JP7269066B2 - Moisture-curable resin composition and cured product - Google Patents

Description

The present invention relates to moisture-curable resin compositions and cured products.

Moisture-curable resin compositions are used for building sealants, adhesives, etc., because they cure at room temperature by moisture or the like to form rubber-like cured products.

Cured products of these moisture-curable resin compositions are required to have adhesion to adherends to which the moisture-curable resin compositions are applied, and to coated materials such as paints applied to the cured products. .

For example, Patent Document 1 discloses a moisture-curable adhesive composition having excellent adhesion to polyolefin (see Patent Document 1).

JP 2013-60589 A

However, conventional moisture-curable resin compositions still have room for improvement in terms of adhesion between the cured product and the coating film when coating is applied on the resulting cured product.

An object of one aspect of the present invention is to provide a moisture-curable resin composition and a cured product thereof that exhibit excellent adhesion between a cured product and a coating film when a coating is applied on the cured product.

The present inventors have made intensive studies to solve the above problems, and found that when a (meth)acrylic acid ester-based polymer having a group having a specific structure in a side chain is blended with a moisture-curable resin, curing The present inventors have independently discovered that excellent adhesion can be achieved between an object and a coating film, and have completed the present invention.

That is, one embodiment of the present invention includes the following configurations.

[1] A moisture-curable resin composition containing a moisture-curable resin (A) and a (meth)acrylic acid ester copolymer (B) having an aromatic ring in a side chain.

[2] The moisture-curable resin composition according to [1], which contains a plasticizer.

[3] The moisture-curable resin composition according to [1] or [2], wherein the (meth)acrylic acid ester-based copolymer (B) having an aromatic ring in a side chain is an adhesion imparting agent.

[4] The moisture-curable resin composition according to [2] or [3], wherein the plasticizer is a reactive plasticizer.

[5] The moisture-curable resin composition according to any one of [1] to [4], wherein the (meth)acrylic acid ester copolymer (B) having an aromatic ring in a side chain contains a reactive silyl group. thing.

[6] The moisture-curable resin (A) is an organic polymer having a reactive silyl group at the molecular chain end, a polysiloxane having a reactive silyl group at the molecular chain end, a urethane-based prepolymer having an isocyanate group, or , a combination of two or more of these, the moisture-curable resin composition according to any one of [1] to [5].

[7] The moisture-curable resin composition according to any one of [1] to [6], wherein the moisture-curable resin (A) is an organic polymer having a reactive silyl group at the molecular chain terminal.

[8] A cured product obtained by curing the moisture-curable resin composition according to any one of [1] to [7].

[9] A laminate obtained by applying a coating material on a cured product obtained by curing the moisture-curable resin composition according to any one of [1] to [7].

According to the moisture-curable resin composition containing a moisture-curable resin and a (meth)acrylic acid ester copolymer having an aromatic ring on a side chain, when a coating is applied on the resulting cured product, Adhesion between the cured product and the coating film can be improved.

An embodiment of the invention will be described below, but the invention is not limited thereto. The present invention is not limited to each configuration described below, and various modifications are possible within the scope of the claims. Further, embodiments or examples obtained by appropriately combining technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. In addition, all the scientific literatures and patent documents described in this specification are used as references in this specification. In addition, unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more (including A and greater than A) and B or less (including B and less than B)".

[1. (Meth)acrylic acid ester-based copolymer (B) having an aromatic ring in a side chain]
A moisture-curable resin composition according to one embodiment of the present invention comprises a moisture-curable resin (A) and a (meth)acrylic acid ester copolymer (B) having an aromatic ring in a side chain (hereinafter referred to as In the book, "(meth)acrylic acid ester copolymer (B) having an aromatic ring on the side chain" may be simply referred to as "(meth)acrylic acid ester copolymer (B)".) including. In this specification, for example, (meth)acrylic acid represents acrylic acid and/or methacrylic acid.

Here, "having an aromatic ring in a side chain" means that a group containing an aromatic ring is one of the repeating units constituting the main chain of the (meth)acrylic acid ester copolymer (B) at each end. is intended to be attached to repeating units other than one repeating unit.

It can be confirmed by NMR that the (meth)acrylic acid ester copolymer (B) has an aromatic ring in its side chain.

The “group containing an aromatic ring” is not particularly limited as long as it is a group containing an aromatic ring, and examples thereof include groups represented by the following general formula (1). The group represented by the following general formula (1) may be directly bonded to the main chain of the (meth)acrylic acid ester copolymer (B), or indirectly via another molecular chain. It may be attached to a chain.
-X-R ¹ -Y-R ² (1)
In general formula (1), X is -CO-O-, -O-CO-, -CO-N(R ³ )-, -O-CO-N(R ³ )-, -N(R ³ )- a bond selected from CO—O—, —N(R ³ )—CO—N(R ³ )—, —S—CO—NH—, —NH—CO—S—, —S—, and a direct bond and R ³ is a hydrogen atom, an optionally halogen-substituted cyclic, linear or branched alkyl group having 1 to 18 carbon atoms, an optionally halogen-substituted cyclic, linear or branched It is a chain alkenyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. Specific examples of R ³ include, for example, a hydrogen atom, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and an aralkyl group such as a benzyl group. . Among these, a hydrogen atom and a methyl group are particularly preferred.

The linking group X is more preferably -CO-O-, -O-CO-, or a direct bond in terms of ease of introduction to the side chain of the group containing the aromatic ring.

R ¹ is an optionally halogen-substituted cyclic, linear or branched C 1-18 alkylene group, an optionally halogen-substituted cyclic, linear or branched C 1 ~18 alkenylene group or a direct bond, R ¹ may be partially substituted with a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom in the main chain carbon atoms, and Y is a substituted or unsubstituted arylene group having 6 to 18 carbon atoms, wherein R ² is a hydrogen atom, a cyclic, linear or branched alkyl group having 1 to 18 carbon atoms which may be halogen-substituted, or It is an optionally halogen-substituted cyclic, linear or branched alkenyl group having 1 to 18 carbon atoms.

Specific examples of R ¹ include an alkylene group having 1 to 6 carbon atoms in which part of the carbon atoms are substituted with oxygen atoms. Specific examples of Y include a phenylene group and a naphthylene group. Specific examples of R ² include a hydrogen atom and a methyl group.

Among them, the group containing the aromatic ring preferably has at least one ether bond between the bonding group X and the aromatic ring, and more preferably the oxygen atom of the ether bond is bonded to the aromatic ring.

The (meth)acrylic acid ester copolymer (B) having the aromatic ring in the side chain is blended with the moisture-curable resin to improve adhesion between the moisture-curable resin composition or the obtained cured product and the coating film. can improve sexuality. That is, it can be said that the (meth)acrylic acid ester-based copolymer (B) having the aromatic ring in the side chain is an adhesion-imparting agent to be added to the moisture-curable resin.

[1.1. Main Chain Structure of (Meth)Acrylic Acid Ester-Based Copolymer (B)]
The (meth)acrylic acid ester copolymer (B) includes, for example, an aromatic ring-containing (meth)acrylic acid ester monomer and an aromatic ring-free (meth)acrylic acid It can be produced by copolymerizing with an ester-based monomer.

The copolymer thus obtained contains repeating units derived from the (meth)acrylic ester containing an aromatic ring and repeating units derived from the (meth)acrylic ester containing no aromatic ring. Then, the (meth)acrylic acid ester-based copolymer (B) has the aromatic ring in the side chain of the repeating unit derived from the (meth)acrylic acid ester containing the aromatic ring.

The aromatic ring-containing (meth)acrylic acid ester-based monomer constituting the (meth)acrylic acid ester-based copolymer (B) is not particularly limited, and various monomers can be used. For example, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethylene glycol (meth) acrylates, hydroxyethylated o-phenylphenol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, and phenylthioethyl (meth)acrylate and the like, with phenoxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl acrylate being more preferred. These monomers may be used alone or may be copolymerized.

The aromatic-ring-free (meth)acrylic acid ester-based monomer constituting the main chain of the (meth)acrylic acid ester-based copolymer (B) is not particularly limited, and various types can be used. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate , (meth)acrylic acid esters in which the alcohol component constituting the ester such as tert-butyl (meth)acrylate is a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms; (meth)acrylic acid n- The alcohol component constituting the ester of pentyl, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, etc. is linear, branched or cyclic and has 5 to 7 carbon atoms. (Meth)acrylate esters of alkyl groups; n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, ( (meth)acrylic acid esters in which the alcohol component constituting the ester such as stearyl methacrylate has a linear, branched or cyclic alkyl group having 8 or more carbon atoms; and the like. These monomers may be used alone or may be copolymerized.

Alternatively, the (meth)acrylic acid ester-based monomer containing no aromatic ring, which constitutes the main chain of the (meth)acrylic acid ester-based copolymer (B), is (meth)acrylic acid (3-trimethoxysilylpropyl ), (meth) acrylate (3-(dimethoxymethylsilyl) propyl), (meth) acrylate (2-trimethoxysilylethyl), (meth) acrylate (2-(dimethoxymethylsilyl) ethyl), (meth) ) trimethoxysilylmethyl acrylate, triethoxysilylmethyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene oxide adduct of (meth)acrylic acid, 2,2,2-trifluoroethyl (meth)acrylate, (meth)acrylic 3,3,3-trifluoropropyl acid, 3,3,4,4,4-pentafluorobutyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, (meth) ) trifluoromethyl acrylate, perfluoroethyl (meth)acrylate, bis(trifluoromethyl)methyl (meth)acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate, (meth) 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, chloroethyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, and the like may also be used. These monomers may be used alone or may be copolymerized. In addition, non-esterified methacrylic acid and acrylic acid can also be used as monomers constituting the polymer (B).

The (meth)acrylate copolymer (B) contains 50.0 to 99.5 parts by weight (more preferably 65.5 parts by weight) of repeating units derived from the aromatic ring-free (meth)acrylate monomer. 0 to 99.2 parts by weight, more preferably 80.0 to 99.0 parts by weight), and repeating units derived from the (meth) acrylic acid ester monomer containing the aromatic ring 0.5 to 50.0 parts by weight (more preferably 0.8 to 35.0 parts by weight, still more preferably 1.0 to 20.0 parts by weight). As a result, when a paint is applied on the resulting cured product, the adhesiveness between the cured product and the coating film can be excellent.

In other words, the (meth)acrylic acid ester-based monomer containing the aromatic ring is preferably 0.5% by weight or more in 100% by weight of the total monomers constituting the (meth)acrylic acid ester-based copolymer (B). , More preferably 0.8% by weight or more, particularly preferably 1.0% by weight or more, preferably less than 50.0% by weight, more preferably 35.0% by weight or less, particularly preferably 20.0% by weight It is below.

Further, the total amount of (meth)acrylic acid alkyl ester-based monomer is preferably 0.5 to 200-fold mol, more preferably 1 to 100-fold mol, relative to the total amount of (meth)acrylic acid ester containing an aromatic ring. It is preferably 2 to 50 times the molar amount.

The (meth)acrylate copolymer (B) may be obtained by copolymerizing the following vinyl monomers together with the (meth)acrylate monomers described above. When the vinyl monomer contains an aromatic ring, the (meth)acrylic acid ester-based copolymer (B) has an aromatic ring in the side chain of the repeating unit derived from the vinyl monomer containing the aromatic ring. become. Vinyl monomers containing such aromatic rings include styrene-based monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; vinyl esters such as vinyl benzoate and vinyl cinnamate; -Acrylamides such as phenylacrylamide and N-benzylacrylamide. Examples of aromatic ring-free vinyl monomers include fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride; , maleic acid, mono- and dialkyl esters of maleic acid; fumaric acid, mono- and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, Maleimide monomers such as stearyl maleimide, phenyl maleimide, cyclohexyl maleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, pivalic acid vinyl esters such as vinyl; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride and allyl alcohol; These monomers may be used alone or may be copolymerized.

The proportion of the vinyl monomer used is preferably 50% by weight or less, more preferably 40% by weight or less, and particularly preferably 30% by weight, based on 100% by weight of the total monomers constituting the (meth)acrylic acid ester copolymer (B). % by weight or less. When the proportion of the vinyl monomer used is 50% by weight or less in 100% by weight of the total monomers, the (meth)acrylic acid ester copolymer (B) is excellent in its effect as an adhesion imparting agent, which is preferable.

When the (meth)acrylic acid ester-based copolymer (B) is obtained by copolymerizing the vinyl monomer together with the (meth)acrylic acid ester-based monomer described above, the (meth)acrylic acid ester-based copolymer containing the aromatic ring The total amount of the acid ester-based monomer and the aromatic ring-containing vinyl monomer used is preferably 0.5% by weight in 100% by weight of the total monomers constituting the (meth)acrylic acid ester-based copolymer (B). % or more, more preferably 0.8 wt% or more, particularly preferably 1.0 wt% or more, preferably less than 50.0 wt%, more preferably 35.0 wt% or less, particularly preferably 20.0 wt% % by weight or less.

When the moisture-curable resin composition according to one embodiment of the present invention contains a plasticizer, from the viewpoint of suppressing the migration (bleed) of the plasticizer to the surrounding substrate on which the moisture-curable resin composition is applied More preferably, the (meth)acrylate copolymer (B) contains a reactive silyl group. Here, the reactive silyl group includes reactive silyl groups similar to the reactive silyl groups contained in the moisture-curable resin (A) described below.

When the (meth)acrylic ester-based copolymer (B) contains a reactive silyl group, the reactive silyl group is present at the end of the main chain of the (meth)acrylic ester-based copolymer (B). may be at the end of the side chain, or at both. Here, the presence of a reactive silyl group at the end of the main chain means that one repeating unit at each end of the repeating units constituting the main chain of the (meth)acrylic acid ester-based copolymer (B) has a reactive silyl group attached directly or indirectly to at least one of In addition, having a reactive silyl group at the end of a side chain means that, of the repeating units constituting the main chain, a reactive silyl group is is intended to be directly or indirectly connected to

The reactive silyl groups contained in the (meth)acrylate copolymer (B) are preferably 0.1 to 3.0, more preferably 0.2 on average per molecule of the polymer. to 2.5, more preferably 0.3 to 1.5. If the number of reactive silyl groups contained in the molecule is 0.1 or more, it is preferable from the viewpoint of suppressing the migration (bleed) of the plasticizer to the peripheral substrate to which the moisture-curable resin composition is applied. . Moreover, if it is 3.0 or less, it is preferable in terms of elongation properties.

[1.2. Method for producing (meth)acrylic ester-based copolymer (B)]
The method for synthesizing the (meth)acrylic acid ester copolymer (B) is not particularly limited, and includes known methods. Specifically, a free radical polymerization method can be used. As a free radical polymerization method, a polymerization initiator, a chain transfer agent, a solvent, etc. are added, and a solution polymerization method in which polymerization is performed at 50 to 150 ° C., an acrylic acid alkyl ester monomer described in JP-A-2001-207157. is synthesized at high temperature and high pressure, and the like.

Examples of the polymerization initiator include 2,2′-azobis(2-methylbutyronitrile), dimethyl 2,2′-azobis(2-methylpropionate), 2,2′-azobis(2,4 -dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis[N-(2-propenyl)-2-methylpropionamide], 1, Azo compounds such as 1'-azobis (cyclohexane-1-carbonitrile); benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, di ( 3,5,5-trimethylhexanoyl) peroxide; diisopropyl purge carbonate, di-sec-butyl purge carbonate, di-2-ethylhexyl purge carbonate, di-1-methylheptyl purge carbonate, di-3- Peroxydicarbonates such as methoxybutyl purged carbonate and dicyclohexyl purged carbonate; tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butyl perpi Peroxyesters such as barate, tert-butyl diperadipate, cumyl perneodecanoate; ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide; di-tert-butyl peroxide, dicumyl peroxide, tert -butylcumyl peroxide, dialkyl peroxides such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane; hydroperoxides such as cumene hydroxyl peroxide and tert-butyl hydroperoxide and peroxides such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane. These polymerization initiators may be used alone or in combination of two or more.

Examples of the chain transfer agent include mercapto group-containing compounds such as n-dodecylmercaptan, tert-dodecylmercaptan, and laurylmercaptan. Further, when it is desired to introduce a reactive silyl group to the molecular chain end of the (meth)acrylic acid ester copolymer, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxy silane, (mercaptomethyl)dimethoxymethylsilane, and the like. These may be used alone or in combination of two or more. Since chain transfer agents may adversely affect weather resistance, the amount used is preferably 2% or less of the total amount of monomers, and is particularly preferably not used.

Examples of solvents include aromatic compounds such as toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-ethylhexyl phthalate, and di-n-butyl phthalate; hexane, heptane, octane, cyclohexane, methylcyclohexane, and the like. Carboxylic acid ester compounds such as butyl acetate, n-propyl acetate and isopropyl acetate; Ketone compounds such as methyl isobutyl ketone and methyl ethyl ketone; Dialkyl carbonate compounds such as dimethyl carbonate and diethyl carbonate; 1-propanol and 2-propanol , 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, and amyl alcohol. Among these, at least one selected from dialkyl carbonate compounds and alcohol compounds is preferable because it is not a substance for which the Ministry of Health, Labor and Welfare has set a guideline value, and in terms of odor and environmental load. Furthermore, boiling point, GEV (Gemeinschaft Emission Contrierte Feligewerkstoffe A.V.) determined by GEV Specification and Classification Criteria February 14, 2001 by the measurement method described Dimethyl carbonate, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, and tert-butyl alcohol are more preferred because they can suppress the emission of all volatile organic compounds from the composition. Preferred are 2-propanol and isobutyl alcohol.

[1.3. (Meth) Molecular Weight of Acrylic Ester-Based Copolymer (B)]
The weight average molecular weight of the (meth)acrylic acid ester copolymer (B) in one embodiment of the present invention is preferably 1,000 to 100,000 in terms of polystyrene in GPC, more preferably 1,500 to 70,000, more preferably 2,000 to 50,000. When the weight average molecular weight of the (meth)acrylic acid ester copolymer (B) exceeds 100,000, the compatibility with the moisture-curable resin (A) is lowered, and workability is lowered due to high viscosity. may cause The (meth)acrylate copolymer (B) preferably has a number average molecular weight of 500 to 50,000, more preferably 800 to 35,000, still more preferably 1,000 to 25, 000.

Although the molecular weight distribution (Mw/Mn) of the (meth)acrylic acid ester copolymer (B) according to one embodiment of the present invention is not particularly limited, it is preferably less than 4.0, more preferably 3.8 or less, 3.5 or less is particularly preferred. Although the lower limit is not particularly limited, it is preferably 1 or more, and may be 1.9 or more.

[2. Moisture Curing Resin (A)]
The moisture-curable resin (A) used in the moisture-curable resin composition according to one embodiment of the present invention includes, for example, an organic polymer having a reactive silyl group at the molecular chain end, and a reactive silyl group at the molecular chain end. group-containing polysiloxane, an isocyanate group-containing urethane-based prepolymer, or a combination of one or more of these.

[2.1. Organic polymer having a reactive silyl group at the molecular chain end]
Hereinafter, an organic polymer having a reactive silyl group at the molecular chain end (hereinafter referred to as "reactive silyl group-containing organic polymer ) will be explained.

(reactive silyl group)
The reactive silyl group of the reactive silyl group-containing organic polymer has the general formula (2):
—SiR ⁴ _3-a X _a (2)
(R ⁴ is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or —OSiR′ ₃ ( Each R′ is independently a hydrocarbon group having 1 to 20 carbon atoms, and each X is independently a hydroxy group or a hydrolyzable group. a is an integer of 1 to 3).

The hydrolyzable group is not particularly limited, and specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, and an acid amide group. groups, aminooxy groups, mercapto groups, and the like. Among these, halogens, alkoxy groups, alkenyloxy groups, and acyloxy groups are more preferred due to their high activity. Further, an alkoxy group such as a methoxy group or an ethoxy group is more preferable, and a methoxy group or an ethoxy group is particularly preferable, since they are moderately hydrolyzable and easy to handle. An ethoxy group and an isopropenoxy group are preferable from the viewpoint of safety because the compounds that are eliminated by the reaction are ethanol and acetone, respectively.

The hydrolyzable groups and hydroxy groups can be bonded to one silicon atom in the range of 1 to 3. When two or more hydrolyzable groups or hydroxy groups are bonded to a reactive silyl group, they may be the same or different.

In the general formula (2), a is more preferably 2 or 3 from the viewpoint of curability, and is preferably 3 when particularly fast curability is desired, and when stability during storage is desired. is preferably 2.

Specific examples of R ⁴ in the general formula (2) include alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, aralkyl groups such as benzyl group, and , trimethylsiloxy group, chloromethyl group, methoxymethyl group and the like. Among these, a methyl group is particularly preferred.

More specific examples of reactive silyl groups include trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, diisopropoxymethylsilyl, tris(2 -propenyloxy)silyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, and (ethoxymethyl)dimethoxysilyl group. A trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable, and a dimethoxymethylsilyl group is particularly preferable, since they are versatile and have high activity and good curability. From the viewpoint of storage stability, a dimethoxymethylsilyl group and a triethoxysilyl group are particularly preferred. A chloromethyldimethoxysilyl group and a methoxymethyldimethoxysilyl group are preferred because they exhibit particularly high curability. A cured product obtained from an organic polymer having a trifunctional silyl group such as a trimethoxysilyl group or a triethoxysilyl group tends to have high restorability, which is preferable.

(Introduction of reactive silyl group)
Introduction of a reactive silyl group may be performed by a known method. That is, for example, the following methods are mentioned.

(I) Hydrosilylation: First, an unsaturated bond is introduced into a polymer that is a raw material for a reactive silyl group-containing organic polymer (hereinafter sometimes referred to as a “precursor polymer” in this specification), and the unsaturated bond is This is a method of adding a hydrosilane compound to a saturated bond by a hydrosilylation reaction. Any method can be used to introduce an unsaturated bond. For example, a precursor polymer having a functional group such as a hydroxyl group is reacted with a compound having a group reactive with the functional group and an unsaturated group. , a method of obtaining an unsaturated group-containing polymer, and a method of copolymerizing a polymerizable monomer having an unsaturated bond.

(II) Reaction of a reactive group-containing polymer (precursor polymer) with a silane coupling agent: a precursor polymer having a reactive group such as a hydroxyl group, an amino group, or an unsaturated bond reacts with the reactive group. A method of reacting a compound (also called a silane coupling agent) having both a group capable of forming a bond with a compound and a reactive silyl group. Combinations of the reactive group of the precursor polymer and the reactive group of the silane coupling agent include hydroxyl group and isocyanate group, hydroxyl group and epoxy group, amino group and isocyanate group, amino group and thioisocyanate group, amino group and epoxy group, Examples include, but are not limited to, Michael addition between an amino group and an acrylic structure, a carboxylic acid group and an epoxy group, an unsaturated bond and a mercapto group, and the like.

The method (I) is preferable because the reaction is simple, the introduction amount of the reactive silyl group can be easily adjusted, and the physical properties of the resulting reactive silyl group-containing polymer are stable. The method (II) is preferable because it has many reaction options and it is easy to increase the rate of introduction of reactive silyl groups.

Specific examples of the hydrosilane compound used in method (I) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and phenyldichlorosilane; trimethoxysilane, triethoxysilane and methyldiethoxysilane. , methyldimethoxysilane, phenyldimethoxysilane, (chloromethyl)dimethoxysilane, (methoxymethyl)dimethoxysilane, 1-[2-(trimethoxysilyl)ethyl]-1,1,3,3-tetramethyldisiloxane, tris Alkoxysilanes such as (2-propenyloxy)silane; Acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane; Bis(dimethylketoximate)methylsilane, Bis(cyclohexylketoximate)methylsilane; Examples include, but are not limited to, ketoximate silanes. Among these, halogenated silanes and alkoxysilanes are preferred in terms of availability. Alkoxysilanes are preferred because they are moderately hydrolyzable and easy to handle.

Silane coupling agents that can be used in method (II) include the following compounds. By way of example, mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, which react with unsaturated bonds; 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyltrimethoxy, which react with hydroxyl groups. isocyanate silanes such as silanes; epoxy silanes such as 3-glycidoxypropylmethyldimethoxysilane and 3-glycidoxypropyltrimethoxysilane that react with hydroxyl groups, amino groups and carboxylic acid groups; isocyanate groups, thioisocyanate groups and aminosilanes such as 3-aminopropylmethyldimethoxysilane and 3-aminopropylmethyltrimethoxysilane; hydroxyalkylsilanes and the like. The aforementioned silane coupling agent is an example, and similar reactions can be used or applied to introduce silyl groups.

The number of reactive silyl groups contained in the reactive silyl group-containing organic polymer is, on average, at least 0.5 or more, preferably 1 to 5, more preferably 1.3 to 4 per molecule of the polymer. , More preferably 1.4 to 3.5, still more preferably 1.5 to 3, preferably 2 to 5, especially from the viewpoint of high elongation and high strength, 2 to 4 is more preferred, and 2 to 3.5 is even more preferred. When the average number of reactive silyl groups contained in the molecule is less than 0.5, the curability tends to be insufficient, making it difficult to develop good rubber elastic behavior. When the number of reactive silyl groups contained in the molecule exceeds 5 on average, the cured product tends to be hard and the elongation properties tend to deteriorate.

A reactive silyl group-containing organic polymer has a reactive silyl group at the molecular chain end. That is, the reactive silyl group may be at the terminal of the main chain of the reactive silyl group-containing organic polymer, at the terminal of the side chain, or at both. Here, the reactive silyl group at the end of the main chain means that at least one of the repeating units at both ends of the repeating units constituting the main chain of the reactive silyl group-containing organic polymer , is intended to be directly or indirectly attached to the reactive silyl group. In addition, having a reactive silyl group at the end of a side chain means that, of the repeating units constituting the main chain, a reactive silyl group is is intended to be directly or indirectly connected to The reactive silyl group-containing organic polymer is a reactive silyl group-containing organic polymer having one or more reactive silyl groups only at at least one terminal of the main chain of the reactive silyl group-containing organic polymer, or , a reactive silyl group-containing organic polymer having one or more reactive silyl groups only on at least one of the terminals of the main chain of the reactive silyl group-containing organic polymer and only on side chains bonded to repeating units in the vicinity thereof It can be used preferably. In particular, when the reactive silyl group is present only at the terminal of the main chain of the reactive silyl group-containing organic polymer, or only at the terminal of the main chain and the side chain in the vicinity thereof, it is contained in the finally formed cured product. Since the effective network length of the organic polymer component to be incorporated becomes long, it becomes easy to obtain a rubber-like cured product exhibiting high strength and high elongation, which is preferable.

(Reactive silyl group-containing organic polymer)
The number average molecular weight of the reactive silyl group-containing organic polymer is about 800 to 50,000, more preferably 1,000 to 40,000, particularly preferably 1,500 to 30,000 in terms of polystyrene in GPC. Yes, more preferably 2,000 to 30,000. When the number-average molecular weight of the reactive silyl group-containing organic polymer is small, the amount of reactive silyl groups introduced increases, which may be disadvantageous in terms of production cost. On the other hand, when the number average molecular weight is large, the viscosity tends to be high, which tends to be inconvenient in terms of workability. When the reactive silyl group-containing organic polymer is a polyoxyalkylene polymer, its number average molecular weight is about 800 to 50,000, more preferably 1,000 to 40,000 in terms of polystyrene in GPC. , particularly preferably 1,500 to 30,000, more preferably 2,000 to 30,000, and most preferably 9,000 to 30,000.

The molecular weight distribution (Mw/Mn) of the reactive silyl group-containing organic polymer is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, further preferably 1.5 or less, 1.4 or less is particularly preferred. Although the lower limit is not particularly limited, it is preferably 1 or more, and may be 1.05 or more.

The main chain skeleton of the reactive silyl group-containing organic polymer is not particularly limited, and those having various main chain skeletons can be used.

Specifically, polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Coalescence: Ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, etc., copolymer of polychloroprene, polyisoprene, isoprene or butadiene with acrylonitrile and/or styrene, polybutadiene, isoprene or butadiene Hydrocarbon polymers such as copolymers of acrylonitrile and styrene, etc., hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; Condensation of dibasic acids such as adipic acid and glycol , or polyester polymers obtained by ring-opening polymerization of lactones; (meth) acrylic ester polymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; ) Vinyl polymers obtained by radical polymerization of monomers such as acrylic acid ester monomers, vinyl acetate, acrylonitrile, and styrene; Graft polymers obtained by polymerizing vinyl monomers in the above organic polymers; Polysulfide polymers Nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6.10 by condensation polymerization of hexamethylenediamine and sebacic acid, condensation polymerization of ε-aminoundecanoic acid nylon 11 by ring-opening polymerization of ε-aminolaurolactam, nylon 12 by ring-opening polymerization of ε-aminolaurolactam, polyamide-based polymers such as copolymer nylon having two or more components among the above nylons; Examples include polycarbonate-based polymers and diallyl phthalate-based polymers to be produced.

Saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth)acrylic acid ester polymers have relatively low glass transition temperatures, and the resulting cured products is more preferable because it has excellent cold resistance.

The glass transition temperature of the organic polymer (B) is not particularly limited, but is preferably 20° C. or lower, more preferably 0° C. or lower, and particularly preferably −20° C. or lower. . If the glass transition temperature is higher than 20°C, the viscosity in winter or in cold climates may increase, resulting in poor workability, and the cured product may have reduced flexibility and elongation. The glass transition temperature can be determined by DSC measurement.

Organic polymers such as saturated hydrocarbon polymers, polyoxyalkylene polymers, and (meth)acrylic acid ester polymers, when used as base polymers for adhesives and sealants, do not form adhesive groups with low molecular weight components. It is preferable because there is little contamination due to transfer to the material.

In addition, polyoxyalkylene-based polymers and (meth)acrylic acid ester-based polymers are particularly preferable because they have high moisture permeability and excellent deep-part curability when made into a one-component composition, and are also excellent in adhesiveness. Polyoxyalkylene-based polymers are most preferred. Among polyoxyalkylene-based polymers, polyoxypropylene-based polymers are particularly preferred.

(Polyoxyalkylene polymer)
The polyoxyalkylene-based polymer is essentially represented by general formula (3):
-R ⁵ -O- (3)
(R ⁵ is a linear or branched alkylene group having 1 to 14 carbon atoms) is a polymer having a repeating unit represented by general formula (3) in all repeating units of the polymer. It is preferred that 50% by weight or more of the repeating units be present. R ⁵ in general formula (3) is a linear or branched alkylene group having 1 to 14 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by formula (3) include -CH ₂ O-, -CH ₂ CH ₂ O-, -CH ₂ CH ₂ CH ₂ O-, and -CH ₂ CH(CH ₃ )O- , -CH ₂ CH(C ₂ H ₅ )O-, -CH ₂ C(CH ₃ ) ₂ O-, -CH ₂ CH ₂ CH ₂ CH ₂ O-, and the like. The main chain skeleton of the polyoxyalkylene polymer may consist of one type of repeating unit, or may consist of two or more types of repeating units. Especially when it is used as a sealant or the like, a polymer containing a propylene oxide polymer as a main component is preferable because it is amorphous and has a relatively low viscosity.

Methods for synthesizing polyoxyalkylene polymers include, for example, a polymerization method using an alkali catalyst such as KOH, and a complex obtained by reacting an organoaluminum compound with porphyrin disclosed in JP-A-61-215623. Polymerization using a transition metal compound-porphyrin complex catalyst, JP-B-46-27250, JP-B-59-15336, US Pat. No. 3,278,457, US Pat. A polymerization method using a double metal cyanide complex catalyst as exemplified in US Pat. A polymerization method using a catalyst composed of a compound may be mentioned, but it is not particularly limited.

Methods for producing polyoxyalkylene polymers having reactive silyl groups are disclosed in JP-B-45-36319, JP-B-46-12154, JP-A-50-156599, JP-A-54-6096, JP-A-55-13767, Nos. 55-13468, 57-164123, JP-B-3-2450, US Pat. No. 3,632,557, US Pat. No. 4,345,053, US Pat. -197631, 61-215622, 61-215623, 61-218632, JP-A-3-72527, JP-A-3-47825, JP-A-8-231707 proposed Polyoxyalkylene polymers having a number average molecular weight of 6,000 or more and a Mw/Mn of 1.6 or less and having a narrow molecular weight distribution can be exemplified, but are not particularly limited to these.

The polyoxyalkylene polymer having a reactive silyl group may be used alone or in combination of two or more.

(Saturated hydrocarbon polymer)
The saturated hydrocarbon-based polymer is a polymer that does not substantially contain carbon-carbon unsaturated bonds other than aromatic rings, and the polymer that forms the skeleton is (1) ethylene, propylene, 1-butene, isobutylene, etc. or (2) homopolymerization of a diene compound such as butadiene or isoprene, or copolymerization with the olefin compound. After that, it can be obtained by a method such as hydrogenation. Isobutylene-based polymers and hydrogenated polybutadiene-based polymers are preferable because it is easy to introduce functional groups to their terminals, the molecular weight can be easily controlled, and the number of terminal functional groups can be increased, and isobutylene-based polymers are particularly preferred. preferable.

Those whose main chain skeleton is a saturated hydrocarbon polymer are characterized by excellent heat resistance, weather resistance, durability, and moisture barrier properties.

The isobutylene-based polymer may have all monomer units formed from isobutylene units, or may be a copolymer with other monomers, but from the standpoint of rubber properties, it should contain at least 50% by weight of repeating units derived from isobutylene. more preferably 80% by weight or more, and particularly preferably 90% to 99% by weight.

Various polymerization methods have hitherto been reported as methods for synthesizing saturated hydrocarbon-based polymers, and in recent years in particular, many so-called living polymerization methods have been developed. In the case of saturated hydrocarbon-based polymers, particularly isobutylene-based polymers, the inifer polymerization found by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. page), it is known that a polymer with a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the ends of the molecules. ing.

Methods for producing saturated hydrocarbon polymers having reactive silyl groups include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, Although described in JP-A-1-197509, JP-A-1-197509, JP-A-2539445, JP-A-2873395, and JP-A-7-53882, the present invention is not particularly limited to these.

The above saturated hydrocarbon polymers having reactive silyl groups may be used alone or in combination of two or more.

((Meth)acrylic acid ester polymer)
The (meth)acrylic acid ester-based monomer constituting the main chain of the (meth)acrylic acid ester-based polymer is not particularly limited, and various monomers can be used. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate , tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-(meth)acrylate -octyl, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3- (meth)acrylate Methoxybutyl, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, (meth)acrylate (3-trimethoxysilyl)propyl acrylate, (3-dimethoxymethylsilyl)propyl (meth)acrylate, (2-trimethoxysilyl)ethyl (meth)acrylate, (2-dimethoxymethylsilyl(meth)acrylate) ) Ethyl, trimethoxysilylmethyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, ethylene oxide adduct of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, (meth)acrylic 2-trifluoromethylethyl acid, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, (meth)acrylate Trifluoromethyl acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, ( (Meth)acrylate monomers such as 2-perfluorodecylethyl methacrylate and 2-perfluorohexadecylethyl (meth)acrylate can be mentioned.

In the (meth)acrylic acid ester-based polymer, the following vinyl-based monomer can be copolymerized together with the (meth)acrylic acid ester-based monomer. Examples of the vinyl-based monomers include silicon-containing vinyl-based monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl fumarate. Esters and dialkyl esters; maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitriles such as acrylonitrile and methacrylonitrile Group-containing vinyl-based monomers; amide-group-containing vinyl-based monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate and vinyl pivalate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene class: vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like.

These may be used alone or may be copolymerized. Among them, a copolymer composed of a styrene-based monomer and a (meth)acrylic acid ester-based monomer is preferable in view of the physical properties of the product. More preferably, it is a (meth)acrylic ester polymer composed of acrylic ester monomers and/or methacrylic ester monomers, and particularly preferably an acrylic ester polymer composed of acrylic ester monomers.

In one embodiment of the present invention, the moisture-curable resin (A) is an organic polymer having a reactive silyl group at the molecular chain terminal, and (meth)acrylic acid having a reactive silyl group at the molecular chain terminal. In the case of an ester-based polymer, the (meth)acrylic acid ester-based polymer having a reactive silyl group at the molecular chain end is, for example, a (meth)acrylic acid ester-based copolymer having an aromatic ring in a side chain ( Other than B), it may be a (meth)acrylic acid ester polymer having a reactive silyl group at the molecular chain end. In other words, the moisture-curable resin (A) can be a moisture-curable resin (A) other than the (meth)acrylate copolymer (B) having an aromatic ring in its side chain.

Butyl acrylate-based monomers are more preferable in terms of physical properties such as low viscosity of the compound, low modulus of the cured product, high elongation, weather resistance, heat resistance, etc. in applications such as general construction. On the other hand, in applications where oil resistance and the like are required, such as automobile applications, copolymers composed mainly of ethyl acrylate monomers are more preferable. A copolymer composed mainly of ethyl acrylate monomers has excellent oil resistance, but tends to be slightly inferior in low-temperature characteristics (cold resistance). It is also possible to replace it with butyl acrylate. However, as the ratio of butyl acrylate is increased, its good oil resistance is impaired. % or less is more preferable.

It is also preferable to use 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, etc. in which oxygen is introduced into the alkyl group of the side chain in order to improve low-temperature properties without impairing oil resistance. However, the introduction of alkoxy groups having an ether bond in the side chain tends to deteriorate the heat resistance, so when heat resistance is required, the weight ratio is preferably 40% or less.

It is possible to obtain a suitable polymer by changing the ratio of monomers in consideration of physical properties such as oil resistance, heat resistance, and low-temperature properties required according to various uses and required purposes. For example, but not limited to, an example that has an excellent balance of physical properties such as oil resistance, heat resistance, and low-temperature properties is ethyl acrylate/butyl acrylate/2-methoxyethyl acrylate (40 to 50/20 in weight ratio). ~30/30~20). In the present invention, these preferred monomers may be copolymerized with other monomers, or may be block-copolymerized. .

(Method for synthesizing (meth)acrylic acid ester polymer)
The method for synthesizing the (meth)acrylic acid ester polymer is not particularly limited, and a known method may be used. However, polymers obtained by conventional free radical polymerization methods using azo compounds, peroxides, etc. as polymerization initiators generally have a large molecular weight distribution value of 2 or more, and have a problem of high viscosity. there is Therefore, in order to obtain a (meth)acrylic acid ester polymer having a narrow molecular weight distribution, a low viscosity, and a crosslinkable functional group at the molecular chain end in a high proportion, It is preferable to use a living radical polymerization method that does not use a non-nitrile azo polymerization initiator or an organic peroxide polymerization initiator.

Among the "living radical polymerization methods", the "atom transfer radical polymerization method" in which a (meth)acrylic acid ester-based monomer is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is In addition to the characteristics of the "living radical polymerization method", it has a halogen etc. at the end, which is relatively advantageous for functional group conversion reactions, and has a large degree of freedom in designing initiators and catalysts, so it has a specific functional group ( It is more preferable as a method for producing a meth)acrylic acid ester polymer. The atom transfer radical polymerization method includes, for example, the method described in Matyjaszewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, Vol. 117, p.

Methods for producing a (meth)acrylic acid ester polymer having a reactive silyl group include, for example, JP-B-3-14068, JP-B-4-55444, JP-A-6-211922, etc., chain transfer A method of preparation using free radical polymerization methods using agents is disclosed. Further, Japanese Patent Application Laid-Open No. 9-272714 discloses a production method using an atom transfer radical polymerization method, but the present invention is not particularly limited thereto. The (meth)acrylic ester-based polymer having a reactive silyl group may be used alone or in combination of two or more.

These organic polymers having a reactive silyl group may be used alone or in combination of two or more. Specifically, a group consisting of a polyoxyalkylene polymer having a reactive silyl group, a saturated hydrocarbon polymer having a reactive silyl group, and a (meth)acrylic acid ester polymer having a reactive silyl group. An organic polymer obtained by blending two or more selected from can also be used.

A method for producing an organic polymer by blending a polyoxyalkylene polymer having a reactive silyl group and a (meth)acrylic acid ester polymer having a reactive silyl group is disclosed in JP-A-59-122541, JP-A-59-122541, Although proposed in JP-A-63-112642, JP-A-6-172631, JP-A-11-116763, etc., the present invention is not limited to these. A preferred specific example is the following general formula (4):
—CH ₂ —C(R ⁶ )(COOR ⁷ )— (4)
(R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkyl group having 1 to 8 carbon atoms) and a (meth)acrylic ester monomer unit having an alkyl group having 1 to 8 carbon atoms; The following general formula (5):
—CH ₂ —C(R ⁶ )(COOR ⁸ )— (5)
(R ⁶ is the same as above, R ⁸ represents an alkyl group with 9 or more carbon atoms) represented by a (meth)acrylic acid ester monomer unit having an alkyl group with 9 or more carbon atoms. 2) is a method of blending a polyoxyalkylene polymer having a reactive silyl group.

R ⁷ in the general formula (4) includes, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a 2-ethylhexyl group, etc., having 1 to 8 carbon atoms, preferably 1 to 1 4, more preferably 1 or 2 alkyl groups. The alkyl group for ^R7 may be used alone or in combination of two or more.

R ⁸ in the general formula (5) includes, for example, a nonyl group, a decyl group, a lauryl group, a tridecyl group, a cetyl group, a stearyl group, a behenyl group, etc., having 9 or more carbon atoms, usually 10 to 30, preferably 10 to 30 carbon atoms. 10 to 20 long chain alkyl groups are included. As in the case of R ⁷ , the alkyl group for R ⁸ may be used alone or in combination of two or more.

The molecular chain of the (meth)acrylic acid ester-based polymer substantially consists of the monomer units of the general formulas (4) and (5), and the term “substantially” as used herein means means that the sum of the monomer units of general formula (4) and general formula (5) present in the above exceeds 50% by weight. The total amount of monomer units of general formula (4) and general formula (5) is preferably 70% by weight or more.

Moreover, the weight ratio of the monomer units of general formula (4) to the monomer units of general formula (5) is preferably from 95:5 to 40:60, more preferably from 90:10 to 60:40.

Examples of monomer units other than those represented by general formulas (4) and (5) which may be contained in the copolymer include acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, and N-methylolacrylamide; , amide groups such as N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, monomers containing amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; other acrylonitrile, styrene, α-methylstyrene, Examples include monomer units derived from alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, and the like.

An organic polymer obtained by blending a saturated hydrocarbon polymer having a reactive silyl group and a (meth)acrylic acid ester polymer having a reactive silyl group is disclosed in JP-A-1-168764 and JP-A-2000-186176. JP-A-2003-200350, etc., but the present invention is not particularly limited to these.

Furthermore, as a method for producing an organic polymer obtained by blending a (meth)acrylic acid ester polymer having a reactive silyl group, there is another method in the presence of an organic polymer having a reactive silyl group (meth ) A method of polymerizing acrylic acid ester-based monomers can be used. This production method is specifically disclosed in each publication such as JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, and JP-A-60-228517. It is not limited to these.

On the other hand, the main chain skeleton of the organic polymer B may contain other components such as a urethane bond component within a range that does not significantly impair the effects of the present invention.

Although the urethane bond component is not particularly limited, a group generated by a reaction between an isocyanate group and an active hydrogen group (hereinafter also referred to as an amide segment) can be mentioned.

The amide segment has the general formula (6):
-NR ⁹ -C(=O)- (6)
( ^R9 represents an organic group or a hydrogen atom). The organic group for R ⁹ is preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. is a group). Since this structure has a relatively high polarity, the strength of the cured product and the adhesiveness to the substrate tend to be high, which is desirable.

Cured products obtained by curing moisture-curable resin compositions made of polymers containing urethane bonds or ester bonds in the main chain may split the main chain at the urethane bonds or ester bonds due to heat, etc. strength may be significantly reduced.

If there are many amide segments in the main chain skeleton of the reactive silyl group-containing organic polymer, the viscosity of the polymer tends to increase. Moreover, the viscosity may increase after storage, and the workability of the resulting composition may decrease. Furthermore, as noted above, the amide segment may be cleaved, such as by heat. Therefore, in order to obtain a composition having excellent storage stability and workability, it is preferred that the amide segment is substantially absent. On the other hand, the amide segment in the main chain skeleton of the reactive silyl group-containing organic polymer tends to improve curability. Therefore, when the main chain skeleton of the reactive silyl group-containing organic polymer contains amide segments, the average number of amide segments per molecule is preferably 1 to 10, more preferably 1.5 to 5, and 2 to 10. Three are particularly preferred. If it is less than 1, the curability may not be sufficient, and if it is more than 10, the polymer may become highly viscous and difficult to handle.

Specifically, the amide segment includes a urethane group generated by the reaction between an isocyanate group and a hydroxy group; a urea group generated by the reaction between an isocyanate group and an amino group; and a urea group generated by the reaction between an isocyanate group and a mercapto group. A thiourethane group and the like can be mentioned. Further, in the present embodiment, the group of general formula (6) also includes a group formed by reaction of the active hydrogen in the urethane group, urea group, and thiourethane group with an isocyanate group.

An example of an industrially easy method for producing a reactive silyl group-containing organic polymer having an amide segment and a reactive silyl group is to react an organic polymer having an active hydrogen-containing group at its end with an excess polyisocyanate compound. After or at the same time as forming a polymer having an isocyanate group at the end of the polyurethane main chain, all or part of the isocyanate group has the general formula (7):
ZR ¹⁰ -SiR ⁴ _3-a X _a (7)
(R ⁴ , X and a are the same as above. R ¹⁰ is a divalent organic group, more preferably a hydrocarbon group having 1 to 20 carbon atoms. Z is a hydroxy group, a carboxy group, a mercapto group and Examples include those produced by a method of reacting the Z group of a silicon compound represented by an amino group (which is an active hydrogen-containing group selected from primary or secondary). Examples of known methods for producing organic polymers related to this production method include JP-B-46-12154 (US Pat. No. 3,632,557), JP-A-58-109529 (US Pat. No. 4,374,237), and JP-A-62. -13430 (US Pat. No. 4645816), JP-A-8-53528 (EP0676403), JP-A-10-204144 (EP0831108), JP-A-2003-508561 (US Pat. No. 6197912), JP-A-6-211879 (US Patent No. 5364955), JP-A-10-53637 (US Patent No. 5756751), JP-A-11-100427, JP-A-2000-169544, JP-A-2000-169545, JP-A-2002-212415, JP-A-3313360 , US Pat. No. 4,067,844, US Pat. No. 3,711,445, and JP-A-2001-323040.

Further, the organic polymer having an active hydrogen-containing group at the end of the general formula (8):
O=C=N-R ¹⁰ -SiR ⁴ _3-a X _a (8)
(R ¹⁰ , R ⁴ , X and a are the same as above), and those produced by reacting a reactive silyl group-containing isocyanate compound can be mentioned. Examples of known methods for producing reactive silyl group-containing organic polymers related to this production method include JP-A-11-279249 (US Pat. No. 5,990,257), JP-A-2000-119365 (US Pat. No. 6,046,270), JP-A-58-29818 (US Pat. No. 4345053), JP-A-3-47825 (US Pat. No. 5068304), JP-A-11-60724, JP-A-2002-155145, JP-A-2002-249538, WO03/ 018658, WO03/059981 and the like.

Examples of organic polymers having terminal active hydrogen-containing groups include oxyalkylene polymers (polyether polyols) having terminal hydroxy groups, polyacrylic polyols, polyester polyols, and saturated hydrocarbon polymers ( polyolefin polyols), polythiol compounds, polyamine compounds, and the like. Among these, polyether polyols, polyacrylic polyols, and polyolefin polyols are preferable because the obtained organic polymers have relatively low glass transition temperatures and the obtained cured products have excellent cold resistance. In particular, polyether polyol is particularly preferred because the resulting organic polymer has low viscosity, good workability, and good deep-part curability and adhesiveness. Further, polyacrylic polyols and saturated hydrocarbon polymers are more preferable because the resulting cured organic polymer has good weather resistance and heat resistance.

As the polyether polyol, those produced by any production method can be used, but those having at least 0.7 hydroxy groups per molecular terminal on the average of all molecules are preferred. Specifically, initiators such as oxyalkylene polymers prepared using conventional alkali metal catalysts, double metal cyanide complexes and/or polyhydroxy compounds having at least two hydroxy groups in the presence of cesium, Examples thereof include oxyalkylene polymers produced by reacting alkylene oxides.

Among the polymerization methods described above, the polymerization method using a double metal cyanide complex has a lower degree of unsaturation, a narrower Mw/Mn, a lower viscosity, and high acid resistance and weather resistance. It is preferred because it is possible to obtain coalescence.

Examples of the polyacrylic polyol include a polyol having a (meth)acrylic acid alkyl ester (co)polymer as a skeleton and having a hydroxy group in the molecule. The method for synthesizing this polymer is preferably a living radical polymerization method, more preferably an atom transfer radical polymerization method, because it has a narrow molecular weight distribution and can be made to have a low viscosity. Further, it is preferable to use a polymer obtained by the so-called SGO process, which is obtained by continuous bulk polymerization of acrylic acid alkyl ester monomers described in JP-A-2001-207157 at high temperature and high pressure. Specifically, Alfon UH-2000 manufactured by Toagosei Co., Ltd. and the like can be mentioned.

Specific examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. .

The silicon compound of general formula (7) is not particularly limited, but specific examples include γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, (N- phenyl)-γ-aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, and the like. group-containing silanes; hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane; In addition, JP-A-6-211879 (US Patent No. 5364955), JP-A-10-53637 (US Patent No. 5756751), JP-A-10-204144 (EP0831108), JP-A-2000-169544, JP-A-2000-169545 No. 1, Michael addition reaction products of various α,β-unsaturated carbonyl compounds and primary amino group-containing silanes, or various (meth)acryloyl group-containing silanes and primary amino group-containing compounds. can also be used as the silicon compound of general formula (7).

The reactive silyl group-containing isocyanate compound of general formula (8) is not particularly limited, but specific examples include γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate. , γ-methyldiethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate and the like. Further, as described in JP-A-2000-119365 (U.S. Pat. No. 6,046,270), a compound obtained by reacting a silicon compound of general formula (7) with an excess of the polyisocyanate compound also has the general formula It can be used as the reactive silyl group-containing isocyanate compound of (8).

[2.2. Polysiloxane having a reactive silyl group at the molecular chain end]
A polysiloxane having a reactive silyl group at the molecular chain terminal is also called a room-temperature-curing organopolysiloxane. It is a coalescence. Here, "at the end of the molecular chain" means [2.1. ]. The polysiloxane having a reactive silyl group at the molecular chain terminal includes a one-component silicone resin containing an organopolysiloxane having a silanol group at the terminal and a reactive silyl group-containing low-molecular-weight compound as a cross-linking component. The number average molecular weight of polysiloxane having a reactive silyl group at the molecular chain end is 1,000 or more, especially 6,000 to 30,000. It is suitable because it has excellent physical properties such as modulus.

[2.3. Urethane Prepolymer Having Isocyanate Group]
A urethane-based prepolymer having an isocyanate group reacts with moisture to form a urea bond to be crosslinked and cured. is preferably obtained by reacting under the condition that the isocyanate group is excessive with respect to the active hydrogen (group). The isocyanate group content of the urethane-based prepolymer having isocyanate groups is preferably 0.1 to 15.0% by weight, more preferably 0.3 to 10.0% by weight. A known urethanization catalyst and organic solvent can also be used for synthesizing the urethane-based prepolymer having an isocyanate group.

Examples of the organic polyisocyanate include aromatic diisocyanates such as diphenylmethane diisocyanate and toluene diisocyanate, aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate, araliphatic diisocyanates such as xylylene diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, hydrogen Alicyclic diisocyanates such as added toluene diisocyanate can be mentioned. Adduct-modified products, buret-modified products, isocyanurate-modified products, uretonimine-modified products, uretdione-modified products, carbodiimide-modified products, etc. of these can also be used. Furthermore, polymeric substances such as polymethylene polyphenyl polyisocyanate can also be used. These can be used alone or in combination of two or more.

Examples of the polymer polyols include polyester polyols, polyesteramide polyols, polycarbonate polyols, polyether polyols, polyolefin polyols, acrylic polyols, animal and plant polyols, copolyols thereof, and mixtures of two or more thereof. Among these polymer polyols, polyether polyols are preferable because they are excellent in workability, adhesiveness, water resistance, weather resistance, and the like. Preferred examples of the chain extender include low-molecular-weight alcohols, low-molecular-weight amines, and low-molecular-weight aminoalcohols having a molecular weight of less than 500, or mixtures of two or more thereof.

[3. Moisture Curing Resin Composition]
The moisture-curable resin composition according to one embodiment of the present invention comprises the moisture-curable resin (A) (hereinafter sometimes simply referred to as "(A) component" in this specification), the (meta) and an acrylic acid ester-based copolymer (B) (hereinafter sometimes simply referred to as "(B) component" in this specification).

The content ratio (% by weight) of component (B) with respect to 100% by weight of component (A) in the moisture-curable resin composition according to one embodiment of the present invention is preferably 1 to 50% by weight, more preferably It is 2 to 40% by weight, more preferably 5 to 30% by weight. If it is 1% by weight or more, the adhesion between the cured product and the coating film can be improved when the coating is applied on the resulting cured product, and if it is 50% by weight or less, the cured product has high elongation. It is preferable because

[3.1] Plasticizer The moisture-curable resin composition according to one embodiment of the present invention may contain a plasticizer in addition to the components (A) and (B).

Examples of plasticizers include non-aromatic dibasic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and diisodecyl succinate; aliphatic esters such as butyl oleate and methyl acetylricinoleate; Phosphate esters such as diyl phosphate and tributyl phosphate; trimellitic esters; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl, partially hydrogenated terphenyl; process oils; epoxidized soybean oil, epoxy stearin Epoxy plasticizers such as benzyl acid may be mentioned.

Dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, di-n-hexyl phthalate, bis(2-ethylhexyl) phthalate, di-n-octyl phthalate, diisononyl phthalate, dinonyl phthalate, diisodecyl phthalate , diisoundecyl phthalate, bisbutylbenzyl phthalate and the like can also be used. When phthalates are used, diisodecyl phthalate or diisoundecyl phthalate is preferred, and diisodecyl phthalate is more preferred. Cyclohexanedicarboxylate obtained by adding water to the above phthalates can also be used. This plasticizer is sold by BASF under the trade name of Hexamoll DINCH and is readily available.

Relatively low-molecular-weight plasticizers such as those mentioned above (hereinafter sometimes referred to as "low-molecular-weight plasticizers" in the present specification) are applied to surrounding substrates to which the moisture-curable resin composition has been applied. It is desirable to use less, as migration (bleeding) may occur and contaminate the substrate. Porous stone materials are particularly prone to contamination, and granite, marble, siding boards and the like are prone to bleeding of the plasticizer, which can impair the aesthetic appearance. In order to suppress such deterioration in appearance, the amount of the low-molecular-weight plasticizer such as a phthalate plasticizer used should be 30 parts by weight or less, more preferably 20 parts by weight, per 100 parts by weight of component (A). parts or less, more preferably 10 parts by weight or less. Alternatively, it is 100% by weight or less, more preferably 80% by weight or less, and still more preferably 50% by weight or less based on component (B). If it is desired to obtain a moisture-curable resin composition that does not cause staining, it is most desirable not to use a low-molecular-weight plasticizer.

When a paint is applied onto the moisture-curable resin composition or its cured product, it is preferable to use a phthalate plasticizer in combination within a range in which the plasticizer does not excessively bleed into the paint. This is because the combined use can improve the adhesion of the coating film and improve the problem of peeling. Specifically, the amount of the phthalate plasticizer used is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, most preferably 3 to 20 parts by weight, per 100 parts by weight of component (A). preferable. Alternatively, it is 1 to 100% by weight, more preferably 2 to 80% by weight, still more preferably 5 to 50% by weight, based on component (B).

Moreover, a polymeric plasticizer can be used in the moisture-curable resin composition according to one embodiment of the present invention. When a polymeric plasticizer is used, the initial physical properties of the resulting cured product are maintained for a long period of time, compared to when a low-molecular-weight plasticizer, which is a plasticizer that does not contain a polymer component in its molecule, is used. Furthermore, the drying property (also referred to as paintability) can be improved when an alkyd paint is applied to the cured product. Specific examples of polymeric plasticizers include vinyl-based polymers obtained by polymerizing vinyl-based monomers by various methods; polyalkylene glycol esters such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol esters; Polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; is 1,000 or more polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or polyethers such as derivatives obtained by converting the hydroxy groups of these polyether polyols into ester groups, ether groups, etc.; polystyrene, poly- Polystyrenes such as α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, etc., but not limited thereto.

Among these polymer plasticizers, those compatible with the polymers of components (A) and (B) are preferred. From this point of view, polyethers and vinyl polymers are preferred. In addition, the use of polyethers as a plasticizer is preferable because it improves the surface curability and the deep part curability and does not cause curing delay after storage, and among them, polypropylene glycol is more preferable. Vinyl polymers are preferred from the viewpoints of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers and/or methacrylic polymers are preferable, and acrylic polymers such as polyacrylic acid alkyl esters are more preferable. The method for synthesizing this polymer is preferably a living radical polymerization method, more preferably an atom transfer radical polymerization method, because it has a narrow molecular weight distribution and can be made to have a low viscosity. Further, it is preferable to use a polymer obtained by the so-called SGO process, which is obtained by continuous bulk polymerization of acrylic acid alkyl ester monomers described in JP-A-2001-207157 at high temperature and high pressure. This plasticizer is sold by Toagosei Co., Ltd. under the trade name of Alfon.

The number average molecular weight of the polymeric plasticizer is preferably 500 to 25,000, more preferably 800 to 22,000, even more preferably 1,000 to 19,000, and particularly preferably 1,000. to 17,000, most preferably 1,000 to 16,000. If the molecular weight is too low, the plasticizer will flow over time due to heat or rainfall, and the initial physical properties of the cured product cannot be maintained for a long period of time, and the alkyd coatability cannot be improved. On the other hand, if the molecular weight is too high, the viscosity will be high and the workability will be poor. Although the molecular weight distribution of the polymeric plasticizer is not particularly limited, it is preferably narrow, preferably less than 3.0, more preferably 2.8 or less, and most preferably 2.50 or less.

Moreover, the polymer plasticizer may have a reactive silyl group. When the polymeric plasticizer has a reactive silyl group, it acts as a reactive plasticizer and can more effectively prevent migration of the plasticizer from the cured product. That is, the term "reactive plasticizer" as used herein means a polymer plasticizer having a reactive silyl group. When the polymeric plasticizer has a reactive silyl group, it preferably contains 1 or less, more preferably 0.8 or less reactive silyl groups on average per molecule. When using a polymer plasticizer having a reactive silyl group, especially a polyether polymer having a reactive silyl group, the number average molecular weight is lower than that of the polyoxyalkylene polymer as the moisture-curable resin (A). must be low. The number average molecular weight of the reactive plasticizer is preferably 500 to 25,000, more preferably 800 to 22,000, even more preferably 1,000 to 19,000, and particularly preferably 1,000. to 13,000, most preferably 1,000 or more and less than 9,000. If the molecular weight is too low, the plasticizer flows out over time due to heat or rainfall, and the initial physical properties of the cured product cannot be maintained for a long period of time. On the other hand, if the molecular weight is too high, the viscosity will be high and the workability will be poor. Although the molecular weight distribution of the reactive plasticizer is not particularly limited, it is preferably narrow, preferably less than 3.0, more preferably 2.8 or less, and most preferably 2.5 or less.

The number average molecular weights of polymeric plasticizers and reactive plasticizers described later are measured by GPC method. Also, the molecular weight distribution (Mw/Mn) is measured by the GPC method (converted to polystyrene).

The said plasticizer may be used individually and may use 2 or more types together. Also, a low-molecular-weight plasticizer and a high-molecular-weight plasticizer may be used in combination. These plasticizers can also be blended during polymer production.

The amount of the high molecular weight plasticizer to be used is 10 to 200 parts by weight, preferably 20 to 180 parts by weight, still more preferably 50 to 150 parts by weight, per 100 parts by weight of component (A). Alternatively, it is 1 to 800% by weight, more preferably 2 to 500% by weight, still more preferably 3 to 300% by weight, based on component (B). If it is less than 10 parts by weight per 100 parts by weight of component (A), the effect as a plasticizer will not be exhibited, and if it exceeds 200 parts by weight, the mechanical strength of the cured product will be insufficient.

As described above, when a coating is applied onto the moisture-curable resin composition or its cured product, it is preferable to use a phthalate ester plasticizer in combination from the viewpoint of adhesion of the coating film. Therefore, commercially available moisture-curable resin compositions generally use phthalate plasticizers. However, although the use of phthalate ester plasticizers improves the adhesion of the paint film, the plasticizer migrates (bleeds) into the paint and softens the paint, making it difficult to apply the paint. There is a problem that the coating film is contaminated.

In order to solve this problem, in recent years, non-bleed formulations that do not use phthalate ester plasticizers and that allow coatings to be applied onto cured products have been increasing. In such non-bleed formulations, the aforementioned polymeric plasticizers, particularly reactive polymeric plasticizers containing reactive groups, are used in place of phthalate plasticizers.

However, with the conventional non-bleed formulation, when the paint is applied on the cured product, the plasticizer does not migrate to the paint, so the paint can be applied, but the adhesion between the cured product and the coating still remains. It was not sufficient, and improvement in coating film adhesion was demanded.

The present inventors added, as a plasticizer, a moisture-curable resin composition containing a moisture-curable resin (A) and a (meth)acrylic acid ester copolymer (B) having an aromatic ring in a side chain, When the reactive plasticizer was added, compared to the case where the reactive plasticizer was added to the moisture-curable resin composition that does not contain the (meth)acrylic acid ester copolymer (B), it was significantly It was found that the adhesion to the coating film was improved.

Therefore, in one embodiment of the present invention, a moisture-curable resin (A), a (meth)acrylic acid ester copolymer (B) having an aromatic ring in a side chain, and a plasticizer as the reactive plasticizer Moisture-curable resin compositions containing agents are also included. With such a configuration, when the paint is applied on the obtained cured product, the moisture-curable resin composition can prevent migration (bleed) of the plasticizer to the paint and has excellent adhesion between the cured product and the coating film. and its cured product can be obtained.

The amount of the reactive plasticizer used is 10 to 200 parts by weight, preferably 20 to 180 parts by weight, still more preferably 50 to 150 parts by weight, per 100 parts by weight of component (A). Alternatively, it is 1 to 800% by weight, more preferably 2 to 500% by weight, still more preferably 3 to 300% by weight, based on component (B). If it is less than 10 parts by weight per 100 parts by weight of component (A), the effect as a plasticizer will not be exhibited, and if it exceeds 200 parts by weight, the mechanical strength of the cured product will be insufficient.

[3.2. Additive〕
The moisture-curable resin composition according to one embodiment of the present invention may contain components (A) and (B), and, if necessary, a plasticizer. body, adhesion imparting agent, antioxidant, light stabilizer, ultraviolet absorber, filler, silicate, physical property modifier, thixotropic agent, epoxy group-containing compound, photocurable substance, oxygen-curable substance, Additives such as flame retardants, solvents, etc. may be included.

(catalyst)
A silanol condensation catalyst can be used in the moisture-curable resin composition according to one embodiment of the present invention. Preferred examples of silanol condensation catalysts include tin-based catalysts, preferably organotin-based curing catalysts. Specific examples of organotin catalysts include dimethyltin diacetate, dimethyltin bis(acetylacetonate), dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis(2-ethylhexanoate ), dibutyltin bis(methyl maleate), dibutyltin bis(ethyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(octyl maleate), dibutyltin bis(tridecyl maleate), dibutyltin Bis(benzyl maleate), dibutyltin diacetate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dibutyltin dimethoxide, dibutyltin bis(nonylphenoxide), dibutenyltin oxide, dibutyltin oxide , dibutyltin bis(acetylacetonate), dibutyltin bis(ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate, dioctyltin dilaurate, dioctyltin dilaurate Tetravalent organic tin compounds such as acetate and dioctyltin bis(acetylacetonate); divalent tin such as tin octylate and tin versatate, but are not limited thereto. Among these, dibutyltin bis(acetylacetonate) or tin octylate is preferred from the viewpoint of curability.

Curing catalysts other than the organotin systems listed above can also be used. Specific examples thereof include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis(acetylacetonate), bis(acetylacetonate) diisopropoxytitanium, diisopropoxytitanium bis(ethylacetoacetate); (acetylacetonate), aluminum tris(ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate and other organoaluminum compounds; and zirconium tetrakis(acetylacetonate) and other zirconium compounds. Carboxylic acids and/or carboxylic acid metal salts can also be used as curing catalysts. Amidine compounds as described in WO2008/078654 can also be used. Examples of amidine compounds include 1-(o-tolyl)biguanide, 1-phenylguanidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,5,7-triazabicyclo[4.4 .0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, etc., but not limited thereto.

The amount of the catalyst used is 0.1 to 10 parts by weight, preferably 0.2 to 8 parts by weight, more preferably 0.3 to 5 parts by weight, per 100 parts by weight of component (A). Department. If the amount is less than 0.1 part by weight, appropriate curability will not be exhibited, and if the amount exceeds 10 parts by weight, the curing will be too fast to form an appropriate cured product and the desired performance will not be exhibited sufficiently.

(Thermal expandable particulate hollow body)
In addition, in the moisture-curable resin composition according to one embodiment of the present invention, the thermally expandable fine hollow particles described in JP-A-2004-51701 or JP-A-2004-66749 can be used. Thermally expansible fine hollow particles are composed of a low boiling point compound such as a hydrocarbon having 1 to 5 carbon atoms as a polymer outer shell material (vinylidene chloride copolymer, acrylonitrile copolymer, or vinylidene chloride-acrylonitrile copolymer). It is a plastic sphere wrapped in a spherical shape by coalescence. By heating the bonded portion using the moisture-curable resin composition according to one embodiment of the present invention, the gas pressure in the shell of the thermally expandable fine hollow body increases, softening the polymer outer shell material. The volume expands dramatically and serves to detach the adhesive interface. By using the heat-expandable fine hollow particles, it is possible to obtain an adhesive composition which can be easily peeled off without destruction of the material only by heating when unnecessary, and which can be heat-peeled without using any organic solvent.

(Adhesion imparting agent)
Aminosilane can be used in the moisture-curable resin composition according to one embodiment of the present invention. Aminosilane is a compound having a reactive silyl group and an amino group in the molecule, and is usually called an adhesion-imparting agent. By using this, various adherends, namely inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, and organic substrates such as vinyl chloride, acrylic, polyester, polyethylene, polypropylene, polycarbonate, etc. When used, it exhibits a remarkable adhesion improving effect under non-primer or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. Aminosilane is also a compound that can function as a physical property modifier, dispersibility improver for inorganic fillers, and the like.

Specific examples of the reactive group of the reactive silyl group of aminosilane include the groups already exemplified, but methoxy group, ethoxy group and the like are preferable from the viewpoint of hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly 3 or more. Specific examples of aminosilanes include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ -(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)amino Propylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, γ-[(2-(2-aminoethyl)aminoethyl]aminopropyltrimethoxysilane, γ-(6-aminohexyl) aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane , N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyl Amino group-containing silanes such as trimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine; N-(1,3-dimethylbutyl and ketimine-type silanes such as liden)-3-(triethoxysilyl)-1-propanamine.

Of these, γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-(2-aminoethyl)aminopropylmethyldimethoxysilane are used to ensure good adhesion. preferable. One type of aminosilane may be used alone, or two or more types may be used in combination. It has been pointed out that γ-(2-aminoethyl)aminopropyltrimethoxysilane is more irritating than other aminosilanes. can reduce irritation.

The amount of the aminosilane compounded is preferably about 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, even more preferably 2 to 5 parts by weight, per 100 parts by weight of component (A). If the aminosilane content is less than 1 part by weight, sufficient adhesion may not be obtained. On the other hand, if the blending amount exceeds 20 parts by weight, the cured product may become brittle, failing to obtain sufficient strength, and the curing speed may become slow.

Adhesion imparting agents other than aminosilane can be used in the moisture-curable resin composition according to one embodiment of the present invention. Specific examples of adhesion promoters other than aminosilane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4- Epoxy group-containing silanes such as epoxycyclohexyl)ethyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyl Isocyanate group-containing silanes such as methyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, (isocyanatomethyl)trimethoxysilane, (isocyanatomethyl)dimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxy Mercapto group-containing silanes such as silane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxy ethoxy)silane, N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane, and other carboxysilanes; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyl vinyl type unsaturated group-containing silanes such as oxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris(trimethoxysilyl)isocyanurate; can. Condensates obtained by partially condensing the silanes can also be used. In addition, modified derivatives thereof, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and silylated polyesters, can also be used as adhesiveness imparting agents. .

The effect of the adhesion imparting agent used in the moisture-curable resin composition according to one embodiment of the present invention is that various adherends, that is, glass, aluminum, stainless steel, zinc, copper, inorganic substrates such as mortar, and When used on organic substrates such as vinyl chloride, acrylic, polyester, polyethylene, polypropylene, polycarbonate, etc., it exhibits a significant improvement in adhesion under non-primer or primer-treated conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. Specific examples other than the adhesion-imparting agents described above are not particularly limited, but include, for example, epoxy resins, phenol resins, sulfur, alkyl titanates, aromatic polyisocyanates, and the like. The adhesion imparting agent may be used alone or in combination of two or more. Adhesion to adherends can be improved by using these adhesion-imparting agents.

Among these, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane are preferred in order to ensure good adhesion.

The amount of the adhesion-imparting agent used is preferably about 0.01 to 20 parts by weight, more preferably about 0.1 to 10 parts by weight, and 1 part by weight per 100 parts by weight of component (A). Part to 7 parts by weight is particularly preferred. If the amount of the adhesion-imparting agent is below this range, sufficient adhesion may not be obtained. On the other hand, if the amount of the adhesion-imparting agent exceeds this range, practical deep-part curability may not be obtained.

As mentioned above, epoxy resins can also be used as adhesion promoters. However, since the epoxy resin may lower the catalytic activity depending on the amount used, it is preferable that the amount of the epoxy resin used in the moisture-curable resin composition according to one embodiment of the present invention is small. The amount of epoxy resin to be used is preferably 5 parts by weight or less, more preferably 0.5 parts by weight or less, and particularly preferably not substantially contained, per 100 parts by weight of component (A).

(Antioxidant)
An antioxidant (antiaging agent) can be used in the moisture-curable resin composition according to one embodiment of the present invention. The heat resistance of the cured product can be enhanced by using an antioxidant. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144, CHIMASSORB944LD, CHIMASSORB119FL (all of which are manufactured by BASF Japan Ltd.); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (any of these Also manufactured by ADEKA Co., Ltd.); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of these are manufactured by Sankyo Lifetech Co., Ltd.) Hindered amine light stabilizers can also be used. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of component (A).

(light stabilizer)
A light stabilizer can be used in the moisture-curable resin composition according to one embodiment of the present invention. The use of a light stabilizer can prevent photo-oxidative deterioration of the cured product. Benzotriazole-based, hindered amine-based, and benzoate-based compounds can be exemplified as light stabilizers, and hindered amine-based compounds are particularly preferred. The light stabilizer is preferably used in an amount of 0.1 to 5 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of component (A). Specific examples of light stabilizers are also described in JP-A-9-194731.

When a photocurable substance is used in combination with the moisture-curable resin composition according to one embodiment of the present invention, particularly when an unsaturated acrylic compound is used, a hindered amine system as described in JP-A-5-70531 It is preferable to use a tertiary amine-containing hindered amine light stabilizer as the light stabilizer in order to improve the storage stability of the composition. Tertiary amine-containing hindered amine light stabilizers include Tinuvin 622LD, Tinuvin 144, Tinuvin 770, CHIMASSORB119FL (all of which are manufactured by BASF Japan Ltd.); MARK LA-57, LA-62, LA-67, LA-63 (and ADEKA Corporation); Sunol LS-765, LS-292, LS-2626, LS-1114, LS-744 (all of which are manufactured by BASF Japan Ltd.).

(Ultraviolet absorber)
A UV absorber can be used in the moisture-curable resin composition according to one embodiment of the present invention. The use of an ultraviolet absorber can enhance the surface weather resistance of the cured product. Benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based and metal chelate-based compounds can be exemplified as UV absorbers, and benzotriazole-based compounds are particularly preferred. As an ultraviolet absorber, for example, tinuvin 326 can be exemplified. The amount of the ultraviolet absorber to be used is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight, per 100 parts by weight of component (A). It is preferable to use a combination of a phenol-based or hindered phenol-based antioxidant, a hindered amine-based light stabilizer, and a benzotriazole-based ultraviolet absorber.

(filler)
A filler can be used in the moisture-curable resin composition according to one embodiment of the present invention. Fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid, and carbon black; ground calcium carbonate, colloidal calcium carbonate, carbonate Magnesium, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, fine aluminum powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenolic resin and chloride fillers such as vinylidene resin organic microballoons, resin powders such as PVC powders and PMMA powders; fibrous fillers such as glass fibers and filaments; When a filler is used, it is used in an amount of 1 to 250 parts by weight, preferably 10 to 200 parts by weight, per 100 parts by weight of component (A).

If you want to obtain a hardened product with high strength by using these fillers, mainly fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid, carbon black, surface treatment A filler selected from fine calcium carbonate, calcined clay, clay, and active zinc white is preferred, and favorable results can be obtained when used in the range of 1 to 250 parts by weight per 100 parts by weight of component (A). , more preferably 1 to 200 parts by weight, still more preferably 50 to 200 parts by weight, even more preferably 80 to 200 parts by weight. In addition, when it is desired to obtain a cured product with low strength and high elongation at break, mainly titanium oxide, calcium carbonate such as ground calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloons are used. Favorable results can be obtained by using a filler selected from 5 to 200 parts by weight per 100 parts by weight of component (A). In general, the greater the specific surface area of calcium carbonate, the greater the effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product. Of course, these fillers may be used alone or in combination of two or more. When calcium carbonate is used, it is desirable to use both surface-treated fine calcium carbonate and calcium carbonate having a large particle size such as ground calcium carbonate. The particle size of the surface-treated fine calcium carbonate is preferably 0.5 μm or less, and the surface treatment is preferably with fatty acid and/or fatty acid salt. In addition, calcium carbonate having a large particle size preferably has a particle size of 1 μm or more and can be used without surface treatment.

In the moisture-curable resin composition according to one embodiment of the present invention, organic balloons and inorganic balloons are used in order to improve the workability (such as sharpness) of the moisture-curable resin composition and to make the surface of the cured product matte. Use is preferred. These fillers can be surface-treated and may be used alone or in combination of two or more. The particle size of the balloon is preferably 0.1 mm or less for improving workability (such as sharpness). The particle diameter of the balloon is preferably 5 μm to 300 μm in order to make the surface of the cured product matte.

The moisture-curable resin composition according to one embodiment of the present invention has good chemical resistance of the cured product. However, it is desirable that the design of the exterior wall and the design of the sealant are in harmony. In particular, sputter coating, colored aggregate, and the like are mixed into the exterior wall to give it a high-class appearance. When a moisture-curable resin composition according to an embodiment of the present invention contains a scaly or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 mm to 5.0 mm, the cured product is It harmonizes with the high-class outer wall like this, and has excellent chemical resistance. Therefore, it is an excellent moisture-curable resin composition in which the appearance of the resulting cured product is maintained over a long period of time. When a granular substance is used, the surface becomes sandy or sandstone-like, and when a scaly substance is used, the surface becomes uneven due to the scaly shape.

Preferred diameters, blending amounts, materials, etc. of the scale-like or granular substances are as follows, as described in JP-A-9-53063.

The diameter is 0.1 mm or more, preferably about 0.1 mm to 5.0 mm. A diameter of about 0.2 mm to 5.0 mm or about 0.5 mm to 5.0 mm can also be used. In the case of a scaly substance, the thickness is about 1/10 to 1/5 of the diameter (about 0.01 mm to 1.00 mm). The scaly or granular material is pre-mixed into the sealing matrix and transported to the construction site as a sealant, or is mixed into the sealing matrix at the construction site during use.

About 1 to 200 parts by weight of the scaly or granular material is blended with 100 parts by weight of the composition such as the sealant composition and the adhesive composition or 100 parts by weight of the component (A). The amount to be added is appropriately selected according to the size of each scaly or granular substance, the material of the outer wall, the pattern, and the like.

As the scaly or granular substance, natural substances such as silica sand and mica, synthetic rubbers, synthetic resins, and inorganic substances such as alumina are used. The moisture-curable resin composition according to the present embodiment is colored in an appropriate color according to the material, pattern, etc. of the outer wall in order to enhance the designability when filled in the joint.

If a balloon (preferably having an average particle size of 0.1 mm or more) is used for the same purpose, the resulting hardened product will have a sandy or sandstone-like rough surface and will be lightweight. can be planned. Preferred diameters, compounding amounts, materials, etc. of the balloon are as follows, as described in JP-A-10-251618.

The balloon is filled with spheres and is hollow inside. Materials for the balloon include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran, but are not limited to these. Alternatively, an inorganic material and an organic material can be combined or laminated to form a plurality of layers. Balloons can be inorganic, organic, or a combination thereof. In addition, the same balloon may be used, or a mixture of balloons made of different materials may be used. Furthermore, the balloon can be used after its surface has been processed and/or coated, or can be used after its surface has been treated with various surface treatment agents. For example, organic balloons may be coated with calcium carbonate, talc, titanium oxide or the like, and inorganic balloons may be surface-treated with an adhesive agent.

In order to obtain a sandy or sandstone-like rough surface, the balloon preferably has a particle size of 0.1 mm or more. Those having a particle size of about 0.2 mm to 5.0 mm or about 0.5 mm to 5.0 mm can also be used. If the particle size is less than 0.1 mm, even if a large amount is blended, it may only increase the viscosity of the composition and may not provide a rough feel. The blending amount of the balloon can be easily determined according to the desired degree of sandy or sandstone-like roughness. Generally, it is desirable to add particles having a particle size of 0.1 mm or more at a volume concentration range of 5 vol % to 25 vol % in the moisture-curable resin composition. When the volume concentration of the balloon is less than 5 vol%, there is no feeling of roughness. It tends to impair the basic performance of the agent. A volume concentration of 8 vol % to 22 vol % is particularly preferable for the balance with the basic performance of the sealing material.

When using a balloon, an anti-slip agent as described in JP-A-2000-154368, and a matte surface of the cured product as described in JP-A-2001-164237 are added to the uneven state. Conditioning amine compounds can be used, especially primary and/or secondary amines with a melting point of 35° C. or higher.

Specific examples of balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113073, JP-A-9-53063, JP-A-10. -251618, JP-A-2000-154368, JP-A-2001-164237 and WO97/05201.

Even when the moisture-curable resin composition according to one embodiment of the present invention contains particles of a cured sealant, it is possible to form irregularities on the surface of the cured product, thereby improving the design. As described in JP-A-2001-115142, preferred diameters, blending amounts and materials of the particles of the cured sealant are as follows. The diameter is preferably from 0.1 mm to 1 mm, more preferably from 0.2 mm to 0.5 mm. The blending amount is preferably 5 to 100% by weight, more preferably 20 to 50% by weight in the moisture-curable resin composition. Materials include urethane resin, silicone, modified silicone, polysulfide rubber, etc., and are not limited as long as they can be used as sealants, but modified silicone-based sealants are preferred.

(silicate)
Also, silicate can be used in the moisture-curable resin composition according to one embodiment of the present invention. This silicate acts as a cross-linking agent and has the function of improving the resilience, durability, and creep resistance of the polymer obtained by curing the moisture-curable resin composition. Furthermore, it also has the effect of improving adhesiveness, water-resistant adhesiveness, and adhesive durability under high-temperature and high-humidity conditions. A tetraalkoxysilane or a partially hydrolyzed condensate thereof can be used as the silicate. When silicate is used, it is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of component (A).

Specific examples of silicates include tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n- Examples include tetraalkoxysilanes (tetraalkylsilicates) such as butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, and partially hydrolyzed condensates thereof.

Partially hydrolyzed condensates of tetraalkoxysilanes are more preferable than tetraalkoxysilanes because they are more effective in improving the resilience, durability, and creep resistance of the resulting cured product than tetraalkoxysilanes.

Examples of the partially hydrolyzed condensate of the tetraalkoxysilane include those obtained by adding water to the tetraalkoxysilane and partially hydrolyzing and condensing the mixture by a conventional method. Moreover, a commercially available product can be used as the partially hydrolyzed condensate of the organosilicate compound. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).

(Physical property modifier)
The moisture-curable resin composition according to one embodiment of the present invention may optionally contain a physical property modifier for adjusting the tensile properties of the resulting cured product. Although the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkylisopropenoxysilanes such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane Alkoxysilanes having a functional group such as silane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane; Silicones varnishes; polysiloxanes; By using the physical property modifier, when the moisture-curable resin composition according to one embodiment of the present invention is cured, the hardness can be increased, or conversely, the hardness can be decreased and the elongation at break can be increased. The physical property modifiers may be used alone or in combination of two or more.

In particular, a compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis has the effect of lowering the modulus of the cured product without worsening the stickiness of the surface of the cured product. Compounds that generate trimethylsilanol are particularly preferred. As a compound that produces a compound having a monovalent silanol group in its molecule by hydrolysis, the compound described in JP-A-5-117521 can be mentioned. In addition, trimethylol, which is a derivative of an alkyl alcohol such as hexanol, octanol, decanol, etc., and produces a silicon compound such as trimethylsilanol that produces R ₃ SiOH by hydrolysis, is described in JP-A-11-241029. Examples include compounds which are derivatives of polyhydric alcohols having 3 or more hydroxy groups such as propane, glycerin, pentaerythritol and sorbitol and which generate silicon compounds such as trimethylsilanol which generate R ₃ SiOH by hydrolysis.

Further, compounds which are derivatives of oxypropylene polymers and which generate silicon compounds such as trimethylsilanol, which generate R ₃ SiOH by hydrolysis, as described in JP-A-7-258534 can also be mentioned. Furthermore, a polymer having a crosslinkable reactive silyl group and a silicon-containing group capable of forming a monosilanol-containing compound by hydrolysis described in JP-A-6-279693 can also be used.

The physical property modifier is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of component (A).

(thixotropic agent)
The moisture-curable resin composition according to one embodiment of the present invention may optionally contain a thixotropic agent (anti-sagging agent) to prevent sagging and improve workability. Examples of anti-sagging agents include, but are not limited to, polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate and barium stearate. In addition, when rubber powder having a particle size of 10 μm to 500 μm as described in JP-A-11-349916 and organic fibers as described in JP-A-2003-155389 are used, thixotropic properties are obtained. A moisture-curable resin composition with high workability can be obtained. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is used in an amount of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of component (A).

(Compound containing an epoxy group)
A compound containing an epoxy group in one molecule can be used in the moisture-curable resin composition according to one embodiment of the present invention. The use of a compound having an epoxy group can enhance the restorability of the cured product. Examples of compounds having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl stearate, Epoxy butyl stearate and the like can be mentioned. Among these, E-PS is particularly preferred. The epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of component (A).

(Photocurable substance)
A photocurable material may be used in the moisture-curable resin composition according to one embodiment of the present invention. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, thereby improving stickiness and weather resistance of the cured product. A photocurable substance is a substance whose molecular structure undergoes a chemical change in a fairly short time due to the action of light, resulting in physical changes such as curing. Many compounds such as organic monomers, oligomers, resins and compositions containing them are known as this type of compound, and any commercially available compounds can be employed. Typical examples include unsaturated acrylic compounds, polyvinyl cinnamates, and azide resins. Examples of unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one to several acrylic or methacrylic unsaturated groups, such as propylene (or butylene, ethylene) glycol di(meth)acrylate, neopentyl Monomers such as glycol di(meth)acrylate and oligoesters having a molecular weight of 10,000 or less are exemplified. Specifically, for example, special acrylates (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (multifunctional) Aronix M-400, especially containing acrylic functional groups. is preferred, and compounds containing three or more of the same functional groups on average in one molecule are preferred (all Aronics are products of Toagosei Co., Ltd.).

Examples of polyvinyl cinnamate include a photosensitive resin having a cinnamoyl group as a photosensitive group, which is obtained by esterifying polyvinyl alcohol with cinnamic acid, and many polyvinyl cinnamate derivatives. Azide resins are known as photosensitive resins having an azide group as a photosensitive group, and are usually rubber photosensitive liquids containing a diazide compound as a photosensitive agent. Publishing, Printing Society Publishing Department, page 93, page 106, page 117). can do. The effect may be enhanced by adding a sensitizer such as ketones or nitro compounds or an accelerator such as amines. The photocurable substance is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of component (A). If the amount is less than 20 parts by weight, there is no effect of improving the weather resistance.

(oxygen-curable substance)
An oxygen-curable material can be used in the moisture-curable resin composition according to one embodiment of the present invention. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, and react with oxygen in the air to form a cured film near the surface of the cured product, making the surface sticky and preventing the surface of the cured product from sticking. It acts to prevent the adhesion of dirt and dust. Specific examples of oxygen-curable substances include drying oils represented by paulownia oil and linseed oil, and various alkyd resins obtained by modifying the drying oils; acrylic polymers modified with drying oils, epoxy-based Resins, silicone resins; 1,2-polybutadiene, 1,4-polybutadiene obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, C5 to C8 diene polymers, etc. and liquid copolymers such as NBR and SBR obtained by copolymerizing these diene compounds and copolymerizable monomers such as acrylonitrile and styrene so that the diene compounds are the main component, and Various modified products thereof (maleated modified products, boil oil modified products, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Among these, paulownia oil and liquid diene polymers are particularly preferred. In some cases, the effect can be enhanced by using a catalyst and/or a metal drier that accelerates the oxidative curing reaction. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate and zirconium octylate, and amine compounds. The amount of the oxygen-curable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of component (A). be. If the amount is less than 0.1 part by weight, the improvement in staining resistance is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in JP-A-3-160053, oxygen-curable substances are preferably used in combination with photo-curable substances.

(Flame retardants)
The moisture-curable resin composition according to one embodiment of the present invention contains phosphorus-based plasticizers such as ammonium polyphosphate and tricresyl phosphate, aluminum hydroxide, magnesium hydroxide, and flame retardants such as thermally expandable graphite. can be added. The flame retardants may be used alone or in combination of two or more.

The flame retardant is used in an amount of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, per 100 parts by weight of component (A).

(solvent)
A solvent can be used in the moisture-curable resin composition according to one embodiment of the present invention for the purpose of reducing the viscosity of the moisture-curable resin composition, increasing the thixotropy, and improving workability. The solvent is not particularly limited, and various compounds can be used. Specific examples include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and petroleum solvents; halogen solvents such as trichlorethylene; ester solvents such as ethyl acetate and butyl acetate; Examples include ketone-based solvents; alcohol-based solvents such as methanol, ethanol, and isopropyl alcohol; and silicone-based solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. These solvents may be used alone or in combination of two or more.

However, if the amount of the solvent is large, the toxicity to the human body may increase, and the volume shrinkage of the cured product may occur. Therefore, the amount of the solvent to be blended is preferably 3 parts by weight or less, more preferably 1 part by weight or less per 100 parts by weight of component (A), and most preferably contains substantially no solvent. preferable.

(Other additives)
In the moisture-curable resin composition according to one embodiment of the present invention, for the purpose of adjusting various physical properties of the moisture-curable resin composition or cured product, if necessary, other additives other than the above-mentioned additives may be used. Examples of such other additives include curability modifiers, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, foaming agents, anti-oxidants. Examples include anti-ant agents and fungicides. These various additives may be used alone or in combination of two or more. Specific examples of other additives include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, and JP-A-2001-72854. etc.

[3.3. Form of moisture-curable resin composition]
The moisture-curable resin composition according to one embodiment of the present invention is prepared as a one-component moisture-curable resin composition that is pre-mixed with all ingredients, sealed and stored, and cured by moisture in the air after application. be able to. Alternatively, the moisture-curable resin composition according to one embodiment of the present invention includes a curing catalyst, a filler, a plasticizer, water as a curing agent, separately from the polymer composition containing the components (A) and (B). It is also possible to prepare a two-component moisture-curable resin composition by blending the above ingredients and mixing the blending material and the polymer composition before use. From the viewpoint of workability, the one-component type is preferred.

When the moisture-curable resin composition is a one-component type, since all the ingredients are pre-blended, the moisture-containing ingredients are preliminarily dehydrated and dried before use, or reduced pressure is applied during compounding and kneading. Dehydration is preferred. When the moisture-curable resin composition is a two-component type, there is no need to add a curing catalyst to the moisture-curable resin (A), so there is no fear of gelation even if the compounding agent contains a small amount of water. Although less, dehydration and/or drying is preferred when long-term storage stability is required. As a method for dehydration and/or drying, in the case of solid substances such as powder, heat drying method or vacuum dehydration method, and in the case of liquid substances, vacuum dehydration method or synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc. The dehydration method used is preferred. In addition to such dehydration and/or drying methods, dehydrating agents include n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercapto An alkoxysilane compound such as propylmethyldiethoxysilane or γ-glycidoxypropyltrimethoxysilane may be added and reacted with water for dehydration. As a dehydrating agent, an oxazolidine compound such as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine may be blended and reacted with water for dehydration. Also, as a dehydrating agent, a small amount of an isocyanate compound may be blended to react the isocyanate groups with water for dehydration. Addition of an alkoxysilane compound, an oxazolidine compound, and an isocyanate compound improves storage stability.

The amount of the dehydrating agent, especially the silicon compound capable of reacting with water such as vinyltrimethoxysilane, is 0.1 to 20 parts by weight, preferably 0.5 parts by weight, per 100 parts by weight of component (A). to 10 parts by weight, more preferably 1 to 5 parts by weight.

[3.4. Manufacturing method of moisture-curable resin composition]
The method for producing the moisture-curable resin composition according to one embodiment of the present invention is not particularly limited, and for example, a method of blending the above-described components and kneading them at room temperature or under heating using a mixer, rolls, kneader, or the like. , dissolving and mixing the components using a small amount of a suitable solvent.

[3.5. Uses of moisture-curable resin composition]
When the moisture-curable resin composition according to one embodiment of the present invention is exposed to the air, it forms a three-dimensional network due to the action of moisture and cures into a solid having rubber-like elasticity. Therefore, one embodiment of the present invention also includes a cured product obtained by curing the moisture-curable resin composition.

An embodiment of the present invention also includes a laminate obtained by coating a cured product obtained by curing the moisture-curable resin composition.

The moisture-curable resin composition according to one embodiment of the present invention is used as a sealing material for buildings, ships, automobiles, roads, etc. , foaming materials, paints, spraying materials, etc. A cured product obtained by curing the moisture-curable resin composition according to one embodiment of the present invention is excellent in flexibility and adhesiveness, and therefore, it is more preferably used as a sealant or adhesive among these.

In addition, electrical and electronic component materials such as backside sealing materials for solar cells, electrical insulating materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact adhesives, spray sealants, crack repair materials, and powder coatings. , casting materials, medical rubber materials, medical adhesives, sealing materials for medical equipment, food packaging materials, joint sealing materials for exterior materials such as siding boards, coating materials, primers, conductive materials for shielding electromagnetic waves, heat conduction materials, hot-melt materials, potting agents for electrical and electronic devices, films, gaskets, various molding materials, sealing materials for rust prevention and waterproofing of wired glass and laminated glass edges (cut parts), automotive parts, electrical parts, And it can be used for various applications such as liquid sealing agents used in various machine parts. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings, etc. alone or with the help of a primer, it can be used as various types of sealing and adhesive compositions. . Further, the moisture-curable resin composition according to one embodiment of the present invention is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiling, an adhesive for stone, a ceiling finishing adhesive, and a floor finishing adhesive. adhesives, wall finishing adhesives, vehicle panel adhesives, electrical/electronic/precision equipment assembly adhesives, direct glazing sealing materials, double glazing sealing materials, SSG construction method sealing materials, or buildings It can also be used as a sealing material for working joints.

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these.

The number average molecular weight and weight average molecular weight in the examples are GPC molecular weights measured under the following conditions.
Liquid delivery system: Tosoh HLC-8120GPC
Column: TSK-GEL H type manufactured by Tosoh Solvent: THF
Molecular weight: Polystyrene equivalent Measurement temperature: 40°C
[Synthesis Example 1] [Comparative Synthesis Examples 1 and 2]
Isobutanol was added to the flask as an initial charge solvent, heated to 105° C., and purged with nitrogen. Then, a mixed solution of (meth)acrylic acid ester-based monomers shown in Table 1 was prepared under a nitrogen atmosphere while stirring. A solution of , V-59 and isobutanol was added dropwise over 5 hours, and polymerization was further carried out after 1 hour. The isobutanol was removed from the obtained isobutanol solution of the (meth)acrylic acid ester copolymer under heating and reduced pressure to obtain a transparent and viscous liquid. As a result, (meth)acrylic acid ester copolymers (polymer (B-1), comparative polymers (B-1) and (B-2)) having molecular weights shown in Table 1 were obtained.

The abbreviations of the (meth)acrylic acid ester-based monomers and solvents in Table 1 and the details of the polymerization initiator are as follows.
MEA: methoxyethyl acrylate NK ester PHE-1G: phenoxyethyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
BA: butyl acrylate TSMA: 3-(trimethoxysilyl)propyl methacrylate IBA: isobutanol V-59: 2,2′-azobis(2-methylbutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)

[Synthesis Example 2]
Polyoxypropylene diol having a number average molecular weight of about 4,500 was used as an initiator, and propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a hydroxyl group-terminated polyoxypropylene having a number average molecular weight of about 17,000. rice field. Subsequently, a methanol solution of 1.2 equivalents of sodium methoxide was added to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene, and methanol was distilled off at 140° C., followed by 1.3 equivalents of 3-chloro-1-propene. was added to convert the terminal hydroxyl group to an allyl group. Next, 36 ppm of a platinum divinyldisiloxane complex (3% by weight of isopropyl alcohol solution in terms of platinum) and 1.3 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene. C. for 2 hours, a polyoxypropylene having an average of 1.2 silyl groups per molecule and a number average molecular weight of 17,000 and having methyldimethoxysilyl groups at the ends (polymer (A-1)) got

[Synthesis Example 3]
Using n-butanol as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene having a number average molecular weight of about 8,000 and a hydroxyl group terminal at one end of the molecular chain. . Subsequently, a methanol solution of 1.2 equivalents of sodium methoxide is added to the hydroxyl groups of this polyoxypropylene, and methanol is distilled off at 140° C., and then 1.5 equivalents of 3-chloro-1-propene are added. to convert the terminal hydroxyl group to an allyl group. Next, 36 ppm of a platinum divinyldisiloxane complex (3% by mass of isopropyl alcohol solution in terms of platinum) and 1.8 parts by weight of methyldimethoxysilane were added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, and the mixture was heated to 90°C. for 2 hours, a polyoxypropylene (polymer (C -1)) was obtained.

[Example 1] [Comparative Examples 1 to 5]
Shown in Tables 2 and 3, component (B) (Synthesis Example 1, or obtained in Comparative Synthesis Examples 1 and 2, (meth)acrylic acid ester copolymer (polymer (B-1), comparative polymer (B-1), (B-2))), component (A) (polyoxypropylene obtained in Synthesis Example 2 (polymer (A-1)), reactive cross-linking agent (obtained in Synthesis Example 3 polyoxypropylene (polymer (C-1)), phthalate plasticizer (DIDP: diisodecyl phthalate), surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: Hakuenka CCR), heavy Calcium carbonate (manufactured by Maruo Calcium Co., Ltd., trade name: Whiten SB), titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name: Typaque R-820), thixotropic agent (manufactured by Kusumoto Kasei Co., Ltd., product Name: Disparon 6500), a light stabilizer (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin 770), an ultraviolet absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin 326). 2 and 3 were weighed, mixed and thoroughly kneaded, passed through three small paint rolls to disperse, then dehydrated under reduced pressure at 120°C for 2 hours, and then cooled to 50°C or less. After cooling, vinyltrimethoxysilane (manufactured by Momentive Performance Materials, trade name: Silquest A-171) was used as a dehydrating agent, and γ-(2-aminoethyl)aminopropyltrimethoxysilane (Momentive Performance Materials, trade name: Silquest A-1120), and dibutyltin bisacetylacetonate (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name: Neostan U-220H) as a curing catalyst are listed in Tables 2 and 3. and kneaded to obtain a moisture-curable resin composition.

[Evaluation of paint adhesion of cured product]
The paint adhesion of the cured product was evaluated by a cross-cut test. Specifically, the moisture-curable resin compositions obtained in Example 1 and Comparative Examples 1 to 5 were made into sheet-shaped specimens with a thickness of 3 mm, and the "curing conditions for the cured product" described in Tables 2 and 3 were obtained. After curing with , a water-based acrylic emulsion paint (manufactured by SK Kaken Co., Ltd., trade name "Please Coat") was applied to the surface of the sheet-shaped specimen. After that, the sheet-shaped specimens to which the paint was applied were cured under the "curing conditions for paint" described in Tables 2 and 3. After curing, the sheet-shaped specimen was cut in a grid pattern from the coating film side so that 25 squares of 2 mm square were formed. Cellotape (registered trademark) was pasted on the cuts of the grid, and when it was peeled off, the number of squares remaining on the surface of the sheet-like specimen without the coating film adhering to Cellotape (registered trademark) was counted. . Paint adhesion evaluation results are the average of two tests.

When the curing condition of the paint in Tables 2 and 3 is "23°C for 7 days", after applying the paint and drying and curing it at 23°C for 7 days, the cross-cut test was performed by making the cross-cut incisions. On the other hand, when the curing conditions of the paint in Table 2 are "23°C 7 days + 50°C hot water 7 days + 23°C 1 day", after applying the paint and drying it at 23°C for 7 days, it is further heated to 50°C. It was immersed for 7 days, taken out, and dried at 23° C. for 1 day to conduct a cross-cut test.

From the results of Table 2, in Example 1 in which a moisture-curable resin composition containing a (meth)acrylic acid ester-based copolymer having an aromatic ring in a side chain and a moisture-curable resin is cured, the same moisture-curable A moisture-curable resin composition containing a resin and a (meth)acrylic acid ester copolymer that does not have an aromatic ring in the side chain (Comparative Examples 2 and 3) or a (meth)acrylic acid ester copolymer As compared with Comparative Examples 1 to 3, in which a moisture-curable resin composition (Comparative Example 1) is cured, the resulting cured product has excellent paint adhesion.

Further, from the results of Table 3, in Example 1 in which a moisture-curable resin composition containing a (meth)acrylic acid ester copolymer having an aromatic ring in a side chain and a moisture-curable resin is cured, the same humidity Even when compared with Comparative Examples 4 and 5 in which a moisture-curable resin composition containing a curable resin and a phthalate ester plasticizer as a plasticizer is cured, the obtained cured product has excellent paint adhesion. . That is, the moisture-curable resin composition according to one embodiment of the present invention, which contains a (meth)acrylic acid ester copolymer having an aromatic ring in a side chain and a moisture-curable resin, is a non-bleed formulation. In addition, the adhesion of the coating film is improved more than when a phthalate plasticizer is used.

INDUSTRIAL APPLICABILITY The present invention is used for sealing materials for buildings, ships, automobiles, roads, etc., pressure-sensitive adhesives, adhesives, molding agents, anti-vibration materials, damping materials, sound-insulating materials, foam materials, paints, spray materials, etc. be able to.

Claims (6)

A moisture-curable resin composition containing a moisture-curable resin (A), a (meth)acrylic acid ester copolymer (B) having an aromatic ring in a side chain , and a plasticizer ,
The moisture-curable resin (A) is an organic polymer containing a reactive silyl group at the molecular chain end,
In the (meth)acrylic ester-based copolymer (B) having an aromatic ring in the side chain, the group represented by the following general formula (1) is the (meth)acrylic ester-based copolymer (B) attached to the main chain,
-XR ¹ -YR ² (1)
In formula (1), X is -CO-O-, -O-CO-, -CO-N(R ³ )-, -O-CO-N(R ³ )-, -N(R ³ )-CO a linking group selected from -O-, -N(R 3 )-CO-N(R 3 )-, -S-CO-NH-, -NH-CO-S-, -S- and ^a direct ^bond and R ³ is a hydrogen atom, an optionally halogen-substituted cyclic, linear or branched alkyl group having 1 to 18 carbon atoms, an optionally halogen-substituted cyclic, linear or branched chain is an alkenyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and R 1 is an ^optionally halogen-substituted cyclic, linear or branched cyclic, linear or branched group having 1 to 18 carbon atoms. an alkylene group, an optionally halogen-substituted cyclic, linear or branched alkenylene group having 1 to 18 carbon atoms, or a direct ^bond ; optionally substituted with an atom, a nitrogen atom, or a sulfur atom, Y is a substituted or unsubstituted arylene group having 6 to 18 carbon atoms, R 2 is a hydrogen atom, an optionally halogen-substituted ^cyclic , a linear or branched alkyl group having 1 to 18 carbon atoms, or an optionally halogen-substituted cyclic, linear or branched alkenyl group having 1 to 18 carbon atoms,
The moisture-curable resin (A) is a moisture-curable resin (A) other than the (meth)acrylic acid ester copolymer (B) having an aromatic ring in the side chain,
The moisture-curable resin composition , wherein the plasticizer is a reactive plasticizer . 2. The moisture-curable resin composition according to claim 1 , wherein the (meth)acrylic acid ester copolymer (B) having an aromatic ring in a side chain is an adhesion imparting agent. 3. The moisture-curable resin composition according to claim 1 , wherein the (meth)acrylic acid ester copolymer (B) having an aromatic ring in a side chain contains a reactive silyl group. The moisture-curable resin according to any one of claims 1 to 3 , wherein the organic polymer is a saturated hydrocarbon-based polymer, a polyoxyalkylene-based polymer, or a (meth)acrylic acid ester-based polymer. Composition. A cured product obtained by curing the moisture-curable resin composition according to any one of claims 1 to 4 . A laminate obtained by coating a cured product obtained by curing the moisture-curable resin composition according to any one of claims 1 to 4 with a coating material.