Method for producing polyether compound having polymerizable unsaturated group

Abstract

To provide a method for producing a polyether compound having a polymerizable unsaturated group and giving a cured product having excellent strength.SOLUTION: A method for producing a polyether compound having a polymerizable unsaturated group, comprising bringing an initiator having an active hydrogen into contact with an alkylene oxide-containing starting material in the presence of a double metal cyanide complex catalyst to polymerize the alkylene oxide in the alkylene oxide-containing starting material into a group having a polymerizable unsaturated group, wherein the total aldehyde content of the obtained hydroxyl group-containing polyether compound measured by a titration method is less than 15 ppm based on the total mass of the alkylene oxide-containing starting material.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polyether compound having a polymerizable unsaturated group. [Background technology]

[0002] Polyether compounds having a polymerizable unsaturated group are used as raw materials for adhesives in fields such as optical component materials and liquid crystal panels (e.g., Patent Document 1). Polyether compounds having a polymerizable unsaturated group are produced using polyether compounds having a hydroxyl group as a raw material. Polyether compounds having a hydroxyl group are produced by polymerizing alkylene oxide with an initiator having active hydrogen. Double metal cyanide complex catalysts are known as polymerization catalysts for obtaining polyether compounds with narrow molecular weight distribution. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-126839 Summary of the Invention [Problem to be solved by the invention]

[0004] However, according to the investigations of the present inventors, polyether compounds having polymerizable unsaturated groups obtained by conventional methods sometimes result in insufficient strength in the cured product.

[0005] An object of the present invention is to provide a production method that can yield a polyether compound having a polymerizable unsaturated group that provides a cured product with excellent strength. [Means for solving the problem]

[0006] A preferred embodiment of the present invention provides the following means: [1] A method for producing a polyether compound having a polymerizable unsaturated group, comprising the steps of: contacting an initiator having active hydrogen with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst to polymerize the alkylene oxide in the alkylene oxide-containing raw material with the initiator, and converting the hydroxyl group of the resulting polyether compound having a hydroxyl group into a group having a polymerizable unsaturated group; The alkylene oxide-containing feedstock has a total aldehyde content of less than 15 ppm, based on the total mass of the alkylene oxide-containing feedstock, as measured by titration. [2] The production method according to [1], wherein the alkylene oxide-containing raw material has an acetaldehyde content of less than 10 ppm based on the total mass of the alkylene oxide-containing raw material. [Effects of the Invention]

[0007] According to the present invention, there can be provided a production method for obtaining a polyether compound having a polymerizable unsaturated group, which provides a cured product with excellent strength. DETAILED DESCRIPTION OF THE INVENTION

[0008] The meanings and definitions of terms used in this specification are as follows: A numerical range expressed as "to" means a numerical range with the numbers before and after "to" as the lower and upper limits. The lower and upper limits of the numerical ranges disclosed in this specification can be combined in any way to create a new numerical range.

[0009] The "unit" constituting the polyether compound having a hydroxyl group means an atomic group formed directly by polymerization of a monomer. The term "main chain" refers to a polymer chain formed by polymerization of two or more monomers. In the case of a polyether compound having a hydroxyl group, which will be described later, the "main chain" refers to a residue obtained by removing active hydrogen from an initiator and a portion containing a repeating unit based on alkylene oxide (polyoxyalkylene chain). The polyether compound having a hydroxyl group and the polyether compound having a polymerizable unsaturated group are polymers consisting of a main chain and terminal groups. The "end group" of a polyether compound having a hydroxyl group and a polyether compound having a polymerizable unsaturated group refers to an atomic group containing the oxygen atom in the polyoxyalkylene chain that is closest to the molecular end. However, if the atomic group contains a residue of an initiator, it is not considered to be an end group but is considered to be part of the main chain. The "number of end groups" in a polyether compound having a hydroxyl group and a polyether compound having a polymerizable unsaturated group is the same as the number of active hydrogen atoms in the initiator, as described below. The "active hydrogen-containing group" refers to at least one group selected from the group consisting of a hydroxyl group bonded to a carbon atom, a carboxyl group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine, a hydrazide group, and a sulfanyl group. "Active hydrogen" refers to a hydrogen atom derived from an active hydrogen-containing group and a hydrogen atom derived from a hydroxyl group of water.

[0010] In this specification, the number average molecular weight (Mn) and weight average molecular weight (Mw) are polystyrene-equivalent molecular weights measured using GPC (Gel Permeation Chromatography) with tetrahydrofuran as an eluent, with a calibration curve prepared using polystyrene polymers of known molecular weights. The molecular weight distribution (Mw / Mn) is the ratio of Mw to Mn.

[0011] The "hydroxyl value" of a polyether compound having a hydroxyl group is a value measured in accordance with Method B (phthalation method) described in JIS K 1557-1:2007. The hydroxyl value-based molecular weight is a value calculated by multiplying the hydroxyl value of the hydroxyl-containing polyether compound by the number of hydroxyl groups in the hydroxyl-containing polyether compound (the number of active hydrogen atoms in the initiator). When two or more types of hydroxyl-containing polyether compounds with different numbers of hydroxyl groups are contained, the number of hydroxyl groups in the hydroxyl-containing polyether compound is the average number of hydroxyl groups.

[0012] The degree of unsaturation of the polyether compound is measured in accordance with JIS K 1557-3:2007. The viscosity of the polyether compound is measured using an E-type viscometer.

[0013] The total aldehyde content of the alkylene oxide-containing raw material is the total amount of compounds having a formyl group, and is measured by titration, as described in detail in the Examples. The alkylene oxide content and acetaldehyde content of the alkylene oxide-containing raw material are measured by gas chromatography, as described in detail in the Examples. "ppm" is by mass unless otherwise specified.

[0014] <Method for producing polyether compound having polymerizable unsaturated group> The method for producing a polyether compound having a polymerizable unsaturated group of the present embodiment involves bringing an initiator having active hydrogen into contact with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst, polymerizing the alkylene oxide in the alkylene oxide-containing raw material with the initiator, and converting the hydroxyl group of the resulting polyether compound having a hydroxyl group into a group having a polymerizable unsaturated group.

[0015] Hereinafter, the polyether compound having a hydroxyl group will be referred to as "polyether compound A," and the polyether compound having a polymerizable unsaturated group will be referred to as "polyether compound B." The production process for polyether compound A and the production process for polyether compound B will be described in order below.

[0016] <Production process of polyether compound having hydroxyl groups> In the process for producing polyether compound A of this embodiment, an initiator having active hydrogen is contacted with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst, and the alkylene oxide in the alkylene oxide-containing raw material is polymerized with the initiator.

[0017] (Alkylene oxide-containing raw material) The alkylene oxide-containing raw material contains alkylene oxide (hereinafter also referred to as "AO"), which is selected depending on the structural unit of the polyoxyalkylene chain of the polyether compound A to be produced. Examples of AO include ethylene oxide (hereinafter also referred to as "EO"), propylene oxide (hereinafter also referred to as "PO"), 1,2-butylene oxide, and 2,3-butylene oxide. From the viewpoint of reactivity, the AO is preferably an AO having 3 or more carbon atoms. As the AO having 3 or more carbon atoms, an AO having 3 to 5 carbon atoms is preferred, and PO is more preferred. The AO-containing raw material may contain one type of AO or two or more types of AO.

[0018] The AO-containing raw material may contain, in addition to AO, components other than AO (hereinafter also referred to as "impurities"). The crude product obtained in the synthesis of AO contains impurities. Normally, the crude product is purified, but some impurities remain even after the purification process. Furthermore, the impurity content may vary depending on the lot, even for the same product. Although impurities vary depending on the AO synthesis method, examples of impurities include water, aldehydes, acids, methanol, methyl formate, and chlorine. Examples of aldehydes include formaldehyde, acetaldehyde, and propionaldehyde. The AO-containing raw material may contain one or more impurities.

[0019] The AO content (AO purity) of the AO-containing raw material is preferably 97% by mass or more, more preferably 98% by mass or more, and even more preferably 99% by mass or more, based on the total mass of the AO-containing raw material. The total content of AO and impurities does not exceed 100% by mass based on the total mass of the AO-containing raw material.

[0020] The total aldehyde content of the AO-containing raw material is less than 15 ppm, preferably less than 14 ppm, and more preferably less than 13 ppm, based on the total mass of the AO-containing raw material. When the aldehyde content is equal to or less than the upper limit, the degree of unsaturation of the polyether compound A can be reduced. The total aldehyde content of the AO-containing raw material is preferably 0 ppm or more, more preferably 0.5 ppm or more, based on the total mass of the AO-containing raw material. When the total aldehyde content is equal to or more than the above lower limit, the performance of the obtained polyether compound A is superior. The upper limit and the lower limit can be combined as appropriate.

[0021] The acetaldehyde content of the AO-containing raw material is preferably less than 10 ppm, more preferably less than 9.5 ppm, even more preferably less than 9 ppm, and particularly preferably less than the detection limit, based on the total mass of the AO-containing raw material. The detection limit of acetaldehyde is usually 0.1 ppm. When the acetaldehyde content is equal to or less than the upper limit, the degree of unsaturation of the polyether compound A can be further reduced.

[0022] The AO-containing raw material may be selected from commercially available AO-containing raw materials so that the impurity content falls within a desired range, or may be produced by a known production method. For example, the target AO-containing raw material may be obtained by synthesizing AO by a known method and adjusting the impurity content of the resulting crude product containing AO, or by adjusting the impurity content of a commercially available AO-containing raw material. Examples of methods for adjusting the impurity content include a method of reducing the impurity content by a purification treatment and a method of adding impurities. Examples of purification treatment include washing with water and drying.

[0023] The type and content of impurities in the crude product or AO-containing raw material can be adjusted by the AO synthesis method and purification treatment conditions.

[0024] (initiator) The number of active hydrogens in the initiator is preferably 1 or more, more preferably 1 to 10, even more preferably 1 to 8, and particularly preferably 1 to 6. The number of active hydrogens in the initiator is preferably selected depending on the number of hydroxyl groups per molecule of the polyether compound A to be obtained. The number of active hydrogens in the initiator and the number of terminal groups in the polyether compound A are the same. The initiator may be used alone or in combination of two or more kinds.

[0025] The initiator preferably has a hydroxyl group as the active hydrogen-containing group. The initiator having one hydroxyl group is preferably a monohydric alcohol having a linear or branched hydrocarbon group, such as methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-butyl alcohol, tert-butyl alcohol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, or oleyl alcohol. Examples of initiators having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol. Water is also an example of an initiator having two hydroxyl groups. Examples of initiators having three hydroxyl groups include glycerin, trimethylolpropane, and trimethylolethane. Examples of initiators having four or more hydroxyl groups include pentaerythritol, diglycerin, meso-erythritol, methyl glucoside, sucrose, glucose, sorbitol, dipentaerythritol, trehalose, and diglycerin. Alternatively, a low molecular weight polymer obtained by polymerizing an alkylene oxide with these initiators in the presence of an alkali metal hydroxide may be used as the initiator. The hydroxyl value of the initiator is, for example, preferably from 3 to 842 mgKOH / g, more preferably from 7 to 561 mgKOH / g.

[0026] (Double metal cyanide complex catalyst) A composite metal cyanide complex catalyst (hereinafter also referred to as "DMC catalyst") functions as a polymerization catalyst for alkylene oxide. DMC catalysts are crystalline solids and contain a reaction product of a metal halide salt and a transition metal cyanide compound, organic ligands, and water of crystallization (such as coordinated water) encapsulated in the crystals. In addition, they may contain trace amounts of impurities unavoidable during production in the metal salt, metal compound, etc., and moisture other than water of crystallization. The metal halide salt, transition metal cyanide compound, and organic ligand that can be used are those known in the production of DMC catalysts.

[0027] The DMC catalyst is believed to be represented by Formula 1 below. M 1 a [M 2 (CN) b ] c d(M 1 e X f )·g(Ligand)·h(H2O) Equation 1 In Equation 1, M 1 e X f is a metal halide salt, and M 1 is a metal atom that becomes a cation, X is a halogen atom that becomes a counter anion, and M 2 is the transition metal atom contained in the transition metal cyanide compound and serves as the active site, and Ligand is an organic ligand. a, b, c, d, e, f, g, and h are integers, and a, b, c, e, and f are electrically neutral numbers.

[0028] M 1 Examples of such metals include Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II), Mn(II), Cr(III), Cu(II), Sn(II), Pb(II), Mo(IV), Mo(VI), W(IV), and W(VI). M 2 Examples of such elements include Co(III), Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), V(IV), and V(V). Examples of X include Cl, Br, and I. M 1 e X f The metal halide salt represented by the formula (I) is preferably one or more selected from zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, and zinc acetate. 2In view of the interatomic distance between and X, it is more preferable that the compound contains at least one selected from zinc chloride and zinc bromide. Examples of the ligand (organic ligand) include alcohols, ethers, esters, aldehydes, ketones, amides, nitriles and sulfides, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and polyoxyalkylene poly(or mono)ols. One type of organic ligand may be used, or two or more types may be used. Examples of the alcohol include tert-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, and ethylene glycol mono-tert-butyl ether. Examples of the polyoxyalkylene poly(or mono)ol include polypropylene diol. Tert-butyl alcohol is preferred as the organic ligand.

[0029] A preferred example of a DMC catalyst is zinc hexacyanocobaltate (Zn3[Co(CN)6]2) containing an organic ligand (Ligand), water, and zinc chloride or zinc bromide. Its chemical formula can be Zn3[Co(CN)6]2·d(ZnCl2)·g(Ligand)·h(H2O) or Zn3[Co(CN)6]2·d(ZnBr2)·g(Ligand)·h(H2O).

[0030] The DMC catalyst is preferably a zinc hexacyanocobaltate (Zn3[Co(CN)6]2) complex with tert-butyl alcohol as the ligand. The complex may be coordinated with water and zinc chloride.

[0031] The DMC catalyst may be used in the production of polyether compound A, for example, in a solid state, or in the production of polyether compound A in the form of a slurry in which DMC catalyst particles are dispersed in a dispersion medium (hereinafter also referred to as a "slurry catalyst").

[0032] The slurry catalyst contains a DMC catalyst and a dispersion medium. The slurry catalyst preferably contains a DMC catalyst and a dispersion medium, and may also contain water and impurities that are unavoidable in the production process.

[0033] As the dispersion medium for the slurry catalyst, a known organic solvent for slurry catalysts can be used. For example, the hardly volatile hydroxy compound described in Japanese Patent No. 3194255 can be used. The hydroxy compound is a hydroxyl group-containing compound having 1 to 8 hydroxyl groups and a molecular weight of 100 to 8000, and a compound having an alcoholic hydroxyl group, such as a polyether compound, is preferred. The dispersion medium for the slurry catalyst is preferably a second polyether compound having a hydroxyl group, since it does not become an impurity for the product (polyether compound A) obtained by polymerization of alkylene oxide. That is, the dispersion medium for the slurry catalyst preferably contains a second polyether compound having a hydroxyl group. The Mn of the second polyether compound having a hydroxyl group used as a dispersion medium is preferably 100 to 8,000, more preferably 600 to 3,000. When Mn is equal to or greater than the lower limit, the compound does not act as a catalyst poison, and when Mn is equal to or less than the upper limit, the slurry catalyst is easy to handle. An initiator for polymerizing alkylene oxide may be used as part of the dispersion medium.

[0034] The dispersion medium of the slurry catalyst preferably contains substantially no water. Specifically, the water content of the dispersion medium is preferably 500 ppm or less, more preferably 200 ppm or less, and may be an undetectable amount. The water content of the dispersion medium is the water content measured by the Karl Fischer measurement method.

[0035] The content of the DMC catalyst relative to the total mass of the slurry catalyst is, for example, preferably from 0.001 to 60 mass%, more preferably from 0.003 to 50 mass%, and even more preferably from 0.006 to 30 mass%. In particular, when the dispersion medium is a second polyether compound having a hydroxyl group, the content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably 1 to 60 mass%, more preferably 3 to 40 mass%, and even more preferably 5 to 30 mass%. In particular, when the dispersion medium contains an initiator, the content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably 0.003 to 0.020 mass%, more preferably 0.004 to 0.015 mass%, and even more preferably 0.006 to 0.010 mass%.

[0036] The DMC catalyst can be produced by a known method. For example, a DMC catalyst is synthesized by reacting a metal halide salt with a transition metal cyanide compound, and then coordinating an organic ligand with the resulting reaction product. After synthesizing the DMC catalyst, the water content of the DMC catalyst may be adjusted.

[0037] A metal halide salt and a transition metal cyanide compound are reacted in the presence of water to obtain a reaction product, and an organic ligand is then coordinated in the presence of water to obtain a mixture containing a DMC catalyst and water. Impurities and water may be removed from the mixture, and the water content of the resulting solid may be reduced to a predetermined range, thereby obtaining the DMC catalyst.

[0038] A preferred embodiment of the method for producing a DMC catalyst is, for example, the following method. First, an aqueous solution of a metal halide salt and an aqueous solution of a transition metal cyanide compound are reacted to produce a reaction product. An aqueous solution of an organic ligand is added to the reaction product and stirred to coordinate the organic ligand, yielding a mixture containing a DMC catalyst and water. The resulting mixture is subjected to solid-liquid separation to obtain a solid. The resulting solid is washed with an aqueous solution containing the organic ligand, and this solid-liquid separation procedure is repeated at least once, preferably at least twice. The resulting solid may then be dried so that its moisture content falls within the specified range, and pulverized as necessary.

[0039] The concentration of the metal halide salt in the aqueous solution of the metal halide salt is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, and is preferably equal to or less than the saturated concentration. The concentration of the transition metal cyanide compound in the aqueous solution of the transition metal cyanide compound is preferably 2 to 50 mass%, more preferably 2 to 20 mass%, and even more preferably 3 to 10 mass%. The molar ratio of the metal contained in the metal halide salt to the transition metal contained in the transition metal cyanide compound is preferably 1.6 to 12, and more preferably 1.8 to 8.

[0040] The reaction temperature in the reaction between the aqueous solution of the metal halide salt and the aqueous solution of the transition metal cyanide compound is preferably 10 to 65°C, more preferably 20 to 60°C, and even more preferably 30 to 55°C.

[0041] The concentration of the organic ligand in the aqueous solution of the organic ligand is preferably 10 to 90% by mass, more preferably 25 to 75% by mass, and even more preferably 35 to 65% by mass.

[0042] The temperature at which the organic ligand is coordinated is preferably 10 to 90°C, more preferably 20 to 80°C, and even more preferably 30 to 70°C.

[0043] After the organic ligand is coordinated, it is preferable to carry out solid-liquid separation. For solid-liquid separation, methods known in the art, such as filtration and centrifugation, can be used. The obtained solid contains the DMC catalyst as well as salts (alkali metal halides) generated in the reaction. Therefore, it is preferable to remove the salts by washing the obtained solid. Specifically, an aqueous solution of the organic ligand is added to the obtained solid, the mixture is stirred, and then solid-liquid separation is carried out again. The washing time is preferably 10 to 90 minutes, more preferably 20 to 60 minutes. It is preferable to carry out washing multiple times.

[0044] When producing a slurry catalyst, a method can be used in which a mixed liquid containing a DMC catalyst and water is obtained as described above, impurities and water are removed from the obtained mixed liquid, and then a dispersion medium is added to prepare a slurry containing the DMC catalyst and the dispersion medium. Before adding the dispersion medium, washing with an aqueous solution of an organic ligand may be performed.

[0045] (AO polymerization) By contacting the initiator with the AO-containing raw material in the presence of a DMC catalyst, the AO in the AO-containing raw material is polymerized with the initiator (ring-opening addition polymerization). When a DMC catalyst is used as the polymerization catalyst for AO, the Mw / Mn of the polyether compound A tends to be smaller and the degree of unsaturation of the polyether compound A tends to be smaller than when a polymerization catalyst other than a DMC catalyst is used.

[0046] When the polyoxyalkylene chain of the polyether compound A is a random copolymer chain consisting of PO units and EO units, a preferred method is to contact an initiator with an AO-containing raw material containing PO and EO in the presence of a DMC catalyst to obtain the polyether compound A. The same applies to combinations of two or more AOs other than the combination of PO and EO.

[0047] When the polyoxyalkylene chain of polyether compound A is a block copolymer chain having a block of PO units and a block of EO units, a precursor may be obtained by reacting an initiator with an AO-containing raw material containing PO in the presence of a DMC catalyst, and then the precursor may be reacted with an AO-containing raw material containing EO to obtain polyether compound A. Alternatively, a precursor may be obtained by reacting an initiator with an AO-containing raw material containing EO in the presence of a DMC catalyst, and then the precursor may be reacted with an AO-containing raw material containing PO to obtain polyether compound A. The same applies to combinations of two or more AOs other than the combination of PO and EO.

[0048] The amount of the DMC catalyst used is preferably 1 to 200 ppm, more preferably 5 to 60 ppm, and particularly preferably 10 to 50 ppm, based on the total mass of the polyether compound finally obtained. When the amount of the DMC catalyst used is equal to or greater than the lower limit, the polymerization reaction is likely to proceed. When the amount of the DMC catalyst used is equal to or less than the upper limit, the amount of the DMC catalyst used can be reduced, which is economical.

[0049] The polymerization may be carried out continuously or batchwise, but is preferably carried out batchwise. The polymerization temperature is preferably from 30 to 180°C, more preferably from 70 to 160°C, and even more preferably from 90 to 140°C. The polymerization pressure is preferably 1.0 MPa or less, more preferably 0.8 MPa or less, and even more preferably 0.3 MPa or less. The AO-containing raw material is preferably fed to the reactor at a rate that maintains the reaction temperature. The reaction atmosphere is preferably one that is less susceptible to moisture contamination, and more preferably an inert gas atmosphere such as nitrogen.

[0050] The reaction solution after polymerization contains polyether compound A and a DMC catalyst. It may also contain a stabilizer and trace amounts of impurities. Therefore, it is preferable to purify the reaction solution by filtration.

[0051] <Polyether compounds having hydroxyl groups> The main chain of the polyether compound A is a polymer chain consisting of a residue obtained by removing active hydrogen from an initiator and an oxyalkylene chain containing one or more repeating units based on alkylene oxide (hereinafter, a repeating unit based on a monomer will be simply referred to as a "monomer unit", for example, a repeating unit based on AO will be referred to as an "AO unit"). When the polymer chain has two or more types of AO units, the AO units may form a block polymer or a random polymer. Examples of the oxyalkylene chain include a polymer chain having an EO unit, a polymer chain having a PO unit, a polymer chain having an EO unit and a PO unit, a polymer chain consisting of an EO unit, a polymer chain consisting of a PO unit, a polymer chain consisting of a butylene oxide unit, a polymer chain consisting of a tetramethylene oxide unit, a polymer chain consisting of an EO unit and a PO unit, and a polymer chain consisting of a PO unit and a butylene oxide unit. As the oxyalkylene chain, a polymer chain consisting of an AO unit having 3 or more carbon atoms is preferred, and a polymer chain consisting of a PO unit is particularly preferred. The terminal groups of the polyether compound A are hydroxyl groups. The number of terminal groups of the polyether compound A (i.e., the number of hydroxyl groups) is the same as the number of active hydrogens of the initiator.

[0052] The Mn of polyether compound A is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. When Mn is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When Mn is equal to or less than the upper limit, the viscosity of polyether compound A and polyether compound B can be kept low, making them easy to handle.

[0053] The hydroxyl value of the polyether compound A is preferably 0.5 to 350 mgKOH / g, more preferably 1 to 200 mgKOH / g, and even more preferably 5 to 100 mgKOH / g. When the hydroxyl value is equal to or greater than the lower limit, sufficient curing is likely to be achieved when resinified. When the hydroxyl value is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties are likely to be achieved.

[0054] The hydroxyl value-based molecular weight of polyether compound A is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. When the hydroxyl value-based molecular weight is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When the hydroxyl value-based molecular weight is equal to or less than the upper limit, the viscosity of polyether compound A and polyether compound B can be kept low, making them easy to handle.

[0055] The Mw of polyether compound A is preferably 1,200 to 120,000, more preferably 2,000 to 90,000, and even more preferably 3,000 to 70,000. When the Mw is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When the Mw is equal to or less than the upper limit, the viscosity of polyether compound A and polyether compound B can be kept low, making them easy to handle.

[0056] The Mw / Mn of the polyether compound A is preferably 1.00 to 1.15, more preferably 1.00 to 1.12, and even more preferably 1.00 to 1.10. When the Mw / Mn is equal to or less than the upper limit, the viscosity of the polyether compound A and the polyether compound B can be kept low, making them easy to handle.

[0057] The degree of unsaturation of polyether compound A is preferably 0.001 to 0.040 meq / g, more preferably 0.002 to 0.030 meq / g, and even more preferably 0.003 to 0.010 meq / g. When the degree of unsaturation is not more than the upper limit, polyether B obtained from polyether compound A tends to have good physical properties when used in the applications described below.

[0058] The viscosity of the polyether compound A at a measurement temperature of 25°C is preferably from 100 to 100,000 mPa·s, more preferably from 200 to 80,000 mPa·s, and even more preferably from 400 to 60,000 mPa·s.

[0059] <Method of producing polyether compound having polymerizable unsaturated group> In the process for producing polyether compound B, the hydroxyl group of polyether compound A is converted into a group having a polymerizable unsaturated group. The method for producing the polyether compound B may be the following method (a1), (b1) or (c1). Method (a1): A method in which a compound having a functional group reactive with a hydroxyl group and a polymerizable unsaturated group (hereinafter also referred to as "compound 1") is reacted with the hydroxyl group of polyether compound A to convert the hydroxyl group into a group having a polymerizable unsaturated group. Method (b1): A method in which the hydroxyl groups of polyether compound A are reacted with polyisocyanate to obtain a prepolymer having an isocyanate group at the molecular end, and then a compound having a functional group reactive with an isocyanate group and a polymerizable unsaturated group (hereinafter also referred to as "compound 2") is reacted to convert the hydroxyl groups into groups having a polymerizable unsaturated group. Method (c1): A method in which the hydroxyl groups of polyether compound A are reacted with polyisocyanate to obtain a prepolymer having hydroxyl groups at the molecular terminals, and then compound 1 is reacted to convert the hydroxyl groups into groups having polymerizable unsaturated groups.

[0060] The prepolymer having an isocyanate group at the molecular terminal in the method (b1) and the prepolymer having a hydroxyl group at the molecular terminal in the method (c1) can be obtained by reacting a polyether compound A with a polyisocyanate. If necessary, a urethanization catalyst may be used. One type of polyether compound A may be used, or two or more types may be used in combination.

[0061] Examples of polyisocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. The number of isocyanate groups in the polyisocyanate is preferably 2 to 3, and more preferably 2.

[0062] Examples of the aliphatic polyisocyanate include linear aliphatic polyisocyanates such as tetramethylene diisocyanate, dodecamethylene diisocyanate, and hexamethylene diisocyanate, and branched aliphatic polyisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate.

[0063] Examples of alicyclic polyisocyanates include isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane.

[0064] Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (diphenylmethane 4,4'-diisocyanate, MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.

[0065] Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α,α,α,α-tetramethylxylylene diisocyanate.

[0066] As the polyisocyanate, alicyclic polyisocyanates and aromatic polyisocyanates are preferred, and IPDI, MDI and TDI are more preferred. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

[0067] The functional groups at the molecular terminals of the prepolymer can be controlled by adjusting the molar ratio of the total number of isocyanate groups in the polyisocyanate to the total number of hydroxyl groups in the polyether compound A (hereinafter also referred to as the "NCO / OH ratio"). For example, when producing a prepolymer whose molecular terminals are isocyanate groups, the NCO / OH ratio is preferably 2 to 10, more preferably 2 to 8, even more preferably 2 to 7, and particularly preferably 2 to 5. When producing a prepolymer whose molecular terminals are hydroxyl groups, the NCO / OH ratio is preferably 0.1 to 0.8, more preferably 0.2 to 0.7, and even more preferably 0.3 to 0.6.

[0068] The urethanization catalyst is preferably one or more selected from tertiary amine compounds and organometallic compounds. When a highly reactive polyisocyanate is used, the urethanization catalyst may not be used.

[0069] Examples of tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7.

[0070] The organometallic compound is preferably one or more selected from tin-based compounds and non-tin-based compounds. Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate. Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanium, and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium compounds such as zirconium naphthenate.

[0071] The urethanization catalyst may be used alone or in combination of two or more kinds. When a urethanization catalyst is used, the amount of the urethanization catalyst used is preferably 0.001 to 1.0 parts by mass per 100 parts by mass of the polyether compound A, for example.

[0072] In producing the prepolymer, a solvent may be used, if necessary. The solvent is preferably one or more selected from ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and aromatic hydrocarbons such as toluene and xylene, etc. One solvent may be used alone, or two or more solvents may be used in combination. When a solvent is used, the amount of the solvent used is not particularly limited, but is preferably 100 to 1000 parts by mass per 100 parts by mass of the polyether compound A.

[0073] Examples of methods for producing the prepolymer include a method of mixing polyether compound A, polyisocyanate, and, if necessary, a urethanization catalyst and a solvent. Alternatively, a method may be used in which polyisocyanate is added dropwise to a mixed liquid obtained by mixing polyether compound A, and, if necessary, a urethanization catalyst and a solvent.

[0074] The reaction temperature is preferably 50 to 120° C., more preferably 50 to 100° C. When the reaction temperature is equal to or higher than the lower limit, the urethane reaction is likely to be accelerated. When the reaction temperature is equal to or lower than the upper limit, side reactions other than the urethane reaction are likely to be suppressed.

[0075] When a urethanization catalyst is used, it is preferable to inactivate the urethanization catalyst after the reaction by adding a reaction terminator such as acetylacetone. The reaction terminator may be used alone or in combination of two or more.

[0076] If unreacted polyisocyanate remains after the reaction, the polyisocyanate may be removed by distillation to purify the prepolymer.

[0077] Compound 1 is preferably a compound having one isocyanate group and a polymerizable unsaturated group, more preferably a (meth)acrylate having one isocyanate group, even more preferably an isocyanate alkyl (meth)acrylate, particularly preferably an isocyanate alkyl (meth)acrylate having 8 or less carbon atoms excluding the carbon in the isocyanate group of the isocyanate alkyl group, and most preferably an isocyanate alkyl (meth)acrylate having 4 or less carbon atoms excluding the carbon in the isocyanate group of the isocyanate alkyl group. "(Meth)acrylate" is a general term for acrylate and methacrylate. Examples of compound 2 include 2-isocyanatoethyl (meth)acrylate, isocyanatemethyl (meth)acrylate, etc. Commercially available products include Karenz-AOI and Karenz-MOI (both are product names of Showa Denko KK).

[0078] Compound 2 is preferably a compound having an active hydrogen-containing group such as a hydroxyl group or an amino group, and a polymerizable unsaturated group, more preferably a (meth)acrylate having an active hydrogen-containing group such as a hydroxyl group or an amino group, further preferably a hydroxyalkyl (meth)acrylate or hydroxycycloalkyl (meth)acrylate having one hydroxyl group, and particularly preferably a hydroxyalkyl (meth)acrylate in which the alkyl group has 8 or less carbon atoms. Examples of compound 2 include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, etc. Commercially available products include Light Ester HO-250(N), Light Ester HOP(N), Light Ester HOA(N), Light Ester HOP-A(N), Light Ester HOB(N) (all trade names of Kyoei Chemical Co., Ltd.), and 4-HBA (trade name of Osaka Organic Chemical Industry Co., Ltd.).

[0079] When the composition containing polyether compound B is a photocurable composition, it is preferable that all of the polymerizable unsaturated groups contained in polyether compound B are acryloyloxy groups. Such a polyether compound B can be obtained by using compounds 1 and 2 in which the polymerizable unsaturated groups are acryloyloxy groups.

[0080] In the methods (a1) and (c1), the molar ratio of the amount of compound 1 used to the amount of hydroxyl groups in polyether compound A or the amount of hydroxyl groups in the prepolymer having hydroxyl groups at the molecular terminals is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05. In the method (b1), the molar ratio of the amount of compound 2 used relative to the amount of isocyanate groups in the prepolymer having isocyanate groups at the molecular terminals may be greater than 1. Excess compound 2 remains unreacted and may be contained in the composition containing polyether compound B. The molar ratio is preferably 0.8 to 1.5, more preferably 0.9 to 1.3, and even more preferably 0.95 to 1.1.

[0081] In the methods (a1), (b1), and (c1), the reaction between a hydroxyl group and a functional group capable of reacting with a hydroxyl group, and the reaction between an isocyanate group and a functional group capable of reacting with an isocyanate group can be carried out by methods known in the art. When the reaction is between a hydroxyl group and an isocyanate group, the above-mentioned urethane catalyst may be used as necessary.

[0082] <Polyether Compound Having Polymerizable Unsaturated Group> Polyether compound B is a reaction product of polyether compound A and a compound having a polymerizable unsaturated group. An example of the polymerizable unsaturated group is a carbon-carbon double bond at the molecular terminal. Preferred polymerizable unsaturated groups are a (meth)acryloyl group and a (meth)acryloyloxy group. "(meth)acryloyl group" is a general term for an acryloyl group and a methacryloyl group. "(meth)acryloyloxy group" is a general term for an acryloyloxy group and a methacryloyloxy group.

[0083] Polyether compound B has an average of 1.0 or more terminal groups per molecule. In order to improve the crosslinking reaction and curing properties when resinified, the average number of terminal groups is preferably 1.0 to 8.0, more preferably 1.0 to 6.0, and even more preferably 1.0 to 4.0. The number of terminal groups of polyether compound B is the same as the number of terminal groups of polyether compound A.

[0084] The average number of polymerizable unsaturated groups per terminal group of the polyether compound B is preferably 0.5 to 2.0, more preferably 0.8 to 1.2. When the average number of polymerizable unsaturated groups is equal to or greater than the lower limit, crosslinking reaction and curing properties tend to be good when resinified. When the average number of polymerizable unsaturated groups is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties tend to be obtained.

[0085] The average number of polymerizable unsaturated groups per molecule of polyether compound B is preferably 1.0 to 8.0, more preferably 1.0 to 6.0, and even more preferably 1.0 to 4.0. When the average number of polymerizable unsaturated groups is equal to or greater than the lower limit, crosslinking reaction and curing properties tend to be good when resinified. When the average number of polymerizable unsaturated groups is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties tend to be obtained.

[0086] The Mn of polyether compound B is preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, and even more preferably 2,000 to 100,000. When Mn is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When Mn is equal to or less than the upper limit, the viscosity of polyether compound C can be kept low, making it easy to handle.

[0087] The Mw / Mn of the polyether compound B is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, and even more preferably 1.00 to 1.40. When the Mw / Mn is equal to or less than the upper limit, good elongation properties are easily obtained, and the viscosity is reduced, resulting in good workability.

[0088] When polyether compound B has a urethane bond, the content of the urethane bond relative to the total mass of polyether compound B is preferably from 0.01 to 40 mass%, more preferably from 0.1 to 30 mass%, and even more preferably from 1 to 15 mass%.

[0089] The viscosity of polyether compound B at a measurement temperature of 25° C. is preferably 100 to 100,000 mPa·s, more preferably 200 to 50,000 mPa·s, and even more preferably 500 to 30,000 mPa / s. When the viscosity is equal to or less than the above upper limit, handling is excellent.

[0090] (Composition containing a polyether compound having a polymerizable unsaturated group) The polyether compound B is used in a curable composition. The curable composition is obtained by mixing the polyether compound B with other optional components. As the polyether compound B, only one type may be used, or two or more types may be used in combination. The content of polyether compound B relative to the total mass of the curable composition is preferably 65 mass % or more, more preferably 75 mass % or more.

[0091] (Composition containing a polyether compound having a polymerizable unsaturated group) The polyether compound B is used in a curable composition. The curable composition is obtained by mixing the polyether compound B with other optional components. As the polyether compound B, only one type may be used, or two or more types may be used in combination. The content of polyether compound B relative to the total mass of the curable composition is preferably 65 mass % or more, more preferably 75 mass % or more.

[0092] The curable composition may contain, in addition to the polyether compound B, a compound having a polymerizable unsaturated group other than the polyether compound B (hereinafter also referred to as "other compounds"), a photopolymerization initiator, and other components.

[0093] Examples of other compounds include the following other compounds 1 and 2. The other compound 1 is a compound other than the polyether compound B, and is preferably a compound having one (meth)acryloyloxy group and one or more hydroxyl groups, and more preferably one or two hydroxyl groups. The other compound may be a compound having a polyoxyalkylene chain, and in this case, a compound having no urethane bond or urea bond (a compound produced by a method other than methods (a2) to (c2)) is preferred. The other compound may also be a compound having an aliphatic polyester chain obtained by ring-opening addition polymerization of lactone.

[0094] Examples of other compounds 1 include hydroxyalkyl (meth)acrylates, dihydroxyalkyl (meth)acrylates, lactone-modified hydroxyalkyl (meth)acrylates, polyoxyalkylene diol mono(meth)acrylates, and (meth)acrylic acid-monoepoxide adducts.

[0095] The number of carbon atoms in the hydroxyalkyl moiety of the hydroxyalkyl (meth)acrylate is preferably 2 to 8, more preferably 2 to 6. The number of carbon atoms in the dihydroxyalkyl moiety of the dihydroxyalkyl (meth)acrylate is preferably 2 to 8, more preferably 2 to 6. Specific examples of the hydroxyalkyl (meth)acrylate include the hydroxyalkyl (meth)acrylates exemplified as Compound 2. Of these, 4-hydroxybutyl acrylate and 6-hydroxyhexyl acrylate are preferred in terms of flexibility and low volatility.

[0096] Examples of lactone-modified hydroxyalkyl (meth)acrylates include compounds obtained by ring-opening addition of lactone to the hydroxyalkyl (meth)acrylate exemplified as Compound 2. The number of lactones added is preferably 1 to 3. Examples of lactones include ε-caprolactone, γ-butyrolactone, and γ-valerolactone.

[0097] The (meth)acrylic acid-monoepoxide adduct is preferably a reaction product of (meth)acrylic acid with a glycidyl ether or a glycidyl ester, such as (meth)acrylic acid with phenyl glycidyl ether.

[0098] Among these, hydroxyalkyl (meth)acrylate and (meth)acrylic acid-monoepoxide adduct are preferred because they are easily available industrially and contain few impurities.

[0099] The other compounds 1 may be used alone or in combination of two or more. When the curable composition contains the other compound 1, the content of the other compound 1 relative to the total mass of the curable composition is preferably 1 to 20 mass%, more preferably 1 to 15 mass%. When the content of the other compound 1 is equal to or greater than the above lower limit, the effect of improving adhesion by adding the other compound 1 is likely to be sufficiently obtained. When the content of the other compound 1 is equal to or less than the above upper limit, good physical properties in terms of low cure shrinkage are likely to be obtained.

[0100] The other compound 2 is a compound other than the polyether compound B and the other compound 1, and is preferably a compound having one (meth)acryloyloxy group and not containing a urethane bond. Preferred examples of the other compound 2 include a (meth)acrylate having a long-chain alkyl group with 8 or more carbon atoms and a (meth)acrylate having an amide group. Examples of other compounds 2 other than these include alkyl (meth)acrylates having 7 or less carbon atoms, alkoxyalkyl (meth)acrylates, and (meth)acrylates having an aliphatic cyclic hydrocarbon group.

[0101] When the curable composition contains a long-chain alkyl (meth)acrylate having 8 or more carbon atoms, bubbles in the cured product tend to disappear when the curable composition is sealed under reduced pressure and then cured in a higher-pressure atmosphere (vacuum sealing-pressure increase curing method). The number of carbon atoms in the long-chain alkyl group is preferably 8 to 22, and more preferably 8 to 18. Examples of long-chain alkyl (meth)acrylates include lauryl (meth)acrylate, isostearyl (meth)acrylate, isodecyl (meth)acrylate, etc. Among these, lauryl acrylate and isostearyl acrylate are preferred in terms of flexibility, low viscosity, and low crystallinity.

[0102] As the (meth)acrylate having an amide group, a compound in which the hydrogen atom bonded to the nitrogen atom of (meth)acrylamide is substituted with a hydrocarbon group such as an alkyl group or a divalent organic group is preferred, as this easily prevents whitening of the cured product of the curable composition under humid and hot conditions. Examples of (meth)acrylamide derivatives include 4-(meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide.

[0103] The other compounds 2 may be used alone or in combination of two or more. When the curable composition contains the other compound 2, the content of the other compound 1 relative to the total mass of the curable composition is preferably 1 to 30 mass%, more preferably 1 to 25 mass%. When the content of the other compound 2 is equal to or greater than the above lower limit, the effect of adding the other compound 2 is likely to be sufficiently obtained. When the content of the other compound 2 is equal to or less than the above upper limit, good physical properties in terms of low cure shrinkage are likely to be obtained.

[0104] The curable composition may be a photocurable resin composition or a thermosetting resin composition. Photocurable resin compositions are preferred because they can be cured at low temperatures and have a fast curing rate. When the curable composition is a photocurable resin composition, it preferably contains a photopolymerization initiator. When a photocurable resin composition is used in the manufacture of a display device, for example, high temperatures are not required, so there is little risk of damage to the display device due to high temperatures.

[0105] Examples of the photopolymerization initiator include acetophenone-based, ketal-based, benzoin or benzoin ether-based, phosphine oxide-based, benzophenone-based, thioxanthone-based, and quinone-based photopolymerization initiators. Among these, phosphine oxide-based and thioxanthone-based photopolymerization initiators are preferred, with phosphine oxide-based being preferred in that coloration after the photopolymerization reaction is easily suppressed. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

[0106] The photopolymerization initiator is not particularly limited, and commercially available products can be used, such as IRGACURE 819, IRGACURE TPO, IRGACURE 184, IRGACURE 2959, IRGACURE 1173, IRGACURE 127, IRGACURE 907, IRGACURE OXE01, and IRGACURE OXE02, all manufactured by BASF. When the curable composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of the curable components.

[0107] Examples of other components include tackifiers such as rosin esters, terpene phenols, and hydrogenated terpene phenols; plasticizers such as adipates and phthalates; polyether compounds having no polymerizable unsaturated groups; and polyether polyols having alkoxylated molecular terminals. When the curable composition contains a plasticizer, flexibility and adhesion tend to be improved. The content of these compounds relative to the total mass of the curable composition is preferably 48% by mass or less, and more preferably 28% by mass or less.

[0108] Examples of other components include polymerization inhibitors, photocuring accelerators, chain transfer agents, light stabilizers (such as ultraviolet absorbers and radical scavengers), antioxidants, flame retardants, adhesion improvers (such as silane coupling agents), pigments, and dyes. Among these, it is preferable to include a polymerization inhibitor and a light stabilizer. In particular, by including a polymerization inhibitor in an amount smaller than that of the polymerization initiator, the storage stability of the curable composition can be improved and the molecular weight after curing can be easily adjusted.

[0109] Examples of the polymerization inhibitor include hydroquinone-based (2,5-di-tert-butylhydroquinone, etc.), catechol-based (p-tert-butylcatechol, etc.), anthraquinone-based, phenothiazine-based, and hydroxytoluene-based polymerization inhibitors.

[0110] The ultraviolet absorber is used to prevent photodegradation of the curable composition and improve weather resistance. Examples of the ultraviolet absorber include benzotriazole-based, triazine-based, benzophenone-based, and benzoate-based ultraviolet absorbers. As the benzotriazole-based ultraviolet absorber, for example, those described in paragraph

[0076] of WO 2014 / 017328 can be used.

[0111] The light stabilizer is used to prevent photodegradation of the curable composition and improve weather resistance. Examples of the light stabilizer include hindered amine light stabilizers. Examples of the hindered amine light stabilizer include those described in paragraph

[0077] of WO 2014 / 017328.

[0112] The antioxidant is used to prevent oxidation of the curable composition and improve weather resistance and heat resistance. Examples of the antioxidant include phenolic and phosphorus-based antioxidants. As the phenolic antioxidant, for example, those described in paragraph

[0078] of WO 2014 / 017328 can be used. As the phosphorus-based antioxidant, those described in paragraph

[0078] of WO 2014 / 017328 can be used.

[0113] Also, products containing a mixture of multiple antioxidants, light stabilizers, etc. can be used, such as IRGASTAB PUR68 and TINUVIN B75 manufactured by BASF.

[0114] When the curable composition contains other components, the total content of the other components is preferably 100 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less, per 100 parts by mass of the curable component.

[0115] The content of the chain transfer agent in the curable composition is preferably small, preferably 3 parts by mass or less, more preferably 2 parts by mass or less, per 100 parts by mass of the curable component, and particularly preferably no chain transfer agent is contained.

[0116] (Use of curable composition containing polyether compound having polymerizable unsaturated group) Suitable applications of the curable composition containing polyether compound B include pressure-sensitive adhesives in the fields of various building materials, packaging materials, printing materials, display materials, electrical and electronic component materials, optical component materials, liquid crystal panels, and the like. [Example]

[0117] Hereinafter, the embodiments will be described in more detail with reference to examples, but the present invention is not limited to the following descriptions. Examples 1 to 4 and 9 are working examples, and Examples 5 to 8 are comparative examples.

[0118] [Total aldehydes in AO-containing raw materials] The total aldehyde content relative to the total mass of the AO-containing raw material was determined by titration. Specifically, the total aldehyde content was measured using the following reagents and by the following procedure. (1) Reagents Sodium bisulfite Starch solution (5g / L): Dissolve 5g of soluble starch in approximately 100mL of water, pour into 1L of hot water while stirring, cool and store. 0.05mol / L (0.1N) iodine solution 0.005 mol / L (0.01 N) iodine solution: 0.05 mol / L (0.1 N) iodine solution diluted 10 times Sodium bicarbonate reagent (2) Operation 1) Using a measuring cylinder, measure 150 mL of distilled water that has been pre-cooled to 0-10°C into a 500 mL Erlenmeyer flask with a stopper. 2) Weigh out 0.05 g of sodium bisulfite reagent on a balance and add it. 3) Measure 36 mL of the sample using a measuring cylinder and transfer it to the flask. Then, re-stopper the flask, mix it, and keep the flask at 0-10°C for 15 minutes. 4) Add 150 mL of distilled water, which has been cooled to 0-10°C in advance, to a measuring cylinder and approximately 2 mL of the starch solution. 5) Titrate with 0.05 mol / L iodine solution until just before the end point, and then continue titrating with 0.005 mol / L iodine solution until the blue color no longer disappears within 1 minute. 6) Add 1g of sodium bicarbonate reagent and mix. 7) Titrate with 0.005 mol / L iodine solution until the pale blue color does not disappear within 1 minute, and read the titer. 8) Calculate the total aldehyde content using the following formula: A=(V×0.00029) / (36×0.83)×100 Here, A represents the total aldehyde content (%), and V represents the titer (mL) of 0.005 mol / L iodine solution.

[0119] [Acetaldehyde and PO content in AO-containing raw materials] The acetaldehyde content (ppm) and AO content (mass%) relative to the total mass of the AO-containing raw material were measured using a gas chromatograph (detector: flame ionization detector (FID)) under the following conditions. Column: Capillary, 60 m x 0.32 mm φ, DB-1301ms, film thickness 1.0 μm Oven temperature: 35℃ (12 min) → 10℃ / min → 100℃ (12 min) INJ / DET temperature: 180 / 180℃ Carrier gas: He Air flow rate: 400mL / min H2 flow rate: 30mL / min Carrier flow rate (pressure): 1.3609 mL / min (24.056 psi) Septum purge flow rate: 5 mL / min Split ratio: 50:1 Split flow rate: 68.047 mL / min Total flow: 74.407mL / min Gas saver: 20mL / min Inlet: Back Injection method: Microsyringe, injection volume 2 μL

[0120] [Hydroxyl value and hydroxyl value-equivalent molecular weight] The hydroxyl value (OHV) was calculated in accordance with Method B of JIS K 1557-1:2007. The OHV-equivalent molecular weight was calculated based on the formula "56,100 / hydroxyl value of polyether compound x number of hydroxyl groups of polyether compound." The number of hydroxyl groups of the polyether compound is the number of hydroxyl groups of the initiator used.

[0121] [Unsaturation degree] The degree of unsaturation (USV) of the polyether compound having a hydroxyl group was measured in accordance with JIS K 1557-3:2007.

[0122] [Physical properties of the cured product] A mixture (curable composition) of 100 parts by mass of a polyether compound having a polymerizable unsaturated group and 0.3 parts by mass of a photopolymerization initiator (Irgacure-819, manufactured by BASF) was poured into a silicone mold measuring 5 mm wide, 15 mm long, and 2 mm thick. Under a nitrogen environment, a conveyor-type UV irradiator (manufactured by ORC) was used, and the curable composition was exposed to a HgXe lamp with an irradiance of 100 mW / cm. 2 , cumulative light intensity 3000mJ / cm 2The cured product was used as a test sample. The test sample was measured for elongation (%), 100% modulus (M100, MPa), and breaking strength (MPa) at a tensile speed of 300 mm / min using a tensile testing device (Tensilon VTM (manufactured by Toyo Boardwin Co., Ltd.)).

[0123] [AO-containing raw materials] Nine types of PO (PO(1)-(9)) from different sources and lots were used as AO-containing raw materials. The acetaldehyde content and total aldehyde content of each of PO(1)-(9) are shown in Table 1 below. The PO content (PO purity) of each of PO(1)-(9) was 99% or higher.

[0124] [Production Example 1: Preparation of Polyol P1 (Initiator)] In the presence of a KOH catalyst, PO(1) was polymerized with propylene glycol and then dealkalized to obtain polyoxypropylene diol (hereinafter also referred to as "polyol P1"). The average number of hydroxyl groups per molecule of polyol P1 was 2, and the molecular weight in terms of OHV was 1,000.

[0125] [Production Example 2: Preparation of Polyol P2 (Initiator)] In the presence of a KOH catalyst, PO(1) was polymerized with glycerin, followed by dealkalization and purification to obtain polyoxypropylene triol (hereinafter also referred to as "Polyol P2"). Polyol P2 had an average of 3 hydroxyl groups per molecule and an OHV-equivalent molecular weight of 1,000.

[0126] [Example 1] Using polyol P1 as an initiator, PO(1) was polymerized in the presence of a tert-butyl alcohol zinc hexacyanocobaltate complex catalyst (hereinafter referred to as "TBA-DMC catalyst") until the OHV-equivalent molecular weight reached 12,000, yielding polyether compound A1 having hydroxyl groups. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound A1.

[0127] To 150 g of polyether compound A1, 0.015 g of dibutyltin dilaurate and 3.42 g of 2-isocyanatoethyl acrylate (NCO content: 29.8% by mass) were added, and the mixture was allowed to react at 80°C for 2 hours. The NCO / OH molar ratio of the isocyanate content of 2-isocyanatoethyl acrylate to the hydroxyl group content of polyether compound A1 was set to 0.97. The reaction was terminated when it was confirmed by IR that there was no absorption due to NCO, yielding polyether compound B1 having a polymerizable unsaturated group.

[0128] [Example 2] Using polyol P1 as an initiator, PO(2) was polymerized in the presence of TBA-DMC catalyst until the OHV-equivalent molecular weight reached 18,000, yielding polyether compound A2 having hydroxyl groups. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound A2. Next, polyether compound B2 having a polymerizable unsaturated group was obtained in the same manner as in Example 1, except that polyether compound A2 was used instead of polyether compound A1 and the amount of 2-isocyanatoethyl acrylate added was 2.28 g.

[0129] [Example 3] Using polyol P2 as an initiator, PO(3) was polymerized in the presence of TBA-DMC catalyst until the OHV-equivalent molecular weight reached 15,000, yielding polyether compound A3 having hydroxyl groups. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound A3. Next, polyether compound B3 having a polymerizable unsaturated group was obtained in the same manner as in Example 1, except that polyether compound A3 was used instead of polyether compound A1 and the amount of 2-isocyanatoethyl acrylate added was 4.10 g.

[0130] [Example 4] Using polyol P1 as an initiator, PO(4) was polymerized in the presence of TBA-DMC catalyst until the OHV-equivalent molecular weight reached 22,000, yielding polyether compound A4 having hydroxyl groups. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 (manufactured by BASF) as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound A4. Next, polyether compound B3 having a polymerizable unsaturated group was obtained in the same manner as in Example 1, except that polyether compound A4 was used instead of polyether compound A1 and the amount of 2-isocyanatoethyl acrylate added was 1.86 g.

[0131] [Example 5] Polyether compound A5 having a hydroxyl group and polyether compound B5 having a polymerizable unsaturated group were produced in the same manner as in Example 1, except that PO(5) was used instead of PO(1).

[0132] [Example 6] Polyether compound A6 having a hydroxyl group and polyether compound B6 having a polymerizable unsaturated group were produced in the same manner as in Example 2, except that PO(6) was used instead of PO(2).

[0133] [Example 7] Polyether compound A6 having a hydroxyl group and polyether compound B6 having a polymerizable unsaturated group were produced in the same manner as in Example 3, except that PO(7) was used instead of PO(3).

[0134] [Example 8] Polyether compound A8 having a hydroxyl group and polyether compound B8 having a polymerizable unsaturated group were produced in the same manner as in Example 4, except that PO(8) was used instead of PO(4).

[0135] [Example 9] Using polyol P1 as an initiator, PO (9) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 12,000, yielding polyether compound A9. The polymerization was carried out with the addition of 0.1% by mass of BASF's Irganox 1010 as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound A9. Next, polyether compound B9 having a polymerizable unsaturated group was obtained in the same manner as in Example 1, except that polyether compound A9 was used instead of polyether compound A1.

[0136] Table 1 shows the number of functional groups of the initiator of polyether compound A in each example, the molecular weight in terms of OHV, USV, and the physical properties of the cured product of polyether compound B in each example.

[0137] [Table 1]

[0138] Comparing Example 1 and Example 5, in which Polyether Compound B was produced under the same conditions except for the AO-containing raw material, Example 1 had a superior breaking strength of the cured product. Similar trends were also confirmed in comparisons between Example 2 and Example 6, Example 3 and Example 7, Example 4 and Example 8, and Example 9 and Example 5.

Claims

1. A method for producing a polyether compound having a polymerizable unsaturated group, comprising: contacting an initiator having active hydrogen with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst to polymerize the alkylene oxide in the alkylene oxide-containing raw material with the initiator, and converting the hydroxyl group of the resulting polyether compound having a hydroxyl group into a group having a polymerizable unsaturated group; The alkylene oxide-containing feedstock has a total aldehyde content of less than 15 ppm, based on the total mass of the alkylene oxide-containing feedstock, as measured by titration.

2. 2. The method according to claim 1, wherein the alkylene oxide-containing feedstock has an acetaldehyde content of less than 10 ppm based on the total mass of the alkylene oxide-containing feedstock.

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