Zinc phenylphosphonate complex, resin composition, and moisture-curable hot-melt urethane resin adhesive

Abstract

The invention provides a zinc phenylphosphonate complex, a resin composition, and a moisture-curable hot-melt urethane resin adhesive. The zinc phenylphosphonate complex can further shorten the curing time of a moisture-curable hot-melt urethane resin and can be suitably used as a crystal nucleating agent. The zinc phenylphosphonate complex is represented by formula (1), and the zinc phenylphosphonate complex has a specific surface area of 20.0 m2 / g or more as measured by a BET method based on nitrogen adsorption. [Chemical Formula 1]

Description

Technical Field

[0001] The present invention relates to a zinc phenylphosphonate complex, a resin composition and a moisture-curable hot-melt urethane resin adhesive. Background Art

[0002] Moisture-curing hot-melt urethane resins have excellent adhesive properties and relatively flexible adjustment of the bonding time, making them suitable for use in forming processes such as bonding and sealing, where continuous production is required. They are therefore used in a variety of fields. However, in applications such as wood packaging with decorative sheets that require initial strength, and in electrical / electronic components and automotive parts that require continuous production on high-speed production lines, there is a risk of the urethane resin not being fully cooled and solidified before being transferred to subsequent processes.

[0003] To address the aforementioned issues, metal salts of phenylphosphonic acid compounds have been added to urethane resins as crystallization nucleating agents, thereby shortening the curing time (also known as the open time). For example, Patent Document 1 discloses a moisture-curing hot-melt urethane resin adhesive comprising an isocyanate-terminated urethane prepolymer obtained by reacting a polyol with a polyisocyanate in the presence of a metal salt of an aromatic phosphonic acid as a crystallization nucleating agent.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2012-177016 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] Research by the present inventors has revealed that there is room for further shortening the curing time of moisture-curing hot-melt urethane resins when using a zinc phenylphosphonate complex as a crystallization nucleating agent. Therefore, one aspect of the present invention is to provide a zinc phenylphosphonate complex that can further shorten the curing time of moisture-curing hot-melt urethane resins and is suitable for use as a crystallization nucleating agent. Another aspect of the present invention is to provide a moisture-curing hot-melt urethane resin adhesive with a further shortened curing time.

[0009] Means for solving problems

[0010] The present inventors have found that the specific surface area of ​​a zinc phenylphosphonate complex affects the curing time of a moisture-curable hot-melt urethane resin, and that the curing time can be shortened when the specific surface area is equal to or greater than a specific value.

[0011] [1] A zinc phenylphosphonate complex, which is a zinc phenylphosphonate complex represented by formula (1),

[0012] [Chemical Formula 1]

[0013]

[0014] The specific surface area of ​​the zinc phenylphosphonate complex measured by the BET method based on nitrogen adsorption was 20.0 m 2 / g or above.

[0015] [2] A resin composition comprising a resin and the zinc phenylphosphonate complex described in [1].

[0016] [3] A moisture-curable hot-melt urethane resin adhesive comprising an isocyanate-terminated urethane prepolymer and the zinc phenylphosphonate complex described in [1].

[0017] Effects of the Invention

[0018] According to one aspect of the present invention, a zinc phenylphosphonate complex is provided that can further shorten the curing time of a moisture-curable hot-melt urethane resin and is suitable for use as a crystallization nucleating agent. Furthermore, according to another aspect of the present invention, a moisture-curable hot-melt urethane resin adhesive having a further shortened curing time is provided. DETAILED DESCRIPTION

[0019] The following describes embodiments of the present invention in detail. One embodiment of the present invention is a zinc phenylphosphonate complex represented by formula (1). The complex can be, for example, in a powdered form. The complex can also be in a liquid form dispersed or dissolved in a solvent.

[0020] [Chemical Formula 2]

[0021]

[0022] The specific surface area of ​​the complex measured by the BET method based on nitrogen adsorption was 20.0 m 2 / g or more. The present inventors believe that by using a zinc phenylphosphonate complex having such a specific surface area as a crystal nucleating agent, the specific surface area of ​​the phenylphosphonate complex is less than 20.0 m 2 When the crystal nucleating agent is mixed with a resin such as an isocyanate group-terminated urethane prepolymer, more crystal nuclei are formed, the crystallization rate of the resin is accelerated, and thus the curing time is shortened.

[0023] The specific surface area of ​​the complex is calculated as the surface area per 1 g of the complex measured from the amount of nitrogen adsorbed by the BET flow method using a fully automatic specific surface area measuring apparatus (eg, Macsorb Model HM-1210 manufactured by Mounttech Co., Ltd.).

[0024] The above specific surface area can be 25.0m 2 / g or above or 29.0m 2 / g or more, and preferably 35.0 m 2 / g or above, 40.0m 2 / g or above, 45.0m 2 / g or above or 50.0m 2 / g or more, more preferably 55.0m 2 / g or above or 60.0m 2 The upper limit of the specific surface area is not particularly limited, and can be, for example, 100.0 m 2 / g or less, 90.0m 2 / g or less, 80.0m 2 / g or below or 70.0m 2 / g or less.

[0025] From the perspective of further shortening the curing time, the 50% particle size (D50, median diameter) of the zinc phenylphosphonate complex is preferably as small as possible. Specifically, it can be preferably 1.15 μm or less, 1.14 μm or less, 1.13 μm or less, 1.12 μm or less, or 1.11 μm or less. The 50% particle size can be 0.95 μm or more, 0.98 μm or more, or 1.00 μm or more.

[0026] From the perspective of further shortening the curing time, the smaller the 10% particle size (D10) of the zinc phenylphosphonate complex, the more preferable. Specifically, it can be preferably 0.60 μm or less, 0.55 μm or less, or 0.50 μm or less. This 10% particle size (D10) can be 0.30 μm or greater, 0.35 μm or greater, or 0.40 μm or greater. The 90% particle size (D90) of the zinc phenylphosphonate complex can be 1.70 μm or greater, 1.80 μm or greater, or 1.90 μm or greater, and can be 3.20 μm or less, 3.10 μm or less, or 3.00 μm or less.

[0027] The 50% particle size (D50, median diameter), 10% particle size (D10), and 90% particle size (D90) are calculated based on the volume-based particle size distribution measured by laser diffraction dry-type particle size distribution analysis. Dry-type particle size distribution analysis can be performed at a dispersion pressure of 3 bar and a suction pressure of 90 mbar.

[0028] The zinc phenylphosphonate complex of the present embodiment described above can be obtained by appropriately pulverizing a conventional zinc phenylphosphonate complex. Specifically, for example, a zinc phenylphosphonate complex synthesized by a conventionally known method or a commercially available zinc phenylphosphonate complex (the specific surface area of ​​any complex is less than 20.0 m2) is pulverized using a medium. 2 / g) was crushed to obtain a 2 If the pulverization is performed without using a medium (for example, by a hammer mill), it is difficult to make the specific surface area of ​​the phenylphosphonate zinc complex 20.0 m 2 / g or above.

[0029] Examples of media include steel balls, alumina balls, zirconium oxide balls, and the like. From the perspective of being able to efficiently crush the zinc phenylphosphonate complex and easily increase the specific surface area of ​​the complex, the diameter of these balls is preferably 5.0 mm or less. The diameter of the balls may be, for example, 1.0 μm or more. Examples of pulverizers when such media are used for pulverization include paint shakers, vibration mills, and bead mills. However, even when such media are used, if a ball mill is used for pulverization, it is difficult to achieve a specific surface area of ​​the zinc phenylphosphonate complex of 20.0 m due to the weak pulverization force. 2 / g or above.

[0030] The zinc phenylphosphonate complex of this embodiment can be used together with a resin. Another embodiment of the present invention is a resin composition containing a resin and the zinc phenylphosphonate complex.

[0031] Examples of the resin include polyurethane resin, polyethylene resin, polypropylene resin, polylactic acid resin, polyester resin, and polyamide resin.

[0032] The zinc phenylphosphonate complex of this embodiment is particularly suitable for use as a crystallization nucleating agent, and more specifically, as a crystallization nucleating agent that promotes the crystallization of urethane resins. Another embodiment of the present invention is a moisture-curable hot-melt urethane resin adhesive comprising an isocyanate-terminated urethane prepolymer and the zinc phenylphosphonate complex described above.

[0033] The isocyanate group-terminated urethane prepolymer can be obtained by reacting a polyol (A) with a polyisocyanate (B).

[0034] Examples of the polyol (A) include polyether polyols, polyester polyols, polyetherester polyols, polycarbonate diols, and polyols having a carbon-carbon bond as the main chain. These polyols may be used alone or in combination of two or more.

[0035] Polyol (A) may include a polyester polyol, and the polyester polyol content in polyol (A) may be the largest. Examples of polyester polyols include aliphatic polyester polyol (a1) and aromatic polyester polyol (a2). Polyol (A) may include one type of polyester polyol (aliphatic polyester polyol (a1) or aromatic polyester polyol (a2)), or two types of polyester polyols (aliphatic polyester polyol (a1) and aromatic polyester polyol (a2)). In addition, polyol (A) may include aliphatic polyester polyol (a1) and / or aromatic polyester polyol (a2), as well as other polyols (a3) ​​other than polyester polyols.

[0036] The aliphatic polyester polyol (a1) is a polyester polyol produced by a known and conventional method using an aliphatic polycarboxylic acid and an aliphatic polyol as main components, and the production method is not particularly limited.

[0037] Preferred aliphatic polycarboxylic acids used in the synthesis of the aliphatic polyester polyol (a1) include aliphatic polycarboxylic acids having 4 to 12 carbon atoms, such as succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosanedioic acid, citraconic acid, itaconic acid, citraconic anhydride, and itaconic anhydride.

[0038] As the above-mentioned aliphatic polycarboxylic acid, for example, lower alkyl ester derivatives such as methyl ester, acid anhydrides, acid halides and other corresponding acid derivatives may be used.

[0039] The aliphatic polyol used in the synthesis of the aliphatic polyester polyol (a1) is an aliphatic polyol having at least two hydroxyl groups in the molecule, preferably an aliphatic polyol having 2 to 12 carbon atoms. The (a1) may have any structure including linear, branched, or cyclic.

[0040] Examples of the aliphatic polyol include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol and other linear aliphatic polyols; and neopentyl glycol, 1,3-butanediol, 2,2-diethyl-1,3- Branched aliphatic polyols such as propylene glycol, 2,2-diethylpropylene glycol, 3-methyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,4-diethyl-1,5-pentanediol, trimethylolethane, trimethylolpropane, and pentaerythritol; or alicyclic polyols such as cyclopentanediol, cyclohexanediol, and cyclohexanedimethanol; among these, ethylene glycol, 1,6-hexanediol, and neopentyl glycol are preferred.

[0041] Adducts obtained by adding various alkylene oxides to hydrogenated bisphenol A, hydrogenated bisphenol F, and the like can also be used. Furthermore, the following polymers, obtained by ring-opening polymerization of γ-butyrolactone, ε-caprolactone, and the like using a low-molecular-weight polyol as an initiator, can also be used. These can be used alone or in combination of two or more.

[0042] It is preferred that the polyol (A) contain an aliphatic polyester polyol (a1) produced from a combination of an aliphatic polycarboxylic acid having 4 to 12 carbon atoms and an aliphatic polyol having 2 to 12 carbon atoms among the combinations of the aliphatic polycarboxylic acid and the aliphatic polyol. This further improves the viscosity stability of the hot-melt urethane resin adhesive during molding processing and exhibits an excellent effect of preventing a decrease in melt viscosity.

[0043] The aromatic polyester polyol (a2) is a polyester polyol produced mainly from aromatic polycarboxylic acid and aliphatic polyol, or aliphatic polycarboxylic acid and aromatic polyol, by a known and conventional method, and the production method is not particularly limited.

[0044] The aromatic polycarboxylic acid is a carboxylic acid having at least two carboxyl groups bonded to an aromatic ring, preferably an aromatic polycarboxylic acid having 8 to 24 carbon atoms, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, biphenyl dicarboxylic acid, and naphthalene dicarboxylic acid. These may be used alone or in combination of two or more.

[0045] As the aromatic polycarboxylic acid, for example, lower alkyl ester derivatives such as methyl ester, acid anhydrides, acid halides and other corresponding acid derivatives can be used.

[0046] Examples of the aliphatic polyol include the same aliphatic polyols as those that can be used for the synthesis of the aliphatic polyester polyol (a1).

[0047] In addition, examples of the aliphatic polyols that can be used in the synthesis of the aromatic polyester polyol (a2) and the aliphatic polyester polyol (a1) include diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-bis(β-hydroxyethoxy)benzene, etc., in which some of the carbon atoms are replaced with oxygen atoms or aromatic rings. These aliphatic polyols can be used alone or in combination of two or more.

[0048] Furthermore, a mixture of polyester polyols obtained from these aromatic polycarboxylic acids and aliphatic polyols may also be used.

[0049] Examples of the aliphatic polycarboxylic acid that can be used for the synthesis of the aromatic polyester polyol (a2) include the same aliphatic polycarboxylic acids having 4 to 12 carbon atoms as those that can be used for the synthesis of the aliphatic polyester polyol (a1).

[0050] The aromatic polyol is not particularly limited, and examples thereof include aromatic polyols obtained from aliphatic polyols such as ethylene glycol and neopentyl glycol and aromatic polycarboxylic acids such as phthalic acid and terephthalic acid.

[0051] Furthermore, as the aromatic polyol, for example, adducts obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to bisphenol A, bisphenol F, or the like can also be used.

[0052] During the synthesis of the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2), the equivalent ratio of the hydroxyl groups of the aliphatic polyol and the aromatic polyol to the carboxyl groups of the aliphatic polycarboxylic acid and the aromatic polycarboxylic acid (i.e., the [OH / COOH equivalent ratio]) is preferably in the range of 1.03 to 1.50, and more preferably in the range of 1.05 to 1.30. When the [OH / COOH equivalent ratio] is within the above range, more hydroxyl-terminated polyols can be produced, which facilitates the urethanization reaction with the polyisocyanate (B), thus being preferred.

[0053] The polycondensation conditions for synthesizing the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2) are not particularly limited as long as abnormal reactions do not occur and a normal product can be obtained. Typically, a predetermined amount of an aliphatic polycarboxylic acid and an aliphatic polyol, or an aromatic polycarboxylic acid and an aliphatic polyol, is subjected to an esterification reaction or transesterification reaction at an internal temperature of 150 to 250° C. for 5 to 50 hours in the presence or absence of a catalyst, followed by a polycondensation reaction.

[0054] The polycondensation reaction is preferably carried out in the presence of a catalyst because the reaction proceeds more easily. The catalyst is not particularly limited, and examples thereof include titanium-based catalysts such as tetrabutoxytitanium and tin-based catalysts such as dibutyltin oxide.

[0055] The above-mentioned catalyst may be added together with the aliphatic polyol and the aliphatic polycarboxylic acid, or the aliphatic polyol and the aromatic polycarboxylic acid, or may be added after prepolymerization in the absence of a catalyst.

[0056] In the production of the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2), it is desirable to have almost all hydroxyl groups at both ends and to minimize the remaining carboxyl groups at the ends. To this end, it is effective and preferred to add the catalyst after prepolymerization.

[0057] The number average molecular weight (Mn) of the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2) is preferably in the range of 500 to 6000, more preferably in the range of 1000 to 5000, and particularly preferably in the range of 2000 to 4000. When the Mn of (a1) and (a2) is within the above range, a balance of physical properties such as strength and elongation can be achieved according to the application, which is preferred.

[0058] Examples of the other polyols (a3) ​​include polycarbonate polyols, polylactone polyols, and polyether polyols. Examples of the polycarbonate polyols include those obtained using linear aliphatic polyols such as 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Examples of the polylactone polyols include polycaprolactone polyols obtained by ring-opening polymerization of caprolactone monomers. Examples of the polyether polyols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

[0059] The content ratio of the aliphatic polyester polyol (a1) / the aromatic polyester polyol (a2) / the other polyol (a3) ​​can be 20-60 parts by mass / 10-50 parts by mass / 0-50 parts by mass, preferably 30-50 parts by mass / 20-40 parts by mass / 10-20 parts by mass, based on 100 parts by mass of the polyol (A). When the content ratio is within the above range, the melt viscosity of the polyol (A) can be adjusted to an appropriate range, resulting in a moisture-curable hot-melt urethane resin adhesive that exhibits excellent workability and compatibility and furthermore has excellent curability.

[0060] Examples of the polyisocyanate (B) include well-known and commonly used aliphatic, aromatic, and alicyclic polyisocyanates, such as diphenylmethane diisocyanate (MDI; its 4,4' isomer, 2,4' isomer, or 2,2' isomer, or a mixture thereof, crude MDI), carbodiimide-modified MDI (modified MDI), polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, xylene diisocyanate, toluene diisocyanate (TDI; its 2,4' isomer, or 2,6' isomer, or a mixture thereof), xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), tetramethylxylene diisocyanate, phenylene diisocyanate, and the like. Aromatic diisocyanates such as isocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), dimer acid diisocyanate, norbornene diisocyanate, lysine diisocyanate, and tetramethylxylylene diisocyanate; or alicyclic diisocyanates such as isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate. Among these, MDI and XDI are preferred due to their rapid reaction with the polyol (A) and moisture (water) and excellent workability. These may be used alone or in combination of two or more.

[0061] The ratio of the polyol (A) to the polyisocyanate (B) used in synthesizing the isocyanate-terminated urethane prepolymer (hereinafter referred to as the "prepolymer") may be within a range that does not adversely affect the reaction behavior, product quality, etc. Generally, the equivalent ratio of isocyanate groups in the polyisocyanate (B) to hydroxyl groups in the polyol (A) (hereinafter referred to as the [NCO / OH equivalent ratio]) is preferably in the range of 1.2 to 4.0, and more preferably in the range of 1.5 to 3.0. When the [NCO / OH equivalent ratio] is within this range, the melt viscosity of the target moisture-curable hot-melt urethane resin composition is within an appropriate range, and excellent workability, film properties, and even excellent curability can be exhibited.

[0062] The reaction conditions are not particularly limited as long as they do not adversely affect the reaction behavior, product quality, etc., but are preferably set at a reaction temperature of 80 to 130° C. for 1 to 10 hours.

[0063] The reaction method can be selected from known reaction methods such as batch reaction, semi-continuous reaction, and continuous reaction.

[0064] In addition, the reaction can be carried out in a solvent or in the absence of a solvent. When the reaction is carried out in a solvent, it is preferred to remove the solvent during or after the reaction to finally leave the reaction in the absence of a solvent. The method for removing the solvent is not particularly limited.

[0065] The higher the content of the zinc phenylphosphonate complex in the moisture-curing hot-melt urethane resin adhesive, the shorter the curing time. The content of the zinc phenylphosphonate complex, based on the total amount of the moisture-curing hot-melt urethane resin adhesive, can be 0.05% by mass or greater, 0.10% by mass or greater, 0.30% by mass or greater, 0.50% by mass or greater, 0.70% by mass or greater, 0.9% by mass or greater, 1.0% by mass or greater, 2.0% by mass or greater, 3.0% by mass or greater, or 4.0% by mass or greater, and can be 8.0% by mass or less, 7.0% by mass or less, or 6.0% by mass or less.

[0066] The moisture-curable hot-melt urethane resin adhesive of this embodiment may further contain other resins such as thermoplastic resins and thermosetting resins, and may further contain other additives. Examples of other additives include foam stabilizers, antioxidants, degassing agents, ultraviolet absorbers, abrasives, fillers, pigments, dyes, colorants, thickeners, surfactants, flame retardants, plasticizers, lubricants, antistatic agents, heat stabilizers, tackifiers, curing catalysts, stabilizers, fluorescent brighteners, silane coupling agents, waxes, and the like.

[0067] [Example]

[0068] Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to the Examples.

[0069] [Example 1]

[0070] A 1-liter four-necked flask was charged with 30.0 parts by mass (190 mmol) of phenylphosphonic acid, 240 parts by mass of water, and 150 parts by mass of a 10% aqueous sodium hydroxide solution to prepare an aqueous solution. While stirring the aqueous solution, an aqueous solution prepared from 25.8 parts by mass (189 mmol) of zinc chloride and 120 parts by mass of water was added dropwise to the flask over 3 hours to allow for reaction. The precipitated white precipitate was filtered, washed with water, and dried at 110°C for at least 12 hours to obtain the phenylphosphonic acid zinc complex represented by the above formula (1) as a white powder (Powder No. 0).

[0071] A 150 mL resin bottle was filled with 16 parts by mass of the phenylphosphonic acid zinc complex obtained above and 240 parts by mass of 3.2 mm diameter steel balls, and pulverized using a paint shaker (manufactured by Toyo Seiki Seisaku-sho, Ltd.) at a vibration speed of 800 times / min for 60 minutes to obtain powder No. 1.

[0072] In a 1-liter four-necked flask, 30 parts by mass of polypropylene glycol (Mn = 1000), 40 parts by mass of an aliphatic polyester polyol (Mn = 4500) obtained by reacting 1,6-hexanediol (HD) and adipic acid (AA) at a mass ratio of HD / AA = 46 / 54, and 30 parts by mass of an aromatic polyester polyol (Mn = 5000) obtained by reacting 1,6-hexanediol (HD), neopentyl glycol (NPG), ethylene glycol (EG), isophthalic acid (iPA), and terephthalic acid (tPA) at a mass ratio of HD / NPG / EG / iPA / tPA = 7 / 14 / 18 / 40 / 21 were mixed and melted to prepare polyol (A). Next, 0.36 parts by mass of Powder No. 1 (0.30% by mass based on the total amount of the moisture-curable hot-melt urethane resin adhesive) was added to the polyol ester (A), which served as a crystallization nucleating agent. The mixture was heated to 110°C and dehydrated under reduced pressure until the water content reached 0.05% by mass. The mixture was then cooled to 70°C, and 19 parts by mass of 4,4-diphenylmethane diisocyanate was added. The mixture was reacted at 90°C for 3 hours until the NCO content (%) reached a constant value, yielding a moisture-curable hot-melt urethane resin adhesive.

[0073] [Example 2]

[0074] A 2 L porcelain jar was filled with 200 parts by mass of the zinc phenylphosphonate complex obtained by the same method as in Example 1 and 3000 parts by mass of 5.0 mm diameter alumina balls. The mixture was then pulverized using a batch vibration mill (Vibropot YAMP-4JND, manufactured by Murakami Seiki Co., Ltd.) at a vibration frequency of 19.4 Hz for 60 minutes to obtain Powder No. 2.

[0075] A moisture-curable hot-melt urethane resin adhesive was obtained by carrying out the same operation as in Example 1 except that Powder No. 2 was used as a crystal nucleating agent instead of Powder No. 1.

[0076] [Example 3]

[0077] A 2 L porcelain jar was filled with 180 parts by mass of the zinc phenylphosphonate complex obtained by the same method as in Example 1 and 5000 parts by mass of zirconia balls with a diameter of 5.0 mm. The mixture was then pulverized using a batch vibration mill (Vibropot YAMP-4JND, manufactured by Murakami Seiki Co., Ltd.) at a vibration frequency of 19.4 Hz for 60 minutes to obtain Powder No. 3.

[0078] A moisture-curable hot-melt urethane resin adhesive was obtained by carrying out the same operation as in Example 1 except that Powder No. 3 was used as a crystal nucleating agent instead of Powder No. 1.

[0079] [Example 4]

[0080] A 3 L stainless steel pot was filled with 200 parts by mass of the zinc phenylphosphonate complex obtained by the same method as in Example 1 and 10,800 parts by mass of 4.8 mm diameter steel balls. The mixture was then pulverized using a batch vibration mill (Vibropot YAMP-6SND, manufactured by Murakami Seiki Co., Ltd.) at a vibration frequency of 19.4 Hz for 30 minutes to obtain Powder No. 4.

[0081] A moisture-curable hot-melt urethane resin adhesive was obtained by carrying out the same operation as in Example 1 except that Powder No. 4 was used instead of Powder No. 1 as a crystal nucleating agent.

[0082] [Example 5]

[0083] A continuous 1 L bead mill (DryStar SDA1, manufactured by Ashizawa Finetech Co., Ltd.) was filled with 3310 parts by mass of 3.2 mm diameter steel balls, and the phenylphosphonic acid zinc complex obtained by the same method as Example 1 was added at a rate of 500 parts by mass per hour. The mixture was pulverized at a peripheral speed of 5.0 m / s to obtain Powder No. 5.

[0084] A moisture-curable hot-melt urethane resin adhesive was obtained by carrying out the same operation as in Example 1 except that Powder No. 5 was used as a crystal nucleating agent instead of Powder No. 1.

[0085] [Example 6]

[0086] A continuous 1 L bead mill (DryStar SDA1, manufactured by Ashizawa Finetech Co., Ltd.) was filled with 2480 parts by mass of zirconia balls with a diameter of 1.5 mm. The phenylphosphonic acid zinc complex obtained by the same method as in Example 1 was added at a rate of 500 parts by mass per hour and pulverized at a peripheral speed of 5.0 m / s to obtain Powder No. 6.

[0087] A moisture-curable hot-melt urethane resin adhesive was obtained by carrying out the same operation as in Example 1 except that Powder No. 6 was used as a crystal nucleating agent instead of Powder No. 1.

[0088] [Comparative Example 1]

[0089] A moisture-curable hot-melt urethane resin adhesive was obtained by carrying out the same operation as in Example 1 except that powder No. 1 was not added as a crystal nucleating agent.

[0090] [Comparative Example 2]

[0091] A moisture-curable hot-melt urethane resin adhesive was obtained by the same operation as in Example 1 except that Powder No. 0 (the powder of the phenylphosphonic acid zinc complex before pulverization) was used as a crystal nucleating agent instead of Powder No. 1.

[0092] [Comparative Example 3]

[0093] A 250 mL resin bottle was filled with 15 parts by mass of the zinc phenylphosphonate complex obtained by the same method as in Example 1 and 225 parts by mass of 3.2 mm diameter steel balls. The mixture was then pulverized using a batch ball mill (benchtop jar mill rotary table ANZ-51D, manufactured by Nippon To Science Co., Ltd.) at a rotation speed of 110 rpm for 60 minutes to obtain Powder No. 7.

[0094] A moisture-curable hot-melt urethane resin adhesive was obtained by carrying out the same operation as in Example 1 except that Powder No. 7 was used instead of Powder No. 1 as a crystal nucleating agent.

[0095] [Comparative Example 4]

[0096] 200 parts by mass of the phenylphosphonic acid zinc complex obtained by the same method as Example 1 was pulverized using a continuous hammer mill (ATOMIZER TASM-1FTS-A1, manufactured by TOKYO ATOMIZER MFG. CO., LTD.) at a rotation speed of 12,000 rpm for about 5 minutes to obtain Powder No. 8.

[0097] A moisture-curable hot-melt urethane resin adhesive was obtained by carrying out the same operation as in Example 1 except that Powder No. 8 was used as a crystal nucleating agent instead of Powder No. 1.

[0098] [Examples 7 to 12]

[0099] A moisture-curable hot-melt urethane resin adhesive was obtained by performing the same operation as in Example 1 except that the content of powder No. 1 (crystallization nucleating agent) based on the total amount of the moisture-curable hot-melt urethane resin adhesive was changed as shown in Table 2.

[0100] (Determination of specific surface area)

[0101] After pretreatment at 140°C for 30 minutes using a fully automatic specific surface area measuring device (Macsorb Model HM-1210 manufactured by MOUNTECH Co., Ltd.), the surface area per 1 g of each powder of Examples and Comparative Examples was measured based on the nitrogen adsorption amount using the BET flow method and was taken as the specific surface area (m 2The results are shown in Table 1.

[0102] (Determination of particle size distribution)

[0103] The particle size distribution of each powder in Examples and Comparative Examples was measured according to the following procedure.

[0104] The volume-based particle size distribution of each powder within the range of 0.1 μm to 35 μm (range R1) was measured using laser diffraction particle size analyzers HELOS (H3355) and ROSDOS (manufactured by Sympatec) under dry conditions of a dispersion pressure of 3 bar and a vacuum pressure of 90 mbar. The 10% particle size (D10), 50% particle size (D50, median diameter), and 90% particle size (D90) were determined from the obtained particle size distribution. The results are shown in Table 1.

[0105] [Table 1]

[0106]

[0107] [Determination of curing time (open time)]

[0108] The curing time of each moisture-curable polyurethane hot-melt adhesive in Examples and Comparative Examples was measured according to the following procedure.

[0109] A moisture-curable polyurethane hot-melt adhesive was heated to 125°C until molten and applied in a linear pattern of 1 g / m2 onto a substrate (Medium Density Fiberboard, manufactured by Daiken Industry Co., Ltd., product name "Customwood MDF U Type 25F****"). After a certain waiting time, another MDF was pressed against the adhesive-coated MDF for 30 seconds to bond. The MDF was then peeled from the other, and the peel strength was measured. Measurements were performed at 23°C and 50% humidity using an ASM-15N adhesion tester manufactured by MEC Co., Ltd. The waiting time was extended by 10 seconds until no adhesion between the MDFs occurred (i.e., until the peel strength was almost zero). The waiting time during which a peel strength of 5N or higher was maintained was defined as the curing time (open time). The results are shown in Table 2.

[0110] [Table 2]

[0111]

Claims

1. A zinc phenylphosphonate complex, which is a zinc phenylphosphonate complex represented by formula (1), The specific surface area of ​​the zinc phenylphosphonate complex measured by the BET method based on nitrogen adsorption was 20.0 m 2 / g or above.

2. A resin composition comprising a resin and the zinc phenylphosphonate complex according to claim 1.

3. A moisture-curable hot-melt urethane resin adhesive comprising an isocyanate-terminated urethane prepolymer and the zinc phenylphosphonate complex according to claim 1.

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