Composition containing zinc phenylphosphonate complex and zinc phosphate complex, method for producing same, use of same as crystal nucleating agent, and moisture-curable hot-melt urethane resin adhesive

Abstract

The object of the present invention is to provide a composition that can be suitably used as a crystal nucleating agent capable of further shortening the solidification time of a moisture-curable hot-melt urethane resin, and a method for producing the same. [Solution] A method for producing a composition containing a zinc phenylphosphonic acid complex and a zinc phosphate complex, comprising a step of simultaneously reacting a phenylphosphonic acid represented by formula (1) and a phosphate represented by formula (2) with a zinc compound. TIFF2024547037000023.tif2563 TIFF2024547037000024.tif2569 In formula (2), R 1 represents an alkyl group, R 2 represents an alkylene group, and n represents an integer of 1 or more. When n is an integer of 2 or more, a plurality of R 2 may be the same or different. 2 At least one of these represents an ethylene group.

Description

[Technical field]

[0001] The present disclosure relates to a composition containing a zinc phenylphosphonate complex and a zinc phosphate complex, a method for producing the same, use of the same as a crystal nucleating agent, 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 for use as adhesives in adhesive processing and molding processes such as sealing, which require continuous production, and are used in a wide range of fields. However, in applications such as wood wrapping for decorative sheets that require initial strength, and in electrical and electronic parts and automotive parts that require continuous production on high-speed lines, problems can arise in that the urethane resin moves to the next process without being sufficiently cooled and solidified.

[0003] In order to solve the above problems, the solidification time has been shortened by adding a metal salt of a phenylphosphonic acid compound as a crystal nucleating agent to a urethane resin.For example, JP2012-177016A discloses a moisture-curable hot-melt urethane resin adhesive containing 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 crystal nucleating agent. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2012-177016 A Summary of the Invention [Problem to be solved by the invention]

[0005] According to the investigations of the present inventors, when a metal salt of an aromatic phosphonic acid is used as a crystal nucleating agent, there is room for further shortening the solidification time of the moisture-curable hot-melt urethane resin.

[0006] Therefore, one aspect of the present invention aims to provide a composition 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, and a method for producing the same. Another aspect of the present invention aims to provide a moisture-curable hot-melt urethane resin adhesive that has a further shortened solidification time. [Means for solving the problem]

[0007] The present inventors have discovered that by using a specific phenylphosphonic acid and a specific phosphate as raw materials and simultaneously reacting them with a zinc compound, a composition containing a specific phenylphosphonic acid zinc complex and a specific phosphate zinc complex can be obtained, and that the composition can be suitably used as a crystal nucleating agent that can further shorten the solidification time of a moisture-curable hot-melt urethane resin.

[0008] The present invention includes the following aspects. [1] A method for producing a composition containing a zinc phenylphosphonic acid complex and a zinc phosphate complex, comprising a step of simultaneously reacting a phenylphosphonic acid represented by formula (1) and a phosphate represented by formula (2) with a zinc compound. TIFF0007626300000001.tif2563 TIFF0007626300000002.tif2569 In formula (2), R 1 represents an alkyl group, R 2 represents an alkylene group, and n represents an integer of 1 or more. When n is an integer of 2 or more, a plurality of R 2 may be the same or different. 2 At least one of these represents an ethylene group. [2] The method according to [1], wherein the molar ratio of the amount of the phosphoric acid ester represented by formula (2) to the amount of the phenylphosphonic acid represented by formula (1) is 1 / 99 to 60 / 40.

[0009] [3] A composition containing a zinc phenylphosphonate complex represented by formula (3) and a zinc phosphate complex represented by formula (4). TIFF0007626300000003.tif2563 TIFF0007626300000004.tif2569 In formula (4), R 1 represents an alkyl group, R 2 represents an alkylene group, and n represents an integer of 1 or more. When n is an integer of 2 or more, a plurality of R 2 may be the same or different. 2 At least one of these represents an ethylene group. [4] The composition according to [3], wherein a molar ratio of an amount of the phosphoric acid ester represented by the formula (4) to an amount of the phenylphosphonic acid represented by the formula (3) is 1 / 99 to 60 / 40. [5] Use of the composition according to [3] or [4] as a crystal nucleating agent.

[0010] [6] A moisture-curable hot-melt urethane resin adhesive comprising an isocyanate-terminated urethane prepolymer, a zinc phenylphosphonate complex represented by formula (3), and a zinc phosphate complex represented by formula (4). TIFF0007626300000005.tif2563 TIFF0007626300000006.tif2569 In formula (4), R 1 represents an alkyl group, R 2 represents an alkylene group, and n represents an integer of 1 or more. When n is an integer of 2 or more, a plurality of R 2 may be the same or different. 2 At least one of these represents an ethylene group. [7] The moisture-curable hot-melt urethane resin adhesive according to [6], wherein the molar ratio of the amount of the phosphoric acid ester represented by formula (4) to the amount of the phenylphosphonic acid represented by formula (3) is 1 / 99 to 60 / 40. [8] The moisture-curable hot-melt urethane resin adhesive according to [6] or [7], wherein the combined amount of the zinc phenylphosphonate complex represented by formula (3) and the zinc phosphate complex represented by formula (4) is 0.1 to 10 mass% based on the total amount of the moisture-curable hot-melt urethane resin adhesive. Effect of the Invention

[0011] According to one aspect of the present invention, there is provided a composition 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, and a method for producing the same. 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 PREFERRED EMBODIMENTS

[0012] Hereinafter, an embodiment of the present invention will be described in detail. One embodiment of the present invention is a method for producing a composition containing a phenylphosphonic acid zinc complex and a phosphate zinc complex, comprising a step (reaction step) of simultaneously reacting a phenylphosphonic acid represented by formula (1) and a phosphate represented by formula (2) with a zinc compound. TIFF0007626300000007.tif2563 TIFF0007626300000008.tif2569

[0013] In formula (2), R 1 represents an alkyl group, R 2 represents an alkylene group, and n represents an integer of 1 or more.

[0014] R 1 The alkyl group represented by R may be linear or branched. 1The number of carbon atoms in the alkyl group represented by formula (2) may be 1 or more, and may be 15 or less, 14 or less, 13 or less, or 12 or less. The phosphate ester represented by formula (2) is 1 It may be a mixture of two or more kinds of phosphate esters having different structures.

[0015] R 2 The alkylene group represented by the formula (I) may be linear or branched. 2 The number of carbon atoms in the alkylene group represented by the formula (I) may be 1 or more, or 2 or more, and may be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or 3 or less. When n is an integer of 2 or more, a plurality of R 2 may be the same or different from each other.

[0016] R 2 At least one of R represents an ethylene group. That is, the phosphate ester represented by formula (2) has at least one oxyethylene group. 2 may all be ethylene groups, R 2 A part of the alkylene group may be an ethylene group, and the remainder may be an alkylene group other than an ethylene group.

[0017] n may be an integer of 2 or more, 3 or more, or 4 or more, or may be an integer of 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4 or less. The phosphate ester represented by formula (2) may be a mixture of two or more kinds of phosphate esters each having a different n.

[0018] The average molecular weight of the phosphate ester represented by formula (2) may be 100 or more, 200 or more, or 300 or more, and may be 900 or less, 800 or less, or 700 or less.

[0019] The average molecular weight in this specification means a number average molecular weight measured by gel permeation chromatography (GPC) under the conditions shown below. Measurement equipment: High-speed GPC equipment (Tosoh Corporation "HLC-8220GPC") Column: The following columns manufactured by Tosoh Corporation are connected in series and used. "TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 "TSKgel G2000" (7.8mmI.D. x 30cm) x 1 Detector: RI (differential refractometer) Column temperature: 40℃ Eluent: tetrahydrofuran (THF) Flow rate: 1.0mL / min Injection volume: 100 μL (sample concentration 0.4% by mass in tetrahydrofuran solution) Standard sample: Prepare a calibration curve using the following standard polystyrene.

[0020] (Standard polystyrene) "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0021] The molar ratio of the amount of the phosphoric ester represented by formula (2) to the amount of the phenylphosphonic acid represented by formula (1) (the amount of the phosphoric ester represented by formula (2) / the amount of the phenylphosphonic acid represented by formula (1)) may be 1 / 99 or more, may be 60 / 40 or less, and may be 1 / 99 to 60 / 40. The lower limit of the molar ratio may be 2 / 98, 5 / 95, 10 / 90, 15 / 85, or 20 / 80. The upper limit of the molar ratio may be 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, or 25 / 75.

[0022] The zinc compound that is reacted simultaneously with the phenylphosphonic acid represented by formula (1) and the phosphoric acid ester represented by formula (2) may be, for example, a zinc halide, zinc oxide, or zinc acetate. The zinc halide may be zinc fluoride, zinc chloride, zinc bromide, or zinc iodide.

[0023] The amount of the zinc compound may be 0.8 mol or more, 0.9 mol or more, or 0.95 mol or more, and may be 1.2 mol or less, 1.1 mol or less, or 1.05 mol or less, relative to 1 mol of the total amount of the phenylphosphonic acid represented by formula (1) and the phosphoric acid ester represented by formula (2).

[0024] In the reaction step, for example, an aqueous solution of a zinc compound dissolved in water is added to an aqueous solution of a phenylphosphonic acid represented by formula (1) and a phosphoric acid ester represented by formula (2) dissolved in water, thereby simultaneously reacting the phenylphosphonic acid represented by formula (1) and the phosphoric acid ester represented by formula (2) with the zinc compound. At this time, the above reaction can be progressed by gradually adding an aqueous alkali solution such as an aqueous sodium hydroxide solution.

[0025] The white precipitate formed by the above reaction is filtered, washed with water, and then dried to obtain a composition containing a zinc phenylphosphonate complex and a zinc phosphate complex as a white powder.

[0026] The composition obtained by the above-described production method contains a phenylphosphonic acid zinc complex represented by formula (3) and a phosphate zinc complex represented by formula (4). That is, another embodiment of the present invention is a composition containing a phenylphosphonic acid zinc complex represented by formula (3) and a phosphate zinc complex represented by formula (4). TIFF0007626300000009.tif2563 TIFF0007626300000010.tif2569

[0027] In formula (4), R 1 represents an alkyl group, R 2 represents an alkylene group, and n represents an integer of 1 or more. When n is an integer of 2 or more, a plurality of R 2 may be the same or different. 2 At least one of R represents an ethylene group. 1 , R 2 The details of n are the same as those described for the phosphate ester represented by formula (2). 1 , R 2 , and n are similar in detail.

[0028] The average molecular weight of the phosphate zinc complex represented by formula (4) may be 150 or more, 250 or more, or 350 or more, and may be 950 or less, 850 or less, or 750 or less.

[0029] In the composition, the molar ratio of the amount of the phosphate zinc complex represented by formula (4) to the amount of the phenylphosphonic acid zinc complex represented by formula (3) (the amount of the phosphate zinc complex represented by formula (4) / the amount of the phenylphosphonic acid zinc complex represented by formula (3)) may be 1 / 99 or more, may be 60 / 40 or less, and may be 1 / 99 to 60 / 40. The lower limit of the molar ratio may be 2 / 98, 5 / 95, 10 / 90, 15 / 85, or 20 / 80. The upper limit of the molar ratio may be 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, or 25 / 75.

[0030] The composition of the present embodiment contains a phosphate zinc complex represented by formula (4) in addition to the phenylphosphonic acid zinc complex represented by formula (3), and therefore the solidification time of the moisture-curable hot-melt urethane resin can be further shortened, for example, compared with a composition containing only the phenylphosphonic acid zinc complex represented by formula (3). In one embodiment, the composition can improve the initial adhesive strength of the moisture-curable hot-melt urethane resin adhesive.

[0031] Therefore, the composition of this embodiment can be suitably used as a crystal nucleating agent, more specifically, as a crystal nucleating agent that promotes the crystallization of urethane resin. That is, another embodiment of the present invention is the use (application) of a composition containing a phenylphosphonic acid zinc complex represented by the above formula (3) and a phosphate ester zinc complex represented by the above formula (4) as a crystal nucleating agent (crystal nucleating agent that promotes the crystallization of urethane resin).

[0032] Another embodiment of the present invention is a moisture-curable hot-melt urethane resin adhesive containing an isocyanate group-terminated urethane prepolymer, a zinc phenylphosphonate complex represented by the above formula (3), and a zinc phosphate complex represented by the above formula (4).

[0033] The isocyanate group-terminated urethane prepolymer can be obtained by reacting a polyol (A) with a polyisocyanate (B) in the presence of a zinc phenylphosphonate complex represented by the above formula (3) and a zinc phosphate complex represented by the above formula (4).

[0034] The polyol (A) may contain an aliphatic polyester polyol, may contain two types of aliphatic polyester polyols (the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2) described below), or may contain two types of aliphatic polyester polyols (the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2) described below) and a polyol (a3) ​​other than the aliphatic polyester polyol.

[0035] The aliphatic polyester polyol (a1) is a polyester polyol produced from an aliphatic polycarboxylic acid and an aliphatic polyol as main components by a known and commonly used method, and the production method is not particularly limited.

[0036] 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.

[0037] The aliphatic polycarboxylic acids may be used in the form of corresponding acid derivatives, such as lower alkyl ester derivatives (eg, methyl esters), acid anhydrides, acid halides, etc.

[0038] 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 a carbon number of 2 to 12. The (a1) may have any of a linear, branched, or cyclic structure.

[0039] 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, and 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 cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, and other alicyclic polyols. Of these, ethylene glycol, 1,6-hexanediol, and neopentyl glycol are preferred.

[0040] Also usable are adducts in which various alkylene oxides are added to hydrogenated bisphenol A, hydrogenated bisphenol F, etc. Also usable are polymers in which γ-butyrolactone, ε-caprolactone, etc. are subjected to ring-opening polymerization using a low molecular weight polyol as an initiator. These may be used alone or in combination of two or more.

[0041] 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 in the polyol (A), since this further improves the viscosity stability during molding of the hot-melt urethane resin adhesive and provides an excellent effect in preventing a decrease in the melt viscosity.

[0042] 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.

[0043] The aromatic polycarboxylic acid is a carboxylic acid having at least two carboxyl groups bonded to an aromatic ring, and is preferably an aromatic polycarboxylic acid having 8 to 24 carbon atoms, and examples thereof include 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 kinds.

[0044] The aromatic polycarboxylic acids may be used in the form of corresponding acid derivatives, such as lower alkyl ester derivatives (eg, methyl esters), acid anhydrides, acid halides, etc.

[0045] Examples of the aliphatic polyol include the same aliphatic polyols as those usable in the synthesis of the aliphatic polyester polyol (a1).

[0046] The aliphatic polyol usable in the synthesis of 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 a portion of the carbon atoms is substituted with an oxygen atom or an aromatic ring. These aliphatic polyols may be used alone or in combination of two or more kinds.

[0047] Furthermore, it may be a mixture of polyester polyols obtained from these aromatic polycarboxylic acids and aliphatic polyols.

[0048] 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).

[0049] 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.

[0050] 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.

[0051] 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, and more preferably in the range of 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 the polyisocyanate (B) can proceed more easily, which is preferable.

[0052] The polycondensation conditions for the synthesis of the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2) are not particularly limited as long as they do not cause abnormal reactions and can produce normal products. Usually, a given amount of aliphatic polycarboxylic acid and aliphatic polyol, or aromatic polycarboxylic acid and aliphatic polyol, are 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, and then a polycondensation reaction is carried out.

[0053] The polycondensation reaction is preferably carried out in the presence of a catalyst, since the reaction proceeds 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.

[0054] 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.

[0055] In the production of the aliphatic polyester polyol (a1) and aromatic polyester polyol (a2), it is desirable to convert most of the terminals to hydroxyl groups and to leave as few carboxyl terminal groups as possible. For this purpose, it is effective and preferable to add the catalyst after carrying out preliminary polymerization.

[0056] 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 the (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.

[0057] Examples of the other polyols (a3) ​​include polycarbonate polyols, polylactone polyols, polyether polyols, etc. Examples of the polycarbonate polyols include polycarbonate polyols obtained by using the linear aliphatic polyols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc. Examples of the polylactone polyols include polycaprolactone polyols obtained by ring-opening polymerization of caprolactone monomers, etc. Examples of the polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.

[0058] The content ratio of the aliphatic polyester polyol (a1) / the aromatic polyester polyol (a2) / the other polyol (a3) ​​may 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, in 100 parts by mass of the polyol (A). If 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 having excellent workability and compatibility and further excellent solidification properties can be obtained.

[0059] The polyisocyanate (B) may be a known and commonly used aliphatic, aromatic, or alicyclic polyisocyanate, such as diphenylmethane diisocyanate (MDI; its 4,4', 2,4', or 2,2' form, 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 form, or 2,6 form, or a mixture thereof), xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), tetramethylxylene diisocyanate, phenylene ... Examples of the diisocyanates include aromatic diisocyanates such as hexamethylene diisocyanate (HDI), dimer acid diisocyanate, norbornene diisocyanate, lysine diisocyanate, tetramethyl xylylene diisocyanate, and other aliphatic diisocyanates; 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.

[0060] The ratio of the polyol (A) and the polyisocyanate (B) used in synthesizing the isocyanate group-terminated urethane prepolymer (hereinafter referred to as "prepolymer") may be within a range that does not adversely affect reaction behavior or product quality, and is usually preferably in the range of 1.2 to 4.0, more preferably 1.5 to 3.0, as the equivalent ratio (hereinafter referred to as [NCO / OH equivalent ratio]) between the isocyanate group of the polyisocyanate (B) and the hydroxyl group of the polyol (A). If the [NCO / OH equivalent ratio] is within this range, the melt viscosity of the intended moisture-curable hot melt urethane resin composition will be in an appropriate range, and excellent workability, film properties, and further excellent solidification properties can be expressed.

[0061] 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 reaction temperature of 80 to 130° C. for 1 to 10 hours.

[0062] The reaction system may be selected from known reaction systems such as a batch reaction, a semi-continuous reaction, or a continuous reaction.

[0063] 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 of removing the solvent is not particularly limited.

[0064] The total amount of the phenylphosphonic acid zinc complex represented by formula (3) and the phosphate zinc complex represented by formula (4) may be 0.1 mass% or more, 10 mass% or less, or 0.1 to 10 mass% based on the total amount of the moisture-curable hot-melt urethane resin adhesive. The lower limit of the total amount may be 0.3 mass%, 0.5 mass%, or 1 mass% based on the total amount of the moisture-curable hot-melt urethane resin adhesive. The upper limit of the total amount may be 7 mass%, 5 mass%, or 3 mass% based on the total amount of the moisture-curable hot-melt urethane resin adhesive.

[0065] In the moisture-curable hot melt urethane resin adhesive, the molar ratio of the amount of the phosphate zinc complex represented by formula (4) to the amount of the phenylphosphonic acid zinc complex represented by formula (3) (the amount of the phosphate zinc complex represented by formula (4) / the amount of the phenylphosphonic acid zinc complex represented by formula (3)) may be 1 / 99 or more, may be 60 / 40 or less, and may be 1 / 99 to 60 / 40. The lower limit of the molar ratio may be 2 / 98, 5 / 95, 10 / 90, 15 / 85, or 20 / 80. The upper limit of the molar ratio may be 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, or 25 / 75.

[0066] The moisture-curable hot-melt urethane resin adhesive of the present embodiment may further contain other resins such as conventionally known thermoplastic resins and thermosetting resins, and may further contain other additives. Examples of other additives include 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, waxes, etc.

[0067] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0068] [Example 1] (Production of a composition containing a zinc phenylphosphonate complex and a zinc phosphate complex) Into a 3-liter, four-neck flask, 12.3 parts by mass (78.0 mmol) of phenylphosphonic acid represented by formula (1) and a compound represented by formula (2A): TIFF0007626300000011.tif2596 (wherein n represents an integer of 1 or more) An aqueous solution was prepared by adding 2.0 parts by mass (4.1 mmol) of a phosphoric acid ester having an average molecular weight of 480 represented by the formula (3) and 600 parts by mass of water. An aqueous solution prepared from 11.2 parts by mass (82.2 mmol) of zinc chloride and 260 parts by mass of water was further added to the flask and mixed. With stirring, 1608 parts by mass of a 0.1 M aqueous sodium hydroxide solution was added to the aqueous solution over a period of 6 hours to react. The white precipitate that separated out was filtered, washed with water, and then dried under reduced pressure at 80° C. for 2 hours or more to obtain a phenylphosphonic acid zinc complex represented by the formula (3) and a phenylphosphonic acid zinc complex represented by the formula (4A): TIFF0007626300000012.tif2596 (wherein n represents an integer of 1 or more) and a zinc phosphate complex having an average molecular weight of 543 represented by the formula (1), was obtained as a white powder.

[0069] (Manufacture of moisture-curing hot melt urethane resin adhesives) In a 1-liter four-neck flask, 30 parts by mass of polypropylene glycol (Mn=1000), 40 parts by mass of 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 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, 1.2 parts by mass of composition 1 (1.0% by mass based on the total amount of the adhesive) was added to the above (A) as a crystal nucleating agent, and the mixture was heated to 110° C. and dehydrated under reduced pressure conditions until the water content was 0.05% by mass. Thereafter, the mixture was cooled to 70° C., 19 parts by mass of 4,4-diphenylmethane diisocyanate was added, and the mixture was reacted at 90° C. for 3 hours until the NCO content (%) became constant, to obtain a moisture-curable hot-melt urethane resin adhesive.

[0070] [Example 2] The same procedure as in Example 1 was carried out except that 11.7 parts by mass (73.9 mmol) of phenylphosphonic acid and 3.9 parts by mass (8.2 mmol) of the phosphoric acid ester represented by formula (2A) were used, to obtain composition 2 as a white powder. In addition, the same procedure as in Example 1 was carried out except that composition 2 was used, to obtain a moisture-curable hot-melt urethane resin adhesive.

[0071] [Example 3] The same procedure as in Example 1 was carried out except that 10.0 parts by mass (63.3 mmol) of phenylphosphonic acid and 9.0 parts by mass (18.8 mmol) of the phosphoric acid ester represented by formula (2A) were used, to obtain composition 3 as a white powder. In addition, the same procedure as in Example 1 was carried out except that composition 3 was used, to obtain a moisture-curable hot-melt urethane resin adhesive.

[0072] [Example 4] The same procedure as in Example 1 was carried out except that 9.1 parts by mass (57.5 mmol) of phenylphosphonic acid and 11.8 parts by mass (24.6 mmol) of the phosphoric acid ester represented by formula (2A) were used, to obtain composition 4 as a white powder. In addition, the same procedure as in Example 1 was carried out except that composition 4 was used, to obtain a moisture-curable hot-melt urethane resin adhesive.

[0073] [Example 5] The same procedure as in Example 1 was carried out except that 6.5 parts by mass (41.1 mmol) of phenylphosphonic acid and 19.7 parts by mass (41.1 mmol) of the phosphoric acid ester represented by formula (2A) were used, to obtain composition 5 as a white powder. In addition, the same procedure as in Example 1 was carried out except that composition 5 was used, to obtain a moisture-curable hot-melt urethane resin adhesive.

[0074] [Example 6] Into a 3-liter, four-neck flask, 12.6 parts by mass (80.0 mmol) of phenylphosphonic acid and a compound represented by the formula (2B): TIFF0007626300000013.tif2593(in the formula, R 1 is C 12 H25 Or C 14 H 29 represents an alkyl group represented by the formula: An aqueous solution was prepared by adding 1.4 parts by mass (2.1 mmol) of a phosphoric acid ester having an average molecular weight of 671 represented by the formula (3) and 600 parts by mass of water. An aqueous solution prepared from 11.2 parts by mass (82.2 mmol) of zinc chloride and 260 parts by mass of water was further added to the flask and mixed. With stirring, 1606 parts by mass of a 0.1 M aqueous sodium hydroxide solution was added to the aqueous solution over a period of 6 hours to cause a reaction. The white precipitate that had separated out was filtered, washed with water, and then dried under reduced pressure at 80° C. for 2 hours or more to obtain a phenylphosphonic acid zinc complex represented by the formula (3) and a phenylphosphonic acid zinc complex represented by the formula (4B): TIFF0007626300000014.tif2593(in the formula, R 1 is C 12 H 25 Or C 14 H 29 represents an alkyl group represented by the formula: and a zinc phosphate complex having an average molecular weight of 735 represented by the formula (1), was obtained as a white powder. Moreover, the same procedure as in Example 1 was carried out except that Composition 6 was used, to obtain a moisture-curable hot-melt urethane resin adhesive.

[0075] [Example 7] The same procedure was carried out as in Example 6, except that 12.3 parts by mass (78.0 mmol) of phenylphosphonic acid and 2.7 parts by mass (4.1 mmol) of the phosphoric ester represented by formula (2B) were used, to obtain composition 7 as a white powder. The same procedure was carried out as in Example 1, except that composition 7 was used, to obtain a moisture-curable hot-melt urethane resin adhesive.

[0076] [Example 8] The same procedure was carried out as in Example 6, except that 11.7 parts by mass (73.9 mmol) of phenylphosphonic acid and 5.4 parts by mass (8.2 mmol) of the phosphoric ester represented by formula (2B) were used, to obtain composition 8 as a white powder. Also, the same procedure was carried out as in Example 1, except that composition 8 was used, to obtain a moisture-curable hot-melt urethane resin adhesive.

[0077] [Example 9] The same procedure was carried out as in Example 6, except that 10.0 parts by mass (63.3 mmol) of phenylphosphonic acid and 12.5 parts by mass (18.7 mmol) of the phosphoric acid ester represented by formula (2B) were used, to obtain composition 9 as a white powder. The same procedure was carried out as in Example 1, except that composition 9 was used, to obtain a moisture-curable hot-melt urethane resin adhesive.

[0078] [Comparative Example 1] The same procedure as in Example 1 was carried out except that Composition 1 was not added, to obtain a moisture-curable hot-melt urethane resin adhesive.

[0079] [Comparative Example 2] The same procedure was carried out as in Example 1, except that instead of composition 1, a phenylphosphonic acid zinc complex obtained by the following procedure was used, to obtain a moisture-curable hot-melt urethane resin adhesive. In a 3-liter, four-neck flask, 10.0 parts by mass (63.3 mmol) of phenylphosphonic acid and 400 parts by mass of water were added to prepare an aqueous solution. An aqueous solution prepared from 8.6 parts by mass (63.3 mmol) of zinc chloride and 200 parts by mass of water was further added to the flask and mixed. With stirring, 1244 parts by mass of 0.1 M aqueous sodium hydroxide solution was added to the aqueous solution over 6 hours to react. The white precipitate that was deposited was filtered, washed with water, and then dried under reduced pressure at 80° C. for 2 hours or more, to obtain a phenylphosphonic acid zinc complex as a white powder.

[0080] [Evaluation of solidification time (open time)] The obtained moisture-curable hot-melt urethane resin adhesive of each of the examples and comparative examples was heated to a molten state at 120°C and applied to a polypropylene sheet substrate to a thickness of 50 μm. Next, craft paper was placed as a surface member on the applied adhesive layer, and immediately placed in a thermostatic chamber at 23°C. The time (unit: seconds) until the craft paper no longer adhered to the adhesive layer was measured, based on the time when it was placed in the thermostatic chamber, and this was taken as the solidification time at 23°C (open time at 23°C). The results are shown in Table 1.

[0081] [Evaluation of initial adhesive strength] The obtained moisture-curing hot-melt urethane resin adhesives of the Examples and Comparative Examples were heated to a molten state at 120°C, and 1 ml of the adhesive was applied to a surface area of ​​4 cm 2 The adhesive was then applied to another wood block substrate that had not been coated with adhesive, and the substrate was left in a thermostatic chamber at 23°C for 3 minutes, after which the tensile strength (mPa) was measured and used as the initial adhesive strength.

[0082] [Table 1] TIFF0007626300000015.tif61163

Claims

1. A method for producing a composition containing a zinc phenylphosphonic acid complex and a zinc phosphate complex, comprising a step of simultaneously reacting a phenylphosphonic acid represented by formula (1) and a phosphate represented by formula (2) with a zinc compound. [In formula (2), R １ represents an alkyl group, R ２ represents an alkylene group, and n represents an integer of 1 or more. When n is an integer of 2 or more, there are multiple R ２ may be the same or different. ２ At least one of represents an ethylene group.

2. The method according to claim 1, wherein a molar ratio of the amount of the phosphoric acid ester represented by the formula (2) to the amount of the phenylphosphonic acid represented by the formula (1) is 1 / 99 to 60 / 40.

3. A composition comprising a zinc phenylphosphonate complex represented by formula (3) and a zinc phosphate complex represented by formula (4). [In formula (4), R １ represents an alkyl group, R ２ represents an alkylene group, and n represents an integer of 1 or more. When n is an integer of 2 or more, there are multiple R ２ may be the same or different. ２ At least one of represents an ethylene group. 。

4. The composition according to claim 3, wherein a molar ratio of the amount of the phosphoric acid ester represented by the formula (4) to the amount of the phenylphosphonic acid represented by the formula (3) is 1 / 99 to 60 / 40.

5. Use of the composition according to claim 3 or 4 as a crystal nucleating agent.

6. A moisture-curable hot-melt urethane resin adhesive comprising an isocyanate-terminated urethane prepolymer, a zinc phenylphosphonate complex represented by formula (3), and a zinc phosphate complex represented by formula (4). [In formula (4), R １ represents an alkyl group, R ２ represents an alkylene group, and n represents an integer of 1 or more. When n is an integer of 2 or more, there are multiple R ２ may be the same or different. ２ At least one of these represents an ethylene group.

7. The moisture-curable hot melt urethane resin adhesive according to claim 6, wherein the molar ratio of the amount of the phosphoric acid ester represented by the formula (4) to the amount of the phenylphosphonic acid represented by the formula (3) is 1 / 99 to 60 / 40.

8. The total amount of the phenylphosphonic acid zinc complex represented by the formula (3) and the phosphate zinc complex represented by the formula (4) is 0.1 to 10 mass% based on the total amount of the moisture-curable hot-melt urethane resin adhesive. The moisture-curable hot-melt urethane resin adhesive according to claim 6 or 7.

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