Moisture-curable resin composition

Abstract

The present invention relates to a moisture-curable resin composition, the cured product of which has excellent flame retardancy equivalent to UL94V-0 and also has excellent displacement followability and resin strength. A moisture-curable resin composition containing the following components (A) to (D). Component (A): an alkylene oxide polymer having a hydrolyzable silyl group, component (B): a flame retardant that is liquid at 25 DEG C, component (C): a flame retardant that is solid at 25 DEG C, and component (D): a curing catalyst.

Description

Technical Field

[0001] The present invention relates to a moisture-curable resin composition. Background Art

[0002] In recent years, with the electrification of automobiles, the number of electrical components installed in automobiles has increased. Examples of electrical components installed in automobiles include batteries. Since highly flammable lithium-ion batteries are installed inside the battery box, the adhesive and sealant of the battery box need to have a flame retardancy equivalent to UL94V-0 (Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Re-publication of WO2011 / 089987 Summary of the invention

[0006] The flame-retardant moisture-curable resin composition disclosed in Patent Document 1 uses a metal hydroxide powder such as aluminum hydroxide as a halogen-free and non-phosphorus flame retardant (claim 1 of Patent Document 1).

[0007] By adding metal hydroxide powders such as aluminum hydroxide to the moisture-curable resin composition, not only flame retardancy is imparted to the cured product, but also the preferred aspect of improving its strength is provided. On the other hand, the inventors have found that the addition of such metal hydroxide powders reduces the displacement followability of the cured product. When the cured product is used as an adhesive or sealant for electrical installation parts of an automobile, it is sometimes unable to follow the vibration during operation, and peeling occurs at the bonding portion. If the softness of the cured product is increased to solve this problem and the displacement followability is increased, the resin strength of the cured product is usually reduced, and the performance as an adhesive or sealant is reduced.

[0008] As described above, resin strength and displacement followability are in a conflicting relationship, and it is difficult to obtain an adhesive or sealant having both sufficient resin strength and displacement followability while maintaining flame retardancy.

[0009] Therefore, an object of the present invention is to provide a moisture-curable resin composition, wherein a cured product obtained after curing the moisture-curable resin composition exhibits flame retardancy equivalent to UL94V-0 and has both excellent resin strength and displacement followability.

[0010] The present inventors have conducted intensive research to achieve the above-mentioned problems, and as a result, have found a method for obtaining a moisture-curable resin composition having excellent resin strength and displacement followability while maintaining flame retardancy equivalent to UL94V-0. It should be noted that the evaluation of displacement followability in the present invention is carried out by measuring the elongation based on JISK6251:2017, and the higher the elongation, the higher the displacement followability.

[0011] Next, the gist of the present invention will be described.

[0012] [1] A moisture-curable resin composition comprising the following components (A) to (D),

[0013] (A) component: an oxyalkylene polymer having a hydrolyzable silyl group,

[0014] (B) component: a flame retardant that is liquid at 25°C,

[0015] (C) component: a flame retardant that is solid at 25°C,

[0016] (D) Component: Curing catalyst.

[0017] [2] The moisture-curable resin composition according to [1], wherein the component (B) contains a phosphorus-based flame retardant.

[0018] [3] The moisture-curable resin composition according to [1] or [2], wherein the component (B) comprises a compound represented by the following formula (3):

[0019] [Chemical formula 1]

[0020]

[0021] In formula (3), R 4 ~R 7 The groups shown are each independently a hydrogen atom, an alkyl group or a monovalent aromatic hydrocarbon group;

[0022] X 1 is a divalent aromatic hydrocarbon group;

[0023] X 2 is a single bond or a divalent aromatic hydrocarbon group;

[0024] The group represented by A is a single bond, an alkylene group or a divalent aromatic hydrocarbon group,

[0025] Here, in X 2 When is a single bond, A is a single bond;

[0026] n represents the degree of polymerization, which is an integer of 1-5.

[0027] [4] The moisture-curable resin composition according to any one of [1] to [3], wherein the component (C) contains a phosphorus-based flame retardant and / or aluminum hydroxide.

[0028] [5] The moisture-curable resin composition according to any one of [1] to [4], wherein the mass ratio of the component (B) to the component (C) is 9:1 to 1:9.

[0029] [6] The moisture-curable resin composition according to any one of [1] to [5], wherein the total amount of the component (B) and the component (C) is 10 to 500 parts by mass based on 100 parts by mass of the component (A).

[0030] [7] The moisture-curable resin composition according to any one of [1] to [6], wherein the component (D) is a zinc catalyst and / or a bismuth catalyst.

[0031] [8] The moisture-curable resin composition according to any one of [1] to [7], further comprising an inorganic filler as the component (E).

[0032] [9] The moisture-curable resin composition according to any one of [1] to [8], further comprising a silane compound as the component (F).

[0033]

[10] A cured product obtained by curing the moisture-curable resin composition according to any one of [1] to [9].

[0034] The present invention provides a moisture-curable resin composition having excellent flame retardancy, and a cured product thereof having both excellent resin strength and displacement followability. DETAILED DESCRIPTION

[0035] Next, the details of the present invention are described. It should be noted that the present invention is not limited to the following embodiments. In addition, in this specification, unless otherwise specified, the operation and the measurement of physical properties are carried out under the conditions of room temperature (above 20°C and below 25°C) / relative humidity above 40%RH and below 50%RH. In addition, "A and / or B" includes all combinations of A and B, specifically, at least one of A and B, and refers to the combination of A, B and A and B. It should be noted that in this specification, "X~Y" is used to include the numerical values ​​(X and Y) recorded before and after as the lower limit and upper limit, and means "above X and below Y". In the case of recording multiple "X~Y", for example, in the case of recording "X1~Y1 or X2~Y2", the disclosure of each numerical value as the upper limit, the disclosure of each numerical value as the lower limit, and the combination of these upper / lower limits are all disclosed (that is, it becomes the legal basis for modification). Specifically, modifications above X1, modifications below Y2, modifications below X1, modifications above Y2, modifications from X1 to X2, modifications from X1 to Y2, etc. should all be deemed legal.

[0036] In the present invention, the term "does not contain" compounds, etc. can mean "does not contain substantially", and can also mean that compounds, etc. are below the detection limit of the measuring instrument. "Does not contain substantially" means that a certain component is not added intentionally, and does not exclude the following situations: for example, the situation where it is included as an impurity produced by an undesirable side reaction. In one embodiment, when a certain compound is set to "does not contain", the content of the compound is preferably less than 10% by mass, more preferably less than 5% by mass, further preferably less than 1% by mass, and further preferably less than 0.1% by mass. In one embodiment, when a certain compound is set to "does not contain", the content of the compound can be less than 1000 mass ppm, less than 100 mass ppm, less than 10 mass ppm, less than 10 mass ppm, less than 1 mass ppm, or less than 0.1 mass ppm.

[0037] In one embodiment of the present invention, a moisture-curable resin composition is provided, which comprises the following components (A) to (D), wherein the component (A): an oxyalkylene polymer having a hydrolyzable silyl group, the component (B): a flame retardant that is liquid at 25° C., the component (C): a flame retardant that is solid at 25° C., and the component (D): a curing catalyst. Thus, a moisture-curable resin composition having excellent flame retardancy and having excellent resin strength and displacement tracking properties after curing can be provided.

[0038] The component (A) used in the present invention is an oxyalkylene polymer having a hydrolyzable silyl group. The oxyalkylene polymer referred to in the present invention (referred to as "oxyalkylene polymer" or "polyoxyalkylene polymer" in this specification, and these terms can be used interchangeably) refers to a polymer (referred to as "polymer having an oxyalkylene portion" or "polymer having a polyoxyalkylene portion" in this specification, and these terms can be used interchangeably) having an oxyalkylene skeleton (polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc.) in the main chain (excluding siloxane polymers (in this specification, polymers whose main chain skeletons are linked by siloxane bonds (Si-O-Si))). The hydrolyzable silyl group of the above-mentioned component (A) can be bonded to the terminal and / or side chain of the oxyalkylene polymer, and is preferably bonded to the terminal from the viewpoint of imparting excellent displacement tracking and resin strength to the cured product. In addition, from the viewpoint of handling, the above-mentioned component (A) is preferably liquid at 25°C. They can be used alone or in combination of two or more.

[0039] The oxyalkylene group as a repeating unit for forming the above-mentioned oxyalkylene skeleton can be a linear or branched oxyalkylene group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, and further preferably 2 to 3 carbon atoms. In one embodiment, the oxyalkylene group as the above-mentioned repeating unit can be oxyethylene, oxypropylene, oxytrimethylene or oxytetramethylene. When the polymer has the structure shown above as a repeating unit, the cured product of the present invention can have both excellent displacement tracking and resin strength. In addition, the polarity of the above-mentioned structure is high, so the polymer with the above-mentioned structure as a repeating unit is also excellent in terms of high compatibility with other compounding components and high adhesion. In addition, the main chain skeleton of the polymer having a polyoxyalkylene portion can be composed of only one repeating unit, or it can be composed of more than two repeating units. In one embodiment, when it is composed of only one repeating unit, the repeating unit can be an oxyalkylene group. In one embodiment, when the polymer is composed of two or more repeating units, the main chain of the polymer having a polyoxyalkylene moiety may contain only two or more repeating units consisting of only oxyalkylene groups, or may contain both repeating units consisting of only oxyalkylene groups and repeating units not containing oxyalkylene groups. Examples of the repeating unit not containing an oxyalkylene group include the following structures:

[0040] [Chemical formula 2]

[0041]

[0042] In formula (1), R is a hydrogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms, and R' is a hydrogen atom or a methyl group, but is not limited thereto. In the case of containing repeating units that do not contain oxyalkylene groups, the sum of repeating units consisting only of oxyalkylene groups in the polymer can be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more. When a polymer having the repeating units described above is used as component (A), a resin composition having excellent displacement followability and resin strength of its cured product can be obtained. In addition, the polymer having the repeating units described above does not contain a structure that can generate low molecular weight siloxane, and therefore, a resin composition without low molecular weight siloxane can be obtained.

[0043] In one embodiment, as an example of the above-mentioned oxyalkylene skeleton, polyethylene glycol, polypropylene glycol, polytrimethylene glycol and polytetramethylene glycol can be used, but it is not limited to this. The above-mentioned polymer containing an oxyalkylene skeleton can be used alone, or two or more kinds can be used in combination. In one embodiment, the above-mentioned polymer having an oxyalkylene part can be a copolymer. As a copolymer, polyethylene glycol-polypropylene glycol copolymer, polypropylene glycol-polytrimethylene glycol copolymer, polyethylene glycol-acrylate copolymer, polypropylene glycol-acrylate copolymer, polyethylene glycol-methacrylate copolymer, polypropylene glycol-methacrylate copolymer, and combinations thereof can be cited, but it is not limited to these. In addition, when it is a copolymer, it can be block-shaped or random. They can be used alone or two or more copolymers can be used in combination. Furthermore, polymers that are not copolymers and copolymers can also be used in combination. In addition, the structure of the above-mentioned polymer having a polyoxyalkylene part can be a linear polymer, a branched polymer, or a mixture thereof. In one embodiment, the above-mentioned oxyalkylene polymer may be a mixture of a polymer not having an oxyalkylene portion in addition to a polymer having an oxyalkylene portion (excluding a siloxane polymer), or may be composed only of a polymer having an oxyalkylene portion. Examples of the above-mentioned polymer not having an oxyalkylene portion include acrylic polymers, methacrylic polymers, vinyl polymers, etc., but are not limited to these. In one embodiment, the above-mentioned polymer not having an oxyalkylene portion may be a polymer having a repeating structure as shown in the above-mentioned formula (1). In one embodiment, the above-mentioned polymer not having an oxyalkylene portion may be a polymer having a repeating structure as shown in the above-mentioned formula (1), wherein R is a linear or branched alkyl group having 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms, and R' is a hydrogen atom. In one embodiment, the above-mentioned polymer not having an oxyalkylene portion may be an acrylic polymer. Here, the acrylic polymer refers to a polymer of a monomer having an ethylenically unsaturated bond such as a (meth)acrylate monomer. The polymer having an oxyalkylene moiety may be used alone or in combination of two or more thereof, and the polymer not having an oxyalkylene moiety may be used alone or in combination of two or more thereof. In the case of a mixture of a polymer having an oxyalkylene moiety and a polymer not having an oxyalkylene moiety, the polymer having an oxyalkylene moiety in component (A) may contain 10% to 90% by mass. In one embodiment, the polymer having an oxyalkylene moiety in component (A) may contain 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.In one embodiment, the polymer having an oxyalkylene moiety in the component (A) may contain 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or 10% by mass or less. In the case of containing two or more of the above-mentioned polymers having an oxyalkylene moiety, the content of the polymer having an oxyalkylene moiety refers to the total value. Since the polymer as described above does not contain a structure capable of generating low molecular weight siloxane, a resin composition that does not contain low molecular weight siloxane (i.e., no low molecular weight siloxane) can be obtained.

[0044] In this specification, "low molecular weight siloxane" and "cyclic low molecular weight siloxane" refer to cyclic dialkyl polysiloxane, in particular to the cyclic body of trimer (D3) to decamer (D10). In the case where the above-mentioned resin composition does not contain low molecular weight siloxane, the occurrence of contact failure can be suppressed when used for electrical installation parts. In one embodiment, "low molecular weight siloxane" is a cyclic polysiloxane with a molecular weight of 200 to 800. Polysiloxane is also expressed as a siloxane polymer, which refers to a polymer whose main chain skeleton is formed by a siloxane bond (Si-O-Si).

[0045] The hydrolyzable silyl group refers to a group having 1 to 3 hydrolyzable groups bonded to a silicon atom. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, a benzyloxy group, an acyl oxide group (also referred to as an acyloxy group), a ketoxymate group, an amino group, an amide group, an aminooxy group, an alkenyl oxide group (also referred to as an alkenyloxy group), and the like. Among them, from the viewpoint of curability, the hydrolyzable group is preferably an alkoxy group or a benzyloxy group, and more preferably an alkoxy group. When a plurality of hydrolyzable groups are bonded to a silicon atom, the plurality of hydrolyzable groups may all be present as the same type, or two or more types may be present as a mixture.

[0046] As the above-mentioned alkoxy group, alkoxy groups having 1 to 4 carbon atoms, preferably alkoxy groups having 1 to 3 carbon atoms, and phenoxy groups can be mentioned. In one embodiment, as the above-mentioned alkoxy group, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutyl, sec-butoxy, tert-butoxy or phenoxy groups can be mentioned. In one embodiment, from the viewpoint of having both displacement followability and resin strength, the above-mentioned alkoxy group is preferably a methoxy group or an ethoxy group, and more preferably a methoxy group. In the case where multiple alkoxy groups are bonded to a silicon atom, the multiple alkoxy groups may all exist in the same type, or two or more types may be mixed. In one embodiment, the multiple alkoxy groups may be two methoxy groups or three methoxy groups, preferably three methoxy groups.

[0047] In addition, as the above-mentioned hydrolyzable silyl group, trialkoxysilyl, dialkoxysilyl, monoalkoxysilyl, etc. can be mentioned, but it is not limited to these. Preferably, trialkoxysilyl or dialkoxysilyl, more preferably trialkoxysilyl. In one embodiment, as the hydrolyzable silyl group, trimethoxysilyl, dimethoxysilyl, monomethoxysilyl, etc. can be mentioned, but it is not limited to these. In one embodiment, the hydrolyzable silyl group is preferably trimethoxysilyl and dimethoxysilyl, and from the viewpoint of the crosslinking degree between polymers and the reactivity of the curing reaction, trimethoxysilyl is particularly preferred.

[0048] The number of hydrolyzable silyl groups present in one molecule of the component (A) is at least 1, preferably 1.1 to 10, more preferably 1.5 to 5, and still more preferably 1.8 to 4 on average. When the number of hydrolyzable silyl groups contained in one molecule of the polymer is within the above range, the cured product of the composition is sufficiently cross-linked, thus exhibiting good resin strength, and the network structure does not become too dense, exhibiting good flexibility, i.e., displacement followability. When a plurality of hydrolyzable silyl groups are present in one molecule of the polymer, the plurality of hydrolyzable silyl groups may all be the same, or two or more may be mixed.

[0049] The number average molecular weight of the component (A) may be 1000 to 100000, 2000 to 50000, or 3000 to 35000, but is not limited to this range. In the present specification, the number average molecular weight of a polymer may be a value measured by gel permeation chromatography (GPC) (polystyrene conversion).

[0050] The viscosity of the component (A) at 23°C is preferably 1 to 500 Pa·s, more preferably 20 to 200 Pa·s, and most preferably 50 to 80 Pa·s. If it is 1 Pa·s or more, the workability as a moisture-curable resin composition is good, and if it is 500 Pa·s or less, there is no concern that the displacement followability will be reduced even if it is mixed with the component (C). The viscosity of the component (A) is a value measured based on JIS K1557:2007.

[0051] There are no particular limitations on commercially available products of the component (A), and examples thereof include Kaneka Silyl (registered trademark) SAT010, SAX115, SAT030, SAT030, SAT200, SAT350, SAT400, SAX220, SAX510, SAX530, SAX575, SAX580, SAX710, SAX720, SAX725, SAX750, SAX770, S203, S303, S203H, S303H, S943S, S911S, and MA440. , MA447, MA451, MA903, MA903M, MA904, S943, MAX923, MAX951, SAX510, SAX520, SAX530, SAX580, etc. (manufactured by KANEKA CORPORATION), EXCESTAR (registered trademark) ES-S2410, ES-S2420, ES-S3430, ES-S3610, ES-S3630 (manufactured by AGC Corporation), etc. These may be used alone or in combination of two or more.

[0052] In one embodiment, the content of the component (A) in the moisture-curable resin composition may be 10% to 70% by mass, preferably 15% to 50% by mass, and more preferably 20% to 40% by mass. When two or more components (A) are contained, the content of the component (A) refers to the total value.

[0053] The component (B) used in the present invention is a flame retardant that is liquid at 25°C. By using it in combination with the component (C) described later, it is possible to impart excellent resin strength and displacement tracking properties to the cured product. In this specification, "liquid at 25°C" means that it is liquid (liquid) at 25°C under atmospheric pressure (1013.25 hPa). As flame retardants that can be used as component (B), phosphorus flame retardants, nitrogen flame retardants, etc. can be cited. In one embodiment, from the viewpoint of not reducing the strength of the resin, component (B) is preferably a phosphorus flame retardant. In addition, from the viewpoint of environmental load, component (B) preferably does not contain halogen atoms.

[0054] In one embodiment, the component (B) comprises a compound represented by the following formula (2):

[0055] [Chemical formula 3]

[0056]

[0057] In formula (2), R 1 , R 2 and R 3 The groups shown may each independently be a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

[0058] In the present specification, the alkyl group may be a linear or branched alkyl group having 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 10 carbon atoms, 1 to 5 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, or 1 to 2 carbon atoms. Examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 2-ethylhexyl, tetradecyl, octadecyl, and eicosyl.

[0059] In the present specification, the aromatic hydrocarbon group may be a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include, but are not limited to, phenyl, benzyl, phenethyl, o-, m- or p-tolyl, 2,3-, 2,4- or 2,5-xylyl, mesityl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, diphenylmethyl, triphenylmethyl, and pyrenyl. Unless otherwise specified, an aromatic substituent refers to a monovalent aromatic substituent.

[0060] In this specification, "substituted" means that a hydrogen atom is replaced by another atom or a substituent. Examples of the above-mentioned atom or substituent include, but are not limited to, a halogen atom, a hydroxyl group, an amino group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.

[0061] In formula (2), R 1 , R 2 and R 3 The groups shown can each independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, tolyl, xylyl, ((4-hydroxyphenyl)dimethylmethyl)phenyl.

[0062] In one embodiment, the compound that may be included in the component (B) may have a repeating structure. In one embodiment, the compound that may be included in the component (B) may have 1 or more than 2 phosphorus atoms in 1 molecule. In one embodiment, the number of phosphorus atoms contained in 1 molecule of the compound that may be included in the component (B) may be 2 or more or 3 or more. In one embodiment, the number of phosphorus atoms contained in 1 molecule of the compound that may be included in the component (B) may be 6 or less or 5 or less.

[0063] In one embodiment, the component (B) includes a compound represented by the following formula (3):

[0064] [Chemical formula 4]

[0065]

[0066] In formula (3), R 4 ~R 7 The groups shown are each independently a hydrogen atom, an alkyl group or a monovalent aromatic hydrocarbon group;

[0067] X 1 is a divalent aromatic hydrocarbon group;

[0068] X 2 is a single bond or a divalent aromatic hydrocarbon group;

[0069] The group represented by A is a single bond, an alkylene group or a divalent aromatic hydrocarbon group,

[0070] Here, in X 2 When is a single bond, A is a single bond;

[0071] n represents the degree of polymerization and is an integer of 1 to 5. When the component (B) contains the compound represented by the above formula (3), the cured product obtained from the moisture-curable resin composition can exhibit excellent displacement followability, and by combining with the component (C), good resin strength and displacement followability can be imparted to the cured product.

[0072] In the present specification, the divalent aromatic hydrocarbon group may be a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms. Examples of the divalent aromatic hydrocarbon group include p-phenylene, m-phenylene, or o-phenylene, but are not limited thereto. In one embodiment, the divalent aromatic hydrocarbon group is preferably a substituted or unsubstituted p-phenylene or m-phenylene, more preferably a substituted or unsubstituted p-phenylene, and further preferably an unsubstituted p-phenylene.

[0073] In one embodiment, R in the above formula (3) 4 ~R 7 The group represented by is preferably an aromatic hydrocarbon group. In one embodiment, R in the above formula (3) 4 ~R 7 The groups shown are each independently preferably a substituted or unsubstituted phenyl group, more preferably an unsubstituted phenyl group.

[0074] In one embodiment, X in the above formula (3) 1 Preferably, it is p-phenylene or m-phenylene, more preferably p-phenylene. 2 Preferably, X is a divalent aromatic hydrocarbon group. 2It is preferably a single bond, p-phenylene or m-phenylene, and more preferably p-phenylene. In one embodiment, A is preferably a single bond or an alkylene group, more preferably a single bond or a substituted or unsubstituted methylene group, and further preferably a dimethylmethylene group.

[0075] In one embodiment, X in the above formula (3) 1 is a divalent aromatic hydrocarbon group, X 2 is preferably a divalent aromatic hydrocarbon group, and A is preferably an alkylene group. In one embodiment, X in the above formula (3) 1 Preferably, X is substituted or unsubstituted p-phenylene. 2 is preferably a substituted or unsubstituted p-phenylene group, and A is preferably a dialkylmethylene group. In one embodiment, X in the above formula (3) 1 Preferably, unsubstituted p-phenylene, X 2 It is preferably unsubstituted p-phenylene, and A is preferably dimethylmethylene.

[0076] In the present specification, the alkylene group may be a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 10 carbon atoms, 1 to 5 carbon atoms, or 1 to 3 carbon atoms. Examples of the alkylene group include methylene, ethylene, propylene, trimethylene, tetramethylene, and dimethylmethylene, but are not limited thereto.

[0077] As a specific example of (B) component, trialkyl phosphates such as trimethyl phosphate and triethyl phosphate can be cited; aromatic phosphates such as tricresyl phosphate, tri(xylyl) phosphate, cresyl diphenyl phosphate, cresyl di(2,6-xylyl) phosphate; aromatic condensed phosphates such as the reaction product of phenol and 4,4'-(propane-2,2-diyl) biphenol and phosphine oxychloride, resorcinol bis-diphenyl phosphate, etc., are preferably aromatic condensed phosphates from the viewpoint of having both resin strength and displacement tracking. They can be used alone, or two or more can be used in combination. In one embodiment, as (B) component, the reaction product of phenol, 4,4'-(propane-2,2-diyl) biphenol and phosphine oxychloride is preferably used.

[0078] In one embodiment, the content of the aromatic condensed phosphate ester relative to the whole component (B) may be 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more. In one embodiment, the content of the aromatic condensed phosphate ester relative to the whole component (B) is 100% by mass.

[0079] The viscosity of the component (B) is preferably 0.1 to 100 Pa·s at 25°C, more preferably 0.1 to 50 Pa·s, further preferably 1 to 40 Pa·s, further preferably 5 to 30 Pa·s, and most preferably 10 to 25 Pa·s. If it is 0.1 Pa·s or more, the compatibility with the component (A) is good, and flame retardancy can be uniformly imparted to the moisture-curable resin composition. If it is 100 Pa·s or less, there is no risk of reducing displacement tracking. The viscosity of the component (B) is a value measured using a B-type viscometer in accordance with JIS K7117-1:1999.

[0080] Commercially available products of the component (B) are not particularly limited, and examples thereof include ADK STAB (registered trademark, the same below), FP-600, PFR, FP-900L (manufactured by ADEKA CORPORATION), REOFOS 35, 50, 65, 95, 110, HYD-110 (manufactured by Ajinomono Fine-Techno Co., Inc.), CR-733S, CR-741, DAIGUARD (registered trademark, the same below)-880 (manufactured by Daihachi Chemical Industry Co., Ltd.), HISHICOLIN (registered trademark) O (manufactured by Nippon Chemical Industry Co., Ltd.), etc. These may be used alone or in combination of two or more.

[0081] The content of the above-mentioned (B) component is preferably 10 to 500 parts by mass, more preferably 20 to 300 parts by mass, further preferably 30 to 200 parts by mass, and most preferably 50 to 120 parts by mass relative to 100 parts by mass of the (A) component. If the (B) component is 10 parts by mass or more, the displacement followability can be improved, and if it is 500 parts by mass or less, there is no risk of reducing the strength of the resin. When containing two or more of the above-mentioned (B) components, the content of the (B) component refers to the total value.

[0082] The component (C) used in the present invention is a flame retardant that is solid at 25°C (i.e., solid at 25°C). In this specification, "solid at 25°C" or "solid at 25°C" means that it is solid at 25°C under atmospheric pressure (1013.25hPa). The component (C) of the present invention can impart excellent displacement tracking properties and resin strength to the cured product by being used in combination with the component (B) in the component (A). From the perspective of being dispersed in the component (A), it is preferably formulated in the form of a powder. As (C) component, for example, halogen flame retardant can be mentioned; phosphorus flame retardant; and flame retardant metal compounds such as zinc stannate, zinc borate, zinc metaborate, zinc carbonate, magnesium carbonate, magnesium oxide, molybdenum oxide, tin oxide, iron oxide, zirconium oxide, antimony oxide, aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; flame retardant nitrogen-containing compounds such as melamine, melamine cyanurate, melamine phosphate, and melamine resin; various particulate inorganic compounds such as polytetrafluoroethylene, thermally expandable graphite, and zeolite. The flame retardant metal compound includes the form of hydroxide (hereinafter referred to as "hydroxide flame retardant"), for example, aluminum hydroxide, magnesium hydroxide, and calcium hydroxide can be mentioned, but it is not limited to these. From the viewpoint of environmental load, the above-mentioned (C) component preferably does not contain halogen atoms. From the viewpoint of dispersibility in (A) component and affinity with (B) component, the above-mentioned (C) component preferably includes phosphorus flame retardant and / or hydroxide flame retardant, and at this time, the hydroxide flame retardant more preferably includes aluminum hydroxide. In one embodiment, the above-mentioned (C) component may be only a phosphorus-based flame retardant. In one embodiment, the above-mentioned (C) component includes both a phosphorus-based flame retardant and aluminum hydroxide. When both a phosphorus-based flame retardant and aluminum hydroxide are included, from the viewpoint of improved flame retardancy and affinity of the (B) component, the mass ratio of the phosphorus-based flame retardant: the mass ratio of the aluminum hydroxide flame retardant is preferably 9:1 to 1:9, more preferably 8:2 to 2:8, further preferably 7:3 to 3:7, and most preferably 4.5:5.5 to 3:7.

[0083] In addition, from the viewpoint of dispersibility in component (A), the phosphorus-based flame retardant that may be contained in component (C) is preferably a phosphate-based flame retardant. The phosphate-based flame retardant in component (C) is preferably an expansion-based phosphate-based flame retardant. An expansion flame retardant refers to a flame retardant that contains phosphorus and nitrogen in the component, forms a carbonized film by combustion, and the carbonized film expands to form a foamed expansion layer (expansion), which contributes to flame retardancy. By including it in the composition, excellent flame retardancy can be imparted to the composition.

[0084] From the viewpoint of dispersibility in component (A), the aluminum hydroxide that may be contained in component (C) may be aluminum hydroxide that has been subjected to surface treatment. The surface treatment that can be applied to the aluminum hydroxide contained in component (C) is preferably a treatment of the surface using fatty acids, resin acids, fatty acid esters, fatty acid metal salts, silane coupling agents, etc., and more preferably a treatment of the surface using silane coupling agents. The silane coupling agent that can be used for surface treatment may have one or more functional groups selected from vinyl, epoxy, styryl, methacryloxy, acryloxy, amino, isocyanurate, urea, mercapto, isocyanate, and acyloxycarbonyl. In one embodiment, as a silane coupling agent that can be used for surface treatment, a silane coupling agent having a methacryloxy group and an acryloxy group is preferred, and a silane coupling agent having a methacryloxy group (methacryloxysilane) is most preferred. Examples of methacryloxysilane include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane, but are not limited thereto.

[0085] In one embodiment, the content of the expanded phosphate flame retardant relative to the whole component (C) can be 30% by mass or more, 50% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more. In one embodiment, the content of the expanded phosphate flame retardant relative to the whole component (C) is 100% by mass.

[0086] In one embodiment, the content of aluminum hydroxide based on the entire component (C) may be 30% by mass or more, 50% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.

[0087] Commercially available products of the phosphorus-based flame retardant as the component (C) are not particularly limited, and examples thereof include ADK STAB FP-2100JC, FP-2500S, FP-2600U (manufactured by ADEKA CORPORATION), PX-200, DAIGUARD-850 (manufactured by Daihachi Chemical Industry Co., Ltd.), etc. These may be used alone or in combination of two or more.

[0088] Commercially available products of the aluminum hydroxide are not particularly limited, and examples thereof include SB303, SB153, SB103, B303, B153, B703, B1403, BF013, B153STM, B303STE, and BF013ST (manufactured by Nippon Light Metal Co., Ltd.) etc. These may be used alone or in combination of two or more.

[0089] The 50% average particle size of the above-mentioned (C) component is preferably 0.1 to 50 μm, more preferably 0.5 to 30 μm, further preferably 1 to 20 μm, and most preferably 5 to 20 μm. If it is 0.1 μm or more, it can be evenly dispersed in the (A) component, and if it is 50 μm or less, there is no risk of reducing the elongation. In one embodiment, when the (C) component is a phosphorus-based flame retardant, such as an expanded phosphate-based flame retardant, the 50% average particle size of the (C) component can be 0.1 to 50 μm, 0.5 to 30 μm, 1 to 20 μm, 5 to 20 μm, or 5 to 10 μm. In one embodiment, when the (C) component is aluminum hydroxide, the 50% average particle size of the (C) component can be 0.1 to 50 μm, 0.5 to 30 μm, 1 to 20 μm, 5 to 20 μm, or 10 to 20 μm. The 50% average particle size referred to in the present invention is a particle size (D50) at which the cumulative volume ratio in the particle size distribution determined by a laser diffraction scattering method is 50%.

[0090] The content of the above-mentioned (C) component is preferably 10 to 500 parts by mass, more preferably 20 to 300 parts by mass, further preferably 30 to 200 parts by mass, and most preferably 80 to 180 parts by mass relative to 100 parts by mass of the (A) component. If it is 10 parts by mass or more, the resin strength can be improved, and if it is 500 parts by mass or less, there is no risk of reducing the displacement followability of the cured product. When containing two or more of the above-mentioned (C) components, the content of the (C) component refers to the total value.

[0091] From the viewpoint of achieving flame retardancy equivalent to V-0, the total content of the above-mentioned (B) component and (C) component is preferably 10 to 500 parts by mass, more preferably 70 to 400 parts by mass, further preferably 100 to 300 parts by mass, and most preferably 150 to 300 parts by mass relative to 100 parts by mass of the (A) component. The mass ratio of the (B) component to the (C) component is preferably 9:1 to 1:9, more preferably 8:2 to 2:8, and most preferably 8:2 to 4:6. In one embodiment, the mass ratio of the (B) component to the (C) component is preferably 4:1 to 1:4, more preferably 3:1 to 1:4, further preferably 2:1 to 1:4, and further preferably 1:1 to 1:3. By the total mass of the (B) component: the total mass of the (C) component = 9:1 to 1:9, it is possible to take into account both the resin strength and displacement tracking properties of the cured product.

[0092] The component (D) that can be used in the present invention is a curing catalyst. There are no particular limitations on the catalyst as long as it is a catalyst that crosslinks the component (A), and examples thereof include dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin distearate, dibutyltin laurate oxide, dibutyltin diacetylacetonate, dibutyltin dioleylmalate, and dibutyltin tantalum. Tin compounds such as dioleylmalate, dibutyltin octanoate, dioctyltin oxide, and dioctyltin dilaurate; titanate compounds such as tetra-n-butoxy titanate and tetraisopropoxy titanate; lead compounds such as lead octanoate and lead naphthenate; nickel compounds such as nickel naphthenate; cobalt compounds such as cobalt naphthenate; zinc catalysts such as zinc octanoate, zinc naphthenate, hexacyanocobaltate zinc complex, 1-methylimidazole-bis(2-hexanoate) zinc complex, and alkylamine zinc complex; iron compounds; bismuth catalysts such as bismuth carboxylate (or "bismuth carboxylate catalyst"); acetylacetone metal complexes such as acetylacetone aluminum complex and acetylacetone vanadium complex, etc. In addition, amine salts such as dibutylamine-2-ethylhexanoate, organic phosphoric acid compounds such as monomethyl phosphoric acid and di-n-butyl phosphoric acid, other acidic catalysts, and basic catalysts can also be used. These can be used alone or in combination of two or more. Among them, from the viewpoint of improving the resin strength and displacement followability of the cured product, it is preferred to include a zinc catalyst or a bismuth catalyst, and it is most preferred to include a zinc catalyst. When a zinc catalyst is used, a zinc catalyst in which an amine is coordinated to zinc is more preferred, and a zinc catalyst in which an alkylamine is coordinated to zinc is most preferred. When a bismuth catalyst is used, a bismuth carboxylate is most preferred.

[0093] The content of the component (D) is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, further preferably 1 to 15 parts by mass, and most preferably 5 to 10 parts by mass relative to 100 parts by mass of the component (A). If it is 0.05 parts by mass or more, a cured product having excellent resin strength can be obtained, and if it is 20 parts by mass or less, there is no risk of reducing displacement followability.

[0094] There are no particular limitations on commercially available products of the component (D). Examples of the tin catalyst include NEOSTANN (registered trademark) U-100, U-130, U-200, and U-303 (manufactured by Nitto Kasei Co., Ltd.). Examples of the titanium catalyst include ORGATIX (registered trademark, hereinafter the same) TA-8, TA-10, TA-21, TA-23, TA-30, TA-80, TC-100, TC-120, and TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.). Examples of the bismuth catalyst include K-KAT348, XC-C227, and XK-640 (manufactured by King Industries, Inc.). Examples of the zirconium catalyst include ORGATIX ZA-45 (manufactured by Matsumoto Fine Chemical Co., Ltd.), K-KAT4205, 6212, and A209 (manufactured by King Industries, Inc.). Industries, Inc.), etc. As aluminum catalysts, for example, DX-9740 (Shin-Etsu Chemical Co., Ltd.), AMD, ASBD, AIPD, ALCH, ALCH-TR, Aluminum chelate M, Aluminum chelate D, Aluminum chelate A (Kawaken Fine Chemicals Co., Ltd.), K-KAT5218 (King Industries, Inc.), etc., as zinc catalysts, for example, K-KAT670 (King Industries, Inc.), etc. These may be used alone or in combination of two or more.

[0095] In the moisture-curable resin composition of the present invention, inorganic filler materials may be further contained as (E) component. By containing (E) component, it is possible to improve resin strength. As (E) component, it is not particularly limited, for example, glass, fumed silica, aluminum oxide, mica, ceramics, silicone rubber powder, calcium carbonate, aluminum nitride, carbon powder, kaolin, dry clay minerals, dry diatomaceous earth, etc. can be cited. From the viewpoint of improving resin strength without reducing displacement followability, preferably fumed silica, talc, calcium carbonate, more preferably fumed silica, calcium carbonate, most preferably fumed silica. In the case of using fumed silica, from the viewpoint of improving dispersibility and resin strength in (A) component, preferably use surface-treated fumed silica, most preferably use fumed silica that has been surface-treated using dimethylpolysiloxane.

[0096] From the viewpoint of improving the resin strength without reducing the displacement followability, the content of the above-mentioned (E) component is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, further preferably 1 to 20 parts by mass, and most preferably 5 to 15 parts by mass, based on 100 parts by mass of the (A) component.

[0097] The moisture-curable resin composition of the present invention may further contain a silane compound (excluding component (A) and component (E)) as component (F). By including component (F), it is possible to suppress the reduction in displacement tracking caused by component (B) and component (C). Component (F) is not particularly limited, and examples thereof include glycidyl-containing silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane; vinyl-containing silane coupling agents such as vinyltri(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane. Silane coupling agents; silane coupling agents containing (meth) acryl groups such as γ-methacryloxypropyltrimethoxysilane; silane coupling agents containing amino groups such as 3-aminopropyltrimethoxysilane N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; other γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, dimethoxydiphenylsilane, methyltrimethoxysilane, etc. Among them, from the viewpoint of suppressing the reduction of displacement follow-up, it is preferred that the silane compound does not have a reactive group other than the alkoxysilyl group, and dimethoxydiphenylsilane and methyltrimethoxysilane are more preferred. Alkylalkoxysilanes such as methyltrimethoxysilane are most preferred. In one embodiment of the present invention, the silane compound does not contain a cyclic low molecular weight siloxane.

[0098] From the viewpoint of suppressing a decrease in displacement followability, the content of the component (F) is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass, and most preferably 1 to 10 parts by mass based on 100 parts by mass of the component (A).

[0099] Various additives may or may not be added to the flame-retardant moisture-curable resin composition of the present invention within the range not impairing the purpose of the present invention. Examples of additives include plasticizers, moisture absorbers, organic fillers that are not flame-retardant, antioxidants, light stabilizers, colorants, and the like.

[0100] As the above-mentioned plasticizer, there is no particular limitation, for example, dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl)phthalate, butyl benzyl phthalate, butyl oleate, diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. can be cited. In addition, polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid, phthalic acid and diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol can be cited. They can be used alone or in combination of two or more. The amount of the plasticizer is preferably 1 to 100 parts by mass relative to 100 parts by mass of component (A). In one embodiment, the amount of the plasticizer blended is 10 parts by mass or less, 5 parts by mass or less, 1 part by mass or less, or 0.1 parts by mass or less, relative to 100 parts by mass of the component (A).

[0101] The moisture absorbent is not particularly limited as long as it is a substance that reacts with the moisture in the composition and absorbs moisture. For example, silicate compounds represented by methyl silicate, ethyl silicate, propyl silicate, and butyl silicate and their oligomers, vinyl silanes, calcium oxide, etc. can be mentioned. They can be used alone or in combination of two or more. The amount of the moisture absorbent is preferably 1 to 100 parts by mass relative to 100 parts by mass of component (A).

[0102] As the above-mentioned non-flame retardant organic filler, it is sufficient that it is a powder of an organic substance that is non-flame retardant and is composed of rubber, elastomer, plastic, polymer (or copolymer), etc. In addition, it can also be an organic filler with a multilayer structure such as a core-shell type. They can be used alone or in combination of two or more. The amount of the organic filler is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of component (A). In one embodiment, the amount of the non-flame retardant organic filler is less than 10 parts by mass, less than 5 parts by mass, less than 1 part by mass, or less than 0.1 parts by mass relative to 100 parts by mass of component (A).

[0103] Examples of the antioxidant include quinone compounds such as β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, and 2,5-di-tert-butyl-p-benzoquinone; phenothiazine, 2,2-methylene-bis(4-methyl-6-tert-butylphenol), catechol, tert-butylcatechol, 2-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-6-(3-tert-butyl-p-cresol), and the like. butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-〔1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl〕-4,6-di-tert-pentylphenyl acrylate, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 3,9-bis〔2-〔3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy〕-1,1-dimethylethyl〕-2,4,8,10-tetraoxaspiro〔5.5〕Undecane, pentaerythritol tetra-〔3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate〕, diethylene thiobis〔3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate〕, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N,N'-hexane-1,6-diylbis〔3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide〕, phenylpropionic acid-3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 side chain alkyl ester, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl〔〔3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl〕methyl〕phosphonate, 3,3',3" ,5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-tolyl) tri-p-cresol, calcium diethyl bis[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6- Phenols such as [2,4-di-tert-butylphenyl] phosphite, tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphinylheptan-6-yl]oxy]ethyl]amine, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphite, tetrakis[2,4-di-tert-butylphenyl] phosphite Phosphorus compounds such as (2,4-di-tert-butylphenyl)〔1,1-diphenyl〕-4,4'-diylbisphosphonite, 6-〔3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy〕-2,4,8,10-tetra-tert-butyldibenzo〔d,f〕〔1,3,2〕dioxaphosphine; amine compounds such as phenothiazine; lactone compounds; vitamin E compounds, etc. They can be used alone or in combination of two or more. The amount of the antioxidant is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of component (A). In one embodiment, the amount of the antioxidant is 0.05 to 10 parts by mass or 0.1 to 5 parts by mass relative to 100 parts by mass of component (A). .

[0104] Examples of the light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,10-diamine, dibutylamine / 1,3,5-triazine / N,N'-bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl) sebacate, reaction products of 1,1-dimethylethyl hydroperoxide and octane, N,N',N",N''-tetrakis-(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazine-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine / 1,3,5-triazine / N,N'-bis(2,2,6,6 Polycondensation product of 1,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]], polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol, 2,2,4,4-tetramethyl-20-(β-lauryloxycarbonyl)ethyl 2,2,4,4-tetramethyl-7-oxa-3,20-diazabispiro[5.1.11.2]heneicosane-21-one, β-alanine, N-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester / tetradecyl ester, N-acetyl-3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-diazabispiro[5.1.11.2]heneicosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazabicyclo[5.1.11.2〕Hindered amines such as heneicosane-20-propionate dodecyl / tetradecyl ester, malonic acid [(4-methoxyphenyl)-methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, higher fatty acid esters of 2,2,6,6-tetramethyl-4-piperidinol, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)1,3-benzenedicarboxylate; benzophenone compounds such as octabenzone; 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-〔2-hydroxy-3-(3,4,5,6-tetrahydrophthalamide Benzotriazole compounds such as benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, a reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate and polyethylene glycol, and 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol; benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; and triazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-〔(hexyl)oxy〕phenol. These compounds may be used alone or in combination of two or more. The amount of the light stabilizer is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the component (A). In one embodiment, the amount of the light stabilizer is 0.05 to 10 parts by mass or 0.1 to 5 parts by mass relative to 100 parts by mass of the component (A).

[0105] As the above-mentioned colorant, inorganic pigments such as titanium oxide, ultramarine, iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, etc. can be cited; azo pigments, phthalocyanine pigments, quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, anthraquinone pigments, dibenzopyrene dione pigments, indanthrone pigments, flavanone pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindoline pigments, organic pigments such as carbon black, etc. The amount of the colorant is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the (A) component. In one embodiment, the amount of the colorant is 0.05 to 10 parts by mass or 0.1 to 5 parts by mass relative to 100 parts by mass of the (A) component.

[0106] In one embodiment of the present invention, the content of low molecular weight siloxane in the moisture-curable resin composition is 0 to 10% by mass. In one embodiment, the content of low molecular weight siloxane in the moisture-curable resin composition is 10% by mass or less, 5% by mass or less, 3% by mass or less, 1% by mass or less, or 0.1% by mass or less. In one embodiment, the content of low molecular weight siloxane in the moisture-curable resin composition may be 1000% by mass or less, 100% by mass or less, 10% by mass or less, 1% by mass or less, or 0.1% by mass or less. In this specification, the content of low molecular weight siloxane in the moisture-curable resin composition is measured using a gas chromatograph mass spectrometer (GC-MS).

[0107] The moisture-curable resin composition of the present invention can be made into a single component type or a two-component type as required. In addition, the moisture-curable resin composition of the present invention is most suitable for use as a sealant, and can also be used as an adhesive, a bonding agent, a coating agent, a potting agent, etc. as required. The moisture-curable resin composition of one embodiment of the present invention can be used for various electrical and electronic fields, buildings, automobiles, civil engineering, etc., because it has excellent resin strength and displacement followability, and does not include cyclic low molecular siloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane, so it is particularly suitable for electrical and electronic components, electrical installation parts of automobiles. In particular, the electrical installation parts (battery boxes) of automobiles mostly use metal plates with low rigidity, and the sealing part is easily deformed due to vibration during operation, etc. Therefore, the cured product of the moisture-curable resin composition derived from the present application, which is endowed with displacement followability, is particularly effective in such uses.

[0108] <Method for producing moisture-curable resin composition>

[0109] The method for manufacturing the moisture-curable resin composition of the present invention is not particularly limited, and a conventionally known method can be appropriately used. For example, for component (A), component (B), component (C), component (D) and any added components, a specified amount is weighed respectively, and added to a stirring tank sequentially or simultaneously, and then a mixing device such as a planetary mixer is used, preferably while vacuum degassing and mixing. The preferred order of addition is that component (D) is the last. By setting the addition of component (D) to the last, it is possible to prevent the curing reaction from occurring at an undesirable stage. At this time, the manufacturing conditions are not particularly limited, and the mixing temperature is preferably set to a temperature of 10°C to 50°C, and the mixing time is preferably 0.1 hours to 5 hours.

[0110] Specifically, for example, first, the above-mentioned (A) to (C) components are weighed in a stirring container and stirred at room temperature for 10 minutes to 1 hour, preferably 10 minutes to 30 minutes. Then, the above-mentioned (E) and (F) components are added to the stirred mixture, and further stirred at room temperature for 1 minute to 1 hour, preferably 5 minutes to 20 minutes. Next, the (D) component is added to the obtained mixture, and further stirred at room temperature for 1 minute to 1 hour, preferably 5 minutes to 20 minutes, to obtain a moisture-curable resin composition.

[0111] The viscosity of the moisture-curable resin composition of the present invention at 25° C. is, for example, 0.01 to 500 Pa·s, preferably 1 to 300 Pa·s, and more preferably 100 to 250 Pa·s, from the viewpoint of workability during coating.

[0112] <Coating method>

[0113] There is no particular limitation on the method of applying the moisture-curable resin composition of the present invention to an adherend, and conventionally known methods of applying sealants and adhesives can be used. For example, methods such as dispensing, spraying, inkjetting, screen printing, gravure printing, dipping, and spin coating using an automatic coating machine can be used. It should be noted that from the viewpoint of coating properties, the moisture-curable resin composition of the present invention is in a liquid state at 25°C.

[0114] <Curing method>

[0115] The moisture-curable resin composition of the present invention is not particularly limited and can be cured by a conventionally known method. For example, the moisture-curable resin composition can be cured by exposing it to air containing moisture, for example, by leaving the moisture-curable resin composition of the present invention to stand for 1 hour to 2 weeks in an air atmosphere with a humidity of 40% RH to 60% RH. The curing temperature when curing the moisture-curable resin composition of the present invention is not particularly limited, but is preferably 10°C to 50°C, and preferably 15°C to 30°C. In addition, the relative humidity during curing is preferably 40% RH or more. The standing time for curing is not particularly limited, but is preferably 1 hour or more and less than 2 weeks, more preferably 3 hours or more and less than 10 days, further preferably 1 day or more and less than 9 days, and further more preferably 3 days or more and less than 8 days. In this way, the moisture-curable resin composition of the present invention has excellent curability.

[0116] <Cured product>

[0117] The cured product of the present invention can be obtained by curing the moisture-curable resin composition of the present invention.

[0118] In one embodiment, the hardness of the cured product of the present invention may be A10 or more, preferably A20 or more, and more preferably A30 or more. The upper limit of the hardness of the cured product is not particularly limited, and may be, for example, A80 or less or A60 or less. In this specification, the hardness of the cured product may be measured using a type A durometer hardness tester based on JIS K6249:2003.

[0119] Therefore, the present invention also provides a moisture-curable resin composition in which the hardness of a cured product obtained during curing is the above-mentioned hardness.

[0120] In addition, in one embodiment, the elongation of the cured product of the present invention based on the tensile test can be 300% or more, preferably 400% or more, and more preferably 500% or more. The upper limit of the elongation of the cured product based on the tensile test is not particularly limited, and can be 1000% or less, 800% or less, or 600% or less.

[0121] Therefore, the present invention also provides a moisture-curable resin composition in which the elongation of a cured product obtained during curing based on a tensile test is the above-mentioned elongation.

[0122] In one embodiment, the tensile strength of the cured product of the present invention based on a tensile test may be 1.0 MPa or more, preferably 1.3 MPa or more, and more preferably 1.5 MPa or more. The upper limit of the tensile strength of the cured product based on a tensile test is not particularly limited, and may be 5.0 MPa or less or 3.0 MPa or less. In this specification, the tensile test uses a dumbbell No. 3 test piece, based on JIS K6251: 2017, and the elongation and tensile strength of the cured product can be calculated from the results of the tensile test.

[0123] Therefore, the present invention also provides a moisture-curable resin composition in which the tensile strength of a cured product obtained during curing by a tensile test is the above-mentioned tensile strength.

[0124] In addition, the cured product of the present invention has a flame retardancy equivalent to or higher than UL94V-0. The flame retardancy of the cured product of the present invention may be, for example, UL94V-0, UL94 5VB or UL94 5VA. The flammability of the cured product may be tested based on the 20 mm vertical combustion test method of the UL94 standard.

[0125] Therefore, the present invention also provides a moisture-curable resin composition in which the flame retardancy of a cured product obtained during curing becomes the above-mentioned flame retardancy.

[0126] <Joint>

[0127] In the joint body of the present invention, the cured product can become the bonding layer of two adherends. In one embodiment, the joint body is not particularly limited as long as it is a joint body formed by bonding adherends using the curable resin composition of the present invention. As adherends, there are no particular limitations, and examples thereof include metals such as iron, copper, zinc, aluminum, and magnesium, plastics such as polycarbonate, polyacrylate, polyphenylene ether, polybutylene terephthalate, polyethylene, polyamide, polyimide, polyphenylene sulfide, polyetheretherketone, and fluoropolymers, and ceramics such as glass and silicon dioxide. In one embodiment, the joint body can be a battery box for an automobile, but is not limited thereto.

[0128] Example

[0129] Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0130] [Examples 1 to 6, Comparative Examples 1 to 5]

[0131] In order to prepare the moisture-curable resin composition, the following components were prepared.

[0132] (A-1): a polymer having a polyoxyalkylene moiety having trimethoxysilyl groups at both ends (polyoxyalkylene polymer), trade name: Kaneka Silyl SAX575 (manufactured by KANEKA CORPORATION), viscosity (23° C.): 50 Pa·s

[0133] (A-2): A mixture of a polymer having a polyoxyalkylene moiety having trimethoxysilyl groups at both ends and an acrylic polymer, trade name: Kaneka Silyl MA451, viscosity (23° C.) 90 Pa·s

[0134] (A'-1): acrylic polymer having dimethoxysilyl groups at both ends, trade name: XMAPSA100S (manufactured by KANEKA CORPORATION), viscosity (23°C): 230 Pa·s

[0135] (A'-2): acrylic polymer having trimethoxysilyl groups at both ends, trade name: XMAPOR110S, viscosity (23°C): 1150 Pa·s

[0136] (B): Aromatic condensed phosphate flame retardant that is liquid at 25°C, reaction product of phenol, 4,4'-(propane-2,2-diyl)biphenol, and phosphine oxychloride, trade name: ADK STAB FP-600 (manufactured by ADEKA CORPORATION), viscosity (25°C): 19 Pa·s

[0137] (C-1): Phosphate-based flame retardant that is solid at 25°C (powdered at 25°C), trade name: ADK STAB FP-2500S (manufactured by ADEKA CORPORATION), 50% average particle size: 7 μm

[0138] (C-2): Aluminum hydroxide flame retardant that is solid at 25° C. and surface-treated with methacryloxysilane, trade name: B153STM (manufactured by Nippon Light Metal Co., Ltd.), 50% average particle size: 15 μm

[0139] (D-1): Zinc catalyst coordinated with an alkylamine, trade name: K-KAT670 (manufactured by King Industries Inc.)

[0140] (D-2): Bismuth carboxylate catalyst, trade name: K-KATXK-640 (manufactured by King Industries Inc.)

[0141] (E): Fumed silica surface-treated with dimethyl polysiloxane, trade name: RY200 (manufactured by NIPPON AEROSIL CO., LTD.)

[0142] (F): Methyltrimethoxysilane, trade name: KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0143] Weigh the above-mentioned (A) to (C) components in a stirring container and stir for 30 minutes. Weigh and add the above-mentioned (E) and (F) components to the stirred mixture, and stir the mixture for further 10 minutes. Then, weigh and add component (D) to the obtained mixture, and stir it for further 10 minutes to obtain a moisture-curable resin composition. The detailed preparation amount is shown in Table 1, and all values ​​are expressed in parts by mass. In addition, the polymer used as component (A) is not a structure that can generate low molecular weight siloxanes, and therefore, the obtained moisture-curable resin composition does not contain low molecular weight siloxanes.

[0144] [hardness]

[0145] Use a scraper made of polytetrafluoroethylene to apply the moisture-curing resin composition to a substrate in the form of a sheet with a thickness of 1 mm, and let it stand for 7 days at 23°C and 50% RH to cure it to obtain a sheet-like cured product. Through the same steps, a total of 6 sheet-like cured products are produced. The 6 prepared sheet-like cured products are overlapped in the thickness direction, and the pressure surface of the A-type durometer hardness tester is kept parallel to the cured product while pressing with a force of 10N to make the pressure surface and the cured product fit tightly. The maximum value of the A-type durometer hardness tester when it is in close contact is set to "hardness". The details are in accordance with JISK6249:2003.

[0146] Acceptable standard: A10 or higher, more preferably A20 or higher.

[0147] The upper limit is not particularly limited, but is A60 or less.

[0148] [Elongation (displacement following property)]

[0149] The moisture-curable resin composition was applied to the substrate in the form of a sheet with a thickness of 2 mm using a polytetrafluoroethylene scraper, and left to stand for 7 days at 23°C and 50% RH to obtain a sheet-like cured product. A dumbbell No. 3 shaped test piece was cut from the sheet-like cured product, and the distance between the baselines was set to 25 mm. The test piece was stretched at 500 mm / min using a tensile testing machine, and the distance between the baselines (mm) until the dumbbell-shaped test piece broke was measured, and the elongation (%) was calculated according to the following formula. The details of the test were carried out in accordance with JIS K6251: 2017.

[0150] [Mathematical formula 1]

[0151] Elongation (%) = {(distance between baselines at break - distance between initial baselines) / distance between initial baselines} × 100

[0152] Acceptable standard: 300% or more, more preferably 400% or more.

[0153] The upper limit is not particularly limited, but may be 800% or less or 600% or less.

[0154] [Tensile strength (resin strength)]

[0155] The moisture-curable resin composition was applied to the substrate in the form of a sheet with a thickness of 2 mm using a polytetrafluoroethylene scraper, and left to stand for 7 days at 23°C and 50% RH to obtain a sheet-like cured product. A dumbbell No. 3-shaped test piece was cut from the sheet-like cured product, and the distance between the base lines was set to 25 mm. The test piece was stretched at 500 mm / min using a tensile testing machine, and the maximum strength until the dumbbell-shaped test piece broke was taken as the tensile strength (MPa).

[0156] Acceptable standard: 1.0 MPa or more, more preferably 1.3 MPa or more.

[0157] The upper limit is not particularly limited, but is 3.0 MPa or less.

[0158] [Combustion test (UL94V-0)]

[0159] The moisture-curable resin composition was applied to the substrate in the form of a sheet with a thickness of 1.5 mm using a polytetrafluoroethylene scraper, and allowed to stand for 7 days at 23°C and 50% RH to obtain a sheet-like cured product. The sheet-like cured product was cut into a size of 12.5 mm wide × 130 mm long × 1.5 mm thick, and tested based on the 20 mm vertical burning test method of the UL94 standard.

[0160] Acceptance criteria: Equivalent to V-0. (All of the following (1) to (5) are met)

[0161] t1: Afterflame time of first contact with flame (seconds)

[0162] t2: Afterflame time of second contact with flame (seconds)

[0163] t3: Afterglow time of second contact with flame (seconds)

[0164] (1) The afterflame time t1 or t2 is less than 10 seconds.

[0165] (2) The total afterflame time (t1+t2) of all the test pieces after the treatment is 50 seconds or less.

[0166] (3) The total of the afterflame time and the afterglow time (t2+t3) of each test piece that is exposed to flame for the second time is 30 seconds or less.

[0167] (4) Until there is no afterflame or afterglow at the holding fixture of each test piece.

[0168] (5) The marking cotton is not ignited by burning substances or dripping materials.

[0169] [Table 1]

[0170]

[0171] As shown in Table 1, Examples 1 to 6 have flame retardancy equivalent to V-0 and excellent hardness, elongation, and tensile strength. On the other hand, Comparative Example 1, which does not use component (C), has low hardness and tensile strength. In addition, Comparative Examples 2 and 5, which do not use component (B), have significantly low elongation. Furthermore, Comparative Examples 3 and 4, which only use a compound whose main skeleton is an acrylic polymer to replace component (A), have low hardness, elongation, and tensile strength. From the above, it can be seen that for the moisture-curable resin composition of the present invention, by containing (A) to (D), while maintaining flame retardancy equivalent to V-0, it has excellent hardness, elongation, and tensile strength as a cured product. Therefore, it can be considered that the moisture-curable resin composition of the present invention contains (A) to (D), thereby maintaining sufficient flame retardancy while showing excellent resin strength and displacement tracking.

[0172] In addition, for the resin combination of embodiment 1 obtained, gas chromatography-mass spectrometer (GC-MS) was used to analyze. At this time, as pre-treatment, headspace method was adopted. As a result, no cyclic low-molecular siloxane was detected from the resin combination of embodiment 1, which was below the determination limit (below 100ppm). As can be seen from this result: according to the present invention, a moisture-curable resin composition not containing cyclic low-molecular siloxane can be obtained.

[0173] Industrial Applicability

[0174] The moisture-curable resin composition of the present invention can obtain a cured product having excellent displacement followability and resin strength while maintaining flame retardancy, and therefore is extremely useful in various fields.

[0175] This application is based on Japanese Patent Application No. 2022-139617 filed on September 2, 2022, the disclosure of which is referenced and cited in the present specification in its entirety.

Claims

1. A moisture-curable resin composition comprising the following components (A) to (D), (A) component: an oxyalkylene polymer having a hydrolyzable silyl group, (B) component: a flame retardant that is liquid at 25°C, (C) component: a flame retardant that is solid at 25°C, (D) Component: Curing catalyst.

2. The moisture-curable resin composition according to claim 1, wherein The component (B) contains a phosphorus-based flame retardant.

3. The moisture-curable resin composition according to claim 2, wherein The component (B) comprises a compound represented by the following formula (3): [Chemical formula 1] In formula (3), R 4 ~R 7 The groups shown are each independently a hydrogen atom, an alkyl group or a monovalent aromatic hydrocarbon group; X 1 is a divalent aromatic hydrocarbon group; X 2 is a single bond or a divalent aromatic hydrocarbon group; The group represented by A is a single bond, an alkylene group or a divalent aromatic hydrocarbon group, Here, in X 2 When is a single bond, A is a single bond; n represents the degree of polymerization, which is an integer of 1-5.

4. The moisture-curable resin composition according to claim 1, wherein The component (C) includes a phosphorus-based flame retardant and / or aluminum hydroxide.

5. The moisture-curable resin composition according to claim 1, wherein The mass ratio of the component (B) to the component (C) is 9:1 to 1:

9.

6. The moisture-curable resin composition according to claim 1, wherein The total amount of the component (B) and the component (C) is 10 to 500 parts by mass based on 100 parts by mass of the component (A).

7. The moisture-curable resin composition according to claim 1, wherein The component (D) is a zinc catalyst and / or a bismuth catalyst. 8 . The moisture-curable resin composition according to claim 1 , further comprising an inorganic filler as component (E). 9 . The moisture-curable resin composition according to claim 1 , further comprising a silane compound as component (F). 10 . A cured product obtained by curing the moisture-curable resin composition according to claim 1 .

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