Curable composition for spray coating

Abstract

A curable composition for spray coating contains 100 parts by weight of a polyalkylene oxide-based polymer (A) having a reactive silicon group, 10 to 50 parts by weight of a hydrocarbon-based diluent (B), 30 to 90 parts by weight of a plasticizer (C) which is a dicarboxylic acid ester containing a cyclic hydrocarbon group, and 0.6 to 7 parts by weight of a polyamide-based rheology modifier (D). A cured film is produced by spraying the above curable composition on the surface of a substrate and curing it.

Description

Technical Field

[0001] The present invention relates to a spray curable composition comprising a polyoxyethylene polymer having a reactive silicon group, and a cured film using the composition or a method thereof. Background Technology

[0002] Organic polymers with silicon-based (hereinafter also referred to as "reactive silicon-based") structures, possessing hydroxyl or hydrolyzable groups on silicon atoms and capable of forming siloxane bonds through hydrolysis / condensation reactions, will react even at room temperature due to moisture absorption, etc. It is known that such organic polymers can be crosslinked through siloxane condensation reactions of reactive silicon-based structures, thereby yielding rubber-like cured products.

[0003] Among these organic polymers, polyoxyethylene polymers with reactive silicon groups have a good balance of mechanical properties, weather resistance, and dynamic durability in their cured forms, and are therefore widely used in sealing materials, adhesives, coatings, and other applications.

[0004] Spraying is being investigated as one method for efficiently coating a curable composition containing a reactive silicon-based polyoxyethylene polymer onto a substrate.

[0005] Patent Document 1 discloses a curable composition for spraying, comprising a polymer having a reactive silicon group, a plasticizer, a filler material having a specific particle size, and a catalyst. It also discloses that this achieves excellent sprayability and deep curing properties, and further improves tile retention (adhesion). As applications, it discloses tile adhesives and sealants.

[0006] Patent Document 2 discloses a sprayable composition comprising an α,ω-telechalic type silyl-terminated polymer such as a silanized polyether and a glycol diester as a plasticizer. It also discloses that the composition can incorporate a thixotropic agent.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2023-7423

[0010] Patent Document 2: Japanese Patent Publication No. 2019-530769 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] One application of curable compositions containing reactive silicon-based polyoxyethylene polymers is being investigated, specifically the application of such compositions to the walls of buildings, where they are sprayed onto surfaces and cured to form a waterproof membrane.

[0013] In such applications, it is desirable to use an airless spray gun for coating in order to cover large areas of substrate in a short time. In this case, the curable composition described above is required to have the property of being easy to spray using such a coating device (sprayability). In addition, it is also required that the coating film does not easily sag after spraying until the composition cures.

[0014] Generally, reducing the viscosity of a composition improves sprayability but tends to decrease anti-sagging properties. Therefore, it is not easy to achieve both sprayability and anti-sagging properties simultaneously.

[0015] As a component that imparts anti-sagging properties to a cured composition, it is generally known to incorporate rheology modifiers.

[0016] Patent Document 1 does not describe its use in forming a waterproof membrane, nor does it use a rheology modifier. Therefore, it is difficult to achieve anti-sagging properties. Furthermore, the embodiments do not investigate the use of a spray gun utilizing air pressure as a coating device for spraying large areas of substrate, nor does it disclose a method for achieving such spraying.

[0017] Patent Document 2 describes the use of a rheology modifier, but also describes spraying under high pressure. Based on the researchers' findings, it is clear that the sprayability of formulations using the plasticizer (diol diester) disclosed in that document is insufficient and requires improvement.

[0018] The inventors investigated how to impart anti-sagging properties by incorporating a rheology modifier, while simultaneously using a low-volatility diluent as a component to reduce the viscosity of the composition. However, it was also clarified that if such a diluent is used, liquid components may sometimes seep out from the surface of the cured film.

[0019] In view of the above, the object of the present invention is to provide a curable composition for spraying containing a polyoxyethylene polymer with reactive silicon groups, which combines sprayability and anti-sagging properties after application, and can suppress exudation after curing.

[0020] Problem Solving Methods

[0021] In order to solve the above problems, the inventors conducted in-depth research and found that for polyoxyethylene polymers with reactive silicon groups, by combining specific rheology modifiers, specific diluents and specific plasticizers, it is possible to balance sprayability and anti-sagging properties after coating.

[0022] Furthermore, it was discovered that by limiting the amount of specific diluents and specific plasticizers used, exudation after curing can be avoided, thus completing the present invention.

[0023] That is, the present invention relates to a curing composition for spraying, comprising:

[0024] 100 parts by weight of a polyoxyethylene polymer (A) with reactive silicon groups

[0025] Hydrocarbon-based diluent (B) 10-50 parts by weight

[0026] 30-90 parts by weight of plasticizer (C) as a dicarboxylic acid ester containing cyclic hydrocarbon groups, and

[0027] 0.6-7 parts by weight of polyamide rheology modifier (D).

[0028] In addition, the present invention relates to a cured film, which is formed by spraying and curing the above-mentioned curable composition.

[0029] Furthermore, the present invention also relates to a method for manufacturing a cured film, the method comprising: spraying the above-mentioned curable composition onto the surface of a substrate and then curing it.

[0030] The effects of the invention

[0031] According to the present invention, a curable composition for spraying can be provided, comprising a polyoxyethylene polymer containing reactive silicon groups, which combines sprayability and anti-sagging properties after application, and can suppress exudation after curing. Detailed Implementation

[0032] The embodiments of the present invention will be described below.

[0033] <<Polyoxyolefin Polymers (A)>>

[0034] The spray curing composition disclosed herein contains a polyoxyethylene polymer (A) having a reactive silicon group as a curing resin.

[0035] <Reactive Silicon-based>

[0036] The reactive silicon group of the polyoxyethylene polymer (A) can be represented by the following general formula (1).

[0037] -Si(R 1 ) 3-a X 1 a (1)

[0038] In general formula (1), R 1 Each of these groups independently represents a monovalent hydrocarbon group with 1 to 20 carbon atoms. As R 1 The number of carbon atoms in the hydrocarbon group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4. The hydrocarbon group can be an unsubstituted hydrocarbon group or a substituted hydrocarbon group.

[0039] As R 1The hydrocarbon group can have heteroatom-containing groups as substituents. These heteroatom-containing groups refer to groups containing heteroatoms. Here, atoms other than carbon and hydrogen atoms are defined as heteroatoms.

[0040] Suitable examples of heteroatoms include N, O, S, P, Si, and halogen atoms. Regarding heteroatom-containing groups, the total number of carbon atoms and heteroatoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0041] Suitable examples of heteroatom-containing groups include: hydroxyl; mercapto; halogen atoms such as Cl, Br, I, and F; nitro; cyano; alkoxy groups such as methoxy, ethoxy, n-propoxy, and isopropoxy; alkylthio groups such as methylthio, ethylthio, n-propylthio, and isopropylthio; acyl groups such as acetyl, propionyl, and butyryl; acyloxy groups such as acetoxy, propionyloxy, and butyryloxy; substituted or unsubstituted amino groups such as amino, methylamino, ethylamino, dimethylamino, and diethylamino; substituted or unsubstituted amino carbonyl groups such as aminocarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, and diethylaminocarbonyl; cyano, etc.

[0042] In R 1 In the case of a hydrocarbon group containing heteroatomic groups, R 1 The total number of carbon atoms and heteroatoms in the sample is preferably 2 to 30, more preferably 2 to 18, even more preferably 2 to 10, and particularly preferably 2 to 6.

[0043] As R 1 Specific examples of hydrocarbon groups having 1 to 20 carbon atoms include: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-octadecyl, n-nonadecanyl, and n-eicosyl; alkenyl groups such as vinyl, 2-propenyl, 3-butenyl, and 4-pentenyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aryl groups such as phenyl, naphth-1-yl, naphth-2-yl, o-phenylphenyl, m-phenylphenyl, and p-phenylphenyl; and aralkyl groups such as benzyl, phenethyl, naphth-1-methyl, and naphth-2-methyl.

[0044] These groups, after being replaced by the aforementioned heteroatom-containing groups, are also preferably used as R. 1 .

[0045] As R 1 Suitable examples include, for instance, alkyl groups such as methyl and ethyl; alkyl groups having heteroatom-containing groups such as chloromethyl and methoxymethyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl; aralkyl groups such as benzyl; etc. As R1 Preferably, it is methyl, methoxymethyl, or chloromethyl, more preferably methyl or methoxymethyl, and even more preferably methyl.

[0046] X 1 Each can independently represent a hydroxyl group or a hydrolyzable group. As X 1 Specific examples include hydroxyl, halogen, alkoxy, acyloxy, ketoxime, amino, amide, acid amide, aminooxy, mercapto, and alkenyloxy groups. Among these, alkoxy groups are preferred from the viewpoint of hydrolytic stability and ease of handling. Generally, the fewer carbon atoms in an alkoxy group, the higher its reactivity. That is, reactivity decreases in the order of methoxy, ethoxy, and propoxy. Utilizing this property, the specific reactive silicon group structure can be appropriately determined based on the manufacturing method and application of the polyoxyethylene polymer (A).

[0047] a can be 1, 2, or 3. To achieve better strength in the cured product, a is preferably 2 or 3. To easily balance the strength and elongation of the cured product, a is more preferably 2.

[0048] Specific examples of reactive silicon groups in the polyoxyethylene polymer (A) include: trimethoxysilyl, triethoxysilyl, tri(2-propenoxy)silyl, triacetoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, and (N,N-diethylaminomethyl)diethoxysilyl, etc., but are not limited to these. Among them, dimethoxymethylsilyl, trimethoxysilyl, triethoxysilyl, and (methoxymethyl)dimethoxysilyl are preferred because they can produce cured products with good mechanical properties. From the viewpoint of activity, trimethoxysilyl, (chloromethyl)dimethoxysilyl and (methoxymethyl)dimethoxysilyl are more preferred, and trimethoxysilyl is particularly preferred in order to improve curability.

[0049] From the viewpoint of balancing softness and resilience, the number of reactive silicon groups in the molecule of polyoxyethylene polymer (A)1 is preferably 1 to 7 on average, more preferably 1.1 to 3.4, and particularly preferably 1.2 to 2.6.

[0050] To obtain a good rubbery cured product, the reactive silica groups in the polyoxyethylene polymer (A) are preferably present at the ends of the main chain. From the viewpoint of exhibiting good curability and readily displaying rubber elastic behavior, the number of reactive silica groups is preferably 0.5 or more on average per end of the polymer (A), more preferably 0.6 or more, further preferably 0.7 or more, even more preferably 0.8 or more, and particularly preferably 0.85 or more.

[0051] The main chain structure of the polyoxyethylene polymer (A) can be linear or branched. When using a linear polyoxyethylene polymer (A), for example, even when spraying a curing film onto a raw material that is prone to thermal expansion, the conformability is good.

[0052] The backbone of the polyoxyethylene polymer (A) has -R 13 -O-(where R is the formula) 13 Polymers of repeating units (linear or branched alkylene groups with 1-14 carbon atoms), R 13 More preferably, it is a straight-chain or branched alkylene group having 2 to 4 carbon atoms. As -R 13 Specific examples of the repeating unit indicated by -O- include: -CH2O-, -CH2CH2O-, -CH2CH(CH3)O-, -CH2C(CH3)(CH3)O-, -CH2CH2CH2CH2O-, etc., preferably -CH2CH2O-, -CH2CH(CH3)O-, and more preferably -CH2CH(CH3)O-.

[0053] In particular, polyoxypropylene polymers having 50% or more, more preferably 80% or more, repeating propylene oxide units in the polymer backbone structure are amorphous and have relatively low viscosity, and are therefore preferred.

[0054] As the polyoxyolefin polymer (A), polyoxyolefin polymers containing other bonds such as urethane bonds, urea bonds, ester bonds, and amide bonds in their main chain structure can be used. However, from the viewpoint of obtaining a curable composition with excellent storage stability and workability, the polyoxyolefin polymer (A) is preferably a polyoxyolefin polymer whose main chain structure does not contain urethane bonds, urea bonds, ester bonds, or amide bonds.

[0055] The number-average molecular weight of the polyoxyethylene polymer (A) is not particularly limited, but as the equivalent molecular weight of polystyrene determined by GPC, it is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, particularly preferably 12,000 to 40,000, and most preferably 13,000 to 30,000. If the number-average molecular weight is within the above range, the amount of reactive silicon groups introduced is appropriate, thereby controlling the manufacturing cost to an appropriate range and easily obtaining a polyoxyethylene polymer (A) with high strength.

[0056] The molecular weight distribution (Mw / Mn) of the polyoxyethylene polymer (A) is not particularly limited, but a narrow distribution is preferred. Specifically, it is preferably 1.6 or less, more preferably 1.4 or less, further preferably 1.3 or less, and particularly preferably 1.2 or less. A molecular weight distribution within the above range is preferred from the viewpoint of ease of handling and adhesion. The molecular weight distribution of the polyoxyethylene polymer (A) can be determined from the number-average molecular weight and weight-average molecular weight obtained by GPC measurement.

[0057] <Method for manufacturing a polyoxyethylene polymer (A) containing reactive silicon groups>

[0058] Next, a method for manufacturing a polyoxyethylene polymer (A) containing reactive silicon groups will be described.

[0059] A polyoxyalkylene polymer (A) containing reactive silicon groups can be manufactured by introducing reactive silicon groups into a precursor polymer capable of incorporating reactive silicon groups. Specifically, the polyoxyalkylene polymer (A) containing reactive silicon groups can be manufactured as follows: an alkenyl group is introduced into a polyoxyalkylene polymer (d1) with hydroxyl groups at the end using the reactivity of hydroxyl groups to obtain a precursor polymer with alkenyl groups, and then a reactive silicon-containing compound that is reactive with the alkenyl group is reacted with the precursor polymer to introduce the reactive silicon group.

[0060] (polymerization)

[0061] The polymer backbone of polyoxyethylene polymers can be formed by polymerizing epoxides with hydroxyl-terminated initiators using conventional methods, thereby obtaining polyoxyethylene polymers (d1) with hydroxyl-terminated ends. While there are no particular limitations on the specific polymerization method, from the viewpoint of obtaining hydroxyl-terminated polymers with small molecular weight distributions (Mw / Mn), polymerization methods using complex metal cyanide complex catalysts such as zinc hexacyanocobaltate ethylene glycol dimethyl ether complexes are preferred.

[0062] There are no particular limitations on the type of initiator containing hydroxyl groups, and examples include: ethylene glycol, propylene glycol, glycerol, pentaerythritol, low molecular weight polyoxypropylene glycol, low molecular weight polyoxypropylene triol, butanol, allyl alcohol, methanol, ethanol, propanol, butanol, pentanol, hexanol, low molecular weight polyoxypropylene monoallyl ether, and low molecular weight polyoxypropylene monoalkyl ether. When obtaining a polymer with three or more main chain ends in one molecule, glycerol, pentaerythritol, and low molecular weight polyoxypropylene triol, etc., containing three or more hydroxyl groups, can be used.

[0063] The epoxy compound mentioned above is not particularly limited, and examples include: ethylene oxide, propylene oxide, and other oxidized alkenes; glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether. Propylene oxide is preferred.

[0064] (Reaction with alkali metal salts)

[0065] When introducing alkenyl groups into a polyoxyalkylene polymer (d1) with hydroxyl-terminated ends, it is preferable to first react an alkali metal salt with the polyoxyalkylene polymer (d1) to convert the terminal hydroxyl groups to alkoxy-terminal groups. Alternatively, a complex metal cyanide catalyst can be used instead of an alkali metal salt. Through the above reaction, an alkoxy-terminated polyoxyalkylene polymer (d2) is formed.

[0066] The alkali metal salts mentioned above are not particularly limited, and examples include sodium hydroxide, sodium ethoxide, potassium hydroxide, potassium ethoxide, lithium hydroxide, lithium ethoxide, cesium hydroxide, and cesium ethoxide. Considering ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred, and sodium methoxide and sodium tert-butoxide are more preferred. From the viewpoint of availability, sodium methoxide is preferred. The alkali metal salts can be supplied for the reaction in a dissolved state in a solvent.

[0067] (Reaction with electrophilic reagent (d3))

[0068] By reacting an electrophilic reagent (d3) with an alkenyl group with an alkoxy-terminated polyoxyalkylene polymer (d2) obtained as described above, the alkoxy terminus can be converted into a structure containing an alkenyl group. This results in a polyoxyalkylene polymer (d4) with an alkenyl group in its terminal structure.

[0069] As an electrophilic reagent with an alkenyl group (d3), any compound that can react with the alkoxy terminus of the polyoxyalkylene polymer (d2) to introduce an alkenyl group into the polyoxyalkylene polymer is acceptable, without particular limitation. Examples include: organohalides with an alkenyl group (d3-1), epoxy compounds with an alkenyl group (d3-2), etc.

[0070] As an electrophilic agent (d3), an alkenyl organohalide (d3-1) reacts with the alkoxy terminus mentioned above via a halogen substitution reaction to form an ether bond, which can introduce a structure containing an alkenyl group as the end structure of a polyoxyalkylene polymer.

[0071] Specific examples of organohalides (d3-1) containing alkenyl groups are not particularly limited, and examples include vinyl chloride, allyl chloride, methyl allyl chloride, vinyl bromide, allyl bromide, methyl allyl bromide, vinyl iodide, allyl iodide, and methyl allyl iodide. From the perspective of ease of processing, allyl chloride and methyl allyl chloride are preferred. Furthermore, from the viewpoint of increasing the average ratio of the number of reactive silicon groups to the number of ends of the polymer backbone, methyl allyl chloride, methyl allyl bromide, and methyl allyl iodide are preferred.

[0072] Alternatively, as an organohalide with an alkenyl group (d3-1), a haloalkanes having a carbon-carbon triple bond can also be used. There are no particular limitations on the haloalkanes having the aforementioned carbon-carbon triple bonds; examples include propargyl chloride, propargyl bromide, and propargyl iodine. Furthermore, haloalkanes having carbon-carbon double bonds can also be used in conjunction with haloalkanes having carbon-carbon triple bonds.

[0073] As an electrophile (d3), an alkenyl-containing epoxy compound (d3-2) reacts with the aforementioned alkoxy terminus via a ring-opening addition reaction of the epoxy group to form an ether bond, thereby introducing a structure containing both an alkenyl and a hydroxyl group as the terminal structure of a polyoxyalkylene polymer. In the aforementioned ring-opening addition reaction, by adjusting the amount of epoxy compound (d3-2) relative to the aforementioned alkoxy terminus and the reaction conditions, one or more epoxy compounds (d3-2) can be added to one alkoxy terminus.

[0074] As a specific example of an epoxide compound (d3-2) having an alkenyl group, there is no particular limitation, but from the viewpoint of reactivity, allyl glycidyl ether, methyl allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and butadiene monooxide are preferred, with allyl glycidyl ether being particularly preferred.

[0075] If an epoxide compound having an alkenyl group (d3-2) is reacted with an alkoxy-terminated polyoxyalkylene polymer (d2) as described above, a new alkoxy group is generated through ring-opening of the epoxide group. Therefore, by reacting this epoxide compound (d3-2), an organohalide having the aforementioned alkenyl group (d3-1) can be reacted continuously.

[0076] (Introduction of reactive silicon groups)

[0077] By hydrosilylating a hydrosilane compound (d6) with a reactive silicon group in its terminal structure (d4) or a polyoxyalkylene polymer (d5) with a carbon-carbon triple bond in its terminal structure (the precursor polymer), the reactive silicon group can be introduced into the polymer. This produces a polyoxyalkylene polymer (A) containing a reactive silicon group. The hydrosilylating reaction is not only easy to perform, but also allows for easy adjustment of the amount of reactive silicon group introduced, and yields a polymer with stable physical properties.

[0078] Specific examples of hydrosilane compounds (d6) having the aforementioned reactive silicon groups include: trichlorosilane, dichloromethylsilane, dichlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, bis(methoxymethyl)chlorosilane, and other halosilanes; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, etc. Dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl)dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane, (3,3,3) (-trifluoropropyl)dimethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)diethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilane Alkoxysilanes such as [(3,3,3-trifluoropropyl)dimethoxysilane]dimethylsilane; Acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; Ketooxime silanes such as bis(dimethylketoxime)methylsilane and bis(cyclohexylketoxime)methylsilane; Isopropenoxysilanes (deacetone type) such as triisopropenoxysilane, (chloromethyl)diisopropenoxysilane, and (methoxymethyl)diisopropenoxysilane.

[0079] To promote the reaction, the hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst. Known hydrosilylation catalysts include metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, as well as their complexes. Specifically, examples include: catalysts with platinum supported on alumina, silica, carbon black, etc.; chloroplatinic acid; chloroplatinic acid complexes formed by chloroplatinic acid with alcohols, aldehydes, ketones, etc.; platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [e.g., Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; platinum-phosphine complexes [e.g., Ph(PPh3)4, Pt(PBu3)4]; platinum-phosphite complexes [e.g., Pt{P(OPh)3}4], etc.

[0080] It is known that when using platinum-based hydrosilylation catalysts, side reactions such as isomerization of the 1-propenyl group (internal olefin) and the formation of a propenyl group due to hydrogenation occur, leading to a decrease in the reactive silane group introduction rate (the average number of reactive silane groups at each end) for the allyl group. As a method to suppress such side reactions and improve the reactive silane group introduction rate, for example, a ruthenium complex with a specific ligand as described in Japanese Patent Application Publication No. 2021-11456 has been proposed.

[0081] As a specific example, a method for using a ruthenium complex with a halogenated olefin compound (1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, and 1,3,5-tribromobenzene, etc.) in a hydrosilylation reaction can be described. By using such a method, a polymer can be obtained with an average of 0.85 or more reactive silicon groups at each end. By using such a polymer in this disclosure, a curable composition capable of forming a cured film exhibiting sufficient strength can be obtained.

[0082] As another method for manufacturing a polyoxyethylene polymer (A) containing reactive silicon groups, the following method can be used: reacting a molecule of a compound (d7) having reactive silicon groups and isocyanate groups with a polyoxyethylene polymer (d1) (precursor polymer) having hydroxyl groups at the end to form a urethane bond and introduce reactive silicon groups.

[0083] As a compound (d7) having both a reactive silicon group and an isocyanate group in one molecule, it is not particularly limited to any compound that has both an isocyanate group and a reactive silicon group in one molecule that can undergo a carbamate reaction with the hydroxyl groups of the polyoxyethylene polymer (d1). Specific examples include: (3-isocyanate propyl)trimethoxysilane, (3-isocyanate propyl)dimethoxymethylsilane, (3-isocyanate propyl)triethoxysilane, (3-isocyanate propyl)diethoxymethylsilane, (isocyanate methyl)trimethoxysilane, (isocyanate methyl)triethoxysilane, (isocyanate methyl)dimethoxymethylsilane, (isocyanate methyl)diethoxymethylsilane, etc.

[0084] Carbamate reactions can be carried out without a carbamate catalyst, but they can also be carried out in the presence of a carbamate catalyst to increase the reaction rate and yield. Such carbamate catalysts include, for example, those listed in Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963, and other previously known carbamate catalysts. Specifically, examples include, but are not limited to, organotin compounds, bismuth compounds, and organic amines as base catalysts.

[0085] As another method for manufacturing a polyoxyethylene polymer (A) containing reactive silicon groups, the following method can be applied: reacting an excess of a polyisocyanate compound (d8) with a polyoxyethylene polymer (d1) having hydroxyl groups at the end to produce a polymer (precursor polymer) having isocyanate groups at the end, and then reacting a compound (d9) having groups (e.g., amino) that react with isocyanate groups and reactive silicon groups with the precursor polymer.

[0086] Examples of polyisocyanate compounds (d8) include aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and phenyl dimethylene diisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.

[0087] Examples of compounds (d9) having a group that reacts with an isocyanate group and a reactive silicon group include: γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxymethylsilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxymethylsilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, and γ-(N-phenyl)aminopropyltrimethoxysilane. Aminosilanes such as γ-(N-phenyl)aminopropyldimethoxymethylsilane, N-ethylaminoisobutyltrimethoxysilane, N-ethylaminoisobutyldimethoxymethylsilane, N-cyclohexylaminomethyltrimethoxysilane, and N-cyclohexylaminomethyldimethoxymethylsilane; hydroxysilanes such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyldimethoxymethylsilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyldimethoxymethylsilane; etc.

[0088] As another method for manufacturing a polyoxyalkylene polymer (A) containing reactive silicon groups, the following method can be used: a compound (d10) having reactive silicon and thiol groups in one molecule reacts with a polyoxyalkylene polymer (d4) (precursor polymer) having an alkenyl group in the terminal structure, thereby forming a thioether bond through the addition of the thiol group to the alkenyl group, thereby introducing the reactive silicon group.

[0089] As a compound (d10) having both reactive silicon and thiol groups in one molecule, it is not particularly limited to any compound that has both a thiol group and a reactive silicon group in one molecule capable of adding to the alkenyl group of the polyoxyolefin polymer (d4). Specific examples include: (3-mercaptopropyl)methyldimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methyldiethoxysilane, (3-mercaptopropyl)triethoxysilane, (mercaptomethyl)methyldimethoxysilane, (mercaptomethyl)trimethoxysilane, (mercaptomethyl)methyldiethoxysilane, (mercaptomethyl)triethoxysilane, etc.

[0090] The addition reaction of thiol groups to alkenes can be carried out without the use of a free radical initiator, but it can also be carried out in the presence of a free radical initiator to increase the reaction rate and yield. Such free radical initiators can be conventionally known free radical initiators. Specifically, examples include azo initiators and peroxide initiators, but these are not limited to.

[0091] Among known free radical initiators, catalysts with low activity to reactive silicon groups are preferred. From this point of view, azo-based initiators such as 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (V-59), and 2,2'-azobis(1-methylcyclohexanecarboxynitrile) (V-40) are particularly preferred.

[0092] <<Hydrocarbon-based diluent (B)>>

[0093] The spray-curing composition disclosed herein contains a hydrocarbon-based diluent (B). By combining the hydrocarbon-based diluent (B) with the plasticizer (C) described later, the viscosity of the spray-curing composition can be reduced, thereby improving its sprayability.

[0094] Hydrocarbon-based diluents (B) refer to compounds whose main components are hydrocarbons, and are liquid at room temperature. Hydrocarbon-based diluents can be aromatic hydrocarbons or non-aromatic hydrocarbons; from the perspective of low odor, non-aromatic hydrocarbons are preferred.

[0095] From the viewpoint of reducing the volatile organic compounds (VOCs) in the curable composition and the cured product obtained by curing the composition, the hydrocarbon-based diluent (B) is preferably non-volatile. Specifically, the boiling point of the hydrocarbon-based diluent (B) is preferably 250°C or higher, more preferably 280°C or higher, even more preferably 290°C or higher, and particularly preferably 300°C or higher. When the hydrocarbon-based diluent (B) has an initial boiling point and a final boiling point, the term "boiling point" refers to the initial boiling point.

[0096] Examples of high-boiling-point hydrocarbon diluents (B) include cycloalkane solvents and alkane solvents. These hydrocarbon solvents are preferably hydrogen-treated hydrocarbon solvents. They can be used alone or in combination of two or more. Furthermore, the alkane solvents mentioned herein include isoalkane solvents.

[0097] There are no particular limitations on the specific examples of hydrocarbon-based diluents (B), and commercially available products can be used, such as TOTALFLUID D-170, Hydroroseal HY, IP SOLVENT 2835, and EXXSOL D130. Among these, TOTAL FLUIDD-170 and Hydroroseal HY are preferred.

[0098] The amount of hydrocarbon diluent (B) is 10 parts by weight or more and 50 parts by weight or less, relative to 100 parts by weight of the polyoxyethylene polymer (A). If the amount of component (B) is less than 10 parts by weight, it is not easy to obtain the viscosity reduction effect caused by the addition of component (B), resulting in insufficient sprayability and difficulty in spraying, requiring a high spray pressure during spraying. In addition, coating spots and uneven film thickness may sometimes occur on the coating film obtained by spraying. From the viewpoint of sprayability, the amount of component (B) is preferably 20 parts by weight or more, more preferably 30 parts by weight or more, and particularly preferably 40 parts by weight or more.

[0099] On the other hand, if the amount of component (B) exceeds 50 parts by weight, there is a tendency for the liquid component to easily seep out from the surface of the cured product obtained by curing the curing composition. In addition, the coating film is prone to sagging during the period from the time the curing composition is applied until it is cured. From the viewpoint of suppressing seepage and suppressing coating film sagging, the amount of component (B) is particularly preferably 45 parts by weight or less.

[0100] <<Plasticizer (C)>>

[0101] The spray-curing composition disclosed herein contains a plasticizer (C) as a dicarboxylic acid ester containing a cyclic hydrocarbon group. By combining the plasticizer (C) with a hydrocarbon-based diluent (B), the viscosity of the spray-curing composition can be reduced, thereby improving sprayability.

[0102] Plasticizer (C) is a dicarboxylic acid ester containing a cyclic hydrocarbon group. This compound has good compatibility with hydrocarbon diluent (B), and the two components can be easily and uniformly mixed. Therefore, component separation does not easily occur in the curing composition, resulting in good physical properties of the cured film.

[0103] The aforementioned cyclic hydrocarbon group can be an aromatic hydrocarbon group or an alicyclic hydrocarbon group. From the viewpoint of compatibility with the hydrocarbon diluent (B), an alicyclic hydrocarbon group is preferred. An alicyclic hydrocarbon group refers to, for example, a cyclohexane ring.

[0104] Specific examples of dicarboxylic acid esters containing cyclic hydrocarbon groups include, for alicyclic forms, cyclohexane dicarboxylic acid esters such as diisononyl 1,2-cyclohexanedicarboxylate (specifically, trade name: Hexamoll DINCH (manufactured by BASF)). For aromatic systems, examples include phthalates such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; and terephthalates such as bis(2-ethylhexyl)-1,4-phthalate.

[0105] The amount of plasticizer (C) is 30 parts by weight or more and 90 parts by weight or less relative to 100 parts by weight of the polyoxyethylene polymer (A). If the amount of component (C) is less than 30 parts by weight, it is difficult to obtain the viscosity reduction effect caused by the addition of component (C), and sometimes the sprayability is insufficient. In addition, if the amount of component (B) is increased to compensate for the deficiency of component (C), the above-mentioned exudation is more likely to occur. From the viewpoint of sprayability and exudation suppression, the amount of component (C) is preferably 40 parts by weight or more, and more preferably 50 parts by weight or more.

[0106] On the other hand, if the amount of component (C) exceeds 90 parts by weight, the amount of component (B) is relatively reduced, making it difficult to obtain the viscosity reduction effect caused by the addition of component (B), resulting in insufficient sprayability. Furthermore, the coating film is prone to sagging. From the viewpoint of sprayability and suppressing coating sagging, the amount of component (C) is preferably 80 parts by weight or less, more preferably 70 parts by weight or less, and even more preferably 60 parts by weight or less.

[0107] The total amount of hydrocarbon diluent (B) and plasticizer (C) can be set within the range of the amounts of the above-mentioned components. From the viewpoint of balancing sprayability and suppressing coating sagging, it is preferably 70 parts by weight or more and 120 parts by weight or less, more preferably 80 parts by weight or more and 110 parts by weight or less, and particularly preferably 85 parts by weight or more and 105 parts by weight or less, relative to 100 parts by weight of the polyoxyethylene polymer (A).

[0108] The ratio of the amount of hydrocarbon-based diluent (B) to the amount of plasticizer (C), (C) / (B), can be set within the range of the amounts of the above-mentioned components, and is preferably 0.8 or more and 3.0 or less by weight. If (C) / (B) is within this range, good sprayability can be achieved through the viscosity reduction effect achieved by the combined use of components (B) and (C), and exudation caused by component (B) can be easily avoided. In addition, sagging of the coating film can be easily suppressed.

[0109] (C) / (B) is preferably 0.9 or more, more preferably 1.0 or more. Furthermore, it is more preferably 2.0 or less, more preferably 1.5 or less, and particularly preferably 1.2 or less.

[0110] Furthermore, the ratio of the total amount of the polyoxyethylene polymer (A) and the plasticizer (C) to the amount of the hydrocarbon diluent (B), [(A)+(C)] / (B), can be set within the range of the amounts of the aforementioned components, and is preferably 2.6 or more and 7.0 or less by weight. If [(A)+(C)] / (B) is within this range, good sprayability can be achieved by reducing viscosity through the combination of components (B) and (C) with component (A), and exudation caused by component (B) can be easily avoided. In addition, sagging of the coating film can be easily suppressed.

[0111] [(A)+(C)] / (B) is more preferably 2.8 or more, and even more preferably 3.0 or more. Furthermore, it is more preferably 6.0 or less, even more preferably 5.0 or less, and particularly preferably 4.0 or less.

[0112] <<Polyamide Rheology Modifiers (D)>>

[0113] The spray-curing composition disclosed herein contains a polyamide-based rheology modifier (D). By incorporating the polyamide-based rheology modifier (D), sagging on the coating immediately after spraying the curing composition can be suppressed. Therefore, the cured film obtained after curing has a good appearance and can form a cured film with uniform physical properties. Furthermore, the polyamide-based rheology modifier is sometimes also referred to as a polyamide wax or a fatty acid amide.

[0114] Rheology modifiers other than polyamide-based ones are commercially available. However, if a non-polyamide-based rheology modifier (D) is used instead of a polyamide-based one, it is difficult to achieve sagging suppression of the coating film, and sometimes the viscosity of the cured composition is too high, resulting in decreased sprayability.

[0115] Commercially available products can be used as rheology modifiers (D) for polyamides. Specifically, examples include Disparlon (registered trademark) manufactured by Kusunoki Chemical Co., Ltd., and Crayvallac SL, Crayvallac SLX, Crayvallac SLT, and Crayvallac SLW manufactured by Arkema Co., Ltd. Among these, Crayvallac SLT is particularly preferred.

[0116] The amount of polyamide rheology modifier (D) is 0.6 parts by weight or more and 7 parts by weight or less, relative to 100 parts by weight of the polyoxyethylene polymer (A). If the amount of component (C) is less than 0.6 parts by weight, the effect of suppressing sagging of the coating film is insufficient. Preferably, it is 0.7 parts by weight or more, more preferably 1 part by weight or more, and even more preferably 2 parts by weight or more. In addition, if it exceeds 7 parts by weight, the viscosity of the curable composition may sometimes be too high, resulting in decreased sprayability. Preferably, it is 6 parts by weight or less, more preferably 5 parts by weight or less.

[0117] The spray-applied curing composition disclosed herein may contain only a polyamide-based rheology modifier (D) as a rheology modifier, or it may contain rheology modifiers other than component (D). In this case, the amount of rheology modifiers other than component (D) is preferably less than or equal to the amount of component (D).

[0118] <<Filler (E)>>

[0119] From the viewpoint of improving the strength of the cured film, the spray curable composition disclosed herein preferably contains a filler (E).

[0120] There are no particular limitations on the filler (E), and examples include: heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium dioxide, fumed silica, precipitated silica, crystalline silica, fused silica, silicic anhydride, hydrated silicic acid, alumina, carbon black, iron oxide, aluminum micropowder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber, and long fibers, etc. Furthermore, for the purpose of making the composition lighter (lower specific gravity), organic hollow spheres or inorganic hollow spheres may also be used. Only one type of filler (E) may be used, or two or more may be used in combination.

[0121] Considering the tendency to improve the sprayability by not easily increasing the viscosity of the curing composition, calcium carbonate is preferred as the filler (E).

[0122] As calcium carbonate, both heavy calcium carbonate and light calcium carbonate can be used. However, from the viewpoint of balancing sprayability and suppressing coating sagging, heavy calcium carbonate is preferred. Here, heavy calcium carbonate refers to calcium carbonate obtained by crushing / classifying limestone.

[0123] Furthermore, surface-treated heavy calcium carbonate is particularly preferred as the heavy calcium carbonate. In this case, the type of surface treatment agent is not particularly limited, but organic materials are preferred, and fatty acids or fatty acid esters are particularly preferred. Commercially available products can be used as such surface-treated heavy calcium carbonate.

[0124] When the filler (E) is incorporated, its amount in the total 100% by weight of the curable composition for spraying disclosed herein can be, for example, 10% by weight or more and 50% by weight or less, preferably 20% by weight or more and 40% by weight or less. If the amount of filler (E) is within this range, the strength-enhancing effect due to the incorporation of component (E) can be achieved, and the sprayability of the curable composition can be maintained within a good range. In addition, sagging suppression of the coating film is easily achieved. More preferably, it is 25% by weight or more and 35% by weight or less.

[0125] When using calcium carbonate as filler (E), calcium carbonate can be used alone or in combination with other fillers. From the viewpoint of sprayability, the content of calcium carbonate in the total filler (E) is preferably 30 to 100% by weight, more preferably 60 to 100% by weight, and particularly preferably 80 to 100% by weight.

[0126] <<Civilized Catalyst (F)>>

[0127] In order to promote the curing reaction of the curable composition by the reactive silane hydrolysis / condensation of the polyoxyethylene polymer (A), the curable composition for spraying disclosed herein preferably contains a curing catalyst (F) (also known as a silanol condensation catalyst).

[0128] Examples of curing catalysts (F) include organotin compounds, metal salts of carboxylic acids, amine compounds, carboxylic acids, alkoxy metals, etc.

[0129] Specific examples of organotin compounds include: dibutyltin dilaurate, dibutyltin dioctanoate, bis(butylmaleic acid) dibutyltin, dibutyltin diacetate, dibutyltin oxide, bis(acetylacetone) dibutyltin, dioctyltin bis(acetylacetone), dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin oxide, reactants of dibutyltin oxide with silicate compounds, reactants of dioctyltin oxide with silicate compounds, and reactants of dibutyltin oxide with phthalates, etc.

[0130] Specific examples of metal salts of carboxylic acids include: tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate. As a carboxylic acid group, the following carboxylic acids can be combined with various metals. Specifically, examples include: iron 2-ethylhexanoate (2-valent), iron 2-ethylhexanoate (3-valent), titanium 2-ethylhexanoate (4-valent), vanadium 2-ethylhexanoate (3-valent), calcium 2-ethylhexanoate (2-valent), potassium 2-ethylhexanoate (1-valent), barium 2-ethylhexanoate (2-valent), manganese 2-ethylhexanoate (2-valent), nickel 2-ethylhexanoate (2-valent), cobalt 2-ethylhexanoate (2-valent), zirconium 2-ethylhexanoate (4-valent), iron neodecanoate (2-valent), iron neodecanoate (3-valent), titanium neodecanoate (4-valent), vanadium neodecanoate (3-valent), calcium neodecanoate (2-valent), potassium neodecanoate (1-valent), and barium neodecanoate (4-valent). Zirconium neodecanoate (2-valent), ferric oleate (2-valent), ferric oleate (3-valent), titanium oleate (4-valent), vanadium oleate (3-valent), calcium oleate (2-valent), potassium oleate (1-valent), barium oleate (2-valent), manganese oleate (2-valent), nickel oleate (2-valent), cobalt oleate (2-valent), zirconium oleate (4-valent), ferric naphthenate (2-valent), ferric naphthenate (3-valent), titanium naphthenate (4-valent), vanadium naphthenate (3-valent), calcium naphthenate (2-valent), potassium naphthenate (1-valent), barium naphthenate (2-valent), manganese naphthenate (2-valent), nickel naphthenate (2-valent), cobalt naphthenate (2-valent), zirconium naphthenate (4-valent), etc.

[0131] Specific examples of amine compounds include: amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; aminosilane coupling agents; and ketimine compounds.

[0132] Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and 2-ethylhexanoic acid (versatic acid).

[0133] Specific examples of alkoxy metals include: titanium compounds such as tetrabutyl titanate, tetra(acetylacetone)titanium, and diisopropoxytitanium bis(ethyl acetoacetate); aluminum compounds such as tri(acetylacetone)aluminum and diisopropoxyaluminum ethyl acetoacetate; and zirconium compounds such as tetra(acetylacetone)zirconium.

[0134] Other compounds containing fluorine anions, such as photoacid generators and photoalkali generators, can also be used as curing catalysts (F).

[0135] As a curing catalyst (F), two or more different catalysts can be used in combination.

[0136] The amount of curing catalyst (F) relative to 100 parts by weight of the polyoxyethylene polymer (A) is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and particularly preferably 0.1 to 10 parts by weight.

[0137] <<Other Ingredients>>

[0138] In the spray-curing composition disclosed herein, in addition to the reactive silicone-based polyoxyethylene polymer (A), hydrocarbon diluent (B), plasticizer (C), polyamide rheology modifier (D), filler (E), and curing catalyst (F), tackifiers, antioxidants, light stabilizers, UV absorbers, property modifiers, tackifying resins, epoxy-containing compounds, photocurable substances, oxygen-curable substances, epoxy resins, and other resins may be added as additives. Furthermore, in the spray-curing composition disclosed herein, various additives may be added as needed to adjust the various properties of the curing composition or cured product. Examples of such additives include: surface modifiers, foaming agents, curing modifiers, flame retardants, silicates, free radical inhibitors, metal passivators, ozone deterioration inhibitors, phosphorus peroxide decomposers, lubricants, pigments, and mildew inhibitors.

[0139] <Tackifier>

[0140] The spray-applied curable composition disclosed herein may include a tackifier. As a tackifier, a silane coupling agent or a reactant of a silane coupling agent may be used.

[0141] Specific examples of silane coupling agents include: γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, and other amino-containing silanes; γ-isocyanate propyltrimethoxysilane, γ-isocyanate propyltrimethoxysilane, etc. Silanes containing isocyanate groups, such as hydroxyl silanes, γ-isocyanate propylmethyl dimethoxysilane, α-isocyanate methyl trimethoxysilane, and α-isocyanate methyl dimethoxymethylsilane; silanes containing mercaptoyl groups, such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyl dimethoxysilane; and silanes containing epoxy groups, such as γ-glycidyl etheroxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0142] Alternatively, condensates of various silane coupling agents, such as aminosilane condensates, condensates of aminosilanes with other alkoxysilanes, and reactants of various silane coupling agents, such as aminosilanes with epoxysilanes and reactants of aminosilanes with (meth)acrylate-containing silanes, can also be used. Specifically, examples include Dynasylan 1146 and Dynasylan 1124 (manufactured by EVONIK).

[0143] As a thickener, one type can be used alone, or two or more types can be used in combination.

[0144] The amount of silane coupling agent is preferably 0.1 to 20 parts by weight, and particularly preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the polyoxyethylene polymer (A).

[0145] Antioxidants

[0146] In the spray-curing composition disclosed herein, an antioxidant (anti-aging agent) may be incorporated. Using an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenolic, monophenolic, bisphenolic, and polyphenolic compounds.

[0147] Examples include: BHT, Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, Irganox 1520, and SONGNOX1076. Similarly, hindered amine light stabilizers as shown in Tinuvin 622LD, Tinuvin 144, Tinuvin 292; Chimassorb 944LD, Chimassorb 119FL (all manufactured by BASF); ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63, ADK STAB LA-68 (all manufactured by ADEKA Corporation); Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all manufactured by Sankyo Lifetech Corporation); and NocRac CD (manufactured by Ouchi Shinsei Chemical Co., Ltd.) can be used. Other antioxidants such as SONGNOX 4120, Naugard 445, and OKABEST CLX050 can also be used.

[0148] Specific examples of antioxidants are described in Japanese Patent Application Publication Nos. 4-283259 and 9-194731.

[0149] The amount of antioxidant is preferably 0.1 to 10 parts by weight relative to 100 parts by weight of the polyoxyethylene polymer (A), and more preferably 0.2 to 5 parts by weight.

[0150] <Light stabilizers>

[0151] A light stabilizer can be incorporated into the spray-curing composition disclosed herein. Incorporating a light stabilizer helps prevent photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole compounds, hindered amine compounds, and benzoate compounds, with hindered amine compounds being particularly preferred.

[0152] Examples of hindered amine light stabilizers include: Tinuvin 123, Tinuvin 144, Tinuvin 249, Tinuvin 292, Tinuvin 312, Tinuvin 622LD, Tinuvin 765, Tinuvin 770, Tinuvin 880, Tinuvin 5866, Tinuvin B97; Chimascorb 119FL, Chimascorb 944LD (all manufactured by BASF); ADKSTAB LA-57, LA-62, LA-63, LA-67, LA-68 (all manufactured by ADEKA Corporation); Sanol LS-292, LS-2626, LS-765, LS-744, LS-1114 (all manufactured by Sankyo Lifetech Corporation); SABOSTAB UV91, SABOSTAB UV119, SONGSORB CS5100, SONGSORB. Light stabilizers such as CS622, SONGSORB CS944 (all manufactured by SONGWON), and NocRac CD (manufactured by Ouchi Shinshin Chemical Industry Co., Ltd.).

[0153] The amount of light stabilizer is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, relative to 100 parts by weight of the polyoxyethylene polymer (A).

[0154] <UV absorber>

[0155] The spray-applied curing composition disclosed herein may incorporate a UV absorber. Incorporating a UV absorber can improve the surface weather resistance of the cured product. Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, triazine-based, substituted acrylonitrile-based, and metal chelate compounds, with benzotriazole-based compounds being particularly preferred. Examples include: Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 350, Tinuvin 571, Tinuvin 900, Tinuvin 928, Tinuvin 1130, and Tinuvin 1600 (all manufactured by BASF); and SONGSORB 3290 (manufactured by SONGWON). In addition, examples of triazine compounds include: Tinuvin 400, Tinuvin 405, Tinuvin 477, and Tinuvin 1577ED (all manufactured by BASF); and SONGSORB CS400 and SONGSORB 1577 (manufactured by SONGWON). Examples of benzophenone compounds include SONGSORB 8100 (manufactured by SONGWON).

[0156] The amount of ultraviolet absorber is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, relative to 100 parts by weight of the polyoxyethylene polymer (A).

[0157] It should be noted that Addworks IBC760 (made by Clariant) can also be used as a product that combines antioxidants, light stabilizers, and UV absorbers.

[0158] <Property Modifier>

[0159] In the spray-curing composition disclosed herein, a property modifier that adjusts the tensile properties of the cured product can be incorporated. There are no particular limitations on the property modifier; examples include: alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropoxysilanes such as dimethyldiisopropoxysilane, methyltriisopropoxysilane, and γ-glycidoxypropylmethyldiisopropoxysilane; trialkylsilyl borates such as tri(trimethylsilyl)borate and tri(triethylsilyl)borate; organosilicones; and polysiloxanes. By using the above-mentioned property modifiers, the hardness of the spray-curing composition disclosed herein can be increased upon curing, and conversely, the hardness can be decreased, while the elongation at break can be increased. The above-mentioned property modifiers can be used alone or in combination of two or more.

[0160] In particular, compounds that generate monovalent silanol groups within their molecules through hydrolysis have the effect of reducing the modulus of the cured product without making the surface of the cured product sticky. Compounds that generate trimethylsilanol are especially preferred. Examples of compounds that generate monovalent silanol groups within their molecules through hydrolysis include derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerol, pentaerythritol, and sorbitol, which are organosilicon compounds that generate monosilane alcohols through hydrolysis. Specifically, examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

[0161] The amount of the property modifier is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the polyoxyethylene polymer (A).

[0162] <Tackifying Resin>

[0163] In the spray-curing composition disclosed herein, a tackifying resin may be incorporated to improve adhesion and bonding to the substrate. There are no particular limitations on the tackifying resin; commonly used tackifying resins can be used.

[0164] Specific examples include: terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin resins, rosin resins, hydrogenated rosin resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene-based block copolymers and their hydrogenates, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These can be used individually or in combination of two or more.

[0165] The amount of tackifying resin is preferably 2 to 100 parts by weight relative to 100 parts by weight of the polyoxyethylene polymer (A), more preferably 5 to 50 parts by weight, and even more preferably 5 to 30 parts by weight.

[0166] <Compounds containing epoxy groups>

[0167] In the spray-curing composition disclosed herein, compounds containing epoxy groups can be incorporated. Incorporating epoxy-containing compounds improves the resilience of the cured product. Examples of epoxy-containing compounds include: epoxidized unsaturated oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specifically, examples include: epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylic acid ester (E-PS), octyl epoxy stearate, and butyl epoxy stearate. The epoxy compound can be incorporated in the range of 0.5 to 50 parts by weight relative to 100 parts by weight of the polyoxyethylene polymer (A).

[0168] <Photocurable substances>

[0169] The spray-applied curable composition disclosed herein can be combined with a photocurable substance. When combined with a photocurable substance, a film of the photocurable substance is formed on the surface of the cured material, which can improve the tackiness and weather resistance of the cured material. Various substances are known to be included in such compounds, such as organic monomers, oligomers, resins, or compositions containing them. Representative photocurable substances include: unsaturated acrylic compounds having one or more acrylic or methacrylic unsaturated groups, monomers, oligomers, or mixtures thereof; polyvinyl cinnamate or azide resins, etc.

[0170] The amount of photocurable substance is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the polyoxyethylene polymer (A).

[0171] <Oxygen-curing substances>

[0172] In the spray-curing composition disclosed herein, an oxygen-curing substance may be incorporated. Examples of oxygen-curing substances include unsaturated compounds capable of reacting with oxygen in the air, forming a cured film near the surface of the cured material, thus preventing surface stickiness and the adhesion of dust and dirt to the cured surface. Specific examples of oxygen-curing substances include: drying oils such as tung oil and linseed oil; various alkyd resins obtained by modifying these compounds; acrylic polymers, epoxy resins, and silicone resins modified from drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and C5-C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. These can be used alone or in combination of two or more.

[0173] The amount of the oxygen-curing substance is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the polyoxyethylene polymer (A). As described in Japanese Patent Application Publication No. 3-160053, the oxygen-curing substance can be used in combination with a photocurable substance.

[0174] <Epoxy Resin>

[0175] In the spray-curing composition disclosed herein, epoxy resins can be used in combination. Examples of epoxy resins include bisphenol A type epoxy resins and phenolic varnish type epoxy resins.

[0176] The ratio of these epoxy resins to polyoxyethylene polymers (A) by weight is preferably in the range of (A) / epoxy resin = 100 / 1 to 1 / 100.

[0177] When epoxy resin is incorporated, a curing agent for curing epoxy resin is preferably incorporated into the spray curing composition disclosed herein. There are no particular limitations on the epoxy resin curing agent that can be used; commonly used epoxy resin curing agents can be employed.

[0178] When an epoxy resin curing agent is incorporated, the amount incorporated is preferably in the range of 0.1 to 300 parts by weight relative to 100 parts by weight of epoxy resin.

[0179] <<Viscosity of Curing Compositions for Spraying>>

[0180] The sprayable curable composition disclosed herein exhibits good sprayability and therefore low viscosity when sprayed under pressure. Consequently, the viscosity measured in the high-shear region preferably shows a low value. Specifically, the viscosity measured at a temperature of 23°C and a shear rate of 2000 / sec is preferably 1.5 Pa·s or less. More preferably, it is 1.4 Pa·s or less. The lower limit is not particularly limited; for example, it can be 0.1 Pa·s or more, preferably 0.5 Pa·s or more, and more preferably 1.0 Pa·s or more.

[0181] On the other hand, the spray-curing composition disclosed herein has the property of not easily sagging after application. Therefore, the viscosity measured in the low shear region preferably shows a high value. Specifically, the viscosity measured at a temperature of 23°C and a shear rate of 2 / sec is preferably 4 Pa·s or more. More preferably, it is 6 Pa·s or more, and even more preferably 8 Pa·s or more. There is no particular upper limit, for example, it can be 30 Pa·s or less, preferably 20 Pa·s or less, and more preferably 15 Pa·s or less.

[0182] As detailed in the examples described below, the viscosity measured at a shear rate of 2 / sec is expected to be determined as follows: the shear rate is increased from 0.1 / sec to 2000 / sec, and then decreased from 2000 / sec to 0.1 / sec, with the measurement taken at 2 / sec of the decrease. Since the decrease at 2 / sec enters the low-shear region after the application of strong shear force, it can be considered to be close to the viscosity of the composition in the coating immediately after spraying.

[0183] <<Preparation of Curing Compositions for Spraying>>

[0184] The spray-applied curing composition disclosed herein can be prepared as a single-component form in which all components are pre-mixed and sealed, and cured by moisture in the air after application. Alternatively, it can be prepared as a two-component form in which curing catalyst, filler, plasticizer, water, etc., are pre-mixed as curing agents, and this mixture is then mixed with the composition containing polymer (A) before use. From an operability point of view, the single-component form is preferred.

[0185] In the case of the above-mentioned curable composition being a single-component form, all compounding components are pre-formulated. Therefore, it is preferable to pre-dehydrate and dry the compounding components containing moisture before use, or to dehydrate them during compounding by means of reduced pressure. In addition to dehydration and drying methods, storage stability is further improved by adding alkoxysilane compounds such as n-propyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane as dehydrating agents.

[0186] The amount of dehydrating agent, particularly a silicon compound that can react with water, such as vinyltrimethoxysilane, is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the polyoxyethylene polymer (A).

[0187] <<Applications of Curing Compositions for Spraying>>

[0188] The spray curing composition disclosed herein is used to cure a substrate after spraying onto the substrate surface to form a cured film.

[0189] As for the equipment used for spraying, there are no particular limitations, but examples include: air spraying devices that apply compressed air to the paint to form a mist; airless spraying devices that apply pressure to the paint without using air and spray it out of the nozzle to form a mist; HVLP spraying devices that use low-pressure and high-volume air to form a mist of paint; and electrostatic spraying devices that charge the paint, etc.

[0190] For large-area, efficient spraying of substrates such as building exteriors, airless spraying equipment is preferred. The curing composition for spraying disclosed herein can be properly sprayed using an airless spraying equipment, resulting in good sprayability. Furthermore, good sprayability can be achieved even when the ejection pressure in the airless spraying equipment is set to a relatively low level.

[0191] The spray pressure (also known as the spray pressure) in the airless spraying device can be appropriately set, for example, within the range of 0.5 to 20 MPa. The lower limit is preferably 5 MPa or more, more preferably 10 MPa or more, and even more preferably 15 MPa or more.

[0192] The substrate for applying the spray-curing composition of this disclosure is not particularly limited, and examples include: the exterior walls of buildings, roofs, and rooftops. In particular, it can be used to form a membrane that seamlessly covers the entire exterior wall material. Such a membrane can function as a waterproof membrane. That is, the spray-curing composition of this disclosure can be used to form a waterproof membrane on the surface of a substrate by spraying. Cured products of polyoxyethylene polymers (A) generally exhibit moisture permeability, therefore the aforementioned waterproof membrane can function as a moisture-permeable waterproof membrane.

[0193] Furthermore, the use of this membrane as a waterproofing membrane differs from its use as a sealing material for filling gaps and joints in the substrate.

[0194] The materials used to form the base material are not particularly limited, and examples include: porous materials such as exterior wall panels, concrete, CMU base wall, mortar, stone, metal, etc.

[0195] There are no particular limitations on the conditions for curing the coating. For example, the coating can be left at room temperature for about 1 to 5 days after spraying.

[0196] The thickness of the cured film formed on the substrate surface is not particularly limited, and can be in the range of approximately 100 μm to 4 mm. Preferably, it is approximately 200 μm to 3 mm, and more preferably, it is approximately 200 μm to 2 mm.

[0197] Preferred embodiments of this disclosure are set forth in the following items, but the invention is not limited to the following items.

[0198] [Project 1]

[0199] A curing composition for spraying, comprising:

[0200] 100 parts by weight of a polyoxyethylene polymer (A) with reactive silicon groups;

[0201] Hydrocarbon-based diluent (B) 10-50 parts by weight;

[0202] Plasticizer (C) 30-90 parts by weight, which is a dicarboxylic acid ester containing a cyclic hydrocarbon group; and

[0203] 0.6-7 parts by weight of polyamide rheology modifier (D).

[0204] [Project 2]

[0205] According to the curable composition described in Project 1, wherein,

[0206] The hydrocarbon-based diluent (B) comprises at least one selected from cycloalkane-based diluents and alkane-based diluents.

[0207] [Project 3]

[0208] According to the curable composition described in item 1 or 2, wherein,

[0209] The hydrocarbon-based diluent (B) has a boiling point of 250°C or higher.

[0210] [Project 4]

[0211] The curable composition according to any one of items 1 to 3 further contains a filler (E).

[0212] The content of the filler (E) is 20 to 40% by weight in 100% of the total amount of the curable composition.

[0213] [Project 5]

[0214] According to the curable composition described in Project 4, wherein...

[0215] The filler (E) contains calcium carbonate.

[0216] [Project 6]

[0217] According to the curable composition described in Project 5, wherein...

[0218] The calcium carbonate is surface-treated heavy calcium carbonate.

[0219] [Project 7]

[0220] The curable composition according to any one of items 1 to 6, wherein,

[0221] The ratio of the plasticizer (C) to the hydrocarbon diluent (B) is 0.8 to 3.0 by weight.

[0222] [Project 8]

[0223] The curable composition according to any one of items 1 to 7, wherein,

[0224] The ratio of the total of the polyoxyethylene polymer (A) and the plasticizer (C) to the hydrocarbon diluent (B) is 2.6 to 7.0 by weight: [(A) + (C)] / (B).

[0225] [Project 9]

[0226] The curable composition according to any one of items 1 to 8, wherein,

[0227] The average number of reactive silicon groups at each end of the polyoxyethylene polymer (A) is greater than 0.85.

[0228] [Project 10]

[0229] The curable composition according to any one of items 1 to 9, wherein,

[0230] The viscosity of the curable composition, measured at a temperature of 23°C and a shear rate of 2 / sec, is 4 Pa·s or higher.

[0231] [Project 11]

[0232] The curable composition according to any one of items 1 to 10, wherein,

[0233] The viscosity of the curable composition, measured at 23°C and a shear rate of 2000 / sec, is less than 1.5 Pa·s.

[0234] [Project 12]

[0235] A cured film, which is formed by spraying and curing the curable composition described in any one of items 1 to 11.

[0236] [Project 13]

[0237] A method for manufacturing a cured film, the method comprising:

[0238] After spraying the curable composition of any one of items 1 to 11 onto the surface of a substrate, it is allowed to cure.

[0239] Example

[0240] The present invention will be described in more detail below with reference to specific embodiments, but the present invention is not limited to these embodiments.

[0241] (Number average molecular weight)

[0242] The number-average molecular weights in the examples are GPC molecular weights measured under the following conditions.

[0243] Liquid delivery system: Tosoh HLC-8220GPC

[0244] Column: Tosoh TSKgel SuperH series

[0245] Solvent: THF

[0246] Molecular weight: Polystyrene conversion

[0247] Measurement temperature: 40℃

[0248] The terminal group-converted molecular weights in the examples were determined by measuring the hydroxyl value using JIS K 1557, the iodine value using JIS K 0070, and taking into account the structure of the organic polymer (the degree of branching determined by the polymerization initiator used).

[0249] The average number of silyl groups introduced per terminal or per molecule of the polymers shown in the examples was calculated by NMR determination.

[0250] (Synthetic Example 1) A-1

[0251] Polypropylene glycol with a number average molecular weight of approximately 4500 was used as an initiator to polymerize propylene oxide using a zinc hexacyanocobaltate ethylene glycol dimethyl ether complex catalyst, yielding polypropylene oxide (P-1) with terminal hydroxyl groups, a number average molecular weight of 14300 (terminal group equivalent molecular weight 9132), and a molecular weight distribution Mw / Mn = 1.21. 1.2 molar equivalents of sodium methoxide were added to the hydroxyl groups of the resulting hydroxyl-terminated polypropylene oxide (P-1) in the form of a 28% methanol solution. After removing the methanol by vacuum devolatilization, 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of the polymer (P-1) to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by vacuum devolatilization. The resulting unpurified polypropylene oxide was mixed with n-hexane and water, stirred, and the water was removed by centrifugation. The metal salt in the polymer was removed by vacuum devolatilization of hexane from the resulting hexane solution. Through these operations, polypropylene oxide (Q-1) with terminal allyl groups was obtained.

[0252] Relative to 500g of polymer (Q-1), 50μl of a platinum-divinyldisiloxane complex solution (3% by weight isopropanol solution converted to platinum) was added, and the mixture was stirred while 8.4g of dimethoxymethylsilane was slowly added dropwise. After reacting at 100°C for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (A-1) with a number average molecular weight of 14600 and terminal dimethoxymethylsilyl groups. It can be seen that polymer (A-1) has an average of 0.8 dimethoxymethylsilyl groups per terminal group and an average of 1.5 dimethoxymethylsilyl groups per molecule.

[0253] (Synthetic Example 2) A-2

[0254] To polymer (Q-1), 50 ppm of (bicyclo[2.2.1]hept-2,5-diene)ruthenium(II) dichloropolymer (Sigma-Aldrich) and 130 ppm of 2,3-dibromonorbornene were added, and the mixture was stirred at 90 °C for 10 minutes. Additionally, 4.0 molar equivalents of dimethoxymethylsilane were added relative to the allyl group of polymer (Q-1), and the mixture was stirred for 1 hour. The volatile components were removed by vacuum distillation, yielding polyoxypropylene (A-2) with a number-average molecular weight of 14600 and terminal dimethoxymethylsilane groups. It was found that polymer (A-2) had an average of 0.93 dimethoxymethylsilane groups at one end.

[0255] (Examples 1-7, Comparative Examples 1-3, Reference Examples 1-2)

[0256] According to the composition (by weight) shown in Table 1, firstly, plasticizer, diluent, filler (calcium carbonate and titanium dioxide), polyamide rheology modifier, UV absorber, and light stabilizer were mixed relative to the polymer (A-1) and stirred using a rotary-stirring degassing mixer (manufactured by Samsung Industries, Ltd., trade name: High-Rotor HR005-04V). After cooling the mixture to below 50°C, A-171 (manufactured by Momentive Performance Materials Holdings Inc.: vinyltrimethoxysilane) as a dehydrating agent, A-1120 (manufactured by Momentive Performance Materials Holdings Inc.: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane) as a tackifier, and NEOSTANN U-220H (Nitto Kasei Corporation: dibutyltin diacetylacetone) as a curing catalyst were added sequentially. After thorough mixing with a spatula, the mixture was stirred and degassed using a rotary-stirring degassing mixer to obtain a curable composition.

[0257] It should be noted that when preparing the curable composition for the sprayability test, a 50L twin-screw mixer (manufactured by Inoue Manufacturing Co., Ltd.) was used for stirring.

[0258] (Exudation test)

[0259] The obtained curable composition was filled into a mold with an inner diameter of 40 mm and a depth of 10 mm, and the surface was finished. It was cured at 23°C and 50% relative humidity, and then placed at 5°C (relative humidity uncontrolled) for the number of days listed in Table 1. When the cured surface was touched with a finger, the absence of liquid compound on the hand was evaluated as "No" (no discharge), and the presence of liquid compound on the hand was evaluated as "Yes" (yes discharge). The results are shown in Table 1.

[0260] (Sprayability test)

[0261] For the obtained cured composition, the sprayability at a spray pressure of 14 MPa was evaluated using a Graco Mark V electric airless sprayer equipped with a #531 spray nozzle. The hose length was set to 30 m. The coating was judged based on whether coating spots were formed on the coating surface when spraying approximately 110 cm horizontally once with the distance between the coating surface and the spray nozzle maintained at approximately 50 cm. Coating spots are defined as uncoated areas appearing as streaks. Cases with coating spots were rated as "×", and cases without coating spots were rated as "○". The results are shown in Table 1.

[0262] The explanations of the terms used in Tables 1 through 4 are as follows.

[0263] DINP (J-Plus: diisononyl phthalate)

[0264] DINCH (BASF: diisononyl 1,2-cyclohexanedicarboxylate)

[0265] Total Fluid D170 (TotalEnergies: Hydrotreated Light Paraffin Oil)

[0266] Hydroseal HY (TotalEnergies: Hydrotreated light paraffin oil)

[0267] White Flower CCR (White Stone Industrial Co., Ltd.: Depositional Calcium Carbonate)

[0268] THITON SB (manufactured by Shiraishi Calcium Co., Ltd.: heavy calcium carbonate)

[0269] Omyacarb 1T-JI (Omya: heavy calcium carbonate, average particle size (D50): 1.8μm)

[0270] Omyacarb 2T-JI (Omya: heavy calcium carbonate, average particle size (D50): 2.8μm)

[0271] Omyacarb 5T-JI (Omya: heavy calcium carbonate, average particle size (D50): 4.9μm)

[0272] Tipaque R-820 (manufactured by Ishihara Sangyo Co., Ltd.: rutile titanium dioxide)

[0273] Crayvallac SLT (ARKEMA: polyamide rheology modifier)

[0274] Crayvallac SLW (ARKEMA: Polyamide rheology modifier)

[0275] Viscoexcel-30 (Shiroishi Kogyo Co., Ltd.: Synthetic Calcium Carbonate)

[0276] Aerosil R974 (AEROSIL Japan: Fumed Silica)

[0277] BYK-R 606 (BYK: Non-polyamide rheology modifier)

[0278] 10wt% CNFsol (10wt% DINP dispersion of cellulose nanofibers)

[0279] TEG2EH (Shandong Kexing Chemical Co., Ltd.: Triethylene glycol bis(2-ethylhexanoate))

[0280] Tinuvin 328 (BASF: Benzotriazole UV absorber)

[0281] Tinuvin 770 (BASF: Hindered amine light stabilizer)

[0282] [Table 1]

[0283]

[0284] As shown in Table 1, in Examples 1-7 where the amount of hydrocarbon-based diluent (B) was in the range of 10-50 parts by weight, no exudation from the cured product was observed at both room temperature and low temperature. In contrast, in Comparative Examples 1-3 where the amount of hydrocarbon-based diluent (B) was greater than 50 parts by weight, exudation was observed at low temperature. Furthermore, sprayability was evaluated in Examples 1 and 2, and the results were good.

[0285] On the other hand, in Reference Examples 1 and 2, evaluation results are shown without the use of hydrocarbon-based diluent (B). No exudation was observed in these reference examples, but coating spots were formed on the coated surface, indicating poor sprayability.

[0286] (Examples 8-15, Comparative Examples 4-9, Reference Examples 3-12)

[0287] According to the composition (weight ratio) shown in Tables 2 and 3, firstly, for polymer (A-1) or (A-2), plasticizer, diluent, filler (calcium carbonate and titanium dioxide), various rheology modifiers, ultraviolet absorbers and light stabilizers were mixed and stirred using a rotation-revolution type degassing mixer (manufactured by Samsung Industrial Co., Ltd., trade name: High-Rotor HR005-04V). After cooling the mixture to below 50°C, A-171 (manufactured by Momentive Performance Materials Holdings Inc.: vinyltrimethoxysilane) as a dehydrating agent, A-1120 (manufactured by Momentive Performance Materials Holdings Inc.: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane) as a tackifier, and NEOSTANN U-220H (Nitto Kasei Corporation: dibutyltin diacetylacetone) as a curing catalyst were added sequentially. After thorough mixing with a spatula, the mixture was stirred and degassed using a rotary stirring and degassing mixer to obtain a curable composition.

[0288] (Viscosity)

[0289] The viscosity of the obtained curable composition was determined using a Hybrid Rheometer Discovery HR-2 manufactured by TA Instruments. A 20 mm diameter plate was used, and the gap between the plate and the stage was adjusted to 0.5 mm. At a stage temperature of 23 °C, the shear rate was increased from 0.1 / s to 2000 / s (increase shear rate) over 4 minutes, followed by a decrease in the shear rate from 2000 / s to 0.1 / s (decrease shear rate) over the next 4 minutes. The sprayability of the curable composition was evaluated using the viscosity at 2000 / s (increase) and 2 / s (decrease).

[0290] The viscosity at 2000 rpm (rising) is in the high-shear region, and therefore can be considered close to the viscosity at the time of spraying. Compositions with a low viscosity at this value are evaluated as having good sprayability (i.e., good workability). Conversely, the viscosity at 2 rpm (falling) is in the low-shear region after strong shear force has been applied, and therefore can be considered close to the viscosity of the composition in the coating immediately after spraying. The higher this value, the less likely the coating is to sag (i.e., better visual appearance after coating).

[0291] (Tension properties)

[0292] The obtained curable composition was filled into a mold and cured at 23°C and 50% relative humidity for 3 days, followed by further curing at 50°C for 4 days to produce a sheet-like cured material with a thickness of approximately 3 mm. The sheet-like cured material was punched into a No. 3 dumbbell shape and subjected to tensile tests at 23°C and 50% relative humidity. The stresses (M50, M100) at 50% and 100% tension and the breaking strength were measured. The measurements were performed using an Autograph (manufactured by Shimadzu Corporation: AGS-J) at a tensile speed of 500 mm / min.

[0293] [Table 2]

[0294]

[0295] As shown in Table 2, in Examples 8-15 using polyamide rheology modifiers, the desired viscosity range is shown at 2000 rpm (rising) and 2 rpm (falling), which can balance sprayability and anti-sagging properties after coating.

[0296] Specifically, Examples 8-15 exhibit viscosities in the range of 1.2-1.5 Pa·s at 2000 rpm (rising pressure) and viscosities of 4.1 Pa·s or higher at 2 rpm (falling pressure). That is, they exhibit low viscosity during spraying, allowing for application with relatively low pressure using a spray gun, resulting in excellent operability. Furthermore, after adhering to the substrate surface via spraying, they exhibit a reasonably high viscosity, preventing sagging and resulting in a good visual effect after coating.

[0297] On the other hand, in Comparative Example 4, where the amount of polyamide rheology modifier was more than 10 parts by weight, and in Comparative Examples 5 to 7, which used rheology modifiers that were not polyamide, a viscosity of more than 1.7 Pa·s was observed at 2000 / s (rise). Therefore, high pressure was required when applying the coating using a spray gun, and the operability could not be said to be good.

[0298] Similarly, in Comparative Example 8, which used a rheology modifier that is not a polyamide, the viscosity at 2 / s (decline) was much lower than 2 Pa·s, and it was easy to sag after application, which could be considered as making it difficult to achieve an aesthetically pleasing visual effect.

[0299] In addition, in Comparative Example 9, which used a plasticizer (diol diester: TEG2EH in Table 2) described in Patent Document 2 that does not belong to a dicarboxylic acid ester containing a cyclic hydrocarbon group, a viscosity of 1.8 Pa·s was observed at 2000 / s (rising), so the sprayability was not sufficient.

[0300] Compared to Example 14, which used a polymer with an average of 0.83 dimethoxymethylsilyl groups at the ends (A-1), Example 15, which used a polymer with an average of 0.93 dimethoxymethylsilyl groups at the ends (A-2), showed higher tensile properties of the cured product. That is, the cured film after coating is more resistant to impact and friction.

[0301] [Table 3]

[0302]

[0303] As shown in Table 3, compared with Reference Examples 3-7 which used a polymer with an average of 0.83 dimethoxymethylsilyl groups at one end (A-1), Reference Examples 8-12 which used a polymer with an average of 0.93 dimethoxymethylsilyl groups at one end showed higher tensile properties of the cured film. That is, it can be said that the cured film after coating is more resistant to impact and friction.

[0304] (Examples 16-20)

[0305] According to the composition (by weight) shown in Table 4, firstly, for polymer (A-1), plasticizer, diluent, filler (calcium carbonate and titanium dioxide), rheology modifier, UV absorber, and light stabilizer were mixed and stirred using a rotary-stirring degassing mixer (manufactured by Samsung Industries, Ltd., trade name: High-Rotor HR005-04V). After cooling the mixture to below 50°C, A-171 (manufactured by Momentive Performance Materials Holdings Inc.: vinyltrimethoxysilane) as a dehydrating agent, A-1120 (manufactured by Momentive Performance Materials Holdings Inc.: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane) as a tackifier, and NEOSTANN U-220H (Nitto Kasei Corporation: dibutyltin diacetylacetone) as a curing catalyst were added sequentially. After thorough mixing with a spatula, the mixture was stirred and degassed using a rotary-stirring degassing mixer to obtain a curable composition.

[0306] It should be noted that when preparing the curable composition for the sprayability test, a 50L twin-screw mixer (manufactured by Inoue Manufacturing Co., Ltd.) was used for stirring.

[0307] (Sprayability test)

[0308] For the obtained cured compositions, the sprayability at a spray pressure of 16–17 MPa was evaluated using a Graco Mark V electric airless sprayer equipped with a spray nozzle of #523 or #531. The hose length was set to 30 m. With the distance between the coating surface and the spray nozzle maintained at approximately 50 cm, the coating surface after only one horizontal spray of approximately 110 cm was evaluated for the presence of coating spots and the maximum and minimum film thicknesses. In addition, spraying was continued until a given film thickness was obtained, and the film thickness at which sagging began was measured. The results are shown in Table 4.

[0309] [Table 4]

[0310]

[0311] As can be seen from Examples 16-20 in Table 4, in addition to hydrocarbon diluent (B) and plasticizer (C) containing dicarboxylic acid ester with cyclic hydrocarbon group, 0.6 parts by weight or more of polyamide rheology modifier (D) are added to 100 parts by weight of reactive silicon-based polyoxyethylene polymer (A), thereby achieving both sprayability and anti-sagging properties after coating.

[0312] On the other hand, preliminary experiments revealed that in a comparative example (not shown in the table) where the amount of polyamide rheology modifier (D) was reduced to 0.5 parts by weight, sagging was likely to occur after coating. Therefore, no sprayability evaluation test was conducted in this case.

Claims

1. A curable composition for spraying, comprising: 100 parts by weight of a polyoxyethylene polymer (A) with reactive silicon groups; Hydrocarbon-based diluent (B) 10-50 parts by weight; Plasticizer (C) 30-90 parts by weight, which is a dicarboxylic acid ester containing a cyclic hydrocarbon group; and 0.6-7 parts by weight of polyamide rheology modifier (D).

2. The curable composition according to claim 1, wherein, The hydrocarbon-based diluent (B) comprises at least one selected from cycloalkane-based diluents and alkane-based diluents.

3. The curable composition according to claim 1 or 2, wherein, The hydrocarbon-based diluent (B) has a boiling point of 250°C or higher.

4. The curable composition according to claim 1 or 2, further comprising a filler (E), The content of the filler (E) is 20 to 40% by weight in 100% of the total amount of the curable composition.

5. The curable composition according to claim 4, wherein, The filler (E) contains calcium carbonate.

6. The curable composition according to claim 5, wherein, The calcium carbonate is surface-treated heavy calcium carbonate.

7. The curable composition according to claim 1 or 2, wherein, The ratio of the plasticizer (C) to the hydrocarbon diluent (B) is 0.8 to 3.0 by weight.

8. The curable composition according to claim 1 or 2, wherein, The ratio of the total of the polyoxyethylene polymer (A) and the plasticizer (C) to the hydrocarbon diluent (B) is 2.6 to 7.0 by weight: [(A) + (C)] / (B).

9. The curable composition according to claim 1 or 2, wherein, The average number of reactive silicon groups at each end of the polyoxyethylene polymer (A) is greater than 0.

85.

10. The curable composition according to claim 1 or 2, wherein, The viscosity of the curable composition, measured at a temperature of 23°C and a shear rate of 2 / sec, is 4 Pa·s or higher.

11. The curable composition according to claim 1 or 2, wherein, The viscosity of the curable composition, measured at 23°C and a shear rate of 2000 / sec, is less than 1.5 Pa·s.

12. A cured film, which is formed by spraying and curing the curable composition according to claim 1 or 2.

13. A method for manufacturing a cured film, the method comprising: The curable composition of claim 1 or 2 is sprayed onto the surface of a substrate and then cured.

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