JP2011148885A - Curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition which can reduce an environmental load, has a sufficient curing rate while securing safety, and further has high adhesion to metallic materials. <P>SOLUTION: The curable resin composition contains a curable resin (A) having, in the molecule, a crosslinkable silicon group with a chemical structure in which a carbon atom is bonded to the silicon atom in the crosslinkable silicon group and furthermore a hetero atom having an unshared electron pair is bonded to the carbon atom, a curable resin (B) having, in the molecule, a crosslinkable silicon group with a structure in which a 2≤C alkylene group binds with the silicon atom, and an epoxy compound (C) and the curable resin (B) is 0-900 pts.mass based on 100 pts.mass curable resin (A), and the epoxy resin (C) is 1-200 pts.mass based on 100 pts.mass sum of the curable resins (A) and (B). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a curable resin composition containing a moisture curable resin and an epoxy compound that can be cured at room temperature, and more specifically, can reduce environmental burden and ensure safety. On the other hand, the present invention relates to a curable resin composition having a sufficient curing rate and high adhesion to a metal material.

  The main chain is an organic polymer, and the curable resin having a crosslinkable silicon group that can be cross-linked between molecules in the molecule crosslinks a crosslinkable silicon group such as an alkoxysilyl group by hydrolysis with moisture in the atmosphere. It is a so-called moisture curable polymer and is widely used as a base polymer for sealing materials, adhesives, pressure-sensitive adhesives, paints, and the like (Patent Documents 1 to 4). When such a moisture curable polymer is used for a sealing material, an adhesive, a paint, or the like, generally an organic tin compound is blended in order to promote the curing of the moisture curable polymer (Patent Document 5). 6).

  However, organotin compounds have a very high curing accelerating activity, but in recent years their toxicity has become a problem, and therefore, a curing accelerator in place of the organic tin compound has been demanded. However, when an amine compound or the like is used as an alternative curing accelerator, for example, there is a problem that the curability is insufficient because the curing accelerating activity is lower than that of the organic tin compound. In addition, when an acidic compound such as carboxylic acid is used, there is a problem that adhesiveness may be insufficient when applied to a sealing material or an adhesive.

  Therefore, in order to solve such problems, it has been proposed that halogenated compounds such as boron trifluoride and halogen compounds such as fluorosilane compounds can be used as curing accelerators for the moisture-curable polymer. (Patent Documents 7 to 9).

JP-A-52-73998 Japanese Patent No. 3030020 Japanese Patent No. 3343604 JP 2005-514504 Gazette JP-A-8-283366 Japanese Patent No. 3062625 JP 2005-054174 A WO2006 / 051799 Publication WO2007 / 123167

  In recent years, not only the global environment but also the usage environment of workers, the demand for the safety of chemical substances has become stronger due to the growing interest in the environment. Some organotin compounds have become problematic in recent years, and it is desired that the amount used be less than 1000 ppm based on the composition. In particular, organic tin compounds containing relatively toxic tributyltin derivatives (for example, dibutyltin compounds may contain tributyltin compounds as by-products), especially for their use. Attention is required. In other words, the content of the organotin compound, which is very useful as a curing accelerator, is suppressed to less than 1000 ppm with respect to the total mass part of the curable resin composition, sufficient curability is exhibited, and various performances are balanced. There has been a demand for the development of a curable resin composition that can be removed.

  Therefore, as a result of intensive studies, the present inventors have found that a curable resin having a chemical structure in the vicinity of a specific crosslinkable silicon group as described in Patent Document 4 and a curing having a conventionally known crosslinkable silicon group. Surprisingly, it was found that the curing performance of the entire system can be increased when used in combination with a functional resin, and this combined system was filed earlier (Japanese Patent Application No. 2008-187669). In addition, an application was also filed for a technique that gives a faster curing speed to this system (Japanese Patent Application No. 2009-113928).

  However, in the above invention, although the environmental load can be reduced and the safety can be ensured, when considering practical application as a sealing material or an adhesive mainly composed of a curable resin composition, adhesion to a metal material Development of a curable resin composition having improved properties has been demanded.

  That is, the problem to be solved by the present invention is a curable resin composition that is capable of reducing the environmental burden, has a sufficient curing rate while ensuring safety, and has high adhesion to a metal material. Is to provide.

  The inventors of the present invention paid attention to the invention for which the above patent application was filed, further deepened the technique, and completed the present invention. The present invention is composed of the following first to tenth inventions.

1st invention is hardening which has a crosslinkable silicon group in a molecule | numerator which has a chemical structure which the carbon atom couple | bonded with the silicon atom of the crosslinkable silicon group, and also the hetero atom which has an unshared electron pair couple | bonded with this carbon atom Resin (A),
A curable resin (B) having in its molecule a crosslinkable silicon group having a structure in which an alkylene group having 2 or more carbon atoms is bonded to a silicon atom;
And a curable resin composition containing an epoxy compound (C),
The curable resin (B) is 0 to 900 parts by mass with respect to 100 masses of the curable resin (A).
The said epoxy compound (C) is 1-200 mass parts with respect to 100 mass parts of total of the said curable resin (A) and the said curable resin (B), The curable resin composition characterized by the above-mentioned. It is about. A curable resin (A) having a crosslinkable silicon group in the molecule having a chemical structure in which a carbon atom is bonded to a silicon atom of a crosslinkable silicon group and a heteroatom having an unshared electron pair is bonded to the carbon atom. A curable resin composition having high curability by containing at a constant ratio and a very high metal adhesion can be obtained by containing the epoxy compound (C) at a constant ratio.

In the second invention, the curable resin (A) is a curable resin having a crosslinkable silicon group represented by the following general formula (1) in the molecule, and the curable resin (B) is a molecule. The present invention relates to a curable resin composition according to the first invention, which is a curable resin having a crosslinkable silicon group represented by the following general formula (2).
^{_{-A-CH 2 -SiR 1 3-}} a (OR 2) a ··· Equation (1)
(However, A is a bonding functional group in which a hetero atom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom contained in a crosslinkable silicon group, and R ¹ is a hydrocarbon group having 1 to 20 carbon atoms. R ² represents an organic group having a molecular weight of 300 or less, and a represents 1, 2 or 3)
-X-SiR ³ _3-b (OR ⁴ ) _b Formula (2)
(Wherein X is a hydrocarbon group having 2 to 20 carbon atoms, R ³ is a hydrocarbon group having 1 to 20 carbon atoms, R ⁴ is an organic group having a molecular weight of 300 or less, b is 1, 2 or 3; Each)
When the curable resin (A) and the curable resin (B) have a crosslinkable silicon group having a specific structure, a curable resin composition having high curability can be obtained.

  A third invention is characterized in that the main chain of the curable resin (A) and / or the curable resin (B) is polyoxyalkylene, the curable resin composition according to the first or second invention. It is about things. When the main chain of the curable resin (A) and / or the curable resin (B) is polyoxyalkylene, it is easy to obtain a curable resin composition having good workability and high flexibility of the cured product.

  The fourth invention is characterized in that the curable resin (A) and / or the curable resin (B) includes a bonding group derived from a urethane group and / or a bonding group derived from a urea group. The present invention relates to a curable resin composition according to any one of the inventions. When the curable resin (A) and / or the curable resin (B) includes a bonding group derived from a urethane group and / or a bonding group derived from a urea group, a highly curable and tough cured product is obtained, A curable resin composition having high metal adhesion can be obtained.

  The fifth invention further relates to a curable resin composition according to any one of the first to fourth inventions, further comprising a curing agent (D). By containing the curing agent (D), a curable resin composition having high curability even at room temperature can be obtained without heating.

  The sixth invention relates to a curable resin composition according to the fifth invention, wherein the curing accelerator (D) is an amine compound. Since the curing accelerator (D) is an amine compound, a curable resin composition having high room temperature curability can be obtained.

  A seventh invention is characterized in that the curing accelerator (D) is one or more compounds selected from a ketimine compound, an aldimine compound, and an oxazolidine compound, and the curable resin composition according to the fifth or sixth invention. It is about things. When the curing accelerator (D) is one or more compounds selected from a ketimine compound, an aldimine compound, and an oxazolidine compound, a one-component moisture-curable curable resin composition having high room temperature curability can be obtained.

  The eighth invention is characterized in that the curing accelerator (D) is an aminosilane compound having a crosslinkable silicon group in the molecule, and the curable resin composition according to any one of the fifth to seventh inventions. It is about. When the curing accelerator (D) is an aminosilane compound, it can act as a curing accelerator / adhesion imparting agent.

  The ninth invention is characterized in that the content of the organic tin compound is 0 to less than 1000 ppm relative to the total mass part of the curable resin composition, and the curability according to any one of the first to eighth inventions. The present invention relates to a resin composition. If the organotin compound (organotin-based catalyst) is in the above range, it is preferable because it is possible to reduce environmental burden and to ensure safety.

  A tenth invention relates to a sealing material composition or an adhesive composition mainly comprising a curable resin composition according to any one of the first to ninth inventions as a curable component. The curable resin composition of the present invention is a curable resin composition that is capable of reducing environmental burden, has a sufficient curing rate while ensuring safety, and has high adhesion to a metal material. Therefore, it can be particularly suitably used as a sealing material composition or an adhesive composition.

  The curable resin composition according to the present invention is capable of reducing the environmental burden, and has an effect of having a sufficient curing rate and ensuring high adhesion to a metal material while ensuring safety. is there.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. In addition, this invention is not limited only to these illustrations, Of course, a various change can be added in the range which does not deviate from the summary of this invention.

[About curable resin (A)]
The curable resin (A) in the present invention has a crosslinkable silicon group having a chemical structure in which a carbon atom is bonded to a silicon atom of a crosslinkable silicon group, and a heteroatom having a lone pair is bonded to the carbon atom. It is a curable resin in the molecule. Since the crosslinkable silicon group in which a carbon atom is bonded to a silicon atom and a heteroatom having a lone pair is bonded to the carbon atom has a high crosslinking activity, the curable resin (A) has a curing accelerating activity. Even if the organotin compound, which is very high but has a concern about toxicity, is not used, or the amount used is much smaller than usual (less than 1000 ppm relative to the total mass of the curable resin composition), sufficient curability is exhibited. . In addition, as the crosslinkable silicon group in the curable resin (A), from the viewpoint of curability, conventionally known hydrolyzable groups are alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, aminooxy groups. A crosslinkable silicon group having a group, a mercapto group, an alkenyloxy group, a halogen group or the like can be used. Among these, an alkoxy group is most preferably used from the viewpoint of high reactivity and low odor.

  Moreover, curable resin which has a crosslinkable silicon group containing functional group represented by the said General formula (1) in a molecule | numerator is also used suitably for curable resin (A). In the present invention, a chemical structure represented by the general formula (1) is expressed as “α-silane structure”. By selecting the α-silane structure, the moisture reactivity is much higher than that of a normal cross-linkable silicon group, so that no organotin compound is used or a much smaller amount than usual (curable resin composition) Even if it is less than 1000 ppm with respect to the total mass part, a sufficient curing rate can be obtained.

The heteroatom is not particularly limited as long as it has an unshared electron pair, but an atom with high nucleophilicity or an atom with high electronegativity is particularly preferable. Of these, nitrogen (N) atoms, oxygen (O) atoms, sulfur (S) atoms, and halogen (I, Br, Cl, F) atoms are preferred because of the availability of raw materials and the ease of synthesis. From the balance of various performances, a nitrogen (N) atom, an oxygen (O) atom, and a sulfur (S) atom are more preferable, and a nitrogen (N) atom is particularly preferable from the viewpoint of high curability. If the heteroatom is a highly nucleophilic atom or an electronegativity atom, the reason why it shows a moisture reactivity much higher than that of a normal crosslinkable silicon group is not clear, but a highly nucleophilic atom In this case, the reactivity of the silicon atom is increased by the interaction of the highly nucleophilic atom with the adjacent silicon atom. In the case of an atom having a high electronegativity, the effect of the high electronegativity atom It is surmised that the reason is that the reactivity of silicon atoms is increased by the flow of electrons from silicon atoms through adjacent carbon atoms.
The curable resin (A) may be appropriately selected in order to obtain desired performance, and may be used alone or in combination of two or more.

  The curable resin (A) will be described in detail with a curable resin having a crosslinkable silicon group represented by the general formula (1) in the molecule as a representative example. In the crosslinkable silicon group, a bonding functional group in which a hetero atom having an unshared electron pair is bonded to a silicon atom via a methylene group. Here, the bond functional group is a structure that connects the crosslinkable silicon group and the main chain, and a heteroatom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom contained in the crosslinkable silicon group. Although not particularly limited, (thio) urethane groups, allophanate groups, other N-substituted urethane groups, linking groups derived from (thio) urethane groups such as N-substituted allophanate groups, (thio) urea groups, biuret groups, N-substituted urea groups, N, N′-substituted urea groups, N-substituted biuret groups, N, N′-substituted biuret groups and other (thio) urea-derived linking groups, amide groups, N-substituted amides Examples include amide group-derived linking groups, nitrogen-containing characteristic groups typified by imino group-derived linking groups, (thio) ester groups, (thio) ether groups, etc., but are not limited thereto. Absent. Among these, a nitrogen-containing characteristic group is preferable because of high curability, and a bonding group derived from (thio) urethane group and a bonding group derived from (thio) urea are more preferable from the viewpoint of ease of synthesis.

In addition to the bond with the methylene group, 1 to 3 alkoxy groups (OR ² ) are bonded as hydrolyzable groups, and the hydrocarbon group (R ¹ ) is used as the remaining bond for the silicon atom. 2 to 0 are bonded. Here, R ² includes, for example, an aryl group such as a phenyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxyalkyl group such as 2- (butoxy) ethyl group, preferably an alkyl having 1 to 20 carbon atoms. It is a group. The alkoxy group (OR ² ) is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a 2- (butoxy) ethoxy group (—O—CH ₂ CH ₂ —OC ₄ H ₉ ), or a phenoxy group. , A methoxy group, an ethoxy group, a propoxy group, and a butoxy group are more preferable, and a methoxy group or an ethoxy group is particularly preferable. The hydrocarbon group (R ¹ ) bonded to the remaining bond of the silicon atom is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group, and is preferably a methyl group, an ethyl group, or a propyl group. A butyl group is more preferable, and a methyl group and an ethyl group are particularly preferable.

  Further, the number of hydrolyzable groups bonded to the crosslinkable silicon group of the curable resin (A) may be appropriately adjusted depending on the performance required for each curable resin composition. In addition, trialkoxy (a = 3) or dialkoxy (a = 2) is preferably used for imparting high modulus properties, and dialkoxy (a = 2) is desired for imparting long pot life or low modulus properties. a = 2) and monoalkoxy (a = 1) are preferably used. Among these, dialkoxy (a = 2) is preferable because it is easily available and the balance between curability and cured product modulus is excellent.

  As the main chain skeleton of the curable resin (A), a conventionally known main chain skeleton of an organic polymer can be used. For example, polyoxyalkylene, vinyl polymer (eg, polyacrylate, polymethacrylate, etc.), saturated hydrocarbon polymer, unsaturated hydrocarbon polymer, polyester resin, polycarbonate, polydimethylsiloxane, etc. One or more skeletons selected from commonly used main chain skeletons can be employed. Among these, a polyoxyalkylene or a vinyl polymer is more preferable from the viewpoint of easy availability and ease of synthesis, and a polyoxyalkylene is preferable from the viewpoint of balance of film properties of a cured product. Is particularly preferred. Here, “essentially” means that the structure is a main element of a repeating unit which is the main chain skeleton of the curable resin (A). Moreover, in the curable resin (A), this structure may be contained independently, and 2 or more types may be contained.

  The molecular weight of the curable resin (A) is not particularly limited, but is preferably 1,000 to 200,000, more preferably 1,500 to 100,000, and particularly preferably 2,000 to 40,000. If the molecular weight is less than 1,000, the cured product obtained may have brittle physical properties because the crosslinking density becomes too high. If the molecular weight exceeds 200,000, the viscosity increases and the workability deteriorates. In some cases, blending may be limited, such as requiring a large amount of plasticizer.

  In order to obtain the curable resin (A), synthesis may be performed by a conventionally known method. For example, (1) a method in which an isocyanate methylalkoxysilane compound is reacted with a polyol compound, (2) an isocyanate group-terminated polymer is synthesized by reacting a polyol compound with a polyisocyanate compound, and then the mercaptomethylalkoxysilane compound is added to the isocyanate group-terminated polymer. Alternatively, a method of reacting a compound in which a hetero atom having an active hydrogen group is bonded to the α-position carbon of the silicon atom of an alkoxysilyl group such as an aminomethylalkoxysilane compound, (3) an organic compound having a double bond group in the molecule (4) having a crosslinkable silicon group having a structure in which a carbon atom is bonded to a silicon atom and a heteroatom having a lone pair is bonded to the carbon atom. A polymerizable vinyl compound alone Or a method of copolymerizing with other polymerizable vinyl compounds, and (5) an organic polymer having a double bond group in the molecule, in which a carbon atom is bonded to a silicon atom, and the carbon atom is not shared. A method of adding an organic group having a structure in which a hetero atom having an electron pair is bonded and a silane compound having at least a hydrogen atom bonded thereto by a hydrosilylation reaction is known.

  Here, trialkoxysilane, alkyldialkoxysilane, and dialkylalkoxysilane are collectively referred to as “alkoxysilane”. The amino group of the aminomethylalkoxysilane compound may be a primary amino group or a secondary amino group, but the viscosity of the curable resin (A) is higher when it is a secondary amino group. It is preferable because it can be adjusted to a relatively low viscosity. The aminomethylalkoxysilane compound having a secondary amino group can also be derived from an aminomethylalkoxysilane compound having a primary amino group. Specifically, a method of reacting an aminomethylalkoxysilane compound having a primary amino group with a compound having a functional group causing a conjugate addition reaction with an amino group such as an α, β-unsaturated carbonyl compound or an acrylonitrile compound. Etc. Furthermore, it can be easily synthesized by the methods described in JP-T-2004-518801, JP-T-2004-536957, JP-T-2005-501146, WO2010 / 004948 and the like.

  The isocyanate group-terminated polymer can be synthesized by reacting a polyol compound and a polyisocyanate compound. A polyol compound having the above main chain skeleton may be selected as the polyol compound, and a conventionally known polyisocyanate compound may be used as the polyisocyanate compound. Moreover, when synthesizing the above-mentioned isocyanate group-terminated polymer, the polyol compound and polyisocyanate compound as raw materials may be appropriately selected in order to obtain desired performance, and may be used alone or in combination of two or more. Good.

  Specific examples of the polyol compound include one or more conventionally known main chain structures such as a polyether skeleton, a polyester skeleton, a polycarbonate skeleton, a polyolefin skeleton, a polyvinyl skeleton, a polyacryl skeleton, a polybutadiene skeleton, and a polyisoprene skeleton. The polyol compound which has is illustrated. Other examples include polyols having a polysiloxane skeleton and polyol compounds containing an organic group having a fluorine atom, a silicon atom, a sulfur atom, or a rosin skeleton. Alternatively, a mixture of a plurality may be used. The average number of hydroxyl groups per molecule is preferably 1.1 or more, more preferably 1.3 or more, and particularly preferably 1.5 or more. Less than can be used as needed.

  Examples of the polyol having a polyether skeleton include homopolymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyhexylene, and polyoxytetramethylene, and ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, and the like. Examples thereof include a copolymer obtained by ring-opening copolymerization of two or more monoepoxides selected from the group consisting of tetrahydrofuran.

  As a commercial item of the polyol which has the said polyether frame | skeleton, ADEKA Corporation P-2000, P-3000, PR-3007, PR-5007 etc., Asahi Glass Co., Ltd. Exenol 2020, Exenol 510, PMLS4012, PMLS4015, PMLS3011 etc. Mitsui Chemicals D-1000, D-2000, D-4000, T-5000, etc., Sumika Bayer Urethane Co., Ltd. Sumifen 3600, Sumifene 3700, Hodogaya Chemical Co., Ltd. PTG-2000, PTG-L2000 Etc. (all are trade names).

  The polyol having a polyester skeleton is obtained by polycondensation of one or more dicarboxylic acids such as maleic acid, adipic acid, sebacic acid and phthalic acid and one or more diols. Examples thereof include ring-opening polymers obtained by ring-opening polymerization of polymers, ε-caprolactone, valerolactone, and the like, and castor oil derivative compounds such as castor oil having two or more active hydrogens. Commercially available products include NS-2400 manufactured by ADEKA Corporation, FSK-2000 manufactured by Kawasaki Kasei Kogyo Co., Ltd., Maximol RDK-133, HS 2N-220S manufactured by Toyokuni Oil Co., Ltd., and URIC PH-5001 manufactured by Ito Oil Co., Ltd. As described above, the product names are exemplified.

  Examples of the polyol having a polycarbonate skeleton include polyols having a polycarbonate skeleton derived from 1,6-hexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and the like. Examples of commercially available products include Nipponran 971, Nipponran 965, Nipponran 963, Nipponran 963, Duranor T5652, Duranol T5650J, Duranol T4672, and Duranol TG3452 (all trade names) manufactured by Asahi Kasei Chemicals Corporation.

  Examples of the polyol having a polyolefin skeleton include a polyol having a hydrogenated polybutadiene skeleton, a polyol having an ethylene / α-olefin skeleton, and a polyol having a polyisobutylene skeleton. Examples of commercially available products include Polytail H, Polytail HA manufactured by Mitsubishi Chemical Corporation, GI-1000, GI-2000 manufactured by Nippon Soda (all are trade names), and the like.

  Examples of the polyol having a polyvinyl skeleton or the polyol having a polyacryl skeleton include a polyol compound obtained by copolymerizing a vinyl polymerizable monomer typified by a vinyl ether compound or an acrylic compound and a vinyl polymerizable monomer having a hydroxyl group. The Examples of commercially available products include Alfon UH-2000 and UH-2032 manufactured by Toagosei Co., Ltd., Actflow UT-1001, UMB-2005, UME-2005, and the like (all are trade names) manufactured by Soken Chemical Co., Ltd. The

  Examples of the polyol having a polybutadiene skeleton or a polyisoprene skeleton include compounds obtained by polymerizing diene monomers represented by butadiene, isoprene and the like. Examples of commercially available products include Poly bd R-15HT, Poly bd R-45HT, Poly ip, Claysol LBH2000, LBH-P3000, etc. (all are trade names) manufactured by Idemitsu Kosan Co., Ltd.

  In addition, as a polyol compound having a plurality of skeletons, a polyol having a polyether skeleton and a polyester skeleton in one molecule, a polyol having a polycarbonate skeleton and a polyester skeleton in one molecule, a polyether skeleton and a polyacryl skeleton in one molecule The polyol etc. which have are illustrated. As a commercial item, Asahi Glass Co., Ltd. brand name Advanol series, Nippon Polyurethane Industry Co., Ltd. brand name Nippon Run 982R etc. are illustrated.

Specific examples of the polyisocyanate compound include aliphatic, alicyclic, araliphatic, and aromatic polyisocyanate compounds. Specific examples thereof will be given below.
Aliphatic diisocyanate compounds: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2, 4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, and the like.
Alicyclic diisocyanate compounds: 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl) Isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and the like.
Aroaliphatic diisocyanate compounds: 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate) -1-methylethyl) benzene or a mixture thereof.
Aromatic diisocyanate compounds: m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and the like.
Aliphatic polyisocyanate compounds: lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-tri Isocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane, and the like.
Alicyclic polyisocyanate compound: 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 3-isocyanate-3,3,5-trimethylcyclohexylisocyanate, 2- (3-isocyanatepropyl)- 2,5-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 5 -(2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3 -Isocyanatopropyl) -bicyclo [2,2,1] heptane, -(2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2- (3-isocyanatopropyl)- Bicyclo [2,2,1] heptane and the like.
Aro-aliphatic polyisocyanate compound: 1,3,5-triisocyanate methylbenzene and the like.
Aromatic polyisocyanate compounds: triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatotoluene, 4,4′-diphenylmethane-2, 2 ', 5,5'-tetraisocyanate and the like.
Other polyisocyanate compounds: diisocyanates containing sulfur atoms such as phenyl diisothiocyanate.

  The polyisocyanate compounds may be used alone or in combination as appropriate depending on the purpose of use and required performance. Moreover, you may use together the multimer (for example, a dimer, a trimer) illustrated above and a monoisocyanate compound for physical property adjustment etc.

As a commercial product of the curable resin (A), GENIOSIL STP-E10 (trade name, manufactured by Wacker Chemie AG, molecular weight of about 10,000 converted from methoxy group equivalent, viscosity of about 10,000 mPa · s / 25 ° C. (catalog value) ), GENIOSIL STP-E30 (trade name manufactured by Wacker Chemie AG, molecular weight of about 16,000 converted from methoxy group equivalent, viscosity of about 30,000 mPa · s / 25 ° C. (catalog value)) and the like. The structure of the crosslinkable silicon group of STP-E10 and STP-E30 is represented by the following formula (3).
_{-O-CO-NH-CH 2} -SiCH 3 (OCH 3) 2 ··· Equation (3)
The curable resin (A) may be appropriately selected in order to obtain desired performance, and may be used alone or in combination of two or more.

[About curable resin (B)]
The curable resin (B) in the present invention is a curable resin having in its molecule a crosslinkable silicon group having a structure in which an alkylene group having 2 or more carbon atoms is bonded to a silicon atom. In the present invention, it is preferable that the curable resin (B) is contained because the storage stability of the curable resin composition is improved.

In addition, as the crosslinkable silicon group in the curable resin (B), from the viewpoint of curability, conventionally known hydrolyzable groups are alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, aminooxy groups. A crosslinkable silicon group having a group, a mercapto group, an alkenyloxy group, a halogen group or the like can be used. Among these, an alkoxy group is most preferably used from the viewpoint of high reactivity and low odor.
The curable resin (B) may be appropriately selected in order to obtain desired performance, and may be used alone or in combination of two or more.

  The curable resin (B) will be described in detail with a curable resin having a crosslinkable silicon group represented by the general formula (2) in the molecule as a representative example. A hydrocarbon group having 2 to 20 carbon atoms is bonded to the silicon atom in the crosslinkable silicon group, and the nitrogen-containing characteristic group is bonded to the hydrocarbon group.

In addition to the bond with the hydrocarbon group having 2 to 20 carbon atoms, 1 to 3 alkoxy groups (OR ⁴ ) are bonded as hydrolyzable groups, and the remaining silicon bonds are carbonized. This is one in which 2 to 0 hydrogen groups (R ³ ) are bonded. Here, R ³ includes, for example, an aryl group such as a phenyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxyalkyl group such as 2- (butoxy) ethyl group, preferably an alkyl having 1 to 20 carbon atoms. It is a group. The alkoxy group (OR ⁴ ) is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a 2- (butoxy) ethoxy group (—O—CH ₂ CH ₂ —OC ₄ H ₉ ), or a phenoxy group. , A methoxy group, an ethoxy group, a propoxy group, and a butoxy group are more preferable, and a methoxy group or an ethoxy group is particularly preferable. The hydrocarbon group (R ³ ) bonded to the remaining bond of the silicon atom is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group, and is preferably a methyl group, an ethyl group, or a propyl group. A butyl group is more preferable, and a methyl group and an ethyl group are particularly preferable.

  Further, the number of hydrolyzable groups bonded to the crosslinkable silicon group of the curable resin (B) may be appropriately adjusted depending on the performance required for each curable resin composition. Or trialkoxy (b = 3) or dialkoxy (b = 2) is preferably used for imparting high modulus properties, and dialkoxy (b = 2) for imparting long pot life or low modulus properties. b = 2) and monoalkoxy (b = 1) are preferably used. Among these, dialkoxy (b = 2) is preferable because it is easily available and the balance between curability and cured product modulus is excellent.

  As the main chain skeleton of the curable resin (B), a conventionally known main chain skeleton of an organic polymer can be used. For example, polyoxyalkylene, vinyl polymer (eg, polyacrylate, polymethacrylate, etc.), saturated hydrocarbon polymer, unsaturated hydrocarbon polymer, polyester resin, polycarbonate, polydimethylsiloxane, etc. One or more skeletons selected from commonly used main chain skeletons can be employed. Among these, a polyoxyalkylene or a vinyl polymer is more preferable from the viewpoint of easy availability and ease of synthesis, and a polyoxyalkylene is preferable from the viewpoint of balance of film properties of a cured product. Is particularly preferred. Here, “essentially” means that the structure is a main element of a repeating unit which is the main chain skeleton of the curable resin (B). Moreover, this structure may be contained independently in curable resin (B), and 2 or more types may be contained.

  As curable resin (B), curable resin which has polar groups, such as a nitrogen-containing characteristic group, can also be used in a molecule | numerator. Specific examples of the nitrogen-containing characteristic groups include (thio) urethane groups, allophanate groups, other N-substituted urethane groups, N-substituted allophanate groups and other (thio) urethane group-derived linking groups, (thio) urea groups. , Biuret groups, other N-substituted urea groups, N, N′-substituted urea groups, N-substituted biuret groups, N, N′-substituted biuret groups and the like (thio) urea-derived linking groups, amide groups , N-substituted amide group-derived amide group-derived linking groups, nitrogen-containing characteristic groups represented by imino group-derived linking groups, (thio) ester groups, (thio) ether groups, and the like. It is not limited. Among these, a nitrogen-containing characteristic group is preferable because of high curability, and a bonding group derived from (thio) urethane group and a bonding group derived from (thio) urea are more preferable from the viewpoint of ease of synthesis. Further, only one nitrogen-containing characteristic group may be contained in the curable resin (B), and a plurality of one or two or more nitrogen-containing characteristic groups may be contained.

  When polar groups, such as the said nitrogen-containing characteristic group, are contained in curable resin (B), the toughness of hardened | cured material will improve and sclerosis | hardenability and adhesive strength will increase. In particular, when the crosslinkable silicon group is connected to the main chain via a polar group such as a nitrogen-containing characteristic group, the curability is further increased. The reason for this is that the polar groups of the nitrogen-containing characteristic group strongly attract each other due to an interaction such as a hydrogen bond. It is considered that the toughness is expressed in the cured product by strongly attracting the polar groups of the nitrogen-containing characteristic group to each other so that the molecules of the curable resin are also strongly bound (form a domain). In addition, when the crosslinkable silicon group is connected to the main chain via a polar group such as a nitrogen-containing characteristic group, the crosslinkable silicon groups also come close to each other when forming a domain between the nitrogen-containing characteristic groups. Thus, the probability of contact between the crosslinkable silicon groups is also improved, and further, the condensation reactivity of the crosslinkable silicon groups is improved by catalytic curing with the polar group in the nitrogen-containing characteristic group.

  The molecular weight of the curable resin (B) is not particularly limited, but is preferably 1,000 to 200,000, more preferably 1,500 to 100,000, and particularly preferably 2,000 to 40,000. If the molecular weight is less than 1,000, the cured product obtained may have brittle physical properties because the crosslinking density becomes too high. If the molecular weight exceeds 200,000, the viscosity increases and the workability deteriorates. In some cases, blending may be limited, such as requiring a large amount of plasticizer.

  As a method for synthesizing the curable resin (B), a conventionally known method may be used similarly to the curable resin (B). For example, a method in which an amino group-containing alkoxysilane compound is reacted with an isocyanate group-terminated polymer, a method in which an isocyanate group-containing alkoxysilane compound is reacted with a hydroxyl group-terminated polyol, and the like are known. Among these, the method of reacting an isocyanate group-terminated polymer with an amino group-containing alkoxysilane compound is preferable because the range of raw material selection is wide. In addition, the amino group-containing alkoxysilane compound is preferably a secondary aminosilane compound whose amino group is a secondary amino group because a low-viscosity curable resin (B) can be prepared. The secondary aminosilane compound can be derived from an alkoxysilane compound (primary aminosilane compound) having a primary amino group in the molecule. For example, α, β-unsaturated carbonyl compounds such as acrylic acid ester, methacrylic acid ester, and maleic acid ester compounds, and a method of conjugate addition of the primary aminosilane compound to acrylonitrile, etc. are exemplified. It is not done. More specifically, it can be easily synthesized by the methods described in Japanese Patent No. 3030020, Japanese Patent No. 3343604, Japanese Patent Application Laid-Open No. 2005-54174, and the like.

  The blending amount of the curable resin (B) is preferably 0 to 900 parts by mass, more preferably 10 to 700 parts by mass, and particularly preferably 20 to 600 parts by mass with respect to 100 parts by mass of the curable resin (A). Most preferred is 40 to 400 parts by mass. Although the effect concerning this invention expresses even if curable resin (B) is not mix | blended, the compounding quantity of curable resin (B) exceeds 900 mass parts with respect to 100 mass parts of curable resin (A). And the effect of curable resin (A) may fade, and sclerosis | hardenability may fall.

[Epoxy compound (C)]
The epoxy compound (C) in the present invention is a conventionally known compound having an oxirane ring in the molecule. Specific examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, epoxy resin in which amine is epoxidized, epoxy resin having a heterocyclic ring, fat Conventionally known epoxy compounds such as a compound containing one or more oxirane rings in one molecule such as a cyclic epoxy resin and a urethane-modified epoxy resin having a urethane bond may be mentioned. In addition, epoxy silane compounds such as 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane can also be used. Epoxy compounds (C) are commercially available and can be used in the present invention. Commercially available products include DIC Corporation Epicron Series; Daicel Chemical Industries, Ltd. Celoxide Series, Epolide Series, EHPE Series, Cyclomer Series; Japan Epoxy Resin Corporation Epicoat Series, Dow Chemical Japan D.M. E. R. Although series etc. are mentioned, it is not necessarily limited to these.

  Since the epoxy compound (C) in the present invention is cured by crosslinking of epoxy groups, it forms a network (crosslinked network structure after curing) different from the curable resin (A) and the curable resin (B). . Generally, the cured product of the epoxy compound (C) is hard and brittle, but in the present invention, it is mixed with the curable resin (A), or the curable resin (A) and the curable resin (B). Each network interacts to obtain a tough cured product. Moreover, when the said epoxy silane compound is used as an epoxy compound (C), the network of curable resin (A) or the mixture of curable resin (A) and curable resin (B), and an epoxy compound Since the (C) network is connected, a toughened cured product is easily obtained. The epoxy compound (C) may be appropriately selected in order to obtain desired performance, and may be used alone or in combination of two or more.

  The compounding amount of the epoxy compound (C) is preferably 1 to 200 parts by mass, more preferably 2 to 150 parts by mass with respect to 100 parts by mass of the total of the curable resin (A) and the curable resin (B). Is particularly preferably 10 to 10 parts by mass, and most preferably 6 to 70 parts by mass. When the compounding quantity of an epoxy compound (C) is less than 1 mass part with respect to 100 mass parts of sum total of curable resin (A) and curable resin (B), it is obtained by adding an epoxy compound (C). In some cases, the toughening of the cured product is not sufficient, and when it exceeds 200 parts by mass, the ratio of the epoxy compound (C) increases, and the cured product may become hard and brittle.

[About curing accelerator (D)]
The curing accelerator (D) in the present invention is a compound that accelerates curing of the curable resin (A), the curable resin (B), and / or the epoxy compound (C), and the curable resin according to the present invention. It is a compound that accelerates the curing of the composition. The curable resin composition according to the present invention can be cured by long-term curing or heating without the curing accelerator (D), but when the curing accelerator (D) is contained, The curability of the resin composition increases, and it becomes easier to apply depending on the use such as a sealing material composition or an adhesive composition. What is necessary is just to select a hardening accelerator (D) suitably in order to obtain desired performance, and you may use it individually by 1 type or in combination of 2 or more types.

  Specific examples of the curing accelerator (D) include conventionally known acidic compounds such as carboxylic acids, phosphoric acids and various Lewis acids and salts thereof, basic compounds such as amines and phosphazenes and salts thereof, non-tin metal compounds, Fluorinating agent proposed in Japanese Patent Application Laid-Open No. 2008-260932, fluorinating agent proposed in Japanese Patent Application Laid-Open No. 2008-260932, alkali of polyvalent fluoro compound proposed in Japanese Patent Application Laid-Open No. 2008-260933 Examples include, but are not limited to, metal salts and fluorosilane compounds. Examples of the Lewis acid include metal halides, boron halide compounds, sulfonium salts, phosphonium salts, iodonium salts, onium salt compounds such as ammonium salts, and acid anhydrides. Among these, basic compounds, non-tin metal compounds, and boron halide compounds are preferably used because of their high activity. In view of safety, it is preferable not to use an organotin compound. However, an organic tin compound can also be used as a curing catalyst depending on the application. In that case, an octyltin compound and a carboxylic acid tin compound are preferable because they do not contain a tributyltin derivative.

  An amine compound is preferably used as the basic compound. The amine compound is a compound having at least a primary amino group, a secondary amino group, or a tertiary amino group in the molecule. The amine compound may be appropriately selected in order to obtain a desired performance, and may be used alone or in combination of two or more.

Specific examples of the amine compound include primary amine compounds such as hexylamine, dodecylamine and stearylamine, secondary amine compounds such as di-n-butylamine, dioctylamine, dilaurylamine and piperidine, triethylamine and tributylamine. , Tertiary amine compounds such as trihexylamine, guanidine, 1,1,3,3-tetramethylguanidine, N, N'-diphenylguanidine, 1-phenylguanidine, phenylbiguanide, 1- (o-tolyl) biguanide Guanidine compounds such as pyridine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca -5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 6-dibutylamino- , 8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-cyclic amine compounds such as _{ene, H 2 N (C 2 H} 4 NH) a compound represented by _n H (n ≧ 1), a polyoxyalkylene having a primary amino group at the end of a molecule such as a product name Jeffamine series manufactured by Huntsman, and a polyethyleneimine such as a product name Epomin series manufactured by Nippon Shokubai Co., Ltd. Aminoethylated acrylic polymers such as the product name Polyment series manufactured by Nippon Shokubai Co., Ltd. can be mentioned, but are not limited thereto. In addition, a ketimine compound which is a reaction product of a primary amino group-containing compound and a ketone in the above amine compound, an aldimine compound which is a reaction product of a primary amino group-containing compound and an aldehyde, β-amino An oxazolidine compound that is a reaction product of an alcohol compound and ketones can also be used.
In addition, various heat-latent amine-based crosslinking agents such as imidazole compounds, isophoronediamine and its modified amine, methylenebicyclohexamine and its modified amine, metaxylenediamine and its modified amine, 1,3 bisaminomethylcyclohexane and its Modified amines, norbornane diamine and modified amines thereof, polyamine compounds, polyether amine compounds, polyamide compounds, polyamide amine compounds, polythiol compounds, inorganic acids, inorganic bases, and the like can also be used.
Among these compounds, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, which have a high promoter effect, A cyclic amine compound such as 1,5,7-triazabicyclo [4.4.0] dec-5-ene is preferred, and since it is liquid, 1,8-diazabicyclo [5.4.0] undec-7 More preferred is -ene, 1,5-diazabicyclo [4.3.0] non-5-ene. Moreover, when using the curable resin composition concerning this invention as a 1-pack type, latent amine compounds, such as the said ketimine compound, an aldimine compound, an oxazolidine compound, are used suitably. The reason for this is that these latent amine compounds react with moisture to produce primary amino compounds, so they are inactive before exposure to air and active after exposure to air. Because it becomes. After being exposed to the air, the primary amine compound is generated by the moisture in the air, and the epoxy compound (C) can be cured, and the basic amino group has a basicity. Curing of the curable resin (A) and / or the curable resin (B) is also accelerated.

  Curing accelerators (D) are commercially available and can be used in the present invention. Commercial products include, but are not limited to, Ancamine series, Sanmide series, DABCO series, POLYCAT series, etc. manufactured by Air Products.

  When the curing accelerator (D) in the present invention acts on the epoxy compound (C), not only the epoxy compound (C) alone or the crosslinking reaction with other compounds is promoted, but also the epoxy compound (C) curing is accelerated. The agent (D) may cause a crosslinking reaction. In the present invention, in either case, these compounds are collectively referred to as a curing accelerator.

  Further, as the curing accelerator (D), an aminosilane compound having one or more amino groups and one or more crosslinkable silicon groups in the molecule can be used. Specific examples of the aminosilane compound include a compound represented by the following general formula (4) and / or a compound represented by the following general formula (5), and more specifically, 3-aminopropyltrimethoxysilane. 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) ) -3-Aminopropylmethyldimethoxysilane, N- (6-aminohexyl) aminomethyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl)- 3-aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane Primary amino group-containing aminosilane compounds such as 4-amino-3-dimethylbutylmethyldimethoxysilane and [2-aminoethyl- (2′-aminoethyl)]-3-aminopropyltrimethoxysilane, N-phenylaminopropyl Secondary amino group-containing aminosilane compounds such as trimethoxysilane, N-phenylaminopropyltriethoxysilane, N-butylaminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, An aminosilane having a tertiary amino group such as an imidazolesilane compound having an imidazole group and a crosslinkable silicon group in the molecule, a ketimine silane compound having a functional group that reacts with water to form a primary amino group (3-triethoxy Silyl-N- (1,3-di Til-butylidene) propylamine, etc.) or aldimine silane compound, MS3301 (trade name, manufactured by Chisso Corporation), MS3302 (trade name, manufactured by Chisso Corporation), X-40-2651 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DYNASYLAN 1146 Examples thereof include, but are not limited to, compounds obtained by condensing silyl groups of aminosilanes alone or partially with other alkoxysilane compounds such as (trade name, manufactured by Evonik Degussa).

R ⁵ R ⁶ N—R ⁷ —SiR ⁸ _3-c (OR ⁹ ) _c Formula (4)
(However, R ⁵ and R ⁶ are organic groups or hydrogen atoms having a molecular weight of 500 or less, R ⁷ is an organic group having a molecular weight of 500 or less, R ⁸ is a hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ is a molecular weight of 300. The following organic groups, c represents 1, 2 or 3, respectively)
_{^{H 2 N-R 10 -NH-}} R 11 -SiR 12 3-d (OR 13) d ··· Equation (5)
(However, R ¹⁰ is an organic group having a molecular weight of 300 or less, R ¹¹ is a hydrocarbon group having 1 to ¹² carbon atoms, R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, and R ¹³ is an organic group having a molecular weight of 300 or less. A group, d is 1, 2 or 3, respectively)
In general, since an aminosilane compound functions as an adhesion promoter for metal materials, the aminosilane compound in the present invention can act as a curing accelerator and adhesion promoter.
Moreover, when the said aminosilane compound is used as a hardening accelerator (D), the network of curable resin (A) or the mixture of curable resin (A) and curable resin (B), and an epoxy compound Since the (C) network is connected, a toughened cured product is easily obtained.

  Examples of the non-tin metal compound include compounds mainly composed of Group 1 alkali metal metal elements, compounds mainly composed of Group 2 alkaline earth metal elements, and transition metal metal elements (for example, Group 1 Group 3 rare earth metal elements, Group 4 titanium group metal elements, Group 5 vanadium group metal elements, Group 6 chromium group metal elements, Group 7 manganese group metal elements, Group 8 Group iron group metal elements, Group 9 metal elements, Group 10 platinum group metal elements, Group 11 copper group metal elements), Group 12 zinc group metal elements A compound mainly composed of a group 13 earth metal metal element, a compound mainly composed of a group 15 nitrogen group metal element, and the like, but is not limited thereto. . The non-tin metal compound may be appropriately selected in order to obtain desired performance, and may be used alone or in combination of two or more.

  The non-tin metal compound has a structure such as alkoxide, carboxylate, chelate, etc., so that the activity as a catalyst is enhanced and the compatibility with each curable resin is enhanced, and the curing accelerating ability is effectively expressed. The In the above-mentioned non-tin metal compound, structures such as alkoxide, carboxylate, chelate and the like may be present singly or a plurality of structures may be mixed in one compound. Further, for example, when alkoxide is taken as an example, a plurality of alkoxide structures (for example, a methoxide structure and a butoxide structure) may be mixed, and a structure such as a carboxylate or a chelate may be mixed. Good.

  Examples of the alkoxide structure include, but are not limited to, methoxide, ethoxide, normal propoxide, isopropoxide, normal butoxide, s-butoxide, isobutoxide, t-butoxide, and the like. Examples of the carboxylate structure include, but are not limited to, naphthenate, octylate, dodecanoate, stearate, isostearate, oleate, and the like. Furthermore, examples of the chelate structure include, but are not limited to, various chelate compounds in addition to an acetylacetonate complex and an ethyl acetoacetate complex.

  Specific examples of the non-tin metal compound include lithium naphthenate, sodium stearate, potassium octylate, etc. as a group mainly composed of a group 1 alkali metal metal element. Examples of the compound mainly composed of a metallic metal element include magnesium naphthenate, calcium octylate, and barium octylate. Examples of the compound mainly composed of a transition metal based metal element include yttrium octylate, titanium tetrabutoxide, titanium acetylacetone complex, titanium dichloride. Isopropoxybis (ethyl acetoacetate), zirconium tetrapropoxide, zirconium tributoxy monoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), vanadyl acetylacetonate, vanadium Cetylacetonate, chromium acetylacetone complex, manganese acetylacetone complex, iron octylate, cobalt naphthenate, cobalt octylate, nickel acetylacetone complex, copper naphthenate, copper acetylacetone complex, etc., mainly composed of group 12 zinc group metal elements Zinc acetylacetonate monohydrate, zinc naphthenate, zinc octylate, etc. as compounds to be used are compounds mainly composed of group 13 earth metal elements such as aluminum acetylacetone complex, aluminum tributoxide, aluminum ethylacetate. Acetate complexes, indium acetylacetone complexes, etc. are compounds mainly composed of Group 15 nitrogen group metal elements such as bismuth naphthenate and bismuth tris (2-ethylhexanoate). But it is not limited.

  The non-tin metal compounds are commercially available and can be used in the present invention. Commercially available products include Nashem Aluminum, Nashem Chrome, Nastem Cobalt, Nasem Cobalt Cobalt, Nashem Copper, Nastem Ferric Iron, Nashem Nickel, Nashem Vanadil, Nashem Zinc, Nashem Indium, Nasem Magnesium, Nasem Manganese, Nasemu Yttrium, Nasemu Cerium, Nasemu Strontium, Nasemu Palladium, Nasemu Barium, Nasemu Molybdenyl, Nasemu Lanthanum, Nasemu Zirconium, Nasemu Titanium, Naphtex Co Series, Nikka Octix Co Series, Naphtex Mn Series, Nikka Octix Mn series, naphthex Zn series, Nikka octix Zn series, naphthex Ca series, Nikka octix Ca series, naphthex K series , Nikka Octix K series, Nikka Octix Bi series, Bidecanoic acid Bi series, Pecat series, PA series, naphthex Zr series, Nikka octix Zr series, naphthex Fe series, Nikka octix Fe series, naphthex Mg series, Naftex Li series, Naphtex Cu series, Naphtex Ba series, Nikka Octix Reals series, Nikka Octix Ni series, etc. (above, Nippon Kagaku Sangyo Co., Ltd. trade name), Olga Chicks ZA-40, Olga Chicks ZA-65, Olga Chicks ZC-150, Olga Chicks ZC-540, Olga Chicks ZC-570, Olga Chicks ZC-580, Olga Chicks ZC-700, Olga Chicks ZB-3 0, ORGATICS TA-10, ORGATICS TA-25, ORGATICS TA-22, ORGATICS TA-30, ORGATICS TC-100, ORGATICS TC-401, ORGATICS TC-200, ORGATICS TC-750, ORGATICS TPHS, etc. (above, trade names made by Matsumoto Fine Chemical Co., Ltd.), SNAPCURE3020, SNAPCURE3030, VERTEC NPZ, etc. (above, trade names made by Johnson Matthey), Neostan U-600, Neostan U-660, etc. (above, Nitto Kasei Co., Ltd.) Product name), Kenriact NZ01, Kenriact NZ33, Kenriact NZ39, etc. (above, product name manufactured by Kenrich), aluminum ethoxide, AIPD, PADM, AMD, ASBD, ALCH, ALCH-TR Aluminum chelate M, aluminum chelate D, aluminum chelate A, algomer, algomer 800AF, algomer 1000SF, pre-act ALM, etc. (above, trade names manufactured by Kawaken Fine Chemical Co., Ltd.), A-1, B-1, TOT, TOG, T-50 , T-60, A-10, B-2, B-4, B-7, B-10, TBSTA, DPSTA-25, S-151, S-152, S-181, etc. (above, manufactured by Nippon Soda Co., Ltd.) Product name), Octope series, Kerop series, Olipe series, Acetoop series, Chemihope series (trade name made by Hope Pharmaceutical Co., Ltd.), etc., but are not limited thereto.

  Among these, when it is at least one selected from the group consisting of zirconium compounds, titanium compounds, aluminum compounds, and bismuth compounds, it is possible to reduce the environmental burden, to ensure safety, and to achieve a curing rate that can withstand actual use. Is preferable in that it is easily obtained. Further, when importance is attached to the stability of the non-tin metal compound, a structure such as a carboxylate or a chelate is preferable, and when importance is attached to the curing promoting ability of the non-tin metal compound, a structure such as an alkoxide or a carboxylate is preferable. Is preferred.

As the boron halide compound, a boron trifluoride compound is preferably used.
Specific examples of boron trifluoride compounds include, but are not limited to, boron trifluoride amine complexes, alcohol complexes, ether complexes, thiol complexes, sulfide complexes, carboxylic acid complexes, water complexes, and the like. Do not mean. Among the boron trifluoride compounds, an alcohol complex or an amine complex is preferable from the viewpoint of availability and ease of blending, and an amine complex is most preferable because it has both stability and catalytic activity.

  Examples of the amine compound used in the amine complex of boron trifluoride include ammonia, monoethylamine, triethylamine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, guanidine, 2, 2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, N-methyl-3,3'-iminobis (propylamine), ethylenediamine, diethylenetriamine, triethylenediamine, pentaethylenediamine, 1 , 2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,4-diaminobutane, 1,9-diaminononane, ATU (3,9-bis (3-aminopropyl) -2,4 , 8,1 -Tetraoxaspiro [5.5] undecane), CTU guanamine, dodecanoic acid dihydrazide, hexamethylenediamine, m-xylylenediamine, dianisidine, 4,4'-diamino-3,3'-diethyldiphenylmethane, diaminodiphenyl ether, 3 , 3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, m-toluylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, melamine, 1,3-diphenylguanidine, di-o -Tolylguanidine, 1,1,3,3-tetramethylguanidine, bis (aminopropyl) piperazine, N- (3-aminopropyl) -1,3-propanediamine, bis (3-aminopropyl) ether, Huntsman Such as Jeffermine A compound having a primary amino group, piperazine, cis-2,6-dimethylpiperazine, cis-2,5-dimethylpiperazine, 2-methylpiperazine, N, N'-di-t-butylethylenediamine, 2-amino Methylpiperidine, 4-aminomethylpiperidine, 1,3-di- (4-piperidyl) -propane, 4-aminopropylaniline, homopiperazine, N, N'-diphenylthiourea, N, N'-diethylthiourea, N -Compounds having a plurality of secondary amino groups such as methyl-1,3-propanediamine, and further methylaminopropylamine, ethylaminopropylamine, ethylaminoethylamine, laurylaminopropylamine, 2-hydroxyethylaminopropylamine , 1- (2-aminoethyl) piperazine, N-aminopropyl Piperazine, 3-aminopyrrolidine, 1-o-tolylbiguanide, 2-aminomethylpiperazine, N-aminopropylaniline, ethylamineethylamine, 2-hydroxyethylaminopropylamine, laurylaminopropylamine, 2-aminomethylpiperidine, 4- Aminomethylpiperidine, a compound represented by the formula H2N (C2H4NH) nH (n≈5) (trade name: Polyate, manufactured by Tosoh Corporation), N-alkylmorpholine, 1,8-diazabicyclo [5.4.0] undecene-7 , 6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5, 1,4-diazabicyclo [2.2.2] Octane, pyridine, N-alkylpiperidine, 1,5,7-triazabisic In addition to bicyclic tertiary amine compounds such as [4.4.0] dec-5-ene and 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene , Γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β ( Aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-3- [amino (dipropyleneoxy)] aminopropyltriethoxysilane, (aminoethylaminomethyl) phenethyltriethoxysilane, N- (6-aminohexyl) Aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N- (2-aminoethyl) -11-a Roh aminosilane compounds such as undecyl triethoxysilane including but not limited to these. Boron trifluoride amine complexes are commercially available and can be used in the present invention. Examples of commercially available products include Anchor 1040, Anchor 1115, Anchor 1170, Anchor 1222, and BAK 1171 manufactured by Air Products Japan.

  The blending amount of the curing accelerator (D) is not particularly limited because it can be selected conveniently according to the required curing rate, but is the sum of the curable resin (A), the curable resin (B), and the epoxy compound (C). 0.001-100 mass parts is preferable with respect to 100 mass parts, 0.01-80 mass parts is more preferable, 0.05-60 mass parts is especially preferable, and 0.1-40 mass parts is the most preferable. When the amount is less than 0.001 part by mass, the curing accelerating effect may not be sufficient, and when it exceeds 30 parts by mass, adhesion may be inhibited.

  Although a hardening accelerator (D) accelerates | stimulates hardening of curable resin (A), curable resin (B), and / or an epoxy compound (C), there exists a more preferable combination respectively. For example, when it is desired to further accelerate the curing of the curable resin (A) and / or the curable resin (B), among the above, conventionally known acidic compounds such as carboxylic acid, phosphoric acid, various Lewis acids, and salts thereof , Basic compounds such as amines and phosphazenes and salts thereof, non-tin metal compounds, fluorinating agents proposed in JP 2008-260932 A, fluorinating agents proposed in JP 2008-260932 A In the case where an alkali metal salt of a polyvalent fluoro compound proposed in JP 2008-260933 A, a fluorosilane compound, or the like is preferably used and the curing of the epoxy compound (C) is to be further promoted, , Basic compounds such as amines and phosphazenes, metal halides, boron halide compounds, sulfonium salts, phosphonium salts, iodonium salts, Thermally latent amine crosslinking agents such as onium salt compounds such as ammonium salts, acid anhydrides and imidazole compounds, isophorone diamine and modified amines thereof, methylenebicyclohexamine and modified amines thereof, metaxylenediamine and modified amines thereof 1,3-bisaminomethylcyclohexane and its modified amine, norbornane diamine and its modified amine, polyamine compound, polyetheramine compound, polyamide compound, polyamidoamine compound, polythiol compound, inorganic acid, inorganic base and the like are preferably used.

[Other ingredients]
In the curable resin composition of the present invention, any conventionally known compound or substance can be blended as other components. For example, various curable resins other than the curable resin used in the present invention (for example, moisture curable resins other than curable resins (A) and curable resins (B), urethane resins, oxetane resins, cyclic carbonate resins) ) And non-curable resins (acrylic resin, polycarbonate resin, polyester resin, polystyrene resin, etc.), silane coupling agents such as γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, calcium carbonate powder, clay powder , Inorganic fillers such as hydrophilic or hydrophobic silica powder, titanium oxide powder, carbon black powder, organic fillers such as polyacryl powder, polystyrene powder, polyurethane powder, phenol resin, terpene resin, terpene Tackifiers such as phenol resin, petroleum resin, rosin resin, amide wax Thixotropic agents, dehydrating agents such as calcium oxide, diluents, plasticizers, flame retardants, various liquid functional oligomers, anti-aging agents, UV absorbers, pigments, titanium coupling agents, aluminum coupling agents, zirconium A coupling agent, drying oil, etc. can be mix | blended.

The curable resin composition in this invention can be used for all the uses to which the conventional curable resin was applied. For example, it can be used as an adhesive, a sealing material, an adhesive, a paint, a coating material, a sealing material, a casting material, a coating material, and the like.
The curable resin composition in the present invention is cured by crosslinking of crosslinkable silicon groups in the presence of moisture. Therefore, when used as a one-component composition, it is handled in a hermetically sealed state so as not to come into contact with moisture in the air during storage or transportation. And if it opens and uses it in arbitrary places at the time of use, it will contact with the water | moisture content in air and a curable resin will harden | cure.
Moreover, when using as an adhesive precursor composition, tackifier resin is further mix | blended with said curable resin composition, and it mixes uniformly, and obtains an adhesive precursor composition. In addition, when mixing curable resin composition and tackifying resin uniformly, for example, when compatibility of both is inadequate, you may use an organic solvent. As the organic solvent, alcohols such as ethanol, ethyl acetate, toluene, methylcyclohexane and the like are used. Further, when the compatibility between the curable resin composition and the tackifier resin is good or when the organic solvent is not preferred, the organic solvent may not be used.
A pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive precursor composition thus obtained to the surface (one side or both sides) of a conventionally known tape base or sheet base and curing it. And an adhesive tape or an adhesive sheet is obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.

[Preparation of curable resin (A)]
As curable resin (A), “GENIOSIL STP-E10” (trade name, manufactured by Wacker Chemie AG, molecular weight of about 10,000 converted from methoxy group equivalent, viscosity of about 10,000 mPa · s / 25 ° C. (catalog value)) Got ready.

[Preparation of curable resin (B)]
(Synthesis of curable resin B-1)
In a reaction vessel, while stirring N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (206.4 parts by mass) at room temperature under a nitrogen atmosphere, methyl acrylate (172.2 parts by mass, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane) is added dropwise over 1 hour, and further reacted at 50 ° C. for 7 days. Silane compound SE-1 having a secondary amino group was obtained.
In a separate reaction vessel, PMLS4012 (trade name, manufactured by Asahi Glass Co., Ltd., polyoxypropylene polyol, average molecular weight 10,000, 100 parts by mass), isophorone diisocyanate (4.83 parts by mass) and nikka octix zirconium 12% (T ) (Nihon Kagaku Sangyo Co., Ltd. trade name, 2-ethylhexanoic acid zirconyl compound solution (Zr content = about 12% by mass), PMLS4012 with 20 ppm in terms of zirconium metal) was stirred and mixed in a nitrogen atmosphere. However, by reacting at 80 ° C. for 3 hours, urethane resin U-1 having a main chain of an oxyalkylene polymer and an isocyanate group in the molecule was obtained.
Further, the silane compound SE-1 (8.39 parts by mass) was added, and while stirring and mixing in a nitrogen atmosphere, the isocyanate group in the urethane resin U-1 and the silane compound SE-1 By reacting with a secondary amino group at 80 ° C. for 1 hour, the main chain is an oxyalkylene polymer, and a urethane group, a urea group in which one active hydrogen is substituted in the molecule, and a methyldimethoxysilyl group. A curable resin B-1 was obtained. After completion of the reaction, IR measurement was performed, and no characteristic absorption (2265 cm ⁻¹ ) attributed to the isocyanate group was observed.

(Synthesis of curable resin B-2)
The reaction vessel was charged with curable resin B-1 (400 parts by mass) and heated to 80 ° C. in a nitrogen atmosphere. 40 parts by mass of methyl methacrylate, 9.0 parts by mass of butyl acrylate, 10 parts by mass of stearyl methacrylate, 5.0 parts by mass of 3-acryloxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxy A monomer mixed solution obtained by mixing 5.0 parts by mass of silane and 0.46 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was dropped over 30 minutes to carry out a polymerization reaction. Furthermore, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.15 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 parts by mass of methyl ethyl ketone was dropped to carry out a polymerization reaction. Next, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.08 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 parts by mass of methyl ethyl ketone was added dropwise to carry out a polymerization reaction. Furthermore, after reacting at 80 ° C. for 3 hours, methyl ethyl ketone was distilled off under reduced pressure, whereby curable resin B-1 and a vinyl polymer having a methyldimethoxysilyl group in the molecule (corresponding to curable resin (B)). A curable resin B-2 was obtained.

  As the curable resin (B), ES-S2410 (trade name, manufactured by Asahi Glass Co., Ltd., a propylene oxide polymer having a crosslinkable silicon group represented by the above formula (2)) was prepared.

[Preparation of epoxy compound (C)]
As the epoxy compound (C), jER828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin) and KBM-403 (3-glycidoxypropyltrimethoxysilane) were prepared.

[Preparation of curing accelerator (D)]
As curing accelerator (D), Ancamine K54 (trade name, tertiary amine compound manufactured by Air Products Japan Co., Ltd.), Silaace S340 (trade name, manufactured by Chisso Corporation, N- (1,3-butylidene) -3-tri Ethoxysilyl-1-propanamine) and KBM-603 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., N- (2-aminoethyl) -3-aminopropyltrimethoxysilane) were prepared.

(Examples 1 and 2, Comparative Examples 1 and 2)
[Preparation of curable resin composition]
Each curable resin composition was prepared by putting each raw material into a reaction vessel at a blending amount shown in Table 1 and kneading for 10 minutes under reduced pressure. Each obtained curable resin composition was filled in an airtight container.

[Skinning time measurement]
The curing rate of each curable resin composition was compared. The comparison of the curing rate was performed using the skinning time. The skinning time was defined as the start time immediately after each curable resin composition was exposed to an atmosphere having a relative humidity of 50 ± 5% at 23 ± 2 ° C. and the time until a cured film was formed on the surface. The time when the cured film was formed was the time when the surface of each curable resin composition exposed with a metal spatula was touched and each curable resin composition was not attached to the spatula. Table 1 shows the skinning time of each curable resin composition.

[Adhesive strength measurement]
The adhesive strength of each curable resin composition was measured. Stainless steel plate (SUS304 2B, thickness 1.5 mm, width 25 mm, length 100 mm), mild steel plate (SPCC-SB, thickness 1.6 mm, width 25 mm, length 100 mm), aluminum plate (A1050P) , Thickness 2.0 mm, width 25 mm, length 100 mm). Each obtained curable resin composition (about 0.2 g) is uniformly applied to each test plate in an area of 25 mm × 25 mm, and each test plate (same material) is bonded to each other with an area of 12.5 mm × 25 mm. It was. Each bonded specimen was cured at 23 ± 2 ° C. and 50 ± 5% relative humidity for 7 days, and the tensile shear bond strength was measured according to JIS K 6850. Table 1 shows the tensile shear bond strength of each curable resin composition.

  As shown in Table 1, it can be seen that the curable resin composition according to the present invention exhibits sufficient curability and exhibits high adhesive strength to the metal material.

(Examples 2-4, Comparative Examples 2-4)
[Preparation of curable resin composition and measurement of skinning time and adhesive strength]
Each raw material was mixed by the mixture ratio (mass part) shown in Table 2, and each curable resin composition was prepared. As above, skinning time and bond strength were measured. In this study, each bonded specimen was cured at 23 ± 2 ° C. and 50 ± 5% relative humidity for 24 hours, and then the tensile shear bond strength was measured. Table 2 shows the skinning time and tensile shear bond strength of each curable resin composition.

  As shown in Table 2, it can be seen that the curable resin compositions (Examples 2 to 5) according to the present invention exhibit high adhesive strength with respect to the metal material in addition to exhibiting sufficient curability. In Comparative Example 2, the curability is sufficient, but since the epoxy compound (C) is not blended, the adhesion strength to the metal material is not sufficient. Moreover, in Comparative Examples 3-5, although the epoxy compound (C) is mix | blended, since curable resin (A) is not mix | blended, sclerosis | hardenability is not enough. Moreover, the comparative example 3 is not even cured. From this, it can be said that the effect concerning this invention is the very specific effect obtained by combining specific curable resin.

  From the above, the curable resin composition according to the present invention is a curable resin composition having a sufficient curing rate and high adhesion to a metal material, and therefore can be used for various sealing materials and adhesives. It can be used suitably. Moreover, since the curable resin composition according to the present invention exhibits sufficient curability without adding an organotin compound having a concern regarding toxicity, it can be said that the curable resin composition has a wide range of applications and is extremely useful industrially.

  The curable resin composition in the present invention can be used for all applications where a one-component or multi-component curable resin composition has been used. For example, it can be used as an adhesive, an adhesive, a sealing material, a paint, a coating material, a sealing material, a casting material, a coating material, and the like. In particular, it is suitably used for applications where the cured product is required to have flexibility.

Claims (10)

A curable resin (A) having a crosslinkable silicon group in the molecule having a chemical structure in which a carbon atom is bonded to a silicon atom of a crosslinkable silicon group and a heteroatom having a lone pair is bonded to the carbon atom;
A curable resin (B) having in its molecule a crosslinkable silicon group having a structure in which an alkylene group having 2 or more carbon atoms is bonded to a silicon atom;
And a curable resin composition containing an epoxy compound (C),
The curable resin (B) is 0 to 900 parts by mass with respect to 100 masses of the curable resin (A).
The said epoxy compound (C) is 1-200 mass parts with respect to 100 mass parts of total of the said curable resin (A) and the said curable resin (B), The curable resin composition characterized by the above-mentioned. . The curable resin (A) is a curable resin having a crosslinkable silicon group represented by the following general formula (1) in the molecule, and the curable resin (B) has the following general formula ( The curable resin composition according to claim 1, which is a curable resin having a crosslinkable silicon group represented by 2).
^{_{-A-CH 2 -SiR 1 3-}} a (OR 2) a ··· Equation (1)
(However, A is a bonding functional group in which a hetero atom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom contained in a crosslinkable silicon group, and R ¹ is a hydrocarbon group having 1 to 20 carbon atoms. R ² represents an organic group having a molecular weight of 300 or less, and a represents 1, 2 or 3)
-X-SiR ³ _3-b (OR ⁴ ) _b Formula (2)
(Wherein X is a hydrocarbon group having 2 to 20 carbon atoms, R ³ is a hydrocarbon group having 1 to 20 carbon atoms, R ⁴ is an organic group having a molecular weight of 300 or less, b is 1, 2 or 3; Each)   The curable resin composition according to claim 1 or 2, wherein the main chain of the curable resin (A) and / or the curable resin (B) is polyoxyalkylene.   The curable resin (A) and / or the curable resin (B) contains a linking group derived from a urethane group and / or a linking group derived from a urea group. The curable resin composition described in 1.   Furthermore, a hardening accelerator (D) contains, The curable resin composition as described in any one of Claims 1-4 characterized by the above-mentioned.   The curable resin composition according to claim 5, wherein the curing accelerator (D) is an amine compound.   The curable resin composition according to claim 5 or 6, wherein the curing accelerator (D) is one or more compounds selected from ketimine compounds, aldimine compounds, and oxazolidine compounds.   The curable resin composition according to any one of claims 5 to 7, wherein the curing accelerator (D) is an aminosilane compound having a crosslinkable silicon group in the molecule.   The curable resin composition according to any one of claims 1 to 8, wherein the content of the organic tin compound is 0 to less than 1000 ppm relative to the total mass part of the curable resin composition.   The sealing material composition or adhesive composition which has the curable resin composition as described in any one of Claims 1-9 as a main component of a sclerosing | hardenable component.