WO2004108774A1

WO2004108774A1 - Curing resin, method for producing same and composition containing such curing resin

Info

Publication number: WO2004108774A1
Application number: PCT/JP2004/007881
Authority: WO
Inventors: Shinichi Sato; Yukihiro Nomura; Jun Inui
Original assignee: Konishi Co., Ltd.
Priority date: 2003-06-03
Filing date: 2004-06-01
Publication date: 2004-12-16
Also published as: JPWO2004108774A1; TW200504154A

Abstract

A curing resin is disclosed which is a moisture-curing resin having a silyl group at the end and exhibits excellent adhesiveness when used in adhesives, sealants, coating compounds or the like. The curing resin has a silicon atom-containing group at the end of the molecule wherein one or more hydrolyzable groups such as alkoxy groups, acetoxy groups and oxime groups are directly bonded to a silicon atom. In addition, the curing resin at least has a thiourethane bond in the molecule, and the main chain skeleton of the curing resin is composed of a polyoxyalkylene polymer, a (meth)acrylate polymer or a hydrocarbon polymer.

Description

Description Curable resin, method for producing the same, and composition containing the curable resin

The present invention relates to a curable resin, a method for producing the same, and a composition containing the curable resin. More specifically, the present invention relates to a curable resin suitable for applications such as an adhesive, a sealant, and a paint, a method for producing the same, and a curability thereof. The present invention relates to a composition containing a resin and exhibiting excellent adhesiveness for the above uses, and a curable resin composition containing a curable resin. Background art

Japanese Unexamined Patent Publication No. Hei 8-337713 discloses a modified silicone resin in which the main chain skeleton is a polyalkylalkylene polymer. However, although this resin has a low viscosity, it does not have active hydrogen in the molecular skeleton, so that it is not a resin having sufficient adhesiveness, and it is desired to improve the adhesiveness. The present invention relates to a curable resin having a silyl group at a terminal, a moisture-curable resin having excellent adhesiveness, a method for producing the same, a composition containing the same, and a curable resin containing the curable resin. It is intended to provide a composition.

As a result of intensive studies, the present inventors have found that the main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylate polymer or a hydrocarbon polymer, and a resin having an aryl group at a terminal. To achieve the object of the present invention by introducing a thioether bond and a thiourethane and / or urea bond or a substituted urea bond into a molecule and introducing a hydrolyzable silyl group such as an alkoxysilyl group at the terminal. The present invention has been completed. Disclosure of the invention

The present invention provides a compound having a silicon atom-containing group in which at least one hydrolyzable group selected from an alkoxy group, an acetyl group and an oxime group is directly bonded to a silicon atom at the molecular terminal, A thioether bond, a thioethane bond and / or a urea bond or a substituted urea bond, (2) a thioether bond, a hydroxyl group and a secondary or tertiary amino group or (3) a thioether bond and a secondary or tertiary bond A curable resin having a primary amino group and having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylate polymer or a hydrocarbon polymer.

Further, the curable resin of the present invention is characterized in that the hydrolyzable group is an alkoxy group.

The gist of the present invention is that the curable resin of the present invention is represented by the following general formula (1).

However, A is a polyoxyalkylene polymer, a (meth) acrylate polymer or a hydrocarbon polymer whose main chain skeleton is a reactive residue of a polyvalent aryl compound whose terminal is an aryl group, n is 1 to 20; R ¹ is a divalent organic group having a molecular weight of 100,000 or less; R ² is a divalent organic group having a molecular weight of 300 or less; X is the following general formula (2) And groups represented by general formula (3), general formula (4), general formula (5) or general formula (6).

However, R is an alkyl group having 1 to 6 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is 1 to 3, and R ⁴ has a side chain having 1 to 10 carbon atoms. A good alkylene group or an arylene group, R ⁵ is an alkylene group or an arylene group which may have a side chain having 1 to 10 carbon atoms, R ⁶ is a hydrogen atom, and a side chain having 1 to 10 carbon atoms. Represents a good alkyl group or an aryl group, respectively. D and E each represent a group represented by the following formula (7), (8), (9) or (10), and D and E may be the same or different. R ⁷ is a hydrogen atom or a group represented by the formula —CO R ⁸ (R ⁸ is an alkyl group having 1 to 20 carbon atoms); R ⁹ is a hydrogen atom; one CH ₂ COOH or a methyl group; An alkylene group or an arylene group which may have a side chain having 1 to 10 carbon atoms, Z is a hydrogen atom, 〇R ^{1 G} , R ¹ . Or NH ₂ and R ^{1 Q} are a hydrogen atom, an organic group having a molecular weight of 500 or less or a group represented by the following general formula (11), and R ¹¹ is a compound having a molecular weight of 300 or less. An organic group, R ¹² represents an organic group having a molecular weight of 200 or less,

Furthermore, the present invention provides a polyvalent aryl compound having a main chain skeleton of a poly (alkylene) -based polymer, a (meth) acrylic acid ester-based polymer or a hydrocarbon-based polymer, the terminal of which is an aryl group; — R ¹ — Dithiol compound represented by SH (R ¹ is as defined above), diisocyanate compound represented by formula OCN—R ² — NCO (R ² is as defined above), and A gist of the present invention is a method for producing a curable resin represented by the above general formula (1), which comprises reacting a compound represented by the formula HX (X has the same meaning as described above).

The gist of the present invention is that the curable resin of the present invention is represented by the following general formula (12).

R ¹³

| H

A- SR ^1- NC— N ~ R ² -NCX (12)

II II

o o

However, A, R ¹ , R ² , n and X are as defined above, and R ¹³ is hydrogen An atom, a group represented by the above general formula (7), the general formula (8), the general formula (10), or the following general formula (13) (R ¹⁴ is an alkyl group having 1 to 20 carbon atoms;

¹⁵ represents an alkyl group having 1 to 20 carbon atoms. ) Are shown.

H _Λα

—— C-C00R ¹⁴

I (13

H ₂ C— C00R ¹⁵

Further, the present invention provides a polyvalent alkylene compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, the terminal of which is an aryl group; R ¹ - Jiisoshi represented by NCO - NHR ^{1 3} thioamine compounds that Ru represented by (R ¹ are as defined above, R ¹³ represents a molecular weight 50 0 following organic groups.), wherein 〇 CN @ - R ² Wherein R ² has the same meaning as described above and a compound represented by the formula HX (X has the same meaning as described above). The gist is a method for producing a curable resin as shown.

Further, the curable resin of the present invention is represented by the following general formula (14).

[14;

^{However, A, R, RR 3,} R 4, R 13, m and n are Ru as defined der above.

More specifically, the present invention relates to a polyvalent alkyl compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic ester polymer or a hydrocarbon polymer, the terminal of which is an aryl group; - R ¹ - NH R ^{1 3} thioamine compounds Ru indicated by (. R ¹ and R ^{1 3} are as defined above) and compounds represented by the following general formula (1 5) (R, R 3, R 4 And m have the same meanings as above.) 4007881

The gist is a method for producing a curable resin.

OCN-

The gist of the present invention is that the curable resin of the present invention is represented by the following general formula (6).

However, A, R, R ¹ , R ³ , R ⁴ , m and n are as defined above. Further, the present invention provides a polyvalent alkylene compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, the terminal of which is an aryl group. R ¹ — a dithiol compound represented by SH (R ¹ has the same meaning as described above) and a compound represented by the above general formula (15), The gist is a method for producing a curable resin as shown.

The gist of the present invention is that the curable resin of the present invention is represented by the following general formula (17).

A, R ¹ , R ² , X and n are as defined above, and R ¹⁶ is a hydrogen atom or an organic group having a molecular weight of 500 or less.

Further, the present invention provides a polyvalent alkylene compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, the terminal of which is an aryl group. R ¹ — a dithiol compound represented by SH (: is as defined above), an arylamine compound represented by the formula CH 2 = CH—CH 2—NHR ¹⁶ (R ¹⁶ is as defined above) It is. ), Wherein O CN @ - R ² -. Jiisoshiane DOO compound represented by NCO (R ² is as defined above) as well as' the compound of formula HX to (X. is as defined above). The gist of the present invention is a method for producing a curable resin represented by the general formula (17), which is characterized by reacting.

The gist of the present invention is that the curable resin of the present invention is represented by the following general formula (18). OR),)

However, A, R, R ¹ R ³ , R ⁴ , R ¹⁶ , m and n are as defined above.

Further, the present invention provides a polyvalent alkylene compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, the terminal of which is an aryl group. R ¹ - dithiol compound represented by SH, the formula _{_{CH 2 = CH- CH 2 (R}} 1 is as defined above.) - Ariruamin compound represented by NHR ^{^{1 6}} (R ^{1 6} is as defined above And a method for producing a curable resin represented by the general formula (18), which comprises reacting the compound represented by the general formula (15).

Further, the present invention provides a polyvalent alkylene compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, the terminal of which is an aryl group. R ¹ - dithiol compound represented by SH, wherein N CO- R ² (R ¹ is as defined above.) - Jiisoshianeto compound represented by NC 0 (R ² is as defined above _D) parallel And a method for producing the curable resin of the present invention (hereinafter, referred to as Production Method A), which comprises reacting a compound represented by the following general formula (19).

However, R, R ³ , R ⁴ and m are as defined above.

Further, in the present invention, the curable resin preferably has the following general formula (20) or (2)

) Is a curable resin.

(20>

)

However, A,, RR ³ , R ¹⁶ , ΙΏ and n have the same meanings as described above. The gist of the present invention is a curable resin in which the curable resin is represented by the following general formula (22) or (23).

(twenty two)

(twenty three)

However, A, R, R ¹ , R ³ , R ⁴ , m and n are as defined above. Further, in the present invention, the curable resin preferably has the following general formula (24) or (2) 5) A curable resin that is represented by

Amo

However, A, R, R ¹ , R ³ , R ⁴ , R ¹⁶ , m and n are as defined above.

Further, the present invention provides a reaction product of an arylglycidyl ether and a compound represented by the following general formula (27), a polyoxyalkylene polymer having a main chain skeleton, a (meth) acrylate polymer or Reacting a polyvalent aryl compound which is a hydrocarbon polymer and the terminal of which is an aryl group, and a dithiol compound represented by the formula HS—R ¹ —SH (R ¹ is as defined above). The gist is a method for producing a curable resin represented by the general formula (20) or (21), which is characterized by the following. )

However, R, R ³ , R ⁴ , R ¹⁶ and m are as defined above.

Further, the present invention provides a reaction product of arylglycidyl ether and a compound represented by the following general formula (28), a polyoxyalkylene polymer having a main chain skeleton, a (meth) acrylate polymer or a hydrocarbon. A polymer-based polymer, characterized by reacting a polyvalent aryl compound whose terminal is an aryl group and a dithiol compound represented by the formula HS—R ¹ —SH (R ¹ is as defined above). The gist of the present invention is a method for producing a curable resin represented by the general formula (22) or (23).

However, R, R ³ , R ⁴ and m are as defined above.

Further, the present invention provides a compound represented by the following general formula (29) and a compound represented by the following general formula:

A reaction product with the compound represented by (30), wherein the main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, and the terminal is an aryl group. Certain polyaryl compounds and the formula HS—

A method for producing a curable resin represented by the above general formula (24) or (25), characterized by reacting a dithiol compound represented by R ¹ —SH (R ¹ is as defined above). Is the gist.

, 0, "j 3-m

H ₂ C——C—R ⁴ —Si— (OR) _m (30) provided that R, R ³ , R ⁴ , R ¹⁶ and m are as defined above.

Further, the present invention provides a compound represented by the following general formula (31), wherein the main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer. Polyvalent aryl compounds having an aryl group at the end and dithiol compounds represented by the formula HS—R ¹ —SH (R ¹ is Is equivalent to The gist of the present invention is a method for producing a curable resin represented by the general formula (26), wherein (31)

,;

However, R,. R ³ , R ⁴ , R ¹⁶ and m are as defined above.

Further, the present invention provides an adhesive composition containing the curable resin as a component.

Further, the present invention provides an adhesive composition containing the curable resin and a Lewis acid and Z or a complex thereof.

Further, the curable resin composition of the present invention is characterized in that the Lewis acid is boron trifluoride.

Further, the present invention ′ comprises a curable resin comprising 100 parts by mass of the curable resin and 5 to 1,000 parts by mass of a vinyl polymer obtained by polymerizing a polymerizable vinyl monomer. The gist is a resin composition.

The gist of the present invention is a method for producing the curable resin composition, characterized by polymerizing a polymerizable vinyl monomer in a curable resin. '

Furthermore, the present invention has a reactive silicon group in the molecule and contains one or more nitrogen or sulfur atoms selected from a (thio) urethane bond, a urea bond, a substituted urea bond and a chemical bond from a Michael addition reaction *. A curable resin composition containing a polymer having a bond or a hydroxyl group in an amount of 1 to 50% by mass based on the total amount of the vinyl polymer.

Furthermore, the present invention relates to the above-mentioned curable resin, which has a polymerizable vinyl monomer and a reactive silicon group in the molecule, and is derived from (thio) urethane bond, urea bond, substituted urea bond and Michael addition reaction. Characterized by polymerizing a compound having at least one nitrogen or sulfur atom-containing bond or a hydroxy group selected from the group consisting of: The gist is a method for producing the curable resin composition.

Further, the present invention provides a curable resin composition containing a Lewis acid and / or a complex thereof.

Further, the curable resin composition of the present invention is characterized in that the Lewis acid is boron trifluoride. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention provides a compound having at least one silicon atom-containing group in which at least one hydrolyzable group selected from an alkoxy group, an acetoxyl group and an oxime group is directly bonded to a silicon atom, and having (1) thioether bond And a thiol bond and / or a urea bond or a substituted urea bond, (2) a thioether bond, a hydroxyl group and a secondary or tertiary amino group, or (3) a thioether bond and a secondary or secondary bond. A curable resin having a tertiary amino group and having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic ester polymer or a hydrocarbon polymer.

As the polyalkylene-based polymer having the main chain skeleton, a hydroxyl-terminated polymer produced by reacting monoepoxide with an initiator in the presence of a catalyst is preferred. Yes. As the initiator, a hydroxy compound having one or more hydroxyl groups or the like can be used.

Monoepoxyds include ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, tetrahydrofuran, etc. Can be used. Examples of the catalyst include an alkali metal catalyst such as a potassium compound and a cesium compound, a composite metal cyanide compound 'catalyst, and a metal polyphenylene catalyst. Is As the composite metal cyanide compound complex catalyst, a complex containing zinc hexocyano cobalt as a main component, an ether and a Z or alcohol complex are preferable. Ether and / or alcohol complex The composition described in JP-B-46-272500 can be essentially used. As the ether, ethylene glycol dimethyl ether (Glyme), diethyl glycol dimethyl ether (DiGlyme), and the like are preferable, and handling during the production of the complex is preferred. Glyme is particularly preferred for this reason. As the alcohol, for example, those described in Japanese Patent Application Laid-Open No. HEI 4-145123 can be used, but tert-butanol is particularly preferred. .

Polyoxyalkylene polymers having two or more functional groups are preferred. Specifically, polyoxyethylene, polyoxypyrene, polyoxybutylene are preferred. And polyoxyhexylene, reoxytetramethylene and the like. Preferred polyalkylene polymers are di- to hexavalent polyoxyethylene diols, polyoxypropylene diols, or mixtures thereof. . Polyoxyethylene diol is used as polyoxyethylene diol, and polyoxypropylene diol is used as polyoxypropylene diol and polyoxypropylene diol is used as polyoxypropylene diol. Rent reals,

Polymethylene-based polymers are available on the market, and they can be used in the present invention. The products are, for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: P—200, P—300, glass manufactured, trade names: PML—300, PML—310

P M L-3 0 1 2, P M L-4 0 0 2, P M L-4 0 1 0

PML-500 5, PML-S-4 0 1 2, PML-S-4

011, manufactured by Sumitomo Bayer Eletan Co., Ltd., trade name: Sumiphen 370, SBU—Polyo 10 319. Examples of the above (meth) acrylic acid ester-based polymer include homopolymers of acrylic acid ester or methacrylic acid ester, and those (meth) acrylic acid ester based polymers. Copolymers of (meth) acrylic acid esters with other (meth) acrylic acid esters; these (meth) acrylic acid esters and biel acetate, acrylonitrile, and styrene Examples of such copolymers with vinyl monomers such as acrylates, etc. Examples of acrylates or methacrylates include methyl (meth) acrylate (what is referred to as (meth) acrylate). And methyl methacrylate), ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate Alkyl such as tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl (meth) acrylate Alkoxyalkyl (meth) acrylates, such as (meth) acrylate, ethoxyxyl (meth) acrylate, butoxyshethyl (meth) acrylate, 2-methoxyethoxyxyl (meth) acrylate, 2-acrylate Alkoxyalkoxyalkyl (meth) acrylates such as methoxyethoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate Acrylate, butoxytrie Alkoxy (poly) alkyleneglycol (meth) acrylates such as styrene glycol (meth) acrylate, methoxydipropylene glycol (methyl) acrylate, and pyrenoxide adduct (meth) acrylate , N, N-dimethylaminoethyl (meth) acrylate, dialkylaminoalkyl (meth) acrylates such as N, N-getylaminoethyl (meth) acrylate, or a combination of two or more. Mixtures are mentioned. Examples of the hydrocarbon polymer include monorefenes having 1 to 6 carbon atoms, such as ethylene, propylene, 1-butene, isobutene, and 1-hexene. Polymers whose main monomer is diolefins, homopolymers of diolefins such as butadiene, isoprene, etc .; these diolefins and the above monolayers Examples include hydrogenated products of a copolymer with fin. Among these hydrocarbon polymers, hydrogenated products of polymers containing isobutene as the main monomer and of butadiene polymer have a functional group introduced into the terminal and a molecular weight This is preferred because it is easy to control and the number of terminal functional groups can be increased.

The polymer containing isobutene as the main monomer contains not only a homopolymer of isobutene but also 50% by mass or less of a monomer copolymerizable with isobutene. A copolymer containing preferably 30% by mass or less, more preferably 10% by mass or less, can also be used.

Examples of the monomer that can be copolymerized with isopten include an olefin having 4 to 12 carbon atoms, a vinyl ether, an aromatic vinyl compound, a vinyl silane, and an aryl silane. Such monomers include, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-11-pentene, 1-1pentene, 4-methyl-1-pentene, 1-1hexene, vinylcyclohexene, Examples thereof include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, polymethylstyrene, divinylstyrene, vinyltrimethoxysilane, vinyltriethoxysilane, arylaminotrimethylsilane, and aryldimethoxysilane.

The polyoxyalkylene polymer, the (meth) acrylic acid ester polymer or the hydrocarbon polymer whose main chain skeleton has a number average molecular weight of 500 to 30,000, especially 2,000. It is preferable to use the ones from 0-20, 00 00. Further, the main chain skeleton is a polyoxyalkylene-based heavy In particular, among the (meth) acrylate polymer and the hydrocarbon polymer, a polyoxyalkylene polymer is preferable.

Specific examples of the curable resin of the present invention include those represented by the above general formulas (1), (12), (14), (16), (17) or (18). . Hereinafter, those curable resins and a method for producing the same will be specifically described.

The curable resin represented by the above general formula (1) (hereinafter referred to as “curable resin 1”) has, for example, a polyoxyalkylene polymer, a (meth) acrylic ester polymer or a hydrocarbon having a main chain skeleton. A polyvalent aryl compound whose terminal is an aryl group, a dithiol compound represented by the formula HS—R ¹ —SH (R ¹ has the same meaning as ±), a formula O CN— R ² — prepared by reacting a diisocyanate compound represented by NCO (R ² has the same meaning as described above) and a compound represented by formula HX (X has the same meaning as described above). be able to.

The above polyvalent aryl compound (hereinafter, referred to as compound (a)) typically has a number average molecular weight in the above range, and the main chain skeleton having a hydroxyl group at the end thereof is a poly (aryl) compound. Oxyalkylene-based polymers, (meth) acrylate polymers or hydrocarbon-based polymers are converted to alkali metals, alkali metal hydrides, alkali metal alkoxides or alkali metal hydroxides, etc. And by reacting it with an organic halogen compound having a terminal aryl group and having 3 to 10 carbon atoms.

As the alkali metal, sodium or potassium is preferable, and as the organic halogen compound, aryl chloride, aryl bromide, vinyl (chloro) is preferable. Examples include rometyl benzene, aryl (chloromethyl) benzene, and aryl (chloromethyl) ether. Further, as the above compound (a), commercially available products are commercially available and can be used. As a commercially available product, manufactured by Asahi Denka Kogyo Co., Ltd. -111, ARA-200, ARA-400, and the like.

The dithiol compound (hereinafter, referred to as compound (b)) used for producing the curable resin 1 is represented by the formula HS—R ¹ —SH, where R ¹ has a molecular weight of 10,0. It is a divalent organic group of 0 or less. Specific examples of the divalent organic group having a molecular weight of 100, 000 or less include an alkylene group having 1 or more carbon atoms which may have a side chain, and 6 or more carbon atoms which may have a side chain. CH ₂ CHR ¹⁷ (G) _q CHR ¹⁸ (J) _r CH _2-

(In the formula, R ¹⁷ is a hydrogen atom or a hydroxy group, G is a sulfur atom or an oxygen atom, q is 0 or more, and R ¹⁸ is a hydrogen atom or a hydrogen atom. A oxy group, J is a sulfur atom or an oxygen atom, and r is 0 or 1 or more).

Examples of the compound (b) include 1,5-dimercapto-13-thiapentane (DMDS), eu, 8-dimercapto-3,6-dioxaoctane (DMDO), 1,3-ethanedithiol, Examples thereof include monodithiothreitol, dithioerythritol, and 3,4-dimercaptotoluene. In addition to these, a compound having a spirane ring skeleton at both terminal thiols can be selected.

Diisocyanate compound used to produce curable resin 1

(Hereinafter, referred to as compound (c)) is represented by the formula OCN—R ² —NCO, where R ² is a divalent organic group having a molecular weight of 10 or less. As the compound (c), for example, aliphatic, alicyclic, araliphatic, aromatic diisocyanate compounds and the like can be mentioned. Hereinafter, specific examples thereof will be described.

Aliphatic diisocyanate compounds: Trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamet Chilled sociate, 1, 2 — Propylene Residential, 1, 2 — Butylene Residual, 2, 3 — Petit Residential, 1, 3 — Petit Residential , 2,4,4-or 2,2,4-trimethylhexyl methyl isopropylate, 2,6-diisomethane dimethylproate.

Alicyclic di-sodium compounds: 1,3—cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3—sic Hexane diisocyanate, 3 — Isolate methyl 1, 3, 5 and 5 — Trimethyl cyclohexyl isocyanate, 4 and 4 '— Bis (cyclohexylisocynate), methyl 2 and 4—cyclohexanediocyanate, methyl 1 and 2 and 6—cyclohexanediocyanate, 1, 3 — bis (isomethine methyl) cyclohexane, 1, 4 bis (isomethine methyl) cyclohexane, isophorone isothiocyanate, etc. .

Aroaliphatic diisocyanate compounds: 1,3 or 1,4 xylylene diisocyanates or mixtures thereof, ω, ω '— diisocyanates — 1, 4 — Jechil Benzen, 1,

3 — 1 or 4 1 bis (1 isocyanate — 1-methylethyl) benzene or a mixture thereof.

Aromatic diisocyanate compounds: m — phenylenediocyanate, ρ — phenylenediocyanate, 4, 4 '— diphenyldiisocyanate, 1, 5-naphthalene socyanate, 4, 4 '-diphenylmetane ssionate, 2, 4 1 or 2, 6-triphenyl socyanate, 4, 4 'Toluene diisocyanate, 4,4'-diphenyl ether diisocyanate, etc. X in the compound represented by the formula HX (hereinafter referred to as compound (d)) used for producing the curable resin 1 is represented by the above general formula (2), (3), (4), (5) Or (6).

The compound (d) in which X is represented by the above general formula (2) is an aminosilane compound represented by the following general formula (32) (provided that R, R ³ , R ⁴ and m are as defined above)

H H

Is significant. (Hereinafter referred to as compound cc = compound (e)) and an α, —unsaturated carbonyl compound represented by the following general formula (33) (wherein R ⁶ , R ⁹ and Ζ are as defined above) (Hereinafter referred to as compound (（)), a maleic acid diester compound represented by the following general formula (34) (provided that R ⁸ and R ^{i C} have the same meanings as above). Compound (g)), acetate nitrile, monoisocyanate compound of the formula R ¹³ —NCO (where R ¹³ has the same meaning as described above), or the following general formula (35) )) (Wherein R ¹² has the same meaning as described above). Further, instead of the above monoisocyanate compound, a diisocyanate compound represented by the formula OCN—R ² —NCO (where R ² is as defined above), a monool compound, a monoamine compound, A reaction product with a compound having an active hydrogen atom such as a monomeric butane compound may be used.

(33)

COOR ¹⁰ 34

COOR ⁸ HC = CH

ヽ people ( ^3S)

R ¹²

X is a compound (d) represented by the above general formula (3) or (4) is an aminosilane compound represented by the following general formula (36) (where R, R ³ , R ⁴ , R ⁵ and m are . mono represented by NC O - wherein the the same meaning) (hereinafter, compound (h) and that), the upper title compound (f), the compound (g), § Se Tonito Lil, the above formula R ^{1 3.} It can be produced by reacting an isocyanate compound or a monomaleimide compound represented by the above general formula (35), and instead of the above monoisocyanate compound, it is represented by the above formula OCN—R ² —NCO A reaction product of a diisocyanate compound and a compound having an active hydrogen atom such as a monol compound, a monoamine compound, or a monomercaptan compound may be used.

In this case, the compound to be reacted with the compound (h) is the compound (f), the compound (g), acetonitrile, a monoisocyanate compound represented by the above formula R ¹³ —NCO, or the general formula (35) )), D and E in the general formula (3) or (4) are the same as those of the compound (f), the compound (g), acetonitrile, When two kinds selected from the monoisocyanate compound represented by the above formula R ¹³ —NCO or the compound represented by the monomaleimide compound represented by the above general formula (35) are used, the general formula ( D and E in .3) or (4) will be different, and if three or more are used, the HX compound will consist of a different mixture of D and E in general formula (3) or (4).

R ³ 3-m

(RO) — Si— R —N— R ⁵ —NH ₂ (36)

H

Compound (d) in which X is represented by the above general formula (5) is represented by the following general formula (37) And an aminosilane compound represented by the formula: R, R ³ , R ⁴ , R ⁶ and m have the same meanings as described above. Examples of the alkyl group of R ⁶ include methyl, ethyl, i-propyl, n-butyl and the like. Examples of the phenyl group include a phenyl group and a tolyl group.

The compound (d) in which X is represented by the above general formula (6) includes an aminosilane compound represented by the following general formula (38). R, R ^3, 1 ⁴ and 111 are as defined before SL.

Examples of the compound (e) include a-amino-proprietary methoxysilane, τ-amino-propyl triethoxylate, and a-amino-propyl Methyldimethoxysilane, D-Aminopropyl Methyljet Xilan, δ-Aminore, Adimethylbutyritrimethylsilan, δ—Aminor, r—Dimethylbutylmethyldimethoxysilane, δ—Aminore, r—Dimethylbutyltriethoxysilane, δ— Aminor, argymethyl, butylmethyl, ethyljet xylan, and the like.

Examples of the compound (f) include (meth) acryl compounds, vinyl ketone compounds, vinyl aldehyde compounds, and other compounds. As (meth) acrylic compounds, methyl (meth) .acrylate, ethyl (meta) acrylate, propyl (methyl) Evening) acrylate, isopropyl (meta) acrylate, butyl (meta) acrylate, isobutyl (meta) acrylate, t-butyl (Meta) acrylate, pentyl (meta) acrylate, amimil (meta) acrylate, isoamyl (meta) acrylate, Hexyl (meta) acrylate, heptyl (meta) acrylate, octyl (meta) acrylate,

2 — Ethylhexyl (meta) acrylate, nonyl (meta) acrylate, decyl (meta) acrylate, isodecyl (methyl) acrylate , Undecyl (meta) acrylate, dodecyl (meta) acrylate, raurisole (meta) acrylate, octadecyl (meta) acrylate Crylate, stearyl (meta) acrylate, tetrahydrofuryl (meta) acrylate, butoxyl (meta) acrylate Relate, ethoxy diethylene glycol (meta) acrylate, benzyl (meta) acrylate, cyclohexyl (meta) acrylate Relate, phenoxyethyl (meta) accredit, polyet Recall (meta) accretion, Polypropylene recall (meta) accrete, methoxy recall (meta) Accelerator, metrology-related call (meta) accredit, metrology-related recall (meta) accredit Rate, methoxy propylene recall (meta) acrylate, dicyclopentane genirelle (meta) acrylate, dicyclope Nil (meta) acrylate, dicyclopentenyl (meta) acrylate, tricyclodecane (meta) acrylate, polnyle (meta) ＞ acrylate, isopornil (meta) acrylate, diaceton (Meta) acrylate, isobutyl methacrylate (meta) acrylate, N-vinylpyrrolidone, N-bi Nilka Prolactam, N-vinylformaldehyde, N, N-dimethyl (meth) acrylamide, t-octyl (meta) acrylamide, Dimethylaminoethyl (meta) acrylate, Jethylaminoethyl (meta) acrylate, 7-amino3,7—dimethylthiomethyl (meta) acrylate Relay, N, N —dimethyl (meta) acrylamide, N, N'-dimethylaminopropyl (meta) acrylamide, acrylic Other than Rumorolin, etc., product names manufactured by Toagosei Co., Ltd .: Aronix M—102, M—111, M—114, M—117, Nippon Kayaku Brand name: KAHAARD TCI 1 OS, 629, R644, brand name of Osaka Organic Chemical Co., Ltd .: Viscoat 3700.

In addition, trimethylol property (meta) crerate, pentaerythrill (meta) crerate, pentaerythrite Tray (meta) clear rate, ethylene glycol (meta) clear rate, Tetray ethylene clear rate (meteor) clear rate , Polyethylene glycol (meta) acrylate, 1,4—butane diol (meta) acrylate, 1,6—hexan diol (Meta) acrylate, neopentyl cholesterol (meta) acrylate, trimethylol propanetrioxyl chelate (meta) acrylate, tritry (2—Hydroxy Shechil) Cryrate, tris (2-hydroxy shetil) Isonurate rate (meta) Accurate, tricyclodecane rate (meta) .〉 Acrylate, bisphenol A darcydil ether with epoxy (meta) acrylate added to (epoxy) (metal) acrylic, etc. Polyfunctional compound and polyfunctional compound Trade name of Takahashi Chemical Co., Ltd .: UPIMAI UV, SA

1002, SA200, trade name of Osaka Organic Chemicals Co., Ltd .: Biscourt 700, trade name of Nippon Kayaku Co., Ltd .: Kayado R600

4, DPC Α-20, DPCA-30, DPCA-60, DPCA-120, HX-62, D-310, D-330, Toagosei Co., Ltd. Ronics M—210, M-2

5, Μ—3 15, M—3 2 5 and the like.

In addition to the above-mentioned compounds, r-methacryloxypropyl methoxysilane having an alkoxysilyl group, fermetacryloxy propyl protry Ethoxy silane, alpha chromium oxymethyl dimethyl silane, ryoku methacryloxy meth, J reject xylan, Ύ Ύ Riloxypro built-in xylan, r-acryloxymethyldimethoxysilane and the like.

Vinyl ketone compounds include vinyl acetate, mesitylene oxide, vinyl ethyl ketone, vinyl butyl ketone, and the like, and pinyl aldehyde compounds include acrolein and metachlorine. And other compounds, such as maleic anhydride, maleic anhydride, itaconic anhydride, itaconic acid, crotonic acid, and thiochloroacetic acid. Cryamide, diacetonitrile amide, standard [3- (dimethylamino) propyl] methacrylate amide, N, N—dimethinoacrylate Amido, N, N—Jetilla creamide, N—t—octyl creamide, Ν—Isopropyl acrylamide, and the like.

In addition to the above compounds, compounds containing a fluorine atom, a sulfur atom, a yellow atom or a phosphorus atom therein are also included. Compounds containing a fluorine atom include perfluorinated octylethyl (meta) acrylate, trifluoroethyl (meta) acrylate, and the like. Examples of such a compound include (meta) acryloxyshelfyl acid phosphate and the like.

Examples of the compound (g) include dimethyl methyl maleate, getyl maleate, dibutyl maleate, di-2-methyl ethylhexyl hexyl, and dioctyl maleate. These may be used alone or in combination of two or more. .

Examples of the monomeric amide compound represented by the above general formula (35) include N—Fenj-Ji-Ray-Mid, N—Cyclohexyi-Rem-Ay-Mid, and Hydroxif-Enil-My. C, N—Raw Lima Remide, Jethyl Fenil Remide, N— (2—Cross Fen) Mleimid, and the like.

Examples of the compound (h) include N— / 3 (aminoethyl) -aminobutyral trimethyoxysilane, N— / 3 (aminoethyl) mono-aminopropylmethyldimethoxysilane, and N— / 3 (aminoethyl) -alpha Aminobutyl pyrtriethoxysilane, N— / 3 (aminoethyl) -1-aminopropylpyrethylethoxysilane, aminopropyldimethylmethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N-1 (6-aminohexyl) -13-aminopropyl trimethoxysilane, N- (2-aminoethyl) 111 aminoundecyltrimethoxysilane and the like. These can be used alone or in combination of two or more.

The contact order of each compound in the reaction of the compound (a), the compound (b), the compound (c) and the compound (d) in preparing the curable resin 1 is not fixed but arbitrary. . Each reaction is carried out in a temperature range of about 120 to + 150 ^ for about 1 to 1,000 hours. The reaction may be performed in the presence of a medium such as an organic solvent. Examples of the organic solvent include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and cycloheptane. Can be The reaction ratio of the compound (a :), the compound (b), the compound (c) and the compound (d) is 0.5 to 1 mol of the aryl group in the compound (a). : L. 2 mol.

The reaction of the above compound (a) with another compound or a contact reaction product of another compound with another compound is carried out in the presence of a radical initiator. Examples of the radical initiator include azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2-methylbutyronitrile), benzoyl peroxide, and t-alkyl alcohol. Peroxides such as oxyester, acetyl valoxide, and diisopropyl propyl carbonate are used. Alternatively, ultraviolet irradiation may be used instead of using the radical initiator.

The above compound (e) and the above compound (f), the above compound (g), acetate nitrile or the above maleimide when preparing the compound (d) in which X is represented by the above general formula (2) The reaction with the compound is carried out in a temperature range of about −20 to + 50 ° C. for about 1 to 1,000 hours. The reaction may be performed in the presence of a medium such as an organic solvent. The reaction ratio of compound (e) with compound (f), compound (g :), acetonitrile or a maleimide compound is such that compound (f), compound (g), and acetonitrile are used per mole of compound (e). The number of active hydrogens in the compound (e) is about (11) X (0.1 to 9) moles for the tolyl or maleimide compound.

The compound (h) and the compound (f), the compound (g), acetonitrile, or the maleimide compound when preparing the compound (d) in which X is represented by the above general formula (3) or (4) Is carried out in the same manner as in the reaction of the above compound (e) with compound (f), compound (g), acetonitrile or maleimide compound.

The curable resin represented by the general formula (12) (hereinafter referred to as “curable resin 2”) includes, for example, a polyoxyalkylene polymer having a main chain skeleton, and a (meth) acrylic polymer. A Le ester polymer or hydrocarbon-based polymer, polyvalent Ariru compound thereof ends are Ariru group, the formula HS- R ¹ - Chio Amin compound represented by NH R ^{1 3} (R ¹ and R ^{1 3} is as defined above), wherein O CN- R ² -.. Jiisoshianeto compound represented by NC O (R ² is Ru as defined der above) and a compound represented by the formula HX (X is the same as above This is significant.)

As the polyvalent aryl compound, the compound (a) used when preparing the curable resin 1 can be used in the same manner. Thioamine compounds (. Hereinafter referred reduction compound (i)) has the formula HS- R ¹ - is represented by NHR ^{1 3,} R ¹ and R ^{1 3} which in formula are as defined above. Above formula odor compounds (i) Te, R ^{1 3} has the formula HS- R ¹ is a compound in the case of hydrogen atom (i) - may be used thioamine compounds of NH ₂ but, R ^{1 3} is the general formula ( In the case of 7), the reaction product of the thioamine compound and the compound (f) or the compound (g) is used. When R ¹³ is the general formula (8), the reaction product of the thioamine compound and acrylonitrile is used. When R ¹³ is the general formula (10), a reaction product of the thioamine compound and the monomer compound represented by the general formula (26) may be used. Specific examples of compound (i) include 2-aminobenzenethiol, 2-aminoethanethiol, 2-aminopurin-1-ol, and the like.

Further, as the diisocyanate compound used in producing the curable resin 2, the compound (c) used in preparing the curable resin 1 can be used in the same manner. As the compound represented by the formula HX, the compound (d) used for preparing the curable resin 1 can be used in the same manner.

The order of contact of the compounds in the reaction of the polyvalent aryl compound, the thioamine compound, the diisocyanate compound, and the compound represented by HX in the preparation of the curable resin 2 is not limited and is arbitrary. You. Each reaction is carried out in a temperature range of about 20 to + 150 ° C. for about 1 to 1,000 hours. The reaction may be performed in the presence of a medium such as an organic solvent. The organic solvent is selected from those mentioned above. In addition, the reaction ratio of the polyvalent aryl compound, the thioamine compound, the diisocyanate compound and the compound represented by the above HX is such that the ratio of the other compound is 1 mole of the aryl group in the polyvalent aryl compound. 0.5 to 1.2 mol.

The reaction between the polyvalent aryl compound and another compound or a contact reaction product of another compound with another compound is performed in the presence of a radical initiator. The radical initiator is selected from the above. Ultraviolet irradiation may be used.

The curable resin represented by the above general formula (14) (hereinafter referred to as “curable resin 3”) includes, for example, a polyoxyalkylene polymer having a main chain skeleton, a (meth) acrylate polymer or a hydrocarbon. a system polymer, polyhydric Ariru compound thereof ends are Ariru group, the formula HS- R ^¹ - NHR ¹ Chio Amin compound represented by ³ (. R ¹ and R ^{1 3} are as defined above) and It can be produced by reacting a compound represented by the above general formula (15) (R, R ³ , R ⁴ and m are as defined above).

As the polyvalent aryl compound, the compound (a) used when preparing the curable resin 1 can be used in the same manner. Further, as the thioamine compound, the compound (i) used in preparing the above-mentioned curable resin 2 can be used in the same manner. Examples of the compound represented by the above general formula (15) include f-cyanatespropyltrimethoxysilane, r-isocyanatepropylmethyldimethylmethoxysilane, f-isocyanatepropyltrimethoxysilane, and f-isocyanoatepropyltrimethoxysilane. Cyanate propyl methyl ethoxysilane and the like.

Each of the polyvalent aryl compounds, the thioamine compounds and the compounds represented by the general formula (15) in the reaction of the curable resin 3 is prepared. The order of contact of the compounds is not fixed but arbitrary. Each reaction is performed in a temperature range of about 120 to 150 ° C. for about 1 to 1,000 hours. The reaction may be performed in the presence of an organic solvent medium. The organic solvent is selected from the above. In addition, the reaction ratio of the polyvalent aryl compound, the thioamine compound and the compound represented by the general formula (15) is such that the other compound is 1 mole of the aryl group in the polyvalent aryl compound. Each is 0.5 to 1.2 mol.

The reaction between the polyvalent aryl compound and another compound or a contact reaction product of another compound with another compound is performed in the presence of a radical initiator. The radical initiator is selected from those described above. Ultraviolet irradiation may be used.

The curable resin represented by the general formula (16) (hereinafter referred to as “curable resin 4”) has, for example, a polyoxyalkylene polymer having a main chain skeleton, a (meth) acrylic acid ester polymer or A polyvalent aryl compound which is a hydrocarbon polymer and the terminal of which is an aryl group; a dithiol compound represented by the formula HS—R ¹ —SH (R ¹ is as defined above); It can be produced by reacting the compound represented by (15).

As the polyvalent aryl compound, the compound (a) used when preparing the curable resin 1 can be used in the same manner. As the dithiol compound, the compound (b) used for preparing the above-mentioned curable resin 1 can be used in the same manner. Further, as the compound represented by the general formula (15), the compound represented by the general formula (15) used when preparing the curable resin 3 can be used in the same manner.

The contact order of each compound in the reaction of the polyvalent aryl compound, the dithiol compound and the compound represented by the general formula (15) when preparing the curable resin 4 is not fixed but arbitrary. . Each reaction is carried out in a temperature range of about 120 to 115 ° C for about 1 to 1,000 hours. Anti The reaction may be performed in the presence of a medium such as an organic solvent. The organic solvent is selected from the above. The reaction ratio of the polyvalent aryl compound, the dithiol compound and the compound represented by the general formula (15) is such that the other compound is Each is 0.5 to 1.2 mol.

The curable resin represented by the above general formula (17) (hereinafter referred to as “curable resin 5”) includes, for example, a polyoxyalkylene polymer having a main chain skeleton, an Esdel polymer (meth) acrylate, or a hydrocarbon. A polyvalent aryl compound whose terminal is an aryl group, a dithiol compound represented by the formula HS—R ¹ —SH (R ¹ is as defined above), a formula CH 2 = CH — CH 2 — an arylamine compound represented by NHR ¹⁶ (R ¹⁶ is a hydrogen atom or an organic group having a molecular weight of less than 500;), a disocyanate compound represented by the formula 0 CN—R ² —NC 0 It can be produced by reacting a compound (R ² is as defined above) and a compound of the formula (X is as defined above).

As the polyvalent aryl compound, the compound (a) used when preparing the curable resin 1 can be used in the same manner. As the dithiol compound, the compound (b) used for preparing the above-mentioned curable resin 1 can be used in the same manner. Further, as the compound represented by diisocyanation, the compound (c) used in preparing the curable resin 1 can be used in the same manner.

The above formula CH _₂ = CH- CH ₂ of Ariruamin compounds - but R ^{1 6} that put the NHR ^{1 6} is a hydrogen atom or a molecular weight 5 0 0 The following organic groups, the organic group Specific examples include an aryl group, the above general formula (7), the above general formula (8), the above general formula (10), the above general formula (13), a group represented by the following (39) (R, R ³ , R ⁴ and m are the same as defined above.) And the like. R ^{1 6} has the formula CH _₂ = CH- CH ₂ as the compound in the case of hydrogen atoms - NH ₂ in § Li Ruamin, the塲合of Ariru group formula _{_{CH 2 = CH- CH 2 - NH-}} CH 2 - CH = CH ₂ may be used, but when R ¹⁶ is the above general formula (7), arylamine and a β-unsaturated carbonyl compound represented by the following general formula (40) (R ¹⁹ is A hydrogen atom, a CH ₂ COOH or a methyl group, and R ⁶ , R ⁷ and Z have the same meanings as above.) And an arylamine in the case of the above general formula (8). The reaction product of acrylonitrile with the above-mentioned general formula (10) is the reaction product of arylylamine with the above-mentioned monomaleimide compound of the general formula (35), and the general formula (13) is the arylamine. And the maleic acid diester compounds ¹³ and R ¹⁴ represented by the following general formula (41) are as defined above. In the case of the following (39), the reaction product with the compound represented by the formula CH ₂ = CH—CH ₂ —NH—CH ₂ —CH == CH ₂ is represented by the above general formula (19) The reaction product with the compound to be used may be used. Further, as the compound represented by diisocyanation, the compound (c) used in preparing the curable resin 1 can be used in the same manner. .

HC—— C00R ¹⁴

(41)

HC—COOR ¹⁵

The polyvalent aryl compound used in preparing the curable resin 5, the dithiol compound, The contact order of each compound in the reaction of the compound represented by the formula (I), the arylamine compound, the diisocyanate compound, and the compound represented by HX is not limited, but is arbitrary. Each reaction is performed in a temperature range of about 120 to 115 ° C. for about 1 to 1,000 hours. The reaction may be performed in the presence of a medium such as an organic solvent. The organic solvent is selected from those mentioned above. The reaction rate of the polyvalent aryl compound, the dithiol compound, the arylyl compound, the diisocyanate compound, and the compound represented by HX is such that the ratio of the other compound to 1 mole of the aryl group in the polyvalent aryl compound is The substances are each 0.5 to 1.2 moles.

The curable resin represented by the general formula (18) (hereinafter referred to as “curable resin 6”) has, for example, a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a carbonized resin having a main chain skeleton. A polyvalent aryl compound whose terminal is an aryl group; a dithiol compound represented by the formula HS—R ¹ —SH (R ¹ is as defined above); a formula CH ₂ = C one CH ₂ - Ariruamin compound represented by NHR ^{1 6,} wherein NC O- R ² (R ^{1 6} are as defined above.) - Jiisoshianeto compound represented by NC O (R ² is the same as above Symbol And the compound represented by the above general formula (15).

As the polyvalent aryl compound, the compound (a) used when preparing the curable resin 1 can be used in the same manner. As the dithiol compound, the compound (b) used for preparing the above-mentioned curable resin 1 can be used in the same manner.

An arylamine compound represented by the above formula CH ₂ = CH— CH ₂ — NH R ¹⁶ As the product, an arylamine compound used for preparing the curable resin 5 can be used in the same manner. Further, as the compound represented by the general formula (15), the compound represented by the general formula (15) used for preparing the curable resin 3 can be used similarly.

The contact order of the compounds in the reaction of the polyvalent aryl compound, the dithiol compound, the arylamine compound, and the compound represented by HX in preparing the curable resin 6 is not fixed but arbitrary. Each reaction is carried out in a temperature range of about 120 to + 150 ° C. for about 1 to 1,000 hours. The reaction may be performed in the presence of a medium such as an organic solvent. The organic solvent is selected from those described above. The reaction ratio of the above polyvalent aryl compound, the above dithiol compound, the above arylamine compound and the compound represented by HX is 0.5 for each mole of the aryl group in the polyvalent aryl compound. ~ 1.2 moles.

The reaction between the polyvalent aryl compound and another compound or a contact reaction product of another compound with another compound is performed in the presence of a radical initiator. The radical initiator is selected from those described above. Ultraviolet irradiation may be used. Further, in the curable resin of the present invention, the main chain skeleton is preferably a polyoxyalkylene polymer, a (meth) acrylic ester polymer or a hydrocarbon polymer, and the terminal is an aryl group. Valyl compounds, dithiol compounds of the formula HS—R ¹ —SH (R ¹ is as defined above), diisocyanate compounds of the formula OCN—R ² —NCO (R ² is as defined above) And the compound represented by the above general formula (19) (R, R ³ , R ⁴ and m are the same as defined above).

As the polyvalent aryl compound, the compound (a) used when preparing the curable resin 1 can be used in the same manner. The dithiol compound is The compound (b) used for preparing the curable resin 1 can be used in the same manner. Further, as the diisocyanate compound, the compound (c) used when preparing the curable resin 1 can be used in the same manner. Examples of the compound represented by the above general formula (19) include α-mercaptopropyltrimethoxysilane, r-mercaptopropylmethyldimethoxysilane, 7-mercaptopropyltriethoxysilane, and α-mercaptopropylmethylethoxyethoxysilane. Can be

The order of contact of each compound in the reaction of the polyvalent aryl compound, the dithiol compound, the arylyl compound, and the compound represented by the general formula (19) in the production method A is not limited. Not optional. Each reaction is performed in a temperature range of about 120 to 150 ° C. for about 1 to 1,000 hours. The reaction may be performed in the presence of a medium such as an organic solvent. The organic solvent is selected from those mentioned above. Further, the reaction ratio of the polyvalent aryl compound, the dithiol compound, the arylyl compound and the compound represented by the general formula (19) is such that the ratio of the other compound to the mole of the aryl group in the polyvalent aryl compound is 1 mol. They are 0.5 to 1.2 mol respectively.

The curable resin represented by the general formula (20) (hereinafter referred to as curable resin 7) or the curable resin represented by the general formula (21) (hereinafter referred to as curable resin 8) is: It can be produced by the following method (1) or (2).

(1) Separately, an arylglycidyl ether is reacted with a compound represented by the above general formula (27) to obtain a reaction product (A) of both. The arylidyl ether and the compound represented by the general formula (27) are The compound represented by the above general formula (27) is used in an amount of 0.8 to 1.2 mol per 1 mol of the polyester, and the reaction is performed for δδ Ο Ο ^,:! To 500 hours. On the other hand, the main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, and a polyvalent aryl compound whose terminal is an aryl group is represented by the formula HS—R ¹ — After reacting with the dithiol compound represented by SH (R ¹ has the same meaning as described above), it is reacted with the above-mentioned reaction product (Α). The reaction is between 50 and 100 ° C. ~ 500 hours. As the polyvalent aryl compound, the compound (a) used for preparing the curable resin 1 can be used in the same manner. Each reaction may be performed in the presence of a medium such as an organic solvent. The organic solvent is selected from those described above.

-(2) After reacting a dithiol compound represented by the formula HS—R ¹ —SH (R ¹ is as defined above) with the reaction product (A), the main chain skeleton is changed to poly Oxyalkylene polymer> (meth) acrylic acid ester polymer or hydrocarbon polymer, which can be produced by reacting with a polyvalent aryl compound whose terminal is an aryl group. . As the polyvalent aryl compound, the compound (a) used when preparing the curable resin 1 can be used in the same manner. The reaction conditions may be in accordance with the method (1). The curable resin represented by the above general formula (22) (hereinafter referred to as curable resin 9) or the curable resin represented by the general formula (23) (hereinafter referred to as curable resin 1). Can be manufactured by the following method (3) or (4).

(3) Separately, an arylglycidyl ether is reacted with the compound represented by the general formula (28) to obtain a reaction product (B) of both. The arylylidyl ether and the compound represented by the general formula (28) are preferably a compound represented by the general formula (28) with respect to 1 mol of the arylglycidyl ether in the presence of the amino compound. 8 to 1.2 moles used, 50 The reaction is carried out for ~ 100, 1 ~ 500 hours. On the other hand, the main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, and a polyvalent aryl compound whose terminal is an aryl group is represented by the formula HS—R ¹ —SH. After reacting the dithiol compound shown (R ¹ has the same meaning as described above) with the above reaction product (B). As the polyvalent aryl compound, the compound (a) used when preparing the curable resin 1 can be used in the same manner. The reaction is carried out at 50-100 ° C. for 1-500 hours. Each reaction may be performed in the presence of a medium such as an organic solvent. The organic solvent is selected from those described above.

(4) After reacting the dithiol-compound represented by the formula S—R ¹ —SH (R ¹ is as defined above) with the reaction product (B), the main chain skeleton is Polyoxyalkylene polymer, (meth) acrylic ester polymer or hydrocarbon polymer, which can be produced by reacting with a polyvalent aryl compound whose terminal is an aryl group. . As the polyvalent aryl compound, the compound (a) used when preparing the curable resin 1 can be used in the same manner. The reaction conditions may be in accordance with the above method (3). The curable resin represented by the general formula (24) (hereinafter referred to as curable resin 11) or the curable resin represented by the general formula (25) (hereinafter referred to as curable resin 12) is used. It can be manufactured by the following method (5) or (6).

(5) The compound represented by the general formula (29) is reacted with the compound represented by the general formula (30) to obtain a reaction product (C) of both. The above—the compound represented by the general formula (29) and the compound represented by the general formula (30.) are the same as the general formula (29) with respect to 1 mol of the compound represented by the general formula (29). The compound represented by the formula (30) is used in an amount of 0.8 to 12 mol, and the reaction is carried out at 50 to 100 for 1 to 500 hours. On the other hand, when the main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylate polymer or a hydrocarbon polymer. After reacting a polyvalent aryl compound whose terminal is an aryl group with a dithiol compound represented by the formula HS—R ¹ —SH (R ¹ is as defined above), React with product (C). As the polyvalent aryl compound, the compound (a) used in preparing the curable resin 1 can be used in the same manner. The reaction is carried out at 50-100 ° C. for 1-500 hours. Each reaction may be performed in the presence of a medium such as an organic solvent. The organic solvent is selected from those described above.

(6) After reacting a dithiol compound represented by the formula HS—R ¹ -SH (R ¹ is as defined above) with the reaction product (C), the main chain skeleton is a polyoxyalkylene-based compound. It is a polymer, a (meth) acrylic ester polymer or a hydrocarbon polymer, and can be produced by reacting with a polyvalent aryl compound whose terminal is an aryl group. As the polyvalent aryl compound, the compound (a) used for preparing the curable resin 1 can be used in the same manner. The reaction conditions may be in accordance with the method (5).

The general formula (2 6) curable resin represented by (hereinafter referred to as a curable resin 1 3.) Is (I) the general formula (3 1) with a compound of formula HS- R ¹ one SH represented by After reacting the dithiol compound shown below (R ¹ is as defined above), the main chain skeleton is changed to a polyoxyalkylene polymer, a (meth) acrylic ester polymer or a hydrocarbon polymer. A polyaryl compound whose terminal is an aryl group or (mouth) a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon After reacting a polyvalent aryl compound whose terminal is an aryl group with a dithiol compound represented by the formula HS—R ¹ —SH (R ¹ is as defined above), Produced by reacting the compound represented by the formula (31). As the polyvalent aryl compound, the compound (a) used for preparing the above-mentioned curable resin 1 can be used in the same manner as the above-mentioned compound represented by the general formula (31), the compound represented by the formula HS — R ¹ — at SH The reaction ratio of the dithiol compound and the polyvalent aryl compound shown in the formula is 0.8 to 1.2 moles of the compound represented by the general formula (31) and 0.1 mole of the polyvalent aryl compound per mole of the dithiol compound. The reaction is carried out at 50-100 ° C. for 1-500 hours. Each reaction may be performed in the presence of a medium such as an organic solvent. The organic solvent is selected from those described above.

The gist of the present invention is a curable resin composition containing the curable resin as a component (hereinafter, referred to as composition 1).

The gist of the present invention is also a curable resin composition (hereinafter, referred to as composition 2) containing, as a component, a polymer (D) obtained by polymerizing the curable resin with a polymerizable vinyl group-containing monomer. I do. Composition 2 is particularly preferred because it can improve the adhesion to various adherends.

Examples of the polymerizable vinyl monomer include compounds selected from acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters (hereinafter, these are referred to as (meth) acrylic compounds). Evening) A portion of the polymerizable vinyl monomer composed of an acrylic compound is converted from nitrogen atoms derived from (thio) urethane bond, urea bond, substituted urea bond, and Michael addition reaction, which have a reactive silicon group in the molecule. It is preferably used instead of a compound having a selected bond or atom (hereinafter, referred to as compound (j)). The curable resin composition containing the polymerizable vinyl monomer and the compound (j) is hereinafter referred to as composition 3. The above (meth) acrylic compound and compound (j) are not limited to one kind, and two or more kinds can be used.

As the (meth) acrylic compound, a (meth) acrylic compound of an α, β-unsaturated carbonyl compound (compound (f)) used for producing the curable resin 1 is selected from the group and used. Can be.

Examples of the compound (j) include the following compound (j-1) and the compound (j-1 2). It can be manufactured by a synthetic method. These compounds (j-1) and (j-12) are obtained by mixing a polymer obtained by polymerizing the compound alone and a polymer obtained by polymerizing a (meth) acrylic compound. However, it is particularly preferable to use it by copolymerizing with the above (meth) acrylic compound. As the copolymerization method, for example, the compound (j-1) is copolymerized with a (meth) acrylic compound, the (j.-2) is copolymerized with a (meth) acrylic compound, and the compound (1-1) is copolymerized. ) And the compound (j-2) and a (meth) acrylic compound are preferably copolymerized.

(1) Compound (j-1)

A monoisocyanate compound having a group represented by the following general formula (42) or (43) and an isocyanate group in a molecule, and a compound represented by the following general formula (44), (45), (4) 6), (47)., (48), (49), (50) or a hydrolyzable silicon-containing unsaturated compound obtained by reacting the compound represented by (51).

R ²⁰

(42)

H ₂ C = C

CH≡C— [43)

00

()

R ^2Q in the above general formula ( ⁴² ) represents a hydrogen atom or a methyl group;

twenty one

In the general formula (44), “” in (51) represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ²² represents a hydrogen atom, an alkyl group having 120 carbon atoms, an aryl group or an aralkyl group. the group, Q is an integer of 1 3, is an alkylene group or Ariren group even if 1 1 0. number of side chain carbon atoms, R ²⁴ is represented by the water atom or formula one C OO R ²⁵ Group (R ²⁵ is a molecule: 500 or less

S "Ϊ4

Shows an organic group. ), Κ 2 "6, I

Is a hydrogen atom or a methyl group, η 27 is a phenyl group, a cyclohexyl group or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and R ²⁸ is a 120 carbon atom. An alkyl group, an aryl group or an aralkyl group, R " ⁹ is a hydrogen atom, a phenyl group or a carbon number; I 20 is a substituted or unsubstituted organic group, and R ^3Q is a compound having a molecular weight of 500 or less. It represents a substituted or unsubstituted divalent organic group.

31

Y represents a hydrogen atom, OR ³¹ , R ″ ¹ or NHo, and R represents a hydrogen atom, an organic group having a molecule of 500 or less, or a group represented by the following general formula (52);

)

(R ²¹ , R ²² and R HC ²³ are as defined above, and x is an integer of 13

2- Show each. )

V ¹ , W ¹ and V ² are groups represented by the following HC general formula (53), (54), (55) or (56), respectively, and W ² is V " There general formula when the general formula (3) (3), (5 4), (5 5) or (5 6), V ² is the general formula. (5 4) formula when (5 3), (5 4), (5 5) or (5 6), V ² is the general formula (5 5) general formula when the (3), (5 4> or (5 5), V beam general formula (5 6) represents a hydrogen atom.

()

CN 54,

()

-c —— R ²⁸

: S6)

o H

However, R ²² , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ and Y in the above general formulas (53), (54), (55) and (56) are as defined above.

Examples of the monoisocyanate compound having a group represented by the above general formula (42) or (43) and an isocyanate group in the molecule include m-isopropenyl-1-α, 0! -Dimethylbenzyliso- Cyanate and 2-methacryloylloxityl isocyanate. These can be used commercially.

Further, the monoisocyanate compound having a group represented by the above general formula (42) or (43) and an isocyanate in a molecule is a diisocyanate compound and the following general formulas (57), (5) It can also be produced by reacting the compound represented by 8) or (59).

(58)

R-SH = \ ()

R—OH

The diisocyanate compound can be appropriately selected from dizocyanate compounds (compound (c)) used in producing the curable resin 1.

Examples of the compound represented by the general formula (57) include a reaction product of acrylamide, arylamine and the like with the above (meth) acrylic compound. ,

Examples of the compound represented by the general formula (58) include full furyl mercaptan, aryl mercaptan and the like.

Examples of the compound represented by the above general formula (59) include 4-hydroxypropyl acrylate, 2-hydroxyshetyl acrylate, 2-hydroxypropyl acrylate, 2-acryloxypropyl acrylate, and methacrylic acid. 2-hydroxyethyl, methacrylic acid 12-hydroxypropyl, N-methylol acrylamide and other hydroxy-containing (meth) acrylates, aryl alcohol, aryl phenol, eugenol, hydroxystyrene, 3- Methyl-1-butyne—3-ol, 3-methyl-1-pentene—3-pentyl, 3,5-dimethyl-11-hexyne—3—ol, propargyl alcohol, 2-methyl-3-butyne—2—o —Toluene, pendecylenic acid, acrylic acid, methacrylic acid, 2-butenoic acid, furfuryl alcohol 9 one Deseno Ichiru - 1, to 5-hexene one 1 -. O Ichiru, 2-arsenide Dorokishechirubi two Rue one ether, 4-hydroxycarboxylic butyl Pini Rue one ether, diethylene glycol Petit ether, etc. can be mentioned, et al are. Next, the compounds represented by the above general formulas (44), (45), (46), (47), (48), (49), (50) and (51) will be described. State.

The compound represented by the general formula (44) is represented by the following general formula (60) By reacting a compound represented by the following general formula (61) with a compound represented by the following general formula (61). R ²¹ , R ²² , ²³ and q in the following general formula (60) and R ²⁴ , R ^2o and Y in the following general formula ( ⁶¹ ) are as defined above. The reaction between the compound represented by the general formula (60) and the compound represented by the general formula (61) is carried out at 20 to 100 ° C for 1 to 500 hours.

Examples of the compound represented by the general formula (60) include araminopropylmethyldimethoxydilan, r-aminopropylmethylethoxysilane, 丫 -aminopropyltrimethoxysilane, τ-aminopropyltriethoxysilane, And aminophenyltrimethoxysilane.

As the compound represented by the general formula (61), any compound can be selected from the above-mentioned (meth) acrylic compound, pinyl ketone compound, vinyl aldehyde compound, maleic acid diester, and other compounds. They are not limited to one kind; two or more kinds can be used.

As the pinyl ketone compound, any one of the vinyl ketone compounds of β-unsaturated carbonyl compound ′ (compound (ί)) used in producing the curable resin 1 can be selected and used.

The compound represented by the general formula (45) can be produced by reacting the compound represented by the general formula (60) with acrylonitrile. The reaction between the two is carried out for 1 to 1,000 hours at 2 ο to ι 0 οτ. The compound represented by the general formula (46) is obtained by reacting the compound represented by the general formula (60) with the compound represented by the following general formula (62). Can be manufactured. R ²⁷ in the following general formula (62) has the same meaning as described above. The reaction between the two is carried out at 20 to 100 ° C. for 1 to 1,000 hours.

Examples of the compound represented by the general formula (62) include N-phenylmaleimide, N-cyclohexylmaleimide, hydroxyphenylmonomaleimide,

N-laurel maleimide, getyl phenyl monomaleimide, N- (2-chlorophenyl) maleimide and the like.

The compound represented by the general formula (47) can be produced by reacting the compound represented by the general formula (60) with the monoisocyanate compound represented by the formula R ²⁸ NCO. In the above formula, has the same meaning as described above. The reaction of both is carried out at 20 to 100 C for 1 to 200 hours. Examples of the monoisocyanate compound include ethyl isocyanate, n-hexyl isocyanate, n-decyl isocyanate, ρ-toluenesulfonyl isocyanate, benzyl isocyanate, and 2-methoxyphenyl isocyanate.

Examples of the compound represented by the above general formula (48) include araminopropylmethyldimethoxysilane, r-aminopropylmethylethoxy, silane, araminopropyltrimethoxysilane, araminopropyltriethoxysilane, and N-phenyl. N-phenylaminopropyl trimethoxysilane, N-naphthyl-r-aminopropyltrimethoxysilane, N- (n-butyl) -aminopropyltrimethoxysilane, N-phenyl r-aminopropylmethyldimethyl Xysilane, N-naphthyl-aminobutyral pyrmethyldimethoxysilane, N- (n-butyl) -aminopro Examples include pyrmethyldimethoxysilane, N-ethyl-aminoaminoisobutyltrimethoxysilane, N-methyl-aminoaminopropylmethyldimethoxysilane, N-methyl-aminopropyltrimethoxysilane and the like.

The compounds represented by the above general formulas (49) and (50) include a compound represented by the following general formula (63), a compound represented by the above general formula (61), acrylonitrile, and a compound represented by the above general formula (6). It can be produced by reacting the compound represented by 2) or the above monoisocyanate compound. The reaction is carried out at 20-100 ° C :! Performed for ~ 1,000 hours.

"3-q

(R ^a1 0) -Si— R ²³ -N— R ³⁰ -NH ₂ ( ⁶³ )

H

R ²¹ , R ²² , R ²³ and R ³⁰ in the general formula (63) have the same meaning as described above, and the compound is one of the compounds (h) represented by the general formula (63) Alternatively, two or more types can be selected and used.

Examples of the compound represented by the general formula (51) include amercaptopropylmethyldimethylsilane, amercaptopropylmethylethoxysilane, amercaptopropylvirmethoxysilane, and amercaptopropyltriethoxysilane.

A monoisocyanate compound having a group represented by the above general formula (42) or (43) and an isocyanate group in a molecule, and a compound of the above general formula (44), (45), (46), (4 An example of the reaction with the compound represented by (7), (48), (49), (50) or (51) (formation of a substituted urea bond) is shown below.

A monoisocyanate compound having a group represented by the above general formula (42) or (43) and an isocyanate group in a molecule, and the following general formulas (44), (45), (46), The reaction with the compound represented by (47), (48), (49), (50) or (51) is performed at 20 to 0.50 ° C for 1 to 200 hours. However, there is no problem even if the reaction is performed at more than 200 hours. At this time, in some cases, a polymerization inhibitor may be present.

(2) Compound (j-2).

A polyvalent (meth) acrylate or polyvalent aryl compound represented by the following general formula (64), and the above-mentioned general formulas (44), (45), (46), (47) ,

A compound having a hydrolyzable silicon group-containing unsaturated double bond obtained by reacting the compound represented by (48), (49), (50) or (51).

However, A is a (meth) acrylic system having a group represented by the following general formula (65) (a) at the molecular terminal and a group represented by the following general formula (65) (b) at the other molecular terminal. Or the residue of an aryl compound, B represents one CO— or one C Η „—, R ³² is a hydrogen atom or a methyl group when B is -CO-, a hydrogen atom when B is -CH _2- , R ³³ is a hydrogen atom, an alkyl group having 110 carbon atoms, an aryl group or an aralkyl group. , R and s each represent an integer of 13.

Polyvalent (meth) acrylate compounds represented by the above general formula (64) include butanediol, hexanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, Neopentyl glycol, trimethylol propane, pen erythritol, dipentyl erythritol, polje. Tylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentane Lithitol tri (meth) acrylate, dipentyl erythritol hexa (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, and the like.夕）キシポポポポ）キシ））））））キシ）キシ）））））））））ポポポ0 0 0 2} can also be used.

The polyvalent aryl compound is a polyvalent (meta) acrylate compound which has at least two terminals at both ends, such as the (meta) acryloyl compound. A compound in which one end is a (meta) acryloyl group and at least the other end is an aryl group, while the compound is an aryl group. is there. These compounds include polyvalent (meta) acrylates. A compound in which the (meth) acryloyl group at one end of the above specific example of the late compound is an aryl group.

A polyvalent (meth) acrylate compound or a polyvalent aryl compound represented by the above general formula (64), and the above general formulas (44), (45), (46), (47), The reaction with the compound represented by (48), (49), (50) or (51) is carried out at 20 to 1.00 for 1 to 1,000 hours. There is no problem if the reaction is carried out for more than 000 hours, and in this case, a polymerization inhibitor may be present in some cases, and these reactions (Michael addition reaction and nitrogen addition resulting from Michael addition reaction) The following is an example of the reaction formula:

The compound (j) is a compound of the compound (j-11) and the compound (j-2), a compound represented by the general formula (31) or an arylglycidyl ester and the compound represented by the general formula (27) A reaction product with the compound represented by (28), (44), (45), (46), (47), (48), (49) or (50); A reaction product of the compound represented by the general formula (29) and the compound represented by the general formula (30) is also included.

The curable resin composition of the present invention preferably comprises a Pier polymer (D) as a component. The vinyl polymer (D) is obtained by (co) polymerizing one or more of the above (meth) acrylic compounds, or one of the above (meth) acrylic compounds or It can be produced by copolymerizing two or more kinds and one or two or more kinds of the compound (j). Preferably, it is a vinyl polymer (D) obtained by copolymerizing the (meth) acrylic compound and the compound (j). The proportion of the polymer of the compound (j) in the vinyl polymer (D) comprising the copolymer of the (meth) acrylic compound and the compound (a) is preferably 1 to 30% by mass. . If the proportion is less than 1% by mass or exceeds 30% by mass, the effect of adding the polymer of the above compound (j) becomes difficult to obtain.

The (co) polymerization of a polymerizable vinyl monomer or the copolymerization of the polymerizable biel monomer with the above compound (j) 'is usually carried out when (co) polymerizing a normal polymerizable pinyl monomer such as a (meth) acrylate compound. Any of known methods such as radical polymerization, anion polymerization, and cationic polymerization can be employed. In particular, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylparaeronitrile), 2,2'-azobis (2-Methyl-41-trimethoxysilylpentonitrile), 2,2'-azobis (2-methyl-1-methyldimethoxysilylpentonitrile), manufactured by Wako Pure Chemical Industries, Ltd., trade name: VA-0 4 6 B, VA-0 3 7, VA-06 1, VA-08 5, VA-08 6, VA-09 &, V-65, VAm-1 10 etc. The radical polymerization method is preferably carried out in the presence of a peroxide polymerization initiator such as benzoyl peroxide, t-alkyl peroxy ester, acetyl peroxide, or diisopropyl propyl carbonate. At this time, laurylmercaptan, amercaptopropyltrimethoxysilane, amercaptopropylmethyldimethoxysilane, thio J3-naphthol, thiophenol, n-butyl mercaptan, ethylthioglycolate, isoprene The polymerization can be carried out in the presence of a chain transfer agent such as pill-mercaptan, tert-butyl mercaptan, arthrimethoxysilylpropyl disulfide. The polymerization reaction is preferably carried out at a temperature of 20 to 200 ° C., particularly 50 to 90 ° C., for several hours to several tens of hours. Further, the polymerization can be carried out in the presence of a solvent such as xylene, toluene, acetone> methyl ethyl ketone, ethyl acetate or butyl acetate.

The (co) polymerization of the above (meth) acrylic compound or the copolymerization of the above (meth) acrylic compound with the above compound (j) is particularly performed in the above-mentioned curable resin. This is desirable because the effect of the present invention is further enhanced.

As the (meth) acrylic compound, the (meta) a of the 0 !, β-unsaturated calponyl compound (compound (f)) used in the production of the curable resin 1 is used. One or more of the chlorinated substances can be selected and used.

Further, the present invention is characterized by a curable resin composition comprising a Lewis acid and Z or a complex thereof in each of the curable resins, the composition 1 or the composition 2.

. Is a Louis scan acid, BF ₃ (boron _{trifluoride), F e C 1 3,} S n C 1 4, A Γ C 1 3, Z n C 1 2, C u C 1 2, Z n C 1 ₄ or the like can be mentioned, et al are. Examples of these complexes of Lewis acid include amine complexes, alcohol complexes, ether complexes and the like. The amine compound used in the amine complex includes ammonia, monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanol. Alcohol compounds used in alcohol complexes such as methanol, triethanolamine, etc. include primary alcohols such as methanol, ethanol, propanol and n-butanol, and isopropanol. Examples of the ether compound used in the ether complex include secondary alcohols such as toluene and 2-butanol, and dimethyl ether, getyl ether, di-n-butyl ether, and the like. Among the above-mentioned luciferic acids and complexes thereof, BF ₃ complexes are particularly preferred because they are easy to handle. Lewis acid and its complex are not limited to one kind, and two or more kinds can be used.

The Lewis acid and Z or a complex thereof are contained in an amount of 0.001 to 10 parts by mass per 100 parts by mass of the curable resin or the curable resin in the composition 1 or the composition 2. Preferably 0.1 to 5 parts by mass is blended.

Although the curable resin and the curable resin composition of the present invention can be produced as described above, the curable resin and the curable resin composition are preferably composed of an adhesive composition, particularly an adhesive, a sealant, An adhesive composition suitable for applications such as paints, casting materials, and coating materials.A curing catalyst, an epoxy resin, a ketimine compound, a tackifying resin, and silica fine powder that are usually or as needed blended. And at least one fine powder selected from organic polymer fine powders, an alkoxypolysiloxane, a filler, a plasticizer, various additives, a solvent, a dehydrating agent, a diluent, and the like. '

As the curing catalyst, an organic tin compound, a metal complex, a basic substance such as an amine compound, an organic phosphoric acid compound, water (moisture in the air), or the like can be used.

Specifically, examples of the organotin compounds include dibutyltin dilaurate, dioctyltin dimalate, dibutyltin phthalate, octylic acid primary salt, and dibutyltin. Examples include tin methoxide, dibutyltin diacetyl acetate, dibutyltin diversate, and reaction products of dibutyltin oxide and diethyl phthalate. Furthermore, Nitto Kasei Co., Ltd., which is a commercial product thereof, trade names: U-700, U-700 ES, U-303 and the like can be mentioned. Examples of the metal complex include titanate compounds such as tetrabutyl titanate, tetraisopropyl propyl titanate, and triethanolamine titanate; lead octylate, naphthenate; Metal carboxylate such as lead titanate, nickel naphthenate, cobalt naphthenate; aluminum acetyl acetonate complex, zonadium acetyl acetyl acetate Examples include metal acetyl acetonate complexes such as sodium complexes.

Examples of the basic substance include amino acids such as T-aminopropyl trimete xylan, aminoamine propyl triethoxysilane, and the like. Quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride; DABCO (Registered by Sankyo Air Products) (Trademark) series, DABCOBL series, 1,8- diazabicyclo [5.4.0] pendase 7 — straight chain containing multiple nitrogen atoms, such as diene Or cyclic tertiary amines and quaternary ammonium salts. In addition, ketimines, aldimines, oxazolidines and the like can also be used.

Examples of the organic phosphoric acid compound include monomethyl phosphoric acid, di-n-butyl phosphoric acid, triphenyl phosphate and the like.

The mixing ratio of the curable catalyst is preferably from 0.02 to 10 parts by mass per 100 parts by mass of the curable resin of the present invention.

As the organotin compound, in addition to the above compounds, poly (dialkyl stanoxane) dicarboxylate represented by the following general formula (6, 6) can also be used.

(66)

In the general formula (6 6), R ^{3 4} and R ^{3 5} is rather replaced young having 1 to 2 carbon is a non-substituted hydrocarbon group, s is indicates an integer of 0 or more, respectively, R ^{3 4} and R ^{3 5} may be Tsu different but the same.

R ^{3 4} and R ^3. It is in the rather substituted young 1 to 1 2 carbons which is table and unsubstituted hydrocarbon groups ^5, methylmercury, Echiru, propyl, i Seo propyl, heptyl , Isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethyl hexyl, decyl, rauryl, etc. Examples include a branched linear alkyl group, and a substituted or unsubstituted phenyl group. s may be an integer greater than or equal to 0, but is preferably an integer from 0 to 3. : R ^{3 4} and ^{3 5} may be different also the same.

Specific examples of the poly (dialkylstannoxane) dicarboxylate represented by the general formula (66) include 1,1,3,3—tetramethyl-1,3 — Bis (acetoxy) distanoxane, 1,1,3,3—tetramethyl—1,3—bis (petityloxy) distanoxane, 1,1, 3,3—Tetramethyl-1., 3—Bis (octanoyloxy) distanoxan, 1,1,3,3—Tetramethyl1 1,3— Bis (2-ethylhexanol): distanoxan, 1, 1, 3, 3 — tetramethyl 1,3 — bis (lau royoxy) Noxane, 1,1,3,3—tetrabutyl-1-1,3—bis (acetoxoxy) distanoxane, 1,1,3,3—tetrabutyl-1,3 - Screw ( (Tyroxy) distanoxane, 1,1,3,3—Tetrabutyl 1,3—Bis (octanoyloxy) distanoxan, 1,1,3,3 3 — tetrabutyl — 1, 3 — bis (2-ethylhexanoyloxy) distanoxane, 1,1,3, 3—Tetrabutyl-1-, 3—bis (lauroyoxy) distanoxane, 1,1,3,3—Tetraoctyl-1,3—pis Toxi) Distanoxane, 1,1,3,3—Tetraoctyl 1,3—Bis (petityloxy) distanoxan, 1,1,3,3— Tetraoctyl 1, 3 — bis (octanoyloxy) distanoxane, 1, 1, 3, 3 — tetraoctyl — 1, 3 — bis (2 to ethyl Kistanylox) Distanoxane, 1,1,3,3—Tetraoctyl-1,3—Bis (lauroyloxy) distanoxane, 1,1,3 , 3-tetralauryl 1, 3--bis (acetoxy) distanoxan, 1, 1, 1, 3, 3-tetralauryl 1, 3- Screws 1) Distanoxane, 1, 1, 3, 3-Tetrarauril 1, 3-Bis (octanoylox) Distanoxane, 1, 1,, 3,3—Tetralauril 1.1,3—Bis (2—ethylhexanoyloxy) distanoxane, 1,1,3,3—Tetralau Lithyl 1,3 — bis (lauroyloxy) dis, tetraalkyldistanoxane dicarboxylates such as oxoxane, 1,1,3,3,5,5 — Hexamethyl-1,5 — bis (acetoxy) tristannoxan, 1,1,3,3,3,5,5 —hexamethyl-1,5 —bis Di) Tristanoxane, 1,1,3,3,5,5—hexamethyl-11,5—bis (octanoyloxy) trisoxanoxane, 1, 1,3,3, 5,5—Hexamethyl-1,5-bis (2-ethylhexanoyloxy) tristannoxane, 1,1,3,3,5,5—hexamethyl —1 , 5 — bis (lauroy) tristannoxan, 1, 1, 3, 3, 3, 5, 5 — hex subtilis — 1, 5 — bis (acetoxy) tris Tanoxane, 1, 1, 3,3,5,5—Hexabutyl-1,5—bis (butyloxy) tristannoxane, 1,1,3,3,3,5,5—Hexabutyl-1,5 — Bis (octanoyloxy) tristanoxan, 1, 1, 3, 3, 5, 5 — hexabutyl; , 5 — bis (2-ethylhexanoyloxy) tristannoxane, 1, 1, 3, 3, 3, 5, 5 — hexabutyl-1,5 — bis (low-mouthed silica) ) Tristanoxane, 1,1,3,3,5,5 — Hexaaryl 1, 5 — Bis (Acetoxy) Tristanoxan, 1, 1, 3, 3, 5, 5 — Hexapoly Rel 1., 5 -bis (petityloxy) tris 1, 2, 1, 1, 3, 3, 5, 5 Peryl 1, 5 — bis (octanoyloxy) tristannoxane, 1, 1, 3, 3, 3, 5, 5 — hexaryl 1, 5 — bis (2—Ethylhexanoyloxy) Tristannoxan, 1,1,3, '3,5,5—Hexaaryl —1,5—Bis (Lauroyloxy) C) Hexane such as tristanoxane Examples include saalkyl tristanoxane dicarboxylates.

Furthermore, the poly (dialkyl stanoxane) dicarboxylate represented by the general formula (66) is formed by the reaction with a silicate compound represented by the following general formula (67). Things can also be used.

^{_{.. 3 6 t S i (}} OR 3 7) t (6 7) ' and have you in the general formula ⁽⁶ 7), R. ³ 6 and R ^{3 7} is the number of carbon atoms:! To 4 alkyl, a group, t represents 0-3 integer, respectively, R ^{3 6} and R ^{3 7} is rather good even Tsu different also the same, R ^{3 6} and R ^{3 7} is double In the case of numbers, they may be the same or different. And have you the formula, an alkyl group having 1 to 4 carbon atoms represented by R ^{3 6} and R ^{3 7} is methylation, Echiru, propyl, i Seo propyl, butyl, I Sobutyl, s-butyl, 1; monobutyl.

Specific examples of the silicate compound represented by the above general formula (67.) include tetramethyxilan, tetraethyxiran, tetraethyl Tetraalkoxysilan, Trietoxicilir, etc. such as Laproboxysilan, Tetraisoproboxylan, Tetrabutoxylan, etc. Trial alcohols such as Lan, Trietixi Sheil Silane, Trieti Xi Provir Silane, Trieti Toxi Soprovirilane, Trieti Xipirsilan etc. KISHIMANO ALKIL SILAN, JET KISIJIMETIL SILAN, JET KISIJETIL SILAN, JET KIJOSHI PROVIL SYLAN, JET KITO SIJI PROPILSILAN, JET KISIJI Dialkoxy dialkyl silane such as butyl silane Ethoxytrimethylsilylane, ethoxytrisil.Ethylsilan, ethoxytripropylsilan, ethoxytriisopropyl mouth bilsilan And monoalkoxy trialkyl silane such as ethoxy tributyl silane. The hydrolyzate of these alkoxysilanes can be used in the same manner as these 0 alkoxysilanes.

Poly (dialkylstannoxane) dicarboxylate represented by the general formula (66) and a silicate compound represented by the general formula (67) and Z or a hydrolyzate thereof The poly (dialkylstannoxane) disiligate compound, which is a reaction product with, is formed by reacting the two with each other at 100 to 130 for about 1 to 3 hours, and producing carbon. It is obtained by removing the acid ester under reduced pressure. The reaction ratio of the two is preferably such that one equivalent of the alkoxy group is reacted with at least one equivalent of the alkoxy group to completely eliminate the epoxy group. If the carboxyl group remains, the catalytic activity decreases. This reaction can be performed in the presence or absence of a solvent. However, it is usually preferred to work in the absence of solvent. The poly (dialkylstannoxane) dicarboxylate represented by the general formula (66) is a silicate compound represented by the general formula (67) and / or its hydrolysis. As a specific example of a poly (dialkylstannoxane) disilicate compound which is a reaction product with a compound, a compound represented by the following general formula (68) can be given.

_{(R ^ o) 3 - Si-} O -Sn- o † -Sn one 0 ~) ~ S DOO (OR ³⁷⁾ ₃ (68) In formula ^{(6 8), R 3 5} , R 3 7 and s I agree with the above.

As epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, nopolox type epoxy resin, and amine Epoxy resin with silylation, epoxy resin with heterocycle, alicyclic epoxy resin, bisphenol hydride A-type epoxy resin, urethane-modified epoxy resin, An epoxy resin, etc., which can be used alone or in combination of two or more. · When an epoxy resin is blended, it is preferable to use a curing agent for the epoxy resin in combination. Examples of the curing agent for the epoxy resin include ethylenediamine, 1,3-propanediamine, hexamethylenediamine, diethylenetriamine, and triethylenetriamine. Ethylenetetramine, 2,2,4-trimethyl-1,6-hexanediamine, p-xylylenediamine, bis (4-aminocyclohexyl) propane, isophoronediamine, tetraethylenepentamine, dipropylene Triamine, bishexamethylenetriamine, 1,3,6-trisaminomethylhexane, trimethylhexamethylenediamine, polyetherdiamine, getylaminopropylamine, mensendia Min, bis (4-amino-3-ethylcyclohexyl) methane, N-aminoethyl biperazine, m-phenylenediamine, diaminodiphenyl sulfone, diaminodiphenylmethane, etc. is there. Examples of the modification method include addition of an epoxy compound, addition of ethylene oxide, addition of propylene oxide, addition of acrylonitrile, addition of Mannich with phenol and its derivatives and formalin, addition of thiourea, and ketone blockade.

In addition, phenol nopolak, polymer butane compounds, polysulfides, ketimines, tertiary amines, organic acid hydrazides, dicyan diamides and derivatives thereof, amide imides, carboxylic esters, boron trifluoride-amine complexes , Imidazoles, acid anhydrides, halogenated acid anhydrides, aromatic diazonium salts, diaryldonium salts, triarylsulfonium salts, triarylselenium salts, polyamidoamines, polyphenols, alcohols , Acetyl acetonato metal salts, phosphines and the like, and one or more of these can be selected and used. '

Ketimine compounds (hereinafter referred to as compound (k)) are compounds having a group represented by the general formula: N-C (X) (Y) (where X is a hydrogen atom or an organic group, and Y is an organic group). In the present invention, for example, the following compounds (1) and (2) are effectively used.

(1) A compound represented by the following general formula (69) and a derivative of the compound, for example, obtained by reacting a compound having an epoxy group with an imino group of the compound. Compounds.

Provided that R ³⁸ , R ³⁹ , R ⁴⁰ and R ⁴¹ are each selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, a phenyl group and a phenyl group having an alkyl group having 1 to 6 carbon atoms. D ¹ , D and ^Du are the same or different alkylene groups each having 2 to 6 carbon atoms, and X is 0 or 1.

Examples of the compound represented by the above general formula (69) include 2,5,8—triaza-11,8—nonagene and 2,10—dimethyl-1,3,6,9 — Trizars 2, 9 — Dendecadiene, 2,10-Diphenyl 1, 3, 5, 9 — Triazas 1, 2, 9 — Tridecane, 3, 1 1 — Dime Chill 4, 7, 10-Triaza 3, 1.0-Tride Cadien, 3, 1 1 Jethyl 4, 7, 10-Triaza 1, 3 10- Tridecadiene, 2,4,12,14—Tetramethylol 5,8,11 1 Triaza4,11 1 Bentadecadiene, 2,4,20 , 2 2 — Tetramethylo 5, 1 2, 1 9 — Triaza 1, 4, 19 Triaicogen, 2, 4, 15, 17 — Tetramethyl 1 5 , 8, 11, 14-14-year-old 14-, 14-year-old, etc. It is.

Examples of the compound having an epoxy group that reacts with the imiso group of the compound represented by the general formula (69) include styrene oxide, butylglycidyl ether, and arylglycidyl. P-ter — butyl phenylidinyl ether, p — sec — butyl phenylidyl ether, m, p — cresylglycidylether, p — cresylglycidyl ether Sidyl ether, vinylcyclohexane dioxide, glycidyl ester of persuccinic acid, modified glycidyl ether of carboxylic acid, glycidyl ester of dimer acid, 1, 6 — Hexane diol diglycidyl ether, resorcinoglycidyl ether, propylene Glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and the like. In particular, derivatives using styrene oxide are preferred. The ketimine derivative may be one in which only one of the two imino groups of the compound represented by the above structural formula has reacted with a compound having an epoxy group.

As the compound of the above (1), compounds represented by the following general formulas (70) and (71) can also be used. In the general formula (70), n represents a number from 1 to 6. In the general formula (71), X, y, and z may be the same or different.

+ + 2 is about 5.3.

(2) A compound obtained by reacting an amine compound having at least one primary amino group in the molecule with a carbonyl compound and a primary amino group in the molecule. It is advantageous for the amine compound having at least one to have a primary amino group equivalent generally in the range of about 2,000 or less, preferably about 30 to 1; It generally has a number average molecular weight of about 5,000 or less, preferably in the range of about 60 to 3,000. It is preferred to do so.

Specific examples of the amine compounds include ethylenediamine, propylenediamine, petylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, penethyleneethylenehexamine, hexamylenediamine, trimethylhexamylenediamine, and N-aminoethylpiamine. Perazine, 1,2-diaminopropane, iminobispropylamine, methyliminobispropylamine, polyamine having a polyoxylen skeleton such as poly (oxypropylene) diamine, etc., a trade name of Santechno Chemical Co., Ltd .: diefamine EDR 1 4 Diamines with polyether skeleton represented by 8, iso-holondiamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexylxylamino 3-aminopropane, 3-aminomethyl-3,3,5- Limethyl-cyclohexylamine, a trade name of Mitsui Chemicals, Inc .: a diamine of a norbornane skeleton represented by NBDA, and a xylylene skeleton represented by meta-xylylenediamine. Trade name of Takahashi Gas Chemical Co., Ltd .: Examples thereof include aliphatic polyamines such as MXDA, diaminodiphenylmethane, phenylenediamine, and polyamides having a primary amino group at the molecular terminal of the polyamide, aromatic polyamines, and alicyclic polyamines.

In addition to these, N-β (aminoethyl) -17-aminopropyl trimethoxysilane, Ν / 3 (aminoethyl) -1-aminopropylmethyl dimethoxysilane, r-aminopropyl trimethoxysilane Examples of the amine compound include a silicon atom-containing amine compound such as r-aminopropyltriethoxysilane. Among the above-mentioned amine compounds, a polyamine compound having two or more primary amino groups in the molecule is particularly preferable.

Examples of the carbonyl compound include acetone, methyldiethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl t-butyl ketone, getyl ketone, dipropyl ketone, and diisobutyl ketone. Examples thereof include ketones such as ethyl propyl ketone, ethyl butyl ketone, cyclohexanone, propiophenone, and benzophenone, and aldehydes such as acetoaldehyde and benzaldehyde.

Ketimines can be formed by blocking the amine compound with the ketones, and aldimines can be formed by blocking with the aldehydes. The compound (k) of the above (2) includes both ketiminized and aldiminated compounds. The reaction between the amine compound and the carbonyl compound can be carried out by a method known per se, wherein substantially all of the primary amino groups present in the amine compound react with the carbonyl compound. The reaction is performed under such quantitative ratios and conditions. The reaction between the two is achieved by heating under reflux in the absence of a solvent, or in the presence of a non-polar solvent such as hexane, cyclohexane, toluene, and benzene, and removing water produced by azeotropic distillation. . In order to facilitate the reaction (dehydration reaction), ketones which are poorly water-soluble and have little steric hindrance such as methylisobutylketone and methylethylketone can be used as the carbonyl compound.

The tackifier resin is not particularly limited, and any resin which is usually used at room temperature, whether solid or liquid, can be used. Specific examples include phenolic resins, modified phenolic resins (for example, cash-oil-modified phenolic resins, tol oil-modified phenolic resins, etc.). ), Terpene phenolic resin, xylene phenolic resin, cyclopentene phenolic resin, coumarone-indene resin, rosin-based resin, b di N'esu ether resin, Mizu添Ro di emissions ester resin, key sheet Ren resins, low molecular weight Po Li styrene les down resin, scan Chi Le emissions copolymer resins, petroleum resins (e.g., C ₅ hydrocarbon resins, C ₉ hydrocarbon resins, C ₅ · C _g hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, terpene emissions resins, DCPD resins and the like et be. These may be used alone or in combination of two or more. Above all of the tackifying resin, terpene down off error Roh Lumpur resin, ii di N'esu ether resin, hydrogenated ii di N'esu ether resin, key sheet Le emissions resins, styrene-les emission copolymer resins, C ₉ hydrocarbon Hydrogen resins, hydrogenated petroleum resins, and terpene resins are preferred because of their particularly good compatibility and good adhesive properties. The tackifying resin is preferably blended in an amount of 5 to 70 parts by mass per 100 parts by mass of the curable resin.

As the one or more fine powders selected from silica fine powders and organic polymer fine powders, those having a particle size of 10 nm to 300 m are suitable, but it is preferable. l OO nml OO ^ m, particularly preferably 1 to 30 fi m.

As the fine silica powder, those having the above-mentioned particle diameters can be used, but hydrophobic fine silica powder is particularly preferable. As hydrophobic silica fine powder, for example, fumed silica (aerosol) is widely used as a thixotropic agent in adhesives and others. Fine silica powder such as gel or silica air gel is used to prepare organosilicon compounds, for example, dimethyldichlorosilan, hexamethyldisilazane, dimethylsiloxane, or trimethoxysiloxane. Hydrophobic materials treated with tilsilane or the like can be used.In particular, smoke-poor silica treated with hexame tildisilazane and silica air mouth gel can be used. Those treated with methylsiloxane and / or hexamethyldisilazane are preferred.

The hydrophobization treatment is performed by stirring the silica fine powder and the organic silicon compound at a high speed of about 100 to 400 ° C. It is desirable to carry out the contact in a medium such as an organic solvent in order to achieve uniform contact between the two. The mixing ratio of the silica fine powder and the organic silicon compound is usually 100 parts by mass of the silica fine powder, The silicon compound is 3 to 40 parts by mass.

Examples of the organic polymer fine powder include urethane resin fine powder, polyster fine powder, polycarbonate fine powder, polymethylsilsesquioxane fine powder, and Fine powders of lithium resin, fine powder of styrene resin, fine powders of vinyl resin such as polyvinyl chloride, and polyolefins such as polyethylene-polypropylene Fine powder Silicone-based fine powder and the like can be mentioned. These organic polymer fine powders may be used alone or in combination of two or more.

In addition, amorphous high-purity fused quartz glass fine powder can be used in the same manner. Is a high purity fused silica glass la scan fine powder, with S 1 〇 ₉ content 9 9.8 mass% or more, even the rather to prefer very little alkali metal other non neat particle size However, those having a diameter of 1 to 100 m, particularly 2 to 50 m, are preferred.

Amorphous high-purity fused quartz glass fine powder may be used as it is or may be surface-treated with a coupling agent. Examples of the capping agent include an organic titanium compound, an organic aluminum compound, an organic zirconium compound, and an alkoxysilane. Examples of organic titanate compounds include tetrapropoxy titan, tetraptoxy titan, tetrax (2-ethylhexyloxy) titan, and tetrastear. Riloxycitane, diproboxy, bis (acetyl acetatenat) titan, titanium proboxyl chitin glycolate, titanate stearate, a Sopropyl trisoyl titanium titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl nitrate (dioctyl pyrophosphate) Titanate, Tetraisopropyl bis (dioctyl phosphite) Titanate, Tetraoctyl bis (ditrido) Decyl phosphite) titanate, tetra (2,2-diaryloxymethyl-1 monobutyl) bis (ditridodecyl) phosphite titanate, bis (Dioctyl pyrophosphate) sodium acetate, tris (dioctyl pyrophosphate) ethylen titanate, and the like. As the organic aluminum compound, acetate alcohol diisopropylate or the like is used, and as the organic zirconium compound, zirconium aluminum oxide is used. , Zirconium acetyl acetate, acetyl aceton zirconium butyrate, zirconium lactic acid, zirconium stearate butyrate, and the like. It is. In addition, examples of the alkoxysilane include vinyl trimethoxysilane, vinyl triethoxysilane, and pistoris (β-methoxysilane). C) Silane, Ν — (/ 3 — Aminoethyl) — — Aminopropyl dimethyl dimethyl シシ, Ν — (β-Aminoethyl) monoaminopropyl Trimethoxysilane, r-Amino-Pro Build Trimetoxiran, a-minino-propyl Triethoxylate, A-Glycid Xiprovir Trimethyloxysilane, α-Glycidoxypropylmethyldichloromethane, β- (γ., Δ-epoxycyclohexyl) ethyl TRIMETRIC SILICON, ARKROPRO PRO Dimethyldimethoxysilane, α-methacryloxypro-build trimethoxysilane, α-methylcaptopropyl trimethoxysilane, hexamethyldisiloxane Razan and the like. Alkoxypolysiloxanes are commercially available, and commercially available products can be used. Specific examples are Shin-Etsu Chemical Co., Ltd., product name: KC-89S, KR-500, X-400-9222,

X — 4 0 — 9 2 4 6, X — 4 0 — 9 2 5 0, R-2 1 7, R-5 1 0, X — 4 0-9 2 2 7, X — 4 1-1 0 5 3, X — 4 1-1 0 5 6, X — 4 1 — 1 8 0 5, X-4 1 — 1 8 1 0, X — 4 1-2 6 5 1, X — 4 0-2 3 0 8, X — 4 0 — 9 2 3 8, etc. Alkoxypolysiloxane having an alkoxy group disclosed in JP-A No. 14-No. 14 and the like can be mentioned. Fillers include fumed silica, calcium carbonate, magnesium carbonate, clay, talc, silica, various balloons, and aluminum hydroxide. Examples include metal hydroxides such as nickel and magnesium hydroxide, and fibrillated fibers.

Examples of the fibrillated fiber include a fibrillated aromatic polyamid fiber, a polyester fiber, a polyolefin fiber, and a polyacrylo fiber. Examples thereof include nitrile fibers, and those having an average fiber length of about 0.1 to 5 mm are preferred. Also, a low-fibrillated fiber having a lower fibrillation than the above-mentioned fibrillated fiber can be used in combination with the above-mentioned fibrillated fiber. . Low fibrillation means that there are few whisker-like branches per unit length of the trunk fiber. Examples of the low-fibrillated fiber include a fiberized or non-fibrillated polyester fiber, a polyolefin fiber, and a polyacrylonitrile. In addition to toll fiber, sepiolite, glass fiber, carbon fiber and the like can be mentioned.

Examples of the plasticizer include esters of phthalic acid such as dioctyl phthalate and diptyl phthalate; fatty acid carboxylates such as dioctyl adipate and dibutyl sepate; Acid ester etc. can be used.

Antioxidants, thixotropic agents, ultraviolet absorbers, pigments, silane coupling agents, titanate cups, etc. Rings, thixotropic agents, oligomers, process oils and the like can be mentioned.

As the antioxidant, a secondary amino group, a tertiary amino group, a hydroxyl group, a carboxyl group, a mercapto group, a Z or a It is a compound having a primary amino group, and is widely used as an anti-degradation agent for various resins.

Specific examples of anti-aging agents include triaceton'diamine, poly [(6-morpholino s-triazine-1,2,4-diyl) {2,2 , 6, 6 — Chitramethyl-4-piperidyl} imino} Hexamethylene {2, 2, 6, 6 — Tetramethyl-1-4-Beverage} i Mino}], bis (2,2,6,6—tetramethylyl 4—piperidyl) sepagates, bis (1,2,2,6,6—pentamethyl 4—piperri Jill) Sebasket, 4—Benzo Roxy—2, 2, 6, 6—Tetramethyl Pyridine, Poli (2, 2, 4—Domestic 1, 2 — dihide mouth quinoline), 6 — ethoxylate 2, 2, 4-1-1, 2, — dihide mouth quinoline, Ν, Ν '— diphenyl ! ) 1-phenylenediamine, Νisopropyl-1N '— phenyl-ρ — phenylenediamine 1, .3 — dimethylbutylamine — Phenyl ρ — Phenylamine, mixed Ν, Ν '— phenyl- ρ .— Phenylamine, alkylated diphenylamine , 8-acetyl-3-dodecyl 7, 7, 9, 9-tetramethyl-1, 3, 8-triaza pillow [4.5] decan 1, 2, 4 — Zion, poly [{6-(1, 1, 3, 3 — tetramethylbutyl) amino 1, 3,

5 — Triazine 1, 2, 4 — Jill} {2,2,6,6 — Tetramethyl 4-Piperidyl} Imino} Hexamethylen {2,2,

6, 6 — tetramethyl 4 — piperidyl imino}], Ν, Ν ' — Bis (3-aminopropyl) ethylenediamine 1,2,4—Bis [N-butyl-N— (1,2,2,6,6—Pentamethyl-1-4— Piperidyl) amino] — 6 — 1,3-, 5-triazine condensate, diphenyldanidinine, di-o—trilugazine, N— Cyclohexyl benzoyl zothiazyl sulfenamide, 2, 2'-dihydroxy 4 meth oxy benzophenone, 2-hydroxyー 4 1 n-Octchi J-leoxy benzophenone, 2 — hydroxy 1 4 — methoxy benzophenone, 2 — hydroxy 1 4-met Xybenzofenone trihydrate, 2,4 "Dihydroxybenzofenone, 2—hydroxy-14—Metoxibenzofenone—5—Sulfuric acid three Japanese, 41 Dodecyloxy — 2 — Hydroxybenzofenon, 4 — Benziloxine 1 2 — Hydroxybenzofenon, 2, 2 ', 4 , 4'-Tetrahedral □ Kishibenzofenon, 2, 2'-Dihydroxy 4,4'-Dimetoxybenzofenon, 2—Hydro Xy 4 — octave benzophenone, 2 — hydro xy 4 — octave benzozonone, 2 — (2'-hydroxy 5 '— t — octylphenyl) benzotriazo, 1-, 2 — (2' — head-opening 1-5'-methylphenyl) benzotriazole , 2 — (2 ′ — Hydroxy 1 3 ′, 5 ′ -di-t-butylphenyl) 1 5 — □ D-Mouth benzotriazole, 2 — (2 ′ — Droxie — 3 — t Methyl phenyl) ― 5 ― black benzotriazole, 2 ― (2'-hydroxy 3 ', 5'-age ― t-mil phenyl) ― 5-Black benzotriazole, 2-(2 '-Hydroxy 1 3', 5 '-t-Butylphenyl) benzotriazole, 2-( 2 — Hydroxy 14-octyl phenyl) 1 2 H-Venzotriazole, 2 — (2—Hydroxy 5—Methyl phenyl) 1 2H—Venzotriazole, 5—Cro mouth 1 2— (3,5—Di-t7

2—Hydroxyphenyl) 1 2 H—Benzotriazole, 21 (3—t-butyl-2) Hydroxy 5—Methylphenyl) 1—5—Cro Mouth 1H—Venzotriazole, 2— (3,5-ge.t—Pentyl-2—Hydroxyphenyl) 1-2H—Venzotriazole , 2 — (3, 5 — di-tert-butyl-2-hydroxyphenyl) 1 2 H — benzotriazole, 2 — (2-hydroxy 1 5 — t-octylphenyl) 1 2H—benzotriazole, 2— [2'-hydroxy-3 '— (3 ", 4",

5 ", 6 テテヒロメ-5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 1-3 ', 5' — Ge-t-amylphenyl) benzotriazole, 2— (2—hydroxy 3—dodecyl 1—methyl Enyl) benzotriazole, 2 — [2 — hydroxy_ 3, 5 — bis (, α — dimethylpentyl) phenyl] — 2Η ^ benzotriazole Riazol, η-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, n-hexadecyl-

3, 5 — Ge-t-butyl 4- 4-hydroxybenzene zone, 2 '

4'-di-t-butylphenyl-1,3,5-di-t-butyl-4-hydroxylbenzoate, 1,3,5—tris (4-t-butyl-1 3 — Hydroxy-1,2,6—Dimethylbenzyl) isocyanuric acid, tris (3,5—Di-t-butyl-14) —Hydroxybenzil isocyan Nurate, 1, 3, 5 — Tris (3,

5 — G — t — butyl 4-hydroxybenzyl) isocyanuric acid, ethyl glycol bis [3 — (3 — t — butyl 1 4 — hydroxy — 5 — Methyl phenyl) propionate], LAKIS [Methylene-3 (3 ', 5'-1 t-butyl-4 '-hydroxyphenyl) propionate] methane, n-Octadecyl 3 (3 ', 5'-di-t-butyl 4 '-hydroxyphenyl) propionate, triethylene glycol bis [3-(3-t-butyl -4-Hydroxy 1-5 — methyl phenyl) propionate], isooctyl 3-(3, 5-di-t-butyl 4-hydroxy phenyl) pro Pionate, 1,6—Hexanediol'bis [3— (3,5—Di-t-butyl-1-4-hydroxyphenyl) propionate], 2,2,1 Diethylenebis [3— (3,5—Jt—Ptyl-4—Hydroxyphenyl) propionate], 4,4'-butyl Bis (3-methyl-6-t-butylphenol), 2,2'-butylidenebis (4-methyl-6-t-butylphenol), 2,, 2'-butylidene-bis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-butylphenol), 2, 2'-Methylene-bis [4-methyl-6-t-butylphenol], 2, '2'-Methylene-bis (4-methyl-t-butylphenol) ), 2, 2 '— Methylene bis (4-ethylen-t-butylenol), 6 — (2 benzotriazole)-4-t -6 '-t-Butyl-4'-1-methyl-2, 2 '-Methylene bisphenol, Styrene diphenol, 2,. 6-Di-t-butyl One 4-methyl phenol, 2,4—dimethyl-6- (1—methyl cyclohexyl) phenol, 2— [4,6—bis (2 , 4 — dimethyl phenyl) 1, 1, 3, 5 — triazine 1 2 — yl] 1 5 — (octylokoxy) phenol, 2, 6 — ge t — Butyl — 4 — ethylenol, 2 — (2H — benzotriazole — 2 — yl) 1 4 — menthol 6 — (3, 4, 5, 6 — tetrahydrofutirimi jirumechiru) phenol, 2 — (4, 6 — di Phenol 1,3,5 — Triazine 12-yl) — 5 — [(Hexyl) oxy] phenol, 2,5-di-tert-butyl hydro Quinone, poly (2,2,4—trimethyl-1,2, -dihydroquinone), 6—ethoxy-1,2,2,4-trimethyl—1,2 — Dihydroquinone, 2, 5 — Di-t — Amyl hydroquinone, 4, 4, 1′-Pteridene-bis (6 — t — Butyl-m-creso) ), 2, 2 '— Methylene bis [6- (1-methylcyclohexyl)-p-cresol], 1-[2-{3-(3, 5-di) 1 t — butyl 1-hydroxy phenol 1-, 2-, 3-, 3-(3-, 3-di-tert-butyl- 4 -hydroxyphenyl) propionyloxy} 1, 2,2,6,6—tetramethyl Chill piperidin, S- (3,5—Jt—Ptyl-4 ^ Hydroxybenzil) 1-2—Ethyl—n—Hexyl-thioglycolate, 4,4′—Chobis (61 t-butyl 1 m-cresol), p-benzoquinone, 1, 6-bis (4-benzene 3-hydroxyl) ) — Hexane, 1, 4 — Bis (4-benzoyl 3 — Hydroxy phenoxy) — Butane, phenyl salicylate, 4 — t 1-butylphenyl salicylate, 1,1,3—tris (2—methyl-t—butyl-14-hydroxy-5-t-butylphenyl) 1) Butane, 1, 11 bis (4-hydroxyphenyl) cyclohexane, 3, 9 — bis [2 — {3-(3 — t — butyral) 14-hydroxy-5-methylphenyl) propionyloxy} 11,1—dimethylethyl] 12,4,8,10-tetraxylazole [5, 5] Indecane, 2-t-butyl— 6 — (3 ′ — t — butyl-5 ′ — methyl 1 2 ′ — hydroxybenzyl) 1 4 — methyl acrylate, dimethyl succinate 1 — (2 — Hydroxyshetyl) 1-4 Hydroxy 2, 2, 6, 6 — tetramethyl piperidine polycondensate, methyl 1 3 — [3 — t — Butyl-5 — (2 H-benzotriazole-1-2-yl) 1-4-hydroxyphenyl] Condensate of propionate with polyethylene glycol, 3, 4 — Dihydro 2, 5, 7, 8 — Tetramethyl 2 — (4, 8, 12 — Trimethyltridecyl) — 2 H — Benzopyran 6 — All (irganox E20), mixture of ilganox E201, glycerin and low-density polyethylene, irganox E2 0 1 Mixture with stearic acid, bis (3,5-di-t-butyl) -4-hydroxyethylsilyl sulfonate Calcium and polyethylene wak 2,4-Bis [(octylthio) methyl] -o-cresole, N, N'-Hexamethylenebis (3,5-di-t.-butyl) 1-4—Hydroxyhydrocinnamide), 3, 5—Di-tert-butyl-14-hydroxybenzyl benzylphosphonate—Jetyl ester, 1,3,5—Tri Chill-1,4,6—tris (3,5—di-tert-butyl-14-hydroxybenzyl) benzene, 2— (3,5—di-butynole 4ー Hydroxybenzil) 1 2 — n — Bis (1,2,2,6,6) pentylmalonate —Pentamethyl-1-4 —Piperidyl , 2, 3-bis [{3-(3, 5-di-t-butyl-14-hydroxyphenyl) propionyl}] propionohydrazide, 2,4-bis ( n — octylthio) 1 6 — (4 — hydroxy 3, 5 — di 1 t — butylanilino) 1, 1, 3, 5 — triazine, 2 — hydroxy 1 4 — METOKISHI 2 '— Karboki Sivenzov Enon, Mercapto Benzothiazol, 2 — Mercapto Benzimidazol, manufactured by Lifetech, Inc., Trade name: Sanol LS — 765, Sanor LS — 292, Sanor LS — 944, Sanor LS — 44 0, Sanor LS — 770, Sanor LS — 744, manufactured by Ciba Specialty Chemicals Inc., trade names: Tinuvin 123, Tinuvin 292, Tinuvin 144, etc.

The antioxidant is obtained by adding the above antioxidant to an aqueous solution selected from an alkoxy group and an acetate group having an organic group (I) having an isocyanate group in the group. Those obtained by reacting with a silicon compound (compound (1)) having a decomposable group directly bonded to a silicon atom can also be used. The use of such a material can improve the effect of preventing aging.

The compound (1) has an organic group (II) having at least one group selected from a primary amino group, a secondary amino group and a (meth) acryloyl group in the group. One or more compounds in which a hydrolyzable group selected from an alkoxy group and an acetate group is directly bonded to 1 to 10 silicon atoms. A compound obtained by reacting a compound with an organic compound capable of reacting with an organic group (II) to form a compound having a secondary amino group, and belonging to a secondary amino group in one molecule obtained by reacting the compound A compound having less than two active hydrogens, and wherein the hydrolyzable group is directly bonded to 1 to 10 silicon atoms, or one mecapcap group or two It has an organic group (III) having a quaternary amino group, and a hydrolyzable group selected from the group consisting of an alkoxy group and an acetyl group is directly present. The compound is preferably a compound obtained by reacting a silicon compound bonded to up to three silicon atoms with a compound having two or more izocyanate groups in the molecule. Examples of the thixotropic agent include anhydrous silica, fatty acid bisamide, hydrogenated castor oil and the like.

Oligomers include polyethylene oligomers, liquid polypropylene, oligostyrene, liquid polychlorinated planes, liquid polyisoprene, Liquid SBR, liquid NBR, liquid butyl rubber, liquid polyisobutylene, liquid polybutadiene, polyhydroxypolyolefin-based oligomers, methyl styrene Ligomer, styrene containing lin-α-α-methyl styrene oligomer, and oligoester acrylate. In addition, process oils such as naphthene, aromatics, and paraffin can be added for the purpose of adjusting viscosity and reducing tack. it can.

As a silane coupling agent, amino silane is particularly preferred. Toxican, aprominopropritrie Torixiran, afaminopropile Tile dimethylprotocyanane, afaminoproprime Chino-rejected xylan, aminophenyl remethod xylan, Ν—) 3 (aminoethyl) -aminopropyl triethoxysilane , N — / 3 (Aminoethyl) monoamine propyl triethoxysilane, N — / 3 (Aminoethyl) mono τ-aminopropyl dimethyl Kissilan, N — 3 (Aminoethyl) (Dipropylenoxy)] amino-produced trim xylan, (aminoethylaminoaminomethyl) phenethyl trimethyl xylan, N — ( 6 — aminohexyl) aminopropyl trimethylsilane, N — (2 — aminoethyl) 1 11-amino undecyl trimethyl Sicilan, N — phenyl-r — a S Noprovir Trimethyloxysilane, N — N-phenylamine Pyrme tildimethoxysilane, N — (n-butyl) r ramino Built-in trimethyl silane, N— (n-butyl) -amino propyl dimethyl dimethoxy silane, N-ethyl amino butyl dimethyl silane , N-methylaminopropyl mouth, pilmetildimethoxysilane, N-methylaminopropyl Umethoxirane, bis (trimethoxysilane) Pill) and the like. Other than these, a special amino silane compound manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM6603, X —

1 2-8 9 6, KBM 5 7 3, X — 1 2 — 5 6 5, X-1 2-5 8 0, X — 1 2 — 8 0 6, X — 1 2 — 6 6 6, X — 1 2 1 5 2 6 3, KBM 6 1 2 3, X — 1 2 — 5 7 7, X-1 2 1 5 7 5, X-1 2-5 6 3 B, X — 1 2 — 5 6 2 And the like.

Any agent may be used as long as it is compatible with the above-mentioned curable resin and has a water content of 500 ppm or less.

Examples of dehydrating agents include quicklime, magnesium oxide, orthosilicate ester, anhydrous sodium sulfate, zeolite, methylsilicylate, and ethyl silicide. , Vinyl alkoxysilane, various alkyl alkoxysilanes, silane coupling agents, etc.

As diluents, manufactured by Toa Gosei Co., Ltd., trade name: XPR — 15, 22, 39, 40, UP 100, 100, 110, 110, 0, 210, 1 0 6 1, 1 0 7 0, 1 0 8 0, 1 1 1 0, UG — 410 0, manufactured by Soken Chemical Co., Ltd., Product name: UMB — 1 0 0 1, 2 0 0 5, 2 0 0 5 B, 2 0 0 5 P, UME-1 0 0 1, UMM 0 1 .4 0 0 5, UT — 1 0 0 1, 2 0 0 1, 2 0 0 1P, 3001, AS—300, 310, ASM—401, CB—360, BGV—11, 12 and the like.

Further, the curable resin composition of the present invention can be obtained by using a silane described in Patent Nos. 3,030,020 and 3,317,353. A urethane-based resin may be blended if necessary.

(Example)

Hereinafter, the present invention will be described in detail based on examples.

(Example 1)

Under a nitrogen atmosphere, isophorone diisocyanate (IPDI) (222 g) was charged into the reaction vessel, and while stirring, A—] inkl 5 (trade name, manufactured by Nihon Nikka Co., N-ethylamino) After the dropping was completed, the mixture was reacted at 80 ° C. for 2 hours to obtain a synthesized product A. Separately, DMDS (trade name, manufactured by Maruzen Chemical Co., Ltd.) was placed in a reaction vessel. , 1,5-dimercap, toe 3-thiapentane) were added thereto, and while stirring, 222 g of Compound 11A was added dropwise to obtain Compound 1-B.

In a reaction vessel, 200 g of SDX-1690 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd., polyallyl ether having an aryl group at both ends, number average molecular weight 3,000) and compound 1 68 g of I-B was added, and the temperature was raised to 90 ° C under a nitrogen atmosphere. Then, a mixed solution of 2 g of 2,2′-azobisisobutyronitrile (AIBN) and 10 g of toluene was added dropwise over 3 hours. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin.

(Example 2)

Under a nitrogen atmosphere, 98.0 g of ethyl acrylate and 162.0 g of KBM 902 (trade name, Shin-Etsu Chemical Co., Ltd., araminopropylmethyldimethylmethoxysilane) were placed in a reaction vessel. The mixture was reacted at 23 ° C for 7 days with mixing to synthesize compound 2-A.

In a reaction vessel under a nitrogen atmosphere, 2,4-tolylene diisocyanate (TD 80 g of I) was added thereto, and while stirring, 138 g of Compound 2A was added dropwise. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 2 hours to obtain a synthesized product 2—: B. Separately, 77 g of DMDS was charged into a reaction vessel, and 110 g of Compound B was added dropwise while stirring to obtain Compounds 2 to C.

200 g of SDX-169 and 55 g of the synthesized product 2-C were placed in a reaction vessel, and the temperature was raised to 90 ° C under a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin.

(Example 3)

In a reaction vessel, add 200.0.0 g of ethyl acrylate> KBM 60.3 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., N— / 3 (aminoethyl) monoaminopropyl trimethoxysilane). The mixture was reacted at 23 ° C. for 7 days while mixing under a nitrogen atmosphere at a ratio of 0 g to synthesize a compound 3-A.

Under a nitrogen atmosphere, 80.0 g of TDI was charged into the reaction vessel, and while stirring, 21.0 g of Compound 3-A was added dropwise. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 2 hours to obtain a synthesized product 3-B. Separately, 77 g of DMDS was charged into a reaction vessel, and 290.0 g of Compound 3-B was added dropwise with stirring to obtain Compound 3-C.

200 g of SDX-169 and 77.0 g of the synthesized product 3-C were put in a reaction vessel, and the temperature was raised to 90 ° C under a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. The mixture was further reacted at the same temperature for I hour to produce a curable resin.

(Example 4)

In a reaction vessel, 72.0 g of dimethyl maleate, 86.5 g of phenylmaleimide, and 179 g of KBM903 (trade name, Shin-Etsu Chemical Co., Ltd., aminobutyl biltrimethoxysilane) were added. Then, the mixture was reacted at 23 ° C. for 7 days while mixing under a nitrogen atmosphere to synthesize a compound 41A. Under a nitrogen atmosphere, 87 g of TDI was charged into a reaction vessel, and while stirring, 169 g of Compound 41A was added dropwise. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 2 hours to obtain a synthesized product 4-B. Separately, 36 g of DMDS was put into a reaction vessel, and while stirring, 128 g of Compound 41B was added dropwise to obtain Compound 41C.

The reaction vessel was charged with 200 g of SDX-1690 and 68 g of the compound 41C, and heated to 90 ^ under a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin.

(Example 5)

In a reaction vessel, 117 g of KBM 5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., acryloxypropyltrimethoxysilane) and 89.5 g of KBM903 in a nitrogen atmosphere. The mixture was reacted at 23 ° C for 7 days with mixing to synthesize compound 5-A.

Under a nitrogen atmosphere, 87 g of TDI was charged into a reaction vessel, and while stirring, 207 g of Compound 5-A was added dropwise. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 2 hours to obtain a synthesized product 5-B. Separately, 36 g of DMDS was charged into a reaction vessel, and while stirring, 137 g of Compound 5-B was added dropwise to obtain Compound 5-C.

The reaction vessel was charged with 200 g of SDX-169 and 85 g of the synthesized product 5-C. The temperature was raised to 90 ° C under a nitrogen atmosphere. Next, a mixed solution of 2 g of A] BN and 10 g of toluene was added dropwise over 3 hours. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin.

(Example 6)

Under an atmosphere of nitrogen, 77 g of 2-aminoethanethiol was charged into a reaction vessel, and 86 g of methyl acrylate was added dropwise while stirring. After completion of the dropwise addition, the reaction was carried out at 40 for 48 hours. In addition, その — 5 1 8 7 (product name, Nippon Tunicer, aisocyanate propyl trimethoxysilane)

The mixture was reacted at 23 ° C. for 7 days while mixing in a nitrogen atmosphere at a rate of 203 g to synthesize a synthetic product 6-A.

Under a nitrogen atmosphere, 300 g of a polyaryl ether having a terminal aryl group (number-average molecular weight: 8,000) and 25 g of a compound 6-A were placed in a reaction vessel. The temperature was raised to ° C. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin.

(Example 7)

Under a nitrogen atmosphere, 154 g of DMDS was charged into the reaction vessel, and 100 g of Y-5 187 was dropped and mixed under a nitrogen atmosphere while stirring. Further, after reacting at 50 ° C. for 10 days, unreacted DMDS was distilled off under reduced pressure at 120 ° C. to obtain a compound 7-A.

Under a nitrogen atmosphere, 300 g of a polyaryl ether having a terminal aryl group (number-average molecular weight: 8,000) and 25 g of a compound 7-A were placed in a reaction vessel, and 90 g of the compound was placed in a nitrogen atmosphere. The temperature was raised to ° C. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin.

(Example 8)

In a nitrogen atmosphere, 57 g of arylamine was charged into a reaction vessel, and 86 g of methyl acrylate was added dropwise with stirring. After completion of the dropwise addition, the mixture was reacted at 40 ° C. for 48 hours to obtain a synthesized product 8-A.

Separately, under a nitrogen atmosphere, lllg of IPDI was charged into a reaction vessel, and KBM 573 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., N-phenylaminoaminopropyl trimethoxysilane) was added while stirring. 128 g were added dropwise. After completion of the dropwise addition, the mixture was reacted at 50 ° C. for 10 days to obtain a synthesized product 8-B. Under a nitrogen atmosphere, put 238 g of compound 8—A in a reaction vessel and drop 72 g of compound 8—B Mixed. Furthermore, to obtain a composite 8- C by reacting 5 0 ^e C 7 days.

In a reaction vessel, under a nitrogen atmosphere, 2 g of the synthesized product 8-C 62 and 15 g of DMDS were mixed, and the temperature was raised to 90 ° C. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours to obtain a synthetic product 8-D.

300 g of polyaryl ether having a terminal aryl group (number-average molecular weight: 8,000) and 55 g of compound 8-D were added, and the temperature was raised to 90 ° C under a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin.

(Example 9)

500 g of polyether HA (trade name, manufactured by Mitsubishi Chemical Corporation, polyolefin polyol) was placed in a reaction vessel, and a 28% by mass methanol solution of sodium toxide was added to the number of hydroxyl groups in 1 mol of the above polyester ether HA. The sodium atom was added in a molar amount of 1.05 times, and the mixture was stirred at 120 ° C for 30 minutes. Next, after methanol removal reaction under reduced pressure, 36 g of aryl chloride was added and reacted for 1 hour. Unreacted components were distilled off under reduced pressure to remove by-product inorganic substances and the like, followed by purification to obtain an aryl-terminated hydrocarbon polymer.

Curable resin in the same manner as in Example 1 except that the terminal arylated polymer obtained above was used instead of SDX-1.690, and the amount of Compound 11-B was changed to 68 g. Was manufactured. -(Comparative Example 1)

Under a nitrogen atmosphere, put 400 g of SDX-1669 and 45 g of KBM803 (trade name, Amercaptoprovir trimethoxysilane) (product name, Shin-Etsu Chemical Co., Ltd.) in a reaction vessel. After the temperature was raised to ° C, a mixed solution of 2 g of AIBN and 10 g of 'toluene was added dropwise over 2 hours. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin. (Comparative Example 2)

Under a nitrogen atmosphere, 400 g of polyaryl ether having a terminal aryl group (number-average molecular weight: 8,000) and 21 g of KBM803 were put into a reaction vessel, and the temperature was raised to 90 ° C. Thereafter, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 2 hours. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin.

(Synthesis Example 1) (Synthesis of hydrolyzable alkoxysilane having amino group by Michael addition reaction)

Put 100 g of ethyl acrylate and 163, 3 g of KBM 902 in a reaction vessel, and react under a nitrogen atmosphere at 23 ° C with stirring for 7 days. Obtained. Similarly, add 0.20.2 g of ethyl acrylate and 22.24 g of acrylate in a reaction vessel, and react under a nitrogen atmosphere with stirring at 23: 7 for 7 days to obtain 11 GB of the reaction product. Obtained.

(Synthesis Example 2) (Synthesis of Amino Group-Containing Compound by Michael Addition Reaction) 100.1 g of ethyl acrylate and 57. 1 g of arylamine were placed in a reaction vessel, and stirred under a nitrogen atmosphere. The reaction was performed at 0 ° C for 7 days to obtain a reaction product 2-GA.

(Synthesis example 3) (Synthesis of compound having isocyanate group and substituted urea bond, thiourethane bond or urethane bond)

The compound shown in Table 1 or the reaction obtained in Synthesis Example 2 was used. The product 2—GA and Sumidule T-180 were used in the ratio (parts by mass) shown in Table 1 and stirred at 40 ° C under a nitrogen atmosphere. After reacting for one day, reaction product 1—AA, reaction product 1 BB, reaction product 1—CC, and reaction product 1—DD were obtained. Reactant 1-AA Reactant 1 -BB Reactant 1 -CC Reactant 1-DD aryl alcohol 58.1

Oike-le 164.2

Aryl Mercuff. Tan 74.1.

Reactant 2-GA 157.2 Smithle

174.2 174.2 174.2 174.2 T-80

(Synthesis example 4)

The compounds shown in Table 2 and the reactants obtained in Synthesis Example 1 1-GA or the reactants 1-GB were used at the ratios (parts by mass) shown in Table 2 and stirred at 50 ° C under a nitrogen atmosphere with stirring. After reacting for days, Reactant 2 — AA, Reactant 2 — BB, Reactant 2 — CC, Reactant 2 — DD and Reactant 2 — EE were obtained. Similarly, the compounds shown in Table 2 or the reactant 1 AA, reactant 1—BB, reactant 1 CC or reactant 1—DD obtained in Synthesis Example 3, and the reactant obtained in Synthesis Example 1 1 Use one GA or reactant 1 — GB or KBM903 in the ratio (parts by mass) shown in Table 2 and react for 1 day at 40 ° C with stirring in a nitrogen atmosphere to obtain reactant 2 — FF, Reaction product 2—GG, reaction product 2—HH, reaction product 2—II, and reaction product 2—JJ were obtained. The compounds represented by the trade names in Table 2 are as follows.

* 1: 2-hydroxy-3-acrylacryloxypropyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.

* 2: Kyoeisha Chemical Co., Ltd., trimethylolpropane acrylate

* 3: Takeda Pharmaceutical Co., Ltd., m-Isoprobe, dimethyl benzyl isocyanate

* 4: Showa Denko KK, 2-isocyanate ethyl methacrylate Table 2 Reactant 2-AA Reactant 2-BB Reactant 2-CC Reactant 2-DD Reactant 2-EE Neopentylglycol diacrylate, 212.0

1,6-hexanediol diacrylate 220.3

Light ester G—201 P (* 1). 214.0

Write acrylate TMP— A (* 2) 296.0

m-TM I (* 3) 201.3 Reactant 1 GA 263.4 263.4 263.4

00 Reactant 11 GB 422.6 845.2

Reactant 2—FF Reactant 2—GG Reactant 2—HH Reactant 2-II Reactant 2—J J Force lens MO I (* 4) 155.1

Reactant 11 AA 232.3

Reactant 1—BB 338.4

Reactant 1 CC 248.3 Reactant 1— DD 331.4 Reactant 1— GA 263.4 263.4 Reactant 1-GB 422.6 422.6

KBM903 221.4

(Synthesis example 5)

In a reaction vessel, put 114 g of allyl glycidyl ether, 196 g of KBM 803 and lg of triethylamine, and react at 50 ° C for 7 days with stirring under a nitrogen atmosphere to obtain a reaction product, 5-GA. Got.

(Examples 10 to 22, Comparative Example 3)

Using the curable resin obtained in Example 6 or Comparative Example 2 as a reaction solvent, the compound shown in Table 3 (1) or Table 3 (2), the reactant obtained in the above Synthesis Example, lauryl mercaptan and AIBN In some cases, a mixed solution of KBM503 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., methacryloxypropyltrimethoxysilane) was added dropwise over 3 hours. Further, the mixture was reacted at 100: for 2 hours to produce a curable resin.

Table 3 (1) 夹 5 丄 U ^ mv ¹ } 丄丄 Upper JmW 丄 ^ B i 丄 Thigh J 丄 t »Thigh 丄, υυυ ，, Lily 1 ΠΩΠ, Re n-butyl acrylate 480 480 480 480 480 480 480 Reactant 2—AA 20

Reactant 2—BB 20

Reactant 2—CC 20

oo Reactant 2-DD 20

Reactant 2—EE 20

Monomer Reactant 2— F F 20

Mixed solution Reactant 2— GG 20 Reactant 2— HH

Reactant 2— I I

Reactant 2—J J

KBM503

Lauryl mercaptan 10 10 10 10 10 10 10 10

AI BM-5 5 5 5 5 5 5

Table 3 (2) Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Comparative Example 3 Example 6 1,000 1,000 1,000 500 1,000 1,000

Reaction solvent

Comparative Example 2 1,000 n-butyl acrylate 480 480 480 400 480 480 480 Reactant 2—AA

Reactant 2—BB

00 Reactant 2— C C

Reactant 2—DD 100

Reactant 2—EE

Reactant 2—FF

Monomer

Reactant 2—GG

Mixed solution

Reactant 2 -HH 20

Reactant 2—I I 20

Reactant 2—J J 20

Reactant 5—GA 20

KBM503 20 20 Lauryl mercaptan 10 10 10 10 10 10 10

AI BM 5 5 5 5 5 5 5

(Example 23)

In a nitrogen atmosphere, 114 g of arylglycidyl ether and 221 g of A-Linkl 5 were charged into a reaction vessel and reacted at 50 ° C. for 14 days to obtain a synthesized product 23-A. .

154 g of DMDS and 160 g of synthesized product 23-A were mixed and stirred, and the temperature was raised to 90 ° C. Next, after a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours, unreacted DMDS was distilled off under reduced pressure to obtain a compound 23-B.

In a reaction vessel, add 300 g of polyallyl ether having a terminal aryl group (number-average molecular weight: 8,000) and 32 g of compound 23-B, and raise to 90 ° C under a nitrogen atmosphere. Warmed up. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin.

(Example 24)

Under a nitrogen atmosphere, into a reaction vessel, 114 g of arylglycidyl ether, 1896 of K8803 and 1 g of ancamine54 (trade name, tertiary amine compound manufactured by Air Products Japan) were added. The reaction was carried out at −50 ° C. for 7 days to obtain a synthesized product 24—A.

A reaction vessel was charged with 300 g of a polyaryl ether having a .aryl group at both ends (number average molecular weight: 8,000) and 24 g of DMDS, and the temperature was raised to 90 ° C under a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was dropped over 3 hours. The mixture was further reacted at the same temperature for 1 hour to obtain a synthesized product 24-B.

Subsequently, 22 g of Compound 24-A and 300 g of Compound 24-B were mixed and stirred, and 90. The temperature was raised to C. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours, and the temperature was raised to 90 ° C. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin. (Example 25)

In a nitrogen atmosphere, 57 g of arylamine was charged into a reaction vessel, and 86 g of methyl acrylate was added dropwise with stirring. After completion of the dropwise addition, the mixture was reacted at 40 ° C. for 48 hours to obtain a synthesized product 25-A.

In a nitrogen atmosphere, 72 g of the synthesized product 25-A was put into a reaction vessel, and 1 ^ 81 ^ 403 was added dropwise while stirring. After completion of the dropwise addition, the mixture was reacted at 50 ° C. for 10 days to obtain a synthesized product 25-B.

Under a nitrogen atmosphere, 154 g of DMDS and 180 of Compound 25-B were mixed and stirred in a reaction vessel, and the temperature was raised to 90 ° C. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours, and unreacted DMDS was distilled off under reduced pressure to obtain a synthesized product 25-C.

300 g of polyarylether (number-average molecular weight: 8,000) having both ends and 35 g of compound 25-C were added, and the temperature was raised to 90 ° C under a nitrogen atmosphere. . Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin.

Compound 24-B was obtained.

(Examples 26 to 30).

Using the curable resin obtained in Example 23 as a reaction solvent, a mixed solution comprising n-butyl acrylate, the reaction product obtained in the above synthesis example shown in Table 4 and laurylmer force butane and ABNBN was added to 3 It was dropped over time. Further, the mixture was reacted at 100 ° C. for 2 hours to produce a curable resin. Table 4

Example 2 6 Example 2 7 Example 2 8 Example 2 Reaction solvent Example 2 3 1,000 1,000 1,000 1,000

Chillacrylate 480 480 480 480 Reactant 2—C C 30

Reactant 2-D D 30

Monomer Reactant 2— F F 30

Mixed solution Reactant 5—GA 30 Reactant 2—J J.

Lauryl null force: 7 ° tongue. 10 10 10 10

AIBN 5 5 5 5

(Examples 31 to 60, Comparative Examples 4 to 6)

1,000 g of each of the curable resins obtained in Examples 1 to 30 and Comparative Examples 1 to 3 was added to MR-10G (trade name: Soken Chemical Co., methacrylic acid resin powder) 4 0 g, silica air mouth gel hydrophobically treated with dimethylsiloxane R-812 (trade name: Nippon Aerosil Co., Ltd.) 0.3 g together with a planetary mixer and heat dehydration kneading at 100 ° C under reduced pressure After that, 5 g of KBM803 and 2 g of boron mifluoride piperidine complex were added and kneaded to obtain a curable resin composition. After leaving these curable resin compositions at 23 ° C for 14 days to 30 days, they were cured at a temperature of 23 ° C and a relative humidity of 60%, and the time until skin application was measured. Table 5 shows the results. Also, using these curable resin compositions, stainless steel sheets were adhered to each other as an adherend, cured at a temperature of 23 ° C and a relative humidity of 50% for 14 days, and their tensile shear adhesion strength was increased. (NZ cm ² ) was measured according to JISK 6850. Table 5 shows the results.

Table 5 Skinning time Tensile shear bond strength Hardening tree S

(Min) (N / cm ² ) Example 31 Example 1 2-3 3 Example 32 Example 2 2-3 123 Example 33 Example 3 2-3 121 Example 34 Example 4 2-3 106 Example 35 Example 5 2-3 133 Example 36 Example 6 1-2 145 Example 37 Example 7 1-2143 Example 38 Example 8 2-3 139 Example 39 Example 9 3-5 81 Example 40 Example 10 4-6 177 Example 41 Example 11 4-6 168 Example 42 Example 12 4-6 169 Example 43 Example 13 4-6 172 Example 44 Example 14 4-6 181 Example Example 45 Example 15 4-6 176 Example 46 Example 16 4-6 185 Example 47 Example 17 4-6 181 Example 48 Example 18 4-6 163 Example 49 Example 19 4-6 187 Example Example 50 Example 20 5 to 7 1 97 Example 51 Example 21 6 to 8 158 Example 52 Example 22 4 to 6 191 Example 53 Example 23 2 to 3 123 Example 54 Example 24 3 to 5 148 Example 55 Example 25 2-3143 Example 56 Example 26 4-6 193 'Example 57 Example 27 4-6 186 Example 58 Example 28 4-6 195 Example 59 Example 29 6 to 8 182 Example 60 Example 30 4 to 6 181 Comparative Example 4 Comparative Example 1 4 to 5 60 Comparative Example 5 Comparative Example 2 4 to 5 92 Comparative Example 6 Comparative Example 6 6 to 8 128 As is clear from the results described in Table 5, the resin compositions according to Examples 1 to 30 have a short skin sticking time and a large tensile adhesive strength.

(Example 61, Comparative Example 7)

500 g of each of the curable resins obtained in Example 23 and Comparative Example 2 and 700 g of calcium carbonate (trade name: NS2300, manufactured by Nitto Powder Chemical Co., Ltd.) were used as a planetary mixer. After heating and dewatering and kneading at 100 under reduced pressure, 15 g of KBM 903 and tin catalyst (trade name: Stan No. 918, manufactured by Sankyoki Gosei Co., Ltd.) g was added to obtain a curable resin composition. Using these curable resin compositions, stainless steel sheets are adhered to each other as adherends, cured at a temperature of 23 and a relative humidity of 50% for 14 days, and their tensile shear strength is increased! ^ / Ji! ! ! ^! It was measured according to 680. Table 6 shows the results.

Table 6

From the results in Table 6, it can be seen that the curable resin composition of Example 61 has a remarkable effect due to the difference in the polar group as compared with the curable resin composition of Comparative Example 7. Industrial applicability

When the curable resin of the present invention is compounded as an adhesive, it has the effect of increasing the adhesive strength, and therefore can be used particularly for adhesives, sealants, paints, etc. Adhesive performance can be exhibited.

Claims

The scope of the claims

1. At least one hydrolyzable group selected from an alkoxy group, an acetoxy group and a oxime group has a silicon atom-containing group directly bonded to a silicon atom at the molecular terminal, and (1) a thioether bond and a thiourethane are present in the molecule. Bond and Z or urea bond or substituted urea bond, (2) thioether bond, hydroxy group and secondary or tertiary amino group, or (3) thioether bond and secondary or tertiary amino group. And a curable resin whose main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylic ester polymer or a hydrocarbon polymer.

2. The curable resin according to claim 1, wherein the hydrolyzable group is an alkoxy group.

3. The curable resin according to claim 1 or 2, wherein the curable resin is represented by the following general formula (1).

(

R ³ 3-m D

(RO) — Si-R ⁴ -NR ⁵ -N- (3)

E

However, R is carbon number;! Alkyl groups having 1 to 6 carbon atoms, ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is 1 to 3, and R ⁴ is an alkylene group or an aryl group which may have a side chain having 1 to 10 carbon atoms. R ⁵ is an alkylene group or an arylene group which may have a side chain having 1 to 10 carbon atoms; R ⁶ is a hydrogen atom; an alkyl group which may have a side chain having 1 to 10 carbon atoms. Or an aryl group. D and E each represent a group represented by the following formula (7), (8), (9) or (10), and D and E may be the same or different. R ⁷ represents a hydrogen atom or a group represented by the formula —CO R ⁸ (R ⁸ represents an alkyl group having 1 to 20 carbon atoms); R ⁹ represents a hydrogen atom; —CH ₂ COOH or a methyl group; Has a side chain with 1 to 10 carbon atoms It is an alkylene group or § Li one alkylene group, Z is a hydrogen ^{^{atom, OR 1 Q, 1 1 (}} ) or _{^{^ [^ 1 2, R 1}} Q is Ku Wakashi hydrogen atom, molecular weight 5 0 0 organic residue Is a group represented by the following general formula (11), R ¹¹ is an organic group having a molecular weight of 3,000 or less, and R ¹² is an organic group having a molecular weight of 200 or less.

(7)

(

H

-C— -R ¹¹

II (9)

o

4. A polyvalent alkylene compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, and a terminal of which is an aryl group, a compound of the formula HS—R ¹ — A dithiol compound represented by SH (R ¹ has the same meaning as described above), a diisocyanate compound represented by the formula OCN—R ² —NCO (R ² has the same meaning as described above), and a formula HX 4. The method for producing a curable resin according to claim 3, wherein a compound (X is as defined above) is reacted.

5. The curable resin according to claim 1, wherein the curable resin is represented by the following general formula (12). _R 13

A + S— R ¹ — N—

However, A, R ¹ , R ² , n and X have the same meanings as above, and R ¹³ is a hydrogen atom, the above general formula (7), the general formula (8), the general formula (10) or the following general formula (1 3) a group represented by (are as defined Z and R ^{1 2} above, R ¹⁴ is an alkyl group having 0 to 2 carbon atoms, R ¹⁵ represents an alkyl group having 0 to 2 carbon atoms.) Are respectively shown.

H, _Λ

C-C00R ¹⁴

(13)

Park C—COOR ¹⁵

6. A polyvalent alkylene compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, the terminal of which is an aryl group, a polyvalent aryl compound having the formula HS—R ¹ — thioamine of compounds represented by NHR ¹³ (R ¹ are as defined above, R ^{1 3} represents a molecular weight 50 0 following organic groups.), the formula OC Ν- R ² - Jiisoshianeto compound represented by NC 0

(R ² is as defined above) and a compound of the formula (X is as defined above) is reacted with the curable resin according to claim 5, Production method.

7. The curable resin according to claim 1 or 2, wherein the curable resin is represented by the following general formula (14).

However, A, R, R ¹ , R ³ , R ⁴ , R ¹³ , m and n are as defined above.

8. Main chain skeleton is polyoxyalkylene polymer, (meth) acrylate An ether-based polymer or hydrocarbon polymers, multivalent Ariru compounds thereof ends are Ariru group, the formula HS- R ¹ - Chioami emissions of compounds represented by NH R ^{1 3} (R ¹ and R ^{1 3} Has the same meaning as described above.) And a compound represented by the following general formula (15) (R, R ³ , R ⁴ and m have the same meanings as described above). 9. The method for producing a curable resin according to item 7 above.

OCN-

9. The curable resin according to claim 1 or 2, wherein the curable resin is represented by the following general formula (16).

^{However, A,. R 1. R} 3, R m and n are as defined above. 10. A polyvalent alkylene compound, a (meth) acrylic acid ester polymer or a hydrocarbon polymer whose main chain skeleton is a polyvalent aryl compound whose terminal is an aryl group, a compound represented by the formula HS— R ¹ — a dithiol compound represented by SH (R ¹ is as defined above) and a compound represented by the above general formula (15) are reacted with each other. The method for producing a curable resin according to the above item.

1 1. The curable resin according to claim 1 or 2, wherein the curable resin is represented by the following general formula (17).

(17)

However, A, R ¹ , R ² , X and n are as defined above, and R ¹⁶ is hydrogen An organic group having an atomic or molecular weight of 500 or less.

1 2. Polyoxyalkylene polymer, (meth) acrylic acid ester polymer or hydrocarbon polymer whose main chain skeleton is a polyvalent aryl compound whose terminal is an aryl group; ¹ — a dithiol compound represented by SH (R ¹ is as defined above); an arylamine compound represented by the formula CH 2 —CH—CH 2 —NHR ^J ⁶ (R ¹⁶ is as defined above. ), A diisocyanate compound of the formula 0 CN—R ² —NCO (R ² is as defined above) and a compound of the formula HX (X is as defined above). 12. The method for producing a curable resin according to claim 11, wherein the curing is performed.

1 3. The curable resin according to claim 1 or 2, wherein the curable resin is represented by the following general formula (18).

H2 Γι

A † "S- R ¹ -S- CCC-

However, A, R, R ¹ , R ³ , R ⁴ , R ¹⁶ , m and n are as defined above.

1. Main chain skeleton polyoxyalkylene polymer, (meth) acrylic Sane ester polymer or hydrocarbon-based polymer, polyvalent Ariru compound that end Ru Ariru group Der formula HS- R ¹ - dithiol compound represented by SH, the formula _{_{CH 2 = CH- CH 2 (R}} 1 is as defined above.) - Ariruamin compound represented by NH R ¹⁶ (R ^{1 6} are as defined above. 14. The method for producing a curable resin according to claim 13, wherein the compound represented by the general formula (15) is reacted.

1 5. Polyvalent alkylene compound whose main chain skeleton is polyoxyalkylene polymer, (meth) acrylic acid ester polymer or hydrocarbon polymer, the terminal of which is an aryl group. Formula HS—R ¹ — dithiol compound represented by SH (Wherein R ¹ is as defined above), a diisocyanate compound represented by the formula OCN—R ² —NCO (R ² is as defined above), and a compound represented by the following general formula (19) 3. The method for producing a curable resin according to claim 1 or 2, wherein

Re

)

^{However, A, R, RR 3,} R 4, R 16, m and n are as defined above. 1 7. The curable resin according to claim 1 or 2, wherein the curable resin is represented by the following general formula (22) or (23).

twenty two

)

However, A, R, RR ³ , R ⁴ , m and n are as defined above. 1 8. The curable resin according to claim 1 or 2, wherein the curable resin is represented by the following general formula (24) or (25). )

However, A, R, R ¹ , R ³ , R ⁴ , R ¹⁶ , m and n are as defined above.

1 9. The curable resin according to claim 1 or 2, wherein the curable resin is represented by the following general formula (26).

(26)

^{However, A, R, RR 3,} R 4, R I 6, m and n are Ru as defined der above.

20. A reaction product of aryl glycidyl ether and a compound represented by the following general formula (27), a polyoxyalkylene polymer having a main chain skeleton, a (meth) acrylic ester polymer or a hydrocarbon A polyaryl compound whose terminal is an aryl group and a dithiol compound represented by the formula HS—R ¹ —SH (R ¹ has the same meaning as described above). 17. The method for producing a curable resin according to claim 16, wherein

However, R, R ³ , R ⁴ and R ¹⁶ warp m are as defined above.

2 1. A reaction product of arylglycidyl ether and a compound represented by the following general formula (28), a polyoxyalkylene polymer having a main chain skeleton, a (meth) acrylic ester polymer or a carbonized polymer. Reacting a polyvalent aryl compound having a hydrogen-based polymer with an aryl group at its end and a dithiol compound represented by the formula HS—R ¹ —SH (R ¹ is as defined above). 18. The method for producing a curable resin according to claim 17, wherein:

However, R, R ³ , R ⁴ and m are as defined above. '

2 2. Below? Reaction product of a compound represented by the following general formula (29) with a compound represented by the following general formula (30), a polyoxyalkylene-based polymer having a main chain skeleton, and a (meth) acrylate-based polymer Alternatively, a polyvalent aryl compound whose end is an aryl group and a dithiol compound represented by the formula HS—R ¹ —SH (R ¹ has the same meaning as described above) are reacted. 19. The method for producing a curable resin according to claim 18, wherein:

Where RR ³ , R ⁴ R ¹⁶ and m are as defined above

2 3. A compound represented by the following general formula (31), wherein the main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylate polymer or a hydrocarbon polymer, and the terminal is an aryl group. 10. The curable composition according to claim 19, wherein a polyvalent aryl compound and a dithiol compound represented by the formula HS—R ¹ —SH (R ¹ is as defined above) are reacted. The method of resin production.

However, R, R ³ , R ⁴ , R ¹⁶ and m are as defined above.

2 4. Claims 1, 2, 3, 5, 7, 9, 11, 13, 16, 17, An adhesive composition comprising the curable resin described in Item 18 or 19 as a component.

2 5. Claims 1, 2, 3, 5, 5, 7, 9, 11, 13, 13, 16, 17, An adhesive composition comprising the curable resin described in Item 18 or 19 and a Lewis acid and / or a complex thereof.

26. The curable resin composition according to claim 25, wherein said Lewis acid is boron trifluoride.

2 7. Claims 1, 2, 3, 5, 7, 9, 11, 13, 16, 17, Polymerization of 100 parts by mass of the curable resin described in Item 18 or 19 and polymerization of a polymerizable vinyl monomer. A curable resin composition comprising 5 to 1,000 parts by mass of a vinyl polymer.

2 8. Claims 1, 2, 3, 5, 5, 7, 9, 11, 13, 13, 16, 17, 28. The method for producing a curable resin composition according to claim 27, wherein a polymerizable vinyl monomer is polymerized in the curable resin according to claim 18 or 19. 2 9. It has a reactive silicon group in the molecule, and contains at least one nitrogen or sulfur atom-containing bond selected from the group consisting of a (thio) urethane bond, a urea bond, a substituted urea bond, and a chemical bond derived from the Michael addition reaction. 28. The curable resin composition according to claim 27, wherein a polymer having a droxyl group is contained in an amount of 1 to 50% by mass based on the total amount of the vinyl polymer.

30. Claims 1, 2, 3, 3, 5, 7, 9, 11, 13, 13, 16, 17, The curable resin described in Paragraph 18 or 19 contains a polymerizable vinyl monomer and a reactive silicon group in the molecule, and has a (thio) urethane bond, urea bond, or substituted urea bond. And a compound having at least one nitrogen atom or sulfur atom-containing bond selected from the chemical bond derived from the Michael addition reaction, or a compound having a hydroxy group. Item 10. The method for producing the curable resin composition according to Item 9.

31. The curable resin composition according to claim 24, 27, or 29, further comprising 'a Lewis acid and Z or a complex thereof.

32. The curable resin composition according to claim 31, wherein said Lewis acid is boron trifluoride.