JP2006199725A - Curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a curable resin composition that has a practical curing rate, excellent adhesivity to various substrates, and hardly generates 4-16C alkyl alcohols to cause curing retardation and adhesion inhibition with time and a moisture curable adhesive composition containing the curable resin composition. <P>SOLUTION: The curable resin composition comprises 100 parts by mass of an oxyalkylene polymer (A) that contains a silicon-containing specific group to be crosslinked by formation of siloxane bond, 10-1,000 parts by mass of a copolymer (B) that contains a silicon-containing specific group to be crosslinked by formation of siloxane bond and is composed of an alkyl (meth)acrylate monomer unit and 0.001-10 parts by mass of boron trifluoride and/or its complex (C) as a curing promoter. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable resin composition that is cured by moisture, and more particularly to a curable resin composition that contains an oxyalkylene polymer having a crosslinkable silicon-containing characteristic group. The curable resin composition of the present invention can be suitably used for an adhesive / sealing material.

A vinyl polymer obtained by copolymerizing a (meth) acrylic acid alkyl ester monomer is very useful. In addition, the curable resin in which a reactive silyl group is introduced into the vinyl polymer has excellent adhesion to various base materials, and thus is widely used for adhesives, sealing agents, paints, coating agents, etc. For example, see Patent Documents 1 and 2). However, the reaction rate of the reactive silyl group does not reach a practical speed unless a curing catalyst is used. However, it is generally known that metal catalysts such as tin, bismuth, and titanium, which are common as curing catalysts for silicon-containing characteristic groups, can also serve as catalysts for ester group hydrolysis and / or transesterification reactions. ing. Therefore, when a C3 or C16 (meth) acrylic acid alkyl ester monomer having an alcohol melting point of 60 ° C. or lower when the ester group is hydrolyzed is used, a curing delay is likely to occur over time. In some cases, the (meth) acrylic acid alkyl ester monomer used mainly causes C1 or C18 or more, which is hard to cause curing delay and adhesion inhibition even when hydrolysis and / or transesterification occurs. (Meth) acrylic acid alkyl ester.
In addition, when a catalyst that hardly causes hydrolysis and / or transesterification of an ester group such as an amine catalyst is used, the curing rate is slow and practical application is difficult.

JP-A-10-251552 Japanese Patent No. 3435351

  The present invention has been made to solve the above-mentioned problems, and the object of the present invention is that the curing speed is practical, the adhesiveness to various substrates is excellent, and the curing delay or adhesion inhibition with time is suppressed. It is to provide a curable resin composition in which an alkyl alcohol of C4 to C16 which causes the above-mentioned is difficult to generate and a moisture curable adhesive composition containing the same.

In order to achieve the above-mentioned object, the present inventors have made extensive studies, and as a result, they are useful as a reaction catalyst for a silicon-containing characteristic group and do not serve as a catalyst for hydrolysis reaction and / or transesterification reaction of an ester site. It has been found that by using a boron fluoride-based catalyst, it is possible to provide a curable resin composition that is excellent in curability and adhesiveness and hardly causes a delay in curing over time, and has completed the present invention.
That is, the first of the present invention forms a siloxane bond with 100 parts by mass of the oxyalkylene polymer (A) having a silicon-containing characteristic group represented by the following formula (1) that can be crosslinked by forming a siloxane bond. A (meth) acrylic acid alkyl ester monomer unit having a silicon-containing characteristic group that can be cross-linked and having a molecular chain substantially having an alkyl group having 1 to 2 carbon atoms, and an alkyl having 4 to 16 carbon atoms 10 to 1000 parts by mass of a copolymer (B) composed of an alkyl (meth) acrylate monomer unit having a group, and boron trifluoride and / or its complex (C) 0.001 to 10 mass as a curing accelerator It is a curable resin composition characterized by containing a part.

According to a second aspect of the present invention, the molecular chain of the polymer (A) is substantially composed of a repeating unit represented by the following general formula (2) and / or (3). The curable resin composition.

3rd of this invention contains 1 or more urethane bond and / or substituted urea bond in the molecule | numerator of a polymer (A), The curable resin composition of 1 or 2 of this invention characterized by the above-mentioned. It is a thing.
A fourth aspect of the present invention is the curable resin composition according to any one of the first to third aspects, wherein the silicon-containing characteristic group of the polymer (A) is an alkoxysilyl group. .
A fifth aspect of the present invention is the curable resin according to any one of the first to fourth aspects of the present invention, wherein at least one silicon-containing characteristic group of the polymer (A) is a trialkoxysilyl group. It is a composition.
A sixth aspect of the present invention includes one or more urethane bonds and / or substituted urea bonds in the molecule of the polymer (A), and the molecular chain is substantially the following formula (2) and / or (3). The curable resin composition according to the first aspect of the present invention, wherein the silicon-containing characteristic group is an alkoxysilyl group and contains a trialkoxysilyl group.

The curable resin composition according to the first invention includes a polymer (A) containing a silicon-containing characteristic group represented by the above formula (1) in the molecule and a (meth) acrylic acid ester copolymer (B). In addition to being excellent in physical properties and adhesion as an adhesive / sealing material, and containing boron trifluoride and / or its complex (C) as a curing catalyst, the curing rate is sufficient for normal use. In spite of its high speed, it is difficult to cause a delay in curing after the storage stability test. Boron trifluoride and / or its complex (C) is well-known as a curing catalyst for heat-curable epoxy resins, but synergistically enhancing curability by the cooperative action with the silicon-containing characteristic group described above. This is a finding discovered by the present inventor and is not known. The reason why the curability is enhanced is that boron trifluoride interacts with the hydrolyzable silyl group or silanol group in the silicon-containing characteristic group, thereby increasing the ability to remove the silicon-containing characteristic group or OH group, As a result, it is presumed that the coupling reaction between silyl groups is promoted. In addition, the reason why the curing delay after the storage stability test does not occur is that boron trifluoride and / or its complex (C) serves as a catalyst for the coupling reaction of the silicon-containing characteristic group, but (meth) acrylic acid It is presumed that this is because it does not serve as a catalyst for transesterification and / or hydrolysis reaction at the ester group site of the ester copolymer (B), and therefore does not produce C4-C16 alkyl alcohol components that cause curing delay or adhesion inhibition. Is done.
In the curable resin composition according to the second invention, the polymer (A) is a polymer whose molecular chain is substantially composed of repeating units represented by the above formula (2) and / or (3). Although the speed is sufficient for normal use, it is difficult to cause a delay in curing after the storage stability test, and it is excellent in various properties such as workability of the curable resin composition and physical properties of the cured product. .
Since the curable resin composition according to the third invention contains at least one urethane bond and / or substituted urea bond in the molecule of the polymer (A), the curing rate is sufficient for normal use. In spite of its high speed, it is difficult for the curing delay after the storage stability test to occur, and the adhesion to the substrate to be adhered is excellent.
In the curable resin composition according to the fourth invention, since the silicon-containing characteristic group of the polymer (A) is an alkoxysilyl group, the curing delay after the storage stability test is excellent despite the excellent curability. It is hard to produce and there are few problems such as odor.
The curable resin composition according to the fifth invention has a very fast curing speed because the silicon-containing characteristic group of the polymer (A) contains a trialkoxysilyl group, but the curing delay after the storage stability test is long. Hard to occur.
The curable resin composition according to the sixth invention contains at least one urethane bond and / or substituted urea bond in the molecule of the polymer (A), and the molecular chain is substantially represented by the general formula (2 ) And / or (3), and the silicon-containing characteristic group is an alkoxysilyl group and contains a trialkoxysilyl group, so that the curing rate is very fast. It is difficult to cause a delay in curing after the stability test, and there are few problems such as odor and excellent adhesion to the adhesive substrate.

I. About the polymer (A) The polymer (A) suitably used in the present invention is a kind selected from the group consisting of a hydrolyzable silyl group and a silanol group represented by the above formula (1) in the molecule. The polymer (A) containing the silicon-containing characteristic group consisting of the above is included.
In the above formula (1), X represents a hydroxyl group or a hydrolyzable group. Specific examples of the hydrolyzable group include a halogen group, a hydride group, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, and an amide group. Aminooxy group, mercapto group, alkenyloxy group, and the like. Among these, an alkoxyl group is most preferable from the viewpoint of high reactivity and low odor.
As the polyoxyalkylene polymer serving as the main chain skeleton of the polymer (A) in the present invention, those produced by reacting a monoepoxide or the like with an initiator in the presence of a catalyst are preferable. As the initiator, a hydroxy compound having one or more hydroxyl groups can be used.
As the monoepoxide, ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, tetrahydrofuran, or the like can be used in combination.

Examples of the catalyst include, but are not limited to, alkali metal catalysts such as potassium compounds and cesium compounds, composite metal cyanide complex catalysts, and metal porphyrin catalysts. The complex metal cyanide complex catalyst is preferably a complex mainly composed of zinc hexacyanocobaltate, an ether and / or alcohol complex. The composition of the ether and / or alcohol complex essentially described in JP-B-46-27250 can be used. As the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) and the like are preferable, and glyme is particularly preferable from the viewpoint of handling during the production of the complex. As the alcohol, for example, those described in JP-A-4-145123 can be used, and tert-butanol is particularly preferable.
The raw material polyoxyalkylene polymer preferably has 2 or more functional groups, and specific examples include copolymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyhexylene, polyoxytetramethylene. It is done. Preferred raw material polyoxyalkylene polymers are di- to hexavalent polyoxypropylene polyols, particularly polyoxypropylene diol and polyoxypropylene triol. Furthermore, a polyoxyalkylene polymer containing an amino group or a mercapto group in the molecule can also be used.
The molecular weight of the main chain skeleton of the polymer (A) in the present invention is not particularly limited, but the number average molecular weight is preferably 500 to 100,000, more preferably 1,000 to 50,000, and 2,000 to 20,000. Is particularly preferred. Furthermore, the molecular weight of the polymer (A) into which the silicon-containing characteristic group is introduced by various chemical reactions is not particularly limited, but the number average molecular weight is preferably 500 to 150,000, more preferably 1,000 to 60,000, 2,000 to 20,000 is particularly preferred.

The polyol compound is a compound having a hydroxyl group in the molecule. The above polyol compounds are commercially available, and they can be used in the present invention. As a commercial item, Asahi Denka Kogyo Co., Ltd. product name; P-2000, P-3000, PR3007, PR5007, Asahi Glass Co., Ltd. product name; PML-3005, PML-3010, PML-3012, PML-4002, PML -4010, PML-S-4011, PML-S-4012, PML-S-1004, PML-5005 and other preminol series, manufactured by Sumika Bayer Urethane Co., Ltd. Trade names; Sumifen 3600, Sumifen 3700, SBU-Polyol 0319, etc., Takeda Mitsui Chemical brand name: P-28, P-21, etc. Daicel Chemical Industries brand name: PTMG-1000, PTMG-2000, PTMG-3000, etc., but are not limited thereto.
Moreover, the compound in which the hydroxyl group site | part of the said polyol compound is a primary amino group and / or a secondary amino group is marketed, and they can be used in this invention. As a commercial item, for example, as a polyoxyalkylene having a primary amino group and / or a secondary amino group in the molecule, trade names manufactured by Sun Techno Japan Co., Ltd .; Jeffamine C-346, D-200, D-230 , D-400, D-2000, D-4000, DU-700, ED-600, ED-900, ED-2001, ED-4000, ED-6000, EDR-148, T-403, T-3000, T -5000 etc. are mentioned, However, It is not limited to these.
Moreover, the polymer by which the terminal of the said polyol compound was alkenylated is obtained by the general etherification reaction of the said polyol compound and halogenated allyl compounds, such as allyl chloride. As a commercial item, Asahi Denka Kogyo Co., Ltd. brand name; SDX-1776, SDX-1777, etc. are mentioned, However, It is not limited to these.

  The method for introducing the silicon-containing characteristic group into the polymer (A) is not particularly limited. Specifically, for example, a method of adding a hydrosilane compound to a polymer having an alkenyl terminal (Japanese Patent Publication Nos. 45-36319, 46-12154, 49-32673, JP-A-50-156599, 51-73561, 54-6096, 55-82123, 55-123620, 55-125121, 55-131022, 55-135135, 55-137129, JP 46-12154, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Publication No. 2512468, Japanese Patent Application Laid-Open No. 64-22904, Japanese Patent Publication No. 2539445, etc.) Method of radically adding a mercaptosilane compound to a polymer (JP 55-137129 A), urethane prepolymer A method of introducing the above silicon-containing characteristic group with an aminosilane compound or the like (for example, Japanese Patent Application Laid-Open Nos. 11-100197, 2000-143757, 2000-169544, 2002-212415, No. 2004-123900, JP-A-2004-123901, Japanese Patent No. 3030020, Japanese Patent No. 3295663, Japanese Patent No. 3313360, Japanese Patent No. 3317353, Japanese Patent No. 3350011) In addition, the synthesis method described in Japanese Patent Application No. 2004-208672 is included.

  The specific manufacturing method of the polymer (A) containing the said silicon-containing characteristic group is not limited. Typical examples include, for example, a method of reacting a polyol compound (a) (a compound having a hydroxyl group in the molecule) with an isocyanate silane compound (b), a polyol compound (a) and a polyisocyanate compound (c) (molecule A method of reacting a terminal isocyanate type polymer obtained by reacting an isocyanate group-containing compound) with a silane compound (d) containing an amino group or a mercapto group (functional group that reacts with an isocyanate group) in the molecule, polyisocyanate Method of reacting an isocyanate group-containing silane compound and a polyol compound (a) obtained by reacting a compound with a silane compound (d) containing an amino group or a mercapto group (functional group that reacts with an isocyanate group) in the molecule, a polyol compound (A) in the molecule such as allyl isocyanate A compound having a vinyl group in the molecule by allowing the compound (e) having a group and an isocyanate group to act, followed by radical addition of a silane compound having a mercapto group in the molecule, having an epoxy group in the molecule A method of reacting the compound (f) with a silane compound (d) containing an amino group or a mercapto group (functional group that reacts with an isocyanate group) in the molecule; a polymerizable compound containing a reactive silyl group in the molecule ( General production methods such as a method of homopolymerizing g) or copolymerizing with other polymerizable compound (h) may be mentioned. Further, the polyol compound in the specific production method of the polymer (A) containing the silicon-containing characteristic group may be a compound having a primary amino group in the molecule or a compound having a mercapto group in the molecule. It can be synthesized similarly. Furthermore, since the specific manufacturing method of the polymer (A) containing the said silicon-containing characteristic group is described in detail in Japanese Patent Application No. 2004-362726, they can be referred to.

The synthesis conditions for the polymer (A) in the present invention are not particularly limited. Specifically, in the case of a nucleophilic addition reaction, the reaction may be performed at −20 ° C. to + 150 ° C. for about 1 hour to 1000 hours, and a reaction catalyst or a reaction solvent can be used in a timely manner. The reaction catalyst and reaction solvent are not particularly limited. Moreover, if it is a radical addition reaction, what is necessary is just to perform reaction for about 1 to 500 hours in the temperature range of 40-150 degreeC. This radical addition reaction is performed in the presence of a radical initiator.
Furthermore, this radical addition reaction is also possible by ultraviolet irradiation. Furthermore, a reaction catalyst can be used for this radical addition reaction. The radical initiator and the reaction solvent are not particularly limited. Moreover, if it is a polymerization reaction, a radical initiator and / or a chain transfer agent will be added as needed, and it will be made to react at 50-150 degreeC for about 1 hour to 12 hours. Moreover, a reaction solvent can be used.
The isocyanate silane compound (b) is a compound having an isocyanate group and the silicon-containing characteristic group in the molecule. Specific examples of the isocyanate silane compound (b) include, but are not limited to, isocyanate propyl trimethoxy silane, isocyanate propyl triethoxy silane, isocyanate propyl methyl dimethoxy silane, and isocyanate propyl methyl diethoxy silane. It is not a thing.
The polyisocyanate compound (c) is a polyisocyanate compound having at least two isocyanate groups in the molecule, and examples thereof include diisocyanate compounds, polyisocyanate compounds excluding diisocyanate compounds, and the like. Examples of the diisocyanate compound include aliphatic, alicyclic, araliphatic, and aromatic diisocyanate compounds. Specific examples thereof will be given below.

Aliphatic diisocyanate compounds: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2 4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, and the like.
Alicyclic diisocyanate compounds: 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl) Isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and the like. Aroaliphatic diisocyanate compounds: 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate) -1-methylethyl) benzene or a mixture thereof. Aromatic diisocyanate compounds: m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and the like.
Examples of the polyisocyanate compound excluding the diisocyanate compound include, but are not limited to, aliphatic, alicyclic, araliphatic, and aromatic polyisocyanate compounds.

Specific examples thereof will be given below.
Aliphatic polyisocyanate compounds: lysine ester triisocyanate, lysine diisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3, 6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane, and the like.
Alicyclic polyisocyanate compound: 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 3-isocyanate-3,3,5-trimethylcyclohexylisocyanate, 2- (3-isocyanatepropyl)- 2,5-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 5 -(2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3 -Isocyanatopropyl) -bicyclo [2,2,1] heptane, -(2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2- (3-isocyanatopropyl)- Bicyclo [2,2,1] heptane and the like.
Aro-aliphatic polyisocyanate compound: 1,3,5-triisocyanate methylbenzene and the like.
Aromatic polyisocyanate compounds: triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatotoluene, 4,4′-diphenylmethane-2, 2 ', 5,5'-tetraisocyanate, etc. Other polyisocyanate compounds: diisocyanates containing sulfur atoms such as phenyl diisothiocyanate.

  The silane compound (d) is a compound containing at least a primary amino group, a secondary amino group, or a mercapto group in the molecule, and further containing the silicon-containing characteristic group. Specific examples of the silane compound (d) include, as aminosilane compounds, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, amino Phenyltrimethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, 4-amino-3-dimethylbutylmethyl Diethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxy Silane, N-β (aminoe Til) -γ-aminopropylmethyldiethoxysilane, N-3- [amino (dipropyleneoxy)] aminopropyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (6-aminohexyl) amino Examples of mercaptosilane compounds such as propyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltri Examples thereof include, but are not limited to, ethoxysilane and γ-mercaptopropylmethyldiethoxysilane.

The compound (e) is a compound containing at least an alkenyl group in the molecule and an isocyanate group. Specific examples of the compound (e) include, but are not limited to, allyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, trade name manufactured by Nippon Cytec Industries, Inc .; m-TMI, and the like. is not.
Moreover, as a polymer (A) in this invention, what is marketed as a modified silicone resin can also be used. As a commercial item, Kaneka Chemical Industry make brand name; S203, S303, S810, SAT010, SAT030, SAT070, SAT200, SAT350, SAT400, S203, S810, S911, S943, EST200, EST250, ESX280, SAT070, SAX720, SAX725, SAX770, etc., trade names manufactured by Asahi Glass Co., Ltd .; ES-S2410, ES-S2420, ES-S3430, ES-S3630, and the like can be mentioned, but are not limited thereto.

II. About (meth) acrylic acid ester copolymer (B) As a manufacturing method of the (meth) acrylic acid ester copolymer (B) in this invention, it is well-known which performs a polymerization reaction using a (meth) acrylic acid ester monomer. It is a common method. Specifically, the radical initiator (II-1) and / or chain transfer agent (II-2) is added to the (meth) acrylic acid ester monomer as necessary, and the temperature is 50 to 150 ° C. for 1 hour to 12 hours. React to a certain extent. Moreover, reaction solvent (II-3) can be used. Furthermore, you may carry out in presence of the polymer (A) as described in this invention. The polymerization method is not particularly limited, and a known radical polymerization reaction, cation polymerization reaction, or anion polymerization reaction can be used, but a radical polymerization reaction is preferable because of the ease of the reaction. The polymerization reaction may be a living polymerization reaction or not a living polymerization reaction.
Examples of the (meth) acrylic acid alkyl ester monomer unit (b-1) having an alkyl group having 1 to 2 carbon atoms include methyl (meth) acrylate and ethyl (meth) acrylate.
As the (meth) acrylic acid alkyl ester monomer unit (b-2) having an alkyl group having 4 to 16 carbon atoms, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) T-butyl acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, etc. However, it is not limited to these.
The radical initiator (II-1) includes 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethyl). Valeronitrile), 2,2'-azobis (2-methyl-4-trimethoxysilylpentonitrile), 2,2'-azobis (2-methyl-4-methyldimethoxysilylpentonitrile), manufactured by Wako Pure Chemical Industries, Ltd. Product names: VA-046B, VA-057, VA-061, VA-085, VA-086, VA-096, V-601, V-65, VAm-110 and other azo compounds, benzoyl peroxide, t-alkyl Peroxides such as peroxyester, acetyl peroxide, diisopropyl peroxycarbonate are used, but are not limited thereto.

As chain transfer agent (II-2), n-butyl mercaptan, ethylthioglycolate, isopropyl mercaptan, t-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thiophenol, thio-β -Mercapto compounds such as naphthol, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-trimethoxysilylpropyl disulfide, aromatic hydrocarbon compounds such as benzene and toluene, disulfide compounds, silanes containing disulfide bonds Examples include, but are not limited to, coupling agents.
Examples of the reaction solvent (II-3) include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and cycloheptane, ethyl acetate, and butyl acetate. Ester compounds, carbonyl compounds such as acetone and methyl ethyl ketone, ether compounds such as diethyl ether and tetrahydrofuran, alcohol compounds such as methanol, ethanol, propanol and butanol, amide compounds such as dimethylformamide and diethylformamide, dimethyl sulfoxide, diethyl sulfoxide and the like Examples thereof include, but are not limited to, sulfoxide compounds.
In addition, as a method for introducing a silicon-containing characteristic group that can be crosslinked by forming a siloxane bond, a method of initiating polymerization with an initiator having a silicon-containing characteristic group that can be crosslinked by forming a siloxane bond, Silicone-containing properties simultaneously with polymerization by a method using a chain transfer agent having a silicon-containing characteristic group that can be cross-linked by forming, a method using a copolymerizable monomer having a silicon-containing characteristic group that can be cross-linked by forming a siloxane bond A method for introducing a group (for example, Japanese Patent Laid-Open Nos. 54-132192; Japanese Patent Laid-Open Nos. 57-172292; Japanese Patent Laid-open No.5-9-782220); JP, 60-2340
No. 5) or a method of synthesizing a vinyl polymer having an alkenyl group and then introducing an alkoxysilyl group by hydrosilylation (for example, Japanese Patent Laid-Open No. 5-4-40 893, Japanese Patent Laid-Open No. 1). 1-8 0 5 7 1) can be used, but the method is not limited to these.

Examples of chain transfer agents and copolymerizable monomers for introducing a silicon-containing characteristic group that can be crosslinked by forming a siloxane bond include mercaptomethyltrimethylsilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyl. Alkoxysilane having a functional group with high chain transfer such as dimethoxymethylsilane; N- (3-acryloyloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 3-acryloyloxypropyldimethylmethoxysilane, 3 -Acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropylmethylbis (trimethylsiloxy) silane, allyltriethoxysilane, allyl Limethoxysilane, 3-allylaminopropyltrimethoxysilane, 3-methacryloyloxypropyldimethylmethoxysilane, 3-methacryloyloxypropyldimethylethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropenyltrimethoxysilane, vinylmethyldiacetoxysilane, vinyltriacetoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, binletriisopropoxysilane, vinyltriphenoxysilane, vinyl Dimethylisopentenyloxysilane, vinyldimethyl-2-((2-ethoxyethoxy) ethoxy) silane, vinyltris (1-methylvinyloxy) silane, vinyltris (2-methoxyethoxy) silane, phenylvinyldiethoxysilane, diphenylvinylethoxy Examples include alkoxysilanes having polymerizable unsaturated groups such as silane, 6-triethoxysilyl-2-norbornene, octa-7-enyltrimethoxysilane, and styrylethyltrimethoxysilane, but are not limited thereto. It is not something.
The blending ratio of the (meth) acrylic acid ester copolymer (B) is preferably 10 to 1000 parts by mass, particularly preferably 20 to 500 parts by mass, per 100 parts by mass of the polymer (A).

III. Boron trifluoride and / or its complex (C) As boron trifluoride and / or its complex (C) in the present invention, in addition to boron trifluoride, a water complex such as boron trifluoride diwater complex, Alcohol complexes such as boron trifluoride methanol complex and boron trifluoride ethanol complex, boron trifluoride dimethyl ether complex, boron trifluoride diethyl ether complex, ether complexes such as boron trifluoride tetrahydrofuran complex, boron trifluoride ethylamine complex Boron trifluoride amine complexes such as boron trifluoride piperidine complex, boron trifluoride sulfide complex, boron trifluoride carbonyl complex and the like are used, but not limited thereto.
The blending ratio of the boron trifluoride and / or its complex (C) is preferably 0.001 to 10 parts by mass, particularly preferably 0.005 to 5 parts by mass per 100 parts by mass of the polymer (A). Part.

The curable resin composition according to the present invention includes, for example, an adhesive, a sealant, a paint, a coating agent, a sealant (for example, a sealant for covering a crack so that an injection agent does not leak in concrete crack repair), It is preferably used for applications such as casting materials and coating materials, but when used in these applications, it is further blended with a curing catalyst, silane coupling agent, filler, various additives, etc. according to the required performance. It is preferable.
As said curing catalyst which can be mix | blended with the curable resin composition which concerns on this invention, it is a curing catalyst other than boron trifluoride and / or its complex (C), and does not raise | generate transesterification easily. Specific examples of the curing catalyst include, as amines, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, trimethylamine, triethylamine, Aliphatic amines such as tributylamine and oleylamine; mensendiamine, isophoronediamine, norbornanediamine, piperidine, N, N'-dimethylpiperazine, N-aminoethylpiperazine, 1,2-diaminocyclohexane, bis (4-amino- 3-methylcyclohexyl) methane, bis (4-amino-methylcyclohexyl) methane, polycyclohexylpolyamine, 1,8-diazabicycle Alicyclic amines such as [5,4,0] undecene-7 (DBU); aromatic amines such as metaphenylenediamine and 4,4′-diaminodiphenylsulfone; m-xylylenediamine, benzyldimethylamine, Aliphatic aromatic amines such as 2- (dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol; 3,9-bis (3-aminopropyl) -2,4,8,10- Amines having an ether bond such as tetraoxaspiro [5,5] undecane (ATU), morpholine, N-methylmorpholine, polyoxypropylenediamine, polyoxypropylenetriamine, polyoxyethylenediamine; hydroxyls such as diethanolamine and triethanolamine Group-containing amines; dimer triamine to dimer acid Polyamides obtained by reacting polyamines such as benzene and diethylenetetramine, polyamide polyamides using polycarboxylic acids other than dimer acid; imidazoles such as 2-ethyl-4-methylimidazole; dicyandiamide, polyoxypropylene diamine Polyoxypropylene-based amines such as polyoxypropylene-based triamines; epoxy-modified amines obtained by reacting the above amines with epoxy compounds, Mannich-modified amines obtained by reacting the above amines with formalin and phenols, Michael Modified amines such as addition-modified amines and ketimines; 2,4,6-tris (dimethylaminomethyl) phenol compounds such as 2-ethylhexanoate, tetramethylammonium chloride, benzalkonium chloride Quaternary ammonium salts such as rholide, DABCO (registered trademark) series, DABCO BL series, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4] manufactured by Sankyo Aero Products .3.0] -5-nonene, 1,4-diazabicyclo [2.2.2] linear or cyclic tertiary amine salt containing a plurality of nitrogen atoms such as octane, the above compound (c), Product Name: Desmolapide DB, Desmolapid PP, Desmolapid PV, Desmolapid 10/9, Desmolapid LA, etc. Organic phosphoric acid compounds such as monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, monoethyl phosphate, diethyl phosphate Triethyl phosphate, di-n-butyl phosphate, mono-n-butyl phosphate, tri-n-butyl phosphate, triphenyl phosphate Etc. The, but not limited thereto.

Examples of the silane coupling agent that can be blended in the curable resin composition according to the present invention include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyl. Methyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyltrichlorosilane, etc. Vinylsilane compounds, bis (3-trimethoxysilylpropyl) tetrasulfane, bis (3-methyldimethoxysilylpropyl) tetrasulfane, bis (3-triethoxysilylpropyl) tetrasulfane, bis (3-methyldie) Toxisilylpropyl) tetrasulfane, bis (3-trimethoxysilylpropyl) disulfide, bis (3-methyldimethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-methyldiethoxysilylpropyl) ) Silane compound having sulfide bond such as disulfide, 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate silane, 1,3,5-N-tris (3-methyldimethoxysilylpropyl) isocyanate Isocyanurate silanes such as nurate silane, 1,3,5-N-tris (3-triethoxysilylpropyl) isocyanurate silane, 1,3,5-N-tris (3-methyldiethoxysilylpropyl) isocyanurate silane Compound, Compound (b) The above compound (d), the above compound (g), manufactured by Nippon Unicar Co., Ltd .; trade names; Y-5187, A-1310, A-1100, A-1102, A-1110, A-1120, A-1122, A-1170 A-9669, A-link15, Y-11637, A-189, AZ-6129, A-186, A-187, A-1160, A-151, A-171, A-172, A-2171, A -174, Y-9936, Z-6134, AZ-6167, A-162, A-163, AZ-6171, AZ-6177, A-137, A-153, A-1230, MAC-2101, FZ-3704 , A-1289, Y-11597, and the like, but are not limited thereto.
The blending ratio of the curing catalyst is preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass per 100 parts by mass of the polymer (A).
Although the said silane coupling agent may be used independently and may be used together 2 or more types, it is preferable to use the silane coupling agent which has an amino group at least. The blending ratio of the silane coupling agent is preferably 0.1 to 20 parts by weight, particularly preferably 1 to 10 parts by weight per 100 parts by weight of the polymer (A).

Examples of the filler that can be blended in the curable resin composition according to the present invention include calcium carbonate, various treated calcium carbonates, magnesium carbonate, organic polymer, clay, talc, silica, and fumed silica. Examples include various balloon systems such as glass balloons and plastic balloons, metal hydroxide systems such as aluminum hydroxide and magnesium hydroxide, and fibrillated fiber systems, but are not limited thereto.
Examples of the silica filler include, but are not limited to, hydrophilic silica powder, hydrophobic silica powder, fused silica glass powder, and the like. Among these, hydrophobic silica-based powder is particularly preferable.
Examples of the hydrophobic silica-based powder include silica-based powders such as fumed silica (fumed silica) and silica airgel, which are often used as thixotropic agents in adhesives and the like, and organic silicon compounds such as dimethyldioxide. Hydrophobic treated with chlorosilane, hexamethyldisilazane, dimethylsiloxane, trimethoxyoctylsilane, etc. can be used, but especially fumed silica treated with hexamethyldisilazane and silica aerogel with dimethylsiloxane and Those treated with hexamethyldisilazane are preferred.

The hydrophobizing treatment is performed by stirring the silica-based powder and the organosilicon compound at a high speed at a temperature of about 100 to 400 ° C. In order to make both contact uniformly, it is desirable to carry out in a medium such as an organic solvent. The mixing ratio of the silica-based powder and the organosilicon compound is usually 3 to 40 parts by weight per 100 parts by weight of the silica-based powder.
As the fused silica glass-based powder, those having a SiO ₂ content of 99.8% or more and extremely low impurities such as alkali metals are preferable. The fused silica glass powder may be used as it is, or may be used after surface treatment with a surface treatment agent. Examples of the surface treatment agent include organic titanate compounds, organic aluminum compounds, organic zirconium compounds, and alkoxysilanes. Examples of organic titanate compounds include tetrapropoxy titanium, tetrabutoxy titanium, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxy titanium, dipropoxy bis (acetylacetonato) titanium, titanium propoxyoctylene glycolate, titanium stearate, isopropyl Triisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridodecylphosphite) titanate, tetra (2,2-diallyloxy) Methyl-1-butyl) bis (ditridodecyl) phosphite titanate, bis (dioctylpyro) Sufeto) oxyacetate titanate, tris (dioctyl pyrophosphate) ethylene titanate, and the like. Examples of the organic aluminum compound include acetoalkoxyaluminum diisopropylate, and examples of the organic zirconium compound include zirconium butyrate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium lactate, and zirconium stearate butyrate. Alkoxysilanes include vinyltrimethoxysilane, vinyltriethoxysilane, bistris (β-methoxyethoxy) silane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl). ) -Γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (γ , Δ-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, hexamethyldisilazaza Include hexamethyldisiloxane or the like.

Examples of the organic polymer filler include polyester powder, polycarbonate powder, urethane resin powder, polymethylsilsesquioxane powder, acrylic resin powder, styrene resin powder, and vinyl chloride. Vinyl resin powder such as resin powder, SBR powder, chloroprene powder, rubber powder such as NBR powder, acrylic rubber powder, polyolefin powder such as polyethylene and polypropylene, silicone Examples thereof include, but are not limited to, system powders.
Examples of the fibrillated fiber filler include fibrillated aromatic polyamide fiber, polyester fiber, polyolefin fiber, polyacrylonitrile fiber and the like, and those having an average fiber length of about 0.1 to 5 mm are preferable. In addition, low fibrillated fibers having lower fibrillation than the fibrillated fibers can be used in combination with the fibrillated fibers. Low fibrillation means that there are few whisker-like branches per unit length of the trunk fiber. Examples of the low fibrillated fibers include fibrillated or non-fibrillated polyester fibers, polyolefin fibers, polyacrylonitrile fibers, sepiolite, glass fibers, carbon fibers, and the like.
The said filler may be used independently and may be used together 2 or more types. The filler preferably has a particle size of 10 nm to 200 μm, preferably 100 nm to 100 μm, particularly preferably 1.0 to 30 μm.
Further, the blending ratio of the filler is preferably 1 to 500 parts by weight, preferably 1 to 300 parts by weight, particularly preferably 1 to 200 parts per 100 parts by weight of the polymer (A). Parts by weight.

The various additives that can be blended in the curable resin composition according to the present invention include tackifiers (tackifiers), thixotropic agents, dehydrating agents, diluents, plasticizers, flame retardants, oligomers, anti-aging agents, Examples include, but are not limited to, ultraviolet absorbers, pigments, titanate coupling agents, aluminum coupling agents, drying oils such as tung oil, and curable compounds other than the polymer (A).
The blending ratio of the various additives is preferably 0.1 to 50 parts by mass, particularly preferably 0.5 to 20 parts by mass per 100 parts by mass of the polymer (A).
There is no limitation in particular as said tackifier, What can be normally used regardless of solid and a liquid at normal temperature can be used. Specific examples include phenolic resins, modified phenolic resins (for example, cashew oil-modified phenolic resin, tall oil-modified phenolic resin, etc.), terpene phenolic resin, xylene-phenolic resin, cyclopentadiene-phenolic resin, coumarone indene resin, rosin type resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, petroleum resins (e.g., C ₅ hydrocarbon resins, C ₉ hydrocarbon resins, C ₅ · C ₉ hydrocarbons Hydrogenated resin, etc.), hydrogenated petroleum resin, terpene resin, DCPD resin and the like. These may be used alone or in combination of two or more. Among the tackifying resins, terpene phenol resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, styrene copolymer resins, C ₉ hydrocarbon resins, hydrogenated petroleum resins, terpene resins, particularly phase It is preferable because it has good solubility and good adhesive properties. The blending ratio of the tackifying resin is preferably 2 to 70 parts by weight per 100 parts by weight of the polymer (A), and particularly preferably 5 to 20 parts by weight per 100 parts by weight of the polymer (A). .
Examples of the thixotropic agent include, but are not limited to, anhydrous silica, amide wax, fatty acid bisamide, hydrogenated castor oil, and the like.
Examples of the dehydrating agent include silane coupling agents such as calcium oxide, magnesium oxide, zinc oxide, calcium chloride, orthosilicate ester and vinyltrimethoxysilane, silicate compounds such as methyl silicate and ethyl silicate, activated carbon and zeolite. However, it is not limited to these.
The mixing ratio of the thixotropic agent is preferably 0.5 to 20 parts by mass, particularly preferably 1 to 10 parts by mass, per 100 parts by mass of the polymer (A).
The diluent can be suitably used without limitation as long as it has a diluting effect, but is preferably compatible with the polymer (A), and particularly preferably has a water content of 500 ppm. It is as follows. The blending ratio of the diluent is not particularly limited.

As the diluent, a reactive diluent containing a crosslinkable functional group such as a hydrolyzable silyl group, an epoxy group, or an isocyanate group in the molecule can be used. Their main chain skeletons are not particularly limited.
Furthermore, the said diluent which has a hydrolyzable silyl group in a molecule | numerator is marketed, and they can be used in this invention. As such a commercial item, Shin-Etsu Chemical Co., Ltd. product name: KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-217, KR-9218, KR-213, KR-510, X-40-9227, X-40-9247, X-41-1053, X-41-1056, X-40-1805, X-40-1810, X-40-2651, Examples thereof include, but are not limited to, X-40-2308 and X-40-9238.
Furthermore, as the diluent, a compound whose main chain is an acrylic polymer can be used. Such compounds are commercially available and can be used in the present invention. Commercially available compounds whose main chain is an acrylic polymer are trade names: XPR-15, 22, 39, 40, UP1000, 1010, 1020, 1021, 1061, 1070, 1080, 1110, UG-4010, manufactured by Toa Gosei Co., Ltd. Product name: UMB-1001, 2005, 2005B, 2005P, UME-1001, UMM-1001, 4005, UT-1001, 2001, 2001P, 3001, AS-300, 301, ASM-4001, CB-3060 , BGV-11, 12 and the like, but are not limited thereto.
The blending ratio of the diluent is preferably 0.1 to 50 parts by mass, particularly preferably 1 to 20 parts by mass per 100 parts by mass of the polymer (A).

Examples of the plasticizer include aromatic carboxylic acid esters such as dioctyl phthalate and dibutyl phthalate, aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate, brand name manufactured by LANXESS; alkyl sulfonic acid ester compounds such as mezamol , Ester compounds such as methyl oleate, methyl stearate, methyl laurate, soybean oil ester, polyalkylene glycol, polyalkylene glycol modified product, (meth) acrylic monomer polymer, terpene or terpene with low polymerization degree Examples include, but are not limited to, liquid tackifiers such as phenol copolymers, naphthenic, aromatic, paraffinic, and silicone oils.
The blending ratio of the plasticizer is preferably 1 to 50 parts by mass and particularly preferably 5 to 30 parts by mass per 100 parts by mass of the polymer (A).
Examples of the flame retardant include, but are not limited to, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, halogen flame retardants, and phosphorus flame retardants.
The blending ratio of the flame retardant is preferably 0.1 to 50 parts by mass, particularly preferably 1 to 20 parts by mass per 100 parts by mass of the polymer (A). Examples of the oligomer include polyethylene oligomer, liquid polypropylene, oligostyrene, liquid polychloroprene, liquid polyisoprene, liquid SBR, liquid NBR, liquid butyl rubber, liquid polyisobutylene, liquid polybutadiene, polyhydroxypolyolefin oligomer, α-methylstyrene oligomer, Examples thereof include, but are not limited to, phosphorus-containing styrene-α-methylstyrene oligomers and oligoester acrylates.

Examples of the anti-aging agent and the ultraviolet absorber include compounds having a primary amino group, secondary amino group, tertiary amino group, hydroxyl group, carboxyl group and / or mercapto group in the molecule. And those widely used as deterioration inhibitors for various resins.
Specific examples of the anti-aging agent and the ultraviolet absorber include triacetonediamine, poly [(6-morpholino-s-triazine-2,4-diyl) {2,2,6,6-tetramethyl-4- Piperidyl) imino} hexamethylene {2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, poly (2,2,4-trimethyl-1,2-dihydroquinoline) 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N, N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenyl Nylenediamine, N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine, mixed N, N′-diallyl-p-phenylenediamine, alkylated diphenylamine, 8-acetyl-3-dodecyl-7,7, 9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-triazine-2,4-diyl} {2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {2,2,6,6-tetramethyl-4-piperidyl) imino}] N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro − , 3,5-triazine condensate, diphenylguanidine, di-o-tolylguanidine, N-cyclohexylbenzothiazyl-sulfenamide, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxy Benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone trihydrate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfate trihydrate, 4- Dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy -4-Octoki Cibenzophenone, 2-hydroxy-4-octoxybenzophenone, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-t-butyl) Phenyl) benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-methyl) Phenyl) -2H-benzotriazole, 5-chloro-2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5) -Methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-t-butyl -2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole, 2- [2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimido-methyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) Benzotriazole, 2- (2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2 ', 4'-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, tris (3,5- Di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanate Nuric acid, ethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], tetrakis [methylene-3 (3 ′, 5′-di-tert-butyl-4′-hydroxy) Phenyl) propionate] methane, n-octadecyl-3 (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, triethylene glycol bis [3- (3-t-butyl-4-hydroxy) -5-methylphenyl) propionate], isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydride) Loxyphenyl) propionate], 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 2,2 ' -Butylidene-bis (4-ethyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-tert-butylphenol), 2,2'-methylene-bis [4-methyl-6 -T-butylphenol], 2,2'-methylene-bis (4-methyl-t-butylphenol), 2,2'-methylene-bis (4-ethyl-t-butylphenol), 6- (2-benzotriazolyl) ) -4-t-octyl-6'-t-butyl-4'-methyl-2,2'-methylenebisphenol, styrenated phenol, 2,6-di-t-butyl-4-methylphenol 2,4-dimethyl-6- (1-methylcyclohexyl) phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5 -(Octyloxy) phenol, 2,6-di-t-butyl-4-ethylphenol, 2- (2H-benzotriazol-2-yl) -4-menthyl-6- (3,4,5,6- Tetrahydrophthalimidylmethyl) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 2,5-di-t-butylhydroquinone , Poly (2,2,4-trimethyl-1,2-dihydroquinone), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinone, 2,5-di-t-amylhydroquinone, 4 , 4 ' Butylidene-bis (6-t-butyl-m-cresol), 2,2'-methylene-bis [6- (1-methylcyclohexyl) -p-cresol], 1- [2- {3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6 -Tetramethylpiperidine, S- (3,5-di-t-butyl-4-hydroxybenzyl) -2-ethyl-n-hexyl-thioglycolate, 4,4'-thiobis (6-t-butyl-m -Cresol), p-benzoquinonedioxime, 1,6-bis (4-benzoyl-3-hydroxyphenoxy) -hexane, 1,4-bis (4-benzoyl-3-hydroxyphenoxy) -butane, sa Phenyllithylate, 4-t-butylphenyl salicylate, 1,1,3-tris (2-methyl-t-butyl-4-hydroxy-5-t-butylphenyl) butane, 1,1-bis (4-hydroxy) Phenyl) cyclohexane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane, 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, dimethyl succinate -(2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, methyl-3- [3-t-butyl-5- (2H-benzotriazo) (Lu-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol, 3,4-dihydro-2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) ) -2H-benzopyran-6-ol (Irganox E201), Irganox E201, a mixture of glycerin and low density polyethylene, Irganox E201 and a mixture of stearic acid, bis (3,5-di-t-butyl- Ethyl 4-hydroxybenzylsulfonate) mixture of calcium and polyethylene wax, 2,4-bis [(octylthio) methyl] -o-cresol, N, N'-hexamethylenebis (3,5-di-t-butyl -4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzyl ester Phonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2- (3,5-di-tert-butyl) -4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), 2,3-bis [{3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionyl}] propionohydrazide, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5- Triazine, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, mercaptobenzothiazole, 2-mercaptobenzimidazole, manufactured by Sankyo Lifetech Co., Ltd. Product name: SANOL LS-765, SA LS-292, Sanol LS-944, Sanol LS-440, Sanol LS-770, Sanol LS-744, manufactured by Ciba Specialty Chemicals, Inc., trade names: Tinuvin 123, Tinuvin 292, Tinuvin 144, etc. However, it is not limited to these.
The blending ratio of the oligomer is preferably 0.1 to 50 parts by mass, particularly preferably 1 to 20 parts by mass per 100 parts by mass of the polymer (A).

In addition, the anti-aging agent and the ultraviolet absorber that can be used in the present invention include functional groups having reactivity with at least one isocyanate group in the molecule of the anti-aging agent and the ultraviolet absorber (for example, , A compound having a primary amino group, a secondary amino group, a hydroxyl group, a carboxyl group and a mercapto group) and a compound synthesized by the reaction of the compound (b) can also be used. When such a compound is used, the effects of aging prevention and ultraviolet absorption can be further improved.
The anti-aging agent and the ultraviolet absorber can be used alone or in combination of two or more. The blending ratio of the anti-aging agent and the ultraviolet absorber is preferably 0.001 to 10 parts by weight per 100 parts by weight of the polymer (A), preferably 0.01 to 5 parts by weight. Preferably it is 0.1-2 weight part.

[Synthesis Example 1] (Synthesis Example of Polymer (A))
To the reaction vessel, 179.3 g of 3-aminopropyltrimethoxysilane was added dropwise over 18 hours with stirring at 80 ° C. under a nitrogen atmosphere over 1 hour, and further reacted at 80 ° C. for 10 hours. Thereafter, a reaction product (SE-1) having a trimethoxysilyl group and a secondary amino group in the molecule was obtained by reacting at 50 ° C. for 7 days.
In another reaction vessel, 700 g of PML4010 (trade name, manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, number average molecular weight 10,000), 300 g of PR5007 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene-containing polyoxypropylene polyol) and 58.8 g of isophorone diisocyanate was added and reacted at 90 ° C. for 8 hours while stirring and mixing in a nitrogen atmosphere, to obtain a polyoxyalkylene resin (PB-1) having an isocyanate group in the molecule. Thereafter, 128.3 g of the reaction product (SE-1) was added, and the mixture was reacted at 90 ° C. for 2 hours while stirring and mixing in a nitrogen atmosphere, so that the main chain was polyoxyalkylene and trimethoxysilyl in the molecule. A curable resin (SB-1) having a group was obtained. The viscosity of the curable resin (SB-1) at 23 ° C. was 50000 mPa · s (BH viscometer).

[Synthesis Example 2] (Synthesis Example of Mixture of Polymer (A) and Copolymer (B))
In the mixing ratio (parts by weight) shown in Table 1, curable resin (SB-1) or S203 (trade name, polyoxyalkylene having a methyldimethoxysilyl group, manufactured by Kaneka Chemical Industry Co., Ltd.) is used as a reaction solvent, and as a polymerization monomer. A (meth) acrylic acid ester monomer and a mixed solution consisting of V-65 (trade name 2,2′-azobis (2,4-dimethylvaleronitrile) manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator is added dropwise over 1 hour. The mixture was reacted for 1 hour at 80 ° C. Further, a mixed solution of 1.0 part by weight of V-65 and 5.0 parts by weight of methyl ethyl ketone was added, and the mixture was reacted at 80 ° C. for 1 hour. Was synthesized.
However, MMA is methyl methacrylate, BA is butyl acrylate, 2EHA is 2-ethylhexyl acrylate, light ester ID (trade name, manufactured by Kyoeisha) is isodecyl methacrylate, light ester L-8 (trade name, manufactured by Kyoeisha) is C12 ~ A mixture of 15 alkyl methacrylates, KBM-503 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) is γ-methacryloxypropyltrimethoxysilane, and AZ-6129 (trade name, manufactured by Nihon Unicar) is γ-mercaptopropyltrimethoxysilane. It is.

(Examples 1-5 and Comparative Examples 1-5)
In the formulation shown in Table 2, MR-10G (trade name: Acrylic polymer powder manufactured by Soken Chemical Co., Ltd.), Silo Hovic 200 (manufactured by Fuji Silysia Chemical Co., Ltd.) as a filler for curable resins SA-1 to SA-6. Hydrophobic treated fine powder silica) and FTR-6100 (aromatic tackifier resin manufactured by Mitsui Chemicals) as a tackifier were mixed and dehydrated by heating for 1 hour. After completion of heating and dehydration, adhesion imparting agent KBM-903 (trade name γ-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), diluent Shellsol TK (trade name, hydrocarbon solvent manufactured by Shell Chemicals Japan) and curing catalyst Were mixed. The curing time (skinning time) after the storage stability test at 50 ° C. for 8 weeks was compared with the initial stage of production (at 50 ° C. for 1 day). The skinning time was determined as the time until the cured film stretched on the surface by finger touch was not transferred to the finger after leaving the curable resin composition in an atmosphere of 23 ° C. and 50% relative humidity. In the boron trifluoride-based catalyst, there was almost no delay in the curing time (skinning time) after the initial stage of production (standing at 50 ° C for 1 day) and after the storage stability test at 50 ° C for 8 weeks. With the system catalyst, the curing time after the stability test was remarkable at about 1.5 to 2 times the initial time.

  As is apparent from the above description, according to the present invention, it becomes possible to introduce a C4-16 (meth) acrylic acid alkyl ester monomer that significantly contributes to adhesiveness into the copolymer (B). As a result, it is possible to provide a curable resin composition having high adhesion, and thus can greatly contribute to the industry.

Claims (6)

100 parts by mass of an oxyalkylene polymer (A) having a silicon-containing characteristic group represented by the following formula (1) that can be crosslinked by forming a siloxane bond, and a silicon-containing characteristic that can be crosslinked by forming a siloxane bond A (meth) acrylic acid alkyl ester monomer unit having a group and a molecular chain substantially having (b-1) an alkyl group having 1 to 2 carbon atoms, and (b-2) 4 to 16 carbon atoms. 10 to 1000 parts by mass of a copolymer (B) composed of an alkyl (meth) acrylate monomer unit having an alkyl group, and boron trifluoride and / or its complex (C) 0.001 as a curing accelerator A curable resin composition containing 10 parts by mass.

X represents a hydroxyl group or a hydrolyzable group, R ¹ represents a substituted or unsubstituted organic group having 1 to 20 carbon atoms, and n represents 0, 1, or 2. The curable resin composition according to claim 1, wherein the molecular chain of the polymer (A) is substantially composed of a repeating unit represented by the following formula (2) and / or (3).

  The curable resin composition according to claim 1, wherein the polymer (A) contains one or more urethane bonds and / or substituted urea bonds in the molecule.   The curable resin composition according to any one of claims 1 to 3, wherein the silicon-containing characteristic group of the polymer (A) is an alkoxysilyl group.   The curable resin composition according to any one of claims 1 to 4, wherein at least one silicon-containing characteristic group of the polymer (A) contains a trialkoxysilyl group. The molecule of the polymer (A) contains one or more urethane bonds and / or substituted urea bonds, and the molecular chain is substantially composed of repeating units represented by the following formulas (2) and / or (3). The curable resin composition according to claim 1, wherein the silicon-containing characteristic group is an alkoxysilyl group and contains a trialkoxysilyl group.