JP2005290265A - Curing composition, sealing material and adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curing composition which uses an organic polymer having cross-linkable silyl groups and has not only excellent adhesiveness but also excellent storage stability, and to provide a sealing material and an adhesive which each uses the curing composition. <P>SOLUTION: This curing composition comprises (a) an organic polymer having at least cross-linkable hydrolyzable silyl groups and (b) an organic polymer having at least one segment selected from the group consisting of tertiary amino groups, N,N-dialkylamide groups, isocyanate group, nitrile group, urethane bonds and urea bonds. Also, the curing composition comprises an organic copolymer comprising a polymer portion having cross-linkable hydrolyzable silyl groups and a polymer portion having at least one segment selected from the group consisting of tertiary amino groups, N,N-dialkylamide groups, isocyanate group, nitrile group, urethane bonds and urea bonds, as a main component. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable composition using a hydrolyzable silyl group-containing polymer that is crosslinked by moisture in an atmosphere and gives a cured product having excellent durability, and more specifically, a paint, a coating agent, and an adhesive. Further, the present invention relates to a curable composition suitably used for a sealant, a sealant, a primer, and the like, and a sealant and an adhesive using the curable composition.

  Vinyl polymers having an alkoxysilyl group are disclosed in, for example, the following Patent Documents 1 to 3. A vinyl polymer having an alkoxysilyl group is crosslinked by moisture in the atmosphere to give a cured product excellent in durability, weather resistance, transparency and adhesiveness. Accordingly, alkoxysilyl group-containing vinyl polymers are used in a wide range of applications such as paints, coating agents, adhesives, pressure sensitive adhesives, sealants, and sealing materials.

  In order to make the composition containing the alkoxysilyl group-containing vinyl polymer into a liquid composition so that the coating operation is easy and that the cured product after curing has rubber elasticity, As the combination, a (meth) acrylic acid ester polymer is preferably used.

  However, the above alkoxysilyl group-containing vinyl polymer has a problem that storage stability is inferior because it is crosslinked and cured by the action of moisture. Therefore, in order to improve the storage stability, in Patent Documents 4 and 5 below, the stability is improved by copolymerization with acrylamide. Moreover, in the structure of the following patent document 6, the method of dehydrating by adding isocyanate like tolylene diisocyanate (TDI), and suppressing the progress of reaction by moisture is disclosed.

  However, when an isocyanate compound is added, the reaction between the isocyanate compound and water results in a low molecular weight compound having a high hydrogen-bonding force or a low molecular weight compound having urea bond, or a bonito rash, resulting in a cloudy composition or organic aggregation. Things may be generated. In addition, when an amide bond having no substituent is used, there is a possibility that the cured product may be yellowed or that the viscosity is likely to be significantly increased due to a hydrogen bond.

JP 57-179210 A JP-A-4-202585 JP 11-43512 A JP-A-57-55954 JP-A-57-55953 JP-A-8-269343

  An object of the present invention is a curable composition using a vinyl polymer (a) having a crosslinkable silyl group represented by the formula (1) at the terminal in view of the current state of the prior art described above, and having an adhesive property. It is another object of the present invention to provide a curable composition excellent in storage stability and a storage stability, and a sealing material and an adhesive using the curable composition.

The curable composition according to the first invention comprises a vinyl polymer (a) having a crosslinkable silyl group represented by the formula (1) at the terminal, and an organic polymer containing at least a crosslinkable hydrolyzable silyl group. A combination (a) and an organic polymer (b) having at least one segment selected from the group consisting of a tertiary amino group, an N, N-dialkylamide group, an isocyanate group, a nitrile group, a urethane bond and a urea bond; It is characterized by comprising.
_{^{- [Si (R 3) 2}} -b (Y) b O] m -Si (R 4) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ Si— ( R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and represents a triorganosiloxy group represented by R ¹ Alternatively, when two or more R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0 or 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 to be satisfied.)

The curable composition according to the second invention comprises a polymer part having a terminal crosslinkable silyl group represented by the formula (1), a tertiary amino group, an N, N-dialkylamide group, an isocyanate group, and a nitrile group. And a curable composition comprising as a main component an organic polymer (c) comprising a polymer portion having at least one segment selected from the group consisting of a urethane bond and a urea bond.
_{^{- [Si (R 3) 2}} -b (Y) b O] m -Si (R 4) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ Si— ( R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and represents a triorganosiloxy group represented by R ¹ Alternatively, when two or more R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0 or 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 to be satisfied.)

  In a specific aspect of the second invention, there is provided a curable composition comprising a vinyl polymer (a) and an organic polymer (c).

In a specific aspect of the first and second inventions (hereinafter collectively referred to as the present invention), the viscosity of the at least one organic polymer at 25 ° C. is in the range of 10 to 500,000 cps. (At least one organic polymer means organic polymers (a), (b), and (c).)
In still another specific aspect of the curable composition of the present invention, the number average molecular weight of the at least one organic polymer is in the range of 5,000 to 100,000.

  In still another specific aspect of the curable composition according to the present invention, the organic polymer is a vinyl polymer, and further includes a polyether polymer (d) having at least a crosslinkable hydrolyzable silyl group. Has been.

  In still another specific aspect of the curable composition according to the present invention, a layered silicate is further blended.

In still another specific aspect of the curable composition according to the present invention, the nitrogen element content is in the range of 0.01 to 5% by weight.
In still another specific aspect of the curable composition according to the present invention, the viscosity at 25 ° C after 60 days at 60 ° C is in the range of 0.5 to 10 times the viscosity at 25 ° C immediately after blending.

  The sealing material and the adhesive according to the present invention are composed of a curable composition constituted according to the present invention.

The curable composition of the present invention contains a vinyl polymer (a) having the general formula (1) at its terminal.
_{^{- [Si (R 3) 2}} -b (Y) b O] m -Si (R 4) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ Si— ( R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and represents a triorganosiloxy group represented by R ¹ Alternatively, when two or more R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0 or 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 to be satisfied.)

  The hydrolyzable group represented by Y is not particularly limited, and examples thereof include an alkoxy group such as hydrogen, a halogen atom, a methoxy group, and an ethoxy group, an acyl oxide group, a ketoximate group, an amino group, an amide group, and an acid amide group. An aminooxy group, a mercapto group, an alkenyl oxide group and the like are preferable examples, and an alkoxy group that is easy to handle and does not generate harmful by-products during the reaction is particularly preferable. The hydroxyl group and hydrolyzable group can be bonded to one silicon atom in the range of 1 to 3, and the total number of hydroxyl groups and hydrolyzable groups in the formula (1), that is, a + mb is 1 to 1 A range of 5 is preferred. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different. The number of silicon atoms constituting the crosslinkable silicon compound may be one or two or more. In the case of silicon atoms linked by a siloxane bond, up to about 20 silicon atoms may be used.

  The vinyl polymer part constituting the vinyl polymer may be a polymer obtained by polymerizing a vinyl monomer, such as polyethylene, polypropylene, polyisobutylene, poly (meth) acrylate, polystyrene, Examples thereof include polyvinyl chloride, polyvinylidene chloride, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, and polyvinyl ether. Moreover, the copolymer which has these vinyl-type polymer parts may be sufficient. Furthermore, a poly (meth) acrylate having a number average molecular weight of 10,000 or more and a copolymer thereof having a good balance between cohesive strength and adhesiveness are preferably used. Here, (meth) acryl is an expression collectively showing methacryl and acryl.

Examples of the monomer for obtaining poly (meth) acrylate and its copolymer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate , Isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydro Rufuryl (meth) acrylate, hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, Polyester acrylate, urethane acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropy (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-3-methylbutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-[(meth) acryloyloxy] ethyl 2-hydroxyethylphthalic acid, 2-[(meth) acryloyloxy] ethyl 2-hydroxypropylphthalic acid,
[Compound 1]
CH2 = CH-C (O) O-CH2CH2O-
[C (O) CH2CH2CH2CH2CH2O] n-H
(N = 1-10)
[Compound 2]
CH2 = C (CH3) -C (O) O-CH2CH2O-
[C (O) CH2CH2CH2CH2CH2O] n-H
(N = 1-10)
[Compound 3]
CH2 = CH-C (O) O- (CH2CH2O) n-H
(N = 1-12)
[Compound 4]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-H
(N = 1-12)
[Compound 5]
CH2 = CH-C (O) O- [CH2CH (CH3) O] n-H
(N = 1-12)
[Compound 6]
CH2 = C (CH3) -C (O) O- [CH2CH (CH3) O] n-H
(N = 1-12)
[Compound 7]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(N = 1-12)
(M = 1-12)
[Compound 8]
CH2 = CH-C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(N = 1-12)
(M = 1-12)
[Compound 9]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-
(CH2CH2CH2CH2O) mH
(N = 1-12)
(M = 1-12)
[Compound 10]
CH2 = CH-C (O) O- (CH2CH2O) n-
(CH2CH2CH2CH2O) mH
(N = 1-12)
(M = 1-12)
[Compound 11]
CH2 = CH-C (O) O- (CH2CH2O) n-CH3
(N = 1-10)
[Compound 12]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-CH3
(N = 1-30)
[Compound 13]
CH2 = CH-C (O) O- [CH2CH (CH3) O] n-CH3
(N = 1-10)
[Compound 14]
CH2 = C (CH3) -C (O) O- [CH2CH (CH3) O] n-CH3 (n = 1-10)
[Compound 15]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(N = 1-10)
(M = 1-10)
[Compound 16]
CH2 = CH-C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(N = 1-10)
(M = 1-10)
[Compound 17]
CH2 = CH-C (O) O- [CH2CH (CH3) O] n
-C (O) -CH = CH2
(N = 1-20)
[Compound 18]
CH2 = C (CH3) -C (O) O- [CH2CH (CH3) O] n
-C (O) -C (CH3) = CH2
(N = 1-20)
[Compound 19]
CH2 = CH-C (O) O- (CH2CH2O) n-C (O) -CH = CH2
(N = 1-20)
[Compound 20]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n
-C (O) -C (CH3) = CH2
(N = 1 to 20).

  Examples of other vinyl monomers include styrene such as styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene, and the like. Derivatives; for example, compounds having vinyl ester groups such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate; maleic anhydride, N-vinylpyrrolidone, N-vinylmorpholine, (Meth) acrylonitrile, (meth) acrylamide, N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, N-benzylmaleimide, n-propylvinylether, n-butylvinylether, isobutylvinylether, ter -Butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether, ethylene glycol butyl vinyl ether, tritylene glycol methyl vinyl ether, benzoic acid (4-vinyloxy) butyl, ethylene Glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1,4-diol-divinyl ether, hexane-1,6-diol-divinyl ether, cyclohexane-1,4-dimethanol -Divinyl ether, di (4-vinyloxy) butyl isophthalate, glu Di (4-vinyloxy) butyl tartrate, di (4-vinyloxy) butyl trimethylolpropane trivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexane-1,4-di succinate Mention may be made of compounds having a vinyloxy group such as methanol-monovinyl ether, diethylene glycol monovinyl ether 3-aminopropyl vinyl ether, 2- (N, N-diethylamino) ethyl vinyl ether, urethane vinyl ether, polyester vinyl ether and the like.

The method for producing a vinyl polymer having a crosslinkable silyl group of formula (1) at the terminal is not particularly limited. For example, the above-described method is performed using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. By polymerizing a vinyl monomer, a vinyl polymer having a terminal structure represented by formula (2) is produced, and the halogen of formula (2) is converted to a crosslinkable silyl group-containing substituent represented by formula (1). A method is mentioned.
-C (R ¹ ) (R ² ) (X) (2)
(In the formula, R ^3, R ⁴ represents a group bonded to an ethylenically unsaturated group of a vinyl monomer. In addition, X represents chlorine, bromine, or halogen atom iodine,.)
It is.

  The method for converting the halogen of the above formula (2) into the crosslinkable silyl group-containing substituent represented by the formula (1) is not particularly limited. For example, a compound having an alkenyl group and a crosslinkable silyl group, a silyl group, A method of reacting a compound having a stabilized carbanion, a compound having a polymerizable alkenyl group and another alkenyl group, an organometallic compound having an alkenyl group, a carboxylic acid metal salt having an alkenyl group, an alkenyl group and a stabilized carbanion For example, a method in which a halogen compound represented by formula (2) is substituted with an alkenyl group and then a hydrosilane having a crosslinkable silyl group is reacted with the alkenyl group.

In addition, when producing a vinyl polymer having a crosslinkable silyl group at the end of formula (1), an organic halide having a crosslinkable silyl group is used as an initiator, and a halogen is contained at one end. After synthesizing a polymer having a crosslinkable silyl group at one end, a polymer having a crosslinkable silyl group at both ends may be prepared by reacting with halogen and glycol, diamine, dicarboxylic acid, etc. After synthesizing a polymer having a halogen at one end and a crosslinkable silyl group at the other end,
Halogen may be converted to a crosslinkable silyl group by the above reaction. Alternatively, after synthesizing a polymer having a halogen at one end and a crosslinkable silyl group at the other end, the halogen may be converted to an alkenyl group by the above-described reaction, and then further converted to a crosslinkable silyl group. good.

Further, when producing a vinyl polymer having a terminal crosslinkable silyl group of formula (1),
After synthesizing a polymer having a halogen at one end and an alkenyl group at the other end using an organic halide having an alkenyl group as an initiator, the halogen is converted to an alkenyl group, And a method of converting to a crosslinkable silyl group by the above method.

(Organic polymer (b))
The curable composition according to the first invention comprises a tertiary amino group, N, N-dialkylamide group, isocyanate group, nitrile group, urethane bond and urea bond in addition to the above-mentioned vinyl polymer (a). An organic polymer (b) having at least one segment selected from the group is blended. Among the above segments, the isocyanate group exhibits a dehydrating action, and the other functional groups and bonds have an action of adjusting the pH of the composition, and all enhance the storage stability. In addition, when N-hydrogen amide in which hydrogen is bonded to a nitrogen atom obtained by copolymerizing acrylamide having no substituent on the nitrogen atom, the composition may be thickened due to hydrogen bonding, Pulling may occur, which is not preferable.

  The organic polymer (b) can be obtained by copolymerizing the following copolymerizable monomer and the above-described polymerizable monomer by an ordinary polymerization method.

  Examples of the copolymerizable monomer for obtaining a segment having a tertiary amino group include N, N-dimethylaminoethyl (meth) acrylate. Examples of the copolymerizable monomer for obtaining a segment having an N, N-dialkylamide group include N-vinylpyrrolidone and N- (meth) acryloylmorpholine.

  A segment having an isocyanate group is introduced to perform a dehydrating action, and examples of the copolymerizable monomer for obtaining the segment include 2- (meth) acryloyloxyethyl isocyanate. However, in this case, as another copolymerizable monomer, a monomer containing a functional group such as a hydroxyl group, a carboxyl group, or an epoxy group may be crosslinked during a polymerization operation performed to obtain a segment. Therefore, it is preferable not to use it.

Examples of the copolymerizable monomer for obtaining a segment having a nitrile group include (meth) acrylonitrile.
Examples of the copolymerizable monomer for obtaining a segment having a urethane bond include a reaction product of urethane acrylate, 2- (meth) acryloyloxyethyl isocyanate and monohydrocarbon.

  Examples of the copolymerizable monomer for obtaining a segment having a urea bond include a reaction product of 2- (meth) acryloyloxyethyl isocyanate and a dialkylamine.

  In 1st invention, since the said organic polymer (b) has the segment mentioned above, it can suppress remarkably that a moisture and an organic polymer (b) react and harden | cure during storage, and storage stability Can increase the sex.

  1st invention WHEREIN: As for the mixture ratio of an organic polymer (b), it is desirable to set it as the range of 1-30 weight part with respect to 100 weight part of vinyl polymers (a). If it is less than 1 part by weight, the effect of enhancing storage stability may not be sufficient, and if it exceeds 30 parts by weight, the elasticity and adhesive strength of the cured product may be reduced.

(Organic polymer (c) used in the second invention)
The organic polymer (c) used in the second invention comprises a polymer part having a crosslinkable silyl group and the above-described segments, that is, a tertiary amino group, an N, N-dialkylamide group, an isocyanate group, a nitrile group, And a polymer portion having at least one segment selected from the group consisting of a urethane bond and a urea bond. In obtaining such an organic polymer (c), a monomer for obtaining the vinyl polymer (a) and a monomer for obtaining the organic polymer (b) were mixed, and an organic peroxide was used. The organic polymer (c) is preferably obtained by radical polymerization. By using an organic peroxide as an initiator, yellowing of the cured product can be suppressed as in the case described above as compared with the case where an azo compound is used as an initiator.

The proportion of the polymer part having a crosslinkable silyl group and the polymer part having the segment in the organic polymer (c) is 1 to 30% by weight of the polymer part having the segment in 100% by weight of the copolymer. It is desirable to be in the range. If the amount is less than 1% by weight, the effect of enhancing the storage stability may not be sufficiently obtained. If the amount exceeds 30% by weight, the adhesive force and the elasticity of the cured product may be lowered.
In 2nd invention, in addition to the said organic polymer (c), the vinyl polymer (a) mentioned above may further be added.

(Viscosity of vinyl polymer (a) and organic polymer (b))
In order to make the curable composition according to the first invention into a liquid or paste-like composition having excellent handleability, the viscosity of at least one of the vinyl polymer (a) and the organic polymer (b) is 25 ° C. In the range of 0.01 to 500 Pa · s. When both viscosities are 0.010 Pa · s, a liquid composition that is easy to handle can be obtained, but it may be difficult to impart thixotropy during viscosity adjustment. When the viscosities of both the vinyl polymer (a) and the organic polymer (b) exceed 500 Pa · s, although cold flow properties are exhibited, coating becomes difficult and the composition may be difficult to handle. More preferably, the viscosity of at least one of the vinyl polymer (a) and the organic polymer (b) is 0.1 to 50 Pa · s, more preferably 1 to 30 Pa · s at 25 ° C. It is desirable to be in the range.

  Moreover, the viscosity range in which the application and coating properties of the curable composition of the first invention are excellent are 0.05 to 500 Pa · s, preferably 0.1 to 100 Pa · s, at 25 ° C.

  Therefore, in the second invention, the preferred viscosity range of the organic polymer (c) is 0.05 to 500 Pa · s, preferably 0.1 to 100 Pa · s, at 25 ° C. .

(Molecular weight)
In order to make the curable composition according to the first invention into a liquid or paste-like composition excellent in elongation of the cured product and difficult to be stringed, at least of the vinyl polymer (a) and the organic polymer (b) One number average molecular weight is preferably in the range of 5000 to 100,000, more preferably in the range of 6000 to 80000, and still more preferably in the range of 7000 to 50000.

  When the number average molecular weights of the vinyl polymer (a) and the organic polymer (b) are both less than 5000, a liquid composition that is easy to handle can be obtained, but the cured product can be sufficiently extended. There may not be. When the molecular weights of the vinyl polymer (a) and the organic polymer (b) are both greater than 100,000, the cured product is excellent in elongation properties, but may become a liquid composition that easily causes stringing. is there.

In the second invention, for the same reason as described above, the number average molecular weight of the organic polymer (c) is preferably 5,000 to 100,000, more preferably 6,000 to 80,000, and still more preferably 7,000 to 50,000. It is desirable.
In addition, the number average molecular weight in this invention is a polystyrene conversion molecular weight calculated | required by the gel permeation chromatography (GPC).

(Nitrogen element content)
In order to further enhance the storage stability in the curable composition according to the present invention, it is desirable that the content of nitrogen element derived from the segment is in the range of 0.01 to 5% by weight in the organic polymer. If it is less than 0.01% by weight, the effect of enhancing the storage stability may not be obtained, and if it exceeds 5% by weight, the storage stability is excellent, but the cohesive force due to the functional group containing nitrogen increases, There is a risk of thickening or stringing. Moreover, the basic effect by nitrogen increases and there exists a possibility that the hydrolyzable silyl group which can be bridge | crosslinked cannot exist stably.

(Viscosity after 60 days)
In the curable composition according to the present invention, the viscosity at 25 ° C. when stored at 60 ° C. for 60 days from immediately after compounding is preferably in the range of 0.5 to 10 times the viscosity at 25 ° C. immediately after compounding. It is desirable. That is, in the curable composition according to the present invention, it is desirable that the increase in the viscosity is limited within the above range even after being stored at a relatively high temperature such as 60 ° C. for 60 days. It is possible to provide an adhesive and a sealing material excellent in properties and handling properties.

(Polyether polymer (d))
In the curable composition according to the present invention, a polyether polymer (d) is preferably added in addition to the vinyl polymer (a), the organic polymer (b), or in addition to the organic polymer (c). Is done. By adding the polyether polymer (d), the water resistance of the cured product can be increased, and the rubber elasticity when a sealing material is formed can be increased. When the polyether polymer (d) is added to the vinyl polymer (a), the organic polymer (b), or the organic polymer (c), the blending ratio is as follows. Crosslinkability with respect to 100 parts by weight of the combined polymer (b), 100 parts by weight of the organic polymer (c), or 100 parts by weight of the vinyl polymer (a) and the organic polymer (c). It is desirable to add the polyether polymer (d) having a silyl group in a proportion of 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight.

  When the blending ratio of the polyether polymer (d) is less than 0.1 parts by weight, the effect of improving the adhesiveness may be reduced, and when it exceeds 200 parts by weight, the weather resistance may be lowered and the adhesiveness may be decreased. This is because the improvement effect is not so high.

  The polyether polymer (d) is a polymer in which the main chain is essentially a polyether polymer and contains a hydrolyzable silyl group capable of crosslinking at the terminal, and the main chain is essentially In the general formula [— (R—O) n —, R in the formula represents an alkylene group having 1 to 4 carbon atoms. ] A polymer containing a hydrolyzable silyl group which can be cross-linked at the terminal.

The polyether polymer (d) may be a copolymer whose main chain is composed of polyether and (meth) acrylic acid ester.
The polymer (d) is synthesized, for example, by reacting a polyalkylene oxide having an allyl group at a terminal with a hydrosilane compound represented by the following chemical formula (3) in the presence of a group VIII transition metal.

Wherein R ⁵ is a group selected from a monovalent hydrocarbon group and a halogenated monovalent hydrocarbon group, a is an integer of 0, 1 or 2, X is a halogen atom, an alkoxy group, an acyloxy group, and Means an atom or group selected from a ketoximate group.)
Examples of the polyalkylene oxide that is the main chain of the polymer (d) include polyethylene oxide, polypropylene oxide, polybutylene oxide, and the like, but a cured product of a room temperature curable composition is excellent in water resistance and sealing. Polypropylene oxide is preferable because it can ensure elasticity as a material.

  The crosslinkable hydrolyzable silyl group is preferably a product that does not produce a harmful by-product after the reaction, like the silyl group contained in the vinyl polymer (a) and the organic polymer (c). , Alkoxysilyl groups such as methoxysilyl group and ethoxysilyl group.

  If the number average molecular weight of the polyether polymer (d) is too small, the elongation of the cured product will be insufficient, the followability to the ground will be lowered, and if it is too large, the viscosity before curing will be increased, The workability of becomes worse. Therefore, the number average molecular weight is preferably 4,000 to 30,000, more preferably 10,000 to 30,000, and the molecular weight distribution is preferably 1.6 or less.

  Examples of the polyether-based polymer (d) include the trade name “MS polymer” (manufactured by Kaneka Chemical Industry Co., Ltd.), MS polymers S-203, S-303, etc. As Sakai Chemical Industry Co., Ltd.), Silyl SAT-200, SAT-350, SAT-400, and trade name "Exester" (manufactured by Asahi Glass Co., Ltd.), Exester ESS-3620, ESS-3430, ESS-2420, ESS -2410 and the like are commercially available.

(Layered silicate)
The layered silicate preferably used in the present invention means a silicate mineral having exchangeable cations between layers. The layered silicate used in the present invention is not particularly limited, and examples thereof include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, and swelling mica. It is done. Among these, montmorillonite and swellable mica are preferable. The layered silicate may be either a natural product or a synthetic product, and one or more of these are used.

As the layered silicate, it is more preferable to use smectites or swelling mica having a large shape anisotropy effect defined by the following formula from the viewpoint of improving the mechanical strength and gas barrier property of the curable composition. In addition, the crystal | crystallization surface (A) and crystal | crystallization end surface (B) of layered silicate are typically shown in FIG.
Shape anisotropy effect = area of crystal surface (A) / area of crystal end face (B)

  As shown in FIG. 2, the exchangeable cations existing between the layers of the layered silicate are ions such as sodium and calcium on the crystal surface, and these ions have ion exchange properties with a cationic substance. Therefore, various substances having a cationic property can be trapped (intercalated) between the layers of the layered silicate.

  Although it does not specifically limit as a cation exchange capacity | capacitance of the said layered silicate, It is preferable that it is 50-200 milliequivalent / 100g. If it is less than 50 milliequivalents / 100 g, the amount of the cationic surfactant that can be trapped (intercalated) between the crystal layers by ion exchange decreases, so the layers may not be sufficiently nonpolarized. On the other hand, when it exceeds 200 milliequivalents / 100 g, the bonding force between the layers of the layered silicate becomes strong, and it may be difficult to increase the distance between the crystal flakes constituting each layer of the layered silicate.

  The layered silicate is blended in an amount of 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, and particularly preferably 1 to 10 parts by weight with respect to 100 parts by weight of the base resin. When the amount is less than 0.1 part by weight, the effect of improving the weather resistance of the cured product and flame retardancy is hardly exhibited, and when the amount exceeds 10 parts by weight, the viscosity of the curable composition is increased and workability and productivity are reduced. There is.

  The base resin refers to the vinyl polymer (a), organic polymer (b) or organic polymer (c), or the vinyl polymer (a), organic polymer (b) or organic polymer (c). ) And the polyether polymer (d) added as necessary.

  The layered silicate preferably has an average interlayer distance of (001) plane measured by wide-angle X-ray diffraction measurement method of 3 nm or more and dispersed including those existing in 5 layers or less. When the average interlayer distance is 3 nm or more and the dispersion is 5 layers or less, it is advantageous for the weather resistance and flame retardancy performance of the curable composition.

  In the present specification, the average interlayer distance of the layered silicate is an average interlayer distance when the fine flaky crystal is used as a layer, and is obtained by X-ray diffraction peak and transmission electron microscope photography, that is, wide-angle X It can be calculated by a line diffraction measurement method. The state where the layers are cleaved to 3 nm or more and dispersed including those existing in 5 layers or less means that a part or all of the layered silicate laminate is dispersed, This is because the interaction between layers is weakened.

  Furthermore, when the average interlayer distance of the layered silicate is 6 nm or more, it is particularly advantageous for expressing functions such as flame retardancy, mechanical properties, and heat resistance. If the average interlaminar distance is 6 nm or more, the lamellar silicate crystal flake layers separate into layers, and the interaction of the lamellar silicate weakens so that it can be almost ignored. The dispersion state in progresses in the direction of delamination stabilization. That is, the layered silicate is present in a stabilized state in the curable composition in a state where the layered silicates are separated in a flake form one by one.

  As a dispersion state of the layered silicate, it is preferable that the flaky crystals of the layered silicate are highly dispersed in the base resin. More specifically, it is preferable that 10% by weight or more of the layered silicate is dispersed in a state where it is present in 5 layers or less, more preferably, 20% by weight or more of the layered silicate is 5 layers or less. It is desirable to exist in a state. Furthermore, if the number of laminated flaky crystals is 5 or less, the effect of the addition of the layered silicate can be obtained satisfactorily, but if it is 3 or less, it is more preferable, and it is dispersed in a single layer. More desirable.

  The layered silicate of the present invention is preferably a layered silicate treated with a quaternary ammonium salt. This is because the dispersibility of the layered silicate in the base resin can be improved by treating with a quaternary ammonium salt. Quaternary ammonium salts are known to have a catalytic action on the crosslinking reaction of the above polyether polymers, and are dispersed in the base resin together with the layered silicate to improve the dispersibility and accelerate the curing rate. It is also possible to make it.

  Examples of the quaternary ammonium salt include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, and N-polyoxyethylene. -N-lauryl-N, N-dimethylammonium salt and the like can be mentioned, and these quaternary ammonium salts may be used alone or in combination of two or more. Among them, a quaternary alkyl ammonium ion salt having an alkyl chain having 6 or more carbon atoms or a polyoxyalkylene chain is preferable because good dispersibility can be obtained.

  Various stirrers can be used to disperse the layered silicate, but if it is difficult to disperse, it may be easy to obtain a desired dispersion state by dispersing using a high shearing device such as a three roll.

(Ultraviolet absorber and light stabilizer)
The curable composition of the present invention preferably contains various ultraviolet absorbers and / or light stabilizers in order to improve the weather resistance. This is because the layered silicate acts so as to suppress bleed-out of various ultraviolet absorbers and light stabilizers in combination with the layered silicate, so that these are retained in the cured product for a long time.

  Examples of the UV absorber include known UV absorbers such as benzotriazole and benzophenone, and among them, a benzotriazole UV absorber is preferable because of its high UV absorption performance. When blending the ultraviolet absorber, 0.5 to 10 parts by weight is preferably blended with respect to 100 parts by weight of the base resin. If the amount is less than 0.5 parts by weight, the effect of improving weather resistance may be insufficient. If the amount exceeds 10 parts by weight, problems such as a loss of appearance as a sealing material due to coloration occur.

  As the light stabilizer, for example, a hindered amine light stabilizer is used. A hindered amine light stabilizer generally exhibits an excellent effect when used in combination with an ultraviolet absorber. Among the hindered amine light stabilizers (hereinafter referred to as light stabilizers), those having a group having a structure represented by the following general formula (A) in the molecule are particularly effective when used in combination with a layered silicate. Examples of such a hindered amine light stabilizer include, for example, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, poly [{6- (1,1,3,3, -tetramethylbutyl). ) Amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidine) imino} hexamethylene {(2,2,6,6-tetramethyl) -4-piperidine) imino}] and the like. These may be used alone or in combination of two or more.

(Other additives)
The curable composition of the present invention includes a curing accelerator for the organic polymers (a) and (c), a viscosity modifier that adjusts the viscosity characteristics of the composition, a thixotropic agent, a tension unless the effects of the present invention are impaired. Add physical property modifiers, extenders, reinforcing agents, plasticizers, colorants, flame retardants, antioxidants, anti-sagging agents, anti-aging agents, solvents, fragrances, pigments, dyes, dehydrating agents, etc. May be.

  As a hardening accelerator of a vinyl polymer (a) and an organic polymer (c), an organometallic compound can be used, for example. Examples of the organometallic compound that can be suitably used include organometallic compounds obtained by substituting a metal element such as germanium, tin, lead, boron, aluminum, gallium, indium, titanium, and zirconium with an organic group. I can do it. Specifically, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis (dibutyltin laurate) oxide, dibutyltin bisacetylacetonate, dibutyltin bis (monoester malate), octylic acid Tin compounds such as tin, dibutyltin octoate and dioctyltin oxide, titanate compounds such as tetra-n-butoxy titanate and tetraisopropoxy titanate, and these can be used alone or in combination of two or more.

  The viscosity modifier is selected from, for example, a polymer compound having good compatibility with the vinyl polymer (a), the organic polymer (c), particularly the vinyl polymer, and is appropriately selected according to the compound to be blended. The For example, acrylic polymers, methacrylic polymers, polyvinyl alcohol derivatives, polyvinyl acetate, polystyrene derivatives, polyesters, polyethers, polyisobutene, polyolefins, polyalkylene oxides, polyurethanes, polyamides, natural rubber, polybutadiene , Polyisoprene, NBR, SBS, SIS, SEBS, hydrogenated NBR, hydrogenated SBS, hydrogenated SIS, hydrogenated SEBS, and the like. Moreover, these copolymers and functional group modified bodies can be mentioned, and these may be combined as appropriate.

  The thixotropic agent is appropriately selected from substances whose composition exhibits thixotropic properties. Examples thereof include colloidal silica, polyvinyl pyrrolidone, hydrophobized calcium carbonate, glass balloons, and glass beads. Regarding the selection of the thixotropic material, one having a surface having a high affinity for the vinyl polymer is desirable.

  Various physical property modifiers that improve tensile properties and the like include various silane coupling agents such as vinyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, and phenyl. Trimethoxysilane, diphenyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N -(2-aminoethyl) -3-aminopropyltriethoxysilane, N, N'-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N'-bis- [3- (triethoxysilyl) Propyl] Eth Diamine, N, N′-bis- [3- (trimethoxysilyl) propyl] hexaethylenediamine, N, N′-bis- [3- (triethoxysilyl) propyl] hexaethylenediamine, and the like. Two or more types may be used in combination.

  As the extender, those which are added to the composition according to the present invention and do not exhibit thixotropic properties can be suitably used. For example, talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrous silicon, calcium silicate, Examples thereof include titanium dioxide and carbon black, and these may be used alone or in combination of two or more.

  Examples of the plasticizer include phosphate esters such as tributyl phosphate and tricresyl phosphate, phthalate esters such as dioctyl phthalate, fatty acid-basic acid esters such as glycerin monooleate, and dioctyl adipate. Examples thereof include fatty acid dibasic acid esters and polypropylene glycols, and these may be used alone or in combination of two or more.

(Sealing material and adhesive)
The sealing material and the adhesive according to the present invention are configured using the curable composition according to the first or second invention described above. Therefore, it is excellent in storage stability and the cured product exhibits excellent adhesive strength and rubber elasticity.

The curable composition according to the present invention includes a vinyl polymer (a) having a crosslinkable silyl group represented by the formula (1), a tertiary amino group, an N, N-dialkylamide group, an isocyanate group, Since it consists of an organic polymer (b) having at least one segment selected from the group consisting of nitrile groups, urethane bonds and urea bonds, it has excellent adhesion and storage stability, and is cured by moisture in the atmosphere. And a cured product having elasticity and good adhesive strength.
In particular, the crosslinkable silyl group-containing vinyl polymer (a) of the present invention has a crosslinkable silyl group at the terminal as described above, so that it has a crosslinkable silyl group in the side chain. The cured product exhibits excellent elongation and elasticity despite its low viscosity before curing and easy handling with little stringing.

Another curable composition according to the present invention comprises a crosslinkable hydrolyzable silyl group, a tertiary amino group, an N, N-dialkylamide group, an isocyanate group, a nitrile group, a urethane bond and a urea bond. Since the organic polymer (c) having at least one kind of segment selected from the group is a main component, it has excellent adhesion and storage stability, is cured by moisture in the atmosphere, has elasticity and good It becomes a cured product having adhesive strength.
Another curable composition according to the present invention is composed of the vinyl polymer (a) and the organic polymer (c), and thus has excellent adhesion and storage stability, and is cured by moisture in the atmosphere. And a cured product having elasticity and good adhesive strength.
In addition, since the curable composition according to the present invention has a viscosity at 25 ° C. of at least one organic polymer of 0.01 to 500 Pa · s, it is further cured with improved handling and coating properties. Composition.
In addition, the curable composition according to the present invention has at least one polymer having a molecular weight of 5,000100,000, so that the curable composition is excellent in stringing and the cured product is excellent in elongation.
Moreover, since the polyether polymer which has a crosslinkable silyl group is added to the other curable composition concerning this invention, it becomes a curable composition which further improved water resistance.

Moreover, since the layered silicate is added to the other curable composition concerning this invention, it becomes a curable composition which further improved the weather resistance and the flame retardance.
In addition, since the other curable composition according to the present invention has a nitrogen content of 0.01 to 5% by weight, it becomes a curable composition with less yellowing.
In addition, other curable compositions according to the present invention are stored because the viscosity at 25 ° C after curing at 60 ° C for 60 days is in the range of 0.5 to 10 times the viscosity at 25 ° C immediately after preparation. It is a curable composition excellent in stability.
Furthermore, since the adhesive and the sealing material according to the present invention are composed of the above curable composition, the adhesive has little stringing phenomenon, excellent storage stability, and excellent weather resistance and adhesiveness after being cured by moisture. And a sealing material.

  Hereinafter, the present invention will be described in more detail by giving specific examples and comparative examples of the present invention. In addition, this invention is not limited to a following example.

(Example 1)
(Preparation of vinyl polymer (a))
A 1 L three-necked round bottom flask equipped with a reflux tube was charged with cuprous bromide (6.25 g, 156 mmol), acetonitrile (50 mL), and pentamethyldiethylenetriamine (9.1 mL) and replaced with nitrogen gas. Acrylic acid-n-butyl (500 mL, 447 g, 3.9 mol) and diethyl-2,5-dibromoadipate (15.7 g, 43.6 mmol) were added, and the mixture was heated and stirred at 70 ° C. for 7 hours. The mixture was diluted with ethyl acetate and treated with activated alumina. Volatiles were distilled off under reduced pressure to obtain 350 g of poly (acrylic acid-n-butyl) having a halogen at the terminal. The number average molecular weight of the polymer was 10700 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.15.

Next, in a 2 L three-necked round bottom flask equipped with a reflux tube, poly (acrylic acid-n-butyl) having halogen at the terminal obtained as described above (350 g), potassium salt of 4-pentenoic acid ( 22.3 g, 161 mmol) and dimethylacetamide (350 mL) were charged and reacted at 70 ° C. for 4 hours in a nitrogen atmosphere. The mixture was diluted with ethyl acetate and washed with 2% hydrochloric acid, brine. The organic layer was dried over Na ₂ SO ₄ and the polymer was isolated by removing the volatiles under reduced pressure. An equivalent amount of aluminum silicate (manufactured by Kyowa Chemical Co., Ltd .: Kyowaard 700PEL) was added to the polymer and stirred at 100 ° C. for 4 hours to obtain poly (butyl acrylate) having an alkenyl group at the terminal. According to ¹ H-NMR analysis, 1.82 alkenyl groups were introduced per oligomer-1 molecule.

Next, the polymer (150 g), dimethoxymethylhydrosilane (18 mL, 145 mmol), dimethyl orthoformate (2.6 mL, 24.2 mmol), and a platinum catalyst were charged into a 200 mL pressure-resistant glass reaction vessel. However, the amount of platinum catalyst used was 2 × 10 ⁻⁴ equivalent in terms of molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 ° C. for 4 hours. The volatile component of the mixture was distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having a silyl group at the terminal. According to ¹ H-NMR analysis, 1.46 silyl groups were introduced per oligomer-1 molecule.

(Preparation of organic polymer (b1) having N, N-dialkylamide group)
4. In a 0.5 L separable flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas inlet, n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) 95 g, N-acryloylmorpholine (manufactured by Wako Pure Chemical Industries, Ltd.) 0 g, 5.0 g of lauryl mercaptan (Wako Pure Chemical Industries, Ltd.) and 100 g of ethyl acetate were added and mixed. After the dissolved oxygen was removed by bubbling the monomer mixed solution with nitrogen gas for 20 minutes, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was increased to reach reflux while stirring. After refluxing, a solution obtained by diluting 0.024 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was added to the polymerization system. After 1 hour, a solution prepared by diluting 0.036 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. Further, 2, 3, and 4 hours after the start of polymerization, a solution prepared by diluting 0.048 g, 0.12 g, and 0.36 g of di (3,5,5-trimethylhexanoyl) peroxide with 1 g of ethyl acetate was added. did. Seven hours after the first introduction of the polymerization initiator, the mixture was cooled to room temperature to terminate the polymerization to obtain an ethyl acetate solution of the organic polymer (b1) having an N, N-dialkylamide group. The number average molecular weight of the obtained organic polymer (b1) was about 3000 (molecular weight measured by gel permeation chromatography was converted to polystyrene).

(Preparation of organic polymer (b2) having tertiary amino group)
4. In a 0.5 L separable flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas inlet, 95 g of n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) and N-vinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) 0 g, 5.0 g of lauryl mercaptan (Wako Pure Chemical Industries, Ltd.) and 100 g of ethyl acetate were added and mixed. After the dissolved oxygen was removed by bubbling the monomer mixed solution with nitrogen gas for 20 minutes, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was increased to reach reflux while stirring. After refluxing, a solution obtained by diluting 0.024 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was added to the polymerization system. After 1 hour, a solution prepared by diluting 0.036 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. Further, 2, 3, and 4 hours after the start of polymerization, a solution prepared by diluting 0.048 g, 0.12 g, and 0.36 g of di (3,5,5-trimethylhexanoyl) peroxide with 1 g of ethyl acetate was added. did. Seven hours after the first introduction of the polymerization initiator, the mixture was cooled to room temperature to terminate the polymerization to obtain an ethyl acetate solution of an organic polymer (b2) having a tertiary amino group. The number average molecular weight of the obtained organic polymer (b2) was about 3000 (molecular weight by gel permeation chromatography was converted to polystyrene).

(Preparation of organic polymer (b3) having nitrile group)
In a 0.5 L separable flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas inlet, 95 g of n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 5.0 g of methacrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), Lauryl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) 5.0 g and ethyl acetate 100 g were added and mixed. After the dissolved oxygen was removed by bubbling the monomer mixed solution with nitrogen gas for 20 minutes, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was increased to reach reflux while stirring. After refluxing, a solution obtained by diluting 0.024 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was added to the polymerization system. After 1 hour, a solution prepared by diluting 0.036 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. Further, 2, 3, and 4 hours after the start of polymerization, a solution prepared by diluting 0.048 g, 0.12 g, and 0.36 g of di (3,5,5-trimethylhexanoyl) peroxide with 1 g of ethyl acetate was added. did. Seven hours after the first introduction of the polymerization initiator, the mixture was cooled to room temperature to terminate the polymerization to obtain an ethyl acetate solution of an organic polymer (b3) having a nitrile group. The number average molecular weight of the obtained organic polymer (b2) was about 3000 (molecular weight by gel permeation chromatography was converted to polystyrene).

(Preparation of organic polymer (b4) having an isocyanate group)
In a 0.5 L separable flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas inlet, n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) 95 g, 2 methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko KK) 5.0 g, lauryl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) 5.0 g and ethyl acetate 100 g were added and mixed. After the dissolved oxygen was removed by bubbling the monomer mixed solution with nitrogen gas for 20 minutes, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was increased to reach reflux while stirring. After refluxing, a solution obtained by diluting 0.024 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was added to the polymerization system. After 1 hour, a solution prepared by diluting 0.036 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. Further, 2, 3, and 4 hours after the start of polymerization, a solution prepared by diluting 0.048 g, 0.12 g, and 0.36 g of di (3,5,5-trimethylhexanoyl) peroxide with 1 g of ethyl acetate was added. did. Seven hours after the first polymerization initiator was charged, the mixture was cooled to room temperature to complete the polymerization, and an ethyl acetate solution of an organic polymer (b4) having an isocyanate group was obtained. The number average molecular weight of the obtained organic polymer (b2) was about 3000 (molecular weight by gel permeation chromatography was converted to polystyrene).

(Preparation of an organic polymer (c) having both a crosslinkable silyl group and an N, N-dialkylamide group)
4. In a 0.5 L separable flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas inlet, n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) 95 g, N-acryloylmorpholine (manufactured by Wako Pure Chemical Industries, Ltd.) 0 g, 0.5 g of 3-methacryloyloxypropyltrimethoxysilane (KBE-503, Shin-Etsu Chemical Co., Ltd.), 0.2 g of 3-mercaptopropyltrimethoxysilane (KBM-803, Shin-Etsu Chemical Co., Ltd.), Lauryl mercaptan (Wako Pure Chemical Industries, Ltd.) 0.1 g) and 100 g of ethyl acetate were added and mixed. After the dissolved oxygen was removed by bubbling the monomer mixed solution with nitrogen gas for 20 minutes, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was increased to reach reflux while stirring. After refluxing, a solution obtained by diluting 0.024 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was added to the polymerization system. After 1 hour, a solution prepared by diluting 0.036 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. Further, 2, 3, and 4 hours after the start of polymerization, a solution prepared by diluting 0.048 g, 0.12 g, and 0.36 g of di (3,5,5-trimethylhexanoyl) peroxide with 1 g of ethyl acetate was added. did. Seven hours after the first introduction of the polymerization initiator, the polymerization was terminated by cooling to room temperature, and an ethyl acetate solution of an organic polymer (c) containing an N, N-dialkylamide group and a hydrolyzable silyl group was obtained. . The number average molecular weight of the obtained organic polymer (c) was about 50,000 (the molecular weight was converted to polystyrene by gel permeation chromatography).

(Example 1)
The vinyl polymer (a) obtained above and the ethyl acetate solution of the carboxyl group-containing acrylic polymer (b) are prepared so that the ratio of the polymer (a) to the polymer (b) is as shown in Table 1. After mixing, the solvent was removed using a rotary evaporator to obtain a viscous liquid composition. The viscosity of this composition was about 300,000 cps at 25 ° C.

(Examples 2-6 and comparative examples)
A curable composition was prepared in the same manner as in Example 1 so that the composition ratio shown in Table 1 below was obtained.

(Example 7)
During the preparation of the curable composition, 10 g of layered silicate Somasifu MPE-100 (swelling fluorinated mica organically treated with polyoxypropylene diethyl quaternary ammonium salt, manufactured by Co-op Chemical), tinuvin 770 (hindered amine light stabilizer, A curable composition was obtained in the same manner as in Example 1 except that 5 g of Ciba Specialty Chemicals Co., Ltd.) and 5 g of Tinuvin 327 (benzotriazole ultraviolet absorber, Ciba Specialty Chemicals Co., Ltd.) were added.

Using the obtained curable composition, the viscosity, tensile test, nitrogen content, and adhesion were evaluated as follows. The results are shown in Table 1.
(Measurement of viscosity)
For the curable compositions of Examples 1 to 6 and Comparative Example 1, the curable composition immediately after preparation was allowed to stand at 25 ° C. for 1 day, and then a B-type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.) was used. The viscosity at 25 ° C. was measured.
Further, after leaving the curable composition stored in an oven at 60 ° C. for 60 days at 25 ° C. for 1 day, the viscosity at 25 ° C. was measured at a rotation speed of 10 rpm using a B-type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.). did. The curable composition of Comparative Example 1 was gelled and could not be measured for viscosity.

〔Tensile test〕
To 100 g of each of the curable compositions of Examples 1 to 6 and Comparative Example 1, 20 g of fatty acid surface-treated calcium carbonate, 50 g of heavy calcium carbonate, and 3 g of a curing accelerator (dibutyltin dilaurate) were added, and uniformly with a sealed stirrer Then, the mixture was degassed under reduced pressure for 10 minutes to obtain a white paste-like curable composition. The curable composition thus obtained was applied on a polyethylene plate so as to have a film thickness of 2.5 mm, and then cured for 7 days in an environment of 20 ° C. and a relative humidity of 50%. A rubbery sheet coating was obtained. The obtained rubber sheet was subjected to a tensile test in a No. 3 dumbbell shape at a crosshead speed of 500 mm / min in accordance with JIS K 6301 to obtain a breaking elongation (%) and a breaking stress (N / mm ² ).

(Measurement of nitrogen content)
The nitrogen content in the curable compositions of Examples 1 to 6 and Comparative Example 1 was measured with an elemental analyzer (P2400II, manufactured by PerkinElmer).

〔Adhesiveness〕
Same as used in the above tensile test on 50 mm x 150 mm (thickness 1 mm) anodized and PVC steel sheet with a 25 mm wide cellophane tape attached to the edge to make it easy to peel off the cured film. The composition was applied (width 10 mm, length 100 mm, thickness 2 mm), and cured for 7 days in an environment of 20 ° C. and 50% RH to produce a test piece for adhesion evaluation. The cured product was pulled in the 90 ° direction with respect to the adherend, and the adhesion was evaluated.

(Measurement of average interlayer distance of layered silicate)
The average interlayer distance of the layered silicate in the curable composition obtained in Example 7 was measured as follows.
Using an X-ray diffractometer (RINT1100, manufactured by Rigaku Corporation), 2θ of the diffraction peak obtained by diffraction of the layered surface of the layered silicate was measured, and (001) of the layered silicate was determined using the following black diffraction formula. ) The surface spacing (d) was calculated, and the surface spacing (d) was taken as the average interlayer distance. The average interlayer distance was 3 nm or more, and the dispersion was good.
λ = 2 dsin θ
In the formula, λ (nm) = 0.154, d (nm) is the surface spacing of the layered silicate, and θ (degree) is the diffraction angle.

[Confirmation of dispersion state of layered silicate]
The dispersion state of the layered silicate in the curable composition obtained in Example 7 was measured as follows.
When the dispersion state of the layered silicate in the cured product was observed with a transmission electron microscope (TEM, “JEM-1200EX II” manufactured by JEOL Ltd.), it was present in 5 layers or less.

〔Weatherability〕
The curable compositions obtained in Examples 1 and 7 were applied to a stainless steel plate of 50 mm × 150 mm (thickness 1 mm) at a thickness of 0.5 mm, and the atmosphere was 20 ° C. × 60% RH for 7 days (168 hours). After leaving it to cure and cure, light irradiation was performed for 150 hours and 400 hours under the following conditions, the surface state was observed visually, and judged according to the following criteria. The results are shown in Table 2.

(Light irradiation conditions)
Test apparatus: Eye super UV tester (SUV-F11 type), manufactured by Iwasaki Electric Co., Ltd. Irradiation intensity: 100 mW / cm <2>
・ Limited wavelength: 295 nm to 450 nm
・ Black panel temperature: 63 ℃
・ Irradiation distance: 235mm (between light source and sample)
Note that the light irradiation test with the iSuper UV tester varies depending on the material system and test conditions, so it cannot be said unconditionally. However, it usually has a 10 times more severe acceleration effect than the test with the sunshine weatherometer. Has been.
(Criteria)
○: No cracks were observed △: Slight cracks were observed, but no problem

The schematic diagram for demonstrating the crystal | crystallization surface (A) and crystal | crystallization end surface (B) of the flaky crystal | crystallization of a layered silicate. The schematic diagram for demonstrating the exchangeable cation between the layers of layered silicate.

Claims (11)

A group comprising a vinyl polymer (a) having a crosslinkable silyl group represented by the formula (1) and a tertiary amino group, N, N-dialkylamide group, isocyanate group, nitrile group, urethane bond and urea bond. A curable composition comprising an organic polymer (b) having at least one segment selected from the group consisting of:
_{^{- [Si (R 3) 2}} -b (Y) b O] m -Si (R 4) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ Si— ( R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and represents a triorganosiloxy group represented by R ¹ Alternatively, when two or more R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0 or 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 to be satisfied.) Selected from the group consisting of a polymer moiety having a terminal crosslinkable silyl group represented by formula (1), a tertiary amino group, an N, N-dialkylamide group, an isocyanate group, a nitrile group, a urethane bond and a urea bond. A curable composition comprising as a main component an organic polymer (c) comprising a polymer portion having at least one segment.
_{^{- [Si (R 3) 2}} -b (Y) b O] m -Si (R 4) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ Si— ( R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and represents a triorganosiloxy group represented by R ¹ Alternatively, when two or more R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0 or 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 to be satisfied.)   A curable composition comprising a vinyl polymer (a) and an organic polymer (c).   The curable composition according to any one of claims 1 to 3, wherein at least one of the vinyl polymer and the organic polymer has a viscosity at 25 ° C in a range of 10 to 500,000 cps.   The curable composition according to any one of claims 1 to 4, wherein the vinyl polymer and the organic polymer have a number average molecular weight in the range of 5,000 to 100,000.   The curable composition according to any one of claims 1 to 5, further comprising a polyether polymer (d) having at least a crosslinkable hydrolyzable silyl group.   The curable composition according to claim 1, further comprising a layered silicate.   The curable composition according to any one of claims 1 to 7, wherein the nitrogen element content is in the range of 0.01 to 5% by weight.   The curable composition according to any one of claims 1 to 8, wherein the viscosity at 25 ° C after 60 days at 60 ° C is in the range of 0.5 to 10 times the viscosity at 25 ° C immediately after blending.   A sealing material comprising the curable composition according to claim 1.   An adhesive comprising the curable composition according to claim 1.

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