JP2010111870A - Curable composition and sealing material for multilayered glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition capable to give a cured product excellent in creep resistance, weather resistant adhesiveness, water proof adhesiveness and low water absorbability, and is particularly effective for application as a sealing material for multilayered glass. <P>SOLUTION: The curable composition includes 100 pts.wt. of, a vinyl polymer (I) having at least one crosslinkable silyl group in average and a stress value of more than 0.10 MPa at 50% extension by the below determination method &lt;1&gt;, and &gt;=10 pts.wt. and &gt;=100 pts.wt. of a polyether polymer (II) having at least one crosslinkable silyl group in average and with a stress value of more than 0.20 MPa oat 50% extension by the below determination method &lt;2&gt;, and further includes (A) component (III) of a metal carboxylate (III-1) and/or a carboxylic acid (III-2), or (B) a titanium catalyst (IV), or (C) 0.01-0.5 pt.wt. of an organic tin catalyst (V) to the total amount of 100 pts.wt. of or the vinyl copolymer (I) and the polyether polymer (II). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

The present invention relates to a curable composition. More specifically, the present invention relates to a sealing material for multi-layer glass containing a vinyl polymer having a crosslinkable silyl group as a main component.

The amount of heat released from the glass window is said to be 20-30% for ordinary houses. Conventionally, in order to improve heat insulation and sound insulation, a plurality of (two or more) plate glasses are stacked. Constructed double glazing is used. This double-glazed glass has a minimum of two glass plates facing each other through a spacer, the glass plate and the spacer are brought into close contact with a butyl sealant (primary sealant) to block the hollow layer and the outside air, and then face each other. The gap formed by the inner surface of the glass plate and the outer periphery of the spacer is sealed with a polysulfide (PS), polyurethane (PU), or silicone (SR) room temperature curable sealing material (secondary sealing material). It is manufactured by the method. This method is called a dual seal method and is widely used.

The gas used for the hollow layer sandwiched between two glasses is generally air, but is filled with an inert gas such as argon, xenon, krypton, or SF ₆ to insulate the multilayer glass. Attempts have been made to improve performance and soundproofing performance.

On the other hand, in order to simplify the process, a single seal construction method using a butyl elastomer material or the like and assembling a multi-layer glass with only one kind of sealing material is disclosed in Patent Document 1 and the like. As pointed out in Patent Document 1, since the sealing material is a thermoplastic material, the problem of creep resistance has been pointed out.

Double-layer glass produced by the dual seal construction method has higher performance than the single seal construction method, but PS and PU which are secondary seal materials of the dual seal construction method are said to have a problem of weather resistance adhesion. Furthermore, as pointed out in Patent Document 2, the sealing material sometimes absorbs water due to the influence of moisture such as rainwater that has entered the sash. Moisture sucked into the sealing material may lower the adhesiveness, and the above-mentioned commercially available sealing material having a large water absorption rate also has a problem of water-resistant adhesiveness.

As pointed out in Patent Document 3, SR, which is the other secondary sealing material, has much higher gas permeability than organic sealing materials such as PS and PU, and is filled in the hollow layer. In addition, there is a problem that the gas reduction rate of the inert gas is large.

As described above, there is no known material that has various properties such as creep resistance, weather resistance adhesion, water resistance adhesion (low water absorption), and low gas permeability in the conventional sealing material for multi-layer glass. It was.

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 organic polymers having a crosslinkable silyl group, polyether polymers or vinyl polymers whose main chain skeleton is disclosed in Patent Document 4 and Patent Document 5 are already industrially produced. Widely used in applications such as sealing materials, adhesives and paints.

Patent Document 6 describes use as a sealing material for double-glazed glass using the vinyl polymer. However, even when the sealing material specifically described in Patent Document 6 is used, there are cases where sufficient creep resistance is not exhibited.

The curable composition containing an organic polymer having a crosslinkable silyl group is cured using a silanol condensation catalyst, and is usually an organic compound having a carbon-tin bond, such as dibutyltin bis (acetylacetonate). Tin-based catalysts are widely used.

Patent Documents 7 to 10 disclose curable compositions using carboxylic acid metal salts and / or carboxylic acids as silanol condensation catalysts other than organotin catalysts. Furthermore, curable compositions using titanium compounds as silanol condensation catalysts other than organotin catalysts are disclosed in Patent Documents 11 to 13, and the like.

WO05 / 108322 (US2007012572) Japanese Patent Laid-Open No. 2005-16188 JP 11-228190 A (US 6238755) JP 55-9669 A (US 4507469) JP-A-1-198673 (US52020379) JP 2005-281073 A JP2003-206410 (US20040198885) JP 2003-246861 A WO04 / 031300 (US20050171315) JP 2007-145880 A WO05 / 108498 WO05 / 108499 (US20080076878) WO05 / 108500

An object of this invention is to provide the curable composition which can obtain the hardened | cured material excellent in creep resistance, a weather-resistant adhesiveness, water-resistant adhesiveness, and low water absorption.

As a result of intensive studies by the present inventors in view of the above-described present situation, a vinyl polymer having a crosslinkable silyl group having a specific elongation stress and a polyether having a crosslinkable silyl group having a specific elongation stress. In addition to the curable composition containing a polymer based on a specific ratio, as a silanol condensation catalyst for these polymers, a carboxylic acid metal salt and / or a carboxylic acid, a titanium catalyst, or a specific amount of an organic tin catalyst The present inventors have found that the above problems can be improved by using the present invention.

That is, the present invention is a vinyl polymer (I) having an average of at least one crosslinkable silyl group, and a vinyl having a stress value at 50% elongation greater than 0.10 MPa according to the following measurement method <1>. 100 parts by weight of the polymer
A polyether polymer (II) having an average of at least one crosslinkable silyl group, and a polyether polymer having a stress value at 50% elongation greater than 0.20 MPa according to the following measurement method <2> A curable composition containing 10 parts by weight or more and 100 parts by weight or less,
further,
(A) As the component (III), carboxylic acid metal salt (III-1) and / or carboxylic acid (III-2),
(B) Titanium catalyst (IV) or
(C) 0.01 to 0.5 parts by weight of organotin catalyst (V) with respect to 100 parts by weight of the total amount of vinyl polymer (I) and polyether polymer (II)
It relates to the curable composition characterized by containing.
[50% elongation stress]
Measuring method <1>
To 100 parts by weight of the vinyl polymer, 2 parts by weight of tin octylate and 0.5 parts by weight of laurylamine are added and mixed, and then the centrifugally defoamed mixture is prevented from entering bubbles in the polyethylene mold. Pour No. 3 dumbbell from a 3 mm thick cured sheet obtained by casting and curing at 50 ° C. for 20 hours, and performing a tensile test at 23 ° C. and 50% RH (tensile speed 200 mm / min) Required 50% elongation stress measurement method <2>
To 100 parts by weight of the polyether polymer, 1.5 parts by weight of tin octylate, 0.25 parts by weight of laurylamine, and 0.6 parts by weight of pure water were added and mixed. Pour No. 3 dumbbells in accordance with JISK6251 from a cured sheet of 3 mm thickness obtained by pouring in a mold to prevent bubbles from entering, and curing at 23 ° C. for 1 hour and further at 70 ° C. for 20 hours, 50% elongation stress obtained by performing a tensile test (tensile speed: 200 mm / min) at 23 ° C. and 50% RH

The molecular weight distribution of the vinyl polymer (I) is preferably less than 1.8.

The crosslinkable silyl group of the vinyl polymer (I) has the general formula (1):
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(Wherein, R ¹ and R ² are the same or different and each represents 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 (In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ′ may be the same or different. When two or more R ¹ or R ² groups are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and two or more Y groups are present. They may be the same or different, a represents 0, 1, 2, or 3. b represents 0, 1, or 2. m represents an integer of 0 to 19. And a + mb ≧ 1 is satisfied.)

The main chain of the vinyl polymer (I) is mainly a monomer 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 manufactured.

The main chain of the vinyl polymer (I) is preferably a (meth) acrylic polymer.

The (meth) acrylic polymer is preferably an acrylic polymer.

The acrylic polymer is preferably an acrylic ester polymer.

The main chain of the vinyl polymer (I) is preferably produced by a living radical polymerization method.

The living radical polymerization method is preferably 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 vinyl polymer (I) preferably has an average of 1.1 to 4.0 crosslinkable silyl groups per molecule.

The number average molecular weight of the vinyl polymer (I) is preferably 10,000 or more and 40,000 or less.

The crosslinkable silyl group of the polyether polymer (II) has the general formula (1):
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(Wherein R ¹ , R ² , Y, a, b, and m are the same as those described above).

It is preferable that the main chain of the polyether polymer (II) is essentially polypropylene oxide.

It is preferable that the polyether polymer (II) is a polyether polymer having one or more branched chains.

The polyether polymer (II) preferably has an average of 1.1 or more and 4.0 or less crosslinkable silyl groups per molecule.

The number average molecular weight of the polyether polymer (II) is preferably 10,000 or more and 50,000 or less.

In the curable composition (A) comprising (I), (II) and (III), the component (III) is only one of the carboxylic acid metal salt (III-1) and the carboxylic acid (III-2). It is preferable to contain.

In the curable composition (A) comprising (I), (II) and (III), the component (III) contains both the carboxylic acid metal salt (III-1) and the carboxylic acid (III-2). Is preferred.

In the curable composition (A) comprising (I), (II) and (III), the carboxylic acid metal salt (III-1) has a tertiary carbon atom adjacent to the carbonyl group constituting the carboxylic acid ion. Or it is preferable that it is a carboxylic acid metal salt which is quaternary carbon.

In the curable composition (A) comprising (I), (II) and (III), the carboxylic acid (III-2) has a tertiary carbon or quaternary carbon atom adjacent to the carbonyl group constituting the acid group. A carboxylic acid that is carbon is preferred.

It is preferable that the curable composition (A) comprising (I), (II) and (III) further contains an amine compound (VI).

It is preferable that the curable composition (A) composed of (I), (II) and (III) further contains silicate (VII).

In the curable composition (B) comprising (I), (II) and (IV), the titanium catalyst (IV) is represented by the general formula (2):
Ti (OR ³ ) ₄ (2)
(Wherein R ³ is an organic group, and four R ^{3 s} may be the same or different from each other).

（式中、ｎ個のＲ^４は、それぞれ独立に炭素原子数１から２０の置換あるいは非置換の炭化水素基である。４−ｎ個のＲ^５は、それぞれ独立に水素原子または炭素原子数１から８の置換あるいは非置換の炭化水素基である。４−ｎ個のＡ^１および４−ｎ個のＡ^２は、それぞれ独立に−Ｒ^６または−ＯＲ^６である（ここでＲ^６は炭素原子数１から８の置換あるいは非置換の炭化水素基である）。ｎは０、１、２、３のいずれかである。）で表される化合物および／または一般式（４）：

（式中、Ｒ^５、Ａ^１、Ａ^２は前記と同じ。Ｒ^７は、炭素原子数１から２０の置換あるいは非置換の二価の炭化水素基である。）で表される化合物であることが好ましい。 The titanium catalyst (IV) has the general formula (3):

(In the formula, n R ^{4 s} are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 4-n R ^{5 s} are independently hydrogen atoms or carbon atoms. A substituted or unsubstituted hydrocarbon group of 1 to 8. 4-n A ¹ and 4-n A ² are each independently —R ⁶ or —OR ⁶ (where R ⁶ is A substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms.) N is 0, 1, 2, or 3) and / or the general formula (4):

(Wherein R ⁵ , A ¹ and A ² are the same as described above. R ⁷ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms). It is preferable.

It is preferable that the curable composition (B) composed of (I), (II) and (IV) further contains an epoxy silane coupling agent (VIII).

It is preferable that the curable composition (B) composed of (I), (II) and (IV) further contains silicate (VII).

In the curable composition (B) comprising (I), (II) and (IV), the vinyl polymer (I) and / or the polyether polymer (II) is represented by the general formula (5):
-SiY ₃ (5)
(Wherein Y represents a hydroxyl group or a hydrolyzable group, and three Ys may be the same as or different from each other) and preferably have a crosslinkable silyl group.

In the curable composition (B) comprising (I), (II) and (IV), the polyether polymer (II) is represented by the general formula (5):
-SiY ₃ (5)
(Wherein Y represents a hydroxyl group or a hydrolyzable group, and three Ys may be the same as or different from each other) and preferably have a crosslinkable silyl group.

In the curable composition (C) comprising (I), (II) and (V), the vinyl polymer (I) and / or the polyether polymer (II) is represented by the general formula (5):
-SiY ₃ (5)
(Wherein Y represents a hydroxyl group or a hydrolyzable group, and three Ys may be the same as or different from each other) and preferably have a crosslinkable silyl group.

In the curable composition (C) comprising (I), (II) and (V), the polyether polymer (II) is represented by the general formula (5):
-SiY ₃ (5)
(Wherein Y represents a hydroxyl group or a hydrolyzable group, and three Ys may be the same as or different from each other) and preferably have a crosslinkable silyl group.

In addition, the present invention relates to a one-component curable composition that is prepared as a one-component type that is preliminarily blended and stored in the curable composition and cured by moisture in the air after construction.

Further, the present invention is the curable composition,
(A) liquid containing vinyl polymer (I) and polyether polymer (II), and (A) carboxylic acid metal salt (III-1) and / or carboxylic acid (III-2),
(B) Titanium catalyst (IV) or
(C) The present invention relates to a two-component or multi-component curable composition comprising at least two components of the (b) solution containing the organotin catalyst (V).

Furthermore, this invention relates to the sealing material for multilayer glass which uses the said curable composition.

The curable composition of the present invention is characterized in that the cured product obtained by curing the curable composition is excellent in creep resistance, weather resistance adhesiveness, water resistant adhesiveness, and low water absorption, particularly in a multilayer glass. It is effective when used as a sealing material.

The curable composition of this invention is explained in full detail below.

<< About the vinyl polymer (I) >>
<Main chain>
The present inventors have so far made numerous inventions relating to vinyl polymers having various crosslinkable functional groups at the polymer terminals, their production methods, curable compositions, and applications (Japanese Patent Laid-Open No. Hei 11-). No. 080249, JP-A-11-080250, JP-A-11-005815, JP-A-11-116617, JP-A-11-116606, JP-A-11-080571, JP-A-11-080570. No. 11-130931, JP-A-11-100333, JP-A-11-116763, JP-A-9-272714, JP-A-9-272715, etc.). Although it does not specifically limit as vinyl-type polymer (I) of this invention, All the polymers disclosed by the invention illustrated above can be used suitably.

It does not specifically limit as a vinyl-type monomer which comprises the principal chain of the vinyl-type polymer of this invention, Various things can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid isononyl, (meth) acrylic acid decyl, (meth) Dodecyl acrylate, phenyl (meth) acrylate, tolyl (meth) acrylate, benzyl (meth) acrylate, (meth) a 2-methoxyethyl toluate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, (meth ) Glycidyl acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (meth) 2-trifluoromethylethyl acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, perfluoroethylperfluorobutylmethyl (meth) acrylate, (meth) acrylic acid 2 -Perfluoroethyl-2-perfluorobutyl ethyl , Perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethyl methyl (meth) acrylate, 2,2-diperfluoromethylethyl (meth) acrylate, (meth) acryl Perfluoromethyl perfluoroethyl methyl acid, 2-perfluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, 2-perfluorohexyl methyl (meth) acrylate, 2-perfluorohexyl ethyl (meth) acrylate , 2-perfluorodecylmethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylmethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate (Meth) acrylic monomers such as styrene, vinyl Aromatic vinyl monomers such as ene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride; vinyltrimethoxysilane, vinyltri Silicon-containing vinyl monomers such as ethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide , Maleimide monomers such as butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide; Acrylonitrile monomers such as nitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; ethylene, Alkenes such as propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or a plurality of these may be copolymerized.

The main chain of the vinyl polymer is mainly polymerized with at least one monomer 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 manufactured. Here, “mainly” means that 30 mol% or more, preferably 50 mol% or more of the monomer units constituting the vinyl polymer are the above monomers.

Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. More preferred are acrylic ester monomers and methacrylic ester monomers, and particularly preferred are acrylic ester monomers. For general architectural use and the like, a butyl acrylate monomer is more preferable from the viewpoint that physical properties such as low viscosity of the blend, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required. On the other hand, in applications that require oil resistance, such as automobile applications, copolymers based on ethyl acrylate are more preferred. This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low temperature characteristics (cold resistance). Therefore, in order to improve the low temperature characteristics, a part of ethyl acrylate is converted into butyl acrylate. It is also possible to replace it. However, as the ratio of butyl acrylate is increased, the good oil resistance is impaired, so that the ratio is preferably 80 mol% or less depending on the application for which oil resistance is required, and 60 mol% or less. More preferably, it is 40 mol% or less, more preferably 30 mol% or less. It is also preferable to use 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, or the like in which oxygen is introduced into the side chain alkyl group in order to improve low-temperature characteristics and the like without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 60 mol% or less, and 40% or less. Is more preferable. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although not limited, examples of excellent physical property balance such as oil resistance, heat resistance, and low-temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (molar ratio of 40-50 / 20- 30 / 20-30).

In addition, in the case of adding an epoxy resin to the vinyl polymer of the present invention, in order to obtain a transparent cured product when the curable composition is cured, the vinyl polymer is an epoxy. Those that are compatible with the resin are preferred, and polymers or copolymers having a higher polarity than the butyl acrylate homopolymer are preferred, and the main chain of the vinyl polymer is represented by the general formula (6):
^{_{- [CH 2 -CR 8 (COOR}} 9)] - (6)
Wherein R ⁸ is hydrogen or a methyl group, and R ⁹ is the same or different and is an alkoxyalkyl group or an alkyl group having 1 to 3 carbon atoms. Or it is more preferable that it is a copolymer.

The polymer or copolymer having a higher polarity than the butyl acrylate homopolymer is not particularly limited, and examples thereof include a copolymer of butyl acrylate and a monomer having a higher polarity than butyl acrylate. Here, examples of the monomer having higher polarity than butyl acrylate include ethyl acrylate and 2-methoxyethyl acrylate. For example, a copolymer of ethyl acrylate / butyl acrylate / acrylic acid 2-methoxyethyl (molar ratio 40-50 / 20-30 / 20-30) is easily compatible with various epoxy resins, and is a transparent cured product. Since it is easy to obtain, it is suitable.

Copolymerizes monomers with long-chain alkyl groups such as stearyl groups and lauryl groups to improve compatibility with other polymers such as modified silicone resins (oxyalkylene polymers having crosslinkable silyl groups) You may let them. Although there is no particular limitation, for example, 5-30 mol% of stearyl acrylate or lauryl acrylate is copolymerized so that the compatibility with the modified silicone resin becomes very good. Since the compatibility varies depending on the molecular weight of each polymer, it is preferable to select the proportion of the monomer to be copolymerized accordingly. In this case, block copolymerization may be performed. The effect may be manifested in a small amount.

The curable composition containing a vinyl polymer having a functional silyl group may have a slow curability upon storage, that is, a poor storage stability. For example, it may be possible to suppress such a decrease by copolymerizing methyl acrylate. Moreover, you may use when you want to improve the intensity | strength of hardened | cured material. Also in this case, the ratio of monomers to be copolymerized may be selected according to the molecular weight and / or may be block copolymerized.

In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably contained in a weight ratio of 40% or more. . In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

The molecular weight distribution of the vinyl polymer of the present invention, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography is not particularly limited. A molecular weight distribution of less than 1.8, particularly 1.3 or less is preferable from the viewpoint of workability. In the GPC measurement in the present invention, chloroform is usually 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 in the present invention represents a value measured by gel permeation chromatography (chloroform is used as a mobile phase, measurement is performed on a polystyrene gel column, and is calculated in terms of polystyrene). The number average molecular weight of the vinyl polymer is not particularly limited, but is generally preferably 500 to 1,000,000, more preferably 5,000 to 100,000, from the viewpoint of workability and physical properties. 10,000 to 40,000 are particularly preferred. The smaller the molecular weight, the easier it is to be compatible with other resins (various polymers), and the resulting cured product tends to have a high modulus and low elongation, while the larger the molecular weight, the opposite is the case.

And the preferable number average molecular weight of the vinyl polymer whose 50% elongation stress as defined in the present invention is larger than 0.10 MPa is as follows. That is, it is 10,000 or more and 40,000 or less, More preferably, it is 15,000 or more and 35,000 or less, More preferably, it is 20,000 or more and 30,000 or less. If the number average molecular weight is less than 10,000, the cured product tends to be disadvantageous in terms of tensile strength and elongation, and if it exceeds 40,000, the cured product tends to be disadvantageous in terms of creep resistance. There is a tendency to be inconvenient in terms of workability due to high viscosity.

<Method of synthesizing the main chain>
The method for synthesizing the vinyl polymer in the present invention is not limited, and free radical polymerization may be used. However, controlled radical polymerization is preferable, living radical polymerization is more preferable, and atom transfer radical polymerization is particularly preferable. These will be described below.

Controlled radical polymerization The radical polymerization method uses an azo compound, a peroxide or the like as a polymerization initiator to simply copolymerize a monomer having a specific functional group and a vinyl monomer. It can be classified into “polymerization method” and “controlled radical polymerization method” in which a specific functional group can be introduced at a controlled position such as a terminal.

The “general radical polymerization method” is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner, so an attempt is made to obtain a polymer having a high functionalization rate. In such a case, it is necessary to use this monomer in a considerably large amount. On the contrary, if the monomer is used in a small amount, there is a problem that the proportion of the polymer in which this specific functional group is not introduced becomes large. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

The “controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, It can be classified as “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing the terminal without causing a termination reaction or the like.

In the “chain transfer agent method”, a polymer having a high functionalization rate can be obtained, but a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator is required. There is an economic problem. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained because of free radical polymerization.

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator. Accordingly, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The method for producing the vinyl polymer having the specific functional group is more preferable.

In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. It also includes pseudo-living polymerization that grows in an equilibrium state. The definition in the present invention is also the latter.

The “living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include those using a cobalt porphyrin complex as shown in, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, Macromolecules. (Macromolecules), 1994, Vol. 27, p. 7228, using a radical capping agent such as a nitroxide compound, “atom transfer radical polymerization” using an organic halide as an initiator and a transition metal complex as a catalyst ( Atom Transfer Radical Polymerization (ATRP).

Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above “living radical polymerization method”. In addition to the features of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts, so the production of vinyl polymers having specific functional groups More preferable as a method. As this atom transfer radical polymerization method, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules 1995, 28, 7901, Science 1996, 272, 866, WO96 / 30421, WO97 / 18247, WO98 / 01480, WO98 / 40415, or Sawamoto et al., Macromolecules. Macromolecules 1995, 28, 1721, JP-A-9-208616, JP-A-8-41117, and the like.

In the present invention, there is no particular restriction as to which of these living radical polymerization methods is used, but an atom transfer radical polymerization method is preferred.

The living radical polymerization will be described in detail below, but before that, one of the controlled radical polymerizations that can be used for the production of vinyl polymers described later, the polymerization using a chain transfer agent will be described. To do. Although it does not specifically limit as radical polymerization using a chain transfer agent (telomer), The following two methods are illustrated as a method of obtaining the vinyl polymer which has the terminal structure suitable for this invention.

JP-A-4-132706 discloses a method for obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent, JP-A-61-271306, JP-A-2594402, This is a method for obtaining a hydroxyl-terminated polymer by using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent as disclosed in JP-A-54-47782.

Below, living radical polymerization is demonstrated.

First, a method using a radical capping agent such as a nitroxide compound will be described. In this polymerization, a stable nitroxy free radical (= N—O.) Is generally used as a radical capping agent. Examples of such compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radical, 2,2,5,5-substituted-1-pyrrolidinyloxy radical, and the like. Nitroxy free radicals from cyclic hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable. Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1, Examples include 1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like. Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

The radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator and the polymerization of the addition polymerizable monomer proceeds. The combination ratio of both is not particularly limited, but 0.1 to 10 mol of the radical generator is suitable for 1 mol of the radical capping agent.

Although various compounds can be used as the radical generator, a peroxide capable of generating a radical under polymerization temperature conditions is preferred. Examples of the peroxide include, but are not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, bis There are peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctate and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable. Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide.

Macromolecules 1995, 28, P.M. As reported in 2993, instead of using a radical capping agent and a radical generator in combination, an alkoxyamine compound as shown below may be used as an initiator.

When an alkoxyamine compound is used as an initiator, if it has a functional group such as a hydroxyl group as shown in the above figure, a polymer having a functional group at the terminal can be obtained. When this is used in the method of the present invention, a polymer having a functional group at the terminal can be obtained.

The polymerization conditions such as the monomer, solvent, polymerization temperature and the like used in the polymerization using a radical capping agent such as the above nitroxide compound are not limited, but may be the same as those used for the atom transfer radical polymerization described below.

Atom transfer radical polymerization Next, an atom transfer radical polymerization method more preferable as the living radical polymerization of the present invention will be described.

In this 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 halogenated compound. A sulfonyl compound or the like is used as an initiator. For example,
_{C 6 H 5 -CH 2 X,} C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2
(However, in the above chemical formula, C ₆ H ₅ is a phenyl group, X is chlorine, bromine, or iodine)
^{_{R 10 -C (H) (X}} ) -CO 2 R 11, R 10 -C (CH 3) (X) -CO 2 R 11, R 10 -C (H) (X) -C (O) R 11 , R ¹⁰ -C (CH ₃ ) (X) -C (O) R ¹¹ ,
(Wherein R ¹⁰ and R ¹¹ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine)
R ¹⁰ -C ₆ H ₄ -SO ₂ X
(Wherein R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine)
Etc.

As an initiator of atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a case, a vinyl polymer having a functional group at one end of the main chain and a growth terminal structure of atom transfer radical polymerization at the other main chain end is produced. Examples of such functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, and the like.

The organic halide having an alkenyl group is not limited. For example, the general formula (7):
^{R 13 R 14 C (X)} -R 15 -R 16 -C (R 12) = CH 2 (7)
(Wherein R ¹² is hydrogen or a methyl group, R ¹³ and R ¹⁴ are hydrogen, or a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, or linked to each other at the other end. ^{things, R 15} is, -C (O) O- (ester group), - C (O) - ( keto group), or o-, m-, p-phenylene ^{group, R 16} is a direct bond or carbon atoms A divalent organic group having 1 to 20 which may contain one or more ether bonds, and X has a structure shown in chlorine, bromine, or iodine) is exemplified. Specific examples of the substituents R ¹³ and R ¹⁴ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group and the like. R ¹³ and R ¹⁴ may be connected at the other end to form a cyclic skeleton.

（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ＸＣＨ_２Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、Ｈ_３ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、
（Ｈ_３Ｃ）_２Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、
ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、

（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数） Specific examples of the organic halide having an alkenyl group represented by the general formula (7) include
_{XCH 2 C (O) O (} CH 2) n CH = CH 2, H 3 CC (H) (X) C (O) O (CH 2) n CH = CH 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n CH = CH 2, CH 3 CH 2 C (H) (X) C (O) O (CH 2) n CH = CH 2 ,

(In the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m CH = CH 2, H 3 CC (H) (X) C (O) O (CH 2) n O (CH 2) m CH = CH ₂ ,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m CH = CH 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m CH = CH 2,

(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m CH = CH 2,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)

The organic halide having an alkenyl group is further represented by the general formula (8):
_{^{H 2 C = C (R 12}} ) -R 16 -C (R 13) (X) -R 17 -R 14 (8)
(Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ and X are the same as above, R ¹⁷ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group) Or a compound represented by o-, m-, p-phenylene group). R ¹⁶ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), and in the case of a direct bond, carbon to which a halogen is bonded. Is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group or a phenylene group as R ¹⁷ , and a direct bond may be used. When R ¹⁶ is not a direct bond, R ¹⁷ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate the carbon-halogen bond.

If the compound of the general formula (8) is specifically exemplified,
_{CH 2 = CHCH 2 X, CH} 2 = C (CH 3) CH 2 X,
_{CH 2 = CHC (H) (} X) CH 3, CH 2 = C (CH 3) C (H) (X) CH 3,
_{CH 2 = CHC (X) (} CH 3) 2,
_{CH 2 = CHC (H) (} X) C 2 H 5,
_{CH 2 = CHC (H) (} X) CH (CH 3) 2,
_{CH 2 = CHC (H) (} X) C 6 H 5,
_{CH 2 = CHC (H) (} X) CH 2 C 6 H 5,
_{CH 2 = CHCH 2 C (H} ) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 3 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 8 C (H) (X) -CO 2 R,
_{CH 2 = CHCH 2 C (H} ) (X) -C 6 H 5,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -C 6 H 5,
_{CH 2 = CH (CH 2)} 3 C (H) (X) -C 6 H 5,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.

If the specific example of the sulfonyl halide compound which has an alkenyl group is given,
_{o-, m-, p-CH 2} = CH- (CH 2) n -C 6 H 4 -SO 2 X,
_{o-, m-, p-CH 2} = CH- (CH 2) n -O-C 6 H 4 -SO 2 X,
(In the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20)
Etc.

The organic halide having a crosslinkable silyl group is not particularly limited. For example, the general formula (9):
^{R 13 R 14 C (X)} -R 15 -R 16 -C (H) (R 12) CH 2 - [Si (R 18) 2-b (Y) b O] m -Si (R 19) 3- _a (Y) _a (9)
(Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , X are the same as above, R ¹⁸ , R ¹⁹ are all alkyl groups, aryl groups, aralkyl groups having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). Represents an organosiloxy group, and when two or more R ¹⁸ or R ¹⁹ are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and Y represents two or more When present, they may be the same or different, a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer from 0 to 19. Provided that a + mb ≧ 1 is satisfied) Those with is exemplified.

If the compound of general formula (9) is specifically illustrated,
XCH ₂ C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (OCH 3) 3,
(CH ₃ ) ₂ C (X) C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{XCH 2 C (O) O (} CH 2) n Si (CH 3) (OCH 3) 2,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
_{(CH 3) 2 C (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 0-20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (CH 3) (OCH 3) 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 1-20, m is an integer of 0-20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
(In the above formulas, X is chlorine, bromine, or iodine)
Etc.

The organic halide having a crosslinkable silyl group is further represented by the general formula (10):
_{^{(R 19) 3-a (}} Y) a Si- [OSi (R 18) 2-b (Y) b] m -CH 2 -C (H) (R 12) -R 16 -C (R 13) ( X) -R ¹⁷ -R ¹⁴ (10)
(Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , a, b, m, X, and Y are the same as above) are exemplified. .

If such a compound is specifically illustrated,
_{(CH 3 O) 3 SiCH 2} CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -C 6 H 5,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.

The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
_{HO- (CH 2) n -OC (} O) C (H) (R) (X)
(In the formula, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

The organic halide having the amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
_{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X)
(In the formula, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

（式中、Ｘは塩素、臭素、またはヨウ素、Ｒは水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数） The organic halide having an epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

(In the formula, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

In order to obtain a polymer having two or more growth terminal structures in one molecule, it is preferable to use an organic halide having two or more starting points or a sulfonyl halide compound as an initiator. For example,

Etc.

There is no restriction | limiting in particular as a vinyl-type monomer used in this superposition | polymerization, All already illustrated 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 uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as a polyamine is added. A preferred ligand is a nitrogen-containing compound, a more preferred ligand is a chelate-type nitrogen-containing compound, and a more preferred ligand is N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine. It is. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Furthermore, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

The polymerization can be carried out without solvent or in various solvents. Solvent types include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ester solvents such as ethyl acetate, butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate, and these can be used alone or in admixture of two or more.

Moreover, although not limited, superposition | polymerization can be performed in 0 to 200 degreeC, Preferably it is 50 to 150 degreeC.

The atom transfer radical polymerization of the present invention includes so-called reverse atom transfer radical polymerization. Reverse atom transfer radical polymerization is a high oxidation state when a normal atom transfer radical polymerization catalyst generates radicals, for example, peroxidation with respect to Cu (II ′) when Cu (I) is used as a catalyst. In this method, a general radical initiator such as a compound is allowed to act, and as a result, an equilibrium state similar to that of atom transfer radical polymerization is produced (see Macromolecules 1999, 32, 2872).

<Functional group>
Number of crosslinkable silyl groups The number of crosslinkable silyl groups in the vinyl polymer is 1 on average in the molecule from the viewpoint of the curability of the composition and the tensile properties and creep resistance of the cured product. It is essential to have at least one, preferably 1.1 to 4.0, more preferably 1.4 to 3.5, and still more preferably 1.6 to 3.0, The number is particularly preferably 1.8 or more and 2.5 or less. If the number of crosslinkable silyl groups is less than 1.1, the cured product tends to be disadvantageous in terms of creep resistance and tensile strength, and if it exceeds 4.0, the cured product tends to be disadvantageous in terms of elongation. There is.

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

A method for producing a vinyl polymer having at least one crosslinkable silyl group at the molecular chain end, in particular, a (meth) acrylic polymer is disclosed in Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, This is disclosed in, for example, Kaihei 6-221922. 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.

These functional groups will be described below.

Crosslinkable silyl group The crosslinkable silyl group of the present invention may be represented by the general formula (1):
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{In the formula, R ¹ and R ² 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 ¹ or When two or more R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
The group represented by these is mention | raise | lifted.

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 fewer 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 (11):
^{_{-Si (R 2) 3-a}} (Y) a (11)
A crosslinkable silyl group represented by the formula (wherein R ² 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 a very fast curing rate is required, such as when used at low temperatures, etc., the curing rate is not sufficient, and if it is desired to provide 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, a is 3 (for example, trimethoxy functional group), that is, general formula (5):
-SiY ₃ (5)
A crosslinkable silyl group represented by the formula (wherein Y is the same as described above) is preferable from the viewpoint of creep resistance.

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 the mechanical properties of the cured product. It 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.

Introduction of crosslinkable silyl group <br/> below is a description of the method for introducing the crosslinkable silyl group into the vinyl polymer of the present invention, but is not limited thereto.

First, a method for introducing a crosslinkable silyl group, alkenyl group, and hydroxyl group by terminal functional group conversion will be described. Since these functional groups can be precursors to each other, they are described in the order from the crosslinkable silyl group.

As a method for synthesizing a vinyl polymer having at least one crosslinkable silyl group,
(A) A method in which a hydrosilane compound having a crosslinkable silyl group is added to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst. (B) One molecule per vinyl polymer having at least one hydroxyl group. A method in which a compound having a group capable of reacting with a hydroxyl group, such as a compound having a crosslinkable silyl group and an isocyanate group, is reacted. (C) When a vinyl polymer is synthesized by radical polymerization, polymerization is performed in one molecule. A method of reacting a compound having both a functional alkenyl group and a crosslinkable silyl group (D) a method of using a chain transfer agent having a crosslinkable silyl group when synthesizing a vinyl polymer by radical polymerization (E) A compound having a crosslinkable silyl group and a stable carbanion in one molecule in a vinyl polymer having at least one high carbon-halogen bond A method of reacting; and the like.

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, the following general formula (12):
_{^{H 2 C = C (R 20}} ) -R 21 -R 22 -C (R 23) = CH 2 (12)
(Wherein R ²⁰ represents hydrogen or a methyl group, R ²¹ represents —C (O) O—, or o-, m-, p-phenylene group, R ²² represents a direct bond, or a carbon number of 1 to 20 represents a divalent organic group having 20 and may contain one or more ether bonds R ²³ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or 7 carbon atoms. And a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as a second monomer.

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. It is preferable to react as the second monomer at the end 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) To a vinyl polymer having at least one highly reactive carbon-halogen bond, the general formula (13):
^{M + C - (R 24)} (R 25) -R 26 -C (R 23) = CH 2 (13)
^{(Wherein, R 23} is as defined ^above, R ^{24, R 25} together carbanion C ^- a is 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 ²⁶ 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 method in which a halogen is substituted by reacting with a stabilized carbanion having an alkenyl group as described in (4).

As the electron withdrawing group for R ²⁴ and R ²⁵ , 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 a carboxylate anion having an alkenyl group as represented by the general formula (14) or (15) 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 23}} ) -R 27 -O - M + (14)
(Wherein R ²³ and M ⁺ are the same as above. R ²⁷ is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
_{^{H 2 C = C (R 23}} ) -R 28 -C (O) O - M + (15)
(In the formula, R ²³ and M ⁺ are the same as above. R ²⁸ is 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. In the hydroxyl group of a vinyl polymer having at least one hydroxyl group,
(Ag) A method of reacting a base such as sodium methoxide 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 a halogen is not directly involved in a method for 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.

When an alkenyl group is introduced by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide having at least one highly reactive carbon-halogen bond, or A vinyl heavy polymer 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 coalescence. 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, When a typical thing is shown, General formula (16):
^{_{H- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (16)
(In the formula, R ¹ and R ² 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 ¹ or When two or more R ² 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 from 0 to 19, provided that a + mb ≧ 1. It shall be satisfied that there is a certain compound.)

Among these hydrosilane compounds, in particular, the general formula (17):
_{^{H-Si (R 2) 3}} -a (Y) a (17)
(In the formula, R ² and Y are the same as 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.

Examples of the method for producing a vinyl polymer having at least one hydroxyl group used in the methods (B) and (Ag) to (Aj) include the following methods, but are limited to these methods. It is not something.

(Ba) When synthesizing a vinyl polymer by radical polymerization, for example, the following general formula (18):
_{^{H 2 C = C (R 20}} ) -R 21 -R 22 -OH (18)
(Wherein R ²⁰ , R ²¹ and R ²² are the same as described above), a compound having a polymerizable alkenyl group and a hydroxyl group in one molecule as a second monomer.

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

(Bb) When a vinyl polymer is synthesized by living radical polymerization, an alkenyl alcohol such as 10-undecenol, 5-hexenol or allyl alcohol is reacted at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. How to make.

(Bc) A method in which a vinyl monomer is radically polymerized using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide disclosed in JP-A-5-262808.

(Bd) A method of radical polymerization of a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as disclosed in, for example, JP-A-6-239912 and JP-A-8-283310.

(Be) A method of radical polymerization of a vinyl monomer using an excessive amount of alcohol as disclosed in, for example, JP-A-6-116312.

(Bf) Hydrolyzing a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond or a hydroxyl group-containing compound by a method such as disclosed in, for example, JP-A-4-132706 A method of introducing a hydroxyl group at the terminal by reacting.

(Bg) To a vinyl polymer having at least one carbon-halogen bond having high reactivity, the general formula (19):
^{M + C - (R 24)} (R 25) -R 26 -OH (19)
(Wherein R ²⁴ , R ²⁵ , and R ²⁶ are the same as above), a method of replacing a halogen by reacting with a stabilized carbanion having a hydroxyl group.

As the electron withdrawing group for R ²⁴ and R ²⁵ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

(Bh) An enolate anion is prepared by allowing a metal polymer such as zinc or an organometallic compound to act on a vinyl polymer having at least one highly reactive carbon-halogen bond, and then aldehydes. Or a method of reacting ketones.

(Bi) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with, for example, an oxyanion or carboxylate anion having a hydroxyl group as shown in the general formula (20) or (21) To replace the halogen.
HO-R ^{< 27 >} -O ^- M ^<+> (20)
(Wherein R ²⁷ and M ⁺ are the same as above)
^{HO-R 28 -C (O)} O - M + (21)
(Wherein R ²⁸ and M ⁺ are the same as above)

(Bj) When synthesizing a vinyl polymer by living radical polymerization, as the second monomer after the end of the polymerization reaction or after the completion of the reaction of the predetermined monomer, an alkenyl group and a hydroxyl group having low polymerizability in one molecule A method of reacting a compound having

Although it does not specifically limit as such a compound, General formula (22):
_{^{H 2 C = C (R 20}} ) -R 27 -OH (22)
(Wherein, R ²⁰ and R ²⁷ are the same as those described above), and the like.

Although it does not specifically limit as a compound shown by the said General formula (22), From an easy acquisition, alkenyl alcohol like 10-undecenol, 5-hexenol, and allyl alcohol is preferable.
Etc.

In the present invention, when halogen is not directly involved in the method of introducing a hydroxyl group such as (Ba) to (Be) and (Bj), a vinyl polymer is obtained by using a living radical polymerization method. It is preferable to synthesize. The method (Bb) is more preferable in terms of easier control.

When introducing a hydroxyl group by converting halogen in a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide or a sulfonyl halide compound is used as an initiator, and a transition metal complex is used as a catalyst. It is preferable to use a vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by radical polymerization of a vinyl monomer (atom transfer radical polymerization method). The method (Bi) is more preferable from the viewpoint of easier control.

Examples of the compound having a crosslinkable silyl group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and γ-isocyanate. Examples thereof include natopropyltriethoxysilane, and a generally known catalyst for urethanization reaction can be used if necessary.

Examples of the compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule used in the method (C) include trimethoxysilylpropyl (meth) acrylate and methyldimethoxysilylpropyl (meth) acrylate. What is shown by the following general formula (23) is mentioned.
_{^{H 2 C = C (R 20}} ) -R 21 -R 29 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) 3-a (Y) a (23)
(In the formula, R ¹ , R ² , R ²⁰ , R ²¹ , Y, a, b and m are the same as above. R ²⁹ is a direct bond or one divalent organic group having 1 to 20 carbon atoms. The above ether bond may be included.)

There is no particular limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule. However, particularly in the case of living radical polymerization, when a rubber-like property is expected, the end of the polymerization reaction or a predetermined value is determined. It is preferable to make it react as a 2nd monomer after completion | finish of reaction of this monomer.

Examples of the chain transfer agent having a crosslinkable silyl group used in the chain transfer agent method of (D) include mercaptans having a crosslinkable silyl group and crosslinkable silyl as shown in, for example, Japanese Patent Publication Nos. 3-14068 and 4-55444. And hydrosilane having a group.

The method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond, which is used in the method (E), uses an organic halide as described above as an initiator, and a transition metal complex. Examples thereof include, but are not limited to, an atom transfer radical polymerization method using a catalyst. A compound having both a crosslinkable silyl group and a stabilized carbanion in one molecule is represented by the general formula (24):
^{M + C - (R 24)} (R 25) -R 30 -C (H) (R 31) -CH 2 - [Si (R 1) 2-b (Y) b O] m -Si (R 2) _3-a (Y) _a (24)
(Wherein R ¹ , R ² , R ²⁴ , R ²⁵ , Y, a, b, m are the same as above. R ³⁰ is a direct bond or one divalent organic group having 1 to 10 carbon atoms. R ³¹ , which may contain the above ether bond, represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. Is mentioned.

As the electron withdrawing group for R ²⁴ and R ²⁵ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

In the case of a curable composition using a vinyl polymer having a crosslinkable silyl group, obtained by a method for introducing a crosslinkable silyl group as described in (Af) or (B) above, Since the crosslinked structure of the resulting cured product contains an ester bond or a urethane bond, the heat resistance tends to be slightly lowered. Therefore, in order to effectively exhibit the effects of the present invention, it is preferable that the terminal functional group is bonded to the polymer by a carbon-carbon bond without a hetero atom.

<Use of multiple vinyl polymers>
Only one kind of the above-mentioned vinyl polymer can be used, or two or more kinds of vinyl polymers can be used in combination. When only one kind is used, it is preferable to use a vinyl polymer having a molecular weight of 5,000 to 50,000 and a number of crosslinkable silyl groups of 1.2 to 3.5. When combining two or more kinds of vinyl polymers, the first polymer is a vinyl polymer having a molecular weight of 5,000 to 50,000 and a number of crosslinkable silyl groups of 1.2 to 3.5, When the second polymer is a polymer having a small number of crosslinkable silyl groups, 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 a 2nd polymer smaller. The polymer having a low molecular weight component preferably has a molecular weight of less than 10,000, more preferably less than 5,000, and the preferred number of crosslinkable silyl groups is less than 1.2, and further 1 or less. Further, since the viscosity can be further reduced, the molecular weight distribution is preferably less than 1.8. When a vinyl polymer having a crosslinkable functional group and a molecular weight distribution of 1.8 or more and a vinyl polymer having a crosslinkable silyl group at one end are added, the effect of reducing the viscosity is remarkable.

As a polymer having such a low molecular weight and a small number of crosslinkable silyl groups, it is definitely possible to use a vinyl polymer having a crosslinkable silyl group at one end obtained by the following production method. It is preferable because it can be introduced.

A vinyl polymer having a crosslinkable silyl group at one end has approximately one crosslinkable silyl group per molecule at the end of the polymer. Use of the above-mentioned living radical polymerization method, particularly the atom transfer radical polymerization method, has a high proportion of crosslinkable silyl groups at the molecular chain ends, a molecular weight distribution of less than 1.8, a narrow molecular weight distribution, and a low viscosity. Since a vinyl polymer is obtained, it is preferable.

About the method of introduce | transducing a crosslinkable silyl group into one terminal, the method shown below can be used, for example. In the method of introducing a crosslinkable silyl group, an alkenyl group, and a hydroxyl group by terminal functional group conversion, these functional groups can be precursors to each other, and therefore, are described in the order starting from the method of introducing the crosslinkable silyl group.

(1) A method of adding a hydrosilane compound having a crosslinkable silyl group to a polymer having one alkenyl group per molecule at the molecular chain end in the presence of a hydrosilylation catalyst,
(2) A method of reacting a polymer having one hydroxyl group per molecular chain end with a compound having both a crosslinkable silyl group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule,
(3) A method in which a polymer having one highly reactive carbon-halogen bond per molecule per molecule is reacted with a compound having a crosslinkable silyl group and a stable carbanion in one molecule.
Etc.

Polymers having one alkenyl group per molecule chain end in the method (1) can be obtained by various methods. Although a manufacturing method is illustrated below, it is not necessarily limited to these.

(1-1) Various polymers having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin in a polymer having one highly reactive carbon-halogen bond per molecular chain end A method of replacing halogen by reacting an organometallic compound.

(1-2) To a polymer having one highly reactive carbon-halogen bond per molecule at the molecular chain end, the general formula (25):
^{M + C - (R 24)} (R 25) -R 26 -C (R 23) = CH 2 (25)
(Wherein, R ^24, R ²⁵ together carbanion C ^- or an electron withdrawing group stabilizing, or one of the other is hydrogen or an alkyl group having 1 to 10 carbon atoms in the electron-withdrawing group or a phenyl group, R ²⁶ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms, and may contain one or more ether bonds, and R ²³ represents hydrogen or an alkyl group having 1 to 20 carbon atoms. Represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and M ⁺ represents a reaction with a stabilized carbanion having an alkenyl group such as an alkali metal ion or a quaternary ammonium ion. To replace the halogen.

As the electron withdrawing group for R ²⁴ and R ²⁵ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

(1-3) An enolate anion is prepared by reacting a polymer having one highly reactive carbon-halogen bond per molecule chain molecule with a metal alone or an organometallic compound such as zinc, Thereafter, an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group, etc. How to react with.

(1-4) A polymer having one highly reactive carbon-halogen bond per molecule per molecule, such as an oxyanion having an alkenyl group as shown in the general formula (26) or (27) A method of substituting halogen by reacting a carboxylate anion.
_{^{H 2 C = C (R 23}} ) -R 27 -O - M + (26)
(In the formula, R ²³ and M ⁺ are the same as above. R ²⁷ is a divalent organic group having 1 to 20 carbon atoms, and may contain one or more ether bonds.)
_{^{H 2 C = C (R 23}} ) -R 28 -C (O) O - M + (27)
(In the formula, R ²³ and M ⁺ are the same as described above. R ²⁸ is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds.)
Etc.

The above-described method for synthesizing a polymer having one highly reactive carbon-halogen bond per molecule at the end of a molecule chain is an atom transfer using an organic halide as described above as an initiator and a transition metal complex as a catalyst. Examples include, but are not limited to, radical polymerization methods.

Further, a polymer having one alkenyl group per molecule at the molecular chain end can be obtained from a polymer having at least one hydroxyl group at the molecular chain end, and the methods exemplified below can be used, but are not limited thereto. It is not done.

In the polymer hydroxyl group having at least one hydroxyl group at the molecular chain end,
(1-5) A method of reacting a base such as sodium methoxide with an alkenyl group-containing halide such as allyl chloride,
(1-6) a method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate,
(1-7) a method of reacting an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine,
(1-8) a method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst,
Etc.

When an alkenyl group is introduced by converting a halogen of a polymer having one highly reactive carbon-halogen bond per molecule at the end of the molecule chain, one highly reactive carbon-halogen bond per molecule A highly reactive carbon-halogen bond is formed at the terminal obtained by radical polymerization (atom transfer radical polymerization) of a vinyl monomer using an organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. It is preferable to use a polymer having one molecule per molecule chain end.

Moreover, there is no restriction | limiting in particular as a hydrosilane compound which has a crosslinkable silyl group, When a typical thing is shown, General formula (28):
^{_{H- [Si (R 1 2-}} b) (Y b) O] m -Si (R 2 3-a) Y a (28)
(Wherein R ¹ , R ² , Y, a, b and m are the same as described above. When two or more R ¹ or R ² are present, they may be the same or different. However, it is assumed that a + mb ≧ 1 is satisfied.) Among these hydrosilane compounds, in particular, the general formula (29):
H-Si (R ² _3-a ) Y _a (29)
(In the formula, R ² and Y are the same as above. A is an integer of 1 to 3)
The compound which has a crosslinkable silyl 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.

The amount of vinyl polymer having a crosslinkable silyl group at one end, preferably a polymer having a molecular weight distribution of less than 1.8, is 5 in terms of modulus and elongation with respect to 100 parts by weight of the vinyl polymer. It is preferable that it is -400 weight part.

As a second embodiment in which two or more kinds of vinyl polymers are used in combination, a vinyl polymer having a molecular weight distribution of 1.8 or more and a vinyl polymer having a molecular weight distribution of less than 1.8 can be used in combination. . A vinyl polymer having a molecular weight distribution of 1.8 or more may or may not have a crosslinkable silicon group, but having a crosslinkable silicon group is preferred because weather resistance, adhesive strength, and strength at break are further improved. Moreover, the improvement of the tear strength of the hardened | cured material of a composition can be anticipated. As the main chain of the vinyl polymer having a molecular weight distribution of less than 1.8, used as the first polymer, the vinyl polymer having a molecular weight distribution of 1.8 or more, or the second polymer, Polymers derived from the vinyl monomers mentioned can be used, and both polymers are preferably acrylate polymers.

A vinyl polymer having a molecular weight distribution of 1.8 or more can be obtained by a usual vinyl polymerization method, for example, a solution polymerization method by radical reaction. The polymerization is usually carried out by adding the above-mentioned monomer, a radical initiator, a chain transfer agent and the like and reacting at 50 to 150 ° C. In this case, generally a molecular weight distribution of 1.8 or more is obtained.

Examples of the radical initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 4,4′-azobis (4-cyanovaleric) acid. 1,1′-azobis (1-cyclohexanecarbonitrile), azobisisobutyric acid amidine hydrochloride, 2,2′-azobis (2,4-dimethylvaleronitrile) and other azo initiators, benzoyl peroxide, diperoxide Organic peroxide-based initiators such as -tert-butyl are exemplified, but use of azo-based initiators is preferable in that they are not affected by the solvent used for polymerization and have a low risk of explosion and the like.

Examples of chain transfer agents include n-dodecyl mercaptan, tert-dodecyl mercaptan, lauryl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyl Examples include mercaptans such as diethoxysilane and halogen-containing compounds.

The polymerization may be performed in a solvent. Examples of the solvent are preferably nonreactive solvents such as ethers, hydrocarbons, and esters.

Examples of the method for introducing a crosslinkable silyl group include a method of copolymerizing a compound having both a polymerizable unsaturated bond and a crosslinkable silyl group with a (meth) acrylate monomer unit. The compound having both a polymerizable unsaturated bond and a crosslinkable silyl group is represented by the general formula (30):
_{^{CH 2 = C (R 32)}} COOR 33 - [Si (R 1 2-b) (Y b) O] m Si (R 2 3-a) Y a (30)
(In the formula, R ³² is the same as above. R ³³ is a divalent alkylene group having 1 to 6 carbon atoms. R ¹ , R ² , Y, a, b, and m are the same as above.)
Or general formula (31):
_{^{CH 2 = C (R 32)}} - [Si (R 1 2-b) (Y b) O] m Si (R 2 3-a) Y a (31)
(In the formula, R ³² , R ¹ , R ² , Y, a, b, m are the same as above.)
Monomers such as γ-methacryloxypropyl polymethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, etc. Γ-acryloxypropyl polyalkoxysilane such as loxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, etc. Examples thereof include vinyl alkyl polyalkoxysilane. Further, when a compound having both a mercapto group and a crosslinkable silyl group is used as a chain transfer agent, the crosslinkable silyl group can be introduced into the polymer terminal. Examples of such chain transfer agents include mercaptans such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxysilane. .

The vinyl polymer having a reactive silicon group used in the present invention is a vinyl polymer regardless of the type of main chain skeleton, the type and number of reactive silicon groups (introduction ratio), the molecular weight, and the presence or absence of branching. It is essential that the stress at 50% elongation of a cured product obtained by curing a single polymer alone is greater than 0.10 MPa. In the present specification and claims, the stress at 50% elongation refers to 100 parts by weight of a vinyl polymer and 2 parts of tin octylate and 0.5 parts by weight of laurylamine are added and mixed well. Thereafter, the centrifugally defoamed mixture was carefully poured into a polyethylene mold so that no bubbles would enter, and was cured at 50 ° C. for 20 hours. From the cured sheet having a thickness of 3 mm, 3 in accordance with JISK6251. This represents the stress at 50% elongation when No. dumbbell was punched and a tensile test (tensile speed 200 mm / min) was performed at 23 ° C. and 50% RH. The stress at 50% elongation of the vinyl polymer is essential to be larger than 0.10 MPa. However, from the viewpoint of curability and elongation characteristics and creep resistance of the obtained cured product, 0.11 MPa to 0 More preferably, it is in the range of 30 MPa, particularly preferably in the range of 0.12 MPa to 0.20 MPa. When it is 0.30 MPa or more, the elongation of the obtained cured product is remarkably reduced, and when used for a sealing material for double-glazed glass, the cured product is fragile and there is a tendency that practical shock absorption cannot be obtained. . On the other hand, when the stress at 50% elongation of the vinyl polymer alone is 0.10 MPa or less, the number of reactive silicon groups (introduction rate) of the vinyl polymer when used for a sealing material for double-glazed glass, etc. Since it becomes too low, practical curability cannot be obtained, or the obtained cured product tends to fail to obtain practical creep resistance.

There are various methods for adjusting the stress at 50% elongation of a single cured product of vinyl polymer. For example, a method of adjusting by changing the number of reactive silicon groups (introduction rate), a method of adjusting by changing the type of reactive silicon group, a method of adjusting by changing the molecular weight of the vinyl polymer, reactivity For example, the introduction position of the silicon group may be adjusted at the molecular end or in the molecule.

Specifically, the molecular weight is 10,000 or more and 40,000 or less, more preferably 15,000 or more and 35,000 or less, still more preferably 20,000 or more and 30,000 or less, or it is contained in one molecule on average. The number of crosslinkable silyl groups is 1.1 or more and 4.0 or less, preferably 1.4 or more and 3.5 or less, more preferably 1.6 or more and 3.0 or less, and particularly preferably 1. A method of 8 to 2.5 can be employed.

<< Polyether polymer (II) >>
The main chain structure of the polyether polymer (II) having a main chain crosslinkable silyl group is not particularly limited, and examples thereof include polyethylene oxide, polypropylene oxide, polybutylene oxide, and polyphenylene oxide. Among these, it is preferably essentially polyoxyalkylene, and more preferably essentially polypropylene oxide, which may contain ethylene oxide, butylene oxide, phenylene oxide and the like in addition to propylene oxide. The polyether polymer may or may not contain a urethane bond in the main chain. Here, “the main chain is essentially polypropylene oxide” means that propylene oxide units occupy 50% or more, preferably 70% or more, more preferably 90% or more of the repeating units constituting the main chain. Say. 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.

The main chain of the polyether polymer may be linear or branched, but a polyether polymer having one or more branched chains is preferable from the viewpoint of creep resistance. 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 polyoxyalkylene can be obtained by a usual polymerization method (anionic polymerization method using caustic alkali), a cesium metal catalyst, Japanese Patent Laid-Open Nos. 61-197631, 61-215622, 61-215623. Porphyrin / aluminum complex catalysts exemplified in JP-A-61-261832 and the like, double 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 of oxy such as 1.5 or less. When an alkylene 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.

The number average molecular weight of the polyether-based polymer in the present invention represents a value measured by gel permeation chromatography (a value obtained by conversion to polystyrene using tetrahydrofuran as a mobile phase and measurement using a polystyrene gel column). The polyether-based number average molecular weight is not particularly limited, but is generally preferably from 500 to 100,000, more preferably from 1,000 to 50,000, from the viewpoint of workability and physical properties. 000 to 30,000 is particularly preferred. The smaller the molecular weight, the higher the cured product tends to have a high modulus and low elongation, and vice versa.

And the preferable number average molecular weight of the polyether polymer whose 50% elongation stress defined by the present invention is larger than 0.20 is as follows. That is, it is 10,000 or more and 50,000 or less, More preferably, it is 15,000 or more and 45,000 or less, More preferably, it is 20,000 or more and 40,000 or less. If the number average molecular weight is less than 10,000, the cured product tends to be disadvantageous in terms of tensile strength, and if it exceeds 50,000, the cured product tends to be disadvantageous in terms of creep resistance. Therefore, it tends to be inconvenient in terms of workability.

Crosslinkable silyl group As the crosslinkable silyl group, a group represented by the general formula (1) can be used as in the vinyl polymer, and the group represented by the general formula (11) can be used. The group represented by the general formula (5) is more preferable from the viewpoint of creep resistance. The description about the group represented by General formula (1), General formula (11), and General formula (5), and the description regarding the introduction method of a crosslinkable silyl group are the polyether system which has a crosslinkable silyl group. The same applies to polymers. 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.

Number and position of crosslinkable silyl groups The number of crosslinkable silyl groups is one or more on average in the molecule from the viewpoints of the curability of the composition and the tensile properties and creep resistance of the cured product. Is preferably 1.1 or more and 4.0 or less, more preferably 1.6 or more and 3.5 or less, still more preferably 1.8 or more and 3.0 or less, particularly preferably 2.0 or more and 2.5 or less. If the number of crosslinkable silyl groups is less than 1.1, the cured product tends to be disadvantageous in terms of creep resistance and tensile strength, and if it exceeds 4.0, the cured product tends to be disadvantageous in terms of elongation. There is. In addition, the crosslinkable silyl group of the polyether polymer is preferably at the end of the molecular chain from the viewpoint of rubber elasticity of the cured product, and more preferably has a functional group at all ends of the polymer main chain. It is.

Method for introducing crosslinkable silyl group The crosslinkable silyl group may be introduced 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 which 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) A functional group (hereinafter referred to as Y ′) having reactivity with this Y functional group to an oxyalkylene polymer having a hydroxyl group, a functional group such as an epoxy group or an isocyanate group (hereinafter referred to as Y functional group) at the terminal. 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-mercaptopropylmethyl Mercapto group-containing silanes such as dimethoxysilane; epoxy-silanes such as γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; vinyltriethoxysilane, γ -Vinyl-type unsaturated group-containing silanes such as methacryloyloxypropyltrimethoxysilane and γ-acryloyloxypropylmethyldimethoxysilane; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; γ-isocyanatopropyl Isocyanate-containing silanes such as triethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltrimethoxysilane; methyldimethoxysilane, trimethoxysilane, methyldiethoxy Specific examples include hydrosilanes such as silane and triethoxysilane, but are not limited thereto.

Use amount of the polyether polymer (II) The use amount of the crosslinkable silyl group to the polyether polymer (II) is 100 parts by weight of the vinyl polymer (I) having a crosslinkable silyl group. On the other hand, it is essential to use 10 to 100 parts by weight, preferably 15 to 80 parts by weight, more preferably 20 to 70 parts by weight, and further preferably 25 to 60 parts by weight. Parts by weight or less, particularly preferably 30 parts by weight or more and 50 parts by weight or less. When the amount of the polyether polymer (II) used is less than 10 parts by weight relative to 100 parts by weight of the vinyl polymer (I), there is a tendency to be inconvenient in terms of the creep resistance and tensile strength of the cured product. If it exceeds the part, the cured product tends to be disadvantageous in terms of weather resistance, weather resistance adhesion, and water absorption.

The polyether-based polymer having a reactive silicon group used in the present invention has no relation to the type of main chain skeleton, the type / number of reactive silicon groups (introduction ratio), the molecular weight, the presence or absence of branching, etc. It is essential that the stress at 50% elongation of the cured product obtained by curing the polyether polymer alone is larger than 0.20 MPa. In the present specification and claims, 50% elongation stress refers to 1.5 parts of tin octylate, 0.25 parts by weight of laurylamine, and 100% by weight of pure polymer. After adding 0.6 parts by weight and mixing well, the centrifugally defoamed mixture is carefully poured to prevent bubbles from entering the polyethylene mold and allowed to cure at 23 ° C for 1 hour and then at 70 ° C for 20 hours. The 50% elongation stress when punching No. 3 dumbbell from the obtained cured sheet with a thickness of 3 mm according to JISK6251 and conducting a tensile test at 23 ° C. and 50% RH (tensile speed: 200 mm / min). Represents. The stress at the time of 50% elongation of the polyether polymer is essential to be larger than 0.20 MPa, but from the viewpoint of curability and elongation characteristics and creep resistance of the obtained cured product, from 0.24 MPa A range of 0.40 MPa is more preferable, and a range of 0.28 MPa to 0.38 MPa is particularly preferable. When the stress at the time of 50% elongation of the polyether polymer alone is 0.40 MPa or more, the elongation of the obtained cured product is remarkably reduced, and the cured product is brittle when used for a sealing material for multi-layer glass, There is a tendency that practical shock absorption cannot be obtained. On the other hand, when the stress at 50% elongation of the polyether polymer alone is 0.20 MPa or less, when used as a sealing material for double-glazed glass, the obtained cured product cannot obtain practical creep resistance. Tend.

There are various methods for adjusting the stress at 50% elongation of a single cured polymer of the polyether polymer. For example, a method of adjusting by changing the number of reactive silicon groups (introduction rate), a method of adjusting by changing the type of reactive silicon group, a method of adjusting by changing the molecular weight of the polyether polymer, reaction For example, a method of adjusting the introduction position of the functional silicon group at the molecular end or in the molecule.

Specifically, the molecular weight is 10,000 or more and 50,000 or less, more preferably 15,000 or more and 45,000 or less, still more preferably 20,000 or more and 40,000 or less, or it is contained in one molecule on average. The number of reactive silicon groups is 1.1 or more and 4.0 or less, preferably 1.6 or more and 3.5 or less, more preferably 1.8 or more and 3.0 or less, and particularly preferably 2. A method of making the number between 0 and 2.5 can be employed.

In the above examples, the main chain skeleton and molecular weight can be obtained without defining the vinyl polymer (I) or the polyether polymer (II) used in the present invention by the value of the stress at 50% elongation of the single cured product. Or it may give the impression that the structure of the organic polymer can be specified by the number of reactive silicon groups (introduction rate). In practice, however, organic polymers that give cured products having various values of 50% elongation stress have a combination of four factors that affect the stress at 50% elongation, just as exemplified above. It is extremely difficult to specify the structure more appropriately.

On the other hand, the present inventors examined a more appropriate definition of the vinyl polymer (I) or the polyether polymer (II) from many experimental data, but the structural factors of the organic polymer are: Since it is involved in multiple properties such as creep resistance, elongation properties, and adhesiveness, in order to clearly define the invention aimed at achieving various properties in a balanced manner as in the present application, The value of stress at 50% elongation was adopted as a parameter.

<< 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.

<< About carboxylic acid metal salt (III-1) and carboxylic acid (III-2) >>
In the curable composition (A) of the present invention, a carboxylic acid metal salt (III-1) and / or a carboxylic acid (III-2) is used as the component (III). The component (III) is a so-called silanol condensation catalyst capable of forming a siloxane bond from a hydroxyl group or hydrolyzable group bonded to a silicon atom contained in the vinyl polymer (I) and the polyether polymer (II). It works.

This component (III) shows a practical curability while being a non-organotin catalyst, and compared with other silanol condensation catalysts such as an organotin catalyst, the resulting cured product has creep resistance, water-resistant adhesion, Low water absorption can be improved.

The carboxylic acid metal salt and / or carboxylic acid used in the present invention is not particularly limited, and various compounds can be used.

As carboxylate metal salt (III-1), tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, carboxylic acid Vanadium, manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, cerium carboxylate are preferred because of their high catalytic activity, and furthermore, tin carboxylate, lead carboxylate, bismuth carboxylate, titanium carboxylate, carboxylic acid Iron and zirconium carboxylate are more preferred, tin carboxylate is particularly preferred, and divalent tin carboxylate is most preferred.

Here, as the carboxylic acid having an acid group of a carboxylic acid metal salt, a hydrocarbon-based carboxylic acid group-containing compound having 2 to 40 carbon atoms including carbonyl carbon is preferably used, and the number of carbon atoms from the viewpoint of availability. 2 to 20 hydrocarbon-based carboxylic acids can be used particularly preferably.

Specifically, 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, pentadecyl Linear saturated fatty acids such as acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, mellicic acid, and laccellic acid; undecylenic acid, lindelic acid, tuzu Acid, fizeteric acid, myristoleic acid, 2-hexadecenoic acid, 6-hexadecenoic acid, 7-hexadecenoic acid, palmitoleic acid, petrothelic acid, oleic acid, elaidic acid, asclepic acid, vaccenic acid, gadoleic acid, gondoic acid, cetoleic acid , Erucic acid, brassic acid, seracole Monoene unsaturated fatty acids such as acid, ximenic acid, lumenic acid, acrylic acid, methacrylic acid, angelic acid, crotonic acid, isocrotonic acid, 10-undecenoic acid; linoelaidic acid, linoleic acid, 10,12-octadecadiene 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, succinic acid, nisic acid , Polyene unsaturated fatty acids such as docosahexaenoic acid; 1-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid, isovaleric acid, tuberc Branched fatty acids such as stearic acid, pivalic acid, neodecanoic acid; fatty acids having triple bonds such as propiolic acid, taliphosphoric acid, stearolic acid, crepenic acid, ximenic acid, 7-hexadesinic acid; naphthenic acid, malvalic acid Alicyclic carboxylic acids such as sterlic acid, hydonocarbic acid, sorghumulinic acid, golphosphoric acid; acetoacetic acid, ethoxyacetic acid, glyoxylic acid, glycolic acid, gluconic acid, sabinic acid, 2-hydroxytetradecanoic acid, iprolic acid, 2 -Hydroxyhexadecanoic acid, yarapinolic acid, uniperic acid, ambretoleic acid, aleurit acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, ricinoleic acid, Muroren acid, licanic, Feron acid, oxygenated fatty acids, such as cerebronic acid; chloroacetic acid, 2-chloro-acrylic acid, halogen substitution products of monocarboxylic acids such as chlorobenzoic acid. Examples of the aliphatic dicarboxylic acid include adipic acid, azelaic acid, pimelic acid, speric acid, sebacic acid, ethylmalonic acid, glutaric acid, oxalic acid, malonic acid, succinic acid, oxydiacetic acid and other saturated dicarboxylic acids; maleic acid, Examples thereof include unsaturated dicarboxylic acids such as fumaric acid, acetylenedicarboxylic acid, and itaconic acid. Examples of the aliphatic polycarboxylic acid include tricarboxylic acids such as aconitic acid, citric acid, and isocitric 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 And aromatic polycarboxylic acids such as acetic acid and pyromellitic acid. In addition, amino acids such as alanine, leucine, threonine, aspartic acid, glutamic acid, arginine, cysteine, methionine, phenylalanine, tryptophan, histidine and the like can be mentioned.

An organic polymer component having a crosslinkable silyl group (hereinafter referred to as “(I) / (II) component”), which is particularly easy to obtain and inexpensive, and which comprises a vinyl polymer (I) and a polyether polymer (II). The carboxylic acid is preferably 2-ethylhexanoic acid, octylic acid, neodecanoic acid, oleic acid, naphthenic acid, or the like from the viewpoint of good compatibility with the carboxylic acid.

When the melting point of the carboxylic acid is high (crystallinity is high), the carboxylic acid metal salt having an acid group also has a high melting point, which makes it difficult to handle (poor workability). Therefore, the melting point of the carboxylic acid is preferably 65 ° C. or less, more preferably −50 to 50 ° C., and particularly preferably −40 to 35 ° C.

When the carbon number of the carboxylic acid is large (molecular weight is large), the carboxylic acid metal salt having the acid group becomes a solid or highly viscous liquid and is difficult to handle (poor workability). . On the other hand, when the carbon number of the carboxylic acid is small (molecular weight is small), the carboxylic acid tin salt having the acid group contains many components that are easily volatilized by heating, and the catalytic ability of the carboxylic acid metal salt is reduced. There is a case. In particular, when the composition is thinly stretched (thin layer), volatilization by heating is large, and the catalytic ability of the carboxylic acid metal salt may be greatly reduced. Therefore, the carboxylic acid preferably has 2 to 20 carbon atoms including carbon of the carbonyl group, more preferably 6 to 17 and particularly preferably 8 to 12.

From the viewpoint of easy handling (workability and viscosity) of the carboxylic acid metal salt, a metal salt of a dicarboxylic acid or a monocarboxylic acid is preferable, and a metal salt of a monocarboxylic acid is more preferable.

In addition, the carboxylic acid metal salt is a carboxylic acid metal salt (such as tin 2-ethylhexanoate) in which the carbon atom adjacent to the carbonyl group is a tertiary carbon or a carboxylic acid metal salt (tin neodecanoate, which is a quaternary carbon). Tin pivalate and the like) are more preferable because of their high curing rate, and carboxylic acid metal salts in which the carbon atom adjacent to the carbonyl group is a quaternary carbon are particularly preferable. Moreover, the carboxylic acid metal salt in which the carbon atom adjacent to the carbonyl group is a quaternary carbon is excellent in adhesiveness as compared with other carboxylic acid metal salts.

（式中、Ｒ^３４、Ｒ^３５およびＲ^３６はそれぞれ独立した置換あるいは非置換の１価炭化水素基であり、カルボキシル基を含んでいてもよい。）で表される鎖状脂肪酸、または一般式(３３)：

（式中、Ｒ^３７は置換あるいは非置換の１価炭化水素基、Ｒ^３８は置換あるいは非置換の２価炭化水素基であり、それぞれカルボキシル基を含んでいてもよい。）および一般式（３４）：

（式中、Ｒ^３９は置換あるいは非置換の３価炭化水素基であり、カルボキシル基を含んでいてもよい。）で表される構造を含有する環状脂肪酸が挙げられる。具体的に例示すると、ピバル酸、２，２−ジメチル酪酸、２−エチル−２−メチル酪酸、２，２−ジエチル酪酸、２，２−ジメチル吉草酸、２−エチル−２−メチル吉草酸、２，２−ジエチル吉草酸、２，２−ジメチルヘキサン酸、２，２−ジエチルヘキサン酸、２，２−ジメチルオクタン酸、２−エチル−２，５−ジメチルヘキサン酸、ネオデカン酸、バーサチック酸、２，２−ジメチル−３−ヒドロキシプロピオン酸などの鎖状モノカルボン酸、ジメチルマロン酸、エチルメチルマロン酸、ジエチルマロン酸、２，２−ジメチルこはく酸、２，２−ジエチルこはく酸、２，２−ジメチルグルタル酸などの鎖状ジカルボン酸、３−メチルイソクエン酸、４，４−ジメチルアコニット酸などの鎖状トリカルボン酸、１−メチルシクロペンタンカルボン酸、１，２，２−トリメチル−１，３−シクロペンタンジカルボン酸、１−メチルシクロヘキサンカルボン酸、２−メチルビシクロ［２．２．１］−５−ヘプテン−２−カルボン酸、２−メチル−７−オキサビシクロ［２．２．１］−５−ヘプテン−２−カルボン酸、１−アダマンタンカルボン酸、ビシクロ［２．２．１］ヘプタン−１−カルボン酸、ビシクロ［２．２．２］オクタン−１−カルボン酸などの環状カルボン酸などが挙げられる。このような構造を含有する化合物は天然物に多く存在するが、もちろんこれらも使用できる。 The carboxylic acid having an acid group of a carboxylic acid metal salt in which the carbon atom adjacent to the carbonyl group is a quaternary carbon is represented by the general formula (32):

(Wherein R ³⁴ , R ³⁵ and R ³⁶ are each independently a substituted or unsubstituted monovalent hydrocarbon group which may contain a carboxyl group), or a general formula (33):

(Wherein R ³⁷ is a substituted or unsubstituted monovalent hydrocarbon group, R ³⁸ is a substituted or unsubstituted divalent hydrocarbon group, each of which may contain a carboxyl group) and the general formula (34 ):

(Wherein, R ³⁹ is a substituted or unsubstituted trivalent hydrocarbon group, which may contain a carboxyl group), and cyclic fatty acids having a structure represented by: Specific examples include 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, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, versatic acid, Chain monocarboxylic acids such as 2,2-dimethyl-3-hydroxypropionic acid, dimethylmalonic acid, ethylmethylmalonic acid, diethylmalonic acid, 2,2-dimethylsuccinic acid, 2,2-diethylsuccinic acid, 2, Chain dicarboxylic acids such as 2-dimethylglutaric acid, chain tricarboxylic acids such as 3-methylisocitric acid and 4,4-dimethylaconitic acid, 1-methylcyclopentane Rubonic acid, 1,2,2-trimethyl-1,3-cyclopentanedicarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2-methylbicyclo [2.2.1] -5-heptene-2-carboxylic acid, 2- Methyl-7-oxabicyclo [2.2.1] -5-heptene-2-carboxylic acid, 1-adamantanecarboxylic acid, bicyclo [2.2.1] heptane-1-carboxylic acid, bicyclo [2.2. 2] Cyclic carboxylic acids such as octane-1-carboxylic acid. Many compounds containing such structures exist in natural products, but of course they can also be used.

In particular, from the viewpoint of good compatibility with the components (I) / (II) and easy handling, monocarboxylic acid metal salts are more preferred, and chain monocarboxylic acid metal salts are more preferred. Furthermore, metal salts such as pivalic acid, neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid and 2-ethyl-2,5-dimethylhexanoic acid are particularly preferred because they are easily available.

Moreover, it is preferable that carbon number of the carboxylic acid which has the acid group of the carboxylic acid metal salt whose carbon atom adjacent to such a carbonyl group is a quaternary carbon is 5-20, and it is more preferable that it is 6-17. Preferably, it is 8-12. When the number of carbons exceeds this range, it tends to become solid and it becomes difficult to achieve compatibility with the components (I) / (II), and the activity tends not to be obtained. On the other hand, when the number of carbon atoms is small, it tends to volatilize and the odor tends to become strong. From these points, metal salts of neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid and 2-ethyl-2,5-dimethylhexanoic acid are most preferable.

When a carboxylic acid metal salt such as the (III-1) component in the present invention is used, a cured product having good creep resistance, water-resistant adhesion, and low water absorption is provided.

The amount of component (III-1) used is preferably about 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the vinyl polymer (I) and the polyether polymer (II). About 0.5 to 10 parts by weight is preferable. When the blending amount of the (III-1) component is below this range, the curing rate may be slow, and the curing reaction tends to be difficult to proceed sufficiently. On the other hand, when the blending amount of the component (III-1) exceeds this range, the pot life tends to be too short and the workability tends to deteriorate, and the storage stability tends to deteriorate.

Moreover, each said carboxylic acid metal salt which is a (III-1) component can be used in combination of 2 or more type besides using it individually.

In the present invention, a carboxylic acid can be used as the component (III-2).

The creep resistance and low water absorption of the cured product obtained using the carboxylic acid metal salt (III-1) as a catalyst are preferable because they are better than when the carboxylic acid (III-2) is used.

The component (III-2) can be used alone as a curing catalyst, but when used in combination with the component (III-1), there is an effect of improving the curing activity of the curable composition of the present invention. Moreover, when the carboxylic acid metal salt which is the (III-1) component is used as a curing catalyst, the curability may be lowered after storage. However, by adding the (III-2) component together, storage is possible. Later deterioration of curability can be suppressed.

Examples of the carboxylic acid of the (III-2) component include the above-mentioned various carboxylic acids having an acid group of the carboxylic acid metal salt which is the (III-1) component.

The carboxylic acid of the (III-2) component has 2 to 20 carbon atoms including the carbon of the carbonyl group, like the carboxylic acid having an acid group of the carboxylic acid metal salt which is the (III-1) component. Is preferable, 6 to 17 is more preferable, and 8 to 12 is particularly preferable. Further, from the viewpoint of easy handling (workability and viscosity) of carboxylic acid, dicarboxylic acid or monocarboxylic acid is preferable, and monocarboxylic acid is more preferable. Further, the carboxylic acid is a carboxylic acid having a tertiary carbon atom adjacent to the carbonyl group (such as 2-ethylhexanoic acid) or a carboxylic acid having a quaternary carbon (such as neodecanoic acid or pivalic acid). Is more preferable, and a carboxylic acid in which the carbon atom adjacent to the carbonyl group is a quaternary carbon is particularly preferable. Also from the viewpoint of adhesiveness, a carboxylic acid in which the carbon atom adjacent to the carbonyl group is a quaternary carbon is preferable.

In view of availability, curability, and workability, the carboxylic acid is particularly 2-ethylhexanoic acid, neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid. preferable.

Moreover, the cured product which has favorable creep resistance, water-resistant adhesiveness, and low water absorption is given by using the carboxylic acid of (III-2) component.

The amount of component (III-2) used is preferably about 0.01 to 20 parts by weight relative to 100 parts by weight of the total amount of vinyl polymer (I) and polyether polymer (II). About 0.5 to 10 parts by weight is preferable. When the blending amount of the (III-2) component is less than this range, the curing rate may be slow, and the curing reaction tends not to proceed sufficiently. On the other hand, when the blending amount of the component (III-1) exceeds this range, the pot life tends to be too short and the workability tends to deteriorate, and the creep resistance tends to deteriorate and the water absorption rate tends to increase. is there. Moreover, (III-2) component can be used in combination of 2 or more type besides using it individually. Although the component (III-1) and the component (III-2) can be used alone, they may be used in combination.

<< About the amine compound (VI) >>
When the carboxylic acid metal salt (III-1) and / or the carboxylic acid (III-2) as the component (III) is low in activity and an appropriate curability cannot be obtained, it is the component (VI) as a promoter. Amine compounds can be added.

Specific examples of the amine compound (VI) include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, Aliphatic primary amines such as cetylamine, stearylamine, cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, Aliphatic secondary amines such as dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine, etc. Aliphatic tertiary amines such as triamylamine, trihexylamine and trioctylamine; aliphatic unsaturated amines such as triallylamine and oleylamine; aromatics such as laurylaniline, stearylaniline and triphenylamine And other amines such as monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine, diethylenetriamine, triethylenetetramine, benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2 4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), 1,5 -Diazabicyclo (4, 3, 0) nonene-5 (DBN) etc. are mentioned, However, It is not limited to these.

Among these, primary amines such as octylamine and laurylamine are preferable, and amine compounds having a hydrocarbon group having at least one heteroatom are preferable from the viewpoint of high promoter ability. Examples of heteroatoms include N, O, S and the like, but are not limited thereto. Examples of such amine compounds include those exemplified for the above-mentioned other amines. Among these, an amine compound having a hydrocarbon group having a hetero atom on the 2nd to 4th carbon atoms is more preferable. Examples of such amine compounds include ethylenediamine, ethanolamine, dimethylaminoethylamine, diethylaminoethylamine, 3-hydroxypropylamine, diethylenetriamine, 3-methoxypropylamine, 3-lauryloxypropylamine, N-methyl-1,3-propane. Examples include diamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3- (1-piperazinyl) propylamine, and 3-morpholinopropylamine. Of these, 3-diethylaminopropylamine and 3-morpholinopropylamine are more preferred because of their high promoter activity. 3-Diethylaminopropylamine is particularly preferred because it provides a curable composition with good adhesion, workability, and storage stability.

The compounding amount of the amine compound as the component (VI) is preferably about 0.01 to 20 parts by weight with respect to 100 parts by weight as a total of the vinyl polymer (I) and the polyether polymer (II). Furthermore, 0.1-5 weight part is more preferable. If the compounding amount of the amine compound is less than 0.01 parts by weight, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, when the compounding amount of the amine compound exceeds 20 parts by weight, the pot life becomes too short, and the workability tends to deteriorate. On the contrary, the curing speed may be slow.

<< About titanium catalyst (IV) >>
In the curable composition (B) of the present invention, a titanium catalyst is used as the component (IV). This titanium catalyst is an organic polymer component having a crosslinkable silyl group composed of a vinyl polymer (I) and a polyether polymer (II) (hereinafter also referred to as “(I) / (II) component”). It functions as a curing catalyst. Conventionally, organotin compounds such as dibutyltin dilaurate and dibutyltin diacetylacetonate have been used as curing catalysts for organic polymers having a crosslinkable silyl group as component (I) / (II). By using the titanium catalyst (IV), a curable composition (B) having practical curing characteristics while being a non-organotin catalyst can be obtained. Moreover, compared with the case where other hardening catalysts, such as an organic tin catalyst, are used, the creep resistance of the hardened | cured material obtained, water-resistant adhesiveness, and low water absorption can be improved.

The titanium catalyst is a compound having a titanium atom bonded to a hydroxyl group or a substituted or unsubstituted alkoxy group. Specifically, the titanium catalyst is represented by the general formula (2):
Ti (OR ³ ) ₄ (2)
(Wherein R ³ is an organic group, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and four R ^{3 s} may be the same or different from each other. Among them, titanium alkoxide can be exemplified as a typical compound. In addition, as the compound represented by the general formula (2), a part or all of the four OR ³ groups in the general formula (2) are represented by the general formula (35):
-OCOR ⁴⁰ (35)
(Wherein, R ⁴⁰ is an organic group, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), and titanium acylate which is an acyloxy group represented by

Moreover, as a titanium catalyst not represented by General formula (2), General formula (36):
TiX ′ _4-e (OR ⁴¹ ) _e (36)
(In the formula, X ′ is a halogen atom, and 4-e X ′s may be the same or different from each other. R ⁴¹ is an organic group, more preferably 1 to 20 carbon atoms. A substituted or unsubstituted hydrocarbon group, and e R ^{41 s} may be the same or different from each other, e being any one of 1, 2, and 3). And titanium alkoxide.

Among these, titanium alkoxide is preferable from the viewpoints of stability to moisture and curability.

（式中、ｎ個のＲ^４は、それぞれ独立に炭素原子数１から２０の置換あるいは非置換の炭化水素基である。４−ｎ個のＲ^５は、それぞれ独立に水素原子または炭素原子数１から８の置換あるいは非置換の炭化水素基である。４−ｎ個のＡ^１および４−ｎ個のＡ^２は、それぞれ独立に−Ｒ^６または−ＯＲ^６である（ここでＲ^６は炭素原子数１から８の置換あるいは非置換の炭化水素基である）。ｎは０、１、２、３のいずれかである。）で表される化合物および／または一般式（４）：

（式中、Ｒ^５、Ａ^１、Ａ^２は前記と同じ。Ｒ^７は、炭素原子数１から２０の置換あるいは非置換の二価の炭化水素基である。）で表される化合物が、（Ｉ）／（ＩＩ）成分との相溶性、触媒活性の高さ、および、貯蔵安定性の点から、より好ましい。一般式（３）のチタニウムキレートは、触媒活性が高いことから、特に好ましい。一般式（３）のｎが２であるチタニウムキレートは、比較的結晶性（融点）が低く、作業性が良好で、触媒活性が高い為、最も好ましい。 Among the titanium catalysts represented by the general formula (2), the general formula (3):

(In the formula, n R ^{4 s} are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 4-n R ^{5 s} are independently hydrogen atoms or carbon atoms. A substituted or unsubstituted hydrocarbon group of 1 to 8. 4-n A ¹ and 4-n A ² are each independently —R ⁶ or —OR ⁶ (where R ⁶ is A substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms.) N is 0, 1, 2, or 3) and / or the general formula (4):

(Wherein R ⁵ , A ¹ and A ² are the same as described above. R ⁷ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.) It is more preferable from the viewpoint of compatibility with the components (I) / (II), high catalytic activity, and storage stability. The titanium chelate of the general formula (3) is particularly preferable because of its high catalytic activity. The titanium chelate having n of 2 in the general formula (3) is most preferable because it has relatively low crystallinity (melting point), good workability, and high catalytic activity.

Specific examples of the titanium alkoxide represented by the general formula (2) include titanium tetramethoxide, titanium tetraethoxide, titanium allyl oxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide. , Titanium tetraisobutoxide, titanium tetra sec-butoxide, titanium tetra t-butoxide, titanium tetra n-pentyl oxide, titanium tetracyclopentyl oxide, titanium tetrahexyl oxide, titanium tetracyclohexyl oxide, titanium tetrabenzyl oxide, titanium tetraoctyl oxide, Titanium tetrakis (2-ethylhexyl oxide), titanium tetradecyl oxide, titanium tet Dodecyl oxide, titanium tetrastearyl oxide, titanium tetrabutoxide dimer, titanium tetrakis (8-hydroxyoctyl oxide), titanium diisopropoxide bis (2-ethyl-1,3-hexanediolato), titanium bis (2-ethylhexyloxy) ) Bis (2-ethyl-1,3-hexanediolato), titanium tetrakis (2-chloroethoxide), titanium tetrakis (2-bromoethoxide), titanium tetrakis (2-methoxyethoxide), titanium tetrakis (2 -Ethoxyethoxide), titanium butoxide trimethoxide, titanium dibutoxide dimethoxide, titanium butoxide triethoxide, titanium dibutoxide diethoxide, titanium butoxide tri Sopuropokishido, titanium dibutoxide diisopropoxide, titanium tetraphenoxide, titanium tetrakis (o-chloro phenoxide), titanium tetrakis (m-nitrophenoxide), titanium tetrakis (p- methyl phenoxide), and the like.

Specific examples of titanium acylate in which some or all of four OR ¹ groups in general formula (1) are groups represented by general formula (35) include titanium acrylate triisopropoxide, titanium methacrylate. Examples include triisopropoxide, titanium dimethacrylate diisopropoxide, titanium isopropoxide trimethacrylate, titanium hexanoate triisopropoxide, titanium stearate triisopropoxide, and the like.

Specific examples of the halogenated titanium alkoxide of the general formula (36) include titanium chloride triisopropoxide, titanium dichloride diisopropoxide, titanium isopropoxide trichloride, titanium bromide triisopropoxide, titanium fluoride triiso Examples thereof include propoxide, titanium chloride triethoxide, and titanium chloride tributoxide.

Specific examples of the titanium chelate of the general formula (3) or the general formula (4) are titanium dimethoxide bis (ethyl acetoacetate), titanium dimethoxide bis (acetylacetonate), titanium diethoxide bis (ethyl acetoacetate). ), Titanium diethyl bis (acetylacetonate), titanium diisopropoxide bis (ethyl acetoacetate), titanium diisopropoxide bis (methyl acetoacetate), titanium diisopropoxide bis (t-butyl acetoacetate), Titanium diisopropoxide bis (methyl-3-oxo-4,4-dimethylhexanoate), titanium diisopropoxide bis (ethyl-3-oxo-4,4,4-trifluoropentanoate), titanium Diisop Poxide bis (acetylacetonate), Titanium diisopropoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate), Titanium di-n-butoxide bis (ethylacetoacetate), Titanium di- n-butoxide bis (acetylacetonate), titanium diisobutoxide bis (ethyl acetoacetate), titanium diisobutoxide bis (acetylacetonate), titanium di-t-butoxide bis (ethyl acetoacetate), titanium di-t- Butoxide bis (acetylacetonate), titanium di-2-ethylhexoxide bis (ethyl acetoacetate), titanium di-2-ethylhexoxide bis (acetylacetonate), 1,2-dioxyethane titanium bis ( Ethyl acetate Acetate), 1,3-dioxypropane titanium bis (ethyl acetoacetate), 2,4-dioxypentane titanium bis (ethyl acetoacetate), 2,4-dimethyl-2,4-dioxypentane titanium bis (ethyl) Acetoacetate), titanium diisopropoxide bis (triethanolaminate), titanium tetrakis (ethyl acetoacetate), titanium tetrakis (acetylacetonate), and the like. Among these, titanium diethoxide bis (ethyl acetoacetate), titanium diethoxide bis (acetylacetonate), titanium diisopropoxide bis (ethylacetoacetate), titanium diisopropoxide bis (acetylacetonate), titanium Dibutoxide bis (ethyl acetoacetate) and titanium dibutoxide bis (acetylacetonate) are preferable from the viewpoint of availability and catalytic activity. Titanium diethoxide bis (ethyl acetoacetate), titanium diisopropoxide bis (ethyl acetoacetate) Acetate) and titanium dibutoxide bis (ethyl acetoacetate) are more preferred, and titanium diisopropoxide bis (ethyl acetoacetate) is most preferred.
Specific examples of titanium catalysts other than those described above include titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzene sulfonate) isopropoxide, dihydroxy titanium bis-lactate, and the like.

Specific examples of the chelating reagent capable of forming the chelate ligand of the titanium chelate include β-diketones such as acetylacetone, β-ketoesters such as ethyl acetoacetate, and β-diesters such as ethyl malonate are curable. From the viewpoint, β-diketone and β-ketoester are more preferable from the viewpoint of curability and storage stability, and β-ketoester is particularly preferable.

When the titanium chelate is added as the component (IV) of the present invention, the following method (d) or (e) can be used. (D) A method of adding a pre-chelated titanium catalyst. (E) A titanium compound capable of reacting with a chelating reagent such as titanium tetraisopropoxide or titanium diisopropoxide and a chelating reagent such as ethyl acetoacetate are added to the composition of the present invention. A method using a chelated titanium chelate.

The amount of the component (IV) used is preferably about 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the vinyl polymer (I) and the polyether polymer (II). About 15 parts by weight is more preferable, and about 1 to 10 parts by weight is particularly preferable. When the blending amount of the component (IV) is below this range, a practical curing rate may not be obtained, and the curing reaction may not proceed sufficiently. On the other hand, when the blending amount of the component (IV) exceeds this range, the pot life tends to be too short and workability tends to be deteriorated. In addition, creep resistance tends to deteriorate and water absorption tends to increase. The titanium catalyst of component (IV) can be used in combination of two or more, in addition to being used alone.

In the present invention, the vinyl polymer (I) and / or the polyether polymer (II) are used to further improve the creep resistance, water resistance adhesion, and low water absorption improvement effect of the titanium catalyst (IV). As the crosslinkable silyl group of general formula (5):
-SiY ₃ (5)
It is preferable to use a crosslinkable silyl group represented by the formula (wherein Y represents a hydroxyl group or a hydrolyzable group, and three Ys may be the same or different from each other).

In particular, as the crosslinkable silyl group of the polyether polymer (II), the general formula (5):
-SiY ₃ (5)
It is more preferable to use a crosslinkable silyl group represented by the formula (wherein Y is the same as above) from the viewpoint of creep resistance of the resulting cured product.

<< About Organotin Catalyst (V) >>
In the curable composition (C) of the present invention, 0.01 to 0.5 parts by weight of organic tin is added to 100 parts by weight of the total amount of the vinyl polymer (I) and the polyether polymer (II). A catalyst is used as component (V). This organotin catalyst is also referred to as an organic polymer component having a crosslinkable silyl group comprising a vinyl polymer (I) and a polyether polymer (II) (hereinafter referred to as “(I) / (II) component”). ) Function as a curing catalyst. Conventionally, as a curing catalyst for an organic polymer having a crosslinkable silyl group which is a component (I) / (II), a relatively large amount of an organic tin compound such as dibutyltin dilaurate or dibutyltin diacetylacetonate can be blended. Generally, in the present invention, it is essential that the amount of the organotin catalyst used is 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the total amount of the components (I) / (II). . Compared with the conventional case using a large amount of an organic tin catalyst, the creep resistance, water-resistant adhesion, and low water absorption of the resulting cured product can be improved.

Specific examples of the organic tin catalyst (V) include dialkyltin carboxylates, dialkyltin oxides, and general formula (37):
_{Q g Sn (OZ) 4-} g, or _{[Q 2 Sn (OZ)]} 2 O (37)
(In the formula, Q is a monovalent hydrocarbon group having 1 to 20 carbon atoms, Z is a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a function capable of forming a coordination bond to Sn inside itself. An organic group having a functional group, and g is any one of 0, 1, 2, and 3). Further, a tetravalent tin compound such as dialkyl tin oxide or dialkyl tin diacetate and a low molecular silicon compound having a hydrolyzable silicon group such as tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane or phenyltrimethoxysilane. The reactant can also be used as component (V). Among these, compounds represented by the general formula (37), that is, chelate compounds such as dibutyltin bisacetylacetonate and tin alcoholates are more preferable because of their high activity as silanol condensation catalysts.

Specific examples of the dialkyltin carboxylates include, for example, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate Dibutyltin diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diiso Examples include octyl malate.

Specific examples of the dialkyl tin oxides include dibutyl tin oxide, dioctyl tin oxide, a mixture of dibutyl tin oxide and phthalate ester, and the like.

等が挙げられるが、これらに限定されるものではない。これらの中では、ジブチル錫ビスアセチルアセトナートは、触媒活性が高く、低コストであり、入手が容易であるために最も好ましい。 Specific examples of the chelate compound include:

However, it is not limited to these. Of these, dibutyltin bisacetylacetonate is most preferred because of its high catalytic activity, low cost, and availability.

等が挙げられるが、これらに限定されるものではない。これらの中ではジアルキル錫ジアルコキサイドが好ましい。特に、ジブチル錫ジメトキサイドは、低コストであり、入手が容易であるためにより好ましい。 Specific examples of the tin alcoholates include:

However, it is not limited to these. Of these, dialkyltin dialkoxide is preferred. In particular, dibutyltin dimethoxide is more preferable because of its low cost and easy availability.

Component (V) must be used in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the total amount of vinyl polymer (I) and polyether polymer (II). However, it is preferably about 0.03 to 0.4 parts by weight, more preferably about 0.05 to 0.3 parts by weight, and particularly preferably about 0.1 to 0.2 parts by weight. When the blending amount of component (V) is below this range, a practical curing rate may not be obtained, and the curing reaction may not proceed sufficiently. On the other hand, when the blending amount of the component (V) exceeds this range, the pot life tends to be too short and workability tends to deteriorate. In addition, creep resistance tends to deteriorate and water absorption tends to increase.

Moreover, (V) component can be used in combination of 2 or more types besides using it individually.

In the present invention, the vinyl polymer (I) and / or the polyether heavy polymer is used in order to further enhance the effect of improving the creep resistance, water resistance adhesion and low water absorption by the specific amount of the organic tin catalyst (V). As the crosslinkable silyl group of the compound (II), the general formula (5):
-SiY ₃ (5)
It is preferable to use a crosslinkable silyl group represented by the formula (wherein Y represents a hydroxyl group or a hydrolyzable group, and three Ys may be the same or different from each other).

In particular, as the crosslinkable silyl group of the polyether polymer (II), the general formula (5):
-SiY ₃ (5)
It is more preferable to use a crosslinkable silyl group represented by the formula (wherein Y is the same as above) from the viewpoint of creep resistance of the resulting cured product.

<< About other curing catalysts >>
In the present invention, the curable composition (A) is used as the curing catalyst, and the carboxylic acid metal salt (III-1) and / or the carboxylic acid (III-2) is used as the (III) component. For the composition (B), a titanium catalyst is used as the component (IV). Further, in the curable composition (C), the vinyl polymer (I) and the polyether polymer (II). 0.01 to 0.5 parts by weight of the organotin catalyst is used as the component (V) with respect to 100 parts by weight of the total amount, and other curing catalysts are used in combination so as not to reduce the effect of the present invention. You can also

Specific examples include organoaluminum compounds such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate; zirconium compounds such as zirconium tetrakis (acetylacetonate). . By using these curing catalysts in combination, the catalytic activity is increased, and the thin layer curability, adhesion, and the like are improved. In addition, the curable compositions (A), (B), and (C) of the present invention require the components (IV), (V), and (VI), respectively, but the effects of the present invention are reduced. It is also possible to use the respective components in combination with each other to the extent that they are not caused. That is, the (V) component and / or (VI) component is added to the curable composition (A), the (IV) component and / or (VI) component is added to the curable composition (B), or the curable composition. It is possible to add (IV) component and / or (V) component to (C) together to such an extent that the effect of the present invention is not lowered.

<< About Silicate (VII) >>
Moreover, silicate (VII) can be used for the composition of this invention. This silicate acts as a crosslinking agent and is an organic polymer component having a crosslinkable silyl group (hereinafter referred to as “(I) / ( II) also has a function of improving the creep resistance, water-resistant adhesion, and low water absorption. Furthermore, it also has the effect of improving the adhesion and adhesion durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane or a partial hydrolysis condensate thereof can be used. When the silicate is used, the amount used is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight based on 100 parts by weight of the total amount of the vinyl polymer (I) and the polyether polymer (II). Parts by weight. If the blending amount of the component (VII) is below this range, the effect of improving creep resistance, water-resistant adhesion, and low water absorption may not be sufficient, and curing if the blending amount of the component (VII) exceeds this range. In some cases, the elongation of the product becomes small, and the curing rate becomes slow.

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 (tetraalkyl silicates) such as silane, tetra-i-butoxysilane, and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.

The partial hydrolysis condensate of tetraalkoxysilane is more preferable because the effect of improving the 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.). The silicate may be used alone or in combination of two or more.

Silicate (VII) has good creep resistance and water-resistant adhesion when combined with component (III) of curable composition (A) of the present invention or component (IV) of curable composition (B). And low water absorption can be obtained. When combined with the component (V) of the curable composition (C), there is an inconvenient tendency that the curing rate is remarkably slowed.

<< About epoxy silane coupling agent (VIII) >>
In the present invention, an epoxy silane coupling agent is used as the component (VIII). The epoxy silane coupling agent is a compound having a crosslinkable silyl group and an epoxy group, and has an effect of improving the creep resistance, water-resistant adhesion, and low water absorption of the curable composition of the present invention.

Examples of the crosslinkable silyl group of the epoxysilane coupling agent include those in which Y of the group represented by the general formula (1) is a hydrolyzable group. Specific examples of the hydrolyzable group include the groups already exemplified, and 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.

Specific examples of the epoxy silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl). ) Ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

Component (VIII) 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 total amount of vinyl polymer (I) and polyether polymer (II). Part. When the blending amount of the component (VIII) is less than this range, the effect of improving creep resistance, water-resistant adhesion, and low water absorption may not be sufficient. When the compounding quantity of (VIII) component exceeds this range, there exists a tendency for hardened | cured material to become low elongation and there exists a tendency for deep part sclerosis | hardenability to worsen.

The epoxy silane coupling agent (VIII) includes the component (III) of the curable composition (A) of the present invention, the component (IV) of the curable composition (B), and the component (C) of the curable composition (C). Even if it is combined with any composition of component V), it is possible to obtain the effect of improving creep resistance, water-resistant adhesion, and low water absorption.

<< Curable composition >>
In the curable composition of the present invention, various compounding agents may be added according to the intended physical properties. Hereinafter, a vinyl polymer (I) having a crosslinkable silyl group and a polyether polymer (II) having a crosslinkable silyl group are collectively referred to as an “organic polymer having a crosslinkable silyl group” or “organic polymer”. Also called.

<Dehydrating agent>
The curable composition increases in viscosity and gelation during storage due to moisture at the time of production, etc., causing difficulty in workability during use, and also increases in viscosity and gelation. By using the advanced curable composition, the physical properties of the cured product after curing may be deteriorated, resulting in a problem that the original sealing property and the like are impaired. That is, the storage stability of the curable composition may be a problem.

In order to improve the storage stability of this curable composition, there is a method of reducing the moisture content of the curable composition by azeotropic dehydration. For example, about 0.1 to 10 parts by weight of a volatile organic compound having a minimum azeotropic point with respect to water is added and mixed uniformly, and then heated to about 50 to 90 ° C. and sucked with a vacuum pump. A method of removing an azeotropic composition of a compound into a body is mentioned. Volatile organic compounds having a minimum azeotropic point with respect to water include halides such as methylene chloride, chloroform, carbon tetrachloride, and trichloroethylene; alcohols such as ethanol, allyl alcohol, 1-propanol, and butanol; ethyl acetate, propionic acid Examples thereof include esters such as methyl; ketones such as methyl ethyl ketone and 3-methyl-2-butanone; ethers such as ethyl ether and isopropyl ether; hydrocarbons such as benzene, toluene, xylene and hexane. However, since this method involves a devolatilization operation, it is necessary to devise other volatile compounding agents, or it is necessary to treat, recover, etc., the volatile organic compound to be azeotroped. Therefore, it may be preferable to add the following dehydrating agents.

As described above, a dehydrating agent for removing moisture in the composition can be added to the composition of the present invention for the purpose of improving storage stability. Examples of the dehydrating agent include inorganic solids such as phosphorus pentoxide, sodium hydrogen carbonate, sodium sulfate (anhydrous bow glass), and molecular sieves. These solid dehydrating agents may be used, but the liquidity after addition tends to be acidic or basic, condensing easily, resulting in poor storage stability and workability such as removing the solid later. In some cases, the liquid hydrolyzable ester compound described below is preferable. Examples of hydrolyzable ester compounds include trialkyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, trialkyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate. And trialkyl orthoacetate such as tributyl orthoacetate, and those selected from the group consisting of these compounds.

Other hydrolyzable ester compounds may further include the formula R _4-n SiY _n (wherein Y is a hydrolyzable group, R is an organic group and may or may not contain a functional group). n is an integer of 1 to 4, preferably 3 or 4, and specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, and methyltrimethoxy. Silane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, methyltriacetoxysilane, tetramethyl orthosilicate (tetramethoxysilane or methyl silicate), tetraethyl orthosilicate (tetraethoxysilane or ethyl silicate), tetra orthosilicate Propyl, tetrabutyl orthosilicate, etc. Lan compounds or partial hydrolysis condensates thereof, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-acryloxy Propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, etc. Examples thereof include silane coupling agents or partial hydrolysis condensates thereof. One or more of these can be used in combination.

The dehydrating agent not only prevents hydrolysis of the vinyl polymer during storage and forms a three-dimensional network structure by silanol condensation reaction, but also decomposes the ketimine with water and reacts with the epoxy resin to cure. Therefore, it is more preferable as a storage stability improver.

The amount of the storage stability improver used is 0.1 to 30 parts by weight, preferably 0.3 to 20 parts by weight, more preferably 0.5 to 100 parts by weight of the organic polymer having a crosslinkable silyl group. -10 parts by weight.

In addition, when adding these storage stability improving agents, it is preferable to carry out after making a curable composition anhydrous, but you may add in the state containing a water | moisture content.

<Adhesive agent>
To the composition of the present invention, a silane coupling agent other than the epoxy silane coupling agent (VIII) and an adhesion promoter other than the silane coupling agent can be added. Addition of an adhesion-imparting agent can further reduce the risk of peeling, and in some cases, it is not necessary to use a primer used for improving adhesion, and simplification of construction work is expected. Specific examples of silane coupling agents other than the epoxy silane coupling agent (VIII) include silane coupling agents having functional groups such as amino groups, mercapto groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, and halogens. Specific examples thereof include isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane , Γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) ) Aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-amino Amino group-containing silanes such as propyltrimethoxysilane and N-vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ -Mercap Mercapto group-containing silanes such as topropylmethyldiethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-amino Carboxysilanes such as propyltrimethoxysilane; Vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-acryloyloxypropylmethyltriethoxysilane; Halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; polysulfanes such as bis (3-triethoxysilylpropyl) tetrasulfane And the like can be given. In addition, a reaction product of the amino group-containing silane and the epoxy group-containing silane, a reaction product of an amino group-containing silane and an acroyloxy group-containing silane, an amino group-containing silane and an isocyanate group-containing silane These reactants can also be used. Further, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, blocked isocyanate silanes, silylated polyesters, etc., which are derivatives of these, are also used as silane coupling agents. Can be used. A ketimine compound obtained by reacting the above amino group-containing silanes with a ketone compound such as methyl isobutyl ketone can also be used as a silane coupling agent.

In the present invention, so-called Dipodal Silane having two or more crosslinkable silyl groups in one molecule can be preferably used from the viewpoint of water-resistant adhesion and low water absorption. Specifically, bis (3-trimethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) ethylenediamine, 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, 1,6-bis (Trimethoxysilyl) hexane, bis (3-triethoxysilylpropyl) polysulfide, and the like. In addition, a reaction product of aminosilane and epoxysilane can be used as Dipodal Silane.

The silane coupling agent used for this invention is normally used in 0.1-20 weight part with respect to 100 weight part of organic polymers which have a crosslinkable silyl group. In particular, it is preferably used in the range of 0.5 to 10 parts by weight. The effects of the silane coupling agent added to the curable composition of the present invention are various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, vinyl chloride, acrylic, polyester, When used for organic base materials such as polyethylene, polypropylene, polycarbonate, etc., it exhibits 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.

Specific examples other than the silane coupling agent are not particularly limited. For example, epoxy resin, phenol resin, polystyrene-polybutadiene-polystyrene, polystyrene-polyisoprene-polystyrene, polystyrene-polyisoprene / butadiene copolymer-polystyrene, polystyrene. -Polyethylene / propylene copolymer-Polystyrene, polystyrene-polyethylene / butylene copolymer-Linear or branched block copolymers such as polystyrene, polystyrene-polyisobutene-polystyrene, alkyl sulfonates, sulfur, alkyl titanates And aromatic polyisocyanate. The epoxy resin can be used by reacting with the above amino group-containing silanes.

The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved. Although not particularly limited, 0.1-20 parts by weight of a silane coupling agent is used in combination with the above-mentioned adhesion-imparting agent in order to improve adhesion, particularly adhesion to a metal-coated surface such as an oil pan. Is preferred.

The type and amount of the adhesion-imparting agent can be selected according to the type of Y and the number of a in the vinyl polymer of the present invention, and the curability and mechanical properties of the present invention depending on the purpose and application. Can be controlled. In particular, care must be taken in selecting it because it affects curability and elongation.

<Plasticizer>
You may use various plasticizers for the curable composition of this invention as needed. When a plasticizer is used in combination with a filler to be described later, it becomes more advantageous because the elongation of the cured product can be increased or a large amount of filler can be mixed, but it is not necessarily added. Although it does not specifically limit as a plasticizer, For purposes, such as adjustment of a physical property and adjustment of properties, phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, etc. Non-aromatic dibasic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate; benzoic acid esters such as 2-ethylhexyl benzoate; butyl oleate, methyl acetylricinoleate, etc. Aliphatic esters; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester; phosphates such as tricresyl phosphate and tributyl phosphate Steryls; trimellitic acid esters; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; alkyldiphenyl, partially hydrogenated terphenyl, Hydrocarbon oils such as; process oils; polyether polyols such as polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer, polytetramethylene glycol, one end or both ends or all of the hydroxyl groups of these polyether polyols Polyethers such as alkyl derivatives whose ends are converted to alkyl ester groups or alkyl ether groups; epoxidized soybean oil, epoxy benzyl stearate, E-PS Xyl group-containing plasticizers; polyester plastics 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 Agents: Examples thereof include vinyl polymers obtained by polymerizing vinyl monomers including acrylic plasticizers by various methods.

In particular, a polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15,000 is added, whereby the viscosity and slump property of the curable composition and the tensile strength of the cured product obtained by curing the composition are obtained. Mechanical properties such as strength and elongation can be adjusted, and the initial physical properties are maintained over a long period of time compared to the case of using a low molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule. It is possible to improve the drying property (also referred to as paintability) when an alkyd paint is applied. Although not limited, the polymer plasticizer may or may not have a functional group.

Although the number average molecular weight of the polymer plasticizer was described as 500 to 15,000 above, it is preferably 800 to 10,000, and more preferably 1,000 to 8,000. If the molecular weight is too low, the plasticizer flows 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.

Among these polymer plasticizers, polyether plasticizers and (meth) acrylic polymer plasticizers are preferable from the viewpoint of high elongation characteristics or high weather resistance. Examples of the synthesis method of the acrylic polymer include those obtained by conventional solution polymerization and solvent-free acrylic polymers. The latter acrylic plasticizer does not use a solvent or a chain transfer agent, and is a high-temperature continuous polymerization method (US Pat. No. 4,414,370, JP-A-59-6207, JP-B-5-58005, JP-A-1-313522). , U.S. Pat. No. 5,010,166), and is more preferable for the purpose of the present invention. Examples thereof include, but are not particularly limited to, for example, ARUFON UP series (UP-1000, UP-1110, UP-2000, UP-2130) (referred to as SGO) of Toagosei Co., Ltd. (waterproof journal, June 2002 issue) reference). Of course, the living radical polymerization method can also be mentioned as another synthesis method. According to this method, the molecular weight distribution of the polymer is narrow and the viscosity can be lowered, and the atom transfer radical polymerization method is more preferable, but it is not limited thereto.

The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow from the viewpoint of viscosity, and preferably less than 1.8. 1.7 or less is more preferable, 1.6 or less is still more preferable, 1.5 or less is more preferable, 1.4 or less is especially preferable, and 1.3 or less is the most preferable.

From the viewpoint of viscosity, it is preferable to have a branched structure in the main chain because the viscosity becomes lower at the same molecular weight. The high temperature continuous polymerization method mentioned above is mentioned as this example.

The plasticizer containing the above-mentioned polymer plasticizer may be used alone or in combination of two or more, but is not necessarily required. Further, if necessary, a high molecular plasticizer may be used, and a low molecular plasticizer may be further used in a range that does not adversely affect the physical properties. The composition of the present invention in which a vinyl polymer and a polyether polymer are mixed is particularly preferably a phthalate ester or an acrylic polymer from the viewpoint of the compatibility of the mixture.

When the curable composition of the present invention is used for a secondary sealing material for double-glazed glass, from the viewpoint of migration to the primary sealing material and water resistant adhesion, a high molecular weight plasticizer or a high polarity It is preferable to use a plasticizer. Specifically, polyether plasticizers, acrylic polymer plasticizers, phthalic acid esters, non-aromatic dibasic acid esters, and benzoic acid esters are preferred, and acrylic polymer plasticizers or benzoic acids are preferred. Acid-based esters are more preferable.

In addition, these plasticizers can also be mix | blended at the time of polymer manufacture.

The amount of the plasticizer used is not limited, but 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 organic polymer having a crosslinkable silyl group. Part. If the amount is less than 5 parts by weight, the effect as a plasticizer is hardly exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product tends to be insufficient.

<Filler>
You may use various fillers for the curable composition of this invention as needed. The filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, silica (fumed silica, sedimentation) Silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, amorphous spherical silica, etc.), reinforcing filler such as 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, zinc dust, zinc carbonate and shirasu balloon, glass microballoon, Organic microballoons of phenolic resin and vinylidene chloride resin, PVC powder, PMMA Fillers such as resin powders such end; asbestos, glass fibers and glass filaments, carbon fibers, Kevlar fibers, fibrous fillers such as polyethylene fiber and the like. Of these fillers, precipitated silica, fumed silica, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable.

In particular, when it is desired to obtain a cured product having high transparency or strength with these fillers, it is mainly fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, crystallinity. A filler selected from silica, fused silica, calcined clay, clay and activated zinc white can be added. These are suitable for transparent architectural sealants, transparent DIY adhesives and the like. Among them, the specific surface area (according to BET adsorption method) of ^{10 m} 2 / g or more, usually 50 to 400 m ² / g, is preferably 100 to 300 m ² / g approximately ultrafine powdery silica preferred. Further, silica whose surface is previously hydrophobically treated with an organosilicon compound such as organosilane, organosilazane, diorganocyclopolysiloxane or the like is more preferable.

More specific examples of silica-based fillers having high reinforcing properties are not particularly limited. However, Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Silica Co., Ltd., which is one of precipitated silicas. Nipsil etc. are mentioned. Silica having an average particle diameter of 1 nm to 30 μm can be used. Particularly for fumed silica, it is more preferable to use fumed silica having an average primary particle diameter of 1 nm to 50 nm because the reinforcing effect is particularly high. In addition, the average particle diameter in this invention is based on the sieving method. Specifically, the powder is classified with various sieves (such as micro sieves), and the value corresponding to the sieve openings through which 50% by weight of the total weight of the powder used for measurement has passed (weight average) Particle size). A composition reinforced with a filler is excellent in quick fixability and suitable for automobile glass glazing adhesion.

Transparency can also be obtained by using a resin powder such as PMMA powder as a filler.

In addition, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. In general, when calcium carbonate has a small specific surface area, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient. The larger the specific surface area value, the greater the effect of improving the strength at break, elongation at break, adhesion and weather resistance of the cured product. As the shape of calcium carbonate, various shapes such as a cubic non-cubic shape and an irregular shape can be used.

Furthermore, it is more preferable that the calcium carbonate is subjected to a surface treatment using a surface treatment agent. When the surface-treated calcium carbonate is used, the workability of the composition of the present invention is improved as compared with the case where calcium carbonate that is not surface-treated is used, and the adhesiveness and weather resistance of the curable composition are improved. The improvement effect is considered to be further improved. As the surface treatment agent, organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents are used. Specific examples include, but are not limited to, fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc. And salts of these fatty acids such as sodium and potassium, and alkyl esters of these fatty acids. Specific examples of the surfactants include polyoxyethylene alkyl ether sulfates and long chain alcohol sulfates, sulfate anion surfactants such as sodium salts and potassium salts thereof, alkylbenzene sulfonic acids, and alkylnaphthalenes. Examples thereof include sulfonic acid, paraffin sulfonic acid, α-olefin sulfonic acid, alkylsulfosuccinic acid and the like, and sulfonic acid type anionic surfactants such as sodium salt and potassium salt thereof. The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight and more preferably in the range of 1 to 5% by weight with respect to calcium carbonate. When the treatment amount is less than 0.1% by weight, the workability, adhesiveness and weatherability may not be sufficiently improved. When the treatment amount exceeds 20% by weight, the storage stability of the curable composition may be reduced. May decrease.

Although there is no particular limitation, when calcium carbonate is used, colloidal calcium carbonate is used when particularly improving effects such as thixotropy of the compound, breaking strength of the cured product, elongation at break, adhesion and weather resistance are expected. Is preferred.

On the other hand, heavy calcium carbonate may be added for the purpose of lowering the viscosity of the compound, increasing the amount, reducing costs, etc. When using this heavy calcium carbonate, use the following as necessary. be able to.

Heavy calcium carbonate is obtained by mechanically pulverizing and processing natural chalk (chalk), marble, limestone, and the like. There are dry and wet methods for the pulverization method, but wet pulverized products are often not preferred because they often deteriorate the storage stability of the curable composition of the present invention. Heavy calcium carbonate becomes products having various average particle sizes by classification. Although not particularly limited, when the effect of improving the breaking strength, breaking elongation, adhesiveness and weather resistance of the cured product is expected, the specific surface area value is 1.5 m ² / g or more and 50 m ² / g or less. , more preferably from ^2m 2 / g or more ^{50 m} 2 / g or less, more preferably 2.4 m ² / g or more ^{50m 2 / g, 3m 2 /} g or more ^{50 m} 2 / g or less is particularly preferred. When the specific surface area is less than 1.5 m ² / g, the improvement effect may not be sufficient. Of course, this is not the case when the viscosity is simply reduced or when the purpose is only to increase the viscosity.

In addition, the value of the specific surface area means a measurement value by an air permeation method (a method for obtaining a specific surface area from air permeability with respect to a powder packed bed) performed according to JIS K 5101 as a measurement method. As a measuring instrument, it is preferable to use a specific surface area meter SS-100 manufactured by Shimadzu Corporation.

These fillers may be used alone or in combination of two or more according to the purpose and necessity. In particular but not limited, for example, if the value of the specific surface area as required combine heavy calcium and colloidal calcium carbonate of more than 1.5 m 2 / ^g, suppressing the increase of viscosity of the formulation in moderation, the cured product The effect of improving the breaking strength, breaking elongation, adhesiveness and weathering adhesion can be greatly expected.

When using the filler, it is preferable to use the filler in the range of 5 to 1,000 parts by weight with respect to 100 parts by weight of the organic polymer having a crosslinkable silyl group, and 20 to 500 parts by weight. More preferably, it is used in the range of 40 to 300 parts by weight. When the blending amount is less than 5 parts by weight, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient, and when it exceeds 1,000 parts by weight, the curable composition Workability may be reduced. A filler may be used independently and may be used together 2 or more types.

It should be noted that dolomite, carbon black, calcium carbonate, titanium oxide, talc and the like may be added in a large amount, thereby hindering the transparency of the present invention and resulting in an opaque cured product.

<Micro hollow particles>
Furthermore, for the purpose of reducing the weight and cost without causing a significant decrease in physical properties, fine hollow particles may be used in combination with these reinforcing fillers.

Such fine hollow particles (hereinafter referred to as “balloons”) are not particularly limited, but as described in “the latest technology of functional filler” (CMC), the diameter is 1 mm or less, preferably 500 μm or less, and more preferably Is a hollow body made of an inorganic or organic material of 200 μm or less. In particular, it is preferable to use a micro hollow body having a true specific gravity of 1.0 g / cm ³ or less, and more preferably to use a micro hollow body having a specific gravity of 0.5 g / cm ³ or less.

Examples of the inorganic balloons include silicate balloons and non-silicate balloons. Silicate balloons include shirasu balloons, perlite, glass (silica) balloons, fly ash balloons, etc., and non-silicate balloons include alumina. Examples include balloons, zirconia balloons, and carbon balloons. As specific examples of these inorganic balloons, Shirasu balloons made by Idichi Kasei Co., Ltd., Sankilite made by Sanki Kogyo Co., Ltd., Fuji Silicia Chemicals Fuji Balloon made by glass (silica) balloons, Nippon Sheet Glass Kaloon, Sumitomo 3M Cellstar Z-28, EMERSON & CUMING made by MICRO BALLON, PITTSBURGE CORNING made by CELAMIC GLASSMMODULES, 3M made by GLAST BUBBLES, Asahi Glass Q-CEL, Taiheiyo Cement made by E-SPHERE, P FILLITE U. S. FILLITE manufactured by A, BW manufactured by Showa Denko as an alumina balloon, HOLLOW ZIRCONIUM SPHEES manufactured by ZIRCOA as a zirconia balloon, clecas sphere manufactured by Kureha Chemical Co., Ltd. and boss sphere manufactured by GENERAL TECHNOLOGIES as a carbon balloon are commercially available.
Examples of the organic balloon include a thermosetting resin balloon and a thermoplastic resin balloon. The thermosetting balloon includes a phenol balloon, an epoxy balloon, and a urea balloon. The thermoplastic balloon includes a saran balloon, a polystyrene balloon, Examples include polymethacrylate balloons, polyvinyl alcohol balloons, and styrene-acrylic balloons. A crosslinked thermoplastic balloon can also be used. The balloon here may be a balloon after foaming or may be foamed after blending a foaming agent-containing one.

Specific examples of these organic balloons include UCAR and PHENOLIC MICROBALLONONS made by Union Carbide as phenolic balloons, ECCOSPHERES made by EMERSON & CUMING as epoxy balloons, ECCOSPHERES VF-O made by EMERSON & CUMING, and DOWEMIC PHALS made by Saran Balloon by Saran Balloon. EXPANSEL made by Nippon Filament, Matsumoto Microsphere made by Matsumoto Yushi Seiyaku, DYLITE EXPANDABLE POLYSTYRENE made by ARCO POLYMERS as polystyrene balloon, EXPANDABLE POLYSTYRENE BEADS made by BASF WYANDOTE, SX863 (P) made by Nippon Synthetic Rubber is commercially available for the cross-linked styrene-acrylic acid balloon.

The balloons may be used alone or in combination of two or more. In order to improve the dispersibility and the workability of the compound by using fatty acid, fatty acid ester, rosin, rosin lignin, silane coupling agent, titanium coupling agent, aluminum coupling agent, polypropylene glycol, etc. on the surface of these balloons. The processed one can also be used. These balloons are designed to improve workability such as cutting properties before curing the composition, reduce costs by reducing weight without losing flexibility and elongation / strength after curing, and further design such as surface matting and sputtering. Used for imparting sex.

Although content of a balloon is not specifically limited, Preferably it is 0.1-50 parts with respect to 100 weight part of organic polymers which have a crosslinkable silyl group, More preferably, it can use in 0.1-30 parts. If this amount is less than 0.1 part, the effect of weight reduction is small, and if it is 50 parts or more, a decrease in tensile strength may be observed among the mechanical properties when this compound is cured. When the specific gravity of the balloon is 0.1 or more, 3 to 50 parts, more preferably 5 to 30 parts are preferred.

<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, the hardness when the composition of the present invention is cured can be increased, the hardness can be decreased, and the elongation can be increased. The said physical property modifier may be used independently and may be used together 2 or more types.

<Silanol-containing compound>
You may add a silanol containing compound to the curable composition of this invention as needed, such as changing the physical property of hardened | cured material. The silanol-containing compound refers to a compound having one silanol group in the molecule and / or a compound capable of producing a compound having one silanol group in the molecule by reacting with moisture. Only one of these may be used, or both compounds may be used simultaneously.

等のようなシラノール基を含有する環状ポリシロキサン化合物、

（式中、Ｒは炭素数１〜１０の炭化水素基を、ｎは１〜２０の整数を示す。）
等のようなシラノール基を含有する鎖状ポリシロキサン化合物、

（式中、Ｒは炭素数１〜１０の炭化水素基を、ｎは１〜２０の整数を示す。）
等のような主鎖が珪素、炭素からなるポリマー末端にシラノール基が結合した化合物、

（式中、Ｒは炭素数１〜１０の炭化水素基を、ｎは１〜２０の整数を示す。）
等のようなポリシラン主鎖末端にシラノール基が結合した化合物、

（式中、ｎは１〜２０の整数、ｍは１〜２０の整数を示す。）
等のような主鎖が珪素、炭素、酸素からなるポリマー末端にシラノール基が結合した化合物等が例示できる。中でも、入手が容易であり、効果の点から分子量の小さい（ＣＨ_３）_３ＳｉＯＨ等が好ましい。 The compound having one silanol group in the molecule which is one of the silanol-containing compounds is not particularly limited, and the compounds shown below,
(CH ₃ ) ₃ SiOH, (CH ₃ CH ₂ ) ₃ SiOH,
_{(CH 3 CH 2 CH 2)} 3 SiOH, (n-Bu) 3 SiOH,
(Sec-Bu) ₃ SiOH, (t-Bu) ₃ SiOH,
(T-Bu) Si (CH ₃ ) ₂ OH, (C ₅ H ₁₁ ) ₃ SiOH,
(C ₆ H ₁₃ ) ₃ SiOH, (C ₆ H ₅ ) ₃ SiOH,
(C ₆ H ₅ ) ₂ Si (CH ₃ ) OH,
(C ₆ H ₅ ) Si (CH ₃ ) ₂ OH,
_{(C 6 H 5) 2 Si} (C 2 H 5) OH,
C ₆ H ₅ Si (C ₂ H ₅ ) ₂ OH,
_{C 6 H 5 CH 2 Si (} C 2 H 5) 2 OH,
C ₁₀ H ₇ Si (CH ₃ ) ₂ OH
(However, in the above formula, C ₆ H ₅ represents a phenyl group, and C ₁₀ H ₇ represents a naphthyl group.)
A compound that can be represented by (R ″) ₃ SiOH, where R ″ is the same or different substituted or unsubstituted alkyl group or aryl group,

Cyclic polysiloxane compounds containing silanol groups, such as

(In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 20).
A chain polysiloxane compound containing a silanol group such as

(In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 20).
A compound in which the main chain is composed of silicon, carbon, and the like, and a silanol group is bonded to the polymer end,

(In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 20).
A compound in which a silanol group is bonded to the polysilane main chain terminal, such as

(In the formula, n represents an integer of 1 to 20, and m represents an integer of 1 to 20.)
Examples thereof include a compound in which a main chain is composed of silicon, carbon, oxygen and a silanol group bonded to a polymer terminal. Among these, (CH ₃ ) ₃ SiOH, which is easy to obtain and has a low molecular weight, is preferable from the viewpoint of effects.

The compound having one silanol group in the molecule reacts with a crosslinkable silyl group of an organic polymer having a crosslinkable silyl group or a siloxane bond formed by crosslinking, thereby reducing the number of crosslinking points, A composition that gives flexibility to the cured product and is excellent in low surface tack and dust resistance.

等が好適に使用できるが加水分解生成物の含有シラノール基の量からは（ＣＨ_３）_３ＳｉＮＨＳｉ（ＣＨ_３）_３が特に好ましい。 Moreover, the compound which can produce | generate the compound which has one silanol group in a molecule | numerator by reacting with a water | moisture content is although it does not specifically limit, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis ( Trimethylsilyl) trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilyl) N-methyltrifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N , N-diethylamino) trimethylsilane, hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (trimethylsilyl) imidazole, trimethylsilyl trifluoromethanesulfonate, trimethylsilylphenoxide Trimethylsilylated product of n-octanol, trimethylsilylated product of 2-ethylhexanol, tris (trimethylsilyl) ated product of glycerin, tris (trimethylsilylated) product of trimethylolpropane, tris (trimethylsilylated) product of pentaerythritol, tetra (trimethylsilylated) product of pentaerythritol , (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ , (CH ₃ ) ₃ SiNSi (CH ₃ ) ₂ , allyloxytrimethylsilane, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl) ) Trifluoroacetamide, N-methyl-N-trimethylsilyl trifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilyl) N-methyl Trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N, N-diethylamino) trimethylsilane, hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (trimethylsilyl) imidazole, Trimethylsilyl trifluoromethanesulfonate, trimethylsilylphenoxide, trimethylsilylated product of n-octanol, trimethylsilylated product of 2-ethylhexanol, tris (trimethylsilyl) ated product of glycerin, tris (trimethylsilyl) ated product of trimethylolpropane, tris (trimethylsilyl) of pentaerythritol product, tetra (trimethylsilyl) ated product of _{pentaerythritol, (CH 3) 3 SiNHSi (} CH 3) 3, (CH 3) 3 SiNSi (CH ) _2,

However, from the amount of silanol groups contained in the hydrolysis product, (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ is particularly preferable.

Although the compound which can produce | generate the compound which has one silanol group in a molecule | numerator by reacting with a water | moisture content is not specifically limited, In addition to the said compound, following General formula (38):
((R ⁴² ) ₃ SiO) _n R ⁴³ (38)
(Wherein R ⁴² is a hydrocarbon group having 1 to 10 carbon atoms, n is a positive number, and R ⁴³ is a group obtained by removing some or all active hydrogens from an active hydrogen-containing compound). Compounds are preferred. R ⁴² is a methyl group, an ethyl group, a vinyl group, t- butyl group, a phenyl group, and more preferably a methyl group. The (R ⁴² ) ₃ Si group is particularly preferably a trimethylsilyl group in which all three R ⁴² are methyl groups. N is preferably 1 to 5.

The active hydrogen-containing compound from which R ⁴³ is derived is not particularly limited.
Methanol, ethanol, n-butanol, i-butanol, t-butanol, n-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propanediol, tetra Alcohols such as methylene glycol, polytetramethylene glycol, glycerin, trimethylolpropane, pentaerythritol; phenols such as phenol, cresol, bisphenol A, hydroquinone; formic acid, acetic acid, propionic acid, lauric acid, palmitic acid, stearic acid, Behenic acid, acrylic acid, methacrylic acid, oleic acid, linoleic acid, linolenic acid, sorbic acid, oxalic acid, malonic acid, kocha Carboxylic acids such as acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid; ammonia; amines such as methylamine, dimethylamine, ethylamine, diethylamine, n-butylamine, imidazole; acetamide, benzamide Acid amides such as urea, ureas such as urea and N, N′-diphenylurea, and ketones such as acetone, acetylacetone and 2,4-heptadione.
The compound capable of generating a compound having one silanol group in the molecule by reacting with the water represented by the general formula (38) is, for example, trimethylsilyl chloride or dimethyl (t It can be obtained by reacting a compound having a group capable of reacting with active hydrogen such as a halogen group together with a (R ⁴² ) ₃ Si group, which is also called a silylating agent such as -butyl) chloride, but is not limited thereto. (However, R ⁵⁸ is the same as described above.)

Specific examples of the compound represented by the general formula (38) include allyloxytrimethylsilane, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N- Methyl-N-trimethylsilyltrifluoroacetamide, bistrimethylsilylurea, N- (t-butyldimethylsilyl) N-methyltrifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (N, N-diethylamino) trimethylsilane, Hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, N- (trimethylsilyl) imidazole, trimethylsilyltrifluoromethanesulfonate, trimethylsilylphenoxide, n-octanol trimethyl Silylation product, trimethylsilylation product of 2-ethylhexanol, tris (trimethylsilyl) ation product of glycerin, tris (trimethylsilyl) ation product of trimethylolpropane, tris (trimethylsilyl) ation product of pentaerythritol, tetra (trimethylsilyl) ation product of pentaerythritol, polypropylene glycol Examples include, but are not limited to, trimethylsilylated products, trimethylsilylated products of polyether polyols such as trimethylsilylated products of polypropylenetriol, trimethylsilylated products of polypropylenetetraol, and trimethylsilylated products of acrylic polyols. These may be used alone or in combination of two or more.

In addition, a compound that can be represented by the general formula (((R ⁴⁴ ) ₃ SiO) (R ⁴⁵ O) _s ) _t Z,
_{CH 3 O (CH 2 CH (} CH 3) O) 5 Si (CH 3) 3,
_{CH 2 = CHCH 2 (CH 2} CH (CH 3) O) 5 Si (CH 3) 3,
(CH ₃ ) ₃ SiO (CH ₂ CH (CH ₃ ) O) ₅ Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO (CH ₂ CH (CH ₃ ) O) ₇ Si (CH ₃ ) ₃
(In the formula, R ⁴⁴ is the same or different substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom, R ⁴⁵ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and s and t are positive integers. , S is 1 to 6, s × t is 5 or more, and Z is a 1 to 6-valent organic group). These may be used alone or in combination of two or more.

Among the compounds that can produce a compound having one silanol group in the molecule by reacting with moisture, the active hydrogen compound produced after hydrolysis is not adversely affecting storage stability, weather resistance, etc. Phenols, acid amides and alcohols are preferred, and phenols and alcohols whose active hydrogen compounds are hydroxyl groups are more preferred.

Among the above compounds, N, O-bis (trimethylsilyl) acetamide, N- (trimethylsilyl) acetamide, trimethylsilylphenoxide, trimethylsilylated product of n-octanol, trimethylsilylated product of 2-ethylhexanol, tris (trimethylsilyl) ated product of glycerin, A tris (trimethylsilyl) product of trimethylolpropane, a tris (trimethylsilyl) product of pentaerythritol, a tetra (trimethylsilyl) product of pentaerythritol and the like are preferable.

A compound that can generate a compound having one silanol group in the molecule by reacting with moisture has one silanol group in the molecule by reacting with moisture during storage, curing or after curing. A compound is produced. The compound having one silanol group in the molecule thus produced reacts with the crosslinkable silyl group of the vinyl polymer or the siloxane bond formed by crosslinking as described above, thereby reducing the number of crosslinking points. It is presumed that it is reduced and the cured product is given flexibility.

The structure of the silanol-containing compound can be selected depending on the type of Y and the number of a in the vinyl polymer of the present invention, and controls the curability and mechanical properties of the present invention according to the purpose and application. It is possible.

The silanol-containing compound may be used in combination with an air oxidation curable material described later, and by using it together, the modulus of the cured product is kept low, and the curability and dust adhesion of the alkyd paint coated on the surface are improved. Therefore, it is preferable.

The addition amount of the silanol-containing compound can be appropriately adjusted according to the expected physical properties of the cured product. The silanol-containing compound can be added in an amount of 0.1 to 50 parts by weight, preferably 0.3 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the organic polymer having a crosslinkable silyl group. . If the amount is less than 0.1 parts by weight, the effect of addition does not appear. If the amount exceeds 50 parts by weight, the crosslinking becomes insufficient, and the strength and gel fraction of the cured product are too low.

Moreover, the time which adds a silanol containing compound is not specifically limited, You may add at the time of manufacture of a polymer, and you may add at the time of preparation of a curable composition.

<Thixotropic agent (anti-sagging agent)>
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.

A thixotropic agent (anti-sagging agent) is also called a thixotropic agent. Thixotropy imparts fluidity when a strong force is applied, such as when extruding from a cartridge into a bead, applying with a spatula, or spraying with a spray, etc., until it hardens after application or construction. It imparts the property of not flowing down.

The thixotropy imparting agent (anti-sagging agent) is not particularly limited, and examples thereof include amide waxes, hydrogenated castor oil, hydrogenated castor oil derivatives, fatty acid derivatives, stears represented by Disparon (manufactured by Enomoto Kasei). Metal soap such as calcium phosphate, aluminum stearate, barium stearate, organic compounds such as 1,3,5-tris (trialkoxysilylalkyl) isocyanurate, calcium carbonate and fine powder surface-treated with fatty acids and resin acids Examples thereof include inorganic compounds such as silica and carbon black.

Fine powder silica means a natural or artificial inorganic filler mainly composed of silicon dioxide. Specific examples include kaolin, clay, activated clay, silica sand, silica stone, diatomaceous earth, anhydrous aluminum silicate, hydrous magnesium silicate, talc, perlite, white carbon, mica fine powder, bentonite, and organic bentonite. it can.

Among these, ultrafine anhydrous silica or organic bentonite produced by reacting a volatile compound containing silicon in the gas phase is preferable. At least ^{50 m} 2 / g, and more preferably has a specific surface area of 50 to 400 m ² / g. Either hydrophilic silica or hydrophobic silica can be used. Hydrophobic silica whose surface is hydrophobically treated with silazane, chlorosilane, alkoxysilane, or polysiloxane having only a methyl group as an organic substituent bonded to a silicon atom is preferable. .

Specific examples of the surface treatment agent include silazanes such as hexamethyldisilazane; halogenated silanes such as trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane; trimethylalkoxysilane and dimethyldialkoxysilane. Alkoxysilanes such as methyltrialkoxysilane (wherein alkoxy groups include methoxy, ethoxy, propoxy, butoxy, etc.); cyclic or linear polydimethylsiloxane, etc. Examples thereof include siloxanes, and these may be used alone or in combination of two or more. Among these, hydrophobic fine powder silica subjected to a surface treatment with siloxanes (dimethylsilicone oil) is preferable from the viewpoint of thixotropic effect.

Moreover, thixotropy is increased when a polyether compound such as diethylene glycol, triethylene glycol, or polyethylene glycol, a reaction product of a polyether compound and a functional silane, or a nonionic surfactant having an ethylene oxide chain is used in combination with fine powder silica. . These nonionic surfactants may be used alone or in combination of two or more.

Specific examples of the fine powder silica include, for example, trade names Aerosil R974, R972, R972V, R972CF, R805, R812, R812S, RY200, RX200, RY200S, # 130, # 200, # 300, R202, etc., manufactured by Nippon Aerosil. And trade name Nippon Sil SS series made by Nippon Silica, trade names Rheorosil MT-10, MT-30, QS-102, QS-103, made by Soda Tokuyama, trade names made by Cabot, Cabosil TS-720, MS-5, MS -7, commercial products such as Sven and Organite manufactured by Toyoshiro Yoko.

The organic bentonite is a powdery substance obtained by finely pulverizing montmorillonite ore, which is surface-treated with various organic substances. As the organic compound, an aliphatic primary amine, an aliphatic quaternary amine (all of which preferably have 20 or less carbon atoms) are used. Specific examples of the organic bentonite include, for example, trade names Orven D, New D Orven, manufactured by Shiraishi Kogyo, trade name Hard Sil, manufactured by Kaolin Tsuchiya, clay # 30 manufactured by Bergess Pigment, Southern Cray # 33, manufactured by National Lead, USA. “Bentone 34” (dimethyloctadecyl ammonium bentonite) and the like.

The thixotropic index means a ratio of apparent viscosity at a low rotation speed (for example, 0.5 to 12 rpm) and a high speed (for example, 2.5 to 60 rpm) in viscosity measurement using a rotational viscometer (however, The ratio of the high speed rotation speed to the low speed rotation speed is preferably at least 5 and more preferably in the range of 5-10.

These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more.

<Photo-curing substance>
You may add a photocurable substance to the curable composition of this invention as needed. The photo-curing substance is a substance in which the molecular structure undergoes a chemical change in a short time due to the action of light, resulting in a change in physical properties such as curing. By adding this photocurable substance, the tackiness (also referred to as residual tack) of the cured product surface when the curable composition is cured can be reduced. This photo-curing substance is a substance that can be cured by exposure to light, but a typical photo-curing substance should be allowed to stand at room temperature for one day, for example, in a room where the sun is exposed (near the window). It is a substance that can be cured by. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and the type thereof is not particularly limited. For example, unsaturated acrylic compounds, polycinnamic acid Examples thereof include vinyls or azide resins, epoxy compounds, vinyl ether compounds and the like.

Specific examples of unsaturated acrylic compounds include (meth) acrylic acid esters (oligoester acrylates) of low molecular weight alcohols such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, and neopentyl alcohol; bisphenol A (Meth) acrylic acid esters of alcohols obtained by modifying acids such as isocyanuric acid or the above-mentioned low molecular weight alcohols with ethylene oxide or propylene oxide; polyether polyols whose main chain is a polyether and having a hydroxyl group at the terminal; Polymer polyols obtained by radical polymerization of vinyl monomers in polyols that are ethers, polyester polyols with a main chain of polyester and a hydroxyl group at the terminal, and main chains of vinyl or (meth) acrylic (Meth) acrylic acid esters such as polyols with hydroxyl groups in the main chain; the main chain is a vinyl or (meth) acrylic polymer and a polyfunctional acrylate is copolymerized in the main chain (Meth) acrylic esters obtained by reacting epoxy resins such as bisphenol A type and novolac type with (meth) acrylic acid; polyol, polyisocyanate and hydroxyl group-containing (meta ) Urethane acrylate oligomers having a urethane bond and a (meth) acryl group in the molecular chain obtained by reacting acrylate or the like.

Polyvinyl cinnamate is a photosensitive resin having a cinnamoyl group as a photosensitive group, and includes many polyvinyl cinnamate derivatives other than those obtained by esterifying polyvinyl alcohol with cinnamic acid.

Azide resin is known as a photosensitive resin having an azide group as a photosensitive group. In general, in addition to a rubber photosensitive solution in which an azide compound is added as a photosensitive agent, “photosensitive resin” (published March 17, 1972). , Published by the Printing Society Press, page 93 to page 106 to page 117), these are detailed examples, and these can be used alone or in combination, and a sensitizer can be added if necessary.

Examples of the epoxy compound and vinyl ether compound include epoxy group-terminated or vinyl ether group-terminated polyisobutylene.

Among the above-mentioned photocurable materials, unsaturated acrylic compounds are preferable because they are easy to handle.

The photocurable substance is preferably added in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the organic polymer having a crosslinkable silyl group. If the amount is less than 0.01 parts by weight, the effect is small. If the amount exceeds 20 parts by weight, the physical properties may be adversely affected. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.

<Air oxidation curable substance>
If necessary, an air oxidation curable material may be added to the curable composition of the present invention. The air oxidation curable substance is a compound having an unsaturated group that can be crosslinked and cured by oxygen in the air. By adding this air oxidation curable substance, the tackiness (also referred to as residual tack) of the cured product surface when the curable composition is cured can be reduced. The air oxidative curable substance in the present invention is a substance that can be cured by contact with air, and more specifically, has a property of being cured by reacting with oxygen in the air. A typical air oxidative curable substance can be cured by, for example, standing in air indoors for 1 day.

Examples of air oxidative curable substances include drying oils such as tung oil and linseed oil; various alkyd resins obtained by modifying these drying oils; acrylic polymers modified with drying oil, epoxy resins, silicone resins, Urethane resin: 1,2-polybutadiene, 1,4-polybutadiene, C5 to C8 diene polymers and copolymers, and various modified products of these polymers and copolymers (maleinized modified products, boiled oil modified products) Etc.) is a specific example. Of these, paulownia oil, diene polymer liquid (liquid diene polymer) and modified products thereof are particularly preferred.

Specific examples of the liquid diene polymer include a liquid polymer obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene, and copolymerizable with these diene compounds. Polymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene having a main component with a diene compound, and various modified products thereof (maleinized modified products, boiled oils) Modified products, etc.). These may be used alone or in combination of two or more. Of these liquid diene compounds, liquid polybutadiene is preferred.

The air oxidation curable substance may be used alone or in combination of two or more. In addition, the effect may be enhanced if a catalyst that promotes the oxidative curing reaction or a metal dryer is used together with the air oxidative curable substance. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, and zirconium octylate, amine compounds, and the like.

The air oxidation curable substance may be used in combination with the above-described photocurable substance, and further, the above-mentioned silanol-containing compound may be used in combination. Combined use of these two components or combination of the three components further demonstrates its effect, especially when exposed to a long period of time, and in a severely contaminated area with a lot of dust and fine earth and sand. This is particularly preferable.

The air oxidation curable substance is preferably added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the organic polymer having a crosslinkable silyl group. If the amount is less than 0.01 parts by weight, the effect is small. If the amount exceeds 20 parts by weight, the physical properties may be adversely affected.

<Antioxidant>
You may add antioxidant to the curable composition of this invention as needed. Various types of antioxidants are known, and are described in, for example, “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242), issued by CMC Chemical, and the like. Although various things are mentioned, it is not necessarily limited to these. For example, phosphoethers such as thioethers such as MARK PEP-36 and MARK AO-23 (all manufactured by Asahi Denka Kogyo), Irgafos 38, Irgafos 168, Irgafos P-EPQ (all manufactured by Ciba Specialty Chemicals) An inhibitor etc. are mentioned. Of these, hindered phenol compounds as shown below are preferred.

Specific examples of the hindered phenol compound include the following. 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) (α methylbenzyl) phenol, 2,2′-methylenebis (4 ethyl-6-tert-butylphenol), 2,2'-methylenebis (4methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4 ' -Thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethylene glycol-bis- [3- (3-t- Butyl-5-methyl-4hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t- Butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl -2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N′-bis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) Benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) -benzotriazole, methyl-3- [3 -T-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (3,5- Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl) -4-piperidyl), 2,4-di -t- butyl-3,5-di -t- butyl-4-hydroxybenzoate, and the like.

In terms of trade names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above Manufactured by Ouchi Shinsei Chemical Industry), MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO-80, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (all manufactured by Asahi Denka Kogyo), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024, IRGANOX 1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all of these are manufactured by Ciba Specialty Chemicals), Sumizer GM, Sumilizer GA-80 (all of which are manufactured by Sumitomo Chemical) However, the present invention is not limited to these examples.

Antioxidants may be used in combination with the light stabilizers described later, and are particularly preferred because they can further exert their effects and improve heat resistance in particular. Tinuvin C353, Tinuvin B75 (both manufactured by Ciba Specialty Chemicals) and the like in which an antioxidant and a light stabilizer are mixed in advance may be used.

It is preferable that the usage-amount of antioxidant is the range of 0.1-10 weight part with respect to 100 weight part of organic polymers which have a crosslinkable silyl group. If the amount is less than 0.1 parts by weight, the effect of improving the weather resistance is small.

<Light resistance stabilizer>
You may add a light-resistant stabilizer to the curable composition of this invention as needed. Various types of light-resistant stabilizers are known, and are described in, for example, “Antioxidant Handbook” issued by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242), issued by CM Chemical Co., Ltd. There are various types. Although not limited to these, among light-resistant stabilizers, an ultraviolet absorber and a hindered amine light stabilizer compound are preferable. Specifically, benzotriazole compounds such as Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, Tinuvin 213 (all of which are manufactured by Ciba Specialty Chemicals), Tinuvin 1577, etc. Examples thereof include triazine-based compounds, benzophenone-based compounds such as CHIMASSORB 81, and benzoate-based compounds such as Tinuvin 120 (manufactured by Ciba Specialty Chemicals).

Hindered amine compounds are also preferred, and such compounds are described below.
Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate of succinate, poly [{6- (1,1,3,3-tetramethylbutyl) Amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (3aminopropyl) ethylenediamine- 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidinyl) ester and the like.

In terms of product names, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944LD, CHIMASSORB 119FL, Irgafos 168 (all of which are manufactured by Ciba Specialty Chemicals), MARK LA-52, MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68, MARK LA-82, MARK LA-87 (all manufactured by Asahi Denka Kogyo), Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Examples include, but are not limited to, sanol LS-1114, sanol LS-744, and sanol LS-440 (all of which are manufactured by Sankyo).

The light-resistant stabilizer may be used in combination with the above-mentioned antioxidant, and is particularly preferable because the effect is further exhibited by using it together, and the weather resistance may be improved. The combination is not particularly limited, but a combination of the above-mentioned hindered phenolic antioxidant and, for example, a benzotriazole-based ultraviolet absorber or a combination of the above-mentioned hindered phenolic antioxidant and a hindered amine light stabilizer compound is preferable. . Or the combination of the above-mentioned hindered phenolic antioxidant, for example, a benzotriazole type ultraviolet absorber and a hindered amine light stabilizer compound is preferable. Tinuvin C353, Tinuvin B75 (both manufactured by Ciba Specialty Chemicals) and the like in which a light stabilizer and an antioxidant are mixed in advance may be used.

The hindered amine light stabilizer may be used in combination with the above-mentioned photo-curing substance, and it is particularly preferable because the hindered amine light stabilizer further exerts its effect and particularly the weather resistance may be improved. The combination is not particularly limited, but in this case, a hindered amine light stabilizer containing a tertiary amine is preferable because the viscosity increase during storage is small and the storage stability is good.

The amount of the light stabilizer used is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the organic polymer having a crosslinkable silyl group. If the amount is less than 0.1 parts by weight, the effect of improving the weather resistance is small.

<Epoxy resin>
You may add an epoxy resin to the curable composition of this invention as needed. Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, novolac type epoxy resin, bisphenol A propylene oxide Adduct glycidyl ether type epoxy resin, hydrogenated bisphenol A type (hydrogenated bisphenol A type) epoxy resin, fluorinated epoxy resin, rubber-modified epoxy resin containing polybutadiene or NBR, glycidyl ether of tetrabromobisphenol A, etc. Flame retardant epoxy resin, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane series Xylene resin, urethane-modified epoxy resin having urethane bond, various alicyclic epoxy resins, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycerin Examples thereof include glycidyl ethers of polyhydric alcohols, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, etc., but are not limited thereto, and are generally used epoxies Resins can be used. These epoxy resins may be used alone or in combination of two or more.

Among these epoxy resins, those having at least two epoxy groups in one molecule are preferable from the viewpoint of high reactivity and easy formation of a three-dimensional network upon curing.

In order to obtain a transparent cured product when the mixture of the vinyl polymer of the present invention and the epoxy resin is cured, the epoxy resin is preferably compatible with the vinyl polymer. Hydrogenated bisphenol A type epoxy resins are easily compatible with various vinyl polymers, and easily obtain a transparent cured product.

A curable composition having a combination of good compatibility between the vinyl polymer and the epoxy resin tends to take a modulation structure when cured, and as a result, a transparent cured product is easily obtained. Furthermore, the mechanical properties may be remarkably improved.

For example, a combination of a vinyl polymer or vinyl copolymer whose main chain is more polar than butyl acrylate homopolymer and an epoxy resin having an aromatic ring, or a vinyl polymer or vinyl copolymer And a preferable combination such as a combination with an epoxy resin having no aromatic ring.

Although it does not specifically limit as an example of the epoxy resin which does not have an aromatic ring, An alicyclic epoxy resin is preferable and the epoxy resin in which a glycidyl group is not directly attached to an alicyclic ring is more preferable.

The vinyl polymer or vinyl copolymer whose main chain is higher in polarity than the butyl acrylate homopolymer is not limited to this, but is represented by the general formula (39) as a preferred example. , Polymers or copolymers.
_{- [CH 2 -CR (COOR '} )] m - (39)
(In the formula, R is hydrogen or a methyl group, and R ′ is the same or different and is an alkoxyalkyl group or an alkyl group having 1 to 3 carbon atoms.)

Specifically, a copolymer of ethyl acrylate / butyl acrylate / acrylic acid 2-methoxyethyl (molar ratio 40-50 / 20-30 / 30-20) and bisphenol A type epoxy resin or bisphenol F type epoxy resin Preferred combinations include, but are not limited to, combinations of hydrogenated bisphenol A type epoxy resins and the like, and combinations of butyl acrylate acrylate homopolymer and hydrogenated bisphenol A type epoxy resins and hexahydrophthalic acid diglycidyl ester. It is not a thing.

Addition amount of epoxy resin The addition amount in the case of adding an epoxy resin is 100/1 to 1 in terms of a weight ratio based on a mixing ratio of an organic polymer having at least one crosslinkable silyl group and an epoxy resin. Is preferably in the range of 100/5 to 5/100, more preferably in the range of 100/10 to 10/100, but the mixing ratio is not limited. It can be set according to each application and purpose. Due to its characteristics, this curable composition can be used as an elastic adhesive for bonding materials with different linear expansion coefficients or for members that are repeatedly displaced by a heat cycle. Taking advantage of its properties, it can be used as a coating agent in applications where the substrate can be seen. For example, in this elastic adhesive application, if the mixing ratio of epoxy resin is too large, the cured product becomes hard and the peel strength decreases, and if too small, the adhesive strength and water resistance decrease conversely. It is usually used in the range of about 10 to 150 parts by weight, preferably in the range of 20 to 100 parts by weight with respect to 100 parts by weight of the combined body.

Epoxy resin curing catalyst / curing agent Further, an epoxy resin curing agent may be included as required. A conventionally well-known thing can be widely used as a hardening | curing agent for epoxy resins. For example, aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, tetramethylguanidine, oleylamine; Diamine, isophorone diamine, norbornane diamine, piperidine, N, N′-dimethylpiperazine, N-aminoethylpiperazine, BASF Ramilon C-260, CIBA Araldit HY-964, Rohm and Haas Mensendiamine, , 2-diaminocyclohexane, diaminodicyclohexylmethane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocycline) (Hexyl) alicyclic amines such as methane, polycyclohexylpolyamine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU); m-xylylenediamine, m-phenylenediamine, 4, 4′- Aromatic amines such as diaminodiphenylmethane and 4,4′-diaminodiphenylsulfone; (CH ₃ ) ₂ N (CH ₂ ) _n N (CH ₃ ) ₂ (where n is an integer of 1 to 10) A linear tertiary amine represented by a linear diamine, (CH ₃ ) ₂ —N (CH ₂ ) _n —CH ₃ (where n is an integer of 0 to 10), N {(CH ₂ ) _n CH ₃ } ₃ alkyl tertiary monoamines (wherein n where integer of 1 to 10) represented by; benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) Fe Fatty aromatic amines such as benzene; 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (ATU), morpholine, N-methylmorpholine, Amines having an ether bond such as polyoxypropylene diamine, polyoxypropylene triamine, polyoxyethylene diamine; hydroxyl-containing amines such as diethanol amine and triethanol amine; triethylene diamine, pyridine, picoline, diazabicycloundecene, phthalic anhydride Acid anhydrides such as dimer, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, dodecyl succinic anhydride; Acid Polyamides obtained by reacting polyamines such as ethylenetriamine and triethylenetetramine, various polyamide resins, polyamideamines such as polyamides using polycarboxylic acids other than dimer acid; various imidazoles such as 2-ethyl-4-methylimidazole Dicyandiamide and derivatives thereof; polyoxypropylene-based amines such as polyoxypropylene-based diamines and polyoxypropylene-based triamines; phenols; epoxy-modified amines obtained by reacting the above-mentioned amines with epoxy compounds; Modified amines such as Mannich-modified amine obtained by reacting formalin and phenol, Michael addition-modified amine, ketimine obtained by condensation reaction of amine compound and carbonyl compound; 2,4,6-tris Compounds having an amino group and a hydrolyzable silyl group in one molecule such as 2-aminohexanoate of methylaminomethyl) phenol; N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane Etc. Specific examples of the ketimine compound include JP-A-7-242737.

These curing agents may be used alone or in combination of two or more. Although not particularly limited, among these curing agents for epoxy resins, 2,4,6-tris (dimethylaminomethyl) phenol and polyoxypropylene-based diamine are preferable from the viewpoint of curability and physical property balance.

Such a curing agent for epoxy resins is usually in the range of about 1 to 60 parts by weight, preferably 2 to 50 parts by weight with respect to 100 parts by weight of the organic polymer having a crosslinkable silyl group, although it depends on the amount of the epoxy resin. It is good to use in the range of about a part. If it is less than 1 part by weight, the epoxy resin is insufficiently cured and the adhesive strength is lowered. On the other hand, when the amount exceeds 60 parts by weight, bleeding to the interface occurs and the adhesiveness is lowered, which is not preferable.

In addition, it is preferable to add a compound having a group capable of reacting to both the crosslinkable silyl group of the organic polymer and the epoxy group of the epoxy resin to the curable resin composition because the strength is further improved. Specific examples thereof include N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Etc.

<Compatibilizer>
A compatibilizing agent can be added to the curable composition of the present invention. As a specific example of such an additive, for example, a copolymer of a plurality of vinyl monomers described in the specification of JP 2001-329025 A can be used.

<Compound having an α, β diol structure or an α, γ diol structure in the molecule>
A compound having an α, β diol structure or an α, γ diol structure may be added to the molecule contained in the curable composition of the present invention. As the compound having an α, β diol structure or an α, γ diol structure, generally well-known compounds can be used. In the present specification, the α, β diol structure represents a structure having two hydroxyl groups at adjacent carbon atoms, and the α, γ diol structure has two hydroxyl groups at adjacent carbon atoms. In addition, as represented by glycerin and the like, both α and β diol structures and α and γ diol structures, or polyols such as triols and tetraols containing either structure are also included.

The compound having an α, β diol structure or an α, γ diol structure in the molecule is not particularly limited. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3 Diols such as butanediol, 2,3-butanediol, pinacol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-hydroxymethyl-1,3-propanediol; glycerin, 1, Triols such as 2,6-hexanetriol, 1,1,1-tris (hydroxymethyl) propane, 2,2-bis (hydroxymethyl) butanol; pentaerythritol, D-sorbitol, D-mannitol, diglycerin, poly Tetravalent or higher polyols such as glycerin; glycerin monostearate, glyce Emissions monoisostearate, glycerin monooleate, glycerin monolaurate, glycerin monopalmitate, glycerin monocaprylate, glycerin monoacetate, glycerin monocarboxylic acid esters such as glycerin monobehenate;

Diglycerol monostearate, diglycerol monooleate, diglycerol monolaurate, tetraglycerol monostearate, tetraglycerol monooleate, tetraglycerol monolaurate, tetraglycerol distearate, tetraglycerol dioleate, tetraglycerol Polyglycerol carboxylates such as dilaurate, decaglycerol monostearate, decaglycerol monooleate, decaglycerol monolaurate, decaglycerol distearate, decaglycerol dioleate, decaglycerol dilaurate; pentaerythritol monostearate, Pentaerythritol such as pentaerythritol monoisostearate, pentaerythritol monooleate, pentaerythritol monolaurate Nokarubon esters; pentaerythritol distearate, pentaerythritol dioleate, pentaerythritol dicarboxylic acid esters such as pentaerythritol dilaurate;

Sorbitan monocarboxylic esters such as sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monobehenate; sorbitan distearate, sorbitan dioleate, sorbitan dilaurate, sorbitan dipalmitate Sorbitan dicarboxylic acid esters such as sorbitan dibehenate; glycerin monoalkyl ethers such as glycerin monostearyl ether, glycerin monooleyl ether, glycerin monolauryl ether, glycerin mono-2-ethylhexyl ether; Glycerol monooleyl ether, diglycerin monolauryl ether, tetraglycerin monostearyl ether, tetraglyceride Monooleyl ether, tetraglycerin monolauryl ether, tetraglycerin distearyl ether, tetraglycerin dioleyl ether, tetraglycerin dilauryl ether, decaglycerin monostearyl ether, decaglycerin monooleyl ether, decaglycerin monolauryl ether, decaglycerin di Polyglycerin alkyl ethers such as stearyl ether, decaglycerin dioleyl ether, decaglycerin dilauryl ether;

Pentaerythritol monoalkyl ethers such as pentaerythritol monostearyl ether, pentaerythritol monooleyl ether and pentaerythritol monolauryl ether; pentaerythritol dialkyl ethers such as pentaerythritol distearyl ether, pentaerythritol dioleyl ether and pentaerythritol dilauryl ether Sorbitan monoalkyl ethers such as sorbitan monostearyl ether, sorbitan monooleyl ether, sorbitan monolauryl ether; sorbitan dialkyl ethers such as sorbitan distearyl ether, sorbitan dioleyl ether, sorbitan dilauryl ether, and the like.

Many of the above compounds are readily available as many general-purpose compounds such as emulsifiers, surfactants, dispersants, antifoaming agents, antifogging agents, solubilizers, thickeners, and lubricants.

The above compounds may be used alone or in combination of two or more. The amount of the compound used is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the organic polymer having a crosslinkable silyl group. If the amount is less than 0.01 parts by weight, the intended effect cannot be obtained. If the amount exceeds 100 parts by weight, the mechanical strength of the cured product is insufficient, which is not preferable. More preferably, it is 0.1-20 weight part.

<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 flame retardants, curability modifiers, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents and the like. These various additives may be used alone or in combination of two or more. Specific examples of such additives include, for example, each specification of JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, and the like. It is described in.

The curable composition of the present invention can be used substantially without a solvent. Although a solvent may be used from the viewpoint of workability and the like, it is desirable not to use it because of environmental influences.

The curable composition of the present invention may be prepared as a one-component type in which all compounding components are preliminarily blended and stored and cured by moisture in the air after construction, and an organic polymer having a crosslinkable silyl group and its Separately used as a curing agent and a curing catalyst, and separately mixed with components such as a filler, a plasticizer, and water, and may be prepared as a two-component type or a multi-component type that is mixed before use. .

For example, although not limited, a main agent composition containing a vinyl polymer (I) having a crosslinkable silyl group and a polyether polymer (II) having a crosslinkable silyl group as an agent A is prepared. As the agent, a curing agent composition containing the curing catalyst component <(III), (IV) or (V)> of the present invention is prepared, and the agent A and the agent B are mixed immediately before construction. Can also be used.

Also, for example, a main polymer in which a vinyl polymer (I) having a crosslinkable silyl group, a polyether polymer (II) having a crosslinkable silyl group, a plasticizer, a filler, various stabilizers, and water are mixed. The composition is an A agent, and the curing catalyst component <(III), (IV) or (V)> of the present invention, a plasticizer, a filler, and a crosslinkable silyl group-containing silicon compound <silicate (VII) Or the epoxy silane coupling agent (VIII), etc.> dehydrated and mixed hardener composition obtained by sealing and storing as a B agent, and using the above A agent and B agent mixed immediately before construction Is also possible. In this case, the obtained cured product is uniformly cured to a deep portion, and a curable composition having a quick rise in hardness is obtained.

Further, for example, a vinyl polymer (I) having a crosslinkable silyl group, a polyether polymer (II) having a crosslinkable silyl group, a plasticizer, a filler, various stabilizers, and various crosslinkable silyl groups. A curing agent component <(III) of the present invention is prepared by sealing and preserving the main component composition obtained by dehydrating and mixing the contained silicon compound <silicate (VII), epoxysilane coupling agent (VIII), etc.> , (IV) or (V)>, a curing agent composition in which a plasticizer, a filler, and water are mixed is used as B agent, and the aforementioned A agent and B agent are mixed and used immediately before construction. Is also possible. Also in this case, the obtained cured product is uniformly cured to a deep portion, and a curable composition having a quick rise in hardness is obtained.

In the case of the one-component type, there is no need for mixing and kneading at the time of construction, and at the same time, there is no weighing error (incorrect mixing ratio), so that errors such as poor curing can be prevented.

When the two-component type is used, it becomes possible to add moisture to one of the compositions. Therefore, the cured product obtained as described above is uniformly cured to the deep portion, and a curable composition having a quick rise in hardness is obtained. . In the multilayer glass manufacturing process, line productivity is an important issue, and the characteristic of the strength that develops in a short time, which is a characteristic of this two-component curable composition, is very important for sealing glass applications. Useful.

<< Usage >>
The curable composition of the present invention includes, but is not limited to, an elastic sealant for buildings, a sealant for siding boards, a sealant for double glazing, a sealant for vehicles such as a sealant for vehicles, and a solar cell back surface. Electrical and electronic parts materials such as sealants, electrical insulation materials such as insulation coating materials for electric wires and cables, adhesives, adhesives, elastic adhesives, contact adhesives, tile adhesives, reactive hot melt adhesives, Coating materials, powder coating materials, coating materials, foams, sealing materials such as can lids, heat dissipation sheets, electrical and electronic potting agents, films, gaskets, marine deck coking, casting materials, various molding materials, artificial marble, and nets Sealing material for rust prevention and waterproofing of glass and laminated glass end face (cut part), anti-vibration / vibration / soundproof / isolation materials used in automobiles, ships, home appliances, etc. Dosha parts, electrical parts, various machine parts liquid sealing agent used in such, it is available in a variety of applications such as waterproofing agents.

Furthermore, the molded product showing rubber elasticity obtained from the curable composition of the present invention can be widely used mainly for gaskets and packings. For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. As engine parts, they can be used for hoses for cooling, fuel supply, exhaust control, etc., sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts. In the home appliance field, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts Packing, electrode packing, safety valve diaphragm, hose for sake can, waterproof packing, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube, Speaker gaskets, speaker edges, turntables for acoustic equipment such as diaphragm valves and air pipes Seat, belts, pulleys, and the like. In the construction field, it can be used for structural gaskets (zipper gaskets), air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like. In the sports field, it can be used for all-weather pavement materials, gymnasium floors, etc. as sports floors, shoe sole materials, midsole materials, etc. as sports shoes, golf balls etc. as ball for ball games. In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like. In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave-absorbing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, Can be used for draging hoses, oil skimmers, etc. In addition, it can be used for sheet rubber, mats, foam boards and the like.

Among them, the curable composition of the present invention is particularly useful as a sealing material and an adhesive, and particularly excellent in creep resistance, weather resistance adhesion, water resistance adhesion, low water absorption, and low gas permeability. It is useful as a sealing material for layer glass, particularly as a secondary sealing material for double-layer glass.

Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following synthesis examples, examples and comparative examples, “part” and “%” represent “part by weight” and “% by weight”, respectively.

In the following synthesis examples, “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, in the case of vinyl polymers of Synthesis Examples 1, 2, 3, 7, and 8, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko) was used as a GPC solvent. As a chloroform. In the case of the polyether polymer having a crosslinkable silyl group in Synthesis Examples 13 to 16, Tosoh HLC-8120GPC is used as a liquid feeding system, Tosoh TSK-GEL H type is used as a column, and THF is used as a solvent. Measured.

Synthesis examples of the vinyl polymer in the present invention are shown below.

(Synthesis Example 1)
Under a nitrogen atmosphere, CuBr (1.09 kg), acetonitrile (11.4 kg), n-butyl acrylate (26.0 kg) and diethyl 2,5-dibromoadipate (2.28 kg) were added to a 250 L reactor. The mixture was stirred at ˜80 ° C. for about 30 minutes. To this was added pentamethyldiethylenetriamine to initiate the reaction. 30 minutes after the start of the reaction, n-butyl acrylate (104 kg) was continuously added over 2 hours. During the reaction, pentamethyldiethylenetriamine was appropriately added so that the internal temperature became 70 ° C to 90 ° C. Four hours after the start of the reaction, volatile components were removed by heating and stirring at 80 ° C. under reduced pressure. Acetonitrile (45.7 kg), 1,7-octadiene (14.0 kg) and pentamethyldiethylenetriamine (439 g) were added thereto, and stirring was continued for 8 hours. The mixture was heated and stirred at 80 ° C. under reduced pressure to remove volatile components.

Toluene is added to this concentrate to dissolve the polymer, diatomaceous earth is added as a filter aid, aluminum silicate and hydrotalcite are added as adsorbents, and an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%) is set to an internal temperature of 100. The mixture was heated and stirred at ° C. The solid content in the mixed solution was removed by filtration, and the filtrate was heated and stirred at an internal temperature of 100 ° C. under reduced pressure to remove volatile components.

Furthermore, aluminum silicate, hydrotalcite, and a heat deterioration inhibitor were added as adsorbents to this concentrate, and the mixture was heated and stirred under reduced pressure (average temperature of about 175 ° C., reduced pressure of 10 Torr or less).

Further, aluminum silicate and hydrotalcite were added as adsorbents, an antioxidant was added, and the mixture was heated and stirred at an internal temperature of 150 ° C. in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%).

Toluene was added to this concentrate to dissolve the polymer, and then the solid content in the mixed solution was removed by filtration. The filtrate was heated and stirred under reduced pressure to remove volatile matter, and the polymer having an alkenyl group < P1> was obtained.

Polymer <P1> having this alkenyl group, dimethoxymethylsilane (2.0 molar equivalent to alkenyl group), methyl orthoformate (1.0 molar equivalent to alkenyl group), platinum catalyst [bis (1, (3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst in xylene solution: hereinafter referred to as platinum catalyst] (as platinum, 10 mg with respect to 1 kg of polymer) and mixed at 100 ° C. in a nitrogen atmosphere. And stirred with heating. After confirming disappearance of the alkenyl group, the reaction mixture was concentrated to obtain a poly (acrylic acid-n-butyl) polymer [I-1] having a dimethoxysilyl group at the terminal. The number average molecular weight of the obtained polymer [I-1] was about 27,000, 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.

(Synthesis Example 2)
In a nitrogen atmosphere, a 250 L reactor was charged with CuBr (1.03 kg), acetonitrile (11.6 kg), n-butyl acrylate (16.3 kg), ethyl acrylate (4.76 kg), stearyl acrylate (4.94 kg). ) And diethyl 2,5-dibromoadipate (2.13 kg) were added, and the mixture was stirred at 70 to 80 ° C. for about 30 minutes. To this was added pentamethyldiethylenetriamine to initiate the reaction. Over 30 minutes after the start of the reaction, a mixture of n-butyl acrylate (65.2 kg), ethyl acrylate (19.0 kg) and stearyl acrylate (19.8 kg) was continuously added over 2 hours. During the reaction, pentamethyldiethylenetriamine was appropriately added so that the internal temperature became 70 ° C to 90 ° C. The total amount of pentamethyldiethylenetriamine used so far was 208 g. Four hours after the start of the reaction, volatile components were removed by heating and stirring at 80 ° C. under reduced pressure. Acetonitrile (46.8 kg), 1,7-octadiene (26.0 kg) and pentamethyldiethylenetriamine (416 g) were added thereto, and stirring was continued for 8 hours. The mixture was heated and stirred at 80 ° C. under reduced pressure to remove volatile components.

Toluene was added to this concentrate to dissolve the polymer, diatomaceous earth was added as a filter aid, and the mixture was heated and stirred at an internal temperature of 100 ° C. in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%). The solid content in the mixed solution was removed by filtration, and the filtrate was heated and stirred at an internal temperature of 100 ° C. under reduced pressure to remove volatile components. Further, aluminum silicate, hydrotalcite and a heat deterioration inhibitor were added as adsorbents to the concentrate, and the mixture was heated and stirred under reduced pressure (average temperature of about 175 ° C., degree of vacuum of 10 Torr or less). Furthermore, aluminum silicate and hydrotalcite were added as adsorbents, an antioxidant was added, and the mixture was heated and stirred at an internal temperature of 150 ° C. in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%).

Toluene is added to the concentrate to dissolve the polymer, and then the solid content in the mixed solution is removed by filtration. The filtrate is heated and stirred under reduced pressure to remove volatile matter, and a polymer having an alkenyl group. <P2> was obtained.

Polymer <P2> having this alkenyl group, dimethoxymethylsilane (3.0 molar equivalent to alkenyl group), methyl orthoformate (1.0 molar equivalent to alkenyl group), platinum catalyst [bis (1, (3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst in xylene solution: hereinafter referred to as platinum catalyst] (as platinum, 10 mg with respect to 1 kg of polymer) and mixed at 100 ° C. in a nitrogen atmosphere. And stirred with heating. After confirming disappearance of the alkenyl group, the reaction mixture was concentrated to obtain a poly (n-butyl acrylate / ethyl acrylate / stearyl acrylate) copolymer [I-2] having a dimethoxysilyl group at the terminal. It was. The number average molecular weight of the obtained polymer [I-2] 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 1.7.

(Synthesis Example 3)
Polymer <P1> having an alkenyl group obtained in Synthesis Example 1, triethoxysilane (3.0 molar equivalents relative to alkenyl group), methyl orthoformate (1.0 molar equivalents relative to alkenyl group), platinum catalyst [Xylene solution of bis (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst: hereinafter referred to as platinum catalyst] (10 mg as platinum relative to 1 kg of polymer) was mixed, and nitrogen was mixed. The mixture was heated and stirred at 115 ° C. in an atmosphere. After confirming disappearance of the alkenyl group, the reaction mixture was concentrated to obtain a poly (acrylic acid-n-butyl) polymer [I-3] having a triethoxysilyl group at the terminal. The number average molecular weight of the obtained polymer [I-3] was about 27,000, 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.

(Synthesis Example 4)
A solution prepared by dissolving 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator was added dropwise to an isobutanol solution of the following monomer mixture heated to 105 ° C. over 5 hours. Post-polymerization "was performed to obtain a (meth) acrylic acid ester polymer <P4>.
Methyl methacrylate: 68.4 parts by weight, 2-ethylhexyl acrylate: 21.6 parts by weight, γ-methacryloyloxypropylmethyldimethoxysilane: 2.5 parts by weight, γ-methacryloyloxypropyltrimethoxysilane: 7.5 parts by weight, n-dodecyl mercaptan: 7.0 parts by weight, 2,2′-azobis (2-methylbutyronitrile): 2.5 parts by weight.

Next, after the polymer (I-1) obtained in Synthesis Example 1 and the above polymer <P4> are mixed at a solid content weight ratio of 5/2, the solvent is distilled off to have a crosslinkable silyl group. A vinyl polymer (I-4) was obtained.

(Synthesis Example 5)
A solution prepared by dissolving 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator was added dropwise to an isobutanol solution of the following monomer mixture heated to 105 ° C. over 5 hours. Post-polymerization "was performed to obtain a (meth) acrylic acid ester polymer <P5>.
Methyl methacrylate: 46.5 parts by weight, n-butyl acrylate: 28.6 parts by weight, stearyl methacrylate: 20.1 parts by weight, γ-methacryloyloxypropyltrimethoxysilane: 4.8 parts by weight, 2,2′-azobis (2-methylbutyronitrile): 3.2 parts by weight.

Next, after the polymer (I-1) obtained in Synthesis Example 1 and the above polymer <P5> are mixed at a solid content weight ratio of 10/3, the solvent is distilled off to have a crosslinkable silyl group. A vinyl polymer (I-5) was obtained.

(Synthesis Example 6)
After the polymer (I-2) obtained in Synthesis Example 2 and the polymer <P5> obtained in Synthesis Example 5 were mixed at a solid content weight ratio of 10/3, the solvent was distilled off to form a crosslinkable silyl group. A vinyl-based polymer (I-6) having the following was obtained.

(Comparative Synthesis Example 7)
Under a nitrogen atmosphere, CuBr (0.84 kg), acetonitrile (8.79 kg), n-butyl acrylate (20.0 kg) and diethyl 2,5-dibromoadipate (1.17 kg) were added to a 250 L reactor. The mixture was stirred at ˜80 ° C. for about 30 minutes. To this was added pentamethyldiethylenetriamine (150 g) to initiate the reaction. 30 minutes after the start of the reaction, n-butyl acrylate (80.0 kg) was continuously added over 2 hours. During the reaction, pentamethyldiethylenetriamine was appropriately added so that the internal temperature became 70 ° C to 90 ° C. Four hours after the start of the reaction, volatile components were removed by heating and stirring at 80 ° C. under reduced pressure. Acetonitrile (35.0 kg), 1,7-octadiene (21.0 kg) and pentamethyldiethylenetriamine (340 g) were added thereto, and stirring was continued for 8 hours. The mixture was heated and stirred at 80 ° C. under reduced pressure to remove volatile components.

Toluene is added to this concentrate to dissolve the polymer, diatomaceous earth is added as a filter aid, aluminum silicate and hydrotalcite are added as adsorbents, and an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%) is set to an internal temperature of 100. The mixture was heated and stirred at ° C. The solid content in the mixed solution was removed by filtration, and the filtrate was heated and stirred at an internal temperature of 100 ° C. under reduced pressure to remove volatile components.

Furthermore, aluminum silicate, hydrotalcite, and a heat deterioration inhibitor were added as adsorbents to this concentrate, and the mixture was heated and stirred under reduced pressure (average temperature of about 175 ° C., reduced pressure of 10 Torr or less).

Further, aluminum silicate and hydrotalcite were added as adsorbents, an antioxidant was added, and the mixture was heated and stirred at an internal temperature of 150 ° C. in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%).

Toluene was added to this concentrate to dissolve the polymer, and then the solid content in the mixed solution was removed by filtration. The filtrate was heated and stirred under reduced pressure to remove volatile matter, and the polymer having an alkenyl group < P7> was obtained.

Polymer <P7> having this alkenyl group, dimethoxymethylsilane (3.0 molar equivalent to alkenyl group), methyl orthoformate (1.0 molar equivalent to alkenyl group), platinum catalyst [bis (1, (3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst in xylene solution: hereinafter referred to as platinum catalyst] (as platinum, 10 mg with respect to 1 kg of polymer) and mixed at 100 ° C. in a nitrogen atmosphere. And stirred with heating. After confirming disappearance of the alkenyl group, the reaction mixture was concentrated to obtain a poly (acrylic acid-n-butyl) polymer [I-7] having a dimethoxysilyl group at the terminal. The number average molecular weight of the obtained polymer [I-7] was about 38000, 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.

(Synthesis Example 8)
Polymer <P2> having an alkenyl group obtained in Synthesis Example 1, triethoxysilane (3.5 molar equivalent to alkenyl group), methyl orthoformate (1.0 molar equivalent to alkenyl group), platinum catalyst [Xylene solution of bis (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst: hereinafter referred to as platinum catalyst] (10 mg as platinum relative to 1 kg of polymer) was mixed, and nitrogen was mixed. The mixture was heated and stirred at 115 ° C. in an atmosphere. After confirming disappearance of the alkenyl group, the reaction mixture was concentrated to obtain a poly (n-butyl acrylate / ethyl acrylate / stearyl acrylate) copolymer [I-8] having a triethoxysilyl group at the terminal. Obtained. The number average molecular weight of the obtained polymer [I-8] 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 1.7.

(Synthesis Example 9)
A solution prepared by dissolving 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator was added dropwise to an isobutanol solution of the following monomer mixture heated to 105 ° C. over 5 hours. Post-polymerization "was performed to obtain a (meth) acrylic acid ester polymer <P9>.
Methyl methacrylate: 14.5 parts by weight, n-butyl acrylate: 68.2 parts by weight, stearyl methacrylate: 14.9 parts by weight, γ-methacryloyloxypropyltrimethoxysilane: 2.4 parts by weight, 2,2′-azobis (2-methylbutyronitrile): 0.5 part by weight.

Next, after mixing the polymer (I-1) obtained in Synthesis Example 1 and the polymer <P9> at a solid content weight ratio of 10/3, the solvent is distilled off to have a crosslinkable silyl group. A vinyl polymer (I-9) was obtained.

(Synthesis Example 10)
A solution prepared by dissolving 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator was added dropwise to an isobutanol solution of the following monomer mixture heated to 105 ° C. over 5 hours. Post-polymerization "was performed to obtain a (meth) acrylic acid ester polymer <P10>.
Methyl methacrylate: 46.8 parts by weight, n-butyl acrylate: 28.6 parts by weight, stearyl methacrylate: 20.1 parts by weight, γ-methacryloyloxypropylmethyldimethoxysilane: 4.5 parts by weight, 2,2′-azobis (2-methylbutyronitrile): 2.7 parts by weight.

Next, after the polymer (I-1) obtained in Synthesis Example 1 and the above polymer <P10> are mixed at a solid content weight ratio of 10/3, the solvent is distilled off to have a crosslinkable silyl group. A vinyl polymer (I-10) was obtained.

(Synthesis Example 11)
A solution prepared by dissolving 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator was added dropwise to an isobutanol solution of the following monomer mixture heated to 105 ° C. over 5 hours. Post-polymerization "was performed to obtain a (meth) acrylic acid ester polymer <P11>.
Methyl methacrylate: 44.1 parts by weight, n-butyl acrylate: 25.8 parts by weight, stearyl methacrylate: 20.1 parts by weight, γ-methacryloyloxypropylmethyldimethoxysilane: 10 parts by weight, 2,2′-azobis (2 -Methylbutyronitrile): 3.2 parts by weight.

Next, after the polymer (I-1) obtained in Synthesis Example 1 and the above polymer <P11> are mixed at a solid content weight ratio of 5/1, the solvent is distilled off to have a crosslinkable silyl group. A vinyl polymer (I-11) was obtained.

(Synthesis Example 12)
After the polymer (I-1) obtained in Synthesis Example 1 and the polymer <P5> obtained in Synthesis Example 5 were mixed at a solid content weight ratio of 5/1, the solvent was distilled off to form a crosslinkable silyl group. A vinyl polymer (I-12) was obtained.

A synthesis example of the polyether polymer in the present invention is shown below.

(Synthesis Example 13)
Polymerization of propylene oxide using polyoxypropylene triol having a molecular weight of about 3,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of about 26,000 (using Tosoh's HLC-8120GPC as the liquid feeding system) The column used a Tosoh TSK-GEL H type, and the solvent was a polystyrene oxide (polystyrene equivalent molecular weight measured using THF). Subsequently, a methanol solution of 1.2 times equivalent of NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and further allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polypropylene oxide, water was removed by centrifugation, and the resulting hexane solution was further added. 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by vacuum devolatilization. Thus, a trifunctional polypropylene oxide having a number average molecular weight of about 26,000 and having an allyl group at the end was obtained (this is referred to as polymer <P13>).

With respect to 100 parts by weight of the polymer <P13>, 150 ppm of a platinum content of a platinum vinylsiloxane complex is used as a catalyst and reacted with 1.4 parts by weight of methyldimethoxysilane for 5 hours at 90 ° C. A polyoxypropylene polymer (II-1) was obtained. In addition, using ¹ H-NMR (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL Ltd.), the terminal relative to the peak integrated value of the methyl group (around 1.2 ppm) of the polypropylene oxide main chain of the polymer P The relative value (assumed to be S) of the peak integral value of the allyl group —CH ₂ —CH═CH ₂ (near 5.1 ppm) and the polypropylene oxide main chain of the silyl-terminated polypropylene oxide (II-1) after the hydrosilylation reaction Methylene group —CH ₂ —CH ₂ —CH ₂ —Si (CH ₃ ) (OCH ₃ ) ₂ (around 0.6 ppm) bonded to the silicon atom of the terminal silyl group with respect to the peak integral value of the methyl group (around 1.2 ppm) ) Peak relative value (referred to as S ′) and the number of silyl groups (introduction rate) (S ′ / S) is examined. It was 2.3 on average per molecule.

(Synthesis Example 14)
Polymerization of propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using a 1/1 (weight ratio) mixture of a polyoxypropylene diol having a molecular weight of about 2,000 and a polyoxypropylene triol having a molecular weight of about 3,000 as an initiator. Using the obtained hydroxyl-terminated polypropylene oxide having a number average molecular weight of about 19,000, allyl-terminated polypropylene oxide was obtained in the same procedure as in Synthesis Example 13. This allyl-terminated polypropylene oxide is reacted with 1.35 parts by weight of methyldimethoxysilane in the same procedure as in Synthesis Example 13, and a polyoxypropylene polymer having an average of 1.7 methyldimethoxysilyl groups at the ends ( II-2) was obtained.

(Synthesis Example 15)
With respect to 100 parts by weight of the polymer <P13> obtained in Synthesis Example 13, the reaction was performed with 1.6 parts by weight of trimethoxysilane at 90 ° C. for 5 hours using 150 ppm of an isopropanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst. Thus, a polyoxypropylene polymer (II-3) having an average of 2.3 trimethoxysilyl groups at the terminal was obtained.

(Comparative Synthesis Example 16)
Synthesis example using hydroxyl-terminated polypropylene oxide having a number average molecular weight of about 30,000 obtained by polymerizing propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using polyoxypropylene glycol having a molecular weight of about 2,000 as an initiator Allyl-terminated polypropylene oxide was obtained by the same procedure as in No. 13. This allyl-terminated polypropylene oxide is reacted with 0.9 parts by weight of methyldimethoxysilane in the same procedure as in Synthesis Example 13, and a polyoxypropylene polymer having an average of 1.5 methyldimethoxysilyl groups at the ends ( II-4) was obtained.

(Tensile test of cured product obtained by curing vinyl polymer alone)
For 100 parts by weight of the vinyl polymer (I-1 to I-12) having a crosslinkable silyl group obtained in Synthesis Examples 1 to 12, 2 parts by weight of tin octylate and 0.5 parts by weight of laurylamine were added. In addition, after mixing, the centrifugally degassed mixture was poured into a polyethylene mold so that no air bubbles would enter, and cured at 50 ° C. for 20 hours, from a 3 mm thick cured sheet, in accordance with JIS K6251. The No. 3 dumbbell was punched out and a tensile test (tensile speed: 200 mm / min) was performed at 23 ° C. and 50% RH to examine the stress at 50% elongation. The results are shown below. (Stress of polymer alone at 50% elongation)
I-1: 0.13 MPa
I-2: 0.11 MPa
I-3: 0.11 MPa
I-4: 0.13 MPa
I-5: 0.15 MPa
I-6: 0.13 MPa
I-7: 0.08 MPa
I-8: 0.11 MPa
I-9: 0.11 MPa
I-10: 0.14 MPa
I-11: 0.19 MPa
I-12: 0.14 MPa

(Tensile test of a cured product obtained by curing a polyether polymer alone)
With respect to 100 parts by weight of the polyether polymer (II-1 to II-4) having a crosslinkable silyl group obtained in Synthesis Examples 13 to 16, 1.5 parts of tin octylate and 0.25 weight of laurylamine Then, 0.6 parts by weight of pure water was added and mixed well, and then the centrifugally defoamed mixture was carefully poured into a polyethylene mold so that no air bubbles would enter, and then at 23 ° C. for 1 hour and further at 70 ° C. for 20 hours. No. 3 dumbbell was punched out from a cured sheet with a thickness of 3 mm obtained by time curing according to JISK6251 and a tensile test (tensile speed 200 mm / min) was performed at 23 ° C. and 50% RH. I investigated. The results are shown below. (Stress of polymer alone at 50% elongation)
II-1: 0.36 MPa
II-2: 0.26 MPa
II-3: 0.37 MPa
II-4: 0.19 MPa

(Examples 1-82 and Examples 116-130, Comparative Examples 1-9)
According to the formulations shown in Tables 1 to 5 and Table 8, an organic polymer having a crosslinkable silyl group, a filler, a plasticizer, a thixotropy imparting agent, various stabilizers, a dehydrating agent, an adhesion imparting agent and a curing catalyst, After weighing and kneading in a substantially dehydrated condition using a mixer, the mixture was sealed in a moisture-proof container (aluminum cartridge) to obtain a one-component curable composition. The one-component compositions shown in Tables 1 to 4 and Table 6 were extruded from each cartridge at the time of use, and evaluated below.

(Examples 83 to 115, Comparative Example 10)
In accordance with the formulations shown in Tables 6 and 7, organic polymers having a crosslinkable silyl group, fillers, plasticizers, thixotropic agents, various stabilizers, water, etc. are weighed and mixed without dehydration. The main composition was kneaded well with this paint roll. However, in Examples 92 to 103, a dehydrating agent, an adhesion-imparting agent, a curing catalyst, and the like were further added, and after kneading in a substantially water-free state under a dehydrating condition using a mixer, moisture resistance Was sealed in a container (aluminum cartridge) to obtain a dehydrated main agent composition.

On the other hand, with respect to the curing agent composition, in accordance with the formulations shown in Tables 6 and 7, the filler, plasticizer, silicate, adhesion-imparting agent, curing catalyst, and the like are substantially moisture-dehydrated using a mixer. After kneading in the absence of water, it was sealed in a moisture-proof container (aluminum pack) to obtain a dehydrated curing agent composition. However, in Examples 92 to 103, water was further added and kneaded without dehydration to obtain a curing agent composition containing water.

Regarding the composition of Table 5, since it is a two-component type, the main agent and the curing agent were uniformly mixed immediately before use, and the evaluation described later was performed.

In addition, the various compounding agents other than the vinyl polymer (I) having a crosslinkable silyl group and the polyether polymer (II) having a crosslinkable silyl group were as shown below.

<Filler>
Ultra-Pflex (Specialty Minerals, colloidal calcium carbonate)
Shiraka Hana CCR (manufactured by Shiraishi Kogyo, colloidal calcium carbonate)
Winnofil SPM (manufactured by Solvay, colloidal calcium carbonate)
Q3T (manufactured by Hubercarb, surface-treated heavy calcium carbonate)
Whiteon SB (Shiraishi calcium, surface untreated heavy calcium carbonate)
Pulplowite 3 (Omya, surface untreated heavy calcium carbonate)
Omycarb 3 (Omya, surface untreated heavy calcium carbonate)
MS (Nihon Talc, Talc)
Ti-Pure R912 (manufactured by DuPont, TiO ₂ )
Asahi # 70 (Asahi Carbon, furnace type carbon black)
Printex 30 (Evonik, carbon black)
Shiraka Hana CCR-B (Shiraishi Kogyo Co., Ltd., Colloidal Calcium Carbonate)
Shiraka Hana CCR-S (manufactured by Shiraishi Kogyo, colloidal calcium carbonate)
Shiraka Hana TDD (manufactured by Shiraishi Kogyo, colloidal calcium carbonate)
Viscolite OS (manufactured by Shiroishi Kogyo, colloidal calcium carbonate)
Calfine 200M (Maruo calcium, colloidal calcium carbonate)
Sealets 200 (Maruo calcium, colloidal calcium carbonate)
Ryton A (Shiraishi calcium, surface-treated heavy calcium carbonate)
Softon 3200 (made of calcium Shiraishi, untreated heavy calcium carbonate)
PO320B15 (Shiraishi calcium, surface-treated heavy calcium carbonate)

<Plasticizer>
Sunsizer DIDP (Nippon Nippon Chemical Co., Ltd., diisodecyl phthalate)
ARUFUON UP-1020 (manufactured by Toagosei, non-functional acrylic polymer)
Actol P-23 (Mitsui Chemicals Polyurethane, Polyoxypropylenediol)
Mesamol (from Bayer, alkyl sulfonic acid phenyl ester)
DBP (Showa ether, dibutyl phthalate)
BBP (Daihachi Chemical, butyl benzyl phthalate)
PN-6120 (Adeka, benzoate)
DMA (Daihachi Chemical, Dimethyl Adipate)
NRS-602 (Adeka, adipic acid ester)

<Thixotropic agent>
Dispalon 6500 (manufactured by Enomoto Kasei, amide wax thixotropic agent)
Crayvallac SL (manufactured by Cray Valley, an amide wax thixotropic agent)
Disparon 305 (manufactured by Enomoto Kasei, hydrogenated castor oil-based thixotropic agent)

<Light stabilizer>
Tinuvin 770 (Ciba Specialty Chemicals)
ADK STAB LA-63P (Adeka)

<Ultraviolet absorber>
Tinuvin 326 (Ciba Specialty Chemicals)
Tinuvin 328 (Ciba Specialty Chemicals)

<Antioxidant>
Irganox 245 (Ciba Specialty Chemicals)

<Air oxidation curable substance>
Tung oil (from China)

<Physical property modifier>
Excel O-95R (Kao, oleyl monoglyceride), trimethylphenoxysilane

<Dehydrating agent>
A-171 (Momentive Performance Materials, vinyltrimethoxysilane)

<Silicate>
Methyl silicate 51 (manufactured by Colcoat)
Ethyl silicate 40 (manufactured by Colcoat)

<Adhesive agent>
A-1120 (Momentive Performance Materials, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane)
A-1170 (Momentive Performance Materials, bis (3-trimethoxysilylpropyl) amine)
SIB1834.1 (Gerest, bis (3-trimethoxysilylpropyl) ethylenediamine)
Y-11597 (Momentive Performance Materials, 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate)
AY 43-083 (Toray Dow Corning, 1,6-bis (trimethoxysilyl) hexane)
A-1289 (Momentive Performance Materials, bis (3-triethoxysilylpropyl) polysulfide)
A-187 (Momentive Performance Materials, γ-glycidoxypropyltrimethoxysilane)
KBM-303 (Shin-Etsu Chemical Co., Ltd., β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane)
Epicoat 828 (Japan epoxy resin, bisphenol A type epoxy resin)

<Curing catalyst>
Neostan U-50 (Nitto Kasei, tin neodecanoate (divalent))
Versatic 10 (Japan epoxy resin, neodecanoic acid)
Diethylaminopropylamine (Wako Pure Chemical Industries)
Tyzor PITA (manufactured by DuPont, titanium diisopropoxide bis (ethyl acetoacetate))
Neostan U-220H (Nitto Kasei, dibutyltin bisacetylacetonate)

(Weather resistance)
Each composition in Table 1 was placed on a glass adherend to a thickness of 3 mm to prepare a sample. The prepared samples were cured at 23 ° C./50% RH × 7 days, then subjected to a weather resistance test, and an adhesion evaluation was performed by a 90-degree hand peel test. In the weather resistance test, a sample was placed in Sunshine Super Long Life Weather Meter WEL-SUN-HC manufactured by Suga Test Instruments Co., Ltd. using sunshine carbon as a light source and a black panel temperature set at 63 ° C., and the weather resistance was 1000 hours. Exposure was in a sex tester (SWOM). In the table, CF indicates cohesive failure, TCF indicates thin layer failure, and AF indicates interface failure. The results are shown in Table 1.

(Curability of curable composition)
Each composition in Tables 2 to 7 was filled into a mold having a thickness of about 5 mm using a spatula, and the surface was adjusted to a flat shape. This time was set as the curing start time, the surface was touched with a spatula, and the time when the composition did not adhere to the spatula was measured as the skinning time. The skinning time was measured under conditions of 23 ° C. and 50% RH. The shorter the skinning time, the better the curability. The results are shown in Tables 2-7.

(Creep measurement using dumbbell pieces)
Each composition shown in Tables 1 to 7 was cured at 23 ° C./50% RH × 3 days + 50 ° C. × 4 days to prepare a sheet having a thickness of about 3 mm. This sheet was punched into a No. 3 dumbbell shape and marked with a 20 mm gap. One end of the dumbbell piece was fixed in a constant temperature and humidity machine of 60 ° C./95% RH, and the dumbbell piece was suspended. A load of 0.18 MPa was applied to the lower end of the suspended dumbbell piece. The displacement difference between the marked lines was measured immediately after applying the load and 100 hours later (Table 1) or 200 hours later (Tables 2 to 7). The smaller the displacement difference, the better the creep resistance. The results are shown in Tables 1-7.

(Water resistant adhesiveness)
Each composition shown in Tables 2 to 5 was placed on a glass adherend to a thickness of 3 mm to prepare a sample. The prepared sample was cured at 23 ° C./50% RH × 7 days + 90 ° C. warm water immersion × 21 days, and then evaluated for adhesion by a 90-degree hand peel test. The results are shown in Tables 2-5. In the table, CF indicates cohesive failure, and AF indicates interface failure.

(Water absorption rate)
Each composition shown in Tables 2 to 7 was cured at 23 ° C./50% RH × 3 days + 50 ° C. × 4 days to prepare a sheet having a thickness of about 3 mm. The sheet having a thickness of 3 mm was cut into a size of about 20 mm × about 20 mm, and the weight before 60 ° C. hot water immersion and after 60 ° C. hot water immersion × 168 hours was measured. The water absorption was calculated by the following formula. The results are shown in Tables 2-7. Further, Table 8 shows the water absorption calculated based on the following formula from the result of weight measurement after 18 days of 60 ° C. warm water immersion × 18 days in the same manner as described above.
Water absorption (wt%) = (weight after 60 ° C. warm water immersion−weight before immersion) / (weight before immersion) × 100

(Tensile property of cured product)
Each composition shown in Tables 2 to 7 was cured at 23 ° C./50% RH × 3 days + 50 ° C. × 4 days to prepare a sheet having a thickness of about 3 mm. This sheet was punched out into a No. 3 dumbbell mold and subjected to a tensile test at a pulling speed of 200 mm / min. M50: 50% tensile modulus (MPa), Tb: strength at break (MPa), Eb: elongation at break (%) did. The results are shown in Tables 2-7.

(Measurement of hardness of cured product)
After uniformly mixing the main agent and the curing agent of Tables 6 and 7, the mixture was filled into a 12 mm × 12 mm × 50 mm mold and cured at 23 ° C./50% RH for 4 hours, and a JIS-A type hardness tester. Was used to measure the hardness value after 4 hours. The results are shown in Tables 6 and 7.

As described above, it can be seen that the curable composition of the present invention is excellent in creep resistance, weather resistance adhesion, water resistance adhesion, and low water absorption.

Claims (34)

100 parts by weight of a vinyl polymer (I) having an average of at least one crosslinkable silyl group and having a 50% elongation stress value of more than 0.10 MPa according to the following measurement method <1> Whereas
A polyether polymer (II) having an average of at least one crosslinkable silyl group, and a polyether polymer having a stress value at 50% elongation greater than 0.20 MPa according to the following measurement method <2> A curable composition containing 10 parts by weight or more and 100 parts by weight or less,
further,
(A) As the component (III), carboxylic acid metal salt (III-1) and / or carboxylic acid (III-2),
(B) Titanium catalyst (IV) or
(C) 0.01 to 0.5 parts by weight of organotin catalyst (V) with respect to 100 parts by weight of the total amount of vinyl polymer (I) and polyether polymer (II)
A curable composition comprising:
[50% elongation stress]
Measuring method <1>
To 100 parts by weight of the vinyl polymer, 2 parts by weight of tin octylate and 0.5 parts by weight of laurylamine are added and mixed, and then the centrifugally defoamed mixture is prevented from entering bubbles in the polyethylene mold. Pour No. 3 dumbbell from a 3 mm thick cured sheet obtained by casting and curing at 50 ° C. for 20 hours, and performing a tensile test at 23 ° C. and 50% RH (tensile speed 200 mm / min) Required 50% elongation stress measurement method <2>
To 100 parts by weight of the polyether polymer, 1.5 parts by weight of tin octylate, 0.25 parts by weight of laurylamine, and 0.6 parts by weight of pure water were added and mixed. Pour No. 3 dumbbells in accordance with JISK6251 from a cured sheet of 3 mm thickness obtained by pouring in a mold to prevent bubbles from entering, and curing at 23 ° C. for 1 hour and further at 70 ° C. for 20 hours, 50% elongation stress obtained by performing a tensile test (tensile speed: 200 mm / min) at 23 ° C. and 50% RH The curable composition according to claim 1, wherein the vinyl polymer (I) has a molecular weight distribution of less than 1.8. The crosslinkable silyl group of the vinyl polymer (I) has the general formula (1):
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are the same or different and each represents 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. (In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ′ may be the same or different. When two or more R ¹ or R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and two or more Y are present. , They may be the same or different, a represents 0, 1, 2, or 3. b represents 0, 1, or 2. m represents an integer of 0 to 19. A + mb ≧ 1).
The curable composition of Claim 1 or 2 represented by these. The main chain of the vinyl polymer (I) is mainly a monomer 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 3, wherein the curable composition is produced by a process. The curable composition according to claim 4, wherein the main chain of the vinyl polymer (I) is a (meth) acrylic polymer. The curable composition according to claim 5, wherein the (meth) acrylic polymer is an acrylic polymer. The curable composition according to claim 6, wherein the acrylic polymer is an acrylic ester polymer. The curable composition according to any one of claims 1 to 7, wherein the main chain of the vinyl polymer (I) is produced by a living radical polymerization method. The curable composition according to claim 8, wherein the living radical polymerization method is an atom transfer radical polymerization method. The curable composition according to any one of claims 1 to 9, wherein the crosslinkable silyl group of the vinyl polymer (I) is at a molecular chain terminal. The curable composition according to any one of claims 1 to 10, wherein the vinyl polymer (I) has an average of 1.1 or more and 4.0 or less crosslinkable silyl groups per molecule. The curable composition according to any one of claims 1 to 11, wherein the vinyl polymer (I) has a number average molecular weight of 10,000 to 40,000. The crosslinkable silyl group of the polyether polymer (II) has the general formula (1):
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(In the formula, R ¹ , R ² , Y, a, b and m are the same as those described above.)
The curable composition of any one of Claims 1-12 represented by these. The curable composition according to any one of claims 1 to 13, wherein the main chain of the polyether polymer (II) is essentially polypropylene oxide. The curable composition according to any one of claims 1 to 14, wherein the polyether polymer (II) is a polyether polymer having one or more branched chains. The curable composition according to any one of claims 1 to 15, wherein the polyether polymer (II) has an average of 1.1 or more and 4.0 or less crosslinkable silyl groups per molecule. The curable composition according to any one of claims 1 to 16, wherein the polyether polymer (II) has a number average molecular weight of 10,000 or more and 50,000 or less. In the curable composition (A) comprising (I), (II) and (III), the component (III) is only one of the carboxylic acid metal salt (III-1) and the carboxylic acid (III-2). The curable composition according to claim 1, comprising: In the curable composition (A) comprising (I), (II) and (III), the component (III) contains both the carboxylic acid metal salt (III-1) and the carboxylic acid (III-2). The curable composition according to any one of claims 1 to 17, wherein: In the curable composition (A) comprising (I), (II) and (III), the carboxylic acid metal salt (III-1) has a tertiary carbon atom adjacent to the carbonyl group constituting the carboxylic acid ion. Or it is a carboxylic acid metal salt which is quaternary carbon, The curable composition of any one of Claims 1-19 characterized by the above-mentioned. In the curable composition (A) comprising (I), (II) and (III), the carboxylic acid (III-2) has a tertiary carbon or quaternary carbon atom adjacent to the carbonyl group constituting the acid group. The curable composition according to claim 1, wherein the curable composition is a carboxylic acid that is carbon. The curable composition (A) comprising (I), (II) and (III) further contains an amine compound (VI), and the curing according to any one of claims 1 to 21 Sex composition. The curable composition according to any one of claims 1 to 22, wherein the curable composition (A) comprising (I), (II) and (III) further contains a silicate (VII). Composition. In the curable composition (B) comprising (I), (II) and (IV), the titanium catalyst (IV) is represented by the general formula (2):
Ti (OR ³ ) ₄ (2)
(In the formula, R ³ is an organic group, and four R ^{3 s} may be the same or different from each other.)
The curable composition according to any one of claims 1 to 17, which is a compound represented by the formula: The titanium catalyst (IV) has the general formula (3):

(In the formula, n R ^{4 s} are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 4-n R ^{5 s} are independently hydrogen atoms or carbon atoms. A substituted or unsubstituted hydrocarbon group of 1 to 8. 4-n A ¹ and 4-n A ² are each independently —R ⁶ or —OR ⁶ (where R ⁶ is (It is a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms.) N is 0, 1, 2, or 3)
And / or general formula (4):

(In the formula, R ⁵ , A ¹ and A ² are the same as described above. R ⁷ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.)
The curable composition according to claim 24, which is a compound represented by the formula: The curable composition (B) comprising (I), (II) and (IV) further contains an epoxy silane coupling agent (VIII). The curable composition of any one of Claims. 27. The curable composition (B) comprising (I), (II) and (IV) further contains silicate (VII), 27. The curable composition according to 1. In the curable composition (B) comprising (I), (II) and (IV), the vinyl polymer (I) and / or the polyether polymer (II) is represented by the general formula (5):
-SiY ₃ (5)
(In the formula, Y represents a hydroxyl group or a hydrolyzable group, and three Ys may be the same as or different from each other.)
The curable composition according to claim 1, which has a crosslinkable silyl group represented by the formula: In the curable composition (B) comprising (I), (II) and (IV), the polyether polymer (II) is represented by the general formula (5):
-SiY ₃ (5)
(In the formula, Y represents a hydroxyl group or a hydrolyzable group, and three Ys may be the same as or different from each other.)
The curable composition according to claim 1, which has a crosslinkable silyl group represented by the formula: In the curable composition (C) comprising (I), (II) and (V), the vinyl polymer (I) and / or the polyether polymer (II) is represented by the general formula (5):
-SiY ₃ (5)
(In the formula, Y represents a hydroxyl group or a hydrolyzable group, and three Ys may be the same as or different from each other.)
The curable composition according to claim 1, which has a crosslinkable silyl group represented by the formula: In the curable composition (C) comprising (I), (II) and (V), the polyether polymer (II) is represented by the general formula (5):
-SiY ₃ (5)
(In the formula, Y represents a hydroxyl group or a hydrolyzable group, and three Ys may be the same as or different from each other.)
The curable composition according to claim 1, which has a crosslinkable silyl group represented by the formula: One-component curing that is prepared as a one-component mold that is pre-blended and sealed and cured by moisture in the air after construction, in which all the blended components in the curable composition according to any one of claims 1 to 31 are preliminarily blended and stored. Sex composition. It is a curable composition of any one of Claims 1-31, Comprising:
(A) liquid containing vinyl polymer (I) and polyether polymer (II), and (A) carboxylic acid metal salt (III-1) and / or carboxylic acid (III-2),
(B) Titanium catalyst (IV) or
(C) A two-component or multi-component curable composition comprising at least two components of the (b) solution containing the organotin catalyst (V). The sealing material for multilayer glass formed using the curable composition in any one of Claims 1-33.