JP2001011190A - Hydrolyzable silicon-containing organic polymer, method for producing the same, and curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a hardenable polymer hardly reducing the hardenability of a hardenable composition and hardly causing the peeling from an adherend by which the hardenable polymer having a conventionally difficult high viscosity can be produced without depending on the viscosity of a raw material while freely regulating the viscosity of the product. SOLUTION: (A) A compound having two or more functional groups capable of carrying out an addition reaction with an unsaturated group, and (B) a compound having the functional group capable of carrying out the addition reaction with the unsaturated group and a hydrolyzable silicon group, are reacted with an unsaturated group-containing organic polymer containing an unsaturated group and a polyoxyalkylene-based polymer chain having <=1.7 ratio of a weight average molecular weight to a number average molecular weight to provide the objective hydrolyzable silicon group-containing organic polymer. The hardenable composition is obtained by adding a filler and a hardening accelerator to the hydrolyzable silicon group-containing organic polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a curable composition which can be cured in the presence of moisture, a hydrolyzable silicon-containing organic polymer as a raw material thereof, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a method of curing various polymers having a hydrolyzable silicon group at a terminal and using them in sealants, adhesives and the like is well known and is an industrially useful method. Among such polymers, particularly those having a main chain of polyoxyalkylene are liquid at room temperature, and the cured product retains flexibility even at a relatively low temperature, and is used as a sealant, an adhesive or the like. , With favorable characteristics. Also, by using these polymers in combination with other resins such as epoxy resins and acrylic resins, methods for improving strength, adhesion, and weather resistance are widely known, and are industrially useful methods. ing. As such a polyoxyalkylene polymer having a hydrolyzable silicon group, a polymer having a relatively high molecular weight is considered to have excellent properties such as curability, elongation, and strength. As a method for obtaining a polymer, a polyoxyalkylene polyol having a relatively easily available molecular weight is used as a raw material, and the molecular weight is increased by reacting a polyvalent halogen compound.
A method of introducing an unsaturated group into the terminal and then reacting the unsaturated group with a hydrolyzable group-containing silicon hydride compound (Japanese Unexamined Patent Publication No.
3-134095 and JP-A-50-156599) have been known.

As a method of increasing the molecular weight, a polyoxyalkylene polymer having a terminally unsaturated group having a relatively low molecular weight has N silicon hydride groups of 1 / N times or less the total unsaturated groups. JP-A-55-13768 discloses a method of increasing the molecular weight by reacting with a compound having the following formula, and further introducing a hydrolyzable silicon group at the molecular terminal. Saturated group-containing polyoxyalkylene polymer or molecular weight 320
A polyoxyalkylene polyol having a molecular weight of about 8000 obtained by reacting a polyoxyalkylene polyol of about 0 with a polyvalent halogen compound as a raw material,
Examples of the produced hydrolyzable silicon group-containing curable polymer having a molecular weight of about 5600 to 17000 are shown. A similar method is also disclosed in JP-A-55-13767. Similarly, as a method for increasing the molecular weight, a hydrolyzable silicon group-containing silicon hydride compound is reacted with a relatively low molecular weight terminal unsaturated group-containing polyoxyalkylene polymer, and then the silicon hydride group is added. A method of producing a curable polymer containing a hydrolyzable silicon group by increasing the molecular weight by reacting and crosslinking a plurality of silicon compounds to form a curable polymer is disclosed in JP-A-57-158226. Typically, a polyoxypropylene glycol having a molecular weight of 3200 is used as a raw material and a molecular weight of 6
A method for producing 800 to 9400 hydrolyzable silicon group-containing curable polymers is disclosed.

Further, JP-A-58-42619 also discloses JP-A-55-13767 and JP-A-57-15.
A polymer containing a hydrolyzable silicon group at a molecular terminal is disclosed by a production method similar to that of JP-A-8226. However, the polymer containing a hydrolyzable silicon group obtained by increasing the molecular weight by these conventionally known methods, as a raw material, a polyoxyalkylene polymer having a molecular weight of about 4000 or less as a raw material, Inevitably, the content of the low molecular weight hydrolyzable silicon group-containing curable polymer cannot be avoided, and the curability is poor due to the presence of such a low molecular weight curable polymer.

By the way, a polyoxyalkylene polyol having a high molecular weight and a narrow molecular weight distribution, which is obtained by polymerizing a cyclic ether in the presence of an initiator and using a double metal cyanide complex as a catalyst, has a hydrolyzable silicon group. A method for producing a polyoxyalkylene-based polymer is described in JP-A-3-72527, which has a lower viscosity than conventionally known polymers and contains no low-molecular-weight polymer. It has been found that it has excellent properties and good physical properties, and is used for curable compositions such as sealing materials. However, such a curable composition containing a polymer containing a hydrolyzable silicon group having a narrow molecular weight distribution has a very high elongation at break and a high strength, but the resin strength exceeds the adhesive strength. For this reason, there was a case where a tendency to cause separation at the interface with the adherend was observed.

Further, the viscosity of such a polymer containing a hydrolyzable silicon group having a high molecular weight and a narrow molecular weight distribution depends on the viscosity of a high molecular weight polyoxyalkylene polyol used as a raw material. In order to obtain a product having a product viscosity of, a raw material polyoxyalkylene polyol having a viscosity corresponding to the viscosity must be produced, and the viscosity is freely controlled during the production process to obtain a polymer having a desired viscosity. They lacked the freedom to manufacture freely. In particular, when it is intended to obtain a very high-viscosity hydrolyzable silicon group-containing organic polymer, such as exceeding 500 poise at room temperature, handling of a very high-viscosity polyoxyalkylene polyol as a raw material, and When the hydroxyl group was converted to an alkali metal alkoxide in the step of converting the terminal hydroxyl group into an unsaturated group, there was a serious problem in handling such as higher viscosity due to ionic crosslinking. In addition, when trying to remove salts, which are by-products when introducing unsaturated groups, by filtration, it is necessary to dilute using a very large amount of solvent in order to reduce the viscosity to a level that allows filtration. For example, it has been difficult to produce a polymer containing a hydrolyzable silicon group that exceeds 500 poise at room temperature substantially.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the curability of the curable composition obtained as compared with a conventionally known polymer containing a hydrolyzable silicon group having a narrow molecular weight distribution. To provide a hydrolyzable silicon-group-containing organic polymer which can be adjusted without any dependence on the viscosity of the raw material in production, without causing the peeling from the adherend. Another object of the present invention is to provide a high-viscosity curable polymer with difficulty. The present inventors have conducted intensive studies and found that the weight average molecular weight (hereinafter referred to as M
By using a polyoxyalkylene-based polymer such as a polyoxyalkylene polyol having a ratio of w) / number average molecular weight (hereinafter, referred to as Mn) (hereinafter, referred to as Mw / Mn) of 1.7 or less, the product viscosity can be reduced. Can be controlled freely,
It has also been found that a high-viscosity polymer, which has conventionally been very difficult, can be produced. Further, the curable composition containing the hydrolyzable silicon group-containing organic polymer of the present invention can be prepared by using a conventionally known polyoxyalkylene polymer having a terminal unsaturated group having a molecular weight of about 3,000 to 4,000 as a raw material. Compared with a curable composition containing a polymer produced by reacting with a silicon hydride compound to increase the molecular weight and further introducing a hydrolyzable silicon group, there is no decrease in curability,
Further, a curable composition containing a polyoxyalkylene polymer containing a hydrolyzable silicon group having a high molecular weight and a narrow molecular weight distribution, produced from a conventionally known polymer such as a high molecular weight polyoxyalkylene polyol. The present inventors have found that a composition that is less likely to be peeled off from the surface to be adhered to the adherend can be obtained as compared with the above, and have completed the present invention.

[0008]

That is, the present invention relates to an unsaturated group-containing organic polymer containing two or more unsaturated groups and having a polyoxyalkylene polymer chain having Mw / Mn of 1.7 or less. In contrast, (A) a compound containing two or more functional groups capable of addition reaction to an unsaturated group, and (B) a compound having a functional group capable of addition reaction to an unsaturated group and a compound having a hydrolyzable silicon group An object of the present invention is to provide a hydrolyzable silicon group-containing organic polymer obtained by reacting. Further, the present invention, in the hydrolyzable silicon group-containing organic polymer, a polyoxyalkylene polymer chain,
Provide a hydrolyzable silicon group-containing organic polymer that is a polymer chain derived from a polyoxyalkylene polymer obtained by ring-opening polymerization of a cyclic ether in the presence of an initiator using a double metal cyanide complex as a catalyst Is what you do. The present invention also provides a hydrolyzable silicon group-containing organic polymer in which the viscosity of the hydrolyzable silicon group-containing organic polymer is 200 poise or more at 23 ° C. The present invention also provides a curable composition containing the hydrolyzable silicon-containing organic polymer, a filler and a curing accelerator. The present invention also relates to (A) an unsaturated group-containing organic polymer containing a polyoxyalkylene-based polymer chain containing two or more unsaturated groups and having Mw / Mn of 1.7 or less. Hydrolysis comprising reacting a compound containing two or more functional groups capable of addition reaction with a group, and (B) a compound having a functional group capable of addition reaction with an unsaturated group and a hydrolyzable silicon group. An object of the present invention is to provide a method for producing a functional silicon group-containing organic polymer. Further, the present invention provides the method for producing a hydrolyzable silicon group-containing organic polymer, wherein the polyoxyalkylene polymer chain undergoes ring-opening polymerization of a cyclic ether in the presence of an initiator using a double metal cyanide complex as a catalyst. An object of the present invention is to provide a method for producing a hydrolyzable silicon group-containing organic polymer which is a polymer chain derived from a polyoxyalkylene polymer obtained by the above method.
Furthermore, the present invention provides a method for producing a hydrolyzable silicon group-containing organic polymer in which the viscosity of the above-mentioned hydrolyzable silicon group-containing organic polymer is 200 poise or more at 23 ° C.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polyoxyalkylene polymer chain in the unsaturated group-containing organic polymer (hereinafter referred to as polymer (U)) used in the present invention is derived from the polyoxyalkylene polymer. As for the molecular weight of the polyoxyalkylene polymer, Mn is preferably 5,000 or more,
In particular, it is preferably 8,000 to 30,000. Mn
Is less than 5,000, the hydrolyzable silicon group-containing organic polymer component obtained from the low molecular weight polyoxyalkylene-based polymer remains in the finally obtained polymer, thereby deteriorating the curability. Sometimes. Further, the polyoxyalkylene polymer has an Mw / Mn of 1.7 or less, and particularly preferably 1.5 or less. When Mw / Mn of the polyoxyalkylene polymer is large, Mw / Mn
However, there is a disadvantage that the curability is inferior to a crosslinkable polymer having the same viscosity obtained from a raw material having a low viscosity.

The polymer (U) is preferably produced from a polyoxyalkylene-based polymer having a functional group as a raw material and having an unsaturated group introduced into the terminal, and a polymer suitable for the terminal hydroxyl group of the polyoxyalkylene polyol. Those produced by introducing an unsaturated group via an organic group are preferable in terms of availability of raw materials. Such a polyoxyalkylene polyol is produced by reacting an initiator with a cyclic ether or the like in the presence of a catalyst.

Examples of catalysts for the polymerization of cyclic ethers include alkali metal catalysts such as potassium compounds and cesium compounds, double metal cyanide complex catalysts, metal porphyrin catalysts, and the like. In order to obtain the following polyoxyalkylene-based polymer, it is particularly preferable to use a cesium-based compound such as cesium hydroxide and a double metal cyanide complex catalyst. As the double metal cyanide complex, a complex containing zinc hexacyanocobaltate as a main component is preferable, and an ether and / or alcohol complex is particularly preferable. Its composition can be essentially the one described in JP-B-46-27250. In this case, as the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) or the like is preferable, and glyme is particularly preferable from the viewpoint of handling during the production of the complex. As the alcohol, t-butanol is preferable, and for example, it is described in JP-A-4-145123. As the initiator, a compound having 2 to 10 active hydrogens is preferable,
A polyhydroxy compound having 2 to 10 hydroxyl groups is more preferable, and a polyhydroxy compound having 2 to 8, particularly 2 to 4 hydroxyl groups is further preferable. Specific examples of the initiator include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
Neopentyl glycol, 1,4-butanediol,
Examples thereof include 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, sucrose, and polyols obtained by reacting any of these with a cyclic ether. Also,
As an initiator, an unsaturated group-containing monohydroxy compound such as allyl alcohol can also be used. The initiator is 1
The species may be used alone or in combination of two or more.

The number of functional groups of the starting polyoxyalkylene polymer is preferably 2 or more, more preferably 2 to 6.
When it is desired to increase flexibility as a cured product characteristic, the number of functional groups of the raw material polyoxyalkylene polymer is 2 or 3
Is particularly preferred. Although those having more than 3 functional groups can be used arbitrarily, in the present invention, since a polyvalent silicon hydride compound is used to increase the molecular weight, an amount of more than 3 unsaturated groups is contained in one molecule. Attention must be paid to the fact that the possibility of gelation in the molecular weight increasing reaction increases as the reaction becomes more likely. Examples of the cyclic ether used in the production of the raw material polyoxyalkylene polymer include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, hexylene oxide, tetramethylene oxide and the like. , Propylene oxide is preferred. The cyclic ethers may be used alone or in combination of two or more.
Examples of the functional group of the raw material polyoxyalkylene polymer include a hydroxyl group and the like. Specific examples of the particularly preferable raw material polyoxyalkylene polymer are polyoxypropylene polyols having 2 to 6 valences, particularly polyoxypropylene diol and polyoxypropylene triol. As the raw material polyoxyalkylene polymer, an olefin-terminated polyoxyalkylene polymer such as an allyl-terminated polyoxypropylene monol can also be used.

As a method for introducing an unsaturated group into a polyoxyalkylene polymer, for example, a compound having an unsaturated group and a functional group is reacted with a terminal hydroxyl group of a polyoxyalkylene polyol to form an ether bond, an ester bond, A method of introducing an unsaturated group by bonding through a urethane bond, a carbonate bond, or the like can be given. When polymerizing a cyclic ether, a method of introducing an unsaturated group into the side chain of the raw material polyoxyalkylene polymer by adding and copolymerizing an unsaturated group-containing epoxy compound such as allyl glycidyl ether can also be used. . The number of unsaturated groups in the polymer (U) corresponds to the number of functional groups and unsaturated groups in the raw material polyoxyalkylene polymer, and is 2 or more, preferably 2 to 6. Regarding the molecular weight of the polymer (U), Mn is preferably 5,000 or more, particularly preferably 8,000 to 50,000. When Mn is less than 5000, the molecular weight increases,
Even after the introduction of the hydrolyzable silicon group, the curing rate may be slow and unsatisfactory due to the presence of the remaining low molecular weight hydrolyzable silicon group-containing curable polymer. The upper limit of the viscosity of the polymer (U) is not limited, and for example, a polymer (U) having a viscosity of 200 poise or more at 23 ° C., particularly 100 poise or more can be obtained. For reasons of handling in the production process, preferably the viscosity of the polymer (U) is 30 at 23 ° C.
It is preferably 0 poise or less, more preferably 200 poise or less, and particularly preferably 160 poise or less.

The main chain is polyester, polycarbonate,
It is also possible to use an organic polymer having an unsaturated group in the molecule in combination with the polymer (U) in any one of polyacrylate, polyolefin and the like or a combination thereof. Examples of such a polyester compound having an unsaturated group in the molecule include JP-A-3-163159 and JP-A-3-139.
No. 558 and JP-A-3-139554 can be used. These can improve the adhesiveness of the finally obtained hydrolyzable silicon group-containing organic polymer to various substrates and the mechanical properties of the cured product.

The hydrolyzable silicon group-containing organic polymer of the present invention is produced by increasing the molecular weight by using an unsaturated group-containing polyoxyalkylene polymer having an Mw / Mn of more than 1.7. When the viscosity after increasing the molecular weight is equal to that of the hydrolyzable silicon group-containing organic polymer, the curability is more excellent. Also, Mw / Mn
Adhesion to adherends rather than high-molecular-weight polyoxyalkylene-based polymers having a molecular weight of 1.7 or less rather than curable polymers having a hydrolyzable silicon group at the terminal and having the same viscosity, without substantially increasing the molecular weight. The characteristic that peeling at the interface becomes difficult is obtained. The causes of these differences are not clear, but are presumed to be due to the following reasons. That is,
When a polymer having an unsaturated group having a wide molecular weight distribution is used as a raw material, even if the polymer is crosslinked to increase the molecular weight, a polymer having a small molecular weight will ultimately remain, which is considered to reduce the curability. Also, when compared with a curable polymer produced without increasing the molecular weight from a high molecular weight polyoxyalkylene polymer, when the viscosity is equivalent, the hydrolyzable silicon group-containing organic polymer is cured. Since the molecular length between the cross-linking points becomes shorter as a result, it is presumed that when the elongation of the cured product becomes large, the cured product itself is more likely to break than peeling off at the interface with the adherend. You.

The hydrolyzable silicon-group-containing organic polymer of the present invention comprises a compound having two or more functional groups capable of undergoing an addition reaction to an unsaturated group in a molecule (hereinafter referred to as a chain extender) and an unsaturated group. It is obtained by reacting a polymer (U) with a compound containing a reactive functional group and a hydrolyzable silicon group (hereinafter, referred to as a silicon group-introducing agent). That is, in the present invention, the polymer (U) and a chain extender are used to increase the molecular weight, and further reacted with a silicon group-introducing agent to obtain a polymer having an increased molecular weight and having a hydrolyzable silicon group. Can be Specific examples of the functional group capable of undergoing an addition reaction to the unsaturated group in the chain extender include a silicon hydride group and a mercapto group. In the chain extender, two or more functional groups capable of undergoing an addition reaction with an unsaturated group are contained in one molecule, and two is particularly preferable. The functional groups capable of undergoing an addition reaction to the unsaturated groups contained in one molecule may be the same or different.

Specific examples of the chain extender include 1,1,3,3-tetramethyldisiloxane, diphenylsilane, 1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylsilyl) Benzene, 1,3-bis (3-mercaptopropyl) tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane,
1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,
Compounds containing two or more silicon hydride groups in the molecule, such as 5,7,9-pentamethylcyclopentasiloxane, or multiple mercapto groups in the polysiloxane skeleton, such as α, ω-dimercaptopolydimethylsiloxane Polysiloxane compounds known as reactive silicone oils, polymers containing a plurality of terminal mercapto groups known as thiochol polymers, 1,4-dimercaptobutane, 1,10
-Dimercaptodecane, 1,2-dimercaptoethane, bis
Compounds having two or more mercapto groups in a molecule such as (2-mercaptoethyl) ether, 1,6-dimercaptohexane, and 1,3-dimercaptopropane can be exemplified. The chain extender may be used alone, or two or more kinds may be used in combination.

The hydrolyzable silicon group in the silicon group-introducing agent includes a hydrolyzable silicon group represented by the following formula (1). -SiX _a R ¹ _3-a ···
(1) (In the formula (1), R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, and a is 1, 2 or 3 it. However, when R ¹ is present in plurality may or may not be those R ¹ the same, when X is present in plurality may be different and their X same.) equation (1) Wherein R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group,
Particularly preferred are an alkyl group having 6 or less carbon atoms and a phenyl group. Particularly preferred alkyl groups include methyl, ethyl, propyl, butyl, hexyl,
And a cyclohexyl group. When a plurality of R ¹ are present, those R ¹ may be the same or different.

Examples of the hydrolyzable group for X include a halogen atom, an alkoxy group, an acyloxy group, a carbamoyl group, an amino group, an aminooxy group, a ketoximate group and the like. Among these, the carbon number of the hydrolyzable group having a carbon atom is preferably 6 or less, and particularly preferably 4 or less. Preferred X is a lower alkoxy group having 4 or less carbon atoms, particularly a methoxy group, an ethoxy group, a propoxy group and a propenyloxy group. When a plurality of Xs exist, those Xs may be the same or different. a is 1, 2 or 3. Examples of the functional group capable of undergoing an addition reaction to the unsaturated group in the silicon group-introducing agent include the same functional groups capable of undergoing an addition reaction to the unsaturated group in the chain extender. The numbers of the functional groups and the hydrolyzable silicon groups in the silicon group-introducing agent are not particularly limited.
Is preferred.

Suitable silicon group-introducing agents include compounds containing a silicon hydride group or a mercapto group and a hydrolyzable silicon group in the molecule.
Silicon hydride compounds such as methyldimethoxysilane, trimethoxysilane, methyldiacetoxysilane, dimethylchlorosilane, methyldichlorosilane, ethyldichlorosilane, trichlorosilane, and 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, -Mercapto group-containing silicon compounds such as mercaptopropyltriethoxysilane. Of these, the chlorosilane compound can be converted to another hydrolyzable silicon group such as an alkoxy group by reacting the chlorine atom with methyl orthoformate and methanol after reacting with the polymer (U). It is. The silicon group-introducing agent may be used alone or in combination of two or more. In order to react these chain extenders and the silicon group-introducing agent with the unsaturated groups of the polymer (U), when the functional group to be reacted is a mercapto group, polymerization of a radical generator or the like is required during the reaction. An initiator may be used, and in some cases, the reaction may be performed by radiation or heat without using a polymerization initiator. Examples of the polymerization initiator include a peroxide-based, azo-based, or redox-based polymerization initiator and a metal compound catalyst. Specific examples of the polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), benzoyl peroxide, t-butyl peroxide, acetyl peroxide, and diisopropylperoxy. Dicarbonate and the like. The amount of the polymerization initiator to be added is not particularly limited, but may be usually 0.01 to 2 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the polymer (U).
0.8 parts by weight. The reaction temperature of the above reaction is 2
0 ° C to 200 ° C is preferable, and particularly preferably 50 ° C to 1 ° C.
50 ° C. The reaction time is not particularly limited, but is usually preferably 1 to 30 hours.

When the functional group to be reacted when the chain extender and the silicon group introducing agent are reacted with the unsaturated group of the polymer (U) is a silicon hydride group, a platinum catalyst,
Rhodium-based catalyst, cobalt-based catalyst, palladium-based catalyst,
A catalyst such as a nickel-based catalyst can be used. Platinum-based catalysts such as chloroplatinic acid, platinum metal, platinum chloride, and platinum-olefin complexes are preferred. The amount of the catalyst to be added is not particularly limited.
The amount is usually 10 to 100 ppm with respect to (U), and preferably 30 to 60 ppm. The reaction temperature at which the silicon hydride compound is reacted is preferably from 30C to 150C, particularly preferably from 60C to 120C.
The reaction time may be appropriately selected, and is usually from 10 minutes to
10 hours is preferred. The ratio between the chain extender and the silicon group-introducing agent to be reacted with the polymer (U) can be arbitrarily changed. The total number of functional groups that undergo an addition reaction with the unsaturated groups in the chain extender and the silicon group-introducing agent is preferably equal to or less than the total number of the unsaturated groups in the polymer (U). Among the chain extenders and silicon group-introducing agents used, the viscosity of the hydrolyzable silicon group-containing organic polymer finally obtained by increasing the amount of the chain extender increases, but silicon that can be introduced is increased. Since the number of groups decreases, the cured product obtained by curing the obtained polymer becomes flexible. The ratio of the chain extender and the silicon group-introducing agent to be used can be arbitrarily selected according to the desired physical properties in consideration of the above-mentioned viscosity and the physical properties of the cured product.

The reaction between the polymer (U) and the chain extender and the silicon group-introducing agent is as follows. 1) First, the polymer (U) is reacted with the chain extender to adjust the viscosity of the polymer, Reacting with a group-introducing agent, 2) simultaneously reacting the polymer (U) with a chain extender and a silicon group-introducing agent, 3) reacting the polymer (U) with the silicon group-introducing agent first and then a chain extender May be used, or any of these methods may be combined. Further, during these reactions, a method of adjusting the amount of the chain extender while checking the viscosity of the reaction mixture is a method of adjusting the viscosity of the reaction product, and is particularly preferable because a product having a constant viscosity can be obtained. Is the way. As described above, an organic polymer having a main chain of polyester, polycarbonate, polyacrylate, polyolefin or the like and having an average of one or more unsaturated groups in the molecule can be used in combination with the polymer (U). is there. The lower limit of the molecular weight of the organic polymer used in combination is preferably Mn is 1
000 or more, particularly preferably 1500 or more, and the upper limit is preferably 50,000 or less, particularly preferably 40,000 or less. As a method to use together,
Such an unsaturated group-containing organic polymer and the polymer (U) may be mixed in advance and reacted with a chain extender and a silicon group-introducing agent. When an organic polymer having an average of at least one unsaturated group in a molecule thereof such as polyester, polycarbonate, polyacrylate, polyolefin or the like is used in combination with the polymer (U), the main chain structure varies depending on the reaction with the chain extender. Crosslinking occurs between the above polymers, and a polymer which does not separate the finally obtained hydrolyzable silicon group-containing organic polymer is obtained. When an organic polymer having an average of at least one unsaturated group in a molecule containing a polyester or polycarbonate in the main chain is used, the adhesion to the base material is improved, and a molecule containing a polyacrylate in the main chain is used. When an organic polymer having an average of at least one unsaturated group is used, adhesion to a substrate and weather resistance are improved, and an average of at least one unsaturated group is included in a molecule containing a polyolefin in a main chain. When an organic polymer containing is used, the water resistance is improved. It is also possible to use a plurality of these in combination. In the case where an organic polymer having a main chain of polyester, polycarbonate, polyacrylate, polyolefin or the like and having an average of one or more unsaturated groups in the molecule is used in combination with the polymer (U), the mixing ratio of the former depends on the required performance. The amount is usually 1 to 50% by weight, preferably 10 to 40% by weight of the total amount of the two. The hydrolyzable silicon-group-containing organic polymer obtained in the present invention has a higher molecular weight than the raw material polymer (U), and is a dimer or a trimer of the polymer (U) via a chain extender. The polymer (U) itself (that is, a monomer) is preferably contained as a main component.

The curable composition of the present invention contains the above-mentioned organic polymer containing a hydrolyzable silicon group, a filler and a curing accelerator, and may optionally contain additives as necessary. it can. Hereinafter, fillers, curing accelerators, and additives that can be used in the curable composition will be described.

(Filler) As the filler, known fillers can be used. Specific examples of the filler include calcium carbonate having a surface treated with a fatty acid or a resin acid-based organic substance, colloidal calcium carbonate having an average particle diameter of 1 μm or less obtained by further pulverizing the calcium carbonate, and an average particle diameter produced by a precipitation method. 1-3 μm light calcium carbonate, average particle size 1-20
μm calcium carbonate such as heavy calcium carbonate, fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black, magnesium carbonate, diatomaceous earth,
Calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc flower, shirasu balloon, glass balloon, organic resin balloon of polystyrene and polyacrylate, wood flour, pulp, cotton chip, Powdery fillers such as mica, walnut flour, fir flour, graphite, aluminum fine powder, flint powder, and the like, and fibrous fillers such as asbestos, glass fiber, glass filament, carbon fiber, Kevlar fiber, and polyethylene fiber. . These fillers may be used alone or in combination of two or more. The most common of these is calcium carbonate.
In this case, it is particularly preferable to use a combination of colloidal calcium carbonate and heavy calcium carbonate. When the colloidal calcium carbonate and the heavy calcium carbonate are used in combination, the weight ratio thereof is not particularly limited, but is usually 10: 1 to 1:10, and preferably 3: 1 to 1: 3. The amount of the filler is from 0 to 10 based on 100 parts by weight of the hydrolyzable silicon-containing organic polymer.
00 parts by weight, especially 50 to 250 parts by weight, is preferred.

(Curing Accelerator) The silicon group of the hydrolyzable silicon group-containing organic polymer of the present invention is hydrolyzed in the presence of moisture to form a silanol group, and is combined with another silanol group or a hydrolyzable silicon group. A condensation reaction takes place between them, and they are cured by crosslinking by siloxane bonds. This reaction proceeds even if there is no compound for accelerating the reaction. However, when the reactive silicon group is an alkoxysilyl group, a curing accelerator is usually used to develop a practically sufficient curing rate. Specifically, the following tin compounds are exemplified. Tin 2-ethylhexanoate, tin naphthenate,
Various compounds of divalent tin such as tin stearate.

Organic tin carboxylate such as dialkyltin dicarboxylate or dialkoxytin monocarboxylate such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin monoacetate, dibutyltin maleate, dialkyltin bisacetylacetonate, dialkyltin monoacetyl Tin chelate compounds such as acetonate monoalkoxide, reactants of dialkyltin oxide and ester compounds, reactants of dialkyltin oxide and alkoxysilane compounds, and various compounds of tetravalent tin such as dialkyltin dialkylsulfide. In addition, examples of the tin chelate compound include dibutyltin bisacetylacetonate, dibutyltin bisethylacetoacetate, and dibutyltin bismonoacetylacetonate monoalkoxide. Examples of the reaction product of the dialkyltin oxide and the ester compound include a tin compound which is made into a liquid state by heating and mixing dibutyltin oxide with a phthalic acid ester such as dioctyl phthalate or diisononyl phthalate. In this case, as the ester compound, in addition to the ester of an aliphatic or aromatic carboxylic acid, tetraethyl silicate or a partially hydrolyzed condensate thereof can be used as the ester compound. Further, a compound obtained by reacting or mixing these tin compounds with a low-molecular alkoxysilane or the like can also be preferably used.

The following curing accelerators can be used in addition to the tin compound. Other metal salts such as alkyl titanates, organosilicon titanates, bismuth organic carboxylate, and the like. Acidic compounds such as phosphoric acid, p-toluenesulfonic acid, phthalic acid and bis (2-ethylhexyl) phosphate; Aliphatic monoamines such as butylamine, hexylamine, octylamine, decylamine, laurylamine, and N, N-dimethyl-octylamine; aliphatic polyamine compounds such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; Aromatic amine compound, alkanolamine, 3- (2-aminoethyl)
Amine compounds such as aminosilane coupling agents such as amino-propyltrimethoxysilane and 3-aminopropyltrimethoxysilane; When a bismuth compound or a tin compound is used in combination with an amine compound, particularly a primary amine compound, the use of the bismuth compound or the tin compound is preferred because the curing accelerated curing is improved. Further, by combining the above acidic compound and a basic compound such as an amine compound, a higher curing promoting effect is exhibited, especially at a high temperature. The curing accelerator can be used alone or in combination of two or more. The amount of the curing accelerator used is preferably 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the hydrolyzable silicon group-containing organic polymer.

As additives, a plasticizer, an adhesion-imparting agent,
Examples include a solvent, a dehydrating agent, a thixotropic agent, an antioxidant, and a curing accelerator. (Plasticizer) As the plasticizer, a known plasticizer can be used. Specific examples of the plasticizer include phthalic esters such as dioctyl phthalate, dibutyl phthalate, butylbenzyl phthalate, and diisononyl phthalate; aliphatics such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate; Carboxylic acid esters; Alcohol esters such as pentaerythritol ester; Phosphoric esters such as trioctyl phosphate and tricresyl phosphate; Epoxy such as epoxidized soybean oil, dioctyl 4,5-epoxyhexahydrophthalate, and benzyl epoxystearate Plasticizers; chlorinated paraffins; polyester plasticizers such as polyesters obtained by reacting a dibasic acid with a dihydric alcohol; polyoxypropylene glycol, polyoxypropylene triol and derivatives thereof, for example, polyoxypropyl Polyethers in which the hydroxyl group of glycol is sealed with an alkyl ether, polyethers in which the hydroxyl group of polyoxypropylene triol is sealed with an allyl compound; oligomers of polystyrene such as poly-α-methylstyrene and polystyrene , Polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene,
Polymer plasticizers such as oligomers such as hydrogenated polybutene and epoxidized polybutadiene, and the like. These plasticizers may be used alone or in combination of two or more. The amount of the plasticizer used is the hydrolyzable silicon-containing organic polymer 10
0 to 100 parts by weight relative to 0 parts by weight is preferred.

[0029] Relatively low-molecular plasticizers such as phthalic acid esters have a large plasticizing effect and are effective in lowering the viscosity of the compound, but on the other hand, when used as an adhesive, there is a problem in that the adhesiveness is reduced. When applying paint on the surface of the cured product, the plasticizer may increase the surface contamination due to the passage of the plasticizer, or the plasticizer may soften the painted surface, which is particularly prominent in alkyd paint. It is known that problems such as the film not being cured occur, and the use of a low-molecular plasticizer may not be suitable for some applications. In such a case,
Either no plasticizer is used or a less migratory plasticizer known as a polymeric plasticizer is used.

(Adhesiveness-imparting agent) An adhesiveness-imparting agent is used for the purpose of further improving the adhesiveness. Examples of these adhesion-imparting agents include silane coupling agents such as silanes containing (meth) acryloyloxy groups, silanes containing amino groups, silanes containing mercapto groups, silanes containing epoxy groups, and silanes containing carboxyl groups. . (Meta)
Examples of the acryloyloxy group-containing silanes include 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and 3-methacryloyloxypropylmethyldimethoxysilane. Examples of the amino group-containing silanes include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, -(2-aminoethyl)
-3-aminopropylmethyldimethoxysilane, N-
(2-aminoethyl) -3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane,
N-[(N-vinylbenzyl) -2-aminoethyl]-
Examples thereof include 3-aminopropyltrimethoxysilane and 3-anilinopropyltrimethoxysilane.

The silanes containing mercapto groups include 3-
Examples thereof include mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. Epoxy group-containing silanes include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and the like. Examples of carboxyl group-containing silanes include 2-carboxyethyltriethoxysilane, 2-carboxyethylphenylbis (2-methoxyethoxy) silane, and N- (N-carboxylmethyl-).
2-aminoethyl) -3-aminopropyltrimethoxysilane and the like. Further, a reaction product obtained by reacting two or more silane coupling agents may be used.
Examples of the reactant include a reactant of an amino group-containing silane and an epoxy group-containing silane, a reactant of an amino group-containing silane and a (meth) acryloyloxy group-containing silane, and an epoxy group-containing silane and a mercapto group. Examples of the reaction product include silane-containing reactants and mercapto group-containing silanes. These reactants can be easily obtained by mixing the silane coupling agent and stirring at a temperature in the range of room temperature to 150 ° C. The reaction time is not particularly limited, but may be generally 1 to 8 hours. The above compounds may be used alone or in combination of two or more. The amount of the silane coupling agent used is preferably 0 to 30 parts by weight based on 100 parts by weight of the hydrolyzable silicon group-containing organic polymer.

An epoxy resin may be added as an adhesion-imparting agent. If necessary, an epoxy resin curing agent may be used in combination. Examples of the epoxy resin that can be added to the curable composition of the present invention include general epoxy resins. Examples of the epoxy resin include flame-retardant epoxy resins such as bisphenol A-diglycidyl ether type epoxy resin, bisphenol F-diglycidyl ether type epoxy resin, tetrabromobisphenol A-glycidyl ether type epoxy resin, and novolak type epoxy resin. Resin, hydrogenated bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A / propylene oxide adduct, diglycidyl such as 4-glycidyloxy glycidyl benzoate, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, etc. Ester-based epoxy resin,
m-aminophenol-based epoxy resin, diaminodiphenylmethane-based epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, poly Generally used epoxy resins such as glycidyl ethers of polyhydric alcohols such as alkylene glycol diglycidyl ether and glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins and petroleum resins, and vinyl resins containing epoxy groups. Coalescence and the like. The amount of the epoxy resin used is preferably from 0 to 100 parts by weight based on 100 parts by weight of the hydrolyzable silicon group-containing organic polymer.

Further, the curable composition of the present invention may be used in combination with the curing agent (or curing catalyst) for the epoxy resin.
Examples of such a curing agent include commonly used curing agents for epoxy resins. Specific examples of curing agents for epoxy resins include, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, Amines such as isophoronediamine, 2,4,6-tris (dimethylaminomethyl) phenol or salts thereof, or blocked amines such as ketimine compounds, polyamide resins, imidazoles, dicyandiamides, boron trifluoride complex compounds , Phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecenyl succinic anhydride, carboxylic anhydrides such as pyromellitic anhydride,
On average, at least one group capable of reacting with an epoxy group, such as a phenoxy resin, a carboxylic acid or an alcohol, is present in the molecule.
Having a polyoxyalkylene polymer (terminally aminated polyoxypropylene glycol, terminally carboxylated polyoxypropylene glycol, etc.),
Examples thereof include liquid terminal functional group-containing polymers such as polybutadiene, hydrogenated polybutadiene, acrylonitrile-butadiene copolymer, and acrylic polymer modified with a carboxyl group, an amino group, and the like, and ketimine compounds. The amount of the epoxy resin curing agent used is 0.1 to 30 with respect to the epoxy resin.
0 parts by weight is preferred.

(Solvent) In the curable composition of the present invention,
A solvent may be added for the purpose of adjusting the viscosity and improving the storage stability of the composition. Such solvents include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, ester alcohols, ketone alcohols, ether alcohols, ketone ethers, Ketone esters and ester ethers can be used. Alcohols are preferred. The use of alcohols is preferred when the curable composition of the present invention is stored for a long period of time because storage stability is improved. As the alcohols, alkyl alcohols having 1 to 10 carbon atoms are preferable, and methanol, ethanol, isopropanol, isoamyl alcohol, hexyl alcohol and the like are particularly preferable. The amount of the solvent used is 0 to 100 parts by weight of the hydrolyzable silicon-containing organic polymer.
500 parts by weight are preferred.

(Dehydrating Agent) In order to further improve the storage stability of the curable composition of the present invention, a small amount of a dehydrating agent can be added as long as the curability and flexibility are not adversely affected.
Specific examples of the dehydrating agent include, for example, methyl orthoformate, alkyl orthoformate such as ethyl orthoformate, methyl orthoacetate, alkyl orthoacetate such as ethyl orthoacetate, methyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, Hydrolyzable organic silicon compounds such as tetraethoxysilane, hydrolyzable organic titanium compounds, and the like can be used. Vinyl trimethoxysilane and tetraethoxysilane are particularly preferred in view of cost and effect. Such dehydrating agents are particularly known as one-part formulations,
It is particularly effective for products in which a curing catalyst has been added to the formulation and filled into a moisture-proof container. (Thixotropic agent) In addition, a thixotropic agent may be used to improve sagging. Examples of the thixotropic agent include calcium carbonate treated with an organic acid, hydrogenated castor oil, calcium stearate, zinc stearate, finely divided silica, and fatty acid amide. The amount of the thixotropic agent used is generally 0.1 to 10 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of the hydrolyzable silicon group-containing organic polymer. Department.

(Anti-aging agent) As the anti-aging agent, generally used antioxidants, ultraviolet absorbers,
Light stabilizers are used as appropriate. Hindered amine, benzotriazole, benzophenone, benzoate, cyanoacrylate, acrylate, hindered phenol, phosphorus, and sulfur compounds can be used as appropriate. In particular, by using a combination of two or all of a light stabilizer, an antioxidant, and an ultraviolet absorber,
This is a preferable method because the effect may be improved as a whole by utilizing each characteristic. Specifically, it is particularly effective to combine a tertiary or secondary hindered amine light stabilizer, a benzotriazole ultraviolet absorber, a hindered phenolic and / or phosphite antioxidant. The amount of each of the antioxidant, the ultraviolet absorber and the light stabilizer is 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the hydrolyzable silicon-containing organic polymer.
Preferably in the range of parts by weight. If the amount is less than 0.1 part by weight, the effect of improving the weather resistance is small, and if it exceeds 5 parts by weight, there is no great difference in the effects and it is economically disadvantageous.

(Others) An air oxidation curable compound or a photocurable compound can be added for the purpose of improving the adhesion and surface tackiness of the paint over a long period of time. Such air oxidation-curable compounds include drying oils such as tung oil and linseed oil, various alkyd resins obtained by modifying the compounds, acrylic polymers modified with the drying oil, silicone resins, and polybutadienes. A diene polymer such as a diene polymer or copolymer having 5 to 8 carbon atoms, and various modified products of the polymer or copolymer (maleated modification,
Boiled oil-modified). As the photocurable compound, a compound containing a (meth) acryloyl group obtained by reacting a polyhydric alcohol such as trimethylolpropane, a hydroxy compound such as a polyether polyol or a polyester polyol with acrylic acid or methacrylic acid is used. You. Typically, trimethylolpropane triacrylate is used. An air oxidation curable compound and a photocurable compound can be used together. The amount of the air oxidation curable compound used is 0 to 50 parts by weight based on 100 parts by weight of the hydrolyzable silicon group-containing organic polymer, and the amount of the photocurable compound used is hydrolyzable silicon group-containing organic polymer 10.
0 to 50 parts by weight relative to 0 parts by weight is preferred. Further, a compound capable of generating trimethylsilanol by hydrolysis may be added for adjusting physical properties and reducing surface stickiness. This compound, by its addition,
When a valence tin carboxylic acid and an organic primary amine compound are used as a curing accelerator, there is an effect of reducing the modulus of the cured product and reducing the stickiness of the surface. As a compound that generates trimethylsilanol, trimethylsilyl ethers such as aliphatic alcohols and aromatic alcohols can be generally used, and the stronger the alcohol acidity, the slower the curing. The curability can be adjusted by arbitrarily changing the type of alcohol, and trimethylsilyl ethers of a plurality of alcohols can be used simultaneously for the purpose. The amount of the compound that generates trimethylsilanol by hydrolysis is preferably 0 to 50 parts by weight based on 100 parts by weight of the hydrolyzable silicon-containing organic polymer.

In addition, inorganic pigments such as iron oxide, chromium oxide and titanium oxide and organic pigments such as phthalocyanine blue and phthalocyanine green can be used as the pigment. The use of pigments is effective not only for coloring but also for the purpose of improving weather resistance. In addition, for the purpose of imparting design properties especially as a sealing material, by adding fine particles of a color different from the color of the composition to the composition, hardening with a surface appearance like granite or granite It can also be a thing. It is also optional to add a known flame retardant or fungicide. It is also possible to add a matting agent used for paint applications. The curable composition of the present invention can be obtained by blending a hydrolyzable silicon group-containing organic polymer, a filler and a curing accelerator, and further optionally blending an additive as needed. The curable composition of the present invention can be cured by moisture. The curing temperature can be various, and can be in a wide range from as low as room temperature to as high as room temperature. Normal,
It is preferable to cure in the range of 0 to 35 ° C.
It is preferable to cure in the range of 0 to 25 ° C. The curable composition of the present invention can be used for sealants, waterproofing materials, adhesives, coating agents, etc., and is particularly suitable for applications requiring sufficient cohesive force of the cured product itself and dynamic followability to adherends. It is.

[0039]

EXAMPLES The present invention will be specifically described below, but the present invention is not limited to only these examples. In addition,
The molecular weight distribution in this example is a value based on the molecular weight in terms of polystyrene measured using gel permeation chromatography. In addition, the molecular weight of the hydroxyl group-containing polyoxyalkylene polymer and polyester polymer as the raw materials is the molecular weight calculated from the number of moles of the hydroxyl group contained and the number of functional groups of the initiator used in polymerizing each polymer. is there.

(Synthesis Example 1) Propylene oxide was reacted with dipropylene glycol in the presence of a zinc hexacyanocobaltate-glyme complex catalyst to give M
A polyoxypropylene diol having n of 8000 and Mw / Mn of 1.3 was obtained. A methanol solution of sodium methoxide 1.05 times the mol number of the hydroxyl group of the polyoxypropylene diol was added, and methanol was distilled off under reduced pressure under heating to convert the hydroxyl group to a sodium alkoxide. The reaction was carried out by adding 1.05 times mol of allyl chloride. After removing unreacted allyl chloride, inorganic salts produced as by-products were removed and purified to obtain 23.
An allyl group-terminated polypropylene oxide (U-1) having a viscosity at 30 ° C. of 30 poise was obtained. U-1 has Mw of 10
920, and Mn was 8,400.

(Synthesis Example 2) Propylene oxide was reacted with glycerin as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst to give Mn of 1000.
At 0, a polyoxypropylene triol having an Mw / Mn of 1.3 was obtained. A methanol solution of sodium methoxide 1.05 times the mole number of the hydroxyl group of the polyoxypropylene triol was added, and methanol was distilled off under heating and reduced pressure at 120 ° C. to convert the hydroxyl group to a sodium alkoxide. 1.05 against
The reaction was performed by adding twice the molar amount of allyl chloride. After removing the unreacted allyl chloride, the inorganic salt produced as a byproduct is removed and purified.
An allyl-terminated polypropylene oxide (U-2) having a viscosity of 3 poise at 24 ° C. was obtained. U-2 has Mw of 1
3650 and Mn was 10500.

(Synthesis Example 3) Mn was reacted with propylene oxide using pentaerythritol as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst.
Of 20000 and Mw / Mn of 1.3 was obtained. A methanol solution of sodium methoxide 1.05 times the mol number of the hydroxyl groups of the polyoxypropylene tetraol was added, and 120
Methanol was distilled off under heating and reduced pressure at ℃ to convert the hydroxyl group to sodium alkoxide, and the reaction was carried out by adding 1.05 times mol of allyl chloride to the added sodium methoxide. After removing unreacted allyl chloride, the by-produced inorganic salt was removed and purified to obtain an allyl-terminated polypropylene oxide (U-3) having a viscosity of 70 poise at 23 ° C. U
-3 had Mw of 27,300 and Mn of 21,000.

(Synthesis Example 4) Propylene oxide was reacted with glycerin as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst to give Mn of 2,000.
At 0, a polyoxypropylene triol having an Mw / Mn of 1.4 was obtained. A methanol solution of sodium methoxide 1.05 times the mole number of the hydroxyl group of the polyoxypropylene triol was added, and methanol was distilled off under heating and reduced pressure at 120 ° C. to convert the hydroxyl group to a sodium alkoxide. 1.05 against
The reaction was performed by adding twice the molar amount of allyl chloride. After removing the unreacted allyl chloride, the inorganic salt produced as a byproduct is removed and purified.
An allyl group-terminated polypropylene oxide (U-4) having a viscosity at 3 ° C. of 150 poise was obtained. U-4 had Mw of 29,400 and Mn of 21,000.

(Synthesis Example 5) Dipropylene glycol was used as an initiator, potassium hydroxide was used as a catalyst, propylene oxide was reacted, and Mn was 3200 and Mw / M
The polyoxypropylene diol whose n was 1.3 was obtained. A methanol solution of sodium methoxide in an amount of 1.05 times the molar number of hydroxyl groups of the polyoxypropylene diol was added, and methanol was distilled off under heating and reduced pressure at 120 ° C. to convert the hydroxyl groups to sodium alkoxide. The reaction was carried out by adding 1.05 mole mol of allyl chloride to the chloride. After removing unreacted allyl chloride, the inorganic salt produced as a by-product was removed and purified to obtain an allyl-terminated polypropylene oxide (U-5) having a viscosity of 7 poise at 23 ° C. U-5 has Mw of 4368 and M
n was 3360.

(Synthesis Example 6) Dipropylene glycol was used as an initiator, potassium hydroxide was used as a catalyst, propylene oxide was reacted, and Mn was 3200 and Mw / M
The polyoxypropylene diol whose n was 1.3 was obtained. A methanol solution of sodium methoxide in an amount of 1.05 times the molar number of hydroxyl groups of this polyoxypropylene diol was added, and methanol was distilled off under heating and reduced pressure at 120 ° C. to convert the hydroxyl groups to sodium alkoxide. Chlorobromomethane was added in an amount such that 63% of the moles of hydroxyl groups of the diol reacted, and reacted. Subsequently, an excess of allyl chloride was added and reacted. After removing unreacted allyl chloride, the inorganic salt produced as a by-product was removed and purified.
An allyl group-terminated polypropylene oxide (U-6) having Mw / Mn of 580 and Mw / Mn of 1.9 was obtained.

(Synthesis Example 7) Clapol L-2010, a polyester having a terminal hydroxyl group obtained by ring-opening polymerization of β-methyl-δ-valerolactone using ethylene glycol as an initiator (manufactured by Kuraray Co., Ltd., molecular weight of about 2,000) ) Was placed in a pressure-resistant reactor and dried under reduced pressure at 100 ° C. for 5 hours. Toluene was added as a solvent, and allyl chloroformate and triethylamine were added little by little, and reacted at 60 ° C. After the reaction, toluene was added for dilution, an aqueous solution of ammonium chloride was added, the mixture was stirred at room temperature, and the organic layer was washed until the strong acid content disappeared. The organic layer was further washed with water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed to obtain a polyester compound having a terminal allyl group (U-7). U-7 had Mn of 2,080.

REFERENCE EXAMPLE 1 Propylene oxide was reacted with glycerin as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst to obtain polyoxypropylene triol having a viscosity at 23 ° C. of 1,000 poise. A methanol solution of sodium methoxide 1.05 times the molar number of the hydroxyl groups of the polyoxypropylene triol was added, and methanol was distilled off under reduced pressure at 120 ° C. to convert the hydroxyl groups to sodium alkoxide. During the distillation of methanol, the torque applied to the stirrer in the reactor became too large, and the stirrer stopped, so that methanol could not be distilled to the end.

(Examples 1 to 8 and Comparative Examples 1 to 4) For the polymers (U-1 to U-7) obtained in the synthesis examples, the amounts of the chain extender and silicon group-introducing agent shown in Table 1 are shown. To obtain a hydrolyzable silicon group-containing organic polymer (S). In addition, the method shown as reaction method A, B, and C in a table | surface shows the following reaction methods.

(Reaction method A) Polymer (U) was placed in a pressure-resistant reactor.
Was replaced with 1 kg of nitrogen. This was heated and stirred at 70 ° C., 1,1,3,3-tetramethyldivinylsiloxane platinum complex (hereinafter referred to as VTS complex) was added so that the concentration of platinum was 2 ppm, and the mixture was further stirred for 30 minutes. . Next, a chain extender or a mixture of a chain extender and a silicon group-introducing agent was added in two portions. After the first addition, the mixture is reacted at 70 ° C. for 5 hours. After the reaction, the viscosity of the polymer is confirmed. Then, the second addition is performed, and the mixture is further reacted at 70 ° C. for 3 hours to obtain a hydrolyzable silicon group-containing organic compound. Polymer (S) was obtained. The first time,
The types and amounts of additives in the second addition are shown in the table.

(Reaction method B) Polymer (U) was placed in a pressure-resistant reactor.
Was replaced with 1 kg of nitrogen. This is divided into a second part and a chain extender or a mixture of a chain extender and a silicon group-introducing agent and a radical generator azobis (2-methylbutyronitrile)
(V-59, manufactured by Wako Pure Chemical Industries, Ltd.). 1
After the second addition, the mixture was reacted at 80 ° C. for 8 hours. After the reaction, the viscosity of the polymer was confirmed. Then, the second addition was performed, and the mixture was reacted at 80 ° C. for 8 hours, thereby obtaining a hydrolyzable silicon-group-containing organic polymer (S ) Got. Azobis (2-methylbutyronitrile)
Is 30 g for the first time, 20 g for the second time, and the types and amounts of other additives are shown in the table.

(Reaction method C) Polymer (U) was placed in a pressure-resistant reactor.
Was replaced with 1 kg of nitrogen. This was heated and stirred at 70 ° C., the VTS complex was added so that the concentration of platinum was 2 ppm, and the mixture was further stirred for 30 minutes. Next, the additives were added in two parts. In the first addition, a chain extender was added and reacted at 70 ° C. for 5 hours. After the reaction, the viscosity of the polymer was confirmed, and then a silicon group-introducing agent and 20 g of azobis (2-methylbutyronitrile) were added thereto.
The reaction was carried out at 0 ° C. for 8 hours to obtain a hydrolyzable silicon group-containing organic polymer (S). The amount of the chain extender added in the first addition and the amount of the silicon group introducing agent added in the second addition are shown in the table.

(Examples 9 to 20 and Comparative Examples 5 to 10)
Polymers, fillers, additives, and the like shown in Tables 3, 4, and 5 are added at room temperature (23 ° C.) to prepare a curable composition, and a thin film is formed on an aluminum plate as an adherend. And cured at 23 ° C. and 65% humidity. The coating was cured by moisture in the air. After a lapse of 6 hours, the thickness of the cured coating film obtained was measured, and further, a tensile property test was carried out in accordance with the test method of a building sealing material according to JISA 1439 to measure physical properties and adhesive strength. With respect to the curable compositions shown in Table 3, commercially available silane-based primers were applied to adherends and dried to prepare samples. No primer was applied to the curable compositions shown in Table 4. The unit of the amount of the filler and additive shown in Tables 3, 4 and 5 is g. In addition, for the purpose of examining the curability of the deep part, the curable composition is placed in a cup having a diameter of 3 cm and a depth of 4 cm, and cured at 23 ° C. and 65% humidity. The thickness of the cured portion was measured.

[0053]

[Table 1]

[0054]

[Table 2]

The components and physical properties to which the subscripts are added in the table are as follows. ^* Abbreviations of chain extenders represent the following. TMDS: 1,1,3,3-tetramethyldisiloxane, BMEE: bis (2-mercaptoethyl) ether, ^** The abbreviations for the silicon group-introducing agent represent the following. MDMS: methyldimethoxysilane, GMTS: γ-mercaptopropyltrimethoxysilane, ^{*** The} value calculated assuming that one molecule of the chain extender reduces the number of polymers by one molecule. In addition, Mw / Mn of the hydrolyzable silicon group-containing organic polymer S-1 is 1.6, and the hydrolyzable silicon group-containing organic polymer S-
Mw / Mn of No. 3 was 1.5, and Mw / Mn of the hydrolyzable silicon group-containing organic polymer S-5 was 1.7.

[0056]

[Table 3]

The various additives and physical properties indicated by the subscripts and subscripts in the table are as follows. *: Neolite SP-T (manufactured by Takehara Chemical Industry Co., Ltd.) **: Whiten SB (manufactured by Shiraishi Calcium Industry Co., Ltd.) ***: Polyoxypropylene diol having a molecular weight of 8000 Mw / Mn = 1.3 ****: 3/1 mixture of trimethylolpropane tristrimethylsilyl ether and phenoxytrimethylsilane *****: Ratio of area of cohesive failure after tensile test 1) Alonix M309: Acrylic special monomer / oligomer, manufactured by Toa Gosei Co., Ltd. 2) Tinuvin 327: UV absorber, manufactured by Nippon Ciba Geigy Co., Ltd. 3) Irganox 1010: Antioxidant, manufactured by Nippon Ciba Geigy Co., Ltd. 4) ADK STAB LA62: Stabilizer, Asahi Denka Kogyo Co., Ltd. , Manufactured by Asahi Denka Kogyo Co., Ltd.

[0058]

[Table 4]

[0059]

[Table 5]

The various additives and physical properties with subscripts in the table are as follows. * 1: Neolite SP-T (manufactured by Takehara Chemical Industry Co., Ltd.) * 2: Whiten SB (manufactured by Shiraishi Calcium Industry Co., Ltd.) * 3: Polyoxypropylene triol Mw10000, Mw / Mn1.3 * 4: Polyoxy Propylene triol Mw10000, Mw / Mn1.3
* 5: 3- (2-aminoethyl) amino-propyltrimethoxysilane * 6: 3-glycidyloxypropyltrimethoxysilane * 7: Dibutyltin oxide / dioctyl phthalate reactant (Sanyo Kikai Co., Ltd. )) * 8: Dibutyltin bisacetylacetonate (manufactured by Nitto Kasei Kogyo Co., Ltd.) * 9: The cured portion from the surface was peeled off and the thickness was measured.

The cohesive failure rates of Examples 9 to 12 are higher than those of Comparative Examples, and it can be seen that the adhesiveness is improved. Further, Examples 13 to 18 show that the thickness of the cured product after curing for 6 hours is large and the curability is excellent, and that the breaking strength and the elongation at break are also excellent, and these physical properties are also excellent. It turns out that the balance is good. In addition, in Example 19, although the elongation at break is slightly inferior, it is excellent in 50% tensile stress and rupture strength, and further, is extremely excellent in curability, and it can be seen that the balance of these physical properties is good. Example 20
Is an example in which a plasticizer is not used, but has excellent 50% tensile stress and rupture strength, and also has remarkably excellent curability, indicating that these properties are well balanced.

(Example 21 and Comparative Example 11)
In accordance with A5758, an H-type tensile test sample was prepared using a polycarbonate board as an adherend. After curing under standard conditions for 14 days and further at 30 ° C. for 14 days, a tensile test was performed to measure the state of breakage with the substrate at the time of breakage. As the fracture state, cohesive failure (CF) is most preferred, followed by thin-layer cohesive failure (TFC), and interfacial fracture (AF) indicates that the adhesiveness is insufficient. No primer was applied to the adherend. Table 6 shows the results.

[0063]

[Table 6]

[0064]

The hydrolyzable silicon-group-containing organic polymer of the present invention has excellent curability, and can give a composition which can be cured by moisture at room temperature. Excellent adhesion. Further, the method for producing a hydrolyzable silicon group-containing organic polymer of the present invention is capable of producing a hydrolyzable silicon group-containing organic polymer using a raw material polyoxyalkylene polyol having a viscosity that is easy to handle. It is also easy to make the resulting hydrolyzable silicon-containing organic polymer very high in viscosity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 71/00 C08L 71/02 4J035 71/02 C09K 3/10 G C09K 3/10 C08K 5/54 (72 ) Inventor Mikio Yokota 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture F-term in Asahi Glass Co., Ltd. DE138 DE189 DE238 DH049 DJ008 DJ018 DJ038 DJ048 DL008 EE049 EF119 EG049 EN009 EV026 EV239 EW139 EX006 EX027 EX036 EX037 EX076 EX086 EX087 EZ049 FA043 FA048 FA103 FA108 FD013 FD018 FD140 FD159 A04 BD03 002A CA25 CA32 CB01 4J035 HA01 HB03 LA04 LB03

Claims (7)

[Claims] 1. An unsaturated group-containing organic polymer containing two or more unsaturated groups and having a polyoxyalkylene polymer chain having a weight average molecular weight / number average molecular weight ratio of 1.7 or less. By reacting (A) a compound containing two or more functional groups capable of addition reaction to an unsaturated group, and (B) a compound having a functional group capable of addition reaction to an unsaturated group and a compound having a hydrolyzable silicon group. A hydrolyzable silicon group-containing organic polymer, which is obtained. 2. A polymer derived from a polyoxyalkylene polymer obtained by ring-opening polymerization of a cyclic ether in the presence of an initiator using a double metal cyanide complex as a catalyst. The hydrolyzable silicon-group-containing organic polymer according to claim 1, which is a chain. 3. The hydrolyzable silicon group-containing organic polymer according to claim 1, wherein the viscosity of the hydrolyzable silicon group-containing organic polymer at 23 ° C. is 200 poise or more. 4. A curable composition comprising the hydrolyzable silicon-group-containing organic polymer according to claim 1, a filler and a curing accelerator. 5. An unsaturated group-containing organic polymer containing a polyoxyalkylene polymer chain having two or more unsaturated groups and having a weight average molecular weight / number average molecular weight ratio of 1.7 or less. (A) reacting a compound containing two or more functional groups capable of undergoing an addition reaction with an unsaturated group, and (B) reacting a compound having a functional group capable of undergoing an addition reaction with an unsaturated group and a compound having a hydrolyzable silicon group. A method for producing a hydrolyzable silicon group-containing organic polymer, which is characterized by the following. 6. A polymer derived from a polyoxyalkylene polymer obtained by subjecting a cyclic ether to ring-opening polymerization in the presence of an initiator using a double metal cyanide complex as a catalyst. The method for producing a hydrolyzable silicon group-containing organic polymer according to claim 5, which is a chain. 7. The method for producing a hydrolyzable silicon group-containing organic polymer according to claim 5, wherein the viscosity of the hydrolyzable silicon group-containing organic polymer at 23 ° C. is 200 poise or more.