vol%.

  When using a balloon, the anti-slip agent as described in JP-A-2000-154368 and the surface of a cured product as described in JP-A-2001-164237 are matted to give an uneven state. An amine compound for obtaining a state, particularly a primary and / or secondary amine having a melting point of 35 ° C. or higher can be added.

  Specific examples of balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113073, JP-A-9-53063, JP-A-10-10. -251618, JP-A-2000-154368, JP-A-2001-164237, WO 97/05201, and the like.

  Even when the composition of the present invention contains particles of cured sealant, the cured product can form irregularities on the surface and improve the design. The preferable diameter, blending amount, material and the like of the cured sealant particles are as follows as described in JP-A-2001-115142. The diameter is preferably about 0.1 mm to 1 mm, more preferably about 0.2 to 0.5 mm. The blending amount is preferably 5 to 100% by weight, more preferably 20 to 50% by weight in the curable composition. Examples of the material include urethane resin, silicone, modified silicone, polysulfide rubber and the like, and are not limited as long as they are used for the sealing material, but a modified silicone-based sealing material is preferable.

  Moreover, a silicate can be used for the composition of this invention. This silicate acts as a cross-linking agent and has a function of improving the resilience, durability, and creep resistance of the organic polymer that is the component (I) of the present invention. Furthermore, it also has the effect of improving adhesiveness, water-resistant adhesiveness, and adhesive durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane or a partial hydrolysis condensate thereof can be used. When using a silicate, the usage-amount is 0.1-20 weight part with respect to 100 weight part of organic polymer of (I) component, Preferably it is 0.5-10 weight part.

Specific examples of the silicate include tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxy. Examples thereof include tetraalkoxysilanes (tetraalkylsilicates) such as silane, tetra-i-butoxysilane, and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.
The partial hydrolysis-condensation product of tetraalkoxysilane is more preferable because the effect of improving the resilience, durability, and creep resistance of the present invention is greater than that of tetraalkoxysilane.

  Examples of the partially hydrolyzed condensate of tetraalkoxysilane include those obtained by adding water to tetraalkoxysilane and condensing it by partial hydrolysis. A commercially available product can be used as the partially hydrolyzed condensate of the organosilicate compound. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).

<Plasticizer>
A plasticizer can be added to the composition of the present invention. By adding a plasticizer, the viscosity and slump property of the curable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted. Examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate and butyl benzyl phthalate; non-aromatics such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate and diisodecyl succinate Dibasic acid esters; Aliphatic esters such as butyl oleate and methyl acetylricinolinate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorinated paraffins; Alkyldiphenyl And hydrocarbon oils such as partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

  Moreover, a polymeric plasticizer can be used. When a high-molecular plasticizer is used, the initial physical properties are maintained over a long period of time as compared with the case where a low-molecular plasticizer that is a plasticizer containing no polymer component in the molecule is used. Furthermore, the drying property (also referred to as paintability) when an alkyd paint is applied to the cured product can be improved. Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester plasticizer obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; Are 1000 or more polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., or the hydroxyl groups of these polyether polyols are ester groups, ethers Polyethers such as derivatives converted into groups, etc .; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like, but are not limited thereto is not.

  Of these polymer plasticizers, those compatible with the vinyl polymer (I) having a crosslinkable silyl group are preferred. From this point, polyethers and vinyl polymers are preferable. Further, when polyethers are used as a plasticizer, the surface curability and deep part curability are improved, and the curing delay after storage does not occur. Polypropylene glycol is more preferred. Moreover, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are preferable, and acrylic polymers such as polyacrylic acid alkyl esters are more preferable. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer described in JP-A-2001-207157 at high temperature and high pressure.

  The number average molecular weight of the polymer plasticizer is preferably 500 to 15000, more preferably 800 to 10000, still more preferably 1000 to 8000, and particularly preferably 1000 to 5000. Most preferably, it is 1000-3000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.80. 1.70 or less is more preferable, 1.60 or less is more preferable, 1.50 or less is more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

  The number average molecular weight is measured by a GPC method in the case of a vinyl polymer, and by a terminal group analysis method in the case of a polyether polymer. Moreover, it is measured by molecular weight distribution (Mw / Mn) GPC method (polystyrene conversion).

  The polymer plasticizer may not have a reactive silicon group, but may have a reactive silicon group. When it has a reactive silicon group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product. In the case of having a reactive silicon group, the average number per molecule is preferably 1 or less, more preferably 0.8 or less. When using a plasticizer having a reactive silicon group, particularly an oxyalkylene polymer having a reactive silicon group, the number average molecular weight must be lower than that of the vinyl polymer (I) having a crosslinkable silyl group. .

A plasticizer may be used independently and may use 2 or more types together. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.
The amount of the plasticizer used is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group. . If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.

  Moreover, the thermally expansible fine particle hollow body as described in Unexamined-Japanese-Patent No. 2004-51701, 2004-66749, etc. can be used. The thermally expandable fine hollow body is a polymer outer shell material (vinylidene chloride copolymer, acrylonitrile copolymer, or vinylidene chloride-acrylonitrile copolymer weight) such as a hydrocarbon having 1 to 5 carbon atoms. It is a plastic sphere wrapped in a spherical shape. By heating the bonding part using this composition, the gas pressure in the shell of the thermally expandable fine hollow body increases, and the volume of the polymer outer shell material softens, so that the volume expands dramatically and the bonding interface is Plays the role of peeling. By adding the thermally expandable fine hollow body, it is possible to obtain an adhesive composition that can be easily peeled off without destroying the material simply by heating when not necessary, and can be peeled off without using any organic solvent.

<Tackifying material>
A tackifier can be added to the composition of the present invention. Although it does not specifically limit as tackifying resin, What is normally used regardless of solid and liquid at normal temperature can be used. Specific examples include styrenic block copolymers, hydrogenated products thereof, phenolic resins, modified phenolic resins (eg, cashew oil-modified phenolic resin, tall oil-modified phenolic resin, etc.), terpene phenolic resins, xylene-phenolic resins, cyclohexane. Pentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon resin, C9) Hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, terpene resin, DCPD resin petroleum resin and the like. These may be used alone or in combination of two or more. Styrene block copolymers and their hydrogenated products include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), and styrene-ethylenebutylene-styrene block copolymers. (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), styrene-isobutylene-styrene block copolymer (SIBS), and the like. The tackifying resins may be used alone or in combination of two or more.

  The tackifying resin is used in an amount of 5 to 1,000 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group.

  A solvent or diluent can be added to the composition of the present invention. Although it does not specifically limit as a solvent and a diluent, Aliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon, alcohol, ester, ketone, ether etc. can be used. When a solvent or diluent is used, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher because of the problem of air pollution when the composition is used indoors. . The said solvent or diluent may be used independently and may be used together 2 or more types.

<Physical property modifier>
You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention. Although it does not specifically limit as a physical property regulator, For example, alkyl alkoxysilanes, such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxy Alkoxysilanes having a functional group such as a silane; silicone varnishes; polysiloxanes and the like. By using the physical property modifier, it is possible to increase the hardness when the composition of the present invention is cured, or to decrease the hardness and break elongation. The said physical property modifier may be used independently and may be used together 2 or more types.

In particular, a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. Particularly preferred are compounds that produce trimethylsilanol. As a compound which produces | generates the compound which has a monovalent silanol group in a molecule | numerator by hydrolysis, the compound described in Unexamined-Japanese-Patent No. 5-117521 can be mention | raise | lifted. In addition, derivatives of alkyl alcohols such as hexanol, octanol, decanol, and the like, which generate a silicon compound that generates R ₃ SiOH such as trimethylsilanol by hydrolysis, trimethylol described in JP-A-11-241029 Examples thereof include compounds that are derivatives of polyhydric alcohols having 3 or more hydroxyl groups such as propane, glycerin, pentaerythritol, sorbitol, and the like, which generate silicon compounds that generate R ₃ SiOH such as trimethylsilanol by hydrolysis.

Further, there may be mentioned also compounds which produce a silicon compound that produces R ₃ SiOH such as trimethyl silanol a derivative of oxypropylene polymer as described in JP-A-7-258534 by hydrolyzing. Furthermore, a polymer having a crosslinkable hydrolyzable silicon-containing group and a silicon-containing group that can be converted into a monosilanol-containing compound by hydrolysis as described in JP-A-6-279893 can also be used.

  The physical property modifier is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group.

  A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, when rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used, thixotropy is high. A composition having good workability can be obtained. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group.

  In the composition of the present invention, a compound containing an epoxy group in one molecule can be used. When a compound having an epoxy group is used, the restorability of the cured product can be improved. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, Examples thereof include epoxy butyl stearate. Of these, E-PS is particularly preferred. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group.

<Photo-curing substance>
A photocurable material can be used in the composition of the present invention. When a photocurable material is used, a film of a photocurable material is formed on the surface of the cured product, and the stickiness and weather resistance of the cured product can be improved. A photocurable substance is a substance that undergoes a chemical change in its molecular structure in a very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like. Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) acrylate or oligoesters having a molecular weight of 10,000 or less. Specifically, for example, a special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400, etc., but particularly contain acrylic functional groups The compound which contains 3 or more same functional groups on average in 1 molecule is preferable. (All Aronix is a product of Toa Gosei Chemical Co., Ltd.)

  Examples of the polyvinyl cinnamates include photosensitive resins having a cinnamoyl group as a photosensitive group, and those obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many polyvinyl cinnamate derivatives. The azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972). There are detailed examples in publishing, publishing society of printing society publication, page 93-, page 106-, page 117-), these may be used alone or in combination, and a sensitizer may be added if necessary. Can do. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect. The photocurable substance is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group. If it is 0.1 parts by weight or less, there is no effect of improving the weather resistance, and if it is 20 parts by weight or more, the cured product tends to be too hard and tends to crack.

<Oxygen curable substance>
An oxygen curable substance can be used in the composition of the present invention. Examples of the oxygen curable substance include unsaturated compounds that can react with oxygen in the air. The oxygen curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product. And prevents dust from adhering. Specific examples of the oxygen curable substance include drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified with drying oils , Silicone resins; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene and 1,3-pentadiene Liquid polymers, liquid copolymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene copolymerizable with these diene compounds so that the main component is a diene compound, Further, various modified products thereof (maleinized modified products, boiled oil modified products, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Of these, drill oil and liquid diene polymers are particularly preferable. Moreover, the effect may be enhanced if a catalyst for promoting the oxidative curing reaction or a metal dryer is used in combination. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds. The amount of the oxygen curable substance to be used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group. -10 parts by weight. If the amount used is less than 0.1 parts by weight, the improvement of the contamination is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in JP-A-3-160053, the oxygen curable substance is preferably used in combination with a photocurable substance.

<Antioxidant>
An antioxidant (antiaging agent) can be used in the composition of the present invention. When antioxidant is used, the heat resistance of hardened | cured material can be improved. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all manufactured by Ciba Geigy Japan); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (all above Also manufactured by Adeka Argus Chemical Co., Ltd.); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Co., Ltd.) A hindered amine light stabilizer can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group having a reactive silicon group. Preferably it is 0.2-5 weight part.

<Light stabilizer>
A light stabilizer can be used in the composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred. The light stabilizer may be used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group. 5 parts by weight. Specific examples of the light stabilizer are also described in JP-A-9-194731.

<Photo-curing substance>
When a photocurable substance is used in combination with the composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine-containing hindered amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. The use of a light stabilizer is preferred for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 119FL (all of which are manufactured by Ciba Geigy Japan); MARK LA-57, LA-62, LA-67, LA-63 (all of which are ADEKA) Examples include light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Corporation).

<Ultraviolet absorber>
An ultraviolet absorber can be used in the composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of ultraviolet absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds, with benzotriazole being particularly preferred. The ultraviolet absorber is used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group. 5 parts by weight. It is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

<Aqueous dispersion>
An aqueous dispersion can be used in the composition of the present invention. Use of an aqueous dispersion brings about an effect of improving the adhesion of the cured product. Examples of such aqueous dispersions include suspensions in which oils and fats of about 0.001 to 5 μm or synthetic resins are forcibly dispersed, thermoplastic resins obtained by forced emulsification, such as styrene butadiene styrene block copolymers, and the like. Although mentioned, the particle | grains which consist of a synthetic resin emulsion obtained by the emulsion polymerization or the emulsion dispersion | distribution process are advantageous on stability and economical efficiency.

  The particles composed of synthetic resin emulsion include styrene butadiene styrene block copolymer emulsion, styrene butadiene copolymer emulsion, acrylonitrile butadiene copolymer emulsion, acrylic resin emulsion, polychloroprene emulsion, vinyl pyridine copolymer emulsion, polyisoprene. Resin particles obtained from emulsion, polybutadiene emulsion, vinyl chloride emulsion, vinylidene chloride emulsion, wax emulsion, urethane resin emulsion, vinyl acetate emulsion, ethylene / vinyl acetate copolymer (EVA) emulsion, etc. A styrene butadiene copolymer emulsion is preferred. These can be used alone or in combination of two or more.

  The styrene butadiene copolymer emulsion can be copolymerized with the following monomers as required. That is, examples of the copolymerizable monomer include a (meth) acrylic acid alkyl ester monomer, an ethylenically unsaturated carboxylic acid monomer, and a vinyl cyanide monomer. These may be used singly or in combination of two or more, but may be used in a range where the sum total does not exceed 30% with respect to the styrene-butadiene copolymer component.

  As an emulsifier, for example, anionic emulsifiers such as fatty acid soap, rosin acid soap, alkyl sulfonate, dialkyl aryl sulfonate, alkyl sulfo succinate, polyoxyethylene alkyl sulfate and polyoxyethylene alkyl aryl sulfate are used. Can do. If necessary, known anionic emulsifiers such as nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether and polyoxyethylene oxypropylene block copolymer can be used. In addition, reactive surfactants having an ethylenic double bond introduced into the chemical structure of a surfactant having a hydrophilic group and a lipophilic group can also be used. Further, amphoteric emulsifiers such as betaine type and water-soluble such as polyvinyl alcohol A protective colloid emulsifier of a functional polymer can be used as necessary.

  The styrene-butadiene copolymer emulsion preferably has a glass transition point in the range of 10 to -50 ° C, more preferably -10 to -50 ° C. If the glass transition point exceeds 10 ° C, the effect of imparting adhesion is difficult to be exhibited at an air temperature of 20 ° C or higher, and if it falls below -50 ° C, it may not be uniformly dispersed during the production process.

  As a compounding quantity of the said synthetic resin emulsion which brings about an adhesive improvement effect, 5-30% is preferable with respect to 100 weight part of vinyl-type polymer (I) which has at least 1 crosslinkable silyl group on average. If it is less than 5%, the adhesion improving effect cannot be obtained, and if it exceeds 30%, the viscosity is remarkably increased, and the emulsion is easily aggregated and is not stable as a product.

  Although details of the mechanism of the adhesion improving action of the styrene-butadiene copolymer emulsion are not clear, the single substance has poor compatibility with the vinyl polymer (I) having at least one crosslinkable silyl group on average and is stable. It is difficult to disperse in the above. In addition, a resin that completely dissolves in the vinyl polymer (I) having at least one crosslinkable silyl group on average cannot obtain an adhesion improving effect. On the other hand, asphalt waterproofing layer terminals are obtained by finely dispersing the styrene-butadiene copolymer, which is an aqueous dispersion in advance, into the vinyl polymer (I) having at least one crosslinkable silyl group on average. It is presumed that it is selectively adsorbed to the interface of the vinyl polymer (I) layer having an average of at least one crosslinkable silyl group on the surface coated with asphalt primer. In addition, a similar effect is obtained on the surface after moisture curing, and the plasticizer component added for improving workability is held inside the cured body, and has an asphalt-based adhesive material to suppress the bleeding phenomenon. Even when the self-attaching roofing is bonded, sufficient adhesion is imparted.

  In the production of a one-component curable composition that is particularly useful as the curable composition according to the present invention, in step 1, vinyl polymer (I) having at least one crosslinkable silyl group on average. And vinyl resin (I) having an average of at least one crosslinkable silyl group by mixing water and a synthetic resin emulsion as an aqueous dispersion uniformly, and heating and dehydrating water contained in the synthetic resin emulsion The synthetic resin emulsion particles are finely dispersed.

When the plasticizer is charged at the same time in Step 1 and uniformly mixed,
A: The aqueous dispersion (synthetic resin emulsion) is compatible with the vinyl polymer (I) having at least one crosslinkable silyl group on the average through a plasticizer, and the adhesion imparting effect cannot be obtained.
B: The vinyl polymer (I) having at least one crosslinkable silyl group on average has a low viscosity, and it is impossible to form a finely dispersed state of the synthetic resin emulsion particles, resulting in a decrease in adhesive force and the like. .

Also, when charging the filler at the same time,
C: While moisture in the synthetic resin emulsion is absorbed into the filler, the heat dehydration efficiency is significantly reduced.
D: The filler is agglomerated to form a lump, and a uniform kneading state cannot be obtained.

  The one-component curable composition can be produced by a conventionally known kneading method. For example, using a closed processing kettle equipped with a stirrer, a condenser, a heating device, a vacuum dehydrating device, and a nitrogen stream device, a vinyl polymer (I) having an average of at least one crosslinkable silyl group in the kettle and synthesis Charge the resin emulsion, mix homogeneously under nitrogen reflux using a nitrogen airflow device, heat depressurize and dehydrate until a predetermined amount of water is reached, and after step 1, insert the filler and use the nitrogen airflow device Then, it has the process 2 which carries out the homogeneous mixing under nitrogen recirculation | reflux, and heat-dehydrates and dehydrates until it becomes a predetermined moisture content.

  After the step 1 and step 2, a plasticizer is added, and the mixture is homogeneously mixed under nitrogen reflux, followed by dehydration by heating under reduced pressure until a predetermined water content is reached.

<Other additives>
Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, curability regulators, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, and anti-anticides. And fungicides. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives listed in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904, It is described in Japanese Laid-Open Patent Publication No. 2001-72854.

<Preparation of one-component curable composition>
The curable composition according to the present invention can be prepared as a one-pack type in which all the ingredients are pre-blended and sealed and cured by moisture in the air after construction. The one-component curable composition of the present invention is excellent in curability and storage stability of viscosity, which have been a problem with conventional one-component curable compositions, and does not impair initial curability and mechanical properties. A cured product that suppresses surface coloring can be provided. In addition, the trouble of mixing and kneading is not required at the time of construction, and at the same time, there is no weighing error (mixing ratio error) occurring at that time, so that errors such as poor curing can be prevented.

  The one-component curable composition that is particularly useful as the curable composition according to the present invention is a composition in which all the compounding components are preliminarily blended and stored and cured by moisture in the air after construction.

  In the one-pack type curable composition, since all the blending components are blended in advance, it is preferable that the blending components containing moisture be used after being dehydrated and dried in advance or dehydrated under reduced pressure during blending and kneading. . For dehydration and drying methods, heat drying method or vacuum dehydration method for solid materials such as powders, dehydration method using vacuum zeolite or activated zeolite, silica gel, quick lime, magnesium oxide for liquid materials The method is preferred. In addition to the dehydration drying method, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ- An alkoxysilane compound such as glycidoxypropyltrimethoxysilane may be added and reacted with water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Addition of an alkoxysilane compound, an oxazolidine compound, and an isocyanate compound improves storage stability.

  The amount of the silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane, is preferably 0.1 to 20 parts by weight, preferably 100 parts by weight of vinyl polymer (I) having a crosslinkable silyl group. Is preferably in the range of 0.5 to 10 parts by weight.

  The method for preparing the curable composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, roll, kneader or the like at room temperature or under heating, or a small amount of a suitable solvent is used. Ordinary methods such as dissolving and mixing the components may be employed.

  When exposed to the atmosphere, the curable composition of the present invention forms a three-dimensional network structure by the action of moisture, and cures to a solid having rubbery elasticity.

<Application>
The one-component curable composition that is particularly useful as the curable composition according to the present invention is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold preparation, a vibration isolator, It can be used for damping materials, soundproof materials, foam materials, paints, spray materials, etc. Since the hardened | cured material obtained by hardening | curing the curable composition of this invention is excellent in a softness | flexibility and adhesiveness, it is more preferable to use as a sealing material or an adhesive agent among these.

  Also, electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact type adhesives, spray type sealing materials, crack repair materials, and tiles Adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical device sealing materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, primers, electromagnetic wave shielding Conductive materials, thermal conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and sealing materials for anticorrosion and waterproofing of meshed glass and laminated glass end faces (cut parts), automobiles It can be used for various applications such as liquid sealants used in parts, electrical parts, various machine parts and the like. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin molding, etc. alone or with the aid of a primer, it can also be used as various types of sealing compositions and adhesive compositions. Further, the curable composition of the present invention is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, adhesives for vehicle panels, adhesives for assembly of electrical / electronic / precision equipment, sealing materials for direct glazing, sealing materials for multi-layer glass, sealing materials for SSG construction methods, or sealing materials for building working joints Can also be used.

  Specific examples of the present invention are shown below, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, “part” represents “part by weight”. “Number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, as a GPC column, a column filled with polystyrene cross-linked gel (shodex GPC K-804, K-802.5; manufactured by Showa Denko KK) was used as the GPC solvent.

The number of functional groups introduced per molecule of polymer was calculated based on the concentration analysis by ¹ H-NMR and the number average molecular weight determined by GPC. NMR was measured at 23 ° C. using Bruker ASX-400 (400 MHz) and deuterated chloroform as a solvent.

<Synthesis example of poly (n-butyl acrylate) polymer having crosslinkable silyl group>
(Synthesis Example 1)
Under a nitrogen stream, 20 parts of n-butyl acrylate, 0.88 parts of copper (I) bromide, 8.7 parts of acetonitrile, and 1.8 parts of diethyl 2,5-dibromoadipate were charged and stirred at 80 ° C. To this was added 0.018 part of pentamethyldiethylenetriamine (hereinafter referred to as triamine) to initiate the reaction. In the middle, 80 parts of n-butyl acrylate was intermittently added, and further stirring was continued while adding triamine as appropriate so that the temperature of the reaction solution became 80 ° C to 90 ° C. After the reaction rate of butyl acrylate reached 95%, the inside of the reaction vessel was depressurized to remove volatile components.

  To this, 34.9 parts of acetonitrile and 22.5 parts of 1,7-octadiene were added, triamine was further added, and the mixture was heated and stirred at 80 ° C. Thereafter, the pressure inside the reaction vessel was reduced to remove volatile components.

  This was diluted with toluene, synthetic hydrotalcite, aluminum silicate and filter aid were added, and the mixture was heated and stirred in an oxygen / nitrogen mixed gas atmosphere. After removing solids, the solution was concentrated. Synthetic hydrotalcite and aluminum silicate were added, and the mixture was heated and stirred under reduced pressure. This was diluted with toluene, and further, synthetic hydrotalcite and aluminum silicate were added and stirred with heating. After removing the solid content, the solution was concentrated to obtain an alkenyl-terminated copolymer [P1].

The number average molecular weight of the alkenyl terminal copolymer [P1] is 25000, the molecular weight distribution is 1.3, and the average number of alkenyl groups introduced into one molecule of the polymer is determined by concentration analysis by ¹ H-NMR analysis. It was 1.8 when it calculated from the number average molecular weight calculated | required by (3).

Polymer having an alkenyl group obtained by the above method, dimethoxymethylsilane (hereinafter referred to as DMS: 2.0 molar equivalent to alkenyl group), methyl orthoformate (1.0 molar equivalent to alkenyl group), platinum A catalyst [bis (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst in an isopropanol solution: hereinafter referred to as a platinum catalyst] (as platinum, 10 mg with respect to 1 kg of a polymer), The mixture was heated and stirred at 100 ° C. in a nitrogen atmosphere. After heating and stirring for about 1 hour, volatile components such as unreacted DMS were distilled off under reduced pressure to obtain a poly (acrylic acid-n-butyl) polymer [P1] having dimethoxysilyl groups at both ends. The number average molecular weight of the obtained polymer [P1] was about 26000, and the molecular weight distribution was 1.3. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H NMR analysis, it was about 1.8.

(Examples 1 to 8, Comparative Examples 1 to 6)
Polymer [P1] obtained in Synthesis Example 1, surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: Shiraka Hana CCR), heavy calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., trade name: Nanox 25A ), Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name: Taipei P-820), plasticizer (manufactured by Kyowa Hakko Co., Ltd., trade name: DIDP), thixotropic agent (manufactured by Enomoto Kasei Co., Ltd.) Name: Disparon # 6500), UV absorber (manufactured by Ciba Geigy Co., Ltd., trade name: Tinuvin 213), light stabilizer (manufactured by Sankyo Co., Ltd., trade name: Sanol LS765), and γ- (2- Aminoethyl) aminopropyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd., trade name: A-1120), vinyl trimethoxysilane (manufactured by Toray Dow Corning Co., Ltd., trade name: -171), 1-phenylguanidine (manufactured by Nippon Carbide Co., Ltd.) as the guanidine compound, neodecanoic acid (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Versatic 10), or ethylenediaminetetraacetic acid (EDTA: sum) According to the formulation tables of Tables 1 and 2, the components other than the dehydrating agent, the adhesion-imparting agent, and the curing catalyst were sufficiently stirred and mixed, and then dispersed through three paint rolls three times. Then, dehydration under reduced pressure at 120 ° C. for 2 hours, cooling to 50 ° C. or less, adding the dehydrating agent, adhesion-imparting agent, and curing catalyst described in Tables 1 and 2 and kneading, and substantially the presence of moisture After kneading in a state where it was not, it was sealed in a moisture-proof container to obtain a one-component curable composition. Tables 1 and 2 show the molar ratio of the added carboxylic acid (III) to the guanidine compound (II).

(Surface hardening)
The one-component curable composition is stretched to a thickness of about 3 mm under a constant temperature and humidity condition of 23 ° C. and 50%, and the surface of the curable composition is occasionally lightly touched using a microspatula. Was measured until the microspatula disappeared. The results are shown in Tables 3 and 4.

(Storage stability)
The one-component curable composition sealed in a moisture-proof container was cured in an oven at 50 ° C. for 4 weeks, and then surface curability and viscosity were measured. The cure delay rate was calculated from the surface curability after curing at 50 ° C. for 4 weeks / surface curability immediately after preparation. The thickening rate was calculated from viscosity at 50 ° C., 4 weeks later / viscosity immediately after preparation. The results are shown in Tables 3 and 4.

(Mechanical properties and appearance of cured product)
The one-component curable composition was applied to a sheet having a thickness of about 2 mm, and this sheet-like construction was allowed to stand at room temperature (23 ° C. × 55% RH) for 3 days, and further to 50 ° C. And cured for 4 days. A 2 (1/3) type dumbbell-shaped test piece shown in JIS K 7113 was punched out from the cured product after curing, and a tensile test (using Shimadzu autograph, measuring temperature: 23 ° C., tensile speed: 200 mm / min), the mechanical properties were measured. Further, the test piece was 23 ° C. × 55% R.D. H. The coloration of the cured product surface after standing for 1 month under the conditions was visually evaluated. The results are shown in Tables 3 and 4.
Coloring: ○ Good, colored yellow

  As shown in Examples 1 to 8, 1-phenylguanidine is contained as guanidine compound (II), Versatic 10 or ethylenediaminetetraacetic acid is further contained as carboxylic acid (III), and the content of carboxylic acid (III) However, when the molar ratio is 1 to 10 equivalents with respect to the content of the guanidine compound (II) contained in the composition, it can be seen that the surface curability and the storage stability of the viscosity are good. On the other hand, Comparative Examples 1, 3 to 5 not containing carboxylic acid (III), and further the content of carboxylic acid (III) is in molar ratio to the content of guanidine compound (II) contained in the composition. In Comparative Examples 2 and 6, which are less than 1, there is a noticeable delay in curing and an increase in viscosity after storage. Further, the mechanical properties are maintained almost constant even when carboxylic acid (III) is added, compared to the case where carboxylic acid (III) is not added. Further, the coloring of the cured product is improved by the addition of carboxylic acid (III).

(Examples 9 to 14, Comparative Examples 7 to 12)
Polymer [P1] obtained in Synthesis Example 1, a commercially available polyether polymer having a crosslinkable silyl group (manufactured by Kaneka Chemical Industry Co., Ltd .: SAX220), surface-treated colloidal calcium carbonate (white glaze CCR), heavy Calcium carbonate (Shiraishi Kogyo Co., Ltd., trade name: Nanox 25A), titanium oxide (Typaque R-820), plasticizer (DIDP), thixotropic agent (Dispalon # 6500), ultraviolet absorber (Tinuvin 213) The light stabilizer (Sanol LS765) was mixed and thoroughly kneaded according to the formulation table of Table 3, dispersed through three paint rolls, and then dehydrated under reduced pressure at 120 ° C. for 2 hours to obtain a main agent. Table 23 shows dehydrating agent (A-171), adhesion-imparting agent (A-1120), guanidine compound (1-phenylguanidine), and carboxylic acid (Versatic 10) with respect to the main agent under constant temperature and humidity conditions of 23 ° C. and 50%. After adding according to the recipe of 5, the surface curability was measured according to Example 1. The results are shown in Table 6.

  As shown in Examples 9 to 14, 1-phenylguanidine is contained as guanidine compound (II), Versatic 10 is further added as carboxylic acid (III), and the content of carboxylic acid (III) is When the molar ratio is 1 to 10 equivalents with respect to the content of the guanidine compound (II) contained therein, it can be seen that the surface curable storage stability is good. On the other hand, Comparative Examples 7, 9 and 11 that do not contain carboxylic acid (III), and the content of carboxylic acid (III) is in molar ratio to the content of guanidine compound (II) contained in the composition. In Comparative Examples 8, 10 and 12, which were 0.5, a significant delay in curing was observed after storage.

Claims (18)

A curable composition containing a vinyl polymer (I) having an average of at least one crosslinkable silyl group, a guanidine compound (II), and a carboxylic acid (III),
Curing characterized in that the content of the carboxylic acid (III) contained in the curable composition is 1 to 10 equivalents in molar ratio with respect to the content of the guanidine compound (II). Sex composition. The guanidine compound (II) is represented by the general formula (1):
R ¹ N═C (NR ¹ ₂ ) ₂ (1)
(Wherein ^one of five R ¹ is an aryl group and the remaining four are each independently a hydrogen atom or a hydrocarbon group in which the carbon atom at the 1-position is saturated). The curable composition according to claim 1.   The curable composition according to claim 1 or 2, wherein the guanidine compound (II) is at least one of 1-phenylguanidine and 1- (2-methylphenyl) guanidine.   The curable composition according to any one of claims 1 to 3, wherein the carboxylic acid compound (III) is an aliphatic monocarboxylic acid having 10 to 20 carbon atoms.   The curable composition according to claim 1, wherein the carboxylic acid compound (III) is an aliphatic polycarboxylic acid.   The curable composition according to any one of claims 1 to 5, wherein the vinyl polymer (I) has a molecular weight distribution of less than 1.8. The crosslinkable silyl group has the general formula (2):
_{^{- [Si (R 2) 2}} -b (Y) b O] m -Si (R 3) 3-a (Y) a (2)
(In the formula, R ² and R ³ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ² or When two or more R ³ are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0, 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1. It shall be satisfied that there is a thing) It is represented by any one of Claims 1-6 Curable composition.   The main chain of the vinyl polymer (I) is at least selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. The curable composition according to any one of claims 1 to 7, which is produced mainly by polymerizing one monomer.   The curable composition according to claim 8, wherein the main chain of the vinyl polymer (I) is a polymer composed of a (meth) acrylic monomer.   The curable composition according to claim 9, wherein the main chain of the vinyl polymer (I) is a polymer composed of an acrylic monomer.   The curable composition according to claim 10, wherein the main chain of the vinyl polymer (I) is a polymer composed of an acrylate ester monomer.   The curable composition according to any one of claims 1 to 11, wherein the main chain of the vinyl polymer (I) is produced by a living radical polymerization method.   The curable composition according to claim 12, wherein the main chain of the vinyl polymer (I) is produced by an atom transfer radical polymerization method.   The curable composition according to any one of claims 1 to 13, wherein the vinyl polymer (I) has the crosslinkable silyl group at a molecular chain terminal.   Furthermore, the curable composition in any one of Claims 1-14 containing polyether polymer (IV).   The curable composition according to claim 15, wherein the main chain of the polyether-based polymer (IV) is essentially polypropylene oxide.   The curable composition according to claim 15 or 16, wherein the polyether polymer (IV) is a polymer having an average of at least one crosslinkable silyl group.   The sealing material which uses the curable composition in any one of Claims 1-17.