WO2011090046A1

WO2011090046A1 - Curable resin composition

Info

Publication number: WO2011090046A1
Application number: PCT/JP2011/050814
Authority: WO
Inventors: 野村　幸弘; 佐藤　慎一
Original assignee: コニシ株式会社
Priority date: 2010-01-20
Filing date: 2011-01-19
Publication date: 2011-07-28
Also published as: TW201139536A; JPWO2011090046A1

Abstract

Disclosed is a curable resin composition which can be reduced in the burden on the environment, while securing safety and having extremely high curability at low temperatures. Specifically disclosed is a curable resin composition which contains: a curable resin (A) that has a crosslinkable silicon group in each molecule, said crosslinkable silicon group having a chemical structure wherein a carbon atom is bonded to a silicon atom in the crosslinkable silicon group and a heteroatom having an unshared electron pair is bonded to the carbon atom; a curable resin (B) that has a crosslinkable silicon group in each molecule and a main chain composed of a vinyl polymer, said crosslinkable silicon group having a structure wherein an alkylene group having two or more carbon atoms is bonded to a silicon atom; and a basic compound (C). The curable resin composition is characterized in that the (mass) ratio of the curable resin (A) to the curable resin (B) is from 5:95 to 95:5, and the basic compound (C) is contained in an amount of 0.1-30 parts by mass relative to 100 parts by mass of the total of the curable resin (A) and the curable resin (B).

Description

Curable resin composition

The present invention relates to a curable resin composition that can be cured at room temperature in the atmosphere, which is composed of a moisture curable resin whose main chain is a vinyl polymer. More specifically, the present invention is capable of reducing environmental burden and is safe. The present invention relates to a curable resin composition having extremely high low-temperature curability while ensuring properties. Furthermore, the present invention relates to a curable resin composition having low temperature dependency of curability.

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 that can replace the organic tin compounds 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).

Japanese Laid-Open Patent Publication No. 52-73998 Japanese Patent No. 3030020 Japanese Patent No. 3343604 Japanese National Table 2005-514504 Japanese Unexamined Patent Publication No. 8-283366 Japanese Patent No. 3062625 Japanese Laid-Open Patent Publication No. 2005-054174 WO2006 / 051799 Publication WO2007 / 123167

In recent years, not only the global environment but also the working 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.

On the other hand, moisture curable resins generally used as base polymers for sealants, adhesives, pressure-sensitive adhesives, paints, etc. are mainly used for improving various properties such as adhesion, heat resistance, oil resistance, and water resistance. A moisture curable resin whose chain is a vinyl polymer may be used in combination. However, the above function is improved by using a moisture curable resin whose main chain is a vinyl polymer, but on the other hand, due to the high hydrophobicity of the moisture curable resin whose main chain is a vinyl polymer. There was a problem that curability at low temperature was low. Therefore, development of a curable resin composition having high low-temperature curability has been demanded after reducing environmental burden and ensuring safety. In addition, development of a curable resin composition having low temperature dependency of curability has been demanded.

That is, the problem to be solved by the present invention is to cure a moisture curable resin whose main chain is a vinyl polymer in order to improve various properties such as adhesion, heat resistance, oil resistance, and water resistance. With respect to the curable resin composition, it is possible to provide a curable resin composition that is capable of reducing the environmental burden and that has extremely low-temperature curability while ensuring safety. Is to provide a low curable resin composition.

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. Curable resin (A), curable resin (B) having a crosslinkable silicon group in the molecule having a structure in which an alkylene group having 2 or more carbon atoms is bonded to a silicon atom, and the main chain is a vinyl polymer, And a curable resin composition containing the basic compound (C), wherein the ratio (parts by mass) of the curable resin (A) and the curable resin (B) is 5:95 to 95: 5, A curable resin composition comprising 0.1 to 30 parts by mass of the basic compound (C) with respect to 100 parts by mass of the total of the curable resin (A) and the curable resin (B). It is about things. 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. The curability is increased by containing at a certain ratio. In addition, a curable resin (B) having 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 molecule and the main chain being a vinyl polymer at a certain ratio. By containing, a curable resin composition having extremely high low-temperature curability can be obtained.

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 (1)
(Wherein 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 the 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 extremely high low-temperature curability and low temperature dependency of curability is obtained. Can do.

The third invention relates to a curable resin composition according to any one of the first and second inventions, wherein the main chain of the curable resin (A) is polyoxyalkylene. When the main chain of the curable resin (A) is polyoxyalkylene, it is easy to obtain a curable resin composition having high flexibility of the cured product.

The fourth invention is the curing according to any one of the first to third inventions, wherein the curable resin (A) has a crosslinkable silicon group linked to the main chain via a nitrogen-containing characteristic group. The present invention relates to a conductive resin composition. When the curable resin (A) is a curable resin in which a crosslinkable silicon group is linked to the main chain via a nitrogen-containing characteristic group, sufficient curability is easily obtained.

In a fifth aspect of the invention, the curable resin (B) is derived from a polymerizable vinyl compound in which the glass transition temperature of the homopolymer (hereinafter sometimes referred to as “Tg”) is −20 ° C. or less. The present invention relates to a curable resin composition according to any one of the first to fourth inventions, characterized in that the polymer is a vinyl polymer containing a structural unit. Since the curable resin (B) is a vinyl polymer containing a structural unit derived from a polymerizable vinyl compound having a homopolymer Tg of −20 ° C. or lower, the low temperature curability is extremely high, and the curing is performed. It is possible to obtain a curable resin composition having low temperature dependency of properties.

A sixth invention provides the curable resin composition according to any one of the first to fifth inventions, wherein the basic compound (C) is an aminosilane compound represented by the following general formula (3): It is about.
R ⁵ R ⁶ N—R ⁷ —SiR ⁸ _3-c (OR ⁹ ) _c Formula (3)
(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)
Since the aminosilane compound (C) is a compound having a specific structure, sufficient adhesiveness is likely to be exhibited when applied to a sealing material, an adhesive, or a pressure sensitive adhesive precursor.

According to a seventh invention, the curable resin composition according to any one of the first to sixth inventions, wherein the basic compound (C) is an aminosilane compound represented by the following general formula (4): It is about.
H ₂ N—R ¹⁰ —NH—R ¹¹ —SiR ¹² _3-d (OR ¹³ ) _d Formula (4)
(However, R ¹⁰ is an organic group having a molecular weight of 200 or less, R ¹¹ is a hydrocarbon group having 1 to 20 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)
Since the aminosilane compound (C) is a compound having a specific structure, sufficient adhesiveness is more easily exhibited when applied to a sealing material, an adhesive, or a pressure sensitive adhesive precursor.

The eighth aspect of the present invention is the curability according to any one of the first to seventh aspects, 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 present invention relates to a resin composition. If the organotin-based catalyst is in the above range, it is preferable because it is possible to reduce environmental burden and to ensure safety.

In the ninth invention, a mixture of the curable resin (A) and the curable resin (B) is obtained by performing a vinyl polymerization reaction for forming the curable resin (B) in the curable resin (A). The present invention relates to a curable resin composition according to any one of the first to eighth inventions. By performing a vinyl polymerization reaction in the curable resin (A), the viscosity of the mixture of the curable resin (A) and the curable resin (B) can be adjusted to be low, and a reaction solvent removing step is not necessary. This is a very useful production method.

A tenth invention relates to a sealing material composition, an adhesive composition or a pressure sensitive adhesive precursor composition mainly comprising the curable resin composition according to any one of the first to ninth inventions as a curable component. . The curable resin composition according to the present invention is capable of reducing the environmental burden, has a very high low temperature curability while ensuring safety, and further has a low curable temperature dependency. Since it is a thing, it can use especially suitably as a sealing material composition, an adhesive composition, or an adhesive precursor composition.

The curable resin composition of the present invention is a curable resin composition in which a moisture curable resin having a specific structure whose main chain is a vinyl polymer is blended, and is capable of reducing environmental burden and is safe. In addition, the low-temperature curability is extremely high and the temperature dependency of curability is low.

Hereinafter, modes 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 if it is used in a much smaller amount than usual (less than 1000 ppm relative to the total mass part of the curable resin composition), sufficient curability is exhibited. .
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 an α-silane structure, the moisture reactivity is much higher than that of a normal cross-linkable silicon group. Therefore, 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. The crosslinkable silicon group has a chemical structure in which a carbon atom is bonded to a silicon atom, and a hetero atom having an unshared electron pair is bonded to the carbon atom. The crosslinkable silicon group represented by the general formula (1) has a structure in which a silicon atom is bonded to a bonding functional group containing a hetero atom having an unshared electron pair via a methylene group, A heteroatom having a bond with a methylene group. In the general formula (1), this bonding functional group is a site having a function of connecting the crosslinkable silicon group and the main chain. That is, the crosslinkable silicon group is linked to a main chain such as polyoxyalkylene described later at the site of the bonding functional group.
The bonding functional group has a structure in which a heteroatom having an unshared electron pair is bonded to a methylene group having a heteroatom having an unshared electron pair and bonded to a silicon atom contained in a crosslinkable silicon group. As long as it is not particularly limited, (thio) urethane groups, allophanate groups, other N-substituted urethane groups and N-substituted allophanate groups such as (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 other (thio) urea-derived linking groups, amide groups, and N-substituted Examples include amide group-derived linking groups derived from amide groups, nitrogen-containing characteristic groups typified by linking groups derived from imino groups, (thio) ester groups, (thio) ether groups, etc. But it is not limited. Among these, a nitrogen-containing characteristic group is preferable because of its high curability, and a bonding group derived from a (thio) urethane group and a bonding group derived from (thio) urea are more preferable from the viewpoint of ease of synthesis. Here, the above-mentioned “(thio)” means a group in which one or more oxygen atoms in each linking group are sulfur atoms. For example, “(thio) urethane group” means urethane group [—NH—C (═O) O—] and thiourethane group [—NH—C (═S) O—, —NH—C ( = O) S- or -NH-C (= S) S-]. In addition, the above-mentioned “N-substitution” means a group in which a hydrogen atom bonded to a nitrogen atom in each linking group is replaced with another organic group. As an example, “N-substituted urethane group” means a linking group having the chemical formula —NR—C (═O) O— (where R represents an organic group).

In addition to the bond with the methylene group, the silicon atom has 1 to 3 alkoxy groups (OR ² ) as hydrolyzable groups and a hydrocarbon group (R ¹ ) as the remaining bonds. 2 to 0 are bonded. Here, R ¹ includes, for example, an aryl group such as a phenyl group and an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group are preferable, a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable, and a methyl group and an ethyl group are preferable. It is particularly preferred.
The alkoxy group (OR ² ) is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a 2- (butoxy) ethoxy group (—O—CH ₂ CH ₂ —O—C ₄ H ₉ ), or a phenoxy group. Are more preferable, and 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. R ² is preferably an organic group having a molecular weight of 300 or less from the viewpoint of hydrolyzability.

Further, the number of hydrolyzable groups bonded to silicon atoms contained in the crosslinkable silicon group of the curable resin (A) may be appropriately adjusted according to the performance required for each curable resin composition, For example, trialkoxy (a = 3) or dialkoxy (a = 2) is preferably used when it is desired to impart fast curability and high modulus, and when it is desired to impart long pot life or low modulus. Is preferably dialkoxy (a = 2) or monoalkoxy (a = 1). 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 the number average molecular weight 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, alkyl dialkoxy silane, and dialkyl alkoxy silane are collectively referred to as “alkoxy silane”. 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 Japan Special Tables 2004-518801, Japan Special Tables 2004-536957, Japan Special Tables 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 copolymers obtained by ring-opening copolymerization of one or more monoepoxides and / or cyclic ethers selected from the group consisting of tetrahydrofuran.

Commercially available polyols having a polyether skeleton include ADEKA 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 include polymers, ring-opening polymers obtained by ring-opening polymerization of one or more cyclic esters such as ε-caprolactone and valerolactone, 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., 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 the commercially available products include Nippon Run 971, Nippon Run 965, Nippon Run 965, Nippon Run 963, Asahi Kasei Chemicals Co., Ltd. Duranol T5652, Duranol T5650J, Duranol T4672, Duranol TG3452 (all are trade names).

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 and GI-2000 manufactured by Nippon Soda (all are trade names).

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 and UME-2005 manufactured by Soken Chemical Co., Ltd. (all of which are trade names). The

Examples of the polyol having a polybutadiene skeleton or a polyisoprene skeleton include compounds obtained by polymerizing diene monomers typified by butadiene and isoprene. Examples of commercially available products include Poly bd R-15HT, Poly bd R-45HT, Poly ip, Claysole LBH2000, LBH-P3000, and the like (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 methylcaproate, 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 compound: 1,3- or 1,4-xylylene diisocyanate or a mixture 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 compounds: 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-triisocyanate toluene, 4,4′-diphenylmethane-2, 2 ', 5,5'-tetraisocyanate and the like.
Other polyisocyanate compounds: diisocyanates containing sulfur atoms such as phenyl diisothiocyanate.

The above polyisocyanate compounds may be used singly or in combination 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 structures of the crosslinkable silicon groups of STP-E10 and STP-E30 are represented by the following general formula (5), and the main chain structure is polyoxypropylene.
—O—CO—NH—CH ₂ —SiCH ₃ (OCH ₃ ) ₂ Formula (5)
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 has a crosslinkable silicon group in the molecule having a structure in which an alkylene group having 2 or more carbon atoms is bonded to a silicon atom, and the main chain is a vinyl polymer. Resin. However, the curable resin included in the curable resin (A) is not included in the curable resin (B).

In addition, the silicon atom contained in the crosslinkable silicon group in the curable resin (B) has a hydrolyzable group. From the viewpoint of curability, a conventionally known hydrolyzable group, an alkoxy group, an acyloxy group, and the like. Groups, ketoximate groups, amino groups, amide groups, aminooxy groups, mercapto groups, alkenyloxy groups, halogen groups and 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 (X) having 2 to 20 carbon atoms is bonded to a silicon atom in the crosslinkable silicon group, and the hydrocarbon group is further bonded to a vinyl polymer which is a main chain skeleton. In addition, the nitrogen-containing characteristic group mentioned above and other coupling groups (for example, ester, ether group, etc.) may exist between the hydrocarbon group (X) and the main chain skeleton.

In addition to the bond with the hydrocarbon group having 2 to 20 carbon atoms, the silicon atom is bonded with 1 to 3 alkoxy groups (OR ⁴ ) as hydrolyzable groups and carbonized as the remaining bonds. One having 2 to 0 hydrogen groups (R ³ ) bonded thereto. Here, R ³ includes, for example, an aryl group such as a phenyl group and an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group are preferable, a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable, and a methyl group and an ethyl group are preferable. It is particularly preferred.
The alkoxy group (OR ⁴ ) is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a 2- (butoxy) ethoxy group (—O—CH ₂ CH ₂ —O—C ₄ H ₉ ), or a phenoxy group. Are more preferable, and 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. R ⁴ is preferably an organic group having a molecular weight of 300 or less from the viewpoint of hydrolyzability.

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.

The molecular weight of the curable resin (B) is not particularly limited, but the number average molecular weight 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.

Examples of the method for synthesizing the curable resin (B) include a polymerizable vinyl compound (b1) having a crosslinkable silicon group represented by the general formula (2) in the molecule, and other polymerizable vinyl compounds. It can be obtained by copolymerizing the compound (b2). Methods and conditions for obtaining the curable resin (B) are not particularly limited, and general radical polymerization methods, anionic polymerization methods, cationic polymerization methods, and polymerization conditions in those polymerization methods may be applied. it can. Various organic solvents may be used as the reaction solvent during polymerization, and a curable or non-curable resin may be used. Such a curable or non-curable resin may be a low molecular weight substance or a high molecular weight substance as long as it is liquid at room temperature. Among these, the method in which the curable resin (A) is regarded as a solvent and the vinyl compound (b1) and the polymerizable vinyl compound (b2) are copolymerized in the curable resin (A) is most preferable. By performing a vinyl polymerization reaction in the curable resin (A), the viscosity of the mixture of the curable resin (A) and the curable resin (B) can be adjusted to be low, and the reaction solvent is essential in the conventional solution polymerization. Since the removal step is not necessary, it can be said that this is an industrially extremely useful production method. The vinyl compound (b1) and the polymerizable vinyl compound (b2) may be appropriately selected in order to obtain desired performance, and may be used alone or in combination of two or more.

Examples of the polymerizable vinyl compound (b1) include vinyltrimethoxysilane, vinyltriethoxysilane, 3- (meth) acryloylpropyltrimethoxysilane, 3- (meth) acryloylpropyltrimethoxysilane, and 3- (meth) acryloyl. Examples include, but are not limited to, propylmethyldimethoxysilane, 3- (meth) acryloylpropyltriethoxysilane, 3- (meth) acryloylpropylmethyldiethoxysilane, p-styryltrimethoxysilane, and the like. Of these, 3-methacryloylpropyltrimethoxysilane and 3-methacryloylpropylmethyldimethoxysilane are most preferable from the viewpoints of cost and ease of polymerization reaction.

Examples of the polymerizable vinyl compound (b2) include an α, β-unsaturated carbonyl compound (b21), an acrylonitrile compound (b22), a vinyl ester compound (b23), a vinyl ether compound (b24), and other vinyl compounds (b25). ) Or more types of compounds selected from.

The α, β-unsaturated carbonyl compound (b21) is a compound having an α, β-unsaturated carbonyl group in the molecule. Specific examples include acrylic acid, methacrylic acid (hereinafter referred to as (meth) acrylic acid together with acrylic acid and methacrylic acid), methyl (meth) acrylate, lauryl (meth) acrylate, and (meth) acrylic acid. Hexahydrophthalimidoalkyl (meth) acrylates such as isostearyl, (meth) acryloylmorpholine, N-isopropyl (meth) acrylamide, N- (meth) acryloyloxyethyl hexahydrophthalimide, N- (meth) acryloyloxypropyl hexahydrophthalimide Compounds such as tetrahydrophthalimide alkyl (meth) acrylate compounds such as N- (meth) acryloyloxyethyl tetrahydrophthalimide, N- (meth) acryloyloxypropyl tetrahydrophthalimide, etc. Acrylic compounds, maleic acid, dimethyl maleate, although maleic acid compounds such as diethyl maleate, and the like, but are not limited to. Of these, (meth) acrylic acid ester compounds and maleic acid ester compounds are preferred, and (meth) acrylic acid ester compounds are particularly preferred from the viewpoint of ease of reaction.

The acrylonitrile compound (b22) is a compound having an acrylonitrile structure in the molecule. Specific examples include, but are not limited to, acrylonitrile, α-methylacrylonitrile, 2,4-dicyanobutene, and the like.

Examples of the vinyl ester compound (b23) include, but are not limited to, vinyl acetate, vinyl butyrate, vinyl neononanoate, neodecanoate, and the like.

Examples of the vinyl ether compound (b24) include butyl vinyl ether and hexyl vinyl ether, but are not limited thereto.

Examples of the other vinyl compound (b25) include α-olefin compounds such as 1-butene, 1-hexene, 1-decene and 1-dodecene 1-octadecene, allyl compounds such as allylamine, allyl chloride and allyl alkyl ether, N Examples thereof include vinylpyrrolidone compounds such as -vinyl-2-pyrrolidone and N-vinylethyl-2-pyrrolidone, but are not limited thereto.

Among these polymerizable vinyl compounds (b2), a vinyl compound having a cyclic amide functional group (for example, the above-mentioned tetrahydrophthalimide alkyl (meth) acrylate compound, hexahydrophthalimide alkyl (meth) acrylate compound, vinyl pyrrolidone) Is preferably used because adhesion to an ABS resin, an acrylic resin, a polystyrene resin, or the like is improved.

As the compounding amount of the polymerizable vinyl compound (b1), the monomer components (polymerizable vinyl compound (b1) and other polymerizable vinyl compounds (b2)) constituting the curable resin (B) are used. Among these, 0.1 to 50% by mass is preferably copolymerized, more preferably 0.5 to 30% by mass, and particularly preferably 1.0 to 15% by mass.

Furthermore, among other polymerizable vinyl compounds (b2), polymerizable vinyl compounds having a homopolymer Tg of −20 ° C. or less are more preferably used. At least low temperature curing of the curable resin composition according to the present invention by introducing a structural unit derived from a polymerizable vinyl compound having a Tg of −20 ° C. or less into the curable resin (B). It becomes possible to improve the property. By including in the curable resin (B) a structural unit derived from a polymerizable vinyl compound having a Tg of -20 ° C. or less in the homopolymer, the low temperature curability is increased. Since the vinyl polymer copolymerized with a vinyl polymerizable vinyl compound having a Tg of −20 ° C. or lower actively undergoes molecular motion even at low temperatures, moisture in the curable resin composition can be absorbed even at low temperatures. It is assumed that it is because of its high permeability. From such an effect, it is possible to obtain a curable resin composition that can be sufficiently adapted even in a curable resin composition used outdoors in winter.

Specific examples of the polymerizable vinyl compound in which the Tg of the homopolymer is -20 ° C. or lower include butyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, and the like, but are not limited thereto.

The glass transition temperature (Tg) in the present invention means the glass transition temperature of the homopolymer in the case of a homopolymer obtained by using one kind of polymerizable vinyl compound. On the other hand, in the case of a copolymer obtained using two or more kinds of polymerizable vinyl compounds, it means a glass transition temperature obtained based on the FOX formula. The formula of FOX is as follows.
1 / Tg = Σ (a _n / Tg _n )
(Wherein, Tg is the glass transition temperature of the copolymer, a _n is the mass fraction of the n-th polymerizable vinyl compound, Tg _n is a homopolymer obtained from the n-th polymerizable vinyl compound (The glass transition temperature used in the equation is the Kelvin temperature.)
That is, according to the formula of FOX, at least a vinyl polymer copolymerized with a vinyl polymerizable vinyl compound having a homopolymer Tg of −20 ° C. or lower has a low glass transition temperature as a copolymer. This leads to the inference that molecular motion is actively performed even at low temperatures as described above.

The polymerizable vinyl compound having a homopolymer Tg of −20 ° C. or lower is preferably blended in an amount of 2 to 95% by mass among the other polymerizable vinyl compounds (b2). More preferably, 10 to 60% by mass is added.

Furthermore, when the curable resin (B) is synthesized by copolymerization, a conventionally known chain transfer agent can be used in addition to the constituent monomer components. By using a chain transfer agent, the molecular weight of the curable resin (B) can be controlled, and the viscosity of the curable resin (B) can be adjusted. Examples of the chain transfer agent include mercapto compounds such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thiophenol, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltri Examples include mercaptosilane compounds such as ethoxysilane and γ-mercaptopropylmethyldiethoxysilane, disulfide compounds such as dibutyl disulfide and γ-trimethoxysilylpropyl disulfide, and aromatic hydrocarbon compounds such as benzene and toluene. It is not limited. Among these, n-dodecyl mercaptan and mercaptosilane compounds are preferable because of their low odor, and the mercaptosilane compounds exhibit an effect as a chain transfer agent and can introduce a crosslinkable silicon group into the molecule. More preferable. The chain transfer initiator is preferably used in an amount of 0.1 to 35% by weight, more preferably 1 to 25% by weight, based on the monomer component constituting the curable resin (B). 15% by mass is particularly preferred.

Furthermore, when synthesizing the curable resin (B) by copolymerization, a conventionally known initiator suitable for the radical polymerization method, the anion polymerization method, and the cation polymerization method may be used. For example, taking a general-purpose radical polymerization method as an example, the polymerization initiator becomes a radical initiator. Examples of the radical initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methyl-4-trimethoxysilylpentonitrile), 2,2'-azobis (2-methyl-4-methyldimethoxysilylpentonitrile), trade name manufactured by Wako Pure Chemical Industries, Ltd .: VA Azo compounds such as -046B, VA-057, VA-061, VA-085, VA-086, VA-096, V-601, V-65 and VAm-110, benzoyl peroxide, t-alkylperoxyesters, Peroxides such as acetyl peroxide and diisopropyl peroxycarbonate can be used. The initiator is preferably used in the range of 0.1 to 10% by weight, particularly preferably 0.5 to 5% by weight, based on the monomer component constituting the curable resin (B).

The blending amount (parts by mass) of the curable resin (B) is used in the range of curable resin (A): curable resin (B) = 5: 95 to 95: 5, and 20:80 to 90:10. Is more preferable, 30:70 to 80:20 is particularly preferable, and 40:60 to 70:30 is most preferable. When the blending ratio (parts by mass) of the curable resin (B) is less than the curable resin (A): curable resin (B) = 95: 5, the effect of adding the curable resin (B) (adhesiveness, The effect of improving various performances such as heat resistance, oil resistance, water resistance, etc.) may be diminished, and when the curable resin (A): curable resin (B) = 5: 95 is exceeded, the viscosity becomes extremely high and the work May deteriorate.
The curable resin (A) and the curable resin (B) are the main components of the cured network in the curable resin composition of the present invention. As will be described later, in the curable resin composition of the present invention, other than the essential components of the present invention, according to each application and required performance such as an adhesive and a sealing material, within a range not impairing the effects of the present invention. Any conventionally known compound or substance can be added as the component. Generally, it is the sum of the curable resin (A) and the curable resin (B), and it may be blended in the curable resin composition by 15% by mass or more (preferably 30% by mass or more). If no other component is blended, the basic compound (C) is contained in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the total of the curable resin (A) and the curable resin (B). Therefore, the content of the curable resin (A) and the curable resin (B) in the curable resin composition is 70 to 99.9% by mass.

Furthermore, the curable resin composition according to the present invention has a crosslinkable silicon group in the molecule having a structure in which an alkylene group having 2 or more carbon atoms is bonded to a silicon atom, and —CH ₂ CH in the main chain. _A curable resin (Z) which is a polymer containing ₂ O- (oxyethylene group) as a structural unit can be used in combination. By using the curable resin (Z) in combination, the low-temperature curability is further increased. The reason is considered to be that the oxyethylene group in the curable resin (Z) increases moisture permeability into the curable resin composition even at low temperatures. The blending amount of the curable resin (Z) is preferably 1 to 100 parts by mass and more preferably 2 to 80 parts by mass with respect to 100 parts by mass of the total of the curable resin (A) and the curable resin (B). 3 to 60 parts by mass is particularly preferable, and 5 to 40 parts by mass is particularly preferable.

[About the basic compound (C)]
The basic compound (C) in the present invention is a compound that accelerates the curing of the curable resin (A) and the curable resin (B). As the basic compound (C), an amine compound or a phosphazene compound is preferably used. 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 basic compound (C) may be appropriately selected in order to obtain 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-1 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) n A compound represented by H (n ≧ 1), a polyoxyalkylene having a primary amino group at the molecular terminal such as a trade name Jeffamine series manufactured by Huntsman, a polyethyleneimine such as a trade name Epomin series manufactured by Nippon Shokubai Co., Ltd., Examples include, but are not limited to, aminoethylated acrylic polymers such as Nippon Shokubai Co., Ltd. trade name Polyment series. In addition, a ketimine compound that is a reaction product of a primary amino group-containing compound and a ketone in the above amine compound, an aldimine compound that 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.
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, Cyclic amine compounds such as 1,5,7-triazabicyclo [4.4.0] dec-5-ene are 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.

Further, as the basic compound (C) in the present invention, 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 general formula (3) and / or a compound represented by the general formula (4).

In the above formula (3), R ⁵ and R ⁶ represent an organic group or a hydrogen atom having a molecular weight of 500 or less, preferably a hydrocarbon group or a hydrogen atom having 20 or less carbon atoms, more preferably a methyl group, an ethyl group, A hydrocarbon group having 6 or less carbon atoms such as a butyl group, a hexyl group and a phenyl group or a hydrogen atom, particularly preferably a hydrogen atom. R ⁵ and R ⁶ may be the same organic group or a hydrogen atom, or may be different.
R ⁷ represents an organic group having a molecular weight of 500 or less, preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a carbon number such as a methylene group, an ethylene group, a propylene group, an isobutylene group, a dimethylbutylene group or a hexylene group. 6 or less hydrocarbon groups, particularly preferably a propylene group, an isobutylene group, and a dimethylbutylene group.
In the above formula (3), the silicon atom bonded to R ⁷ is bonded with 1 to 3 alkoxy groups (OR ⁹ ) as hydrolyzable groups and hydrocarbon groups (R ⁸ ) as the remaining bonds. In which 2 to 0 are bonded. Here, R ⁸ includes, for example, an aryl group such as a phenyl group and an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group are preferable, a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable, and a methyl group and an ethyl group are preferable. It is particularly preferred.
The alkoxy group (OR ⁹ ) is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a 2- (butoxy) ethoxy group (—O—CH ₂ CH ₂ —O—C ₄ H ₉ ), or a phenoxy group. Are more preferable, and 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. R ⁹ is preferably an organic group having a molecular weight of 300 or less from the viewpoint of hydrolyzability.

In addition, the number of hydrolyzable groups bonded to the silicon atom of the basic compound (C) represented by the general formula (3) can be appropriately adjusted depending on the performance required for each curable resin composition. For example, trial alkoxy (c = 3) or dialkoxy (c = 2) is preferably used for imparting fast curability and high modulus, and imparts a long pot life and low modulus. If desired, dialkoxy (c = 2) or monoalkoxy (c = 1) is preferably used. Among these, dialkoxy (c = 2) is preferable because it is easily available and the balance between curability and cured product modulus is excellent.

In the above formula (4), R ¹⁰ represents an organic group having a molecular weight of 200 or less, preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, an isobutylene group, or a dimethylbutylene group. , A hexylene group or other hydrocarbon group having 6 or less carbon atoms, particularly preferably a propylene group, an isobutylene group or a dimethylbutylene group.
R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 6 or less carbon atoms such as a methylene group, an ethylene group, a propylene group, an isobutylene group, a dimethylbutylene group, or a hexylene group, and is particularly preferable. Is a propylene group, an isobutylene group, or a dimethylbutylene group.
In the above formula (4), the silicon atom bonded to R ¹¹ has 1 to 3 alkoxy groups (OR ¹³ ) bonded as a hydrolyzable group and a hydrocarbon group (R ¹² ) as the remaining bond. In which 2 to 0 are bonded. Here, R ¹² 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. 20 alkyl groups, particularly preferably an alkyl group having 1 to 20 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group are preferable, a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable, and a methyl group and an ethyl group are preferable. It is particularly preferred.
The alkoxy group (OR ¹³ ) is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a 2- (butoxy) ethoxy group (—O—CH ₂ CH ₂ —O—C ₄ H ₉ ), or a phenoxy group. Are more preferable, and 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. R ¹³ is preferably an organic group having a molecular weight of 300 or less from the viewpoint of hydrolyzability.

In addition, the number of hydrolyzable groups bonded to the silicon atom of the basic compound (C) represented by the general formula (4) can be appropriately adjusted depending on the performance required for each curable resin composition. For example, trial alkoxy (d = 3) or dialkoxy (d = 2) is preferably used to provide fast curability and high modulus, giving long pot life and low modulus. If desired, dialkoxy (d = 2) or monoalkoxy (d = 1) is preferably used. Among these, dialkoxy (d = 2) is preferable because it is easily available and the balance between curability and cured product modulus is excellent.

As the above general formula (3) and general formula (4), more specifically, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyl Diethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (6-aminohexyl) aminomethyltriethoxy Silane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, 4 -Amino-3-dimethylbutylmethyldimethoxysilane, [2-aminoethyl (2'-aminoethyl)]-3-aminopropyltrimethoxysilane and other primary amino group-containing aminosilane compounds, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-butylaminopropyl Secondary amino group-containing aminosilane compounds such as trimethoxysilane, N-ethylaminoisobutyltrimethoxysilane and bis (trimethoxysilylpropyl) amine, imidazolesilane compounds having an imidazole group and a crosslinkable silicon group in the molecule, etc. An aminosilane having a tertiary amino group, a ketimine silane compound having a functional group that reacts with water to form a primary amino group (3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, etc.) or Aldiminesilane compounds, MS Silyl of aminosilane such as 301 (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 (trade name, manufactured by Evonik Degussa) A compound obtained by condensing a group alone or with another alkoxysilane compound may be used, but it is not limited thereto.
Since an aminosilane compound generally functions as an adhesion promoter for metal materials, the aminosilane compound according to the present invention can be used as a curing accelerator and adhesion promoter.

The compounding amount of the basic compound (C) is not particularly limited as long as the curable resin (A) and the curable resin (B) are cured, but the curable resin (A) and the curable resin ( 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1.0 to 10 parts by mass with respect to 100 parts by mass as a sum of B). If it is less than 0.1 parts by mass, the effect of promoting curing may not be sufficient, and if it exceeds 30 parts by mass, the balance of the film of the final cured product may be deteriorated.

[Other ingredients]
In the curable resin composition of the present invention, any conventionally known compound or substance can be blended as other components within a range that does not impair the effects of the present invention. For example, various curable resins other than the curable resin used in the present invention (for example, moisture curable resins other than the curable resin (A) and the curable resin (B), epoxy resins, urethane resins, oxetane resins, Cyclic carbonate resins) and non-curing resins (acrylic resins, polycarbonate resins, polyester resins, polystyrene resins, etc.), silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, calcium carbonate powder Body, clay powder, hydrophilic or hydrophobic silica powder, titanium oxide powder, inorganic filler such as carbon black powder, organic filler such as polyacryl powder, polystyrene powder, polyurethane powder, phenol resin , Terpene resin, terpene phenol resin, petroleum resin, rosin resin and other tackifiers Polar group-containing polyolefins such as chlorinated polypropylene, maleic anhydride-modified polypropylene, and polyethylene oxide that improve adhesion to low-polar substrates, thixotropic agents such as amide wax, dehydrating agents such as calcium oxide, diluents, plastics Agents, flame retardants, various liquid functional oligomers, anti-aging agents, ultraviolet absorbers, pigments, titanium coupling agents, aluminum coupling agents, zirconium coupling agents, drying oils and the like can be blended.

In the present invention, a curing accelerator other than the basic compound (C) can be used depending on the application. The curing accelerator 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 curing accelerator include conventionally known acidic compounds such as carboxylic acids, phosphoric acids and various Lewis acids and salts thereof, non-tin organometallic compounds, and Japanese Patent Application Laid-Open No. 2008-260932. Fluorinating agents, fluorinating agents proposed in Japanese Unexamined Patent Publication No. 2008-260932, alkali metal salts of polyvalent fluoro compounds proposed in Japanese Unexamined Patent Publication No. 2008-260933, fluorosilane compounds, etc. However, it is not necessarily limited to these. Examples of the Lewis acid include metal halides and boron halide compounds. Of these, basic compounds, non-tin organic 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, organic tin compounds can also be used as curing accelerators 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.

Examples of the non-tin-based organometallic compounds include compounds mainly composed of Group 1 alkali metal based metal elements, compounds composed mainly of Group 2 alkaline earth metal based metal elements, transition metal based metal elements (for example, 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 iron group metal elements, Group 9 metal elements, Group 10 platinum group metal elements, Group 11 copper group metal elements), Group 12 zinc group metals Examples include compounds mainly composed of elements, compounds mainly composed of Group 13 earth metal-based metal elements, and compounds mainly composed of Group 15 nitrogen-based metal elements, but are not limited thereto. Absent. The non-tin organometallic 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 organometallic compound has a structure such as alkoxide, carboxylate, chelate, etc., so that the activity as a curing accelerator is increased and the compatibility with each curable resin is increased, thereby effectively promoting the curing acceleration ability. Is expressed. In the non-tin-based organometallic compound, a single compound may have a structure such as alkoxide, carboxylate, chelate or the like, or a plurality of structures may be mixed. 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, ethoxyside, 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-based organometallic compound include lithium naphthenate, sodium stearate, potassium octylate, etc. as a compound mainly composed of a group 1 alkali metal group metal element. Magnesium naphthenate, calcium octylate, barium octylate, etc. as compounds mainly composed of metal-based metal elements, and yttrium octylate, titanium tetrabutoxide, titanium acetylacetone complex, titanium as compounds mainly composed of transition metal-based metal elements Diisopropoxybis (ethyl acetoacetate), zirconium tetrapropoxide, zirconium tributoxy monoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), vanadyl acetylacetonate, vana Umum acetylacetonate, 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 the compounds to be used are compounds mainly composed of Group 13 earth metal elements, such as aluminum acetylacetone complex, aluminum tributoxide, aluminum ethyl Examples of the compound mainly composed of a group 15 nitrogen group metal element such as an acetoacetate complex and an indium acetylacetone complex include bismuth naphthenate and bismuth tris (2-ethylhexanoate). But it is not limited to these.

The above-mentioned non-tin organometallic compounds are commercially available and can be used in the present invention. Specific examples of commercially available products include nursem aluminum, nursem chromium, nursem first cobalt, nursem second cobalt, nursem copper, nursem ferric iron, nursem nickel, nursem vanadyl, nursem zinc, nursem indium, nursem magnesium, nurse Sem Manganese, Nasemu Yttrium, Nasemu Cerium, Nasemu Strontium, Nasemu Palladium, Nasemu Barium, Nasem Molybdenyl, Nasemu Lanthanum, Nasem Zirconium, Nasemu Titanium, Naphtex Co Series, Nikka Octix Co Series, Naphtex Mn Series, Nikka Octix Mn Series, Naphtex Zn Series, Nikka Octix Zn Series, Naftex Ca Series, Nikka Octics Ca Series, Naphtec 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, product names manufactured by Nippon Chemical Industry Co., Ltd.), Olgatics ZA-40, Olgatics ZA-65, ORGATICS ZC-150, ORGATICS ZC-540, ORGATICS ZC-570, ORGATICS ZC-580, ORGATICS ZC-700, ORGATICS B-320, ORGATICS TA-10, ORGATICS TA-25, ORGATICS TA-22, ORGATICS TA-30, ORGATICS TC-100, ORGATICS TC-401, ORGATICS TC-200, ORGATICS TC- 750, Olga Tix TPHS, etc. (named Matsumoto Fine Chemical, trade name), SNAPCURE3020, SNAPCURE3030, VERTEC NPZ, etc. (named, Johnson Matthey, trade name), Neostan U-600, Neostan U-660, etc. (named, Nitto) Kasei Co., Ltd. product name), Kenriact NZ01, Kenriact NZ33, Kenriact NZ39, etc. (above, product name produced by Kenrich), Aluminum Etoxide, AIPD, PADM, AMD, ASBD, ALCH, ALC H-TR, aluminum chelate M, aluminum chelate D, aluminum chelate A, algomer, algomer 800AF, algomer 1000SF, pre-act ALM, etc. (above, product 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. Nippon Soda Co., Ltd. trade name), Octope series, Kerop series, Olipe series, Acetop series, Chemihope series etc. (trade name made by Hope Pharmaceutical Co., Ltd.), etc. 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-based organometallic 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-based organometallic compound, an alkoxide or a carboxylate is preferred. The structure 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 curing acceleration activity.

Examples of amine compounds used in the boron trifluoride amine complex 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 H ₂ N (C ₂ H ₄ NH) _n H (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-triazabi Such as bicyclic tertiary amine compounds such as chloro [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, etc. Other, 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) ) Aminomethyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N- (2-aminoethyl) -11- An aminosilane compound such as aminoundecyltriethoxysilane may be mentioned, but is not limited thereto. 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 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. Since the curable resin composition concerning this invention has little temperature dependency of sclerosis | hardenability, since temperature control at the time of adhesive tape preparation can be made comparatively flexible, it can be used suitably for this use.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the examples.

[Preparation of curable resin (A) and curable resin (B)]
As 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)) was prepared. .

(Preparation of curable resin AB-1)
In a reaction vessel, 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), 100 parts by mass) The temperature was raised to 80 ° C. in a nitrogen atmosphere. There, 37.5 parts by mass of methyl methacrylate, 25 parts by mass of lauryl methacrylate, 3.0 parts by mass of 3-acryloxypropyltrimethoxysilane, 7.0 parts by mass of 3-mercaptopropyltrimethoxysilane, and 2,2 A monomer mixture mixed with 0.50 parts by mass of '-azobis (2,4-dimethylvaleronitrile) was added dropwise over 30 minutes to conduct a polymerization reaction. Furthermore, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.20 part 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. Next, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.10 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. Further, after reacting at 80 ° C. for 3 hours, methyl ethyl ketone was distilled off under reduced pressure to obtain STP-E10 (corresponding to the curable resin (A)) and a vinyl polymer having a trimethoxysilyl group in the molecule (cured). Curable resin AB-1 which is a mixture containing the equivalent of the polymerizable resin (B) and the ratio of the polymerizable vinyl compound in which the Tg of the homopolymer in the polymerizable vinyl compound is −20 ° C. or less: about 38% by mass) Got.

(Preparation of curable resin AB-2)
In a reaction vessel, 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), 100 parts by mass) The temperature was raised to 80 ° C. in a nitrogen atmosphere. There, 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 added dropwise 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 dropped to carry out a polymerization reaction. Furthermore, after reacting at 80 ° C. for 3 hours, methyl ethyl ketone was distilled off under reduced pressure to obtain STP-E10 (corresponding to the curable resin (A)) and a vinyl polymer having a methyldimethoxysilyl group in the molecule (cured). Curable resin AB-2, which is a mixture containing the equivalent of the polymerizable resin (B) and the ratio of the polymerizable vinyl compound in which the Tg of the homopolymer in the polymerizable vinyl compound is −20 ° C. or less: about 14% by mass) Got.

(Preparation of curable resin AB-3)
In a reaction vessel, while stirring N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (222.4 parts by mass) at room temperature under a nitrogen atmosphere, methyl acrylate (172.2 parts by mass, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane) was added dropwise over 1 hour and further reacted at 50 ° C. for 7 days. A silane compound SE-1 having a secondary amino group was obtained.
In the reaction vessel, ADEKA polyether PR-5007 (trade name, manufactured by ADEKA Corporation, random copolymer of ethylene oxide and propylene oxide, ethylene oxide: propylene oxide = 7: 3 (molar ratio), hydroxyl value 22.2, 100 parts by mass), isophorone diisocyanate (8.79 parts by mass) and Nikka Octix Zirconium 12% (T) (trade name, 2-ethylhexanoic acid zirconyl compound solution (Zr content = about 12 parts by mass) %) And 20 ppm) in terms of zirconium metal with respect to PR-5007, and the reaction is carried out at 80 ° C. for 5 hours while stirring and mixing in a nitrogen atmosphere, so that the main chain is a copolymer of ethylene oxide and propylene oxide. The urethane-based tree having an isocyanate group in its molecule To obtain a U-1.
Further, the silane compound SE-1 (15.1 parts by mass) was added, and while stirring and mixing in a nitrogen atmosphere, the isocyanate group in the urethane-based resin U-1 and the silane compound SE-1 in the silane compound SE-1 were mixed. By reacting with a secondary amino group at 80 ° C. for 1 hour, the main chain is a copolymer of ethylene oxide and propylene oxide, a urethane bond in the molecule, a urea bond substituted with one active hydrogen, and Thus, a curable resin SU-1 having a trimethoxysilyl group (corresponding to a moisture curable resin other than the curable resin (A) and the curable resin (B)) 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.
A reaction vessel is charged with AB-1 (100 parts by mass), added with a curable resin SU-1 (10 parts by mass) in a nitrogen atmosphere, and kneaded for 30 minutes under reduced pressure, thereby providing STP-E10 (curable resin). (Corresponding to (A)), a vinyl polymer having a trimethoxysilyl group in the molecule (corresponding to curable resin (B)), and a curable resin whose main chain is a random copolymer of ethylene oxide and propylene oxide. A curable resin AB-3, which is a mixture containing SU-1 (corresponding to a moisture curable resin other than the curable resin (A) and the curable resin (B)), was obtained.

(Preparation of curable resin PB-1)
In a reaction vessel, while stirring N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (222.4 parts by mass) at room temperature under a nitrogen atmosphere, methyl acrylate (172.2 parts by mass, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane) was added dropwise over 1 hour and further reacted at 50 ° C. for 7 days. A 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, number average molecular weight of about 10,000, 100 parts by mass), isophorone diisocyanate (4.83 parts by mass) and dioctyltin diversate ( The urethane resin U having a main chain of an oxyalkylene polymer and an isocyanate group in the molecule is prepared by reacting at 80 ° C. for 3 hours while stirring and mixing in a nitrogen atmosphere. -1 was obtained.
Further, the silane compound SE-1 (8.90 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 in the silane compound SE-1 were mixed. 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 substituted with one active hydrogen in its molecule, and a trimethoxysilyl group A curable resin P-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.

In a reaction vessel, curable resin P-1 (100 parts by mass) was placed and heated to 80 ° C. in a nitrogen atmosphere. There, 37.5 parts by mass of methyl methacrylate, 25 parts by mass of lauryl methacrylate, 3.0 parts by mass of 3-acryloxypropyltrimethoxysilane, 7.0 parts by mass of 3-mercaptopropyltrimethoxysilane, and 2,2 A monomer mixture mixed with 0.50 parts by mass of '-azobis (2,4-dimethylvaleronitrile) was added dropwise over 30 minutes to conduct a polymerization reaction. Furthermore, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.20 part 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. Next, after reacting at 80 ° C. for 30 minutes, a mixed solution of 0.10 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 to obtain a curable resin P-1 (a curable resin not applied to the curable resin (A)) and a trimethoxysilyl group in the molecule. And a vinyl polymer (corresponding to the curable resin (B), the ratio of the polymerizable vinyl compound in which the Tg of the homopolymer in the polymerizable vinyl compound is −20 ° C. or less: about 38% by mass). A curable resin PB-1 was obtained.

(Preparation of curable resin PB-2)
In a reaction vessel, SAT400 (trade name, manufactured by Kaneka Corporation, polyoxyalkylene having a methyldimethoxysilyl group at the end, 100 parts by mass) was placed, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. There, 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 added dropwise 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 dropped 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 SAT400 (a curable resin not applied to the curable resin (A)) and a vinyl polymer having a methyldimethoxysilyl group in the molecule ( A curable resin PB-, which is a mixture containing a curable resin (B) and a proportion of a polymerizable vinyl compound in which the Tg of the homopolymer in the polymerizable vinyl compound is −20 ° C. or less: about 14% by mass) 2 was obtained.

(Preparation of curable resin PB-3)
PB-1 (100 parts by mass) is placed in a reaction vessel, curable resin SU-1 (10 parts by mass) is added in a nitrogen atmosphere, and the mixture is kneaded for 30 minutes under reduced pressure, whereby curable resin P-1 ( A curable resin not applied to the curable resin (A)), a vinyl polymer having a trimethoxysilyl group in the molecule (corresponding to the curable resin (B)), and a random copolymer of ethylene oxide and propylene oxide in the main chain. A curable resin PB-3, which is a mixture containing the curable resin SU-1 (corresponding to a moisture curable resin other than the curable resin (A) and the curable resin (B)) as a coalescence, was obtained.

[Preparation of basic compound (C)]
As basic compounds (C), KBM-903 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltrimethoxysilane), KBM-603 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), N- (2-aminoethyl) ) -3-aminopropyltrimethoxysilane).

[Preparation of metal catalyst]
Neostan U-830 (trade name, manufactured by Nitto Kasei Co., Ltd., octyltin compound) and dibutyltin dimethoxide were prepared as metal catalysts that can be used as curing accelerators.

(Examples 1 to 3, Comparative Examples 1 to 3)
[Evaluation of low-temperature curability]
Each curable resin composition was prepared by mixing each raw material for 30 seconds using a spatula under the conditions of 5 ± 2 ° C. and relative humidity of 35 ± 5% at the blending ratio (parts by mass) shown in Table 1. The curing rates of the obtained curable resins were compared. The comparison of the curing rate was performed using the skinning time. In this measurement, the starting time is the time immediately after mixing each raw material for 30 seconds, the time when the film formed on the surface of the cured product is not transferred to the spatula is the end time, and the time from the start to the end is skinned. It was time. Each skinning time is shown in Table 1. The condition of 5 ± 2 ° C. relative humidity 35 ± 5% may be referred to as “low temperature condition”.

From the results in Table 1, it can be seen that the curable resin composition according to the present invention has very high curability even under low temperature conditions. Specifically, Comparative Examples 1 to 3 which do not apply to the present invention require 12 hours or more for skinning, whereas Examples 1 to 3 according to the present invention require less than 1 hour. You can see that it is skinned. Since Example 1 and Comparative Example 1, Example 2 and Comparative Example 2 are the same as Example 3 and Comparative Example 3 except for the curable resin, these effects are the same as those of the curable resin according to the present invention. It can be said that it is a peculiar effect by using together (A) and curable resin (B). From these facts, the curable resin composition according to the present invention can be sufficiently applied to, for example, a sealing material and an adhesive used outdoors in winter and can be said to be very useful industrially. Further, Examples 1 and 3 do not use a dibutyltin compound that has a concern about toxicity, and also in Example 2 using an organic tin compound, the organic tin compound is safe among the organic tin compounds. In addition to the relatively high dioctyltin compound, the addition amount thereof is less than 1,000 ppm relative to the total mass part of the curable resin composition. From this, the curable resin composition according to the present invention has a wide range of applications and can be said to be extremely useful industrially because safety is ensured and low-temperature curability is high.

(Examples 4 and 5, Comparative Examples 4 and 5)
[Evaluation of low-temperature curability]
Each raw material is mixed for 30 seconds using a spatula under the conditions of 5 ± 2 ° C. relative humidity 35 ± 5% and 23 ± 2 ° C. relative humidity 50 ± 5% at the blending ratio (parts by mass) shown in Table 2. Thus, each curable resin composition was prepared. The curing rates of the obtained curable resins were compared. The comparison of the curing rate was performed using the skinning time. In this measurement, the starting time is the time immediately after mixing each raw material for 30 seconds, the time when the film formed on the surface of the cured product is not transferred to the spatula is the end time, and the time from the start to the end is skinned. It was time. Each skinning time is shown in Table 2. The condition of 23 ± 2 ° C. and relative humidity 50 ± 5% may be referred to as “room temperature condition”.

From the results of Table 2, it can be seen that the curable resin composition according to the present invention has very high curability even under low temperature conditions, and there is little difference in curability between normal temperature conditions and low temperature conditions. Specifically, Comparative Examples 4 and 5 which are not related to the present invention have a skinning time magnification (low temperature condition / normal temperature condition) of about 5 times, whereas Examples 4 and 5 according to the present invention are 2. Since it is 4 times, there is little fall of sclerosis | hardenability at low temperature. In general, when the temperature is low, the cross-linking reaction between cross-linkable silicon groups decreases, so that the curability decreases. However, the decrease is small in the curable resin composition according to the present invention. Such an effect cannot be obtained with a conventional curable resin composition, and is a unique result obtained by using the curable resin (A) and the curable resin (B) according to the present invention in combination. You can say that. From the above, it can be said that the curable resin composition according to the present invention is very useful in the industry because it makes it easy to set the pot life and the curing time in various temperature ranges. Further, Example 4 does not use a dibutyltin compound that has a concern of toxicity, and also in Example 5 that uses an organic tin compound, the organic tin compound is a safety comparison among the organic tin compounds. In addition to a particularly high dioctyltin compound, the addition amount thereof is less than 1,000 ppm with respect to the total mass part of the curable resin composition. Therefore, the curable resin composition according to the present invention has a wide range of applications and is extremely useful industrially because safety is ensured and low-temperature curability is high and the change in curability due to temperature is small. You can say that.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
Note that this application is based on a Japanese patent application filed on January 20, 2010 (Japanese Patent Application No. 2010-010541), which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

The curable resin composition in the present invention can be used for all uses 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.

Claims

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 a crosslinkable silicon group in the molecule having a structure in which an alkylene group having 2 or more carbon atoms is bonded to a silicon atom, and the main chain is a vinyl polymer;
as well as,
A curable resin composition containing a basic compound (C),
The ratio (parts by mass) of the curable resin (A) and the curable resin (B) is 5:95 to 95: 5,
A curable resin composition comprising 0.1 to 30 parts by mass of the basic compound (C) with respect to 100 parts by mass of the total of the curable resin (A) and the curable resin (B). object.
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 (1)
(Wherein 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 the 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) is polyoxyalkylene.
The curable resin composition according to any one of claims 1 to 3, wherein the curable resin (A) has a crosslinkable silicon group linked to the main chain via a nitrogen-containing characteristic group. .
The curable resin (B) is a vinyl polymer containing at least a structural unit derived from a polymerizable vinyl compound in which the glass transition temperature of the homopolymer is -20 ° C or lower. The curable resin composition according to any one of 1 to 4.
The curable resin composition according to any one of claims 1 to 5, wherein the basic compound (C) is an aminosilane compound represented by the following general formula (3).
R 5 R 6 N—R 7 —SiR 8 3-c (OR 9 ) c Formula (3)
(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)
The curable resin composition according to any one of claims 1 to 6, wherein the basic compound (C) is an aminosilane compound represented by the following general formula (4).
H 2 N—R 10 —NH—R 11 —SiR 12 3-d (OR 13 ) d Formula (4)
(However, R 10 is an organic group having a molecular weight of 200 or less, R 11 is a hydrocarbon group having 1 to 20 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)
The curable resin composition according to any one of claims 1 to 7, wherein the content of the organic tin compound is 0 to less than 1000 ppm with respect to the total mass part of the curable resin composition.
A mixture of the curable resin (A) and the curable resin (B) is prepared by performing a vinyl polymerization reaction for forming the curable resin (B) in the curable resin (A). The curable resin composition according to any one of claims 1 to 8.
A sealing material composition, an adhesive composition or a pressure sensitive adhesive precursor composition comprising the curable resin composition according to any one of claims 1 to 9 as a main component of a curable component.