JP2022143083A - Method for producing organic polymer, organic polymer, curable composition, and cured product - Google Patents

Abstract

To provide a hydrolyzable silyl group-containing organic polymer which achieves both good curability and high restorability, and a method for producing the same.SOLUTION: An organic polymer (A) having a structure of formula (1) and a structure of formula (2) in the same molecule is produced by: preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule; forming the structure of formula (2) by a hydrosilylation reaction of the carbon-carbon unsaturated bond with a hydrolyzable silyl group-containing hydrosilane compound; and forming the structure of formula (1) by a urethanization reaction of the hydroxyl group with a compound having a hydrolyzable silyl group and an isocyanate group. -O-CO-NH-(CR12)m-SiR2aX3-a (1). -O-(CR32)n-SiR4bY3-b (2).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a method for producing an organic polymer having a hydrolyzable silyl group, an organic polymer having a hydrolyzable silyl group, a curable composition containing the polymer, and a cured product thereof.

An organic polymer having a hydroxyl group or a hydrolyzable group on a silicon atom and having a silicon-containing group capable of forming a siloxane bond (hereinafter referred to as a "hydrolyzable silyl group") is known as a moisture-reactive polymer. It is contained in many industrial products such as adhesives, sealants, coating materials, paints, and adhesives, and is used in a wide range of fields. As such a hydrolyzable silyl group-containing organic polymer, various polymers having a main chain skeleton such as a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth)acrylic acid ester copolymer are known. It is

As a method for producing a hydrolyzable silyl group-containing organic polymer, for example, after synthesizing a polyoxyalkylene polymer having a terminal hydroxyl group by ring-opening polymerization of an epoxy compound, the hydroxyl group is converted into a carbon-carbon double bond. A method of introducing a hydrolyzable silyl group into a polymer by converting the carbon-carbon double bond and a silane compound into a hydrosilylation reaction is known (see, for example, Patent Document 1).

As another production method, a hydrolyzable silyl group is introduced via a urethane bond by reacting a hydrolyzable silyl group-containing isocyanate compound with the hydroxyl group of the polyoxyalkylene polymer. (See Patent Document 2, for example).

JP-A-52-73998 JP-A-10-245482

When a hydrolyzable silyl group-containing organic polymer is used as a sealant or the like, the cured product is often required to exhibit high restorability.
Organic tin compounds are known to be highly active as curing catalysts used to cure hydrolyzable silyl group-containing organic polymers. It is recommended to use a curing catalyst of Therefore, there is a demand for a hydrolyzable silyl group-containing organic polymer that can exhibit good curability even when using a non-tin catalyst with relatively low activity.
However, it has been difficult for conventionally known hydrolyzable silyl group-containing organic polymers to achieve both high restorability and good curability.

In view of the above situation, an object of the present invention is to provide a hydrolyzable silyl group-containing organic polymer that achieves both good curability and high restorability, and a method for producing the same.

As a result of intensive studies, the present inventors have produced an organic polymer having two specific types of structures in the same molecule as structures containing hydrolyzable silyl groups. The inventors have found that both good curability and high restorability can be achieved, and have completed the present invention.

That is, the present invention provides a method for producing an organic polymer (A) having a structure represented by the following formula (1) and a structure represented by the following formula (2) in the same molecule,
—O—CO—NH—(CR ¹ ₂ ) _m —SiR ² _a X _3-a (1)
—O—(CR ³ ₂ ) _n —SiR ⁴ _b Y _3-b (2)
(In formula (1), R ¹ is the same or different and represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. R ² is a substituted or unsubstituted represents a hydrocarbon group, X represents a hydroxyl group or a hydrolyzable group, a is 0, 1 or 2, and m is an integer of 1-5.
In formula (2), R ³ are the same or different and represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. R ⁴ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group. b is 0, 1 or 2; n is an integer from 1 to 10; )
a step of preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule; ), and a step of urethanizing a compound having a hydrolyzable silyl group and an isocyanate group to the hydroxyl group to form a structure represented by the formula (1), Containing, it relates to a method for producing an organic polymer (A).
Preferably, the step of preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule includes reacting an organic polymer having a hydroxyl group with a carbon-carbon unsaturated bond-containing halide to obtain the hydroxyl group. part of is converted to a carbon-carbon unsaturated bond-containing group.
Further, preferably, the step of preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule is a step of reacting a polymer having a hydroxyl group with an epoxy compound containing a carbon-carbon unsaturated bond. be.
Preferably, the organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule is an organic polymer having a structure represented by formula (4) described below.
The present invention also relates to an organic polymer (A') having a structure represented by formula (3) described later. In the formula (3), m is preferably 1. Preferably n is three. Preferably, the polymer backbone of the organic polymer is a polyoxyalkylene polymer.
Furthermore, the present invention also relates to a curable composition containing the organic polymer (A'). The curable composition may further contain an organic polymer (B) having one hydrolyzable silyl group per molecule. The curable composition may be free of organic tin compounds.
Furthermore, the present invention also relates to a cured product obtained by curing the curable composition.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a hydrolyzable silyl group-containing organic polymer having both good curability and high restorability, and a method for producing the same.

Embodiments of the present invention are described in detail below.
[Organic polymer (A)]
The production method according to this embodiment is a method for producing an organic polymer (A) having a hydrolyzable silyl group. The organic polymer (A) has a structure represented by the following formula (1) and a structure represented by the following formula (2) in the same molecule.
—O—CO—NH—(CR ¹ ₂ ) _m —SiR ² _a X _3-a (1)
—O—(CR ³ ₂ ) _n —SiR ⁴ _b Y _3-b (2)

In the structure represented by formula (1), the hydrolyzable silyl group (-SiR ² _a X _3-a ) is bonded to the polymer skeleton through a urethane bond, and in the structure represented by formula (2), A hydrolyzable silyl group (-SiR ⁴ _b Y _3-b ) is attached to the polymer backbone through an oxygen atom. The organic polymer (A) has a different structure in the same molecule as a linking group in which the hydrolyzable silyl group is attached to the polymer skeleton. It is possible to achieve both excellent curability. The organic polymer (A) having the structure of formula (1) and the structure of formula (2) in the same molecule is an organic polymer having a structure of formula (1) and an organic polymer having a structure of formula (2). It can exhibit higher resilience than a mixture with coalescence.

In formula (1), R ¹ are the same or different and represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. R ² represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a is 0, 1 or 2; m is an integer from 1 to 5;

In formula (2), R ³ are the same or different and represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. R ⁴ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group. b is 0, 1 or 2; n is an integer from 1 to 10;

R ¹ and R ³ each represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as chloro, alkoxy groups such as methoxy, and amino groups such as N,N-diethylamino. . Each of R ¹ and R ³ is particularly preferably a hydrogen atom. R ¹ and R ³ may be the same or different. Moreover, a plurality of R ¹ may be the same or different. A plurality of R ³ may also be the same or different.

R ² and R ⁴ each represent a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as chloro, alkoxy groups such as methoxy, and amino groups such as N,N-diethylamino. . R ² and R ⁴ may be the same or different. Moreover, when there are multiple R ² s, they may be the same or different. When there are multiple ^R4 's, they may be the same or different.

Specific examples of R ² and R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, 2-ethylhexyl group, n-dodecyl group and the like. unsubstituted alkyl group; chloromethyl group, methoxymethyl group, substituted alkyl group such as N,N-diethylaminomethyl group; vinyl group, isopropenyl group, unsaturated hydrocarbon group such as allyl group; cyclo such as cyclohexyl group Alkyl group; Aryl group such as phenyl group, toluyl group and 1-naphthyl group; Aralkyl group such as benzyl group, and the like. Preferred are substituted or unsubstituted alkyl groups, more preferred are methyl groups, ethyl groups, chloromethyl groups and methoxymethyl groups, still more preferred are methyl groups and methoxymethyl groups, and particularly preferred are methyl groups. is the base.

X and Y each represent a hydroxyl group or a hydrolyzable group. Examples of X and Y include hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group and alkenyloxy group. The above alkoxy group and the like may have a substituent. An alkoxy group is preferred because it is moderately hydrolyzable and easy to handle, methoxy, ethoxy, n-propoxy and isopropoxy are more preferred, methoxy and ethoxy are still more preferred, and methoxy is particularly preferred. X and Y may be the same or different. Moreover, when multiple Xs exist, they may be the same or different. When there are multiple Y's, they may be the same or different.

a in formula (1) and b in formula (2) each represent 0, 1, or 2; Preferably 0 or 1. In particular, it is preferable that a is 1 and b is 0 from the viewpoint of curability, storage stability and restorability.

m in the formula (1) represents an integer of 1-5. An integer from 1 to 3 is preferred, with 1 or 3 being more preferred. From the viewpoint of curability, m is most preferably 1.

n in the formula (2) represents an integer of 1-10. An integer of 1 to 5 is preferred, an integer of 1 to 3 is more preferred, and 2 or 3 is even more preferred. From a manufacturing point of view, n is most preferably 3.

The hydrolyzable silyl groups possessed by the organic polymer (A) are the groups represented by —SiR ² _a X _3-a in the formula (1) and —SiR ⁴ _b Y in the formula (2). It is a group represented by _3-b . Specific examples of the hydrolyzable silyl group include, for example, a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a methyldimethoxysilyl group, a methyldiethoxysilyl group, Dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group , (N,N-diethylaminomethyl)diethoxysilyl group and the like. Only one type of hydrolyzable silyl group may be used, or two or more types may coexist.

The ratio of the structure of formula (1) to the structure of formula (2) contained in the organic polymer (A) can be appropriately set by those skilled in the art, and the curability and restorability can be adjusted by changing the ratio. can. Although the ratio is not particularly limited, the molar ratio is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30.

The production method according to this embodiment includes at least the following steps (I) to (III).
Step (I): Step of preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule Step (II): A hydrosilyl group-containing hydrosilane compound is added to the carbon-carbon unsaturated bond Forming a structure represented by the formula (2) by chemical reaction Step (III): The hydroxyl group is subjected to a urethanization reaction with a compound containing a hydrolyzable silyl group and an isocyanate group to form the formula ( 1) The step of forming the structure represented by

The order of performing steps (I) to (III) is preferably in the order of step (I), step (II), and step (III), but step (I), step (III), step (II) ) may be used. Each step will be described below.

[Step (I)]
Step (I) is a step of preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule. Although the method for obtaining the polymer is not particularly limited, it is preferable to obtain an organic polymer (F) having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule from an organic polymer (E) having a hydroxyl group.

(Hydroxyl group-containing organic polymer (E))
Organic polymers have a polymer backbone composed of multiple repeating units. The polymer backbone of the organic polymer may be linear or branched. The position at which the hydroxyl group is bonded to the polymer skeleton is not particularly limited, but it is preferably the terminal of the polymer skeleton.

The polymer skeleton of the organic polymer is not particularly limited, and various polymer skeletons can be used. Specific examples of polymer backbones include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers. ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, etc., copolymers of polychloroprene, polyisoprene, isoprene or butadiene with acrylonitrile and/or styrene, etc. Saturated hydrocarbon polymers such as coalescence, polybutadiene, isoprene or copolymers of butadiene with acrylonitrile and styrene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; Coalescence; (meth)acrylic acid ester-based polymers obtained by radical polymerization of (meth)acrylic acid ester-based monomers such as ethyl (meth)acrylate and butyl (meth)acrylate, as well as (meth)acrylic acid-based monomers and acetic acid Vinyl polymers such as polymers obtained by radical polymerization of monomers such as vinyl, acrylonitrile, and styrene; graft polymers obtained by polymerizing vinyl monomers in the above polymers; polysulfide polymers; polyamides type polymer; polycarbonate type polymer; diallyl phthalate type polymer; and other organic polymers. Each of the above polymers may be mixed in block form, graft form, or the like. Among these, saturated hydrocarbon-based polymers, polyoxyalkylene-based polymers, and (meth)acrylic acid ester-based polymers have relatively low glass transition temperatures, and the obtained cured products have excellent cold resistance. are preferred, polyoxyalkylene-based polymers are more preferred, and polyoxypropylene is particularly preferred.

The organic polymer may be a polymer having one type of polymer skeleton, or a mixture of two or more types of polymers having different polymer skeletons. The mixture may be a mixture of polymers produced separately, or a mixture produced at the same time so as to have an arbitrary composition.

The number average molecular weight of the organic polymer is not particularly limited. ,000 to 30,000. When the number average molecular weight is 3,000 or more, the relative amount of hydrolyzable silyl groups with respect to the whole polymer is within an appropriate range, which is desirable in terms of production cost. Moreover, when the number average molecular weight is 100,000 or less, it is easy to achieve a desired viscosity from the viewpoint of workability. The number average molecular weight can be determined in terms of polystyrene by GPC measurement.

Although the molecular weight distribution (Mw/Mn) of the organic polymer is not particularly limited, it is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, still more preferably 1.5 or less, and particularly preferably 1.4 or less. Moreover, from the viewpoint of improving mechanical properties such as durability and elongation of the cured product, it is preferably 1.2 or less. The molecular weight distribution (Mw/Mn) can be calculated from the number-average molecular weight and the weight-average molecular weight obtained in terms of polystyrene by GPC measurement.

Next, a method for producing the hydroxyl-containing organic polymer (E) will be described.
(Polyoxyalkylene polymer)
When the polymer skeleton of the hydroxyl group-containing organic polymer (E) is a polyoxyalkylene polymer, the polymer can be produced by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method. . As a result, a hydroxyl-terminated polyoxyalkylene polymer is obtained. Although the specific polymerization method is not particularly limited, a polymerization method using a double metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is preferable because a polymer with a small molecular weight distribution (Mw/Mn) can be obtained. .

Examples of hydroxyl-containing initiators include, but are not limited to, ethylene glycol, propylene glycol, glycerin, pentaerythritol, low-molecular-weight polyoxypropylene glycol, low-molecular-weight polyoxypropylene triol, allyl alcohol, and low-molecular-weight polyoxypropylene. Organic compounds having one or more hydroxyl groups, such as monoallyl ethers and low-molecular-weight polyoxypropylene monoalkyl ethers, can be mentioned.

Although the epoxy compound is not particularly limited, examples thereof include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether. Propylene oxide is preferred.

((Meth)acrylic acid ester polymer)
When the polymer skeleton of the hydroxyl group-containing organic polymer (E) is a (meth)acrylic acid ester-based polymer, the method for producing the hydroxyl group-containing organic polymer includes (I) combining a polymerizable unsaturated group and a hydroxyl group. A compound having (e.g., 2-hydroxyethyl acrylate) is copolymerized with a monomer having a (meth)acrylic structure to obtain a polymer, (II) by a living radical polymerization method such as atom transfer radical polymerization (meth) Examples include a method of polymerizing a monomer having an acrylic structure to obtain a polymer, and then introducing a hydroxyl group at any position (preferably at the molecular chain end) in the resulting polymer.

(Saturated hydrocarbon polymer)
When the polymer skeleton of the hydroxyl group-containing organic polymer (E) is a saturated hydrocarbon polymer, the method for producing the hydroxyl group-containing organic polymer includes ethylene, propylene, 1-butene, isobutylene, and the like. After obtaining a polymer by polymerizing an olefinic compound having 2 to 6 carbon atoms as a main monomer, a method of introducing a hydroxyl group at any position (preferably at the molecular chain terminal) of the obtained polymer, and the like. be done.

[Step (Ia)]
According to one aspect of the present embodiment, step (I) includes reacting an organic polymer (E) having a hydroxyl group with a halide containing a carbon-carbon unsaturated bond to convert part of the hydroxyl groups to a carbon-carbon unsaturated bond. It can be a step of obtaining an organic polymer (F) having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule by converting to a saturated bond-containing group. The step (I) according to this aspect is hereinafter also referred to as step (Ia).

(Reaction with alkali metal salt)
In converting a part of the hydroxyl groups of the organic polymer to carbon-carbon unsaturated bond-containing groups, first, the hydroxyl group-containing organic polymer (E) is reacted with an alkali metal salt to convert the hydroxyl groups of the organic polymer into It is preferable to convert part of the hydroxyl groups to metaloxy groups. A double metal cyanide complex catalyst can also be used instead of the alkali metal salt. A metaloxy group-containing organic polymer is formed in the above manner.

Examples of the alkali metal salt include, but are not limited to, sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. Sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred from the viewpoint of ease of handling and solubility, and sodium methoxide and sodium tert. -butoxide is more preferred. From the standpoint of availability, sodium methoxide is particularly preferred, and from the standpoint of reactivity, sodium tert-butoxide is particularly preferred. The alkali metal salt may be dissolved in a solvent before being subjected to the reaction.

The amount of the alkali metal salt to be used is not particularly limited. 9 or less is more preferable, 0.8 or less is still more preferable, and 0.7 or less is particularly preferable. The molar ratio is preferably 0.1 or more, more preferably 0.2 or more, and particularly preferably 0.3 or more.

In order to efficiently proceed with the reaction of converting the hydroxyl groups of the organic polymer (E) into metaloxy groups, it is recommended to remove moisture and substances having hydroxyl groups other than the organic polymer from the reaction system in advance. preferable. For removal, known methods may be used, such as heat evaporation, vacuum devolatilization, spray vaporization, thin film evaporation, azeotropic devolatilization, and the like.

The temperature at which the alkali metal salt is allowed to act can be appropriately set by those skilled in the art. The time for which the alkali metal salt is allowed to act is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.

(Reaction with carbon-carbon unsaturated bond-containing halide (G1))
By reacting the metaloxy group-containing organic polymer with a carbon-carbon unsaturated bond-containing halide (G1), the metaloxy group of the organic polymer is converted to a carbon-carbon unsaturated bond-containing group. be able to. The halide (G1) reacts with the metaloxy group through a halogen substitution reaction to form an ether bond. As a result, an organic polymer (F) having hydroxyl groups and carbon-carbon unsaturated bonds in the same molecule can be formed.

The carbon-carbon unsaturated bond-containing halide (G1) can be represented by the following formula (5).
Z-(CR ³ ₂ ) _n-2 -C(R ³ )=CR ³ ₂ (5)
In formula (5), R ³ is the same as R ³ described above for formula (2). n is an integer from 2 to 10; Z represents a halogen atom. In the step (II), a hydrolyzable silyl group is introduced into the organic polymer (F) having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule obtained by reacting the halide (G1). When done, structures represented by formula (2) above can be formed.

Specific examples of the carbon-carbon unsaturated bond-containing halide (G1) are not particularly limited, but vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, iodide allyl, methallyl iodide, and the like. Allyl chloride and methallyl chloride are preferred for ease of handling.

The amount of the carbon-carbon unsaturated bond-containing halide (G1) to be added is not particularly limited, but the molar ratio of the organic halide (G1) to the metaloxy groups possessed by the organic polymer should be 0.7 or more. is preferred, and 1.0 or more is more preferred. Moreover, the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.

The temperature at which the metaloxy group-containing organic polymer is reacted with the carbon-carbon unsaturated bond-containing halide (G1) is preferably 50° C. or higher and 150° C. or lower, more preferably 110° C. or higher and 140° C. or lower. preferable. The reaction time is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.

[Step (Ib)]
According to another aspect of the present embodiment, the step (I) comprises reacting an organic polymer (E) having a hydroxyl group with an epoxy compound containing a carbon-carbon unsaturated bond to obtain a hydroxyl group and a carbon-carbon unsaturated bond. in the same molecule to obtain an organic polymer (F). The step (I) according to this alternative aspect is hereinafter also referred to as step (Ib).

(Reaction with alkali metal salt)
In reacting the hydroxyl-containing organic polymer (E) with the carbon-carbon unsaturated bond-containing epoxy compound, first, the hydroxyl-containing organic polymer (E) is reacted with an alkali metal salt to give the organic polymer It is preferable to convert the hydroxyl group possessed to a metaloxy group. A double metal cyanide complex catalyst can also be used instead of the alkali metal salt. A metaloxy group-containing organic polymer is formed in the above manner. The details are the same as those described in detail for step (Ia), except for the amount of alkali metal salt used, which will be described below.

Since it is not necessary to leave some of the hydroxyl groups unreacted in step (Ib), the amount of the alkali metal salt used is not particularly limited, but the molar ratio to the hydroxyl groups of the organic polymer (E) is 0.5. 0.6 or more is more preferable, 0.7 or more is still more preferable, and 0.8 or more is even more preferable. The molar ratio is preferably 1.2 or less, more preferably 1.1 or less.

(Reaction with carbon-carbon unsaturated bond-containing epoxy compound (G2))
When the carbon-carbon unsaturated bond-containing epoxy compound (G2) is allowed to act on the metaloxy group-containing organic polymer, the carbon-carbon unsaturated bond-containing epoxy compound (G2) is converted by the ring-opening addition reaction of the epoxy group. It can react with a metaloxy group to form an ether bond and introduce a structure containing a carbon-carbon unsaturated bond and a hydroxyl group into the organic polymer. As a result, an organic polymer (F) having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule is obtained. In the ring-opening addition reaction, by adjusting the amount of the carbon-carbon unsaturated bond-containing epoxy compound (G2) used for the metaloxy group and the reaction conditions, one or more of the epoxy compound (G2) can be added.

The carbon-carbon unsaturated bond-containing epoxy compound (G2) can be represented by the following formula (6).

In formula (6), R ³ is the same as R ³ described above for formula (2). R ⁵ represents a direct bond or a divalent linking group having 1 to 6 carbon atoms. n is an integer from 2 to 10;

R ⁵ may be a divalent organic group having 1 to 6 carbon atoms. The organic group is preferably a hydrocarbon group. The number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 to 2. ^R5 is preferably a direct bond or a methylene group, most preferably a methylene group.

Specific examples of the carbon-carbon unsaturated bond-containing epoxy compound (G2) include, but are not limited to, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, and 1,4-cyclopentadiene monoepoxide. is preferred from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferred.

The amount of the carbon-carbon unsaturated bond-containing epoxy compound (G2) to be added can be any amount in consideration of the introduction amount and reactivity of the carbon-carbon unsaturated bond to the polymer. In particular, the molar ratio of the epoxy compound (G2) to the hydroxyl groups of the organic polymer (E) is preferably 0.2 or more, more preferably 0.5 or more. Moreover, the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.

The temperature at which the carbon-carbon unsaturated bond-containing epoxy compound (G2) is reacted with the metaloxy group-containing organic polymer is preferably 60° C. or higher and 150° C. or lower, more preferably 110° C. or higher and 140° C. or lower. preferable. The reaction time is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.

As described above, when the carbon-carbon unsaturated bond-containing epoxy compound (G2) is allowed to act on the metaloxy group-containing organic polymer, a new metaloxy group is generated by ring opening of the epoxy group. By reacting the metaloxy group with a protic solvent, the metaloxy group is converted to a hydroxyl group, forming an organic polymer (F) having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule. Examples of the protic solvent include, but are not limited to, alcohols such as methanol and ethanol; carboxylic acids such as formic acid and acetic acid; nitromethane and water. Methanol, ethanol, and water are particularly preferred because of ease of handling.

The reaction with the alkali metal salt and the reaction with the epoxy compound (G2) may be repeated multiple times in order to increase the rate of introduction of carbon-carbon unsaturated bonds into the organic polymer. When these reactions are repeated multiple times, the reactants (alkali metal salt or epoxy compound (G2)) used in each step may be the same or different.

In step (Ib), by using the carbon-carbon unsaturated bond-containing epoxy compound (G2) represented by the formula (6), an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule As (F), an organic polymer having a structure represented by the following formula (4) can be obtained.

In formula (4), R ³ and R ⁵ are the same as the groups described above for formula (6). d is an integer from 1 to 10; n is an integer from 2 to 10;

[Step (II)]
In step (II), the carbon-carbon unsaturated bond of the organic polymer is subjected to a hydrosilylation reaction with a hydrosilane compound containing a hydrolyzable silyl group to form a structure represented by the formula (2) in the organic polymer. It is a process of introducing Step (II) is preferably carried out after step (I). In this case, step (II) is carried out on the organic polymer (F) having hydroxyl groups and carbon-carbon unsaturated bonds in the same molecule obtained in step (I). As a result, an organic polymer having a hydroxyl group and a hydrolyzable silyl group (the structure of formula (2) above) in the same molecule is obtained.

Specific examples of the hydrosilane compounds containing hydrolyzable silyl groups include trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, Halosilanes such as (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, Methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl) ) dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane, (3,3,3-trifluoropropyl)dimethoxysilane, (N,N-diethylaminomethyl) Dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethyl Alkoxysilanes such as silane, [(methoxymethyl)diemethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-trifluoropropyl)dimethoxysilyloxy]dimethylsilane, etc. ; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; Examples include isopropenyloxysilanes (deacetone type) such as methyl)diisopropenyloxysilane and (methoxymethyl)diisopropenyloxysilane.

The amount of the hydrosilane compound containing a hydrolyzable silyl group to be used may be appropriately set in consideration of the amount of carbon-carbon unsaturated bonds possessed by the organic polymer and the desired number of hydrolyzable silyl groups to be introduced.

The hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst in order to promote the reaction. As the hydrosilylation catalyst, metals such as cobalt, nickel, iridium, platinum, palladium, rhodium and ruthenium, and complexes thereof can be used. Specifically, platinum supported on a carrier such as alumina, silica, carbon black; chloroplatinic acid; chloroplatinic acid complexes composed of chloroplatinic acid and alcohols, aldehydes, ketones, etc.; Pt( _CH2 = _CH2 ) ₂ (PPh3), Pt( _{CH2 = CH2} ) _2Cl2 ]; platinum _- vinylsiloxane complexes [e.g. Pt {(vinyl) _{Me2SiOSiMe2 (} vinyl)}, Pt{ Me(vinyl)SiO} ₄ ]; platinum-phosphine complexes [eg Ph(PPh ₃ ) ₄ , Pt(PBu ₃ ) ₄ ]; platinum-phosphite complexes [eg Pt{P(OPh) ₃ } ₄ ]; be done. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum-vinylsiloxane complexes are preferred.

The hydrosilylation reaction can be carried out without using a solvent, but for the purpose of uniformly dissolving the organic polymer, hydrosilane compound, and hydrosilylation catalyst, temperature control of the reaction system, hydrosilylation catalyst In order to easily realize the addition of, it may be carried out by adding an organic solvent.

The temperature during the hydrosilylation reaction is not particularly limited and can be appropriately set by those skilled in the art. However, for the purpose of reducing the viscosity of the reaction system and improving the reactivity, heating conditions are preferred, specifically 50° C. to 150° C. °C, more preferably 70°C to 120°C. The reaction time may also be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that an unintended condensation reaction between polymers does not proceed. Specifically, the reaction time is preferably 30 minutes or more and 5 hours or less, more preferably 3 hours or less.

[Step (III)]
In the step (III), a compound having a hydrolyzable silyl group and an isocyanate group (hereinafter, also referred to as a silyl group-containing isocyanate compound) is subjected to a urethanization reaction on the hydroxyl group of the organic polymer to convert the organic polymer into the above This is the step of introducing the structure represented by formula (1). Step (III) is preferably carried out after step (II). In this case, step (III) is carried out on the organic polymer having hydroxyl groups and hydrolyzable silyl groups in the same molecule obtained in step (II). An organic polymer (A) is thus obtained.

The silyl group-containing isocyanate compound is a compound having an isocyanate group capable of undergoing a urethanization reaction with a hydroxyl group of an organic polymer and a hydrolyzable silyl group in the same molecule. The silyl group-containing isocyanate compound can be represented by the following formula (7).
OCN-(CR ¹ ₂ ) _m -SiR ² _a X _3-a (7)
R ¹ , R ² , X, a, and m in formula (7) are the same as described above for formula (1).

Specific examples of the silyl group-containing isocyanate compounds include (3-isocyanatopropyl)trimethoxysilane, (3-isocyanatopropyl)dimethoxymethylsilane, (3-isocyanatopropyl)triethoxysilane, and (3-isocyanatopropyl). diethoxymethylsilane, (isocyanatomethyl)trimethoxysilane, (isocyanatomethyl)triethoxysilane, (isocyanatomethyl)dimethoxymethylsilane, (isocyanatomethyl)diethoxymethylsilane and the like. A silyl group-containing isocyanate compound may be used alone or in combination of two or more.

The amount of the silyl group-containing isocyanate compound to be used can be appropriately determined in consideration of the amount of hydroxyl groups possessed by the organic polymer and the desired amount of hydrolyzable silyl groups to be introduced, and is not particularly limited. , preferably 0.1 to 10 mol times, more preferably 0.3 to 5 mol times, still more preferably 0.5 to 3 mol times the hydroxyl groups of the organic polymer.

The structure represented by the formula (1) is added to the organic polymer by urethanizing the isocyanate group of the silyl group-containing isocyanate compound with the hydroxyl group of the organic polymer to form a urethane bond. can be introduced.

The urethanization reaction may be carried out without using a urethanization catalyst, but may be carried out in the presence of a urethanization catalyst for the purpose of improving the reaction rate or improving the reaction rate. Such urethanization catalysts include, for example, conventionally known urethanization catalysts listed in Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963. A catalyst can be used. Specific examples thereof include base catalysts such as organic tin compounds, bismuth compounds, and organic amines, but are not limited to these.

As the urethanization catalyst, an organic tin compound is preferable because of its high activity. Specifically, tin octoate, tin stearate, dibutyltin dioctoate, dibutyltin dioleyl maleate, dibutyltin dibutyl maleate, dibutyltin dilaurate, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl Distannoxane, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin bis(o-phenylphenoxide), dibutyltin oxide, dibutyltin bis(triethoxysilicate), dibutyltin distearate, dibutyltin bis(isononyl-3-mercaptopropionate) ), dibutyltin bis(isooctyl mercaptopropionate), dibutyltin bis(isooctylthioglycolate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin diversatate and the like. Furthermore, a urethanization catalyst with low activity to a hydrolyzable silyl group is preferred, and from this point of view, an organic tin compound containing a sulfur atom is preferred. Particularly preferred are dibutyltin bis(isooctyl mercaptopropionate) and dibutyltin bis(isooctylthioglycolate).

As the urethanization catalyst, an organic bismuth compound is preferable in terms of good activity and good storage stability of the hydrolyzable silyl group-containing organic polymer. Bismuth-containing catalysts are, for example, under the trade names Borchi(R) Kat 22, Borchi(R) Kat 24, Borchi(R) Kat 320, Borchi(R) Kat 315 EU, Borchi(R) Kat 315 EU from Borchers GmbH. Kat VP 0243, a catalyst having Borchi (R) Kat VP 0244, trade name manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Bismuth 2-ethylhexanoate (III) 2-ethylhexanoate solution (Bi: 25%), 2- Bismuth(III) ethylhexanoate, 70-75% in xylenes (~24% Bi) (99.99+%-Bi) PURATREM, etc., but not particularly limited as long as it promotes the urethanization reaction.

The amount of the urethanization catalyst to be added can be appropriately determined by those skilled in the art, but from the viewpoint of reaction activity, it is preferably 1 to 1000 ppm, more preferably 10 to 100 ppm, relative to 100 parts by weight of the organic polymer. Within this range, in addition to obtaining sufficient reaction activity, the physical properties of the produced hydrolyzable silyl group-containing organic polymer can be maintained satisfactorily.

The urethanization reaction can be carried out without using a solvent, but for the purpose of uniformly dissolving the organic polymer, the silyl group-containing isocyanate compound, and the urethanization catalyst, the temperature control of the reaction system, In order to easily realize the addition of the urethanization catalyst, an organic solvent may be added.

When an organic solvent is used, its type is not particularly limited and may be selected as appropriate. Hydrogen, aliphatic halogenated hydrocarbons such as dichloroethane and chloroform, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and isopropylbenzene, aromatic halogenated hydrocarbons such as chlorobenzene and chlorotoluene, tetrahydrofuran (THF ), ether solvents such as tetrahydropyran (THP), and the like. As the organic solvent, only one type may be used, or two or more types may be used in combination.

The temperature during the urethanization reaction can be appropriately set by those skilled in the art, but it is preferably 50° C. or higher and 120° C. or lower, more preferably 70° C. or higher and 100° C. or lower. The reaction time may also be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that an unintended condensation reaction between polymers does not proceed. Specifically, the reaction time is preferably from 15 minutes to 5 hours, more preferably from 30 minutes to 3 hours.

By carrying out the steps (I) to (III) described above, an organic polymer (A ) can be manufactured.

[Organic polymer (A')]
When step (Ib) is carried out as step (I) to obtain an organic polymer having a structure represented by the formula (4), then steps (II) and (III) are carried out to obtain An organic polymer (A') having a structure represented by the following formula (3) can be produced. The organic polymer (A') corresponds to the organic polymer (A), and is a novel polymer that has not been previously reported.

In formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X, Y, a, b, d, m, and n are the same as described above. The structure represented by the formula (3) includes both the structure represented by the formula (1) and the structure represented by the formula (2). Thus, in the organic polymer (A'), the positions at which the structure of the formula (1) and the structure of the formula (2) are introduced are controlled, and each end of the organic polymer (A') is It may have the structure of formula (1). Therefore, the organic polymer (A') can exhibit particularly good curability among the organic polymers (A).

The details of the polymer skeleton, the number average molecular weight, and the range of the molecular weight distribution of the organic polymer (A') are the same as those of the hydroxyl group-containing organic polymer (E), so descriptions thereof are omitted.

(Curable composition)
The organic polymer (A') has a hydrolyzable silyl group and can constitute a curable composition containing the polymer. In the curable composition, the organic polymer (A') may be used alone or in combination of two or more.

(Organic polymer (B))
The curable composition according to this embodiment may contain an organic polymer (B) having one hydrolyzable silyl group in one molecule together with the organic polymer (A'). By blending the organic polymer (B) having one hydrolyzable silyl group in one molecule, the modulus of the cured product obtained by curing the curable composition can be reduced, making it suitable for sealant applications. physical properties can be adjusted. Only 1 type may be used for an organic polymer (B), and it may use 2 or more types together. Moreover, the hydrolyzable silyl group possessed by the organic polymer (B) may be the same as or different from the hydrolyzable silyl group possessed by the organic polymer (A').

The organic polymer (B) may have a structure represented by the formula (1) described above for the organic polymer (A), or may have a structure represented by the formula (2). may be Moreover, a hydrolyzable silyl group may be included in a structure that does not correspond to either the structure of formula (1) or the structure of formula (2).

As the polymer skeleton of the organic polymer (B), the same polymer skeleton as that of the hydroxyl group-containing organic polymer (E) can be mentioned. Polyoxyalkylene polymers are preferred, and polyoxypropylene is particularly preferred. preferable.

When the polymer skeleton of the organic polymer (B) is a polyoxyalkylene-based polymer, such an organic polymer (B) is, for example, in the presence of an initiator having only one hydroxyl group in one molecule. It can be produced by polymerizing an epoxy compound and then conducting a one-step or two-step reaction to introduce a hydrolyzable silyl group. According to this method, a polyoxyalkylene polymer having a hydrolyzable silyl group at one end can be produced.

Regarding the number-average molecular weight or molecular weight distribution of the organic polymer (B), the description given above for the hydroxyl group-containing organic polymer (E) can be applied.

The blending ratio of the organic polymer (A′) and the organic polymer (B) is not particularly limited, but the weight ratio is preferably 99:1 to 50:50, more preferably 95:5 to 60:40. , 90:10 to 70:30 are more preferred.

(Curing catalyst)
The curable composition according to the present embodiment preferably contains a curing catalyst for the purpose of promoting the reaction of hydrolyzing and condensing the hydrolyzable silyl groups, that is, the curing reaction.

As the curing catalyst, conventionally known ones can be used. Specifically, organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids and the like can be used.

Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin oxide and silicate compounds. reaction product with dibutyltin oxide and phthalate ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate) phosphate), a reaction product of dioctyltin oxide and a silicate compound, and the like. Dioctyltin compounds are preferred due to recent heightened environmental concerns. However, since the organic polymer (A') can exhibit rapid curing, the curable composition according to the present embodiment does not contain an organic tin compound and is generally less active than an organic tin compound. A curing catalyst (in particular, an amine compound or the like) may be contained. Even if the curable composition according to the present embodiment contains an amine compound, it can exhibit good curability.

Specific examples of carboxylate metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate. As the carboxylic acid group, the following carboxylic acid and various metals can be combined.

Specific examples of amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine; pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1, Nitrogen-containing heterocyclic compounds such as 5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine and diphenylguanidine; biguanides such as phenylbiguanide; and ketimine compounds.

Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate), diisopropoxytitanium bis (ethylacetoacetate), aluminum tris (acetylacetonate), and diisopropoxyaluminum ethylacetoacetate. and zirconium compounds such as zirconium tetrakis (acetylacetonate).

As other curing catalysts, fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.

As the curing catalyst, two or more different catalysts may be used in combination. For example, the combined use of the amine compound and the carboxylic acid may provide the effect of improving the reactivity.

In addition, since the organic polymer (A') has a highly active hydrolyzable silyl group, it is possible to reduce the amount of the curing catalyst, use a less active curing catalyst, or use an amino group-containing silane coupling agent. Aminosilanes can also be used as curing catalysts. Since aminosilane is usually added as an adhesion imparting agent in many cases, when aminosilane is used as a curing catalyst, a curable composition that does not use a commonly used curing catalyst can be produced. Therefore, it is preferable not to add other curing catalysts. In particular, when m in the structure represented by the formula (1) is 1, or when the hydrolyzable silyl group contains a trimethoxysilyl group or a methoxymethyldimethoxysilyl group, only aminosilane is used as a curing catalyst. Shows excellent curability even when used.

Specific examples of the aminosilane include 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-(2-(2-aminoethyl)aminoethyl)aminopropyltrimethoxysilane, γ-(6-aminohexyl) aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane , N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyl Amino group-containing silanes such as trimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine; N-(1,3-dimethylbutyl and ketimine-type silanes such as liden)-3-(triethoxysilyl)-1-propanamine. Only one type of aminosilane may be used, or two or more types may be used in combination.

The amount of the curing catalyst is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and 0.01 to 10 parts by weight with respect to 100 parts by weight of the organic polymer (A'). is particularly preferred. If the amount of the curing catalyst is less than 0.001 part by weight, the reaction rate may be insufficient. On the other hand, when the amount of the curing catalyst exceeds 20 parts by weight, the reaction rate is too fast, and the usable time of the composition is shortened, resulting in poor workability and poor storage stability. Furthermore, some curing catalysts may exude to the surface of the cured product or contaminate the surface of the cured product after the curable composition is cured. In such a case, by setting the amount of the curing catalyst to 0.01 to 3.0 parts by weight, it is possible to maintain good surface conditions of the cured product while ensuring curability.

The curable composition according to the present embodiment contains other additives such as a silicon compound, an adhesion imparting agent, a plasticizer, a solvent, a diluent, a silicate, a filler, an anti-sagging agent, an antioxidant, and a light stabilizer. , UV absorbers, physical property modifiers, tackifier resins, compounds containing epoxy groups, photo-curing substances, oxygen-curing substances, surface property modifiers, epoxy resins, other resins, flame retardants, foaming agents. can be In addition, various additives may be added to the curable composition according to the present embodiment as necessary for the purpose of adjusting various physical properties of the composition or cured product. Examples of such additives include curability modifiers, radical inhibitors, metal deactivators, antiozonants, phosphorus peroxide decomposers, lubricants, pigments, antifungal agents, and the like. be done.

(filler)
Various fillers can be added to the curable composition according to the present embodiment. Fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, active zinc white, PVC powder, PMMA powder, glass fiber and filament, and the like.

The amount of filler used is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, per 100 parts by weight of the organic polymer (A').

Organic balloons and inorganic balloons may be added for the purpose of weight reduction (lower specific gravity) of the composition. The balloon is hollow inside with a spherical filler, and is made of inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran. materials.

The amount of the balloon used is preferably 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the organic polymer (A').

(Adhesion imparting agent)
An adhesion imparting agent can be added to the curable composition according to the present embodiment. A silane coupling agent or a reactant of the silane coupling agent can be added as the adhesion imparting agent.
Specific examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ- Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane; isocyanate group-containing silanes such as ethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, α-isocyanatomethyldimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; . The adhesiveness-imparting agent may be used alone or in combination of two or more.

The amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the organic polymer (A').

(Plasticizer)
A plasticizer can be added to the curable composition according to the present embodiment. Specific examples of plasticizers include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), phthalate compounds such as butylbenzyl phthalate; bis(2-ethylhexyl )-terephthalate compounds such as 1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, Aliphatic polyvalent carboxylic acid ester compounds such as tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; phenyl alkylsulfonic acid esters; phosphoric acid ester compounds; trimellitic acid ester compounds; Paraffin; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate;

Also, polymeric plasticizers can be used. Specific examples of polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more; polyethers such as derivatives converted to polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like. A plasticizer may be used individually and may use 2 or more types together.

The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight, based on 100 parts by weight of the organic polymer (A').

(solvent, diluent)
A solvent or diluent can be added to the curable composition according to the present embodiment. Solvents and diluents that can be used include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers. When a solvent or diluent is used, the boiling point of the solvent is preferably 150° C. or higher, more preferably 200° C. or higher, and particularly preferably 250° C. or higher, because of the problem of air pollution when the composition is used indoors. . The above solvents or diluents may be used alone or in combination of two or more.

(anti-sagging agent)
An anti-sagging agent may be added to the curable composition according to the present embodiment to prevent sagging and improve workability, if necessary. The anti-sagging agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.
The amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of the organic polymer (A').

(Antioxidant)
An antioxidant (antiaging agent) can be used in the curable composition according to the present embodiment. The use of an antioxidant can enhance the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.
The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the organic polymer (A').

(light stabilizer)
A light stabilizer can be used in the curable composition according to the present embodiment. The use of a light stabilizer can prevent photo-oxidative deterioration of the cured product. Benzotriazole-based, hindered amine-based, and benzoate-based compounds can be exemplified as light stabilizers, and hindered amine-based compounds are particularly preferred.
The amount of light stabilizer used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the organic polymer (A').

(Ultraviolet absorber)
A UV absorber can be used in the curable composition according to the present embodiment. The use of an ultraviolet absorber can enhance the surface weather resistance of the cured product. Benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based and metal chelate-based compounds can be exemplified as UV absorbers, and benzotriazole-based compounds are particularly preferred, and commercially available names are Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571, Tinuvin 1600, Tinuvin B75 (manufactured by BASF).
The amount of the ultraviolet absorbent used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the organic polymer (A').

(Physical property modifier)
A physical property modifier for adjusting the tensile properties of the resulting cured product may be added to the curable composition according to the present embodiment, if necessary. Although the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane. arylalkoxysilanes such as; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as silyl)borate; silicone varnishes; polysiloxanes; By using the physical property modifier, the hardness of the cured curable composition according to the present embodiment can be increased, or conversely, the hardness can be decreased to increase elongation at break. The physical property modifiers may be used alone or in combination of two or more.

In particular, a compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis has the effect of lowering the modulus of the cured product without worsening the stickiness of the surface of the cured product. Compounds that generate trimethylsilanol are particularly preferred. Examples of compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, which are hydrolyzed into silane monovalent groups. Mention may be made of silicon compounds that produce ols.

The amount of the physical property modifier used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the organic polymer (A').

(tackifying resin)
A tackifying resin can be added to the curable composition according to the present embodiment for the purpose of enhancing the adhesiveness or adhesion to a substrate, or for other purposes. As the tackifying resin, there is no particular limitation, and those commonly used can be used.

Specific examples include terpene-based resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin-based Resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and hydrogenated products thereof, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, and the like. These may be used alone or in combination of two or more.

The amount of the tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the organic polymer (A'). More preferred.

(Compound containing an epoxy group)
A compound containing an epoxy group can be used in the curable composition according to the present embodiment. The use of a compound having an epoxy group can enhance the restorability of the cured product. Examples of compounds having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl stearate, epoxy butyl stearate and the like. The epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of the organic polymer (A').

(Photocurable substance)
A photocurable substance can be used in the curable composition according to the present embodiment. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. Many compounds such as organic monomers, oligomers, resins, or compositions containing them are known as this type of compound. Unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, etc., which are monomers, oligomers, or mixtures thereof can be used.

The amount of the photocurable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the organic polymer (A').

(oxygen-curable substance)
An oxygen-curable substance can be used in the curable composition according to this embodiment. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, and react with oxygen in the air to form a hardened film near the surface of the cured product, which causes the surface to become sticky and dust on the surface of the cured product. and prevent the adhesion of dust. Specific examples of oxygen-curable substances include drying oils such as paulownia oil and linseed oil, various alkyd resins obtained by modifying these compounds; acrylic polymers modified with drying oils, and epoxy resins. , silicone resins; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc. Examples include liquid polymers. These may be used alone or in combination of two or more.

The amount of the oxygen-curable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the organic polymer (A'). As described in JP-A-3-160053, oxygen-curable substances are preferably used in combination with photo-curable substances.

(Epoxy resin)
An epoxy resin can be used in combination with the curable composition according to the present embodiment. A composition containing an epoxy resin is particularly preferred as an adhesive, especially an adhesive for exterior wall tiles. Examples of epoxy resins include bisphenol A type epoxy resins and novolac type epoxy resins.

The weight ratio of the epoxy resin to the organic polymer (A') is preferably in the range of organic polymer (A')/epoxy resin=100/1 to 1/100. If the ratio of the organic polymer (A')/epoxy resin is less than 1/100, it becomes difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin, and the organic polymer (A')/epoxy resin exceeds 100/1, the strength of the cured polymer becomes insufficient.

When an epoxy resin is added, a curing agent for curing the epoxy resin can be used in combination with the curable composition according to the present embodiment. The epoxy resin curing agent that can be used is not particularly limited, and generally used epoxy resin curing agents can be used.

When an epoxy resin curing agent is used, the amount used is preferably in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

<<Preparation of curable composition>>
The curable composition according to the present embodiment can be prepared as a one-component type in which all the ingredients are preformed and sealed and cured by moisture in the air after application, and a curing catalyst is separately added as a curing agent. , a filler, a plasticizer, water, etc., and mixed with the organic polymer composition before use. From the viewpoint of workability, the one-component type is preferred.

When the curable composition is a one-component type, since all the ingredients are pre-blended, the ingredients containing water are preliminarily dehydrated and dried before use, or dehydrated by decompression or the like during blending and kneading. is preferred. In addition to the dehydration drying method, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane. Storage stability is further improved by adding an alkoxysilane compound such as silane.

<Application>
The curable composition according to the present embodiment includes adhesives, sealing materials for buildings, ships, automobiles, roads, etc., adhesives, waterproofing materials, coating film waterproofing materials, molding agents, vibration-proof materials, vibration-damping materials, Can be used as soundproofing material, foaming material, paint, spraying material. A cured product obtained by curing the curable composition according to the present embodiment is excellent in flexibility and adhesiveness, and thus can be suitably used as a sealant or an adhesive.

In addition, the curable composition according to the present embodiment can be used for electrical and electronic component materials such as solar cell backside sealing materials, electrical and electronic components such as insulating coating materials for electric wires and cables, electrical insulating materials for devices, and acoustic insulation. Materials, elastic adhesives, binders, contact adhesives, spray sealing materials, crack repairing materials, tiling adhesives, asphalt waterproofing adhesives, powder coatings, casting materials, medical rubber materials, medical Adhesives, medical adhesive sheets, sealing materials for medical equipment, dental impression materials, food packaging materials, joint sealing materials for exterior materials such as sizing boards, coating materials, anti-slip coating materials, cushioning materials, primers, electro-conductive materials for shielding electromagnetic waves Materials, thermally conductive materials, hot melt materials, potting agents for electric and electronic devices, films, gaskets, concrete reinforcing materials, adhesives for temporary fixing, various molding materials, and protection of wire glass and laminated glass edge faces (cut parts) Various applications such as sealing materials for rust and waterproofing, automotive parts, large vehicle parts such as trucks and buses, parts for train cars, aircraft parts, marine parts, electrical parts, and liquid sealants used in various machine parts. available for Taking automobiles as an example, it can be used in a wide variety of ways, such as adhesive attachment of plastic covers, trims, flanges, bumpers, windows, interior members, and exterior parts. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings, etc. alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. . Further, the curable composition according to the present embodiment is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiling, an adhesive for stone, a ceiling finishing adhesive, a floor finishing adhesive, a wall Finishing adhesives, vehicle panel adhesives, electrical, electronic and precision equipment assembly adhesives, adhesives for bonding leather, textiles, fabrics, paper, boards and rubber, reactive post-crosslinking pressure sensitive adhesives , a sealing material for direct glazing, a sealing material for double glazing, a sealing material for the SSG construction method, a sealing material for working joints of buildings, a material for civil engineering, and a bridge material. Furthermore, it can be used as an adhesive material such as an adhesive tape and an adhesive sheet.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
The number average molecular weight in the examples is the GPC molecular weight measured under the following conditions.
Liquid delivery system: Tosoh HLC-8220GPC
Column: TSK-GEL H type manufactured by Tosoh Solvent: THF
Molecular weight: Polystyrene equivalent Measurement temperature: 40°C

(Synthesis example 1)
Polyoxypropylene triol having a number average molecular weight of about 4,500 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a branched polyoxypropylene having a terminal hydroxyl group and a number average molecular weight of 23,300. Oxypropylene (E-1) was obtained.
A 28% methanol solution of sodium methoxide was added in an amount of 0.60 mole equivalent to the hydroxyl group of the obtained polymer (E-1). After removing methanol by distillation under reduced pressure, allyl chloride was added in an amount of 0.69 molar equivalents relative to the hydroxyl groups of polymer (E-1), and the mixture was reacted at 130° C. for 1 hour, and then allyl chloride was distilled off. left. The obtained unpurified polyoxypropylene was dissolved in n-hexane, and aluminum silicate (Kyoward R700SEN-S manufactured by Kyowa Kagaku Co., Ltd.) was mixed and stirred to allow the metal salt in the polymer to be adsorbed onto the aluminum silicate. Thereafter, aluminum silicate was removed by filtration, and hexane was distilled off under reduced pressure from the resulting hexane solution. Thus, a polyoxypropylene (F-1) having a carbon-carbon unsaturated bond (allyl group) and a hydroxyl group was obtained.
Then, at 90° C., 50 ppm of a platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) and 0.87 parts by weight of trimethoxysilane are added to 100 parts by weight of the polymer (F-1). Then, the allyl group of the polymer (F-1) was subjected to a hydrosilylation reaction to form the structure represented by the formula (2). After reacting at 90° C. until the allyl groups were completely consumed, the volatile components were distilled off.
Subsequently, at 90° C., bismuth 2-ethylhexanoate (III) 2-ethylhexanoic acid solution (Bi: 25%) was added at 30 ppm with respect to 100 parts by weight of the polymer, and 0.5 ppm was added to the hydroxyl groups of the polymer. 95 molar equivalents of (isocyanatomethyl)dimethoxymethylsilane were added to carry out a urethanization reaction on the hydroxyl groups of the polymer to form the structure represented by the above formula (1).
As a result, a branched polyoxypropylene (A-1) having the structure represented by the formula (1) and the structure represented by the formula (2) in the same molecule was obtained.

(Synthesis example 2)
Polyoxypropylene glycol having a number average molecular weight of about 4,500 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene having a number average molecular weight of 27,900 and having hydroxyl groups at both ends. (E-2) was obtained.
A 28% methanol solution of sodium methoxide was added in an amount of 1.0 molar equivalent to the hydroxyl groups of the polymer (E-2). After removing methanol by distillation under reduced pressure at 140° C., allyl glycidyl ether was added in an amount of 1.5 molar equivalents relative to the hydroxyl groups of the polymer (E-2) and reacted at 140° C. for 2 hours. Thereafter, 3.0 molar equivalents of methanol was added to the hydroxyl groups of the polymer (E-2) at 80° C. to convert terminal sodium alkoxide groups to hydroxyl groups. The obtained unpurified polyoxypropylene was dissolved in n-hexane, and aluminum silicate (Kyoward R700SEN-S manufactured by Kyowa Kagaku Co., Ltd.) was mixed and stirred to allow the metal salt in the polymer to be adsorbed onto the aluminum silicate. Thereafter, aluminum silicate was removed by filtration, and hexane was distilled off under reduced pressure from the resulting hexane solution. As a result, polyoxypropylene (F-2) having a carbon-carbon unsaturated bond (allyl group) and a hydroxyl group in one end was obtained. The polymer (F-2) has a structure represented by the formula (4).
Then, at 65° C., 50 ppm of a platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) and 1.3 parts by weight of trimethoxysilane are added to 100 parts by weight of the polymer (F-2). Then, the allyl group of the polymer (F-2) was subjected to a hydrosilylation reaction to form the structure represented by the formula (2). After reacting at 85° C. until the trimethoxysilane was completely consumed, the volatile components were distilled off.
Subsequently, at 90° C., bismuth 2-ethylhexanoate (III) 2-ethylhexanoic acid solution (Bi: 25%) was added at 30 ppm with respect to 100 parts by weight of the polymer, and 0.5 ppm was added to the hydroxyl groups of the polymer. 95 molar equivalents of (isocyanatomethyl)dimethoxymethylsilane were added to carry out a urethanization reaction on the hydroxyl groups of the polymer to form the structure represented by the above formula (1).
As a result, polyoxypropylene (A-2) having the structure represented by the formula (1) and the structure represented by the formula (2) in the same molecule was obtained. The polymer (A-2) has a structure represented by the formula (3).

(Comparative Synthesis Example 1)
Polyoxypropylene glycol having a number average molecular weight of about 4,500 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene having a number average molecular weight of 15,000 and having hydroxyl groups at both ends. (E-3) was obtained.
Bismuth 2-ethylhexanoate (III) 2-ethylhexanoic acid solution (Bi: 25%) 30 ppm with respect to 100 parts by weight of polymer (E-3), and 0.95 mol with respect to hydroxyl groups possessed by the polymer An equivalent amount of (isocyanatomethyl)dimethoxymethylsilane was added to urethanize the hydroxyl groups of the polymer to form the structure represented by the formula (1).
As a result, polyoxypropylene (C-1) having a structure represented by the formula (1) was obtained.

(Comparative Synthesis Example 2)
A 28% methanol solution of sodium methoxide was added in an amount of 1.1 molar equivalents relative to the hydroxyl groups of the polymer (E-1) obtained in Synthesis Example 1. After removing methanol by distillation under reduced pressure, allyl chloride is added in an amount of 1.5 molar equivalents relative to the hydroxyl groups of the polymer (E-1) and reacted at 130° C. for 1.5 hours, followed by allyl chloride. was distilled off. The obtained unpurified allyl-terminated polyoxypropylene was mixed with n-hexane and water and stirred, and the water was removed by centrifugation. removed. As a result, polyoxypropylene (F-3) having carbon-carbon unsaturated bonds (allyl groups) at the ends was obtained.
Then, at 90° C., 50 ppm of a platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) and 1.35 parts by weight of trimethoxysilane are added to 100 parts by weight of the polymer (F-3). Then, the allyl group of the polymer (F-3) was subjected to a hydrosilylation reaction to form the structure represented by the formula (2). After reacting at 90° C. until the trimethoxysilane was completely consumed, the volatile components were distilled off.
As a result, a branched polyoxypropylene (C-2) having a structure represented by the formula (2) was obtained.

(Comparative Synthesis Example 3)
A 28% methanol solution of sodium methoxide was added in an amount of 1.0 molar equivalent to the hydroxyl groups of the polymer (E-2) obtained in Synthesis Example 2. After methanol was distilled off under reduced pressure, 1.1 molar equivalent of allyl glycidyl ether was added to the hydroxyl groups of the polymer (E-2), and the mixture was reacted at 140° C. for 3 hours. Furthermore, allyl chloride was added in an amount of 1.22 molar equivalents relative to the hydroxyl groups of polymer (E-2), and the mixture was reacted at 130° C. for 1 hour, after which allyl chloride was distilled off. After that, 0.30 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl groups of the polymer (E-2). After removing methanol by distillation under reduced pressure at 130° C., 0.79 molar equivalent of allyl chloride is added to the hydroxyl groups of the polymer (E-2), and the reaction is carried out at 130° C. for 2 hours. Allyl was distilled off. After that, 0.2 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl groups of the polymer (E-2). After removing methanol by distillation under reduced pressure at 130° C., 0.3 molar equivalent of allyl chloride is added to the hydroxyl groups of the polymer (E-2) and reacted at 130° C. for 2 hours. Allyl was distilled off.
The obtained unpurified allyl-terminated polyoxypropylene was mixed with n-hexane and water and stirred, and the water was removed by centrifugation. removed. As a result, polyoxypropylene (F-4) having a plurality of carbon-carbon unsaturated bonds (allyl groups) per terminal site was obtained.
Then, at 90° C., 50 ppm of a platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) and 1.92 parts by weight of trimethoxysilane are added to 100 parts by weight of the polymer (F-4). Then, the allyl group of the polymer (F-4) was subjected to a hydrosilylation reaction to form the structure represented by the formula (2). After reacting at 90° C. until the trimethoxysilane was completely consumed, the volatile components were distilled off.
As a result, polyoxypropylene (C-3) having a plurality of structures represented by the above formula (2) per terminal site was obtained.

(Reference example 1)
Using butanol as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (E-4) having a number average molecular weight of 7800 and having a hydroxyl group at one end.
Then, at 90 ° C., bismuth 2-ethylhexanoate (III) 2-ethylhexanoic acid solution (Bi: 25%) 30 ppm with respect to 100 parts by weight of polymer (E-4), and hydroxyl groups possessed by the polymer 0.95 molar equivalent of (isocyanatomethyl)dimethoxymethylsilane was added to the polymer, and the hydroxyl groups of the polymer were subjected to a urethanization reaction. As a result, polyoxypropylene (B-1) having an alkoxysilyl group at one end was obtained.

(Reference example 2)
At 90 ° C., bismuth 2-ethylhexanoate (III) 2-ethylhexanoic acid solution (Bi: 25%) 30 ppm with respect to 100 parts by weight of the polymer (E-4) obtained in Reference Example 1, and the polymer 0.95 molar equivalent of (3-isocyanatopropyl)trimethoxysilane was added to the hydroxyl groups of the polymer, and the hydroxyl groups of the polymer were subjected to a urethanization reaction. As a result, polyoxypropylene (B-2) having an alkoxysilyl group at one end was obtained.

(Reference example 3)
A 28% methanol solution of sodium methoxide was added in an amount of 0.75 mole equivalent to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-4) obtained in Reference Example 1. After methanol was distilled off under reduced pressure, allyl chloride was added in an amount of 1.1 molar equivalents relative to the hydroxyl groups of polymer (E-4) and reacted at 130° C. for 1 hour, then allyl chloride was distilled off. left. After that, 0.47 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl groups of the polymer (E-4). After removing methanol by distillation under reduced pressure at 130° C., allyl chloride was added in an amount of 2.1 molar equivalents relative to the hydroxyl groups of the polymer (E-4) and reacted at 130° C. for 2 hours. Allyl was distilled off. The obtained unpurified allyl-terminated polyoxypropylene was mixed with n-hexane and water and stirred, and the water was removed by centrifugation. removed. As a result, polyoxypropylene (F-5) having a carbon-carbon unsaturated bond (allyl group) at one end was obtained.
Then, at 90° C., 50 ppm of a platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) and 2.07 parts by weight of trimethoxysilane are added to 100 parts by weight of the polymer (F-5). Then, a hydrosilylation reaction was carried out on the allyl groups possessed by the polymer (F-5). After reacting at 90° C. until the trimethoxysilane was completely consumed, the volatile components were distilled off. As a result, polyoxypropylene (B-3) having a trimethoxysilyl group at one end was obtained.

(Example 1, Comparative Examples 1 to 3)
Based on the total 100 parts by weight of the polymer shown in Table 1, DINP (manufactured by J-Plus Co., Ltd.: diisononyl phthalate) 90 parts by weight, Shiroenka CCR (manufactured by Shiraishi Calcium Co., Ltd.: precipitated calcium carbonate) 160 parts by weight, white SB (manufactured by Shiraishi Calcium Co., Ltd.: ground calcium carbonate) 54 parts by weight, Typaque R820 (manufactured by Ishihara Sangyo Co., Ltd.: titanium oxide) 5 parts by weight, Disparlon 6500 (manufactured by Kusumoto Chemical Co., Ltd.: fatty acid amide wax) 2 parts by weight, 1 part by weight of Tinuvin 770 (manufactured by BASF: bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate), and 1 part by weight of Tinuvin 326 (manufactured by BASF: 2-(3-tert-butyl-2 -Hydroxy-5-methylphenyl)-5-chlorobenzotriazole) 1 part by weight, A-171 (manufactured by Momentive: vinyltrimethoxysilane) 2 parts by weight, the amount (parts by weight) shown in Table 1 A-1120 (manufactured by Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane) and DBU (diazabicycloundecene) in the amount (parts by weight) shown in Table 1 were added and mixed. did. A-1120 (above aminosilane) and DBU (above amine compound) accelerate the condensation of hydrolyzable silyl groups and accelerate the curing of the polymer.

(Skin covering time)
The obtained composition was filled into a mold with a thickness of about 5 mm using a spatula, and the time when the surface was flattened was set as the curing start time, and the surface was touched with a spatula, and the composition for evaluation adhered to the spatula. The curing time was measured by taking the time when it disappeared as the skinning time. Results are shown in each table.

(Dumbbell tensile properties)
The obtained composition was filled in a mold and cured at 23° C. and 50% RH for 3 days and further at 50° C. for 4 days to prepare a sheet-like cured product having a thickness of about 3 mm. The cured sheet material was punched into a No. 3 dumbbell shape and subjected to a tensile strength test at 23° C. and 50% RH to measure modulus at 50% or 100% elongation, strength at break and elongation. The measurement was performed using an autograph (AGS-J) manufactured by Shimadzu Corporation at a pulling speed of 200 mm/min. Results are shown in each table.

(recovery rate)
The obtained composition was filled in a mold and cured at 23° C. and 50% RH for 3 days and further at 50° C. for 4 days to prepare a sheet-like cured product having a thickness of about 3 mm. The sheet-like cured product was punched into a No. 7 dumbbell shape, the dumbbell shape was stretched by 10 mm, both ends were fixed with clips, and the product was allowed to stand at 23° C. and 50% RH for 24 hours. After that, the clip was removed, and it was left to stand on a smooth glass plate in a state where the force causing deformation was removed, and it was confirmed how much the original shape was restored after 24 hours. Taking the elongation of the dumbbell after 24 hours as X (mm), the recovery rate was calculated as follows. Results are shown in each table.
Restoration rate (%) = (10-X) / 10 x 100

As is clear from Table 1, the curable composition of Comparative Example 2 containing the polymer (C-2) having only the structure represented by the formula (2) contains an aminosilane (A-1120) and an amine compound ( In the presence of DBU), the curability was remarkably low and it was not sufficiently cured. The curable composition of Example 1 containing coalescence (A-1) exhibited good curability. Furthermore, the curable composition of Example 1 includes the curable composition of Comparative Example 1 containing the polymer (C-1) having only the structure represented by the formula (1), and the curable composition of Comparative Example 3. It showed a higher restorability than the composition. In Comparative Example 3, at the content ratio of the structure represented by the formula (1) and the structure represented by the formula (2) contained in the polymer (A-1), A curable composition containing a polymer (C-2). That is, the polymer having the structure represented by the formula (1) and the structure represented by the formula (2) in the same molecule is the polymer having the structure represented by the formula (1) and the polymer having the structure represented by the formula It can be seen that the recovery property is higher than that of the mixture with the polymer having the structure represented by (2).

(Example 2, Comparative Examples 1, 4, 5)
Based on the total 100 parts by weight of the polymer shown in Table 2, DINP (manufactured by J-Plus Co., Ltd.: diisononyl phthalate) 90 parts by weight, Shiroenka CCR (manufactured by Shiraishi Calcium Co., Ltd.: precipitated calcium carbonate) 160 parts by weight, white SB (manufactured by Shiraishi Calcium Co., Ltd.: ground calcium carbonate) 54 parts by weight, Typaque R820 (manufactured by Ishihara Sangyo Co., Ltd.: titanium oxide) 5 parts by weight, Disparlon 6500 (manufactured by Kusumoto Chemical Co., Ltd.: fatty acid amide wax) 2 parts by weight, 1 part by weight of Tinuvin 770 (manufactured by BASF: bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate), and 1 part by weight of Tinuvin 326 (manufactured by BASF: 2-(3-tert-butyl-2 -Hydroxy-5-methylphenyl)-5-chlorobenzotriazole) 1 part by weight, A-171 (manufactured by Momentive: vinyltrimethoxysilane) 2 parts by weight, and A-1120 (manufactured by Momentive: N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane) (3 parts by weight) was added and mixed.

As is clear from Table 2, the curable composition of Comparative Example 4 containing the polymer (C-3) having only the structure represented by the formula (2) was cured in the presence of aminosilane (A-1120). The polymer (A-2) having a structure represented by the formula (1) and a structure represented by the formula (2) in the same molecule, while its curability was extremely low and it was not sufficiently cured. The curable composition of Example 2 containing showed good curability. Furthermore, the curable composition of Example 2 includes the curable composition of Comparative Example 1 containing the polymer (C-1) having only the structure represented by the formula (1), and the curable composition of Comparative Example 5. It showed a higher restorability than the composition. In Comparative Example 5, at the content ratio of the structure represented by the formula (1) and the structure represented by the formula (2) contained in the polymer (A-2), A curable composition containing a polymer (C-3). That is, the polymer having the structure represented by the formula (1) and the structure represented by the formula (2) in the same molecule is the polymer having the structure represented by the formula (1) and the polymer having the structure represented by the formula It can be seen that the recovery property is higher than that of the mixture with the polymer having the structure represented by (2). Furthermore, Example 2 also exhibited higher curability than Comparative Example 5.

(Examples 3-5, Comparative Examples 6-8)
Based on the total 100 parts by weight of the polymer shown in Table 3, DINP (manufactured by J-Plus Co., Ltd.: diisononyl phthalate) 90 parts by weight, Shiroenka CCR (manufactured by Shiraishi Calcium Co., Ltd.: precipitated calcium carbonate) 160 parts by weight, white SB (manufactured by Shiraishi Calcium Co., Ltd.: ground calcium carbonate) 54 parts by weight, Typaque R820 (manufactured by Ishihara Sangyo Co., Ltd.: titanium oxide) 5 parts by weight, Disparlon 6500 (manufactured by Kusumoto Chemical Co., Ltd.: fatty acid amide wax) 2 parts by weight, 1 part by weight of Tinuvin 770 (manufactured by BASF: bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate), and 1 part by weight of Tinuvin 326 (manufactured by BASF: 2-(3-tert-butyl-2 -Hydroxy-5-methylphenyl)-5-chlorobenzotriazole) 1 part by weight, A-171 (manufactured by Momentive: vinyltrimethoxysilane) 2 parts by weight, and A-1120 (manufactured by Momentive: N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane) (3 parts by weight) was added and mixed.

As is clear from Table 3, Examples 3 to 5 in which polymers (B-1) to (B-3) having a hydrolyzable silyl group at one end were mixed with the polymer (A-2). Compared to the curable compositions of Comparative Examples 6 to 8 in which the polymers (B-1) to (B-3) were mixed with the polymers (C-1) and (C-3) showed high resilience. That is, a polymer having a structure represented by the formula (1) and a structure represented by the formula (2) in the same molecule is used in combination with a polymer having a hydrolyzable silyl group at one end. It can be seen that high resilience is exhibited even when the modulus is reduced.

Claims (12)

A method for producing an organic polymer (A) having a structure represented by the following formula (1) and a structure represented by the following formula (2) in the same molecule,
—O—CO—NH—(CR ¹ ₂ ) _m —SiR ² _a X _3-a (1)
—O—(CR ³ ₂ ) _n —SiR ⁴ _b Y _3-b (2)
(In formula (1), R ¹ is the same or different and represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. R ² is a substituted or unsubstituted represents a hydrocarbon group, X represents a hydroxyl group or a hydrolyzable group, a is 0, 1 or 2, and m is an integer of 1-5.
In formula (2), R ³ are the same or different and represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. R ⁴ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group. b is 0, 1 or 2; n is an integer from 1 to 10; )
preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule;
a step of hydrosilylating the carbon-carbon unsaturated bond with a hydrosilane compound containing a hydrolyzable silyl group to form the structure represented by the formula (2); A method for producing an organic polymer (A), comprising the step of forming a structure represented by the formula (1) by subjecting a compound having an isocyanate group to a urethanization reaction. The step of preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule includes reacting an organic polymer having a hydroxyl group with a carbon-carbon unsaturated bond-containing halide to obtain a portion of the hydroxyl group. The method for producing the organic polymer (A) according to claim 1, which is a step of converting to a carbon-carbon unsaturated bond-containing group. Claim 1, wherein the step of preparing an organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule is a step of reacting a polymer having a hydroxyl group with an epoxy compound containing a carbon-carbon unsaturated bond. A method for producing the organic polymer (A) according to 1. The organic polymer (A) according to claim 3, wherein the organic polymer having a hydroxyl group and a carbon-carbon unsaturated bond in the same molecule is an organic polymer having a structure represented by the following formula (4): manufacturing method.

(In formula (4), R ³ is the same as above. R ⁵ represents a direct bond or a divalent linking group having 1 to 6 carbon atoms. d is an integer of 1 to 10. n is , an integer from 2 to 10.) An organic polymer (A') having a structure represented by the following formula (3).

(In formula (3), R ¹ is the same or different and represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. R ² is a substituted or unsubstituted R ³ is the same or different and represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms R ⁴ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms represents a hydrocarbon group of R ⁵ represents a direct bond or a divalent linking group having 1 to 6 carbon atoms X represents a hydroxyl group or a hydrolyzable group Y represents a hydroxyl group or a hydrolyzable group represents a group, a is 0, 1 or 2, b is 0, 1 or 2, d is an integer of 1 to 10, m is an integer of 1 to 5, n is , an integer from 1 to 10.) 6. The organic polymer (A') according to claim 5, wherein m is 1. 7. The organic polymer (A') according to claim 5 or 6, wherein n is 3. The organic polymer (A') according to any one of claims 5 to 7, wherein the polymer backbone of the organic polymer is a polyoxyalkylene polymer. A curable composition containing the organic polymer (A') according to any one of claims 5 to 8. 10. The curable composition according to claim 9, further comprising an organic polymer (B) having one hydrolyzable silyl group per molecule. 11. The curable composition according to claim 9 or 10, which does not contain an organic tin compound. A cured product obtained by curing the curable composition according to any one of claims 9 to 11.