WO2018179455A1

WO2018179455A1 - Polymer having reactive silicon-containing group and production method therefor

Info

Publication number: WO2018179455A1
Application number: PCT/JP2017/018337
Authority: WO
Inventors: 山田　哲郎; 宗直廣神
Original assignee: 信越化学工業株式会社
Priority date: 2017-03-30
Filing date: 2017-05-16
Publication date: 2018-10-04
Also published as: JP2017141467A

Abstract

A polymer which has a main-chain skeleton comprising a given polymer, e.g., a polyurethane, polyurea, or polyoxyalkylene, and which has, in the molecule, at least one reactive silicon-containing group represented by structural formula (1). The polymer has satisfactory rapid-curing properties regardless of whether no curing catalyst is contained or an amine-based compound is used as a curing catalyst. The polymer is highly safe. (R1 and R2 each independently represent a C1-10 alkyl, etc.; two R3's each independently represent a C1-10 alkyl, etc. or are bonded to each other to represent a C1-10 alkylene, etc.; R5 represents a C1-10 alkylene; R6 represents a hydrogen atom, etc.; X represents O, S, etc.; m is an integer of 1 to 3; and * indicates a linking bond.)

Description

Polymer having reactive silicon-containing group and method for producing the same

The present invention relates to a polymer having a reactive silicon-containing group and a method for producing the same, and more specifically, as a silicon group that can be crosslinked by forming a siloxane bond (hereinafter also referred to as “reactive silicon group”). The present invention relates to a polymer containing an alkoxy group bonded to a silicon atom at a molecular chain end and a method for producing the same.

Since reactive silicon groups, especially alkoxysilyl groups, have the property of hydrolytic condensation in the presence of moisture, polymers having reactive silicon groups are cured by crosslinking and curing in the presence of moisture or moisture. Can be used as a composition.
Among these polymers, those whose main chain is a polyoxyalkylene polymer are generally known as modified silicones, and those whose main chain is a silicon-containing compound are generally known as end-capped silicones. It has been. In addition, a curable composition using a polymer having a reactive silicon group as typified by these is liquid at room temperature and has a characteristic of becoming a rubber elastic body upon curing. It is widely used for coating agents, adhesives, architectural sealants, etc.

Numerous proposals have been made for a method for producing a polymer having a reactive silicon group at the molecular chain terminal, and some have already been industrially produced.
For example, as a compound in which the main chain is a polyoxyalkylene group and the molecular chain terminal is an alkoxysilyl group, a polymer in which the main chain is polyoxypropylene and a methyldimethoxysilyl group is bonded to both ends of the molecular chain is known. As a typical example of such a polymer, a room temperature curable composition containing an alkoxysilyl end-capped polyoxyalkylene compound as a main agent (base polymer) is known (Patent Documents 1 and 2).
However, the room temperature curable compositions disclosed in Patent Documents 1 and 2 have low reactivity with moisture in the air and insufficient curability, so that sufficient curability at room temperature is ensured. In general, however, it is indispensable to add a catalyst such as an organotin compound, but the organotin compound is concerned about toxicity to the human body and the environment. In recent years, environmental regulations have become strict, and its use is avoided.

Patent Document 3 discloses an alkoxysilyl end-capped polymer obtained by reacting a polymer having a hydroxyl group at a terminal with isocyanate silane or the like in order to improve reactivity.
However, in the compound of Patent Document 3, although the reactivity is improved to some extent, when it does not contain a curing catalyst, its curability is very slow, and when used as a room temperature curable composition, the curability is low. Not only is it insufficient, but when we actually confirmed the curability when using an amine compound as a curing catalyst, the curability is still not satisfactory and there is room for improvement in terms of curability. .

JP 2004-099908 A JP 2010-209205 A JP-T-2004-518801

The present invention has been made in view of the above circumstances, and in both cases where no curing catalyst is contained and when an amine compound is used as a curing catalyst, fast curability is good and the reactivity is excellent in safety. It is an object of the present invention to provide a polymer having a silicon-containing group and a method for producing the same.

As a result of intensive studies to solve the above problems, the present inventors have determined that a predetermined polymer containing a specific tertiary amino-methylene-silyl bond as a linking group between the alkoxysilyl group at the molecular chain terminal and the main chain structure And a method for producing the same, and a composition containing this polymer is suitable as a curable composition for forming a material such as a coating agent, an adhesive, and a sealant, in order to give a cured product excellent in rapid curing. The headline and the present invention were completed.

That is, the present invention
1. Polyurethane, polyurea, polyoxyalkylene, polycarbonate, polyester, polyamide, polyimide, polyamideimide, poly (meth) acrylate, polystyrene, polyolefin, polyvinyl ester, polytetrafluoroethylene, polyacetal, polyphenylene ether, polyphenylene sulfide, polysulfone, poly Ether sulfone, polyether ether ketone, polysiloxane, polysiloxane-polyurethane copolymer and polysiloxane-polyurea copolymer, and a main chain skeleton selected from these copolymers, and in one molecule A polymer having at least one reactive silicon-containing group represented by the following structural formula (1):

(Wherein, R ^{1 s} , independently of each other, represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, and R ² represents Independent of each other, it represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, and R ³ , independently of each other, is unsubstituted or Represents a substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, or an unsubstituted or substituted carbon atom having 1 to 10 carbon atoms in which R ³ is bonded to each other. Represents an alkylene group, or an unsubstituted or substituted arylene group having 6 to 20 carbon atoms, R ⁵ represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, R ⁶ represents a hydrogen atom, or Non-replacement Ku denotes an alkyl group having 1 to 10 carbon atoms substituted, X is represents O or S, m is an integer of 1-3, * represents a bond.)
2. A polymer having one reactive silicon-containing group represented by the following structural formula (2);

Wherein R ¹ , R ² , R ³ and m represent the same meaning as described above, R ⁵ represents the same meaning as described above independently of each other, and R ⁶ represents the same meaning as described above independently of each other. X represents the same meaning as described above independently of each other, A represents polyurethane, polyurea, polyoxyalkylene, polycarbonate, polyester, polyamide, polyimide, polyamideimide, poly (meth) acrylate, polystyrene, polyolefin, Polyvinyl ester, polytetrafluoroethylene, polyacetal, polyphenylene ether, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, polysiloxane, polysiloxane-polyurethane copolymer and polysiloxane-polyurea copolymer, and These copolymers Represents a divalent linking group having a structure selected et.)
3. The polymer having 1 or 2 reactive silicon-containing groups represented by the following formula (3):

(Wherein R ⁶ and X each independently represent the same meaning as described above, and Y each independently represents an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, an unsubstituted or substituted carbon, Represents an aralkylene group having 7 to 20 atoms or an unsubstituted or substituted arylene group having 6 to 20 carbon atoms, n represents an integer of 1 or more, and Z represents a polyurethane, polyurea, polyoxyalkylene, polycarbonate , Polyester, polyamide, polyimide, polyamideimide, poly (meth) acrylate, polystyrene, polyolefin, polyvinyl ester, polytetrafluoroethylene, polyacetal, polyphenylene ether, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, poly Siloxane, Polysiloxane - represents polyurea copolymer, and a divalent linking group having a structure selected from these copolymers, * represents a bond) - polyurethane copolymers and polysiloxanes.
4). The polymer having a reactive silicon-containing group of any one of 1 to 3, wherein Z is a divalent linking group having a polyoxyalkylene structure;
5). A polymer in which the divalent linking group having a polyoxyalkylene structure has a reactive silicon-containing group of any one of 1 to 4 represented by the following formula (4):

(In the formula, R ⁴ represents a divalent hydrocarbon group, p represents an integer of 1 or more, and * represents a bond.)
6). A polymer whose molecular chain ends are blocked with an isocyanate group or an isothiocyanate group, and a compound of formula (5)

(In the formula, R ¹ , R ² , R ³ , R ⁵ and m have the same meaning as described above.)
A process for producing a polymer having a reactive silicon-containing group according to any one of 1 to 5, which comprises reacting a compound having a secondary amino group, a tertiary amino group and an alkoxysilyl group,
7). A method for producing a polymer in which the polymer having the molecular chain terminal blocked with an isocyanate group or an isothiocyanate group has 6 reactive silicon-containing groups represented by the following formula (6):

(In the formula, A represents the same meaning as described above. X represents O or S independently of each other.)
8). A process for producing a polymer having 7 reactive silicon-containing groups, wherein A in the formula (6) is a divalent linking group having a polyoxyalkylene structure,
9. (A) a curable composition comprising a polymer having a reactive silicon-containing group according to any one of 1 to 5,
10. Further, (B) 9 curable composition containing a curing catalyst,
11. (10) the curable composition (B), wherein the curing catalyst is an amine compound;
12 A coating agent comprising any one of the curable compositions of 9 to 11,
13. An adhesive comprising any one of the curable compositions of 9 to 11,
14 A cured article obtained by curing any of the curable compositions of 9 to 11,
15. A cured article having a coating layer formed by curing 12 coating agents;
16. A cured article having an adhesive layer formed by curing 13 adhesives is provided.

The polymer having a reactive silicon-containing group of the present invention has good fast curability even when an amine compound is used as a curing catalyst so as not to contain an organotin compound, and further the curing catalyst. Even if it does not contain, the fast curability is good.
The compound of the present invention having such properties can be suitably used as a main agent (base polymer) such as a coating agent, an adhesive, and a sealant.

Hereinafter, the present invention will be specifically described.
The polymer having a reactive silicon-containing group according to the present invention has a polymer main chain and at least one reactive silicon-containing group represented by the following structural formula (1) in one molecule, which is bonded to the main chain. .

(In the formula, * represents a bond.)

In the formula (1), R ^{1 s} , independently of each other, are unsubstituted or substituted alkyl groups having 1 to 10, preferably 1 to 4 carbon atoms, or unsubstituted or substituted carbon atoms having 6 to Represents an aryl group of 10 and R ² independently of each other is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, or an unsubstituted or substituted carbon atom 6 Represents an aryl group of ˜10.

In the above R ¹ and R ² , the alkyl group having 1 to 10 carbon atoms may be linear, cyclic or branched, and specific examples thereof include methyl, ethyl, n-propyl, i- Linear or branched alkyl groups such as propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl group, Examples thereof include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl group and the like.
Some or all of the hydrogen atoms in these groups may be substituted with a halogen atom such as an alkyl group, an aryl group, F, Cl, or Br, a cyano group, or the like. Examples include chloropropyl group, 3,3,3-trifluoropropyl group, 2-cyanoethyl group and the like.
Among these, as R < ¹ >, R < ² >, a methyl group, an ethyl group, and a phenyl group are preferable, and a methyl group is more preferable from the surface of sclerosis | hardenability, availability, productivity, and cost.

In the formula (1), R ^{3 s} independently of each other are unsubstituted or substituted alkyl groups having 1 to 10, preferably 1 to 6 carbon atoms, or unsubstituted or substituted carbon atoms having 6 to 6 carbon atoms. It represents a 10 aryl group, R ³ together are bonded, an unsubstituted or substituted C 1 -C 10, preferably an alkylene group having 1 to 4 carbon atoms or an unsubstituted or substituted C 6 -C, 20 arylene groups are represented, and examples of these alkyl groups and aryl groups include the same groups as those exemplified above for R ¹ and R ² .

Specific examples of the alkylene group having 1 to 10 carbon atoms in R ³ include methylene, ethylene, trimethylene, propylene, tetramethylene, isobutylene, dimethylethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, heptamethylene Linear or branched alkylene groups such as octamethylene, nonamethylene, decylene (decamethylene) groups; cycloalkylene groups such as cyclopentylene groups and cyclohexylene groups.
Examples of the arylene group having 6 to 20 carbon atoms include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, oxybisphenylene, sulfonebisphenylene, toluenediyl, xylenediyl, naphthalenediyl group and the like. And an arylene group.
Some or all of the hydrogen atoms in these groups may be substituted with a halogen atom such as an alkyl group, an aryl group, F, Cl, or Br, a cyano group, or the like. Examples thereof include a chlorotrimethylene group, a 2,3,3-trifluorotrimethylene group, and a 2-chloro-1,4-phenylene group.

Of these, when R ³ is not bonded to each other and does not form a ring, R ³ is preferably a methyl, ethyl, t-butyl, or phenyl group, which is advantageous in terms of curability, availability, productivity, and cost. In consideration, methyl and t-butyl groups are more preferable.
On the other hand, when R ³ is bonded to each other to form a ring, R ³ is preferably methylene or ethylene group. In view of curability, availability, productivity, and cost, methylene group is more preferable. preferable.

In the formula (1), R ⁵ represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms.
Examples of the alkylene group for R ⁵ include the same groups as those exemplified for R ³ above. Among them, methylene and ethylene groups are preferable, and in consideration of curability, availability, productivity, and cost. An ethylene group is more preferable.

In the formula (1), R ⁶ is a hydrogen atom or an unsubstituted or substituted C 1 -C 10, preferably an alkyl group having 1 to 4 carbon atoms, examples of the alkyl group, the above R ¹ The thing similar to the illustrated group is mentioned.
Among these, as R ⁶ , a hydrogen atom, a methyl group, and a phenyl group are preferable, and a hydrogen atom is more preferable in consideration of curability, availability, productivity, and cost.

In Formula (1), X represents O (oxygen atom) or S (sulfur atom), and O is preferable in consideration of curability, availability, productivity, and cost.
M represents an integer of 1 to 3, preferably 2 to 3, more preferably 3 from the viewpoint of reactivity.

If the polymer of the present invention is a polymer having at least one reactive silicon group represented by the structural formula (1) in one molecule, the structure of the main chain skeleton to which the reactive silicon group is linked is particularly limited. The main chain skeleton may have a linear structure, a branched structure, or a crosslinked structure.

Specific examples of the main chain skeleton of the polymer of the present invention include: polyurethane; polyurea; polyoxyalkylene (polyether); polycarbonate; polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, Polyesters such as amorphous polyarylate and liquid crystal polymer; polyamide; polyimide; polyamideimide; poly (meth) acrylate; polystyrene; polyethylene, polypropylene, polyvinyl chloride, cyclic polyolefin, polybutadiene, polyisoprene, polyisobutylene, styrene-butadiene copolymer Polymer, polychloroprene, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, isobutylene-iso Polyethylene, such as polyolefin copolymer such as len copolymer, ethylene-propylene copolymer, ethylene-propylene-cyclic olefin copolymer, polyvinyl acetate; polytetrafluoroethylene; polyacetal; polyphenylene ether; polyphenylene sulfide; polysulfone; poly Ether sulfone; polyether ether ketone; (dimethyl) polysiloxane, (dimethyl) polysiloxane-polyurethane copolymer, (dimethyl) polysiloxane-polyurea copolymer, and the like. It may be a main chain composed of a copolymer of more than one component.

Among these, as the main chain skeleton of the polymer of the present invention, polyurethane, polyurea, polyoxyalkylene (polyether), polyester, poly (meth) acrylate, polyolefin, (dimethyl) polysiloxane, (dimethyl) polysiloxane- Polyurethane copolymers and (dimethyl) polysiloxane-polyurea copolymers are preferred. In view of curability, availability, productivity, and cost, polyurethane, polyurea, polyoxyalkylene (polyether), (Dimethyl) polysiloxane-polyurethane copolymer and (dimethyl) polysiloxane-polyurea copolymer are more preferred, and polyurethane, polyurea and polyoxyalkylene (polyether) are even more preferred.

Further, in the polymer of the present invention, at least one reactive silicon group represented by the structural formula (1) is contained in one molecule at the molecular chain terminal, but the structural formula (1) contained in one molecule. If the average number of reactive silicon groups represented by is less than 1, the curability of the composition containing this as the main agent and the mechanical properties of the cured product become insufficient.
On the other hand, if there are too many reactive silicon groups, the crosslink density becomes too high, and the resulting cured product may not exhibit good mechanical properties, or the storage stability of the composition may deteriorate. Therefore, the number of reactive silicon groups contained in one molecule is preferably 1.1 to 5, more preferably 2 to 4, and even more preferably 2 (for example, one at each end of the molecular chain). Each).

Therefore, as the polymer of the present invention, those represented by the following structural formula (2) are preferable. By using such a polymer, the mechanical properties of the obtained cured product and the storage stability of the composition are further improved. Become.

In the formula (2), R ¹ , R ² , R ³ and m represent the same meaning as described above, R ⁵ represents the same meaning as described above independently of each other, and R ⁶ represents the same as defined above independently of each other. The same meaning is represented and X represents the same meaning as the above independently of each other.
A is not particularly limited as long as A is a divalent linking group having a structure corresponding to the above-described polymer main chain skeleton, and similarly to the above, a linear structure in the main chain skeleton, It may have a branched structure or a crosslinked structure.

Specific examples of A include: polyurethane; polyurea; polyoxyalkylene (polyether); polycarbonate; polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, amorphous polyarylate, liquid crystal polymer Polyamide; Polyimide; Polyamideimide; Poly (meth) acrylate; Polystyrene; Polyethylene, Polypropylene, Polyvinyl chloride, Cyclic polyolefin, Polybutadiene, Polyisoprene, Polyisobutylene, Styrene-butadiene copolymer, Polychloroprene, Acrylonitrile— Butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, isobutylene-isoprene copolymer, ethylene Polyolefin such as propylene copolymer, ethylene-propylene-cyclic olefin copolymer, polyvinyl ester such as polyvinyl acetate; polytetrafluoroethylene; polyacetal; polyphenylene ether; polyphenylene sulfide; polysulfone; polyethersulfone; polyetherether Ketones: (dimethyl) polysiloxane, (dimethyl) polysiloxane-polyurethane copolymer, (dimethyl) polysiloxane-polyurea copolymer and other divalent linking groups containing a polymer structure. It may be a divalent linking group contained or a divalent linking group comprising a copolymer of two or more components.

Among these, A includes polyurethane, polyurea, polyoxyalkylene (polyether), polyester, poly (meth) acrylate, polyolefin, (dimethyl) polysiloxane, (dimethyl) polysiloxane-polyurethane copolymer, (dimethyl) ) A divalent linking group containing a polysiloxane-polyurea copolymer is preferable. In view of curability, availability, productivity, and cost, polyurethane, polyurea, polyoxyalkylene (polyether) Divalent linking groups containing (dimethyl) polysiloxane-polyurethane copolymer and (dimethyl) polysiloxane-polyurea copolymer are more preferred, and contain polyurethane, polyurea, polyoxyalkylene (polyether) structure A divalent linking group is more preferred.

That is, as the polymer of the present invention, it is preferable that A in the above formula (2) is represented by the following structural formula (3). By using such a polymer, the mechanical properties and composition of the cured product obtained are obtained. The storage stability of the product is further improved.

(In the formula, * represents a bond.)

In the formula (3), R ⁶ and X each independently represent the same meaning as described above.
Y is independently of each other an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, an unsubstituted or substituted aralkylene group having 7 to 20 carbon atoms, or an unsubstituted or substituted carbon atom having 6 to 20 carbon atoms. Represents an arylene group.
Specific examples of the alkylene group having 1 to 20 carbon atoms include the same groups as those exemplified above for R ³ , but a chain portion and a cyclic portion represented by the following formula (A) are included. It may be a divalent group that coexists.

(In the formula, Me represents a methyl group, and * represents a bond.)

Examples of the arylene group having 6 to 20 carbon atoms include the same groups as those exemplified for R ³ above.
Specific examples of the aralkylene group having 7 to 20 carbon atoms include methylene bisphenylene, dimethylmethylene bisphenylene, ethylene bisphenylene, and tetramethylene bisphenylene groups. In addition, some or all of hydrogen atoms of these groups may be substituted with a halogen atom such as an alkyl group, an aryl group, F, Cl, or Br, a cyano group, or the like. Specific examples thereof include difluoromethylene. A bisphenylene group etc. are mentioned.
Among these, Y is preferably hexamethylene, methylenebisphenylene, 1,4-phenylene, toluenediyl, naphthalenediyl, or a divalent group represented by the above formula (A), and is curable or easily available. In view of productivity, cost, and environmental considerations, hexamethylene, methylenebisphenylene, toluenediyl, and a divalent group represented by the above formula (A) are more preferable, represented by the above formula (A). Divalent groups are even more preferred.

N in the formula (3) is a number of 1 or more, but is preferably 1 to 1,000, more preferably 1 to 500, from the viewpoint of mechanical properties of the resulting cured product and workability of the composition. Is even more preferable.
Z is not particularly limited as long as Z is a divalent linking group containing a structure corresponding to the above-described polymer main chain skeleton, and as described above, the structure is linear in the main chain skeleton. It may have a structure, a branched structure, or a crosslinked structure.

Specific examples of Z include: polyurethane; polyurea; polyoxyalkylene (polyether); polycarbonate; polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, amorphous polyarylate, liquid crystal polymer Polyamide; Polyimide; Polyamideimide; Poly (meth) acrylate; Polystyrene; Polyethylene, Polypropylene, Polyvinyl chloride, Cyclic polyolefin, Polybutadiene, Polyisoprene, Polyisobutylene, Styrene-butadiene copolymer, Polychloroprene, Acrylonitrile— Butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, isobutylene-isoprene copolymer, ethylene Polyolefin such as propylene copolymer, ethylene-propylene-cyclic olefin copolymer, polyvinyl ester such as polyvinyl acetate; polytetrafluoroethylene; polyacetal; polyphenylene ether; polyphenylene sulfide; polysulfone; polyethersulfone; polyetherether Ketones: (dimethyl) polysiloxane, (dimethyl) polysiloxane-polyurethane copolymer, (dimethyl) polysiloxane-polyurea copolymer and other divalent linking groups containing a polymer structure. It may be a divalent linking group contained or a divalent linking group comprising a copolymer of two or more components.

Among these, as Z, polyurethane, polyurea, polyoxyalkylene (polyether), polyester, poly (meth) acrylate, polyolefin, (dimethyl) polysiloxane, (dimethyl) polysiloxane-polyurethane copolymer, (dimethyl) ) A divalent linking group containing a polysiloxane-polyurea copolymer is preferable. In view of curability, availability, productivity, and cost, polyurethane, polyurea, polyoxyalkylene (polyether) Divalent linking groups containing (dimethyl) polysiloxane-polyurethane copolymer and (dimethyl) polysiloxane-polyurea copolymer are more preferred, and contain polyurethane, polyurea, polyoxyalkylene (polyether) structure And more preferably a divalent linking group From the viewpoint of the storage stability of the mechanical properties and composition of the product, a divalent linking group having a polyoxyalkylene structure are particularly preferred.

The polyoxyalkylene structure may have any of a linear structure, a branched structure, and a crosslinked structure. From the viewpoint of the mechanical properties of the resulting cured product and the storage stability of the composition, the polyoxyalkylene structure is linear. A polyoxyalkylene structure is preferred.
In the present invention, the polyoxyalkylene structure being “linear” means that the divalent oxyalkylene groups, which are repeating units constituting the polyoxyalkylene structure, are linearly linked. This means that each oxyalkylene group itself may be linear or branched (for example, a propyleneoxy group such as —CH ₂ CH (CH ₃ ) O—).

Accordingly, the polymer of the present invention preferably has a linear structure in which Z in the above formula (3) has a repeating unit represented by the following structural formula (4). The mechanical properties of the resulting cured product and the storage stability of the composition are further improved.

(In the formula, * represents a bond.)

In the formula (4), R ⁴ is not particularly limited as long as it is a divalent hydrocarbon group, preferably a divalent aliphatic hydrocarbon group, but it is linear or branched having 1 to 14 carbon atoms. A chain alkylene group is preferable, and a linear or branched alkylene group having 2 to 4 carbon atoms is more preferable. Examples of the alkylene group include the same groups as those exemplified for R ³ above.
Further, p is an integer of 1 or more, but is preferably 5 to 700, more preferably 10 to 500, and still more preferably 20 to 300, from the viewpoint of mechanical properties of the obtained cured product and workability of the composition. . When p is 2 or more, a plurality of R ⁴ may be the same or different from each other.

Specific examples of the unit represented by —OR ⁴ — in the above formula (4) include —OCH ₂ —, —OCH ₂ CH ₂ —, —OCH ₂ CH ₂ CH ₂ —, —OCH ₂ CH (CH ₃ ). -, -OCH ₂ CH (CH ₂ CH ₃ )-, -OCH ₂ C (CH ₃ ) _2- , -OCH ₂ CH ₂ CH ₂ CH _2- and the like.

In the present invention, the main chain skeleton of the oxyalkylene polymer may be composed of one type of repeating units represented by the above formula (4), or may be composed of two or more types of repeating units. In particular, when used for materials such as a coating agent, an adhesive, and a sealant, a polymer containing propylene oxide (—CH ₂ CH (CH ₃ ) O—) as a main component is preferable from the viewpoint of durability.

The number average molecular weight of the polymer of the present invention is not particularly limited, but the workability is improved within the appropriate range of the viscosity of the curable composition containing the polymer, and sufficient curability is imparted. In view of the above, the number average molecular weight is preferably 200 to 200,000, more preferably 1,000 to 100,000. In addition, the number average molecular weight in this invention is a polystyrene conversion value in a gel permeation chromatography (GPC) analysis (hereinafter the same).

The viscosity of the polymer of the present invention is not particularly limited, but it is considered that the viscosity of the curable composition containing the polymer is within an appropriate range to improve workability and provide sufficient curability. Accordingly, the viscosity is preferably 10 to 200,000 mPa · s, more preferably 50 to 100,000 mPa · s, and particularly preferably 100 to 50,000 mPa · s. Here, the viscosity is a value measured at 25 ° C. by a B-type rotational viscometer.

The polymer of the present invention described above is a compound having a polymer having a molecular chain end blocked with an isocyanate group or an isothiocyanate group, and a secondary amino group, a tertiary amino group and an alkoxysilyl group represented by the following formula (5): (Hereinafter referred to as “secondary-tertiary diaminosilane”).
More specifically, a urea bond or thiourea is formed between the isocyanate group or isothiocyanate group of the polymer whose molecular chain end is blocked with an isocyanate group or isothiocyanate group and the secondary amino group of the secondary-tertiary diaminosilane. A reaction to form a bond (urea reaction or thiourea reaction) is performed.

(In the formula, R ¹ , R ² , R ³ , R ⁵ and m have the same meaning as described above.)

Specific examples of the secondary-tertiary diaminosilane represented by the above formula (5) include N- (trimethoxysilylmethyl) piperazine, N- (methyldimethoxysilylmethyl) piperazine, N- (dimethylmethoxysilylmethyl). Piperazine, N- (triethoxysilylmethyl) piperazine, N- (methyldiethoxysilylmethyl) piperazine, N- (dimethylethoxysilylmethyl) piperazine, N- (trimethoxysilylmethyl) imidazolidine, N- (methyldimethoxysilyl) Methyl) imidazolidine, N- (dimethylmethoxysilylmethyl) imidazolidine, N- (triethoxysilylmethyl) imidazolidine, N- (methyldiethoxysilylmethyl) imidazolidine, N- (dimethylethoxysilylmethyl) imidazolidine, N, N'-dimethyl -N- (trimethoxysilylmethyl) ethylenediamine, N, N'-dimethyl-N- (methyldimethoxysilylmethyl) ethylenediamine, N, N'-dimethyl-N- (dimethylmethoxysilylmethyl) ethylenediamine, N, N'- Dimethyl-N- (triethoxysilylmethyl) ethylenediamine, N, N'-dimethyl-N- (methyldiethoxysilylmethyl) ethylenediamine, N, N'-dimethyl-N- (dimethylethoxysilylmethyl) ethylenediamine, N, N '-Di-t-butyl-N- (trimethoxysilylmethyl) ethylenediamine, N, N'-di-t-butyl-N- (methyldimethoxysilylmethyl) ethylenediamine, N, N'-di-t-butyl-N- ( Dimethylmethoxysilylmethyl) ethylenediamine, N, N'-di-t- Cyl-N- (triethoxysilylmethyl) ethylenediamine, N, N'-di-t-butyl-N- (methyldiethoxysilylmethyl) ethylenediamine, N, N'-di-t-butyl-N- (dimethylethoxysilylmethyl) ) Ethylenediamine, N, N'-diphenyl-N- (trimethoxysilylmethyl) ethylenediamine, N, N'-diphenyl-N- (methyldimethoxysilylmethyl) ethylenediamine, N, N'-diphenyl-N- (dimethylmethoxysilyl) Methyl) ethylenediamine, N, N'-diphenyl-N- (triethoxysilylmethyl) ethylenediamine, N, N'-diphenyl-N- (methyldiethoxysilylmethyl) ethylenediamine, N, N'-diphenyl-N- (dimethyl) Ethoxysilylmethyl) ethylenediamine and below Although not limited to these, any secondary-tertiary diaminosilane represented by the above formula (5) can be used.

Among these, from the viewpoint of hydrolyzability, N- (trimethoxysilylmethyl) piperazine, N- (methyldimethoxysilylmethyl) piperazine, N- (triethoxysilylmethyl) piperazine, N, N′-dimethyl-N— (Trimethoxysilylmethyl) ethylenediamine, N, N'-dimethyl-N- (methyldimethoxysilylmethyl) ethylenediamine, N, N'-di-t-butyl-N- (trimethoxysilylmethyl) ethylenediamine, N, N'- Di-t-butyl-N- (methyldimethoxysilylmethyl) ethylenediamine, N, N'-diphenyl-N- (trimethoxysilylmethyl) ethylenediamine is preferred, N- (trimethoxysilylmethyl) piperazine, N- (methyldimethoxysilyl) Methyl) piperazine, N, N'-dimethyl- -(Trimethoxysilylmethyl) ethylenediamine, N, N'-dimethyl-N- (methyldimethoxysilylmethyl) ethylenediamine, N, N'-di-t-butyl-N- (trimethoxysilylmethyl) ethylenediamine, N, N ' -Di-t-butyl-N- (methyldimethoxysilylmethyl) ethylenediamine is more preferable, N- (trimethoxysilylmethyl) piperazine, N, N'-dimethyl-N- (trimethoxysilylmethyl) ethylenediamine, N, N ' -Di-t-butyl-N- (trimethoxysilylmethyl) ethylenediamine is more preferred.

If the polymer having the molecular chain terminal blocked with an isocyanate group or isothiocyanate group is a polymer containing an isocyanate group or isothiocyanate group at the molecular chain terminal, the structure of the main chain skeleton to which these groups are linked is particularly limited. The main chain skeleton may have a linear structure, a branched structure, or a crosslinked structure.
Among these, a linear structure is preferable from the viewpoint of mechanical properties of the obtained cured product and storage stability of the composition.

Specific examples of the main chain skeleton of the polymer whose molecular chain terminal is blocked with an isocyanate group or an isothiocyanate group include those exemplified for the main skeleton of the polymer represented by the above formula (1). Among them, polyurethane, polyurea, polyoxyalkylene (polyether), polyester, poly (meth) acrylate, polyolefin, (dimethyl) polysiloxane, (dimethyl) polysiloxane-polyurethane copolymer, (dimethyl) polysiloxane-poly Urea copolymers are preferred, and in view of curability, availability, productivity, and cost, polyurethane, polyurea, polyoxyalkylene (polyether), (dimethyl) polysiloxane-polyurethane copolymer, ( (Dimethyl) polysiloxane-polyurea copolymer is more preferred , Polyurethanes, polyureas, polyoxyalkylene (polyether) is more preferable.

In addition, the polymer whose molecular chain terminal is blocked with an isocyanate group or isothiocyanate group contains at least one isocyanate group or isothiocyanate group in one molecule, but the isocyanate group contained in one molecule. Alternatively, if the number of isothiocyanate groups on average is less than 1, the curability of the composition of the present invention and the mechanical properties of the cured product become insufficient.
On the other hand, if there are too many isocyanate groups or isothiocyanate groups, the crosslinking density becomes too high, and the resulting cured product may not exhibit good mechanical properties, or the storage stability of the composition may deteriorate. Therefore, the number of isocyanate groups or isothiocyanate groups contained in one molecule is 1 or more, preferably 1.1 to 5, more preferably 2 to 4, and still more preferably 2 (for example, molecular chain One at each end).

Therefore, as the polymer whose molecular chain terminal is blocked with an isocyanate group or an isothiocyanate group, a polymer represented by the following structural formula (6) is preferable. By using such a polymer, mechanical properties of the obtained cured product are obtained. Further, the storage stability of the composition is further improved.

(In the formula, A represents the same meaning as described above.)

In the formula (6), X represents O (oxygen atom) or S (sulfur atom) independently of each other, but O is preferable from the viewpoint of curability, availability, productivity, and cost.

As the polymer in which the molecular chain terminal represented by the formula (6) is blocked with an isocyanate group or an isothiocyanate group, a polymer compound which is available as a commercially available product is a polyol compound whose molecular chain terminal is blocked with a hydroxyl group. Prepared by performing a urethanization reaction or a thiourethanization reaction between a hydroxyl group and an isocyanate group or isothiocyanate group of a polyisocyanate compound or polyisothiocyanate compound (generally known as an isocyanate prepolymer) It may be used.

The structure of the main chain skeleton to which the hydroxyl group is linked is not particularly limited as long as the polyol compound having the molecular chain end blocked with a hydroxyl group has a hydroxyl group at the molecular chain end. May have a linear structure, a branched structure, or a crosslinked structure.
Among these, a linear structure is preferable from the viewpoint of mechanical properties of the obtained cured product and storage stability of the composition.

Specific examples of the polyol compound whose molecular chain end is blocked with a hydroxyl group include polyoxyalkylene polyol (polyether polyol), polyester polyol, acrylic polyol, epoxy polyol, polyolefin polyol, fluorine-containing polyol, α, ω-hydroxyalkyl ( Dimethyl) polysiloxane and the like. These may be used as a single component, or may be used as a mixture or copolymer by combining two or more components.
Among these, polyoxyalkylene polyols (polyether polyols), polyester polyols, polyolefin polyols, and α, ω-hydroxyalkyl (dimethyl) polysiloxanes are preferred as the polyol compounds whose molecular chain ends are blocked with hydroxyl groups, and are curable. In view of availability, productivity, and cost, polyoxyalkylene polyol (polyether polyol) and α, ω-hydroxyalkyl (dimethyl) polysiloxane are more preferable, and polyoxyalkylene polyol (polyether polyol). Is even more preferable.

Further, the polyol compound whose molecular chain end is blocked with a hydroxyl group contains at least one hydroxyl group in one molecule, but the average number of hydroxyl groups contained in one molecule is less than one. When it is, the sclerosis | hardenability of the composition containing the polymer of this invention prepared using this as a main ingredient, and the mechanical characteristic of the cured | curing material will become inadequate.
On the other hand, if there are too many hydroxyl groups, the crosslinking density becomes too high, and the resulting cured product may not show good mechanical properties, or the storage stability of the composition may deteriorate. Therefore, the number of hydroxyl groups contained in one molecule is 1 or more, preferably 1.1 to 5, more preferably 2 to 4, and even more preferably 2 (for example, at both ends of the molecular chain, respectively). One by one).

Therefore, as the polyol compound whose molecular chain end is blocked with a hydroxyl group, those represented by the following structural formula (7) are preferable. By using such a compound, the mechanical properties of the resulting cured product and the composition Storage stability is further improved.

(In the formula, R ⁴ and p have the same meaning as described above.)

Specific examples of the polyol compound in which the molecular chain terminal is blocked with a hydroxyl group include those represented by the following structural formulas, but are not limited thereto, and the molecular chain terminal is blocked with a hydroxyl group. Any polyol compound can be used.

(Wherein p represents the same meaning as described above.)

The number average molecular weight of the polyol compound in which the molecular chain terminal is blocked with a hydroxyl group is not particularly limited, but it is sufficient to improve workability by setting the viscosity of the curable composition of the present invention within an appropriate range. In view of imparting sufficient curability, the number average molecular weight is preferably 200 to 50,000, more preferably 1,000 to 20,000.

On the other hand, the polyisocyanate compound or polyisothiocyanate compound is not particularly limited as long as it contains at least two isocyanate groups or isothiocyanate groups in one molecule at the molecular chain end, and is not limited in the main chain skeleton. May have a linear structure, a branched structure, or a crosslinked structure.
Among these, those containing a linear structure and / or a branched structure are preferred from the viewpoint of the mechanical properties of the resulting cured product and the storage stability of the composition.

The polyisocyanate compound or polyisothiocyanate compound contains at least two isocyanate groups or isothiocyanate groups in one molecule, but the number of isocyanate groups or isothiocyanate groups contained in one molecule. If the average number is less than 2, the curability of the composition containing the polymer of the present invention prepared using this as a main ingredient and the mechanical properties of the cured product become insufficient.
On the other hand, if there are too many isocyanate groups or isothiocyanate groups, the crosslinking density becomes too high, and the resulting cured product may not exhibit good mechanical properties, or the storage stability of the composition may deteriorate. Therefore, the number of isocyanate groups or isothiocyanate groups contained in one molecule is 2 or more, preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 (for example, both molecular chains One at each end).

Therefore, as the polyisocyanate compound or polyisothiocyanate compound, those represented by the following structural formula (8) are preferable. By using such a compound, the mechanical properties of the resulting cured product and the storage stability of the composition are obtained. Is even better.

(In the formula, X and Y represent the same meaning as described above.)

Specific examples of the polyisocyanate compound or polyisothiocyanate compound include hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 4,4'-bis- (isocyanatemethyl) -diphenylmethane, polymethylene polyphenyl polyisocyanate, and phenylene. Diisocyanate, toluene diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate, tris (6-isocyanatohexyl) isocyanurate, hexamethylene diisothiocyanate, 4,4'-methylenebis (cyclohexyl isothiocyanate), cyclohexane diisothiocyanate, 3 -Isothiocyanato -3,5,5-trimethylcyclohexyl isothiocyanate, phenylene diisothiocyanate, toluene diisothiocyanate, 4,4'-methylenedi (phenylisothiocyanate), and the like. Considering that the viscosity of the composition containing the polymer of the present invention as a main ingredient is improved within a suitable range and workability is improved, and sufficient curability is given, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate Are preferred, and hexamethylene diisocyanate and isophorone diisocyanate are more preferred.

When preparing a polymer in which the molecular chain terminal represented by the above formula (6) is blocked with an isocyanate group or an isothiocyanate group, the production method is not particularly limited. What is necessary is just to select suitably from the well-known manufacturing method currently used by the urethanation reaction.
More specifically, the reaction ratio of the polyol compound whose molecular chain end is blocked with a hydroxyl group and the polyisocyanate compound or polyisothiocyanate compound suppresses by-products during the urethanization reaction or thiourethanization reaction, In consideration of enhancing the storage stability and characteristics of the resulting polymer, the isocyanate group or isothiocyanate group of the polyisocyanate compound or polyisothiocyanate compound is 1 mol of the hydroxyl group in the polyol compound whose molecular chain end is blocked with a hydroxyl group. A ratio of greater than 1 mol to 100 mol or less is preferred, a ratio of 1.1 to 50 mol is more preferred, and a ratio of 1.2 to 10 mol is even more preferred.

In the urethanization reaction or thiourethanation reaction, a catalyst may not be used, but a catalyst may be used for improving the reaction rate.
The catalyst may be appropriately selected from those generally used in the urethanization reaction or thiourethanation reaction, and specific examples thereof include dibutyltin oxide, dioctyltin oxide, tin (II) bis (2-ethyl). Hexanoate), dibutyltin dilaurate, dioctyltin dilaurate and the like.
The amount of the catalyst used may be a catalytic amount, but is usually 0.001 to 1% by mass based on the total of the polyol compound and the polyisocyanate compound or polyisothiocyanate compound whose molecular chain ends are blocked with a hydroxyl group.

Furthermore, a solvent that does not adversely influence the reaction can be used in the urethanization reaction or thiourethanation reaction.
Specific examples thereof include hydrocarbon solvents such as pentane, hexane, heptane, octane, decane and cyclohexane; aromatic solvents such as benzene, toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; formamide Amide solvents such as N, N-dimethylformamide, pyrrolidone and N-methylpyrrolidone, ester solvents such as ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol-1-monomethyl ether-2-acetate; diethyl ether, Examples include ether solvents such as dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane. These may be used alone or in combination of two or more.

The reaction temperature during the urethanization reaction or thiourethanization reaction is not particularly limited, but is preferably 25 to 90 ° C. in consideration of suppressing side reactions such as allophanatization while making the reaction rate appropriate. 40 to 80 ° C. is more preferable.
The reaction time is not particularly limited, but is usually 10 minutes to 24 hours.

The polymer having a reactive silicon-containing group of the present invention is obtained by reacting a polymer whose molecular chain end is blocked with an isocyanate group or an isothiocyanate group and a secondary-tertiary diaminosilane represented by the above formula (5). Can be obtained.
The specific method is not particularly limited, and may be appropriately selected from known production methods generally used in the urea reaction or thiourea reaction.
More specifically, the reaction ratio between the secondary / tertiary diaminosilane represented by the above formula (5) and the polymer whose molecular chain terminal is blocked with an isocyanate group or an isothiocyanate group is represented by urea reaction or thiourea. In consideration of suppressing the by-product of the polymerization reaction and enhancing the storage stability and properties of the resulting polymer, 1 mol of the secondary amino group in the secondary-tertiary diaminosilane represented by the above formula (5) On the other hand, the ratio of the isocyanate group or isothiocyanate group in the polymer whose molecular chain end is blocked with an isocyanate group or isothiocyanate group is preferably 0.1 to 2.0 mol, and the ratio of 0.4 to 1.5 mol is preferable. More preferably, the ratio of 0.8 to 1.2 mol is even more preferable.

In addition, during the urea reaction or thiourea reaction, it is not necessary to use a catalyst, but a catalyst may be used to improve the reaction rate.
The catalyst may be appropriately selected from those generally used in urea reaction or thiourea reaction, and specific examples thereof include dibutyltin oxide, dioctyltin oxide, tin (II) bis (2-ethylhexa). Noate), dibutyltin dilaurate, dioctyltin dilaurate and the like.
The catalyst may be used in any catalytic amount, but is usually the sum of the secondary and tertiary diaminosilane represented by the above formula (5) and the polymer whose molecular chain ends are blocked with isocyanate groups or isothiocyanate groups. The content is 0.001 to 1% by mass.

Furthermore, a solvent that does not adversely influence the reaction can be used for the urea reaction or thiourea reaction.
Specific examples thereof include hydrocarbon solvents such as pentane, hexane, heptane, octane, decane and cyclohexane; aromatic solvents such as benzene, toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; formamide Amide solvents such as N, N-dimethylformamide, pyrrolidone and N-methylpyrrolidone, ester solvents such as ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol-1-monomethyl ether-2-acetate; diethyl ether, Examples include ether solvents such as dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane. These may be used alone or in combination of two or more.

The reaction temperature at the time of urea reaction or thiourea reaction is not particularly limited, but it is preferably 0 to 90 ° C. in consideration of suppressing side reactions such as allophanatization while making the reaction rate appropriate. 25 to 80 ° C. is more preferable.
The reaction time is not particularly limited, but is usually 10 minutes to 24 hours.

The first curable composition, the coating agent composition and the adhesive composition of the present invention (hereinafter sometimes collectively referred to as the first composition) are (A) at least one in one molecule. It contains a polymer containing a reactive silicon group represented by the structural formula (1) at the molecular chain terminal, and (B) a curing catalyst.
The polymer of the above component (A) is derived from the structure of the polymer, and a cured product obtained by coating or adhering using a composition containing this polymer has excellent curability compared to conventional compositions. give.

The curing catalyst (B) used in the first composition of the present invention promotes a reaction in which a hydrolyzable group contained in a polymer having a reactive silicon-containing group (A) is hydrolytically condensed with moisture in the air. It is a component that accelerates the curing of the composition and is added for efficient curing.

The curing catalyst is not particularly limited as long as it is a curing catalyst used for curing a general moisture condensation curable composition. Specific examples thereof include alkyltin compounds such as dibutyltin oxide and dioctyltin oxide. Alkyltriester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, dioctyltin dioctoate, dioctyltin diversate; tetraisopropoxy titanium, tetra n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium , Titanate esters such as dipropoxybis (acetylacetonato) titanium, titanium diisopropoxybis (ethylacetoacetate), titanium isopropoxyoctylene glycol, and titanium chelate compounds Partially hydrolyzed products thereof: zinc naphthenate, zinc stearate, zinc-2-ethyl octoate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate Organometallic compounds such as cobalt naphthenate, aluminum trihydroxide, aluminum alcoholate, aluminum acylate, aluminum acylate salt, aluminosyloxy compound, aluminum chelate compound; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N -Β (Ami Ethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, bis [3- (trimethoxysilyl) propyl] amine, bis [3- (triethoxysilyl) propyl] Amines, N, N′-bis [3- (trimethoxysilyl) propyl] ethane-1,2-diamine, N, N′-bis [3- (triethoxysilyl) propyl] ethane-1,2-diamine, Aminoalkyl group-substituted alkoxysilanes such as N-phenyl-3-aminopropyltrimethoxysilane; amine compounds such as hexylamine and dodecylamine phosphate and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; potassium acetate; Lower fats of alkali metals such as sodium acetate and lithium oxalate Salt; dialkylhydroxylamine such as dimethylhydroxylamine, diethylhydroxylamine; tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxysilane, tetramethylguanidylpropyltriethoxysilane, tetramethylguanidyl Silanes and siloxanes containing guanidyl groups such as propylmethyldiethoxysilane and tetramethylguanidylpropyltris (trimethylsiloxy) silane; N, N, N ′, N ′, N ″, N ″ -hexamethyl-N Examples include silanes and siloxanes containing phosphazene bases such as' ''-[3- (trimethoxysilyl) propyl] -phosphorimidic triamide, and these may be used alone or in combination of two or more. May be.

Among these, since it is more excellent in reactivity, dioctyltin dilaurate, dioctyltin diversate, tetraisopropoxy titanium, tetra n-butoxy titanium, titanium diisopropoxy bis (ethylacetoacetate), 3-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, bis [3- (trimethoxysilyl) propyl] amine, N, N′-bis [3- (trimethoxysilyl) propyl] ethane-1,2- Diamine and tetramethylguanidylpropyltrimethoxysilane are preferred, and dioctyltin dilaurate, dioctyltin divertate, 3-aminopropyltrimethoxysilane, and tetramethylguanidylpropyltrimethoxysilane are more preferred from the viewpoint of curability of the composition. In addition, 3-aminopropyltrimethoxysilane and tetramethylguanidylpropyltrimethoxysilane are more preferred because they contain no organotin compound and are less toxic. From the viewpoint of curability of the composition, tetraaminosilane is preferred. Methylguanidylpropyltrimethoxysilane is particularly preferred.

(B) The addition amount of the curing catalyst is not particularly limited, but considering that the workability is improved by adjusting the curing rate to an appropriate range, 0.01 to 15 parts by mass is preferable, and 0.1 to 5 parts by mass is more preferable.

The second curable composition, coating agent composition and adhesive composition of the present invention (hereinafter sometimes collectively referred to as the second composition) contain (A) component, but (B) cure. It does not contain a catalyst.
The polymer having a reactive silicon-containing group (A) of the present invention is derived from the structure of the polymer, and (B) a coating treatment using a composition containing a polymer without containing a curing catalyst. The cured product obtained by the adhesion treatment gives a cured product that is superior to the conventional composition in terms of curability.

Furthermore, the first and second compositions of the present invention may contain a solvent.
The solvent is not particularly limited as long as it has the ability to dissolve the component (A). Specific examples thereof include hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, and cyclohexane; benzene , Aromatic solvents such as toluene and xylene; amide solvents such as formamide, N, N-dimethylformamide, pyrrolidone and N-methylpyrrolidone, ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol-1-monomethyl ether Ester solvents such as 2-acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and ether solvents such as diethyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane. Used alone It may also be used in combination of two or more thereof.
Among these, aromatic solvents such as toluene and xylene are preferable from the viewpoints of solubility and volatility.
The amount of the solvent added is preferably 10 to 20,000 parts by mass, more preferably 100 to 10,000 parts by mass with respect to 100 parts by mass of component (A).

The first and second compositions of the present invention include an adhesion improver, an inorganic and organic ultraviolet absorber, a storage stability improver, a plasticizer, a filler, a pigment, and a fragrance depending on the purpose of use. Various additives such as can be added.

The coating composition of the present invention described above is applied to the surface of a solid substrate and cured to form a coating layer, whereby a coated solid substrate is obtained, and the adhesive composition of the present invention is applied to the solid substrate. After applying another solid base material on the surface, and then curing the composition to form an adhesive layer, an adhesive laminate can be obtained.
The application method of each composition is not particularly limited, and specific examples thereof are appropriately selected from known methods such as spray coating, spin coating, dip coating, roller coating, brush coating, bar coating, and flow coating. Can do.

The solid substrate is not particularly limited, and specific examples thereof include epoxy resins, phenol resins, polyimide resins, polycarbonate resins such as polycarbonates and polycarbonate blends, acrylic resins such as poly (methyl methacrylate), poly (ethylene Terephthalate), poly (butylene terephthalate), polyester resins such as unsaturated polyester resin, polyamide resin, acrylonitrile-styrene copolymer resin, styrene-acrylonitrile-butadiene copolymer resin, polyvinyl chloride resin, polystyrene resin, polystyrene and polyphenylene Organic resin base materials such as ether blends, cellulose acetate butyrate, polyethylene resin; metal base materials such as iron plate, copper plate, steel plate; paint application surface; glass; ceramic; concrete; Sheet; textile; wood, stone, tile, inorganic filler such as (hollow) silica, titania, zirconia, alumina; glass fiber including glass fiber, glass tape, glass mat, glass paper, etc. The material and shape of the substrate are not particularly limited.

When the composition of the present invention is brought into contact with moisture in the atmosphere, (A) the hydrolysis and condensation reaction of the polymer having a reactive silicon-containing group proceeds. As an index of moisture in the atmosphere, any humidity of 10 to 100% RH may be used. In general, the higher the humidity, the faster the hydrolysis proceeds. Therefore, moisture may be added to the atmosphere as desired.
The curing reaction temperature and time can be appropriately changed according to factors such as the substrate used, the moisture concentration, the catalyst concentration, and the type of hydrolyzable group. Usually, the curing reaction temperature is preferably about 25 ° C. from the viewpoint of workability, etc., but in order to accelerate the curing reaction, it is cured by heating within a range not exceeding the heat resistance temperature of the substrate to be used. May be. The curing reaction time is usually about 1 minute to 1 week from the viewpoint of workability and the like.

The composition of the present invention cures well even at room temperature, and therefore, even when room temperature curing is indispensable for on-site construction or the like, there is no stickiness (tack) on the surface of the coating film in several minutes to several hours, and curability. Although it is excellent in workability, the heat treatment may be performed within a range not exceeding the heat-resistant temperature of the substrate.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to these Examples.
In the following, the viscosity is a value measured at 25 ° C. using a B-type rotational viscometer, and the molecular weight and the degree of polymerization (the number of repeating dimethylpolysiloxane or polyoxyalkylene units) are measured by GPC (gel permeation chromatograph). These are the number average molecular weight and number average degree of polymerization calculated in terms of polystyrene.

[1] Synthesis of polymer having reactive silicon-containing group [Example 1-1] Synthesis of polymer 1 In a 200 mL separable flask equipped with a stirrer, reflux condenser and thermometer, a number average molecular weight of 7,800 and polymerization 100 g of both-end hydroxyl group-containing polypropylene glycol having a degree of 130 (0.039 mol in terms of functional group of the terminal hydroxyl group) was charged and heated to 90 ° C. Into this, 17.3 g of isophorone diisocyanate (functional amount of isocyanate group 0.078 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. Thereafter, 8.6 g of N- (trimethoxysilylmethyl) piperazine (secondary amino group functional group amount: 0.039 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. It was confirmed that the absorption peak derived from the isocyanate group of the raw material disappeared completely by IR measurement, and that an absorption peak derived from a urea bond and a urethane bond was generated instead, and the reaction was completed.
The obtained reaction product was a pale yellow transparent liquid having a number average molecular weight of 9,100 and a viscosity of 5,300 mPa · s.

[Example 1-2] Synthesis of polymer 2 A 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 100 g of both end hydroxyl groups-containing polypropylene glycol having a number average molecular weight of 7,800 and a polymerization degree of 130 (terminal hydroxyl groups). Was converted to a functional group equivalent of 0.039 mol) and heated to 90 ° C. Into this, 17.3 g of isophorone diisocyanate (functional amount of isocyanate group 0.078 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. Thereafter, 8.0 g of N- (methyldimethoxysilylmethyl) piperazine (secondary amino group functional group amount 0.039 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. It was confirmed that the absorption peak derived from the isocyanate group of the raw material disappeared completely by IR measurement, and that an absorption peak derived from a urea bond and a urethane bond was generated instead, and the reaction was completed.
The obtained reaction product was a pale yellow transparent liquid having a number average molecular weight of 9,000 and a viscosity of 5,100 mPa · s.

[Example 1-3] Synthesis of polymer 3 In a 200 mL separable flask equipped with a stirrer, reflux condenser and thermometer, 100 g of both ends hydroxyl group-containing polypropylene glycol having a number average molecular weight of 7,800 and a polymerization degree of 130 (terminal hydroxyl group) Was converted to a functional group equivalent of 0.039 mol) and heated to 90 ° C. Into this, 17.3 g of isophorone diisocyanate (functional amount of isocyanate group 0.078 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. Thereafter, 10.2 g of N- (triethoxysilylmethyl) piperazine (secondary amino group functional group amount 0.039 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. It was confirmed that the absorption peak derived from the isocyanate group of the raw material disappeared completely by IR measurement, and that an absorption peak derived from a urea bond and a urethane bond was generated instead, and the reaction was completed.
The obtained reaction product was a pale yellow transparent liquid having a number average molecular weight of 9,200 and a viscosity of 4,900 mPa · s.

[Example 1-4] Synthesis of polymer 4 In a 200 mL separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 100 g of polypropylene glycol containing hydroxyl groups at both ends having a number average molecular weight of 5,100 and a polymerization degree of 50 (terminal hydroxyl groups) Of 0.070 mol in terms of functional group) and heated to 90 ° C. Into this, 24.3 g of toluene diisocyanate (the amount of functional group of isocyanate group was 0.14 mol) was added and stirred with heating at 90 ° C. for 1 hour. Thereafter, 15.4 g of N- (trimethoxysilylmethyl) piperazine (secondary amino group functional group amount 0.070 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. It was confirmed that the absorption peak derived from the isocyanate group of the raw material disappeared completely by IR measurement, and that an absorption peak derived from a urea bond and a urethane bond was generated instead, and the reaction was completed.
The obtained reaction product was a pale yellow transparent liquid, which had a number average molecular weight of 6,500 and a viscosity of 1,080 mPa · s.

[Example 1-5] Synthesis of polymer 5 A 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 100 g of polypropylene glycol containing both hydroxyl groups at a number average molecular weight of 15,500 and a polymerization degree of 250 (terminal hydroxyl groups). In terms of functional group of 0.025 mol) and 0.1 g of dioctyltin dilaurate were charged and heated to 90 ° C. Into this, 8.4 g of hexamethylene diisocyanate (isocyanate group functional amount 0.050 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. Thereafter, 5.5 g of N- (trimethoxysilylmethyl) piperazine (secondary amino group functional group amount 0.025 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. It was confirmed that the absorption peak derived from the isocyanate group of the raw material disappeared completely by IR measurement, and that an absorption peak derived from a urea bond and a urethane bond was generated instead, and the reaction was completed.
The obtained reaction product was a pale yellow transparent liquid having a number average molecular weight of 17,400 and a viscosity of 32,000 mPa · s.

[Example 1-6] Synthesis of polymer 6 In a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, 100 g of polypropylene glycol containing both hydroxyl groups at a number average molecular weight of 7,800 and a polymerization degree of 130 (terminal hydroxyl group) Was converted to a functional group equivalent of 0.039 mol) and heated to 90 ° C. Into this, 17.3 g of isophorone diisocyanate (functional amount of isocyanate group 0.078 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. Thereafter, 8.7 g of N, N′-dimethyl-N- (trimethoxysilylmethyl) ethylenediamine (secondary amino group functional group amount: 0.039 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. It was confirmed that the absorption peak derived from the isocyanate group of the raw material disappeared completely by IR measurement, and that an absorption peak derived from a urea bond and a urethane bond was generated instead, and the reaction was completed.
The obtained reaction product was a pale yellow transparent liquid, which had a number average molecular weight of 8,900 and a viscosity of 4,900 mPa · s.

[Example 1-7] Synthesis of polymer 7 In a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, 100 g of polypropylene glycol containing both end hydroxyl groups having a number average molecular weight of 7,800 and a polymerization degree of 130 (terminal hydroxyl group) Was converted to a functional group equivalent of 0.039 mol) and heated to 90 ° C. Into this, 17.3 g of isophorone diisocyanate (functional amount of isocyanate group 0.078 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. Thereafter, 12.0 g of N, N′-di-t-butyl-N- (trimethoxysilylmethyl) ethylenediamine (the amount of secondary amino group functional group: 0.039 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. did. It was confirmed that the absorption peak derived from the isocyanate group of the raw material disappeared completely by IR measurement, and that an absorption peak derived from a urea bond and a urethane bond was generated instead, and the reaction was completed.
The obtained reaction product was a pale yellow transparent liquid having a number average molecular weight of 9,100 and a viscosity of 5,100 mPa · s.

[Example 1-8] Synthesis of polymer 8 A 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 100 g of both end hydroxyl groups-containing polypropylene glycol having a number average molecular weight of 7,800 and a polymerization degree of 130 (terminal hydroxyl groups). Was converted to a functional group equivalent of 0.039 mol) and heated to 90 ° C. Into that, 15.0 g of phenylene diisothiocyanate (functional amount of isothiocyanate group: 0.078 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. Thereafter, 13.5 g of N, N′-diphenyl-N- (trimethoxysilylmethyl) ethylenediamine (the amount of secondary amino group functional group: 0.039 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. By IR measurement, it was confirmed that the absorption peak derived from the isothiocyanate group of the raw material disappeared completely, and the absorption peak derived from the thiourea bond and thiourethane bond was generated instead, and the reaction was terminated.
The obtained reaction product was a pale yellow transparent liquid having a number average molecular weight of 9,500 and a viscosity of 6,400 mPa · s.

[Example 1-9] Synthesis of polymer 9 A 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer was mixed with a hydroxyl group-containing polypropylene glycol / polyethylene glycol having a number average molecular weight of 5,200 and a polymerization degree of 65. A polymer 100 g (polypropylene glycol structural unit / polyethylene glycol structural unit molar ratio 25/75, terminal hydroxyl group equivalent 0.068 mol) was charged and heated to 90 ° C. Into this, 30.2 g of isophorone diisocyanate (the amount of functional group of isocyanate group was 0.14 mol) was added and heated and stirred at 90 ° C. for 1 hour. Thereafter, 15.0 g of N- (trimethoxysilylmethyl) piperazine (secondary amino group functional group amount 0.068 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. It was confirmed that the absorption peak derived from the isocyanate group of the raw material disappeared completely by IR measurement, and that an absorption peak derived from a urea bond and a urethane bond was generated instead, and the reaction was completed.
The obtained reaction product was a pale yellow transparent liquid having a number average molecular weight of 6,400 and a viscosity of 1,260 mPa · s.

[Example 1-10] Synthesis of polymer 10 In a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, α, ω-hydroxypropyl (dimethyl) poly having a number average molecular weight of 15,000 and a polymerization degree of 200 was added. 100 g of siloxane (0.013 mol in terms of functional group of terminal hydroxyl group) was charged and heated to 90 ° C. Into this, 5.8 g of isophorone diisocyanate (functional amount of isocyanate group: 0.026 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. Thereafter, 2.9 g of N- (trimethoxysilylmethyl) piperazine (secondary amino group functional group content 0.013 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. It was confirmed that the absorption peak derived from the isocyanate group of the raw material disappeared completely by IR measurement, and that an absorption peak derived from a urea bond and a urethane bond was generated instead, and the reaction was completed.
The obtained reaction product was a colorless and transparent liquid, and had a number average molecular weight of 16,800 and a viscosity of 16,000 mPa · s.

[Comparative Example 1-1] Synthesis of polymer 11 In a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, 100 g of polypropylene glycol containing both end hydroxyl groups having a number average molecular weight of 7,600 (in terms of functional groups of terminal hydroxyl groups) 0.040 mol) and 7.1 g of isocyanate methyltrimethoxysilane (isocyanate group functional group amount 0.040 mol) were charged and heated to 80 ° C. The dioctyltin dilaurate 0.1g was thrown in in it, and it heat-stirred at 80 degreeC for 3 hours. By IR measurement, it was confirmed that the absorption peak derived from the isocyanate group of the raw material completely disappeared and an absorption peak derived from the urethane bond was generated instead, and the reaction was terminated.
The obtained reaction product was a pale yellow transparent liquid having a number average molecular weight of 8,000, a degree of polymerization of 130, and a viscosity of 3,700 mPa · s.

[Comparative Example 1-2] Synthesis of Polymer 12 In a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, 100 g of both-end hydroxyl group-containing polypropylene glycol having a number average molecular weight of 7,800 and a polymerization degree of 130 (terminal hydroxyl group) Was converted to a functional group equivalent of 0.039 mol) and heated to 90 ° C. Into this, 17.3 g of isophorone diisocyanate (functional amount of isocyanate group 0.078 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. Thereafter, 8.9 g of N-phenylaminomethyltrimethoxysilane (secondary amino group functional group amount: 0.039 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. It was confirmed that the absorption peak derived from the isocyanate group of the raw material disappeared completely by IR measurement, and that an absorption peak derived from a urea bond and a urethane bond was generated instead, and the reaction was completed.
The obtained reaction product was a pale yellow transparent liquid having a number average molecular weight of 8,700 and a viscosity of 5,000 mPa · s.

[Comparative Example 1-3] Synthesis of polymer 13 In a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, 100 g of polypropylene glycol containing both end hydroxyl groups having a number average molecular weight of 7,600 (in terms of functional groups of terminal hydroxyl groups) 0.040 mol) and 6.1 g (0.040 mol) of tetramethoxysilane were charged, and the mixture was heated and stirred at 80 ° C. for 3 hours. By IR measurement, it was confirmed that the absorption peak derived from the hydroxyl group of the raw material had completely disappeared, and the reaction was completed.
The obtained reaction product was a colorless and transparent liquid and had a number average molecular weight of 22,000 and a viscosity of 6,800 mPa · s.

[Comparative Example 1-4] Synthesis of polymer 14 In a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, 100 g of both ends hydroxyl group-containing polypropylene glycol having a number average molecular weight of 7,800 and a polymerization degree of 130 (terminal hydroxyl group) Was converted to a functional group equivalent of 0.039 mol) and heated to 90 ° C. Into this, 17.3 g of isophorone diisocyanate (functional amount of isocyanate group 0.078 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. Thereafter, 9.7 g of N- (3-trimethoxysilylpropyl) piperazine (secondary amino group functional group amount: 0.039 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. It was confirmed that the absorption peak derived from the isocyanate group of the raw material disappeared completely by IR measurement, and that an absorption peak derived from a urea bond and a urethane bond was generated instead, and the reaction was completed.
The obtained reaction product was a pale yellow transparent liquid having a number average molecular weight of 9,200 and a viscosity of 5,300 mPa · s.

[Comparative Example 1-5] Synthesis of polymer 15 In a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, 100 g of polypropylene glycol containing allyl groups at both ends with a number average molecular weight of 7,800 (functionality of terminal allyl groups) Group conversion 0.039 mol), trimethoxysilane 4.8 g (functional amount of Si—H group 0.039 mol) and platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex 0.15 g of toluene solution (1.0 × 10 ⁻⁴ mol as a platinum atom with respect to 1 mol of trimethoxysilane) was added and stirred at 80 ° C. for 3 hours. It was confirmed by IR measurement that the absorption peak derived from the Si—H group of the raw material had completely disappeared, and the reaction was completed.
The obtained reaction product was a colorless and transparent liquid, and had a number average molecular weight of 11,300 and a viscosity of 7,500 mm ² / s.

[Comparative Example 1-6] Synthesis of Polymer 16 In a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, 100 g of both end hydroxyl groups-containing polypropylene glycol having a number average molecular weight of 7,800 and a polymerization degree of 130 (terminal hydroxyl group) Was converted to a functional group equivalent of 0.039 mol) and heated to 90 ° C. Into this, 17.3 g of isophorone diisocyanate (functional amount of isocyanate group 0.078 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. Thereafter, 7.6 g of N-2- (aminoethyl) -aminomethyltrimethoxysilane (secondary amino group functional group amount: 0.039 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. Gelled and a reaction product could not be obtained.

[2] Preparation of composition and cured film [Example 2-1]
100 parts by mass of the polymer 1 obtained in Example 1-1 above and 0.5 parts by mass of tetramethylguanidylpropyltrimethoxysilane as a curing catalyst were uniformly mixed using a stirrer while blocking moisture. A composition was prepared.
The obtained composition was subjected to bar coater No. 5 under air at 25 ° C. and 50% RH. 14 was applied to a glass plate and dried and cured for 1 day in air at 25 ° C. and 50% RH to prepare a cured film.

[Examples 2-2 to 2-10 and Comparative Examples 2-1 to 2-5]
Except for changing the polymer 1 of Example 2-1 to the polymers 2 to 10 obtained in Examples 1-2 to 1-10 and the polymers 11 to 15 obtained in Comparative Examples 1-1 to 1-5, respectively. Produced a composition and a cured film in the same manner as in Example 2-1.

[Example 2-11]
The composition and curing were carried out in the same manner as in Example 2-1, except that 5 parts by mass of 3-aminopropyltrimethoxysilane was used as a curing catalyst instead of 0.5 parts by mass of tetramethylguanidylpropyltrimethoxysilane. A coating was prepared.

[Example 2-12]
A composition and a cured film were prepared in the same manner as in Example 2-1, except that 5 parts by mass of dioctyltin diversate was used as a curing catalyst instead of 0.5 parts by mass of tetramethylguanidylpropyltrimethoxysilane. .

[Example 2-13]
The composition was the same as in Example 2-1, except that 2 parts by mass of titanium diisopropoxybis (ethylacetoacetate) was used as a curing catalyst instead of 0.5 parts by mass of tetramethylguanidylpropyltrimethoxysilane. And cured coatings were prepared.

[Example 2-14]
A composition and a cured film were produced in the same manner as in Example 2-1, except that tetramethylguanidylpropyltrimethoxysilane was not used.

[Example 2-15]
A composition and a cured film were produced in the same manner as in Example 2-7, except that tetramethylguanidylpropyltrimethoxysilane was not used.

[Comparative Example 2-6]
A composition and a cured film were prepared in the same manner as in Comparative Example 2-1, except that tetramethylguanidylpropyltrimethoxysilane was not used.

[Comparative Example 2-7]
A composition and a cured film were prepared in the same manner as in Comparative Example 2-2 except that tetramethylguanidylpropyltrimethoxysilane was not used.

[Comparative Example 2-8]
A composition and a cured film were produced in the same manner as in Comparative Example 2-4 except that tetramethylguanidylpropyltrimethoxysilane was not used.

[Comparative Example 2-9]
A composition and a cured film were produced in the same manner as in Comparative Example 2-5 except that tetramethylguanidylpropyltrimethoxysilane was not used.

The cured film prepared in Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2-9 was evaluated as follows. The results are also shown in Tables 1 to 3.
[Finger touch drying time]
The test piece obtained by applying the composition to a glass plate by the above application method is left in air at 25 ° C. and 50% RH, and moisture curing proceeds, so that the coating surface can be applied even if the applied surface is pressed with a finger. Indicates the time until no longer sticks to the finger. It shows that sclerosis | hardenability is so favorable that a value is small.

As shown in Tables 1 to 3, the cured coatings produced in Examples 2-1 to 2-15 using the polymers 1 to 10 obtained in Examples 1-1 to 1-10 were used in Comparative Example 2- It can be seen that the cured film is excellent in curability as compared with the cured film prepared in 1 to 2-9, and further, the curability is good even when no curing catalyst is contained.
On the other hand, the cured coatings produced in Comparative Examples 2-1 to 2-9 cannot ensure sufficient curability. In Comparative Examples 2-5 to 2-9, the curability of the coating film was poor and the curing did not proceed at all.
In Comparative Example 1-6, the reaction solution gelled, and no reaction product could be obtained.

As described above, a cured film having excellent curability can be obtained by using the polymer having a reactive silicon-containing group of the present invention. Moreover, even when an amine compound is used as a curing catalyst so as not to contain a highly toxic organotin compound, a curable composition having good curability, which was difficult with the prior art, can be obtained. Furthermore, even if it does not contain a curing catalyst, a curable composition having good curability can be obtained.

Claims

Polyurethane, polyurea, polyoxyalkylene, polycarbonate, polyester, polyamide, polyimide, polyamideimide, poly (meth) acrylate, polystyrene, polyolefin, polyvinyl ester, polytetrafluoroethylene, polyacetal, polyphenylene ether, polyphenylene sulfide, polysulfone, poly Ether sulfone, polyether ether ketone, polysiloxane, polysiloxane-polyurethane copolymer and polysiloxane-polyurea copolymer, and a main chain skeleton selected from these copolymers, and in one molecule A polymer having at least one reactive silicon-containing group represented by the following structural formula (1).

(Wherein, R 1 s , independently of each other, represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, and R 2 represents Independent of each other, it represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, and R 3 , independently of each other, is unsubstituted or Represents a substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, or an unsubstituted or substituted carbon atom having 1 to 10 carbon atoms in which R 3 is bonded to each other. Represents an alkylene group, or an unsubstituted or substituted arylene group having 6 to 20 carbon atoms, R 5 represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, R 6 represents a hydrogen atom, or Non-replacement Ku denotes an alkyl group having 1 to 10 carbon atoms substituted, X is represents O or S, m is an integer of 1-3, * represents a bond.)
The polymer having a reactive silicon-containing group according to claim 1 represented by the following structural formula (2).

(Wherein R 1 , R 2 , R 3 and m represent the same meaning as described above, R 5 represents the same meaning as described above independently of each other, and R 6 represents the same meaning as described above independently of each other. X represents the same meaning as described above independently of each other, A represents polyurethane, polyurea, polyoxyalkylene, polycarbonate, polyester, polyamide, polyimide, polyamideimide, poly (meth) acrylate, polystyrene, polyolefin, polyvinyl Ester, polytetrafluoroethylene, polyacetal, polyphenylene ether, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, polysiloxane, polysiloxane-polyurethane copolymer and polysiloxane-polyurea copolymer, and these A copolymer of It represents a divalent linking group having a structure selected.)
The polymer having a reactive silicon-containing group according to claim 1 or 2, wherein the A is represented by the following formula (3).

(Wherein R 6 and X each independently represent the same meaning as described above, and Y each independently represents an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, an unsubstituted or substituted carbon, Represents an aralkylene group having 7 to 20 atoms or an unsubstituted or substituted arylene group having 6 to 20 carbon atoms, n represents an integer of 1 or more, and Z represents a polyurethane, polyurea, polyoxyalkylene, polycarbonate , Polyester, polyamide, polyimide, polyamideimide, poly (meth) acrylate, polystyrene, polyolefin, polyvinyl ester, polytetrafluoroethylene, polyacetal, polyphenylene ether, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, poly Siloxane, Polysiloxane - represents polyurea copolymer, and a divalent linking group having a structure selected from these copolymers, * represents a bond) - polyurethane copolymers and polysiloxanes.
The polymer having a reactive silicon-containing group according to any one of claims 1 to 3, wherein Z is a divalent linking group having a polyoxyalkylene structure.
The polymer having a reactive silicon-containing group according to any one of claims 1 to 4, wherein the divalent linking group having a polyoxyalkylene structure is represented by the following formula (4).

(In the formula, R 4 represents a divalent hydrocarbon group, p represents an integer of 1 or more, and * represents a bond.)
A polymer whose molecular chain ends are blocked with an isocyanate group or an isothiocyanate group, and a compound of formula (5)

(In the formula, R 1 , R 2 , R 3 , R 5 and m have the same meaning as described above.)
The polymer having a reactive silicon-containing group according to any one of claims 1 to 5, which is reacted with a compound having a secondary amino group, a tertiary amino group and an alkoxysilyl group represented by the formula: Manufacturing method.
The method for producing a polymer having a reactive silicon-containing group according to claim 6, wherein the polymer whose molecular chain terminal is blocked with an isocyanate group or an isothiocyanate group is represented by the following formula (6).

(In the formula, A represents the same meaning as described above. X represents O or S independently of each other.)
The method for producing a polymer having a reactive silicon-containing group according to claim 7, wherein A in the formula (6) is a divalent linking group having a polyoxyalkylene structure.
(A) A curable composition comprising a polymer having a reactive silicon-containing group according to any one of claims 1 to 5.
The curable composition according to claim 9, further comprising (B) a curing catalyst.
The curable composition according to claim 10, wherein the (B) curing catalyst is an amine compound.
A coating agent comprising the curable composition according to any one of claims 9 to 11.
An adhesive comprising the curable composition according to any one of claims 9 to 11.
A cured article obtained by curing the curable composition according to any one of claims 9 to 11.
A cured article having a coating layer formed by curing the coating agent according to claim 12.
A cured article having an adhesive layer formed by curing the adhesive according to claim 13.