One-component sealant

Abstract

To provide a one-component sealant that has an appropriate pot life, an appropriate touch-dry time, excellent conformability to WJ joint movement when uncured or during curing, and excellent internal and / or surface appearance. [Solution] A one-component sealant comprising (A) a crosslinkable silyl group-containing polymer, (B) a plasticizer, (C) a filler, and (D) a tin catalyst, wherein (A) comprises (A1) a crosslinkable silyl group-containing polymer having a crosslinkable dimethoxy group, and (D) comprises two or more tetravalent tin catalysts, wherein (D) contains (D1) dibutyltin oxide as the tetravalent tin catalyst. This one-component sealant can be suitably used for building applications.

Description

Technical Field

[0001] The present invention relates to a one-component sealing material, and more particularly to a one-component sealing material suitably used for construction.

Background Art

[0002] In recent years, there has been a shortage of skilled workers at construction sites. Therefore, in sealing work, since the number of man-hours is less, the demand for one-component sealing materials that do not require a mixing process is increasing compared to two-component sealing materials that require a mixing process.

[0003] However, when a one-component sealing material that takes time to cure is used for working joints (hereinafter referred to as "WJ") of buildings such as buildings, generally, insufficient durability and / or poor appearance during curing may occur. The WJ joint becomes narrower (compressed) during the day due to the expansion of metal due to heat (sunlight), and becomes wider (expands) at night due to the contraction of metal due to heat dissipation. The WJ joint can cause a displacement (movement) of about ±10 to 15% in width in 24 hours. Usually, an uncured or curing one-component sealing material cannot follow the movement of the WJ joint, and wrinkles and cracks occur on the surface and inside of the one-component sealing material, which may cause poor appearance of the one-component sealing material (see FIG. 1). Therefore, a two-component sealing material that can be cured in a shorter time is often used for the WJ joint.

[0004] Patent Document 1 discloses a one-component curable composition for working joints containing a polyoxyalkylene polymer having an average of 1.2 to 5 specific reactive silicon groups (particularly, trialkoxysilyl groups) per molecule, a specific silane compound, and a specific tetravalent organotin compound. Patent Document 1 can provide a cured product excellent in compression recovery rate, displacement followability, and durability, and applicable as a sealing material for working joints of buildings (see Summary, Claims,

[0001] ,

[0011] ,

[0014] , Examples 1 to 9, etc.).

Prior Art Documents

[0005] [Patent Document 1] WO2019 / 159972 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] Patent Document 1 describes conducting a durability test (JIS durability classification 9030) and visually observing the state of cracks at the adhesive interface between the adherend and the cured material to evaluate the presence or absence of cracks at the adhesive interface between the adherend and the cured material. However, Patent Document 1 does not mention in any way whether wrinkles and cracks occur on the surface or inside the one-component sealant, or whether there are any defects in the appearance of the one-component sealant. Patent Document 1 does not teach in any way that an uncured or curing one-component sealant can follow the movement of a WJ joint.

[0007] WJ joints widen at night and narrow during the day. One-component sealants are applied to WJ joints during the day and are thought to harden from the surface inward. After application, one-component sealants begin to harden from the surface, but during this time, the WJ joint width widens at night and narrows during the day. As a result, one-component sealants are prone to wrinkling and developing cosmetic defects (see Figure 1). Therefore, one-component sealants are required to effectively follow the movement of WJ joints, preventing wrinkles and appearance defects (excellent movement-following ability).

[0008] The objective of this specification is to provide a one-component sealant that has an appropriate pot life, an appropriate touch-dry time, excellent conformability to WJ joint movement when uncured or during curing, and excellent appearance of the interior and / or surface of the one-component sealant (no wrinkles and / or cracks). [Means for solving the problem]

[0009] As a result of diligent research, the inventors have found that a one-component sealant containing a specific crosslinkable silyl group polymer having a dimethoxysilyl group, containing dibutyltin oxide, and containing at least two types of tetravalent tin catalysts has an appropriate pot life and appropriate touch-dry time, exhibits excellent movement-following properties of WJ joints in its uncured or partially cured state, and has excellent internal and / or surface appearance (no wrinkles or / or cracks). Furthermore, they have found that such a one-component sealant is suitable for building applications, thus completing the present invention.

[0010] That is, this specification includes one-component sealants of the embodiments described below. 1. A one-component sealing material comprising (A) a crosslinkable silyl group-containing polymer, (B) a plasticizer, (C) a filler, and (D) a tin catalyst, (A) Crosslinkable silyl group-containing polymers include (A1) Crosslinkable silyl group-containing polymers having dimethoxysilyl groups, (D) The tin catalyst contains two or more types of tetravalent tin catalysts. (D) The tin catalyst is a one-component sealing material containing (D1) dibutyltin oxide as a tetravalent tin catalyst. 2. The (A) crosslinkable silyl group-containing polymer comprises 50 to 100 parts by mass of (A1) a silyl group-containing polymer having a dimethoxysilyl group, as described in 1 above. 3. The one-component sealing material according to 1 or 2 above, wherein the (A) crosslinkable silyl group-containing polymer does not contain the (A2) crosslinkable silyl group-containing polymer having a trimethoxy group, triethoxy group, or diethoxy group, or contains 10 parts by mass or less of the (A) crosslinkable silyl group-containing polymer in 100 parts by mass. 4. (A) The crosslinkable silyl group-containing polymer is a one-component sealant according to any one of 1 to 3 above, comprising (A3) a crosslinkable silyl group-containing polymer having three or more dimethoxysilyl groups. 5. The (A) crosslinkable silyl group-containing polymer comprises 20 to 80 parts by mass of a crosslinkable silyl group-containing polymer having 3 or more (A3) dimethoxysilyl groups per 100 parts by mass of the (A) crosslinkable silyl group-containing polymer, as described in 4 above. 6. (D) The tin catalyst is a one-component sealing material according to any one of 1 to 5 above, comprising 10 to 90 parts by mass of (D1) dibutyltin oxide per 100 parts by mass of tetravalent tin catalyst. 7. (D) The tin catalyst comprises, in addition to (D1) dibutyltin oxide, at least one selected from dibutyltin dilaurate, dibutyltin acetyl acetate, and dibutyltin ethyl silicate, a one-component sealing material according to any one of 1 to 6 above. 8. A one-component sealant according to any one of 1 to 7 above, comprising 0.1 to 6.0 parts by mass of (D) tin catalyst per 100 parts by mass of (A) crosslinkable silyl group-containing polymer, or comprising 0.05 to 3.0 parts by mass of (D) tin catalyst per 100 parts by mass of one-component sealant. 9. A one-component building sealant as described in any one of items 1 to 8 above. [Effects of the Invention]

[0011] The one-component sealant of the embodiment of the present invention has a suitable pot life and touch-dry time, exhibits excellent joint movement-following properties when uncured or during curing, and has excellent internal and / or surface appearance (no wrinkles or / or cracks). Furthermore, the one-component sealant of the embodiment of the present invention can be suitably used for building applications. [Brief explanation of the drawing]

[0012] [Figure 1] Figure 1 schematically shows a working joint (WJ) joint. [Figure 2] Figure 2 shows front and side views of the dynamic exposure testing machine. [Figure 3] Figure 3 schematically shows a test joint. [Modes for carrying out the invention]

[0013] In one embodiment of the present invention, there is provided a one-component sealing material containing (A) a polymer containing a crosslinkable silyl group (hereinafter also referred to as "(A) polymer"), (B) a plasticizer, (C) a filler, and (D) a tin catalyst. (A) The polymer containing a crosslinkable silyl group includes (A1) a polymer containing a crosslinkable silyl group having a dimethoxysilyl group (hereinafter also referred to as "(A1) polymer"). (D) The tin catalyst includes two or more tetravalent tin catalysts. (D) The tin catalyst includes (D1) dibutyltin oxide as a tetravalent tin catalyst. The one-component sealing material can be suitably used as a one-component building sealing material.

[0014] In an embodiment of the present invention, the (A) polymer containing a crosslinkable silyl group includes "(A1) a polymer containing a crosslinkable silyl group having a dimethoxysilyl group", and is not particularly limited as long as the one-component sealing material aimed at by the present invention can be obtained. As used herein, the "crosslinkable silyl group" refers to a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom, which can form a siloxane bond and crosslink by a reaction catalyzed by a curing catalyst. The "hydrolyzable group" is not particularly limited as long as the one-component sealing material aimed at by the present invention can be obtained, and may be a conventionally known hydrolyzable group. Specific examples of the hydrolyzable group include, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, etc. The crosslinkable group is preferably a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, an alkenyloxy group, and an alkoxy group is particularly preferred because of its mild hydrolyzability and easy handling.

[0015] The crosslinkable silyl group may have a group other than the crosslinkable group as long as the one-component sealing material targeted by the present invention can be obtained, and examples of the group other than the crosslinkable group include an alkyl group. More specifically, examples of the crosslinkable silyl group include trialkoxysilyl groups (such as trimethoxysilyl group and triethoxysilyl group), alkyldialkoxysilyl groups (such as methyldimethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl group, and ethyldiethoxysilyl group), and the like are particularly preferred.

[0016] The “(A) polymer” has a crosslinkable silyl group in the polymer chain and is not particularly limited as long as the one-component sealing material targeted by the present invention can be obtained. The polymer chain of the (A) polymer may include, for example, a “polyoxyalkylene skeleton”, a “skeleton made of poly(meth)acrylate (or a skeleton derived from poly(meth)acrylate)”, and the like. The “polyoxyalkylene skeleton” refers to a skeleton made of polyalkylene oxide (or alkylene oxide polymer) obtained by polymerizing alkylene oxide, and is not particularly limited as long as the curable composition targeted by the present invention can be obtained.

[0017] Examples of the “polyoxyalkylene” include polypropylene oxide, polyethylene oxide, propylene oxide-ethylene oxide copolymer, and the like. Among them, polypropylene oxide is preferred in terms of easy availability. The “polyoxyalkylene skeleton” preferably has a number average molecular weight of 8,000 to 50,000, and more preferably 20,000 to 50,000.

[0018] The “skeleton made of poly(meth)acrylate (or a skeleton derived from poly(meth)acrylate)” refers to a skeleton made of poly(meth)acrylate obtained by polymerizing (meth)acrylate, and is not particularly limited as long as the one-component sealing material targeted by the present invention can be obtained. The term "poly(meth)acrylate skeleton" refers to a skeleton made of poly(meth)acrylate (or poly(meth)acrylic acid ester polymer) obtained by polymerizing (meth)acrylate (or (meth)acrylic acid ester), and is not particularly limited as long as it can obtain the one-component sealing material targeted by the present invention.

[0019] Examples of "poly(meth)acrylate" include poly(meth)acrylate (or (meth)acrylic acid ester polymer) obtained by polymerization of (meth)acrylate (or (meth)acrylic acid ester). Examples of such (meth)acrylates include the following compounds: Alkyl methacrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, 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-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, etc. (Meth)acrylic acid esters having aromatic hydrocarbon groups, such as phenyl(meth)acrylate, toluyl(meth)acrylate, benzyl(meth)acrylate, and biphenyl(meth)acrylate; (Meth)acrylic acid esters having alkoxy groups, such as 2-methoxyethyl (meth)acrylate and 3-methoxybutyl (meth)acrylate; (Meth)acrylic acid esters having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; (Meth)acrylic acid esters having epoxy groups, such as glycidyl (meth)acrylate; (meth)acrylic acid esters having an amino group and / or an imino group, such as 2-aminoethyl (meth)acrylate; (Meth)acrylic acid esters having tertiary amines such as diethylaminoethyl (meth)acrylate; (meth)acrylic acid esters containing halogens, such as trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate. These (meth)acrylates may be used individually or in combination of two or more types.

[0020] Furthermore, the poly(meth)acrylate may contain monomer units copolymerizable with the repeating units described above. Such monomers may include, for example, monomer units containing a carboxyl group, such as acrylic acid and methacrylic acid; monomer units containing an amide group, such as acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide; and compounds having an ether linkage, such as aminoethyl vinyl ether, polyoxyethylene acrylate, and polyoxyethylene methacrylate. Furthermore, it may contain monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, etc.

[0021] The monomer composition of the poly(meth)acrylate described above can be appropriately selected as long as it is sufficient to obtain the one-component sealant that is the target of the present invention. The poly(meth)acrylate preferably contains an alkyl (meth)acrylate ester and an aromatic hydrocarbon group-containing (meth)acrylate ester, and more preferably contains an alkyl (meth)acrylate ester. The poly(meth)acrylate preferably contains an alkyl (meth)acrylate ester and an aromatic hydrocarbon group-containing (meth)acrylate ester, and more preferably contains an alkyl (meth)acrylate ester.

[0022] The number-average molecular weight of the "poly(meth)acrylate skeleton (or skeleton derived from poly(meth)acrylate)" is preferably 3,000 to 100,000, more preferably 13,000 to 50,000, and even more preferably 20,000 to 35,000.

[0023] (A) polymer includes (A1) polymer. (A1) The polymer contains a crosslinkable silyl group having a dimethoxysilyl group as the crosslinkable silyl group. The "crosslinkable silyl group having a dimethoxysilyl group" preferably includes, for example, an alkyldimethoxysilyl group. The number of carbon atoms in the alkyl group of the alkyldimethoxysilyl group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2. More specifically, the alkyldimethoxysilyl group preferably includes at least one selected from methyldimethoxysilyl group, ethyldimethoxysilyl group, and propyldimethoxysilyl group, etc.

[0024] (A1) The polymer chain of the polymer preferably includes at least one selected from, for example, "polyoxyalkylene skeleton" and "a skeleton made of poly(meth)acrylate (or a skeleton derived from poly(meth)acrylate)". (A1) When the polymer chain of the polymer contains a polyoxyalkylene backbone, it can provide advantageous effects such as superior flexibility (elongation) and lower viscosity of the composition, and when it contains a polyacrylate backbone, it can provide advantageous effects such as superior durability and weather resistance. By combining both, the advantages of each can be enjoyed.

[0025] (A1) The number of crosslinkable silyl groups having dimethoxysilyl groups in the polymer is not particularly limited and can be appropriately selected as long as a one-component sealing material for which the present invention is intended can be obtained. (A1) The number of crosslinkable silyl groups having dimethoxysilyl groups in the polymer may be 1, 2, 3, or 4 or more. Furthermore, polymer (A1) may be a combination of a polymer containing two crosslinkable silyl groups having dimethoxysilyl groups and a polymer containing three crosslinkable silyl groups having dimethoxysilyl groups. This may be a combination of a polymer containing two crosslinkable silyl groups having dimethoxysilyl groups and a polymer containing four or more crosslinkable silyl groups having dimethoxysilyl groups. A polymer containing three crosslinkable silyl groups having dimethoxysilyl groups may be a combination of a polymer containing four or more crosslinkable silyl groups having dimethoxysilyl groups.

[0026] The polymer (A) preferably contains 50 to 100 parts by mass of polymer (A1) per 100 parts by mass of polymer (A), more preferably 60 to 98 parts by mass of polymer (A1), even more preferably 70 to 95 parts by mass of polymer (A1), and particularly preferably 75 to 90 parts by mass of polymer (A1). When polymer (A) contains 50 to 100 parts by mass of polymer (A1) per 100 parts by mass of polymer (A), it exhibits the advantageous effect of superior curability and conformability.

[0027] (A) The polymer preferably does not contain (A2) a crosslinkable silyl group-containing polymer having a trimethoxy group, a triethoxy group, or a diethoxy group (hereinafter also referred to as "(A2) polymer"). Alternatively, polymer (A) may contain polymer (A2) in amounts of 100 parts by mass of polymer (A), preferably 10 parts by mass or less, preferably 8 parts by mass or less, more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably not contain polymer (A2) at all. (A) exhibits the advantageous effect of superior curability and conformability when it does not contain polymer (A2), or when polymer (A) is included in amounts of 10 parts by mass or less of polymer (A2) per 100 parts by mass of polymer (A).

[0028] (A2) The polymer may contain, for example, a silyl group selected from a trimethoxysilyl group-containing polymer, a triethoxysilyl group-containing polymer, and an alkyldiethoxysilyl group. The number of carbon atoms in the alkyl group of the alkyldiethoxysilyl group may be 1, 2, or 3. More specifically, the alkyldiethoxysilyl group may include at least one selected from a methyldiethoxysilyl group, an ethyldiethoxysilyl group, and a propyldiethoxysilyl group, etc.

[0029] (A2) The polymer chain of the polymer may include, for example, at least one selected from "polyoxyalkylene backbone" and "backbone made of poly(meth)acrylate (or backbone derived from poly(meth)acrylate)". If a case could fall under both (A1) and (A2), it will be considered included in (A2) but not included in (A1).

[0030] (A) The silyl group-containing polymer preferably includes (A3) a crosslinkable silyl group-containing polymer having three or more dimethoxysilyl groups (hereinafter also referred to as "(A3) polymer"). (A3) A crosslinkable silyl group-containing polymer having 3 or more dimethoxysilyl groups may include a crosslinkable silyl group-containing polymer having 3 to 12 dimethoxysilyl groups, a silyl group-containing polymer having 4 to 8 dimethoxysilyl groups, and a crosslinkable silyl group-containing polymer having 5 to 7 dimethoxysilyl groups. (A) polymers, when containing (A3) polymers, exhibit the advantageous effect of superior curability and physical properties.

[0031] The "dimethoxysilyl group" preferably includes, for example, an alkyldimethoxysilyl group. The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2. More specifically, the alkyldimethoxysilyl group preferably includes at least one selected from methyldimethoxysilyl, ethyldimethoxysilyl, and propyldimethoxysilyl groups.

[0032] (A3) The polymer chain of the polymer may include, for example, at least one selected from "polyoxyalkylene backbone" and "backbone made of poly(meth)acrylate (or backbone derived from poly(meth)acrylate)".

[0033] The polymer (A) preferably contains 20 to 80 parts by mass of polymer (A3) per 100 parts by mass of polymer (A), more preferably 25 to 75 parts by mass of polymer (A3), even more preferably 30 to 70 parts by mass of polymer (A3), and particularly preferably 35 to 65 parts by mass of polymer (A3). When polymer (A) contains 20 to 80 parts by mass of polymer (A3) per 100 parts by mass of polymer (A), it may exhibit advantageous effects such as superior curability and physical properties.

[0034] The (A1) polymer preferably contains 20 to 80 parts by mass of (A3) polymer per 100 parts by mass of (A1) polymer, more preferably 25 to 75 parts by mass of (A3) polymer, even more preferably 30 to 70 parts by mass of (A3) polymer, and particularly preferably 35 to 65 parts by mass of (A3) polymer. When polymer (A1) contains 20 to 80 parts by mass of polymer (A3) per 100 parts by mass of polymer (A1), it may exhibit advantageous effects such as superior curability and physical properties.

[0035] The one-component sealant of the embodiment of the present invention includes (B) a plasticizer. As long as the one-component sealant desired by the present invention can be obtained, the plasticizer is not particularly limited, and known plasticizers used in one-component sealants can be used. Examples of plasticizers include acrylic acid ester plasticizers such as non-functional acrylic polymers, phthalate diesters, epoxidized hexahydrophthalate diesters, alkylenedicarboxylic acid diesters, alkylbenzenes, and polyalkylene glycols.

[0036] The one-component sealant of the embodiment of the present invention preferably contains 5 to 60 parts by mass of plasticizer (B) per 100 parts by mass of the one-component sealant, more preferably 10 to 50 parts by mass of plasticizer (B), even more preferably 15 to 40 parts by mass of plasticizer (B), and even more preferably 20 to 35 parts by mass of plasticizer (B). The one-component sealant of the embodiment of the present invention, when containing 5 to 60 parts by mass of plasticizer (B) per 100 parts by mass of the one-component sealant, can exhibit advantageous effects such as lower viscosity (workability) and greater flexibility of the cured product.

[0037] The one-component sealant of the embodiment of the present invention includes (C) a filler. The filler (C) is not particularly limited as long as the one-component sealant for which the present invention is aimed can be obtained, and any known filler (C) used in one-component sealants can be used. Examples of fillers include heavy calcium carbonate, fatty acid-treated calcium carbonate, fume silica, precipitated silica, carbon black, talc, and titanium dioxide.

[0038] The one-component sealant of the embodiment of the present invention preferably contains 10 to 70 parts by mass of filler (C) per 100 parts by mass of the one-component sealant, more preferably 15 to 65 parts by mass of filler (C), even more preferably 20 to 60 parts by mass of plasticizer (C), and even more preferably 25 to 50 parts by mass of filler (C). The one-component sealant of the embodiment of the present invention exhibits a superior balance of strength and elongation when it contains 10 to 70 parts by mass of filler (C) per 100 parts by mass of the one-component sealant.

[0039] The one-component sealant of the embodiment of the present invention includes (D) a tin catalyst. The tin catalyst (D) is not particularly limited as long as the one-component sealant for which the present invention is intended can be obtained, and any known tin catalyst (D) used in one-component sealants can be used. (D) The tin catalyst contains two or more types of tetravalent tin catalysts. (D) The tin catalyst contains (D1) dibutyltin oxide as a tetravalent tin catalyst.

[0040] Examples of tin catalysts include dimethyltin diacetate, dimethyltin bis(acetylacetonate), dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin dioctate, 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), Examples of tetravalent tin catalysts include dibutyltin dimethyloxide, dibutyltin bis(nonylphenoxide), dibutyltin oxide, dibutyltin bis(acetylacetonate) (dibutyltin diacetylacetonate), dibutyltin bis(ethylacetonate), reaction products of dibutyltin oxide and silicate compounds, reaction products of dibutyltin oxide and phthalate esters, dibutyltin diethylhexanoate, dibutyltin bisethoxysilicate, dioctyltin dilaurate, dioctyltin oxide, dioctyltin diacetate, dioctyltin bis(acetylacetonate), and reaction products of dioctyltin oxide and silicate compounds.

[0041] As these tetravalent tin catalysts, dibutyltin-based compounds or dioctyltin-based compounds are preferred, with dibutyltin-based catalysts being particularly preferred. Among dibutyltin-based catalysts, dibutyltin oxide is particularly preferred from the viewpoint of movement tracking ability.

[0042] (D) The tin catalyst preferably contains, in addition to (D1) dibutyltin oxide, at least one selected from dibutyltin dilaurate, dibutyltin acetyl acetate, and dibutyltin ethyl silicate. (D) When the tin catalyst contains at least one selected from dibutyltin dilaurate, dibutyltin acetyl acetate, and dibutyltin ethyl silicate in addition to (D1) dibutyltin oxide, it can exhibit the advantageous effect of having superior curability and conformability of the one-component sealant.

[0043] (D) The tin catalyst preferably contains 10 to 90 parts by mass of (D1) dibutyltin oxide per 100 parts by mass of tetravalent tin catalyst, more preferably 15 to 80 parts by mass of (D1) dibutyltin oxide, even more preferably 20 to 65 parts by mass of (D1) dibutyltin oxide, and particularly preferably 25 to 50 parts by mass of (D1) dibutyltin oxide. (D) When the tin catalyst contains 10 to 90 parts by mass of (D1) dibutyltin oxide per 100 parts by mass of tetravalent tin catalyst, it can exhibit the advantageous effect of having superior curing and conformability of one-component sealants.

[0044] The one-component sealant of the embodiment of the present invention is It is preferable to contain 0.1 to 6.0 parts by mass of (D) tin catalyst per 100 parts by mass of (A) polymer, more preferably 0.5 to 5 parts by mass of (D) tin catalyst, even more preferably 1 to 4 parts by mass of (D) tin catalyst, and particularly preferably 1.5 to 3.7 parts by mass of (D) tin catalyst. or The one-component sealant of the embodiment of the present invention is The sealant preferably contains 0.05 to 3.0 parts by mass of (D) tin catalyst per 100 parts by mass of one-component sealant, more preferably 0.1 to 2.5 parts by mass of (D) tin catalyst, even more preferably 0.15 to 2.0 parts by mass of (D) tin catalyst, and particularly preferably 0.2 to 1.5 parts by mass of (D) tin catalyst.

[0045] The one-component sealant of the embodiment of the present invention is When 0.1 to 6.0 parts by mass of (D) tin catalyst are included per 100 parts by mass of (A) polymer, a more advantageous effect of superior curability can be achieved. The one-component sealant of the embodiment of the present invention is When 0.05 to 3.0 parts by mass of (D) tin catalyst are included per 100 parts by mass of one-component sealant, the curing properties are superior.

[0046] The one-component sealant of the embodiment of the present invention may include, in addition to the above-mentioned components, various additives commonly used in one-component sealants. Examples of such additives include colorants, organic solvents, adhesives, anti-aging agents, thixotropes, moisture-retaining agents, ultraviolet absorbers and / or light stabilizers, antioxidants, stain-resistant agents, storage stability enhancers, and the like.

[0047] Examples of colorants include red iron oxide, titanium dioxide, carbon black, other coloring pigments, dyes, and the like. Examples of organic solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, butanol, acetone, methyl ethyl ketone, ligroin, ethyl acetate, tetrahydrofuran, n-hexane, heptane, and isoparaffinic high-boiling point solvents.

[0048] Examples of adhesives include silane coupling agents and silane coupling agent reactions. The silane coupling agent is not particularly limited, as long as it is commonly used as a silane coupling agent and can yield the one-component sealing material targeted by the present invention. Examples of silane coupling materials include silane coupling materials containing mercapto groups, silane coupling materials containing epoxy groups, and silane coupling materials containing amino groups. The above adhesion-improving agents may be used individually or in mixtures of two or more types. Furthermore, reaction products of various silane coupling materials can also be used as adhesion agents.

[0049] The one-component sealing material of the embodiment of the present invention may contain 0.1 to 10 parts by mass of silane coupling material, 0.2 to 5 parts by mass of silane coupling material, or 0.3 to 4 parts by mass of silane coupling material per 100 parts by mass of the one-component sealing material. Furthermore, it is preferable that the one-component sealing material of the embodiment of the present invention does not contain a silane coupling material containing amino groups, or contains 0.2 parts by mass or less of a silane coupling material containing amino groups per 100 parts by mass of the one-component sealing material.

[0050] Examples of anti-aging agents include hindered phenols, mercaptans, sulfides, dithiocarboxylates, thioureas, thiophosphates, and thioaldehydes. Examples of thixotropes include colloidal silica, organic bentonite, fatty acid amides, polyamide waxes, and hydrogenated castor oil. Examples of moisture-retaining agents include water, hydrates of inorganic salts, and the like. Examples of UV absorbers and light stabilizers include benzotriazoles and hindered amines. Examples of antioxidants include hindered phenols. Examples of stain-resistant agents include fluorine compounds. Vinylsilane can be used as an example of a storage stability enhancer.

[0051] The one-component sealant of the embodiment of the present invention may contain 0.1 to 20 parts by mass of various additives, 0.2 to 10 parts by mass of various additives, 0.3 to 5 parts by mass of various additives, or 0.5 to 3 parts by mass of various additives per 100 parts by mass of the one-component sealant.

[0052] The one-component sealing material according to the embodiment of the present invention can be obtained by mixing the above-mentioned components (A) to (D) and adding additives as appropriate if necessary. The mixing order, mixing apparatus (machine), etc., can be selected as appropriate. The one-component sealant according to the embodiment of the present invention exhibits excellent stability at room temperature.

[0053] The one-component sealant of the embodiment of the present invention can be cured at normal temperatures, but preferably in the range of 5 to 50°C.

[0054] The one-component sealant of the embodiment of the present invention can be used for various applications, for example, as a sealant for buildings, a sealant for civil engineering, and a sealant for various other applications. The one-component sealant of the embodiment of the present invention can be suitably used as a building sealant. For example, it can be suitably used as a sealant for exterior walls with a matte finish, an orange peel finish, or a sandstone-like finish. Furthermore, it can be more suitably used as a working joint sealant. [Examples]

[0055] The present invention will be described in detail below with reference to examples and comparative examples, but these examples represent only one aspect of the present invention, and the present invention is not limited in any way by these examples. In the descriptions of the examples, unless otherwise specified, portions that do not consider the solvent are given as reference values ​​in parts by weight and weight percent.

[0056] The components used in this example are shown below. (A) Crosslinkable silyl group-containing polymer (a1) A silyl group-containing polymer with a polyoxyalkylene skeleton having three or more methyldimethoxysilyl groups in one molecule (MS Polymer S817 (product name) manufactured by Kaneka Corporation) (a2) A silyl group-containing polymer having fewer than three methyldimethoxysilyl groups at the terminal and a poly(meth)acrylate skeleton as the main chain (SA410S (product name) manufactured by Kaneka Corporation) (a3) Silyl group-containing polymer having fewer than 3 methyldimethoxysilyl groups at the terminal (monofunctional) (EXCESTAR S-1000N (product name) manufactured by AGC Inc.)

[0057] (B) Plasticizer (b1) Polypropylene glycol (EXCENOL3020 (product name) manufactured by AGC Inc.) (b2) Diisononyl phthalate (DINP (product name) manufactured by Shin Nippon Rika Co., Ltd.)

[0058] (C) Filler (c1) Heavy calcium carbonate (Whiteon SB Red (product name) manufactured by Shiraishi Kogyo Co., Ltd.) (c2) Surface-treated calcium carbonate (Viscolite-EL-20 (product name) manufactured by Shiraishi Kogyo Co., Ltd.) (c3) Inorganic hollow body (3M Glass Bubbles S-22 (product name) manufactured by Sumitomo 3M Co., Ltd.)

[0059] (D) Tetravalent tin catalyst (d1) Dibutyltin oxide (40% of DSC4 (product name) manufactured by Daikyo Chemical Co., Ltd.) (60% of DINP is listed in addition to b2.) (d2) A tin catalyst containing 90 parts by mass of dibutyltin acetylacetonate and 10 parts by mass of dibutyltin dilaurate (C501S (product name) manufactured by Nippon Chemical Industrial Co., Ltd.) (d3) Dibutyltin acetylacetonate (manufactured by Nitto Chemical Co., Ltd., U-220H (product name)) (d4) Dibutyltin ethyl silicate (manufactured by Nitto Chemical Co., Ltd., product name U-303)

[0060] (E) Additives (e1) Antioxidant (Adeka Stab AO-60P (product name) manufactured by Adeka Co., Ltd.) (e2) Vinyltrimethoxysilane (KBM-1003 (product name) manufactured by Shin-Etsu Chemical Co., Ltd.) (e3)3-Glycidoxypropyltrimethoxysilane (KBM-403 (product name) manufactured by Shin-Etsu Chemical Co., Ltd.) (e4) 3-Aminopropyltrimethoxysilane (KBM-903 (product name) manufactured by Shin-Etsu Chemical Co., Ltd.) (e5) Shared Toner, New Gray

[0061] These components were blended in the parts by mass shown in Tables 1 and 2 to produce the one-component sealants of Examples 1 to 8 and Comparative Examples 1 to 5. For each of the one-component sealants described above, the temperature sensitivity of deep curing (difference in curing time between curing at 23°C and curing at 5°C (mm)), pot life (hr), touch-dry time (TFT) (hr), movement-following ability, and JIS 9030 durability were measured and evaluated using the following methods. The results are shown in Tables 1 and 2.

[0062] [Table 1]

[0063] [Table 2]

[0064] Temperature sensitivity of deep hardening Deep hardening was measured at both the TFT evaluation temperature (5°C) and the pot life evaluation temperature (23°C), as described later, and the temperature sensitivity was evaluated based on the difference between the two temperatures. A simulated joint (10mm wide, 10mm deep) was created on a flexible board using a 10mm wide, 10mm thick rectangular closed-cell foamed polyethylene backing material. Double-sided tape and aluminum foil were used to block air inflow from the sides and bottom of the simulated joint. A one-component sealant was applied (coated) to the simulated joint in constant temperature chambers at 5°C and 23°C. After storage in the constant temperature chambers for 24 hours, the simulated joint was cut with a utility knife 20mm from the edge, perpendicular to both the side and bottom surfaces. The hardening status was observed by observing the cut surface, and the depth (mm) of the hardened portion from the surface of the simulated joint was recorded using calipers. The temperature sensitivity of deep hardening was evaluated by the difference (mm) between the hardened portion depth (mm) at 23°C and the hardened portion depth (mm) at 5°C. A one-component sealant with an appropriate difference (mm) of 3.3mm to 4.5mm is preferred. Because curing at low temperatures is suppressed and curing progresses at a moderate temperature, it is considered to have the more desirable property of suppressing nighttime curing and curing during the day.

[0065] pot life Polyethylene adhesive tape was applied to the flexible board, taking care to prevent air bubbles from forming. Each one-component sealant was applied to the flexible board in a constant temperature chamber at a predetermined temperature, and then smoothed to a thickness of approximately 2 mm using a spatula. The time required until it was determined that it was no longer possible to smooth the surface of the sealant with a spatula was then recorded. The table shows the time at which it was determined that it was no longer possible to smooth the surface of the sealant with a spatula. The TFTs described below were evaluated based on whether it was impossible to smooth the surface of the sealant with a spatula for more than 2 hours at a temperature 18-20°C higher than the specified temperature at which they were measured (23°C for non-summer use, 40°C for summer use). One-component sealants with a pot life of less than 2 hours were deemed unacceptable.

[0066] Drying time by finger touch (TFT) Polyethylene adhesive tape was applied to a flexible board, ensuring no air bubbles were trapped. Each one-component sealant was then applied to the flexible board in a constant temperature chamber at a specified temperature and smoothed to a thickness of approximately 2 mm. Subsequently, in accordance with the touch-dry time test method described in JIS A 1439 (Test Methods for Building Sealants), the surface of the sealant was lightly touched with a fingertip, and the time required until the sealant no longer adhered to the finger was recorded. The table shows the time it took for the sealant to no longer adhere to the finger. The sealant was evaluated based on whether it became non-sticky to the finger within 24 hours at a specified temperature (5°C for non-summer use, 20°C for summer use). One-component sealants with a TFT exceeding 24 hours were deemed unacceptable.

[0067] WJ joint movement tracking The WJ joint movement-following performance was measured using a Japan Sealing Industry Association type dynamic exposure tester (manufactured by Nikken Co., Ltd.). Front and side views of the dynamic exposure tester are shown in Figure 1. For more information on this type of dynamic exposure tester and WJ joint movement-following performance, please refer to Non-Patent Literature 1 (Journal of Structural Engineering, Architectural Institute of Japan, No. 615, 39-46, May 2007). A black acrylic panel approximately 2m long (thermal expansion coefficient = 8 × 10 -5 A WJ joint installation section is provided to divide the structure into four sections. One side of the WJ joint installation section is fixed to the acrylic panel, and the other side is fixed to the frame. Due to temperature fluctuations and exposure to sunlight, the black acrylic panel undergoes temperature changes and expands and contracts. This expansion and contraction of the black acrylic panel causes displacement (movement) in the width of the WJ joint installation section. The movement of the WJ joint installation section of this dynamic exposure test machine and the movement of an actual WJ joint were measured using a Hall element joint displacement sensor. It was confirmed that the movements of both were very similar.

[0068] The test joint was prepared and used as shown below. The bonding surfaces of the aluminum plates (A5052P) were cleaned with paper wipes (Kimwipes) manufactured by Nippon Paper Crecia Co., Ltd., soaked in a cleaning solvent (toluene), and the solvent was allowed to dry. Then, the dedicated primer for each material was applied to the surface of the bonding surfaces of the aluminum plates using a No. 5 joint brush, and allowed to dry at room temperature for approximately 30 minutes. A test joint as shown in Figure 3 was prepared using a dedicated L-angle, a cleaned JIS aluminum plate (A5052P) (50 x 50 x 5 mm), a 15x expanded PE backer (10 mm x 10 mm x 10 mm), and a square bait (20 mm x 10 mm x mm). A test joint was placed in the WJ joint installation section of the dynamic exposure testing machine described above. The width of the test joint was adjusted to 20 mm. A one-component sealant was applied to the test joint (20 mm x 100 mm x 10 mm) and left outdoors for 3 days at approximately 5°C at night and approximately 20°C during the day. After that, the surface of the one-component sealant was visually observed. The evaluation criteria are as follows: ○: Wrinkles and / or cracks hardly occur. △: Slight wrinkles and / or cracks may occur, but this is acceptable. ×: Wrinkles and / or cracks will clearly appear.

[0069] durability Durability was measured in accordance with JIS durability classification 9030. The adhesive interface between the aluminum substrate and the cured product of the one-component sealant was observed and evaluated visually. The evaluation criteria are as follows: ○: No clear cracks / peeling at the adhesive interface. △: Slight cracks (depth between 1mm and 2mm) at the adhesive interface. ×: Clear cracks (2mm or deeper) are present at the adhesive interface.

[0070] The one-component sealants of Examples 1 to 8 are excellent overall as one-component sealants, with no shortcomings in any of the following aspects: temperature sensitivity for deep curing (difference in curing time between curing at 23°C and curing at 5°C (mm)), pot life (hr), touch-dry time (TFT) (hr), movement-following ability, and durability (JIS classification 9030).

[0071] In contrast, the one-component sealants of Comparative Examples 1 to 5 are unsuitable in terms of any or more of the following: temperature sensitivity for deep curing (difference in curing time between curing at 23°C and curing at 5°C (mm)), pot life (hr), touch-dry time (TFT) (hr), movement-following ability, and durability (JIS classification 9030), and are therefore overall insufficient as one-component sealants. [Industrial applicability]

[0072] The one-component sealant of the embodiment of the present invention exhibits no unsuitable properties in terms of deep curing temperature sensitivity (difference in curing time between curing at 23°C and curing at 5°C (mm)), pot life (hr), touch-dry time (TFT) (hr), movement-following ability, and durability (JIS classification 9030), and is overall superior as a one-component sealant. The one-component sealant of the embodiment of the present invention can be suitably used in building applications.

Claims

1. A one-component sealing material comprising (A) a crosslinkable silyl group-containing polymer, (B) a plasticizer, (C) a filler, and (D) a tin catalyst, (A) The crosslinkable silyl group-containing polymer includes (A1) a crosslinkable silyl group-containing polymer having a dimethoxysilyl group. (D) The tin catalyst contains two or more types of tetravalent tin catalysts. (D) The tin catalyst is a one-component sealing material containing (D1) dibutyltin oxide as a tetravalent tin catalyst.

2. The one-component sealing material according to claim 1, wherein the (A) crosslinkable silyl group-containing polymer comprises 50 to 100 parts by mass of (A1) a crosslinkable silyl group-containing polymer having dimethoxysilyl groups, in proportion to 100 parts by mass of the (A) crosslinkable silyl group-containing polymer.

3. (A) The crosslinkable silyl group-containing polymer does not contain (A2) the crosslinkable silyl group-containing polymer having a trimethoxy group, a triethoxy group, or a diethoxy group, or contains 10 parts by mass or less of (A) the crosslinkable silyl group-containing polymer in 100 parts by mass, as described in claim 1.

4. (A) The crosslinkable silyl group-containing polymer comprises (A3) a crosslinkable silyl group-containing polymer having three or more dimethoxysilyl groups, as described in claim 1.

5. The one-component sealing material according to claim 4, wherein the crosslinkable silyl group-containing polymer comprises 20 to 80 parts by mass of a silyl group-containing polymer having 3 or more dimethoxysilyl groups per 100 parts by mass of the (A) crosslinkable silyl group-containing polymer.

6. The one-component sealing material according to claim 1, wherein the (D) tin catalyst contains 10 to 90 parts by mass of (D1) dibutyltin oxide per 100 parts by mass of tetravalent tin catalyst.

7. (D) The tin catalyst comprises, in addition to (D1) dibutyltin oxide, at least one selected from dibutyltin dilaurate, dibutyltin acetyl acetate, and dibutyltin ethyl silicate, as described in claim 1.

8. Each 100 parts by mass of (A) crosslinkable silyl group-containing polymer contains 0.1 to 6.0 parts by mass of (D) tin catalyst, or The one-component sealant according to claim 1, comprising 0.05 to 3.0 parts by mass of (D) tin catalyst per 100 parts by mass of the one-component sealant.

9. The one-component building sealant according to claim 1.

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