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

Abstract

To provide a zinc phenylphosphonate complex that can be suitably used as a crystallization nucleating agent for further reducing the solidification time of moisture-curable hot-melt urethane resins.SOLUTION: A zinc phenylphosphonate complex represented by formula (1), the complex having a specific surface area of 20.0 m2 / g or more as measured by the BET method using nitrogen gas adsorption.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Moisture-curing hot-melt urethane resins have excellent adhesive properties and the adhesive time can be adjusted relatively freely, making them suitable as adhesives for use in molding processes such as bonding and sealing, which require continuous production, and are used in a wide range of fields. However, in applications such as wood wrapping for decorative sheets, which require initial strength, or in electrical and electronic parts and automotive parts, which require continuous production on high-speed lines, problems can arise in which the urethane resin moves on to the next process before it has cooled and solidified sufficiently.

[0003] To solve the above problems, attempts have been made to shorten the solidification time (also called open time) by adding a metal salt of a phenylphosphonic acid compound as a nucleating agent to a urethane resin. For example, Patent Document 1 discloses a moisture-curable hot-melt urethane resin adhesive containing an isocyanate-terminated urethane prepolymer obtained by reacting a polyol and a polyisocyanate in the presence of a metal salt of an aromatic phosphonic acid as a nucleating agent. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-177016 Summary of the Invention [Problem to be solved by the invention]

[0005] According to the inventors' studies, when a zinc phenylphosphonate complex is used as a crystal nucleating agent, there is room for further shortening the solidification time of a moisture-curable hot-melt urethane resin. Therefore, one aspect of the present invention aims to provide a zinc phenylphosphonate complex that can be suitably used as a crystal nucleating agent that can further shorten the solidification time of a moisture-curable hot-melt urethane resin. Another aspect of the present invention aims to provide a moisture-curable hot-melt urethane resin adhesive with a further shortened solidification time. [Means for solving the problem]

[0006] The present inventors have found that the specific surface area of ​​a zinc phenylphosphonate complex affects the solidification time of a moisture-curable hot-melt urethane resin, and further that the solidification time can be shortened when the specific surface area is equal to or greater than a certain value. [1] A zinc phenylphosphonate complex represented by formula (1):

[0007] [ka] The specific surface area measured by the BET method using nitrogen gas adsorption is 20.0 m 2 / g or more of zinc phenylphosphonate complex. [2] A resin composition containing a resin and the zinc phenylphosphonate complex described in [1]. [3] A moisture-curable hot-melt urethane resin adhesive containing an isocyanate-terminated urethane prepolymer and the zinc phenylphosphonate complex described in [1]. [Effects of the Invention]

[0008] According to one aspect of the present invention, there is provided a zinc phenylphosphonate complex that can be suitably used as a crystal nucleating agent that can further shorten the solidification time of a moisture-curable hot-melt urethane resin. Also, according to another aspect of the present invention, there is provided a moisture-curable hot-melt urethane resin adhesive having a further shortened solidification time. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present invention will be described in detail. One embodiment of the present invention is a zinc phenylphosphonate complex represented by formula (1). This complex may be in the form of, for example, a powder. The complex may also be in the form of a liquid dispersed or dissolved in a solvent.

[0010] [ka]

[0011] The specific surface area of ​​this complex measured by the BET method using nitrogen gas adsorption was 20.0 m 2 By using a zinc phenylphosphonate complex having such a specific surface area as a crystal nucleating agent, it is possible to obtain a crystal having a specific surface area of ​​20.0 m / g or more. 2 The present inventors believe that, compared with a case where the concentration is less than 1 / g, 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 increases, and the solidification time is shortened.

[0012] 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 gas adsorbed by the BET flow method using a fully automatic specific surface area measuring device (for example, Macsorb Model HM-1210 manufactured by Mountec Co., Ltd.).

[0013] The specific surface area is 25.0m 2 / g or more, or 29.0m 2 / g or more, and from the viewpoint of further shortening the solidification time, it is preferably 35.0 m 2 / g or more, 40.0m 2 / g or more, 45.0m 2 / g or more, or 50.0m 2 / g or more, more preferably 55.0m 2 / g or more, or 60.0m 2 The upper limit of the specific surface area is not particularly limited, and may be, for example, 100.0 m 2 / g or less, 90.0m2 / g or less, 80.0m 2 / g or less, or 70.0m 2 / g or less.

[0014] The 50% diameter (D50, median diameter) of the zinc phenylphosphonate complex is preferably small from the viewpoint of further shortening the solidification time, and specifically, may 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% diameter may be 0.95 μm or more, 0.98 μm or more, or 1.00 μm or more.

[0015] The 10% diameter (D10) of the zinc phenylphosphonate complex is preferably small, since this further shortens the solidification time. Specifically, it may be preferably 0.60 μm or less, 0.55 μm or less, or 0.50 μm or less. The 10% diameter (D10) may be 0.30 μm or more, 0.35 μm or more, or 0.40 μm or more. The 90% diameter (D90) of the zinc phenylphosphonate complex may be 1.70 μm or more, 1.80 μm or more, or 1.90 μm or more, or may be 3.20 μm or less, 3.10 μm or less, or 3.00 μm or less.

[0016] The 50% diameter (D50, median diameter), 10% diameter (D10), and 90% diameter (D90) are determined from the volumetric particle size distribution measured by laser diffraction dry particle size distribution measurement. The conditions for the dry particle size distribution measurement may be a dispersion pressure of 3 bar and a suction pressure of 90 mbar.

[0017] The zinc phenylphosphonate complex of the present embodiment described above can be obtained by appropriately grinding 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 (both complexes have a specific surface area of ​​20.0 m) can be used. 2 / g) by grinding using media, 2A zinc phenylphosphonate complex having a specific surface area of ​​20.0 m / g or more can be obtained. By grinding without using media (for example, grinding with a hammer mill), the specific surface area of ​​the zinc phenylphosphonate complex can be increased to 20.0 m / g or more. 2 It is difficult to achieve a value of more than / g.

[0018] Examples of media include steel balls, alumina balls, zirconia balls, and the like. The diameter of these balls is preferably 5.0 mm or less, from the viewpoint of efficiently pulverizing the zinc phenylphosphonate complex and easily increasing the specific surface area of ​​the complex. The diameter of the balls may be, for example, 1.0 μm or more. Examples of mills for pulverizing using such media include paint shakers, vibration mills, and bead mills. However, even when such media are used, pulverization using a ball mill may not be able to reduce the specific surface area of ​​the zinc phenylphosphonate complex to 20.0 m due to the weak pulverizing force. 2 It is difficult to achieve a value of more than / g.

[0019] The zinc phenylphosphonate complex of the present 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.

[0020] Examples of the resin include polyurethane resin, polyethylene resin, polypropylene resin, polylactic acid resin, polyester resin, and polyamide resin.

[0021] The zinc phenylphosphonate complex of this embodiment can be particularly suitably used as a crystal nucleating agent, more specifically, as a crystal nucleating agent that promotes the crystallization of urethane resins. Another embodiment of the present invention is a moisture-curable hot-melt urethane resin adhesive containing an isocyanate group-terminated urethane prepolymer and the above-mentioned zinc phenylphosphonate complex.

[0022] The isocyanate group-terminated urethane prepolymer can be obtained by reacting a polyol (A) with a polyisocyanate (B).

[0023] Examples of the polyol (A) include various polyols such as polyether polyols, polyester polyols, polyether ester polyols, polycarbonate diols, polyols having a carbon-carbon bond main chain, etc. The various polyols may be used alone or in combination of two or more. The polyol (A) may contain a polyester polyol, and the content of the polyester polyol in the polyol (A) may be the highest. Examples of polyester polyols include aliphatic polyester polyol (a1) and aromatic polyester polyol (a2). The polyol (A) may contain one type of polyester polyol (aliphatic polyester polyol (a1) or aromatic polyester polyol (a2)), or may contain two types of polyester polyols (aliphatic polyester polyol (a1) and aromatic polyester polyol (a2)). The polyol (A) may also contain aliphatic polyester polyol (a1) and / or aromatic polyester polyol (a2) and a polyol (a3) ​​other than the polyester polyol.

[0024] The aliphatic polyester polyol (a1) is a polyester polyol produced by a known, commonly used method using an aliphatic polycarboxylic acid and an aliphatic polyol as main components, and the production method is not particularly limited.

[0025] The aliphatic polycarboxylic acid used in the synthesis of the aliphatic polyester polyol (a1) is preferably an aliphatic polycarboxylic acid having 4 to 12 carbon atoms, such as succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosadionic acid, citraconic acid, itaconic acid, citraconic anhydride, or itaconic anhydride.

[0026] The aliphatic polycarboxylic acid may be, for example, a lower alkyl ester derivative such as a methyl ester, or a corresponding acid derivative such as an acid anhydride or an acid halide.

[0027] The aliphatic polyol used in the synthesis of the aliphatic polyester polyol (a1) has at least two hydroxyl groups in the molecule, and is preferably an aliphatic polyol having 2 to 12 carbon atoms. The (a1) may have any of a linear, branched, or cyclic structure.

[0028] Examples of the aliphatic polyol include linear aliphatic polyols such as ethylene glycol, 1,3-propanediol, 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, and tetraethylene glycol, as well as neopentyl glycol, 1,3-butanediol, and 2,2-diethyl-1,3-propanediol. , 2,2-diethylpropanediol, 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, pentaerythritol, and other branched aliphatic polyols; and alicyclic polyols such as cyclopentanediol, cyclohexanediol, and cyclohexanedimethanol. Of these, ethylene glycol, 1,6-hexanediol, and neopentyl glycol are preferred.

[0029] Also usable are adducts in which various alkylene oxides are added to hydrogenated bisphenol A, hydrogenated bisphenol F, etc. Also usable are polymers obtained by ring-opening polymerization of γ-butyrolactone, ε-caprolactone, etc. using a low-molecular-weight polyol as an initiator. These may be used alone or in combination of two or more.

[0030] Among the combinations of the aliphatic polycarboxylic acids and the aliphatic polyols, it is preferable to incorporate an aliphatic polyester polyol (a1) produced by combining an aliphatic polycarboxylic acid having 4 to 12 carbon atoms with an aliphatic polyol having 2 to 12 carbon atoms into the polyol (A), since this further improves the viscosity stability of the hot-melt urethane resin adhesive during molding and provides an excellent effect in preventing a decrease in melt viscosity.

[0031] The aromatic polyester polyol (a2) is a polyester polyol produced by a known, commonly used method using an aromatic polycarboxylic acid and an aliphatic polyol, or an aliphatic polycarboxylic acid and an aromatic polyol, as the main components, and the production method is not particularly limited.

[0032] 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, such as orthophthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, etc. These may be used alone or in combination of two or more.

[0033] The aromatic polycarboxylic acid may be a corresponding acid derivative such as a lower alkyl ester derivative such as a methyl ester, an acid anhydride, or an acid halide.

[0034] Examples of the aliphatic polyol include the same aliphatic polyols as those usable in the synthesis of the aliphatic polyester polyol (a1).

[0035] Furthermore, the aliphatic polyols that can be used in synthesizing the aromatic polyester polyol (a2) and the aliphatic polyester polyol (a1) may be, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-bis(β-hydroxyethoxy)benzene, etc., in which some of the carbon atoms have been substituted with oxygen atoms or aromatic rings. These aliphatic polyols may also be used alone or in combination of two or more.

[0036] Furthermore, a mixture of polyester polyols obtained from these aromatic polycarboxylic acids and aliphatic polyols may also be used.

[0037] Examples of the aliphatic polycarboxylic acid that can be used in the synthesis of the aromatic polyester polyol (a2) include aliphatic polycarboxylic acids having 4 to 12 carbon atoms, similar to the aliphatic polycarboxylic acids that can be used in the synthesis of the aliphatic polyester polyol (a1).

[0038] The aromatic polyol is not particularly limited, but examples thereof include aliphatic polyols such as ethylene glycol and neopentyl glycol, and aromatic polyols obtained from aromatic polycarboxylic acids such as orthophthalic acid and terephthalic acid.

[0039] Furthermore, as the aromatic polyol, for example, an adduct of bisphenol A, bisphenol F, or the like with an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide can also be used.

[0040] The equivalent ratio (i.e., [OH / COOH equivalent ratio]) of the hydroxyl groups of the aliphatic polyol and aromatic polyol to the carboxyl groups of the aliphatic polycarboxylic acid and aromatic polycarboxylic acid during synthesis of the aliphatic polyester polyol (a1) and aromatic polyester polyol (a2) is preferably in the range of 1.03 to 1.50, more preferably 1.05 to 1.30. When the [OH / COOH equivalent ratio] is in this range, a larger amount of hydroxyl-terminated polyol can be produced, and the urethane reaction with polyisocyanate (B) can proceed more easily, which is preferable.

[0041] The polycondensation conditions for synthesizing the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2) are not particularly limited as long as they do not cause an abnormal reaction and a normal product can be obtained. Typically, a predetermined amount of aliphatic polycarboxylic acid and aliphatic polyol, or aromatic polycarboxylic acid and aliphatic polyol, is subjected to an esterification reaction or an ester exchange 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.

[0042] The polycondensation reaction is preferably carried out in the presence of a catalyst, since the reaction proceeds more easily. The catalyst is not particularly limited, and examples thereof include titanium-based catalysts such as titanium tetrabutoxide and tin-based catalysts such as dibutyltin oxide.

[0043] The catalyst may be charged together with the aliphatic polyol and the aliphatic polycarboxylic acid, or together with the aliphatic polyol and the aromatic polycarboxylic acid, or may be added after prepolymerization without a catalyst.

[0044] In the production of the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2), it is desirable to convert most of the terminals to hydroxyl groups and to minimize the amount of carboxyl terminal groups remaining. For this purpose, it is effective and preferable to add the catalyst after prepolymerization.

[0045] 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. If the Mn of (a1) and (a2) is in this range, a balance of physical properties such as strength and elongation depending on the application can be obtained, which is preferable.

[0046] Examples of the other polyols (a3) ​​include polycarbonate polyols, polylactone polyols, and polyether polyols. Examples of the polycarbonate polyols include polycarbonate polyols 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.

[0047] The content ratio of the aliphatic polyester polyol (a1) / the aromatic polyester polyol (a2) / the other polyol (a3) ​​may be 20 to 60 parts by mass / 10 to 50 parts by mass / 0 to 50 parts by mass, preferably 30 to 50 parts by mass / 20 to 40 parts by mass / 10 to 20 parts by mass, per 100 parts by mass of the polyol (A). When the content ratio is within this range, the melt viscosity of the polyol (A) can be adjusted to an appropriate range, and a moisture-curable hot-melt urethane resin adhesive can be obtained that exhibits excellent workability and miscibility and further has excellent solidification properties.

[0048] The polyisocyanate (B) may be a known and commonly used aliphatic, aromatic, or alicyclic polyisocyanate, 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, tolylene 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, Examples of suitable diisocyanates include aromatic diisocyanates such as methyl anate, aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), dimer acid diisocyanate, norbornene diisocyanate, lysine diisocyanate, and tetramethylxylylene diisocyanate, and 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 because they react quickly with the polyol (A) and moisture (water) and have excellent workability. These may be used alone or in combination of two or more.

[0049] The ratio of the polyol (A) and the polyisocyanate (B) used in synthesizing the isocyanate-terminated urethane prepolymer (hereinafter referred to as "prepolymer") may be within a range that does not adversely affect reaction behavior or product quality. Typically, the equivalent ratio of the isocyanate groups in the polyisocyanate (B) to the 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, more preferably 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 falls within an appropriate range, and the composition can exhibit properties such as excellent workability, film properties, and further excellent solidification properties.

[0050] The reaction conditions are not particularly limited as long as they are set within a range that does not adversely affect the reaction behavior or product quality, but it is usually preferable to carry out the reaction at a temperature of 80 to 130°C for 1 to 10 hours.

[0051] The reaction method can be selected from known reaction methods such as a batch reaction, a semi-continuous reaction, or a continuous reaction.

[0052] The reaction can be carried out in a solvent or without a solvent. However, when the reaction is carried out in a solvent, it is preferable to remove the solvent during or after the reaction, and finally to make the reaction solvent-free. The method for removing the solvent is not particularly limited.

[0053] The higher the content of the zinc phenylphosphonate complex in the moisture-curable hot-melt urethane resin adhesive, the shorter the solidification time. The content of the zinc phenylphosphonate complex may be 0.05% by mass or more, 0.10% by mass or more, 0.30% by mass or more, 0.50% by mass or more, 0.70% by mass or more, 0.9% by mass or more, 1.0% by mass or more, 2.0% by mass or more, 3.0% by mass or more, or 4.0% by mass or more, based on the total amount of the moisture-curable hot-melt urethane resin adhesive, and may be 8.0% by mass or less, 7.0% by mass or less, or 6.0% by mass or less.

[0054] 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 such as foam stabilizers, antioxidants, defoamers, UV absorbers, abrasive grains, fillers, pigments, dyes, colorants, thickeners, surfactants, flame retardants, plasticizers, lubricants, antistatic agents, heat stabilizers, tackifiers, curing catalysts, stabilizers, fluorescent brighteners, silane coupling agents, and waxes. [Example]

[0055] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0056] [Example 1] An aqueous solution was prepared by adding 30.0 parts by mass (190 mmol) of phenylphosphonic acid, 240 parts by mass of water, and 150 parts by mass of 10% aqueous sodium hydroxide to a 1-liter four-neck flask. While stirring this 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 the reaction to occur. The resulting white precipitate was filtered, washed with water, and then dried at 110°C for 12 hours or more, yielding the phenylphosphonic acid zinc complex represented by the above formula (1) as a white powder (Powder No. 0).

[0057] 16 parts by mass of the phenylphosphonic acid zinc complex obtained above and 240 parts by mass of 3.2 mm diameter steel balls were filled into a 150 mL plastic bottle and pulverized for 60 minutes using a paint shaker (manufactured by Toyo Seiki Seisakusho, Ltd.) at a vibration speed of 800 rpm to obtain Powder No. 1.

[0058] In a 1-liter four-neck 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) in a HD / AA=46 / 54 (mass ratio), 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) in a HD / NPG / EG / iPA / tPA=7 / 14 / 18 / 40 / 21 (mass ratio) 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) as a nucleating agent, and 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 allowed to react at 90°C for 3 hours until the NCO content (%) remained constant, yielding a moisture-curable hot-melt urethane resin adhesive.

[0059] [Example 2] 200 parts by mass of the phenylphosphonic acid zinc complex obtained in the same manner as in Example 1 and 3,000 parts by mass of 5.0 mm diameter alumina balls were charged into a 2 L porcelain pot and pulverized for 60 minutes at a vibration frequency of 19.4 Hz using a batch vibration mill (Vibropot YAMP-4JND, manufactured by Murakami Seiki Kosakusho Co., Ltd.) to obtain Powder No. 2. A moisture-curable hot-melt urethane resin adhesive was obtained in the same manner as in Example 1, except that Powder No. 2 was used instead of Powder No. 1 as the crystal nucleating agent.

[0060] [Example 3] 180 parts by mass of the phenylphosphonic acid zinc complex obtained in the same manner as in Example 1 and 5,000 parts by mass of zirconia balls with a diameter of 5.0 mm were charged into a 2 L porcelain pot and pulverized for 60 minutes at a vibration frequency of 19.4 Hz using a batch vibration mill (Vibropot YAMP-4JND, manufactured by Murakami Seiki Kosakusho Co., Ltd.) to obtain Powder No. 3. A moisture-curable hot-melt urethane resin adhesive was obtained in the same manner as in Example 1, except that Powder No. 3 was used instead of Powder No. 1 as the nucleating agent.

[0061] [Example 4] 200 parts by mass of the phenylphosphonic acid zinc complex obtained in the same manner as in Example 1 and 10,800 parts by mass of 4.8 mm diameter steel balls were charged into a 3 L stainless steel pot and pulverized for 30 minutes at a vibration frequency of 19.4 Hz using a batch vibration mill (Vibropot YAMP-6SND, manufactured by Murakami Seiki Kosakusho Co., Ltd.) to obtain Powder No. 4. A moisture-curable hot-melt urethane resin adhesive was obtained in the same manner as in Example 1, except that Powder No. 4 was used instead of Powder No. 1 as the crystal nucleating agent.

[0062] [Example 5] A continuous 1 L bead mill (Drystar SDA1, manufactured by Ashizawa Finetech Co., Ltd.) was filled with 3,310 parts by mass of 3.2 mm diameter steel balls, and the zinc phenylphosphonate complex obtained in the same manner as in Example 1 was added at a rate of 500 parts by mass per hour. Powder No. 5 was obtained by pulverizing at a peripheral speed of 5.0 m / s. A moisture-curable hot-melt urethane resin adhesive was obtained in the same manner as in Example 1, except that Powder No. 5 was used instead of Powder No. 1 as the nucleating agent.

[0063] [Example 6] A continuous 1 L bead mill (Drystar SDA1, manufactured by Ashizawa Finetech Co., Ltd.) was filled with 2,480 parts by mass of 1.5 mm diameter zirconia balls, and the zinc phenylphosphonate complex obtained in the same manner as in Example 1 was added at a rate of 500 parts by mass per hour. Powder No. 6 was obtained by pulverizing at a peripheral speed of 5.0 m / s. A moisture-curable hot-melt urethane resin adhesive was obtained in the same manner as in Example 1, except that Powder No. 6 was used instead of Powder No. 1 as the nucleating agent.

[0064] [Comparative Example 1] The same procedure as in Example 1 was carried out except that Powder No. 1 was not added as a crystal nucleating agent, to obtain a moisture-curable hot-melt urethane resin adhesive.

[0065] Comparative Example 2 The same procedure as in Example 1 was carried out, except that Powder No. 0 (the powder of zinc phenylphosphonate complex before grinding) was used as the nucleating agent instead of Powder No. 1, to obtain a moisture-curable hot-melt urethane resin adhesive.

[0066] [Comparative Example 3] 15 parts by mass of the phenylphosphonic acid zinc complex obtained in the same manner as in Example 1 and 225 parts by mass of 3.2 mm diameter steel balls were charged into a 250 mL plastic bottle and pulverized for 60 minutes at 110 rpm using a batch-type ball mill (tabletop pot mill with rotating table ANZ-51D, manufactured by Nitto Kagaku Co., Ltd.) to obtain Powder No. 7. A moisture-curable hot-melt urethane resin adhesive was obtained in the same manner as in Example 1, except that Powder No. 7 was used instead of Powder No. 1 as the nucleating agent.

[0067] Comparative Example 4 200 parts by mass of the phenylphosphonic acid zinc complex obtained in the same manner as in 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. A moisture-curable hot-melt urethane resin adhesive was obtained in the same manner as in Example 1, except that Powder No. 8 was used instead of Powder No. 1 as the nucleating agent.

[0068] [Examples 7 to 12] The same operation as in Example 1 was carried out, except that the content of Powder No. 1 (crystal nucleating agent) based on the total amount of moisture-curable hot-melt urethane resin adhesive was changed as shown in Table 2, to obtain a moisture-curable hot-melt urethane resin adhesive.

[0069] (Measurement of specific surface area) After pretreatment at 140°C for 30 minutes using a fully automatic specific surface area measuring device (Mountec Co., Ltd., Macsorb Model HM-1210), the surface area per 1 g of each powder in the Examples and Comparative Examples was measured from the amount of nitrogen gas adsorbed by the BET flow method. The results are shown in Table 1.

[0070] (Measurement of particle size distribution) The particle size distribution of each powder in the examples and comparative examples was measured by the following procedure. Using a laser diffraction particle size analyzer HELOS (H3355) & ROSDOS (Sympatec), the volumetric particle size distribution of each powder was measured in the range of 0.1 μm to 35 μm (range R1) under dry conditions of a dispersion pressure of 3 bar and a suction pressure of 90 mbar. From the obtained particle size distribution, the 10% diameter (D10), 50% diameter (D50, median diameter), and 90% diameter (D90) were calculated. The results are shown in Table 1.

[0071] [Table 1]

[0072] [Measurement of solidification time (open time)] The hardening time of each moisture-curable polyurethane hot-melt adhesive in the examples and comparative examples was measured by the following procedure. A moisture-curing polyurethane hot-melt adhesive was heated to a molten state at 125°C and applied in a line at 1 g / m onto the substrate (medium-density fiberboard, Daiken Corporation, product name "Customwood MDF U Type 25 F****"). After a certain waiting time, another MDF was pressed onto the adhesive-coated MDF for 30 seconds to adhere it. One MDF was then peeled from the other, and the peel strength was measured. Measurements were performed using an ASM-15N adhesive strength tester manufactured by MEC Corporation at a temperature of 23°C and a humidity of 50%. The waiting time was extended by 10 seconds at a time until the MDF no longer bonded to each other (i.e., until the peel strength was nearly zero). The solidification time (open time) was determined as the waiting time at which a peel strength of 5 N or greater could be maintained. The results are shown in Table 2.

[0073] [Table 2]

Claims

1. A zinc phenylphosphonate complex represented by formula (1): 【Chemical 1】 The specific surface area measured by the BET method using nitrogen gas adsorption is 20.0 m ２ / g or more.

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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