Polyalkylene oxide composition and building material using same

Abstract

To provide a polyalkylene oxide composition that exhibits low contamination and high solubility, and has excellent handleability, and to obtain a building material using the same and having excellent productivity and bleed resistance.SOLUTION: A polyalkylene oxide composition (A) is provided, including : a polyalkylene oxide (A1) having a propylene oxide residue and 3 to 8 hydroxyl groups; and a polyalkylene oxide (A3) having a propylene oxide residue and / or an ethylene oxide residue and 2 hydroxyl groups, the total content ratio of which is 80 wt.% or more, wherein the unsaturation degree of the polyalkylene oxide composition (A) is less than 0.07 meq / g, and a molar ratio between polyalkylene oxide (A1) and polyalkylene oxide (A3) is in the range of 86 / 14 to 99.99 / 0.01.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to polyalkylene oxide compositions and building materials using the same. [Background technology]

[0002] It is known industrially that polyalkylene oxides are produced by addition polymerization of alkylene oxides such as propylene oxide and ethylene oxide using an alkali metal such as potassium hydroxide as a catalyst. However, when polyalkylene oxides are produced by this method, the resulting polyalkylene oxides have problems in that a large amount of monool is by-produced, making it difficult to increase the molecular weight, and the polyalkylene oxides contain a large amount of low-molecular-weight components having unsaturated groups. When such highly unsaturated polyalkylene oxides are used as plasticizers for building materials such as modified silicone sealants and urethane sealants, the compatibility with the building materials is insufficient due to the allyl group at the molecular end, and low-molecular-weight components tend to bleed over time.

[0003] Patent Document 1 discloses a polyalkylene oxide with a significantly narrow molecular weight distribution and a low degree of unsaturation. However, because such polyalkylene oxides contain almost no low-molecular-weight components, when used as plasticizers for building materials, etc., they have a high bleeding-suppressing effect, but are insufficiently compatible with building materials, resulting in problems such as time-consuming composition preparation, poor handling, and poor productivity. Furthermore, because they have a high molecular weight and contain hydroxyl groups at almost all molecular ends, they have low fat solubility, low compatibility, and poor compatibility.

[0004] That is, there has been a demand for a polyalkylene oxide composition that has a low degree of unsaturation, is less likely to stain, exhibits good compatibility, and is easy to handle. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6878765 Summary of the Invention [Problem to be solved by the invention]

[0006] One aspect of the present invention is to provide a polyalkylene oxide composition that exhibits low staining properties and good compatibility, and a building material using the same that has good bleeding resistance and productivity. [Means for solving the problem]

[0007] The various aspects are [1] to [7] shown below. [1] A polyalkylene oxide composition (A) comprising: a polyalkylene oxide (A1) having a propylene oxide residue and 3 to 8 hydroxyl groups; and a polyalkylene oxide (A3) having a propylene oxide residue and / or an ethylene oxide residue and two hydroxyl groups, the total content of which is 80% by weight or more, The polyalkylene oxide composition (A) has a degree of unsaturation of less than 0.07 meq / g, and the molar ratio of polyalkylene oxide (A1) to polyalkylene oxide (A3) is in the range of 86 / 14 to 99.99 / 0.01. [2] The polyalkylene oxide composition (A) according to claim 1, wherein the polyalkylene oxide (A3) consists of only propylene oxide residues and / or ethylene oxide residues and two hydroxyl groups. [3] The polyalkylene oxide composition (A) according to [1] or [2], wherein the molecular weight of the polyalkylene oxide (A3) with the highest peak intensity measured by MALDI-TOF-MS is in the range of 1,000 or more and less than 5,500. [4] The polyalkylene oxide composition (A) according to any one of [1] to [3], wherein the polyalkylene oxide composition (A) has a number average molecular weight calculated by gel permeation chromatography (GPC) of 2,000 or more and less than 20,000. [5] A plasticizer comprising the polyalkylene oxide composition (A) according to any one of [1] to [4]. [6] A building material containing the plasticizer described in [5]. [7] The building material according to [6], which comprises a polymer having an alkylene oxide residue, and the polymer is a modified silicone or polyurethane. [Effects of the Invention]

[0008] The polyalkylene oxide composition according to one embodiment of the present invention exhibits low contamination, high compatibility, and excellent handleability. Furthermore, by using the polyalkylene oxide composition as a plasticizer for building materials and the like, building materials with good bleeding resistance can be produced with high productivity. DETAILED DESCRIPTION OF THE INVENTION

[0009] Exemplary embodiments for carrying out the present invention are described in detail below. <Polyalkylene oxide composition (A)> A polyalkylene oxide composition (A) according to one embodiment of the present invention comprises a polyalkylene oxide (A1) having a propylene oxide residue and 3 to 8 hydroxyl groups, and a polyalkylene oxide (A3) having a propylene oxide residue and / or an ethylene oxide residue and two hydroxyl groups, the total content of which is 80% by weight or more, wherein the polyalkylene oxide composition (A) has a degree of unsaturation of less than 0.07 meq / g and the molar ratio of polyalkylene oxide (A1) to polyalkylene oxide (A3) is in the range of 86 / 14 to 99.99 / 0.01.

[0010] The degree of unsaturation of the polyalkylene oxide composition (A) is less than 0.07 meq / g. If the degree of unsaturation of the polyalkylene oxide composition (A) is 0.07 meq / g or more, the composition will contain a large amount of low-molecular-weight components such as monools having unsaturated groups at the molecular terminals, which tend to bleed over time. Furthermore, the composition will have insufficient fat solubility and reduced compatibility and wettability with other materials, such as building materials, due to the presence of allyl groups at the molecular terminals, making it difficult to use. Furthermore, the large amount of unsaturated groups tends to reduce chemical stability and increase colorability, making it difficult to use in applications such as building materials and cosmetics, which require high stability and appearance.

[0011] The degree of unsaturation of the polyalkylene oxide composition (A) is not particularly limited as long as it is less than 0.07 meq / g, but since the inclusion of a trace amount of unsaturated monool makes it easier to achieve both stain resistance and compatibility, it is preferably in the range of 0.015 to 0.05 meq / g, and more preferably in the range of 0.025 to 0.04 meq / g.

[0012] Such a low-unsaturation polyalkylene oxide composition (A) can be obtained by ring-opening polymerization of an alkylene oxide using two or more active hydrogen-containing compounds as initiators in the presence of a catalyst such as, but not limited to, a phosphazene compound, an iminophosphazene compound, a composite metal cyanide complex (DMC), trispentafluorophenyl borate, or cesium hydroxide. Alternatively, polyalkylene oxide (A1) may be produced by ring-opening polymerization of an alkylene oxide using one active hydrogen-containing compound as an initiator, and then mixed with polyalkylene oxide (A3), etc. For applications requiring stronger stain resistance, ring-opening polymerization of an alkylene oxide using two or more active hydrogen-containing compounds as initiators in the presence of a phosphazene compound and a Lewis acid catalyst, or an iminophosphazene compound and a Lewis acid catalyst, can further reduce monools having unsaturated groups, and although plasticizing effect and compatibility may be reduced, stain resistance may be improved.

[0013] Here, the "degree of unsaturation (meq / g)" of the polyalkylene oxide (A) refers to the amount of unsaturated groups contained in 1 g of the polyalkylene oxide, and corresponds to the number of unsaturated mono-ols contained in the polyalkylene oxide. That is, the higher the degree of unsaturation, the more unsaturated mono-ols there are, and the lower the degree of unsaturation, the fewer unsaturated mono-ols there are.

[0014] In this embodiment, the degree of unsaturation of the polyalkylene oxide was measured in accordance with the NMR method described in Kobunshi Ronbunshu 1993, 50, 2, 121-126. In this embodiment, since the polyalkylene oxide having a small amount of unsaturated monool is the object of measurement, the number of scans in the NMR measurement is 500 or more to improve the measurement accuracy.

[0015] The molar ratio of polyalkylene oxide (A1) to polyalkylene oxide (A3) in the polyalkylene oxide composition (A) is in the range of 86 / 14 to 99.99 / 0.01. If the polyalkylene oxide (A3) is not contained in addition to the polyalkylene oxide (A1), compatibility with building materials and the like is poor, resulting in low-molecular-weight components such as unsaturated monools easily bleeding out and poor stain resistance. In addition, the polyalkylene oxide (A1) having 3 to 8 hydroxyl groups and having low fat solubility is poor in building materials, requiring time for mixing, resulting in poor handleability and productivity, making it difficult to use. Furthermore, if the content of polyalkylene oxide (A3) relative to polyalkylene oxide (A1) exceeds 14% in molar ratio (molar ratio: less than 86 / more than 14), stain resistance becomes insufficient and the composition is difficult to use.

[0016] In particular, the molar ratio of polyalkylene oxide (A1) to polyalkylene oxide (A3) in the polyalkylene oxide composition (A) is preferably in the range of 95 / 5 to 99.99 / 0.01, more preferably 97 / 3 to 99.8 / 0.2, and most preferably 97 / 3 to 99 / 1, since this easily achieves both higher stain resistance and good compatibility. The method for calculating the molar ratio of polyalkylene oxide (A1) to polyalkylene oxide (A3) in the polyalkylene oxide composition (A) is not particularly limited. When the ratio of initiators used as raw materials is known, the approximate ratio may be calculated using the charge ratio. Alternatively, the ratio can be calculated by fractionating each component or by various analyses.

[0017] The polyalkylene oxide composition (A) may contain other components in addition to the polyalkylene oxide (A1) and polyalkylene oxide (A3) described above. Among these, it is preferable to contain, in addition to the polyalkylene oxide (A3), a monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group at its terminal, in order to improve the fat solubility and stain resistance of the polyalkylene oxide composition (A) and to improve compatibility with building materials and the like and plasticizing effect, and the molar ratio of the polyalkylene oxide (A1) to the polyalkylene oxide (A2) is preferably in the range of 86 / 14 to 99.99 / 0.01.

[0018] The peak top molecular weights (M) of the polyalkylene oxide (A1) and the polyalkylene oxide (A3) in the polyalkylene oxide composition (A) measured by MALDI-TOF-MS preferably satisfy the following relational expression:

[0019] Peak top molecular weight of (A3) × 6 > Peak top molecular weight of (A1) It is preferable that the peak top molecular weight of the polyalkylene oxide (A1) is less than 6 times the peak top molecular weight of the polyalkylene oxide (A3) according to the above formula, because this will result in higher stain resistance and make it more likely to function as a compatibilizer.

[0020] In particular, the peak top molecular weight of the polyalkylene oxide (A1) is preferably higher than the peak top molecular weight of the polyalkylene oxide (A3), since this will more easily act as a compatibilizer and will more likely have a high plasticizing effect, and it is preferable that the following formula is satisfied: Peak top molecular weight of (A3) × 4 > Peak top molecular weight of (A1) > Peak top molecular weight of (A3). The number average molecular weight of the polyalkylene oxide composition (A), calculated by gel permeation chromatography (GPC), is preferably 2,000 or more and less than 20,000, more preferably 2,500 or more and less than 13,000, and most preferably 3,000 or more and less than 10,000, in order to achieve low contamination and even more excellent plasticizing effects. The hydroxyl value (mgKOH / g) of the polyalkylene oxide composition (A) is not particularly limited, but is preferably 3 or more and 250 or less, more preferably 5 or more and 180 or less, and most preferably 8 or more and 70 or less.

[0021] The polyalkylene oxide composition (A) may contain, as necessary, antioxidants, light stabilizers, solvents, leveling agents, plasticizers, antistatic agents, catalysts, reaction retarders, coloration inhibitors, antifoaming agents, foam stabilizers, foaming agents, and other additives. Among these, it is preferable to include at least one of antioxidants and light stabilizers, as these tend to improve chemical stability and inhibit degradation and odor of the polyalkylene oxide. The content of additives in the polyalkylene oxide composition (A) is not particularly limited, but is preferably 0.01% by weight to 20% by weight, and more preferably 0.03% by weight to 0.5% by weight, which tends to reduce bleeding of the additives and improve stain resistance. In the case of solvents, the content is preferably 1% by weight to 90% by weight, and more preferably 1% by weight to 60% by weight, which tends to be economical.

[0022] The antioxidant is not particularly limited, and examples thereof include compounds that have the effect of suppressing oxidation of polymer chains, such as thioether compounds, phosphorus-based antioxidants, and hindered phenol compounds, and examples of such compounds include Irganox manufactured by Ciba Corporation and Adekastab manufactured by Adeka Corporation. Among these, hindered phenol antioxidants are preferred, and it is particularly preferred to use one or more antioxidants selected from Irganox-1010, Irganox-1024, Irganox-1035, Irganox-1076, Irganox-1081, and Irganox-1098 manufactured by Ciba Japan, as these easily provide antioxidant properties for polyalkylene oxide chains and are less likely to cause odor.

[0023] The light stabilizer is not particularly limited, but examples include compounds that have the effect of imparting light resistance and weather resistance, such as ultraviolet absorbers such as benzotriazole compounds, triazine light stabilizers, benzophenone light stabilizers, and benzoate compounds, and hindered amine light stabilizers, trade names of which include Tinuvin manufactured by Ciba Japan. Of these, it is preferable to use one or more light stabilizers selected from Tinuvin 234, Tinuvin 144, Tinuvin C353, and Tinuvin B75. These antioxidants and light stabilizers can also be used in combination.

[0024] The solvent is used for the purpose of diluting the curable resin composition to reduce its viscosity and improve its workability, and examples thereof include petroleum-based solvents such as acetone, methyl ethyl ketone, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, dipropyl ether, n-hexane, n-heptane, toluene, xylene, cyclohexane, and mineral spirits.

[0025] Examples of the leveling agent include an acrylic leveling agent, a fluorine-based leveling agent, and a silicone-based leveling agent.

[0026] The plasticizer is not particularly limited and includes, for example, phthalate esters, non-aromatic dibasic acid esters, aliphatic esters, esters of polyalkylene glycols, phosphate esters, trimellitic acid esters, chlorinated paraffins, hydrocarbon oils, process oils, polyethers, epoxy plasticizers, polyester plasticizers, etc., preferably phthalate esters. Specific examples include dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, tricresyl phosphate, tributyl phosphate, epoxidized soybean oil, and benzyl epoxy stearate.

[0027] The antistatic agent is not particularly limited, but examples thereof include alkali metal salts and ionic liquids, such as lithium salts such as lithium bis(trifluoromethanesulfonyl)imide, quaternary ammonium salts, imidazolium salts, phosphonium salts, and pyridinium salts.

[0028] The catalyst is not particularly limited, and examples thereof include polyalkylene oxide synthesis catalysts, urethanization catalysts, modified silicone curing catalysts, etc. For example, examples of polyalkylene oxide synthesis catalysts include iminophosphazenium compounds, phosphazene compounds, composite metal cyanide complexes (DMC), trispentafluorophenyl borate, cesium hydroxide, etc. Examples of urethanization catalysts and modified silicone curing catalysts include organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and tin 2-ethylhexanoate, iron compounds such as iron acetylacetonate and iron chloride, lead compounds such as lead octoate, bismuth compounds such as bismuth octoate, titanium compounds, zirconium compounds, platinum compounds, and tertiary amine catalysts such as triethylamine and triethylenediamine, and preferably at least one selected from organic tin compounds, lead octoate, bismuth octoate, and platinum compounds.

[0029] Examples of the reaction retarder include acid compounds such as acidic phosphate esters, keto-enol tautomeric compounds such as acetylacetone and ethyl acetoacetate, and low molecular weight diols.

[0030] The viscosity of the polyalkylene oxide composition (A) at 25°C is not particularly limited, but is typically from 1 mPa·s to 300,000 mPa·s. In particular, a viscosity of from 10 mPa·s to 50,000 mPa·s is preferred, and a viscosity of from 100 mPa·s to 10,000 mPa·s is even more preferred, as this enhances the plasticizing effect and facilitates better handling. Having a viscosity of the polyalkylene oxide composition (A) at 25°C within the above range facilitates stirring and handling of the composition when stirring with various stirrers to prepare the polyalkylene oxide composition (A) or when mixing it with building materials, etc., using a heated kneader, and is therefore preferred because it facilitates the development of a high plasticizing effect. Furthermore, since the polyalkylene oxide composition (A) has few unsaturated groups and tends to have excellent chemical stability, it is easy to suppress odor and discoloration after storage in a heat-resistant environment. In particular, since it is easy to use in applications with stricter odor and appearance requirements, such as residential building materials, it preferably has an odor index of less than 10 and a Hazen color number of less than 200 after storage for 18 hours at 50°C, and more preferably has an odor index of less than 5 and a Hazen color number of less than 100 after storage for 18 hours at 50°C. Such a polyalkylene oxide composition (A) that is easy to suppress odor and discoloration after storage in a heat-resistant environment is easily obtained by, but not limited to, synthesizing it at a low temperature of 130°C or less using an iminophosphazenium catalyst, removing the catalyst, and suppressing thermal history and side reactions during production. Although not particularly limited, it is preferable to use a hindered phenol-based antioxidant, because this more easily suppresses discoloration over time due to allyl groups and the like during storage in a heat-resistant environment and also easily suppresses discoloration after heat-resistant storage after production. Among these, it is preferable to use a hindered phenol-based antioxidant with a molecular weight of 300 or more during production, because this significantly reduces odor generation even when the product is placed in an environment where the temperature rises during use or after application, and it is easy to suppress odor for a long period of time and to suppress discoloration over time. When using a hindered phenol-based antioxidant with a molecular weight of 300 or more, the amount used is preferably within the range of the additive amount described above, but is more preferably in the range of 0.04% by weight to 0.2% by weight, and most preferably in the range of 0.06% by weight to 0.1% by weight, because this effectively suppresses bleeding over time and significantly suppresses discoloration and odor over time even after storage in a heat-resistant environment.

[0031] The odor index is a numerical value that quantifies the level of odor using the human sense of smell, and is a value determined by the following formula using the dilution ratio at which odorless air is mixed with the air volume at the time of opening to make the odor undetectable. In this specification, the average value of the judgments made by two people was used.

[0032] Odor index = 10 x Log 10 Dilution ratio In addition, in order to improve the compatibility of the polyalkylene oxide composition (A) with building materials, all or part of the hydroxyl groups at the molecular terminals can be blocked by acetylation, etherification, urethane modification, etc., as necessary, depending on the polarity, etc., of the building materials to be mixed, thereby further reducing the hydrophilicity.

[0033] The preparation of the polyalkylene oxide composition (A) is not particularly limited as long as it can uniformly disperse the raw materials contained therein, and various conventional stirring methods can be used, such as a method of stirring using a stirrer. Examples of stirrers include general-purpose stirrers, planetary mixers, disperser dispersers, dissolvers, kneaders, mixers, laboplastomills, and planetary mixers. Among these, general-purpose stirrers, disperser dispersers, and dissolvers are preferably used. Alternatively, the respective initiators may be mixed and reacted with the alkylene oxide, and then the resulting mixture may be prepared in one shot. <Polyalkylene oxide (A1)> The polyalkylene oxide composition (A) contains, as an essential component, a polyalkylene oxide (A1) having a propylene oxide residue and 3 to 8 hydroxyl groups.

[0034] The polyalkylene oxide (A1) may contain, in addition to a propylene oxide residue, an alkylene oxide residue having 2 or more carbon atoms. The alkylene oxide residue having 2 or more carbon atoms is not particularly limited, and examples thereof include alkylene oxide residues having 2 to 20 carbon atoms. Specific examples include ethylene oxide residue, 1,2-butylene oxide residue, 2,3-butylene oxide residue, isobutylene oxide residue, butadiene monoxide residue, pentene oxide residue, styrene oxide residue, and cyclohexene oxide residue. Among these alkylene oxide residues, ethylene oxide residue is preferred because the raw materials for obtaining the polyalkylene oxide (A1) are easily available and have high industrial value.

[0035] The polyalkylene oxide (A1) may contain only a single alkylene oxide residue or two or more types of alkylene oxide residues as the alkylene oxide residue having two or more carbon atoms. When two or more types of alkylene oxide residues are contained, for example, one type of alkylene oxide residue may be linked in a chain to another alkylene oxide residue, or two or more types of alkylene oxide residues may be linked randomly.

[0036] Among these, although not particularly limited, it is preferable that the polyalkylene oxide (A1) contains ethylene oxide residues in addition to a propylene oxide residue having a carbon number of 3 as an essential component, because this improves dispersibility with building materials, including fillers, and thus tends to improve the flatness of applied products such as coating films and enhances their design. By containing a small amount of ethylene oxide residues in addition to the propylene oxide residues having a carbon number of 3, the dispersibility of fillers and the like tends to be improved while maintaining high compatibility with building materials containing propylene oxide residues in the main chain. In this case, the ratio of propylene oxide residues to ethylene oxide residues is preferably in the range of 99 / 1 to 70 / 30, because this tends to further improve the dispersibility of fillers and the like. Furthermore, the structure of such polyalkylene oxide (A1) is more preferably a block adduct, and a suitable structure can be represented by the following general formula:

[0037] [ka]

[0038] [In the above general formula (1), R represents an active hydrogen-containing compound (R[-H] m is an m-valent group obtained by removing m active hydrogen atoms from (Z), Z is an alkylene group or cycloalkylene group having 2 to 12 carbon atoms, and A is an alkylene group having 3 carbon atoms. When there are multiple Z or A, they may be the same or different. m is 3 to 8, p is 0 or an integer of 1 to 500, q is an integer of 1 to 1000, and r is an integer of 1 to 500.] The relationship between p, q, and r in the general formula (1) preferably satisfies p+q>2r (p+q is 3 to 1000, q is 3 to 1000, and r is 1 to 100) because it is less likely to crystallize and more likely to exhibit flexibility at low temperatures. It is more preferable that p+q>3r (p+q is 5 to 300, q is 5 to 300, and r is 1 to 100), and most preferably that 10r>p+q>2r (where p+q is 7 to 150, q is 7 to 150, and r is 3 to 50). Furthermore, m in the general formula (1) is preferably 3 to 6, more preferably 3 to 4, and most preferably 3, because it is more likely to improve compatibility with the main chain polymer of the building material.

[0039] The polyalkylene oxide (A1) may contain an initiator residue. The initiator residue is not particularly limited and may contain the residue of any initiator typically used in the production of polyalkylene oxides. Suitable initiator residues include residues of active hydrogen-containing compounds such as hydroxy compounds, amine compounds, carboxylic acid compounds, and thiol compounds. Among these, the initiator residue is preferably a residue of a hydroxy compound having 3 to 8 hydroxyl groups per molecule, and more preferably a residue of a polyether polyol having a molecular weight of 200 to 3,000, because of its versatility, high compatibility, and tendency to produce low coloration. These active hydrogen-containing compounds may be used alone or in combination.

[0040] The polyalkylene oxide (A1) has 3 to 8 hydroxyl groups per molecule. If the number of hydroxyl groups per molecule of the polyalkylene oxide (A1) exceeds 8, the hydrophilicity increases, which reduces compatibility with building materials and makes the building materials more susceptible to moisture absorption, making it difficult to use. If the number of hydroxyl groups per molecule is 2, the viscosity of the polyalkylene oxide composition tends to increase, which reduces the plasticizing effect. If the number of hydroxyl groups per molecule is less than 2, productivity during alkylene oxide addition is poor, making it difficult to use.

[0041] In particular, the number of hydroxyl groups per molecule is preferably in the range of 3 to 6, more preferably 3 to 4, because this reduces hydrophilicity and reduces the hygroscopicity of the building material, and most preferably 3, because this tends to achieve higher compatibility while maintaining a high plasticizing effect. Note that the calculation of the preferred number of hydroxyl groups per molecule does not take into account changes in the number of functional groups due to unsaturated monools.

[0042] The degree of unsaturation of the polyalkylene oxide (A1) is not particularly limited as long as the degree of unsaturation of the polyalkylene oxide composition (A) is less than 0.07 meq / g, but the same preferred range as that of the polyalkylene oxide composition (A) can be exemplified as a preferred range of the polyalkylene oxide (A1).

[0043] The polyalkylene oxide (A1) can be identified by the initiator structure and the alkylene oxide structural unit using MALDI-TOF-MS, and the molecular weight at which the peak intensity of the polyalkylene oxide (A1) is highest (peak top molecular weight) measured by MALDI-TOF-MS is preferably in the range of 2,000 or more and less than 18,000, since this facilitates both a higher plasticizing effect and compatibility. In particular, the peak top molecular weight of the polyalkylene oxide (A1) measured by MALDI-TOF-MS is preferably in the range of 2,500 or more and less than 13,000, and most preferably in the range of 4,000 or more and less than 10,000, since this facilitates low contamination and a more excellent plasticizing effect. Furthermore, if the molecular weight of the polyalkylene oxide (A1) exceeds 30,000, identification by MALDI-TOF-MS tends to be difficult, but if the peak top molecular weight is less than 26,000, analysis is possible.

[0044] The number average molecular weight of the polyalkylene oxide (A1) before mixing can be calculated from the hydroxyl value of the polyalkylene oxide (A1) calculated by the method described in JIS K-1557-1 and the number of hydroxyl groups in one molecule of the polyalkylene oxide (A1).

[0045] The number average molecular weight of the polyalkylene oxide (A1) calculated from the hydroxyl value is not particularly limited, but the range of the preferred peak top molecular weight of the polyalkylene oxide (A1) measured by MALDI-TOF-MS can be exemplified as a preferred molecular weight range. The hydroxyl value (mg KOH / g) of the polyalkylene oxide (A1) is not particularly limited, but is preferably 3 to 250, more preferably 5 to 180, and most preferably 8 to 70. <Polyalkylene oxide (A3)> The polyalkylene oxide composition (A) is characterized by containing, as essential components, a polyalkylene oxide (A3) having propylene oxide residues and / or ethylene oxide residues and two hydroxyl groups, the total content of which is 80% by weight or more, i.e., a diol having propylene oxide residues, ethylene oxide residues, and two hydroxyl groups in a total content of 80% by weight or more, as essential components.

[0046] The inclusion of a small amount of a diol with a similar structure to the polyalkylene oxide (A1) and a relatively low molecular weight in the polyalkylene oxide composition (A) acts as a compatibilizer for building materials containing a large amount of propylene oxide residues and ethylene oxide residues in the molecular chain, making the monool at the unsaturated end less likely to bleed. In addition, building materials such as modified silicone sealants and urethane sealants, which are building materials having alkylene oxide residues, usually contain residues selected from the group consisting of propylene oxide residues and ethylene oxide residues as alkylene oxide residues, and therefore have improved compatibility with the polyalkylene oxide composition (A), resulting in building materials with excellent stain resistance.

[0047] In particular, since compatibility is likely to be higher, the total content of propylene oxide residues and / or ethylene oxide residues and two hydroxyl groups in the polyalkylene oxide (A3) is preferably 90% by weight or more, more preferably 95% by weight or more, and most preferably 100% by weight, i.e., the polyalkylene oxide (A3) is preferably composed of only propylene oxide residues and / or ethylene oxide residues and two hydroxyl groups. Note that the content of the residues and the number of hydroxyl groups in the polyalkylene oxide (A3) do not take into account the unsaturated groups and the decrease in the number of functional groups in the unsaturated monool produced as a small amount by-product.

[0048] The polyalkylene oxide (A3) is not particularly limited as long as the total content of the residue selected from the group consisting of propylene oxide residues and ethylene oxide residues and two hydroxyl groups is 80% by weight or more. However, since propylene oxide residues are often contained as the main component of building materials, which improves compatibility and makes it easier to suppress bleeding, the weight ratio (w / w) of propylene oxide residues to ethylene oxide residues in the polyalkylene oxide (A3) is preferably in the range of 100 / 0 to 70 / 30, more preferably in the range of 100 / 0 to 80 / 20, and most preferably 100 / 0.

[0049] The polyalkylene oxide (A3) may contain an initiator residue. The initiator residue is not particularly limited and may include residues of any initiator typically used in the production of polyalkylene oxides. Examples of suitable initiator residues include residues of active hydrogen-containing compounds such as hydroxy compounds, amine compounds, carboxylic acid compounds, and thiol compounds. Among these, initiators consisting only of propylene oxide residues, ethylene oxide residues, and hydroxyl groups, initiators with a high content of the above residues, and residues of low-molecular-weight initiators are preferred, as they have a high total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups and tend to exhibit higher compatibility. Examples include residues of propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, water, polypropylene glycol with a molecular weight of 1000 or less, polyethylene glycol with a molecular weight of 1000 or less, hexanediol, nonanediol, pentanediol, butanediol, and the like.

[0050] The method for producing such polyalkylene oxide (A3) having a low content of residues other than propylene oxide residues, ethylene oxide residues, and two hydroxyl groups is not particularly limited, but can be achieved by using an initiator consisting only of propylene oxide residues, ethylene oxide residues, and hydroxyl groups, an initiator having a high content of such residues, or a low-molecular-weight initiator, and adding propylene oxide and / or ethylene oxide as the alkylene oxide. Furthermore, when using a low-boiling initiator such as propylene glycol, ethylene glycol, or water, volatilization may occur during synthesis. Therefore, it is preferable, but not limited to, to use a diol initiator to which a small amount of alkylene oxide has been added, such as dipropylene glycol, tripropylene glycol, or tetraethylene glycol. For example, when producing using a combination initiator system, the polyalkylene oxide can be alcoholated with the other initiator using an alkylene oxide polymerization catalyst, and then immediately before the reaction, an initiator consisting only of propylene oxide residues, ethylene oxide residues, and hydroxyl groups can be added and reacted.

[0051] The degree of unsaturation of the polyalkylene oxide (A3) is not particularly limited as long as the degree of unsaturation of the polyalkylene oxide composition (A) is less than 0.07 meq / g, but the same preferred range as that of the polyalkylene oxide composition (A) can be exemplified as a preferred range. The polyalkylene oxide (A3) can be identified by the initiator structure and the alkylene oxide structural unit using MALDI-TOF-MS, and since this makes it easier to achieve both a higher plasticizing effect and a higher compatibility-improving effect and to more easily suppress bleeding, the molecular weight at which the peak intensity of the polyalkylene oxide (A3) is highest (peak top molecular weight) measured by MALDI-TOF-MS is preferably in the range of 1,000 or more and less than 5,500. In particular, the peak top molecular weight of the polyalkylene oxide (A3) measured by MALDI-TOF-MS is preferably 1,500 or more and less than 4,500, and most preferably 1,900 or more and less than 4,000, since this makes it easier to achieve lower contamination, a more excellent plasticizing effect, and improved compatibility.

[0052] The number average molecular weight of the polyalkylene oxide (A3) before mixing can be calculated from the hydroxyl value of the polyalkylene oxide (A3) calculated by the method described in JIS K-1557-1 and the number of hydroxyl groups in one molecule of the polyalkylene oxide (A3), and this value may be used.

[0053] The number average molecular weight of the polyalkylene oxide (A3) calculated from the hydroxyl value is not particularly limited, but a preferable molecular weight range can be, for example, the same range as the preferable peak top molecular weight range of the polyalkylene oxide (A3) measured by MALDI-TOF-MS. <Other polyalkylene oxides> The polyalkylene oxide composition (A) may contain other components in addition to the polyalkylene oxide (A1) and the polyalkylene oxide (A3). Among these, it is preferable to contain the polyalkylene oxide (A2) having a saturated hydrocarbon residue at its terminal and one hydroxyl group, because this exhibits a high plasticizing effect and higher compatibility with building materials having alkylene oxide residues, and is likely to have excellent stain resistance.

[0054] The saturated hydrocarbon group contained in the polyalkylene oxide (A2) is not particularly limited, and examples thereof include residues having a saturated hydrocarbon structure with 1 to 100 carbon atoms. Among these, residues having a saturated hydrocarbon structure with 2 to 100 carbon atoms are preferred because they have higher fat solubility and are more likely to improve compatibility with building materials, and more preferred are residues having a saturated hydrocarbon structure with 2 to 8 carbon atoms because they are less likely to precipitate or solidify at low temperatures in the polyalkylene oxide composition (A) and therefore have good handleability.

[0055] The polyalkylene oxide (A2) is not particularly limited as long as it contains an alkylene oxide residue, but it preferably contains an alkylene oxide residue having 3 carbon atoms because this tends to increase compatibility, and the molecular weight is preferably in the range of 1,000 to 5,500.

[0056] The degree of unsaturation of the polyalkylene oxide (A2) is not particularly limited as long as the degree of unsaturation of the polyalkylene oxide composition (A) is less than 0.07 meq / g, but the same preferred range as that of the polyalkylene oxide composition (A) can be exemplified as a preferred range. <Other> The polyalkylene oxide composition (A) can be reacted with various isocyanates, etc., to form urethane bonds, in the same way as general polyalkylene oxides. In particular, when used as a plasticizer for building materials, etc., it may be used as is, but in order to prepare a product with desired viscosity, hydrophobicity, and reactivity, some or all of the hydroxyl groups may be reacted with isocyanates, etc., to prepare a urethane-modified product.

[0057] The isocyanate used when forming a polyurethane, polyurethane foam, or partially modified urethane product using the polyalkylene oxide composition (A) is not particularly limited, but examples thereof include isocyanates used in ordinary urethane materials, such as hexyl monoisocyanate, cyclohexyl isocyanate, t-butyl isocyanate, octyl isocyanate, dodecyl isocyanate, triethoxysilyl isocyanate, fluorophenyl isocyanate, benzyl isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and lysine diisocyanate. Examples include isocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, pentamethylene diisocyanate, norbornane diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, isocyanate-containing prepolymers obtained by reacting these with polyols, and mixtures of two or more of these. Furthermore, modified products of these isocyanates (for example, modified products containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, an isocyanurate group, an amide group, an imide group, a uretonimine group, a uretdione group, or an oxazolidone group) and condensates (sometimes referred to as polynuclear compounds) of polymethylene polyphenylene polyisocyanate (polymeric MDI) are also included.Among these, it is preferable to use hexyl monoisocyanate, cyclohexyl isocyanate, t-butyl isocyanate, octyl isocyanate, dodecyl isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, pentamethylene diisocyanate, and norbornane diisocyanate, because they are highly versatile and tend to exhibit high strength, transparency, stain resistance, and moisture absorption resistance. The amount of isocyanate used is not particularly limited and can be selected as appropriate, but is usually an amount added such that the molar ratio of active hydrogen groups to isocyanate groups (NCO / OH ratio) is in the range of 0.01 to 5.0, and preferably in the range of 0.2 to 2.0. The polyalkylene oxide composition (A) can also be reacted with a melamine crosslinking agent to form a melamine-modified product modified at any ratio. <Uses of the polyalkylene oxide composition (A)> The application of the polyalkylene oxide composition (A) is not particularly limited, and it can be used for any application, for example, in general applications in which polyalkylene oxides are generally used, specifically urethane foam applications such as flexible polyurethane foams, semi-rigid polyurethane foams, and rigid polyurethane foams, non-foam polyurethane applications such as sealants, waterproof coating materials, pressure-sensitive adhesives, urethane paints, and elastomer materials, and non-urethane applications such as plasticizers, surfactants, and wetting agents.

[0058] Among these, the polyalkylene oxide composition (A) contains a polyalkylene oxide (A3) with a low degree of unsaturation (low unsaturated monool content), a high content of alkylene oxide residues, and a small number of hydroxyl groups, and therefore exhibits low contamination, high compatibility, and excellent handleability, making it suitable for use as a plasticizer. Furthermore, the low content of unsaturated groups provides excellent chemical stability and low coloration, and the low content of impurities makes it suitable for use as a moisturizing component in cosmetics.

[0059] Furthermore, the polyalkylene oxide composition (A) has remarkably good compatibility with polymers containing alkylene oxide residues and is less likely to bleed, making it particularly suitable for use as a plasticizer for building materials, and is most preferably used in building materials containing polymers having alkylene oxide residues, where the polymer is a modified silicone or polyurethane.

[0060] Such building materials include sealants, caulking materials, flooring materials, waterproofing materials, adhesives, paints, etc., and can be suitably used for general housing, condominiums, civil engineering, DIY, repair, ceramic siding, renovation, etc. Among these, modified silicone-based sealants, urethane-based sealants, etc. are preferred, and by using the polyalkylene oxide composition (A) as a plasticizer or reactive plasticizer, building materials with significantly high stain resistance, low coloration, and low odor can be easily obtained, and can be suitably used.

[0061] The method for producing a building material using the polyalkylene oxide composition (A) is not particularly limited. It can be prepared by mixing the main building material components, such as modified silicone or urethane, with fillers and additives, such as calcium carbonate or titanium oxide, in any desired ratio using a kneader or mixer, and then applying the mixture with a spatula, comb, roller, trowel, or rake, or by extrusion or spraying with a sealing gun, or by hand or machine application to form a coating film, film sheet, thick object, or any other desired shape. Furthermore, a compound with anti-sagging properties can be incorporated and applied to vertical surfaces, wall surfaces, curved surfaces, depressions, etc. using a roller, lysine gun, airless gun, or the like to form a coating film or cured product. In particular, the composition is suitable for a wide range of shapes, from thick shapes due to its excellent flexibility to thin shapes due to its excellent physical properties. For example, it is suitable for use in shapes with a thickness of 10 mm or less, and particularly suitable for shapes with a thickness of 5 mm or less. After slight curing, it can also be layered to form even thicker shapes. When used as a sealing material, flooring material, or waterproof coating material, the thickness is preferably 1 to 10 mm, and more preferably 2 to 4 mm.

[0062] When polyalkylene oxide composition (A) is used as a plasticizer for modified silicone sealants or urethane sealants, it can be suitably used in one-component moisture-curing, two-component curing, or 1.5-component sealants. Application methods typically include loading the composition into a sealing gun, applying it directly to a cleaned or primed and dried substrate as needed, and allowing it to harden. For construction applications, the adhesive surface is typically cleaned, a back-up material or bond breaker is applied, masking tape is applied around the joints, and then a primer is applied to the application area as a pretreatment. The sealant is then filled into the desired area, such as the joints, with a sealing gun, and finished with a spatula, followed by cleaning and curing.

[0063] In this case, if the plasticizing effect is small, it takes time to extrude when filling joints, etc., and workability tends to be poor, so it is preferable that the cartridge extrusion time can be completed within 5 seconds, and more preferably within 4 seconds. If the sealant is too viscous, it may take time to clean up any deposits on the surrounding area, or the curable resin composition may stick to the spatula during spatula finishing, making application and molding difficult. Therefore, it is preferable that the composition has a viscosity that allows application with a spatula or trowel, which are common application methods, and is easy to handle.

[0064] The uses of the sealant are not particularly limited, and examples include construction materials such as civil engineering and construction sealants and siding joint caulking. However, the sealant may also be used as a vehicle sealant such as direct glazing or body sealer, a potting material for electrical and electronic equipment, a potting agent for medical use, etc. [Example]

[0065] The present invention will be explained in more detail below with reference to examples, but the present invention should not be construed as being limited to the following examples as long as the gist of the invention is not exceeded. The raw materials and evaluation methods used in the following examples and comparative examples are as follows. (Raw material 1) Polyol (Raw Material 1-1) Polyalkylene Oxide (A1), (AC1) Polyalkylene oxide (A1-1) was prepared by mixing an aqueous solution of tetrakis(1,1,3,3-tetramethylguanidino)iminophosphazenium hydroxide salt (IPZ catalyst aqueous solution) with a trifunctional polypropylene glycol initiator having a molecular weight of 600, and then removing water by dehydration under reduced pressure at 100°C for more than 3 hours. The reaction was then carried out by continuously supplying propylene oxide at a reaction temperature of 90°C and 0.3 MPa. After removing the remaining propylene oxide, the reaction was carried out by continuously supplying ethylene oxide at a reaction temperature of 130°C and 0.4 MPa or less. The resulting trifunctional polyalkylene oxide had a molecular weight of 7000 and an unsaturated group monool content of 0.032 meq / g, and was then obtained by removing the residual monomer and catalyst by conventional methods.

[0066] Polyalkylene oxide (A1-2) was prepared by mixing an aqueous solution of IPZ catalyst with a tetrafunctional pentaerythritol-propylene oxide adduct initiator having a molecular weight of 600, dehydrating the mixture under reduced pressure at 100°C for at least 3 hours to remove water, and then continuously supplying propylene oxide at a reaction temperature of 90°C and a pressure of 0.3 MPa to carry out the reaction. Subsequently, residual monomers and catalyst were removed by standard methods to obtain a tetrafunctional polyalkylene oxide having a molecular weight of 8900 and an unsaturated group monool content of 0.039 meq / g.

[0067] Polyalkylene oxide (A1-3) is a trifunctional polyalkylene oxide having a molecular weight of 2900 and an unsaturated group monool content of 0.024 meq / g, obtained by using no ethylene oxide and reducing the amount of propylene oxide added in the production method of (A1-1).

[0068] Polyalkylene oxide (A1-4) is a bifunctional polyalkylene oxide having a molecular weight of 7000 and an unsaturated group monool content of 0.002 meq / g, synthesized under the same conditions as in the production method of polyalkylene oxide (A1-1), except that an aqueous IPZ catalyst solution and an initiator were mixed and dehydrated, followed by adding and mixing a toluene solution of triisobutylaluminum, removing toluene and by-product isobutane under reduced pressure at 100°C for 3 hours or more, and then reacting propylene oxide at a reaction temperature of 110°C and 0.3 MPa.

[0069] Poly(alkylene oxide) (AC1-1) is a trifunctional poly(propylene oxide)-poly(ethylene oxide) block copolymer with an unsaturation level exceeding 0.07 meq / g, synthesized by conventional methods.

[0070] The polyalkylene oxide (AC1-2) is a tetrafunctional polypropylene oxide having an unsaturation degree of more than 0.07 meq / g, synthesized by a conventional method.

[0071] The properties of the polyalkylene oxides (A1) and (AC1) are summarized in the table below.

[0072] [Table 1]

[0073] (Raw material 1-2) Bifunctional polyalkylene oxide (A3) having a propylene oxide residue, ethylene oxide residue, and hydroxyl group content of 80% by weight or more, and bifunctional polyol (AC3) having a total content of propylene oxide residue, ethylene oxide residue, and hydroxyl group of less than 80%. Polyalkylene oxides (A3-1) and (A3-2) are bifunctional polyalkylene oxides consisting of propylene oxide residues, ethylene oxide residues, and hydroxyl groups, synthesized under the same conditions as polyalkylene oxide (A1-2) using tripropylene glycol (a reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as an initiator, excluding the by-product unsaturated monool.

[0074] Polyalkylene oxide (A3-3) is a bifunctional polyalkylene oxide with a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of 97%, excluding the by-product unsaturated monool, synthesized under the same conditions as polyalkylene oxide (A1-2) using hexanediol (a reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as an initiator.

[0075] Polyalkylene oxide (A3-4) is a bifunctional polyalkylene oxide having a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of 92%, excluding the by-product unsaturated monool, synthesized under the same conditions as polyalkylene oxide (A1-2) using nonanediol (a reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as an initiator.

[0076] The polyol (AC3-1) is a trifunctional polypropylene oxide synthesized by a conventional method, and is a highly hydrophilic polyalkylene oxide containing more than two hydroxyl groups.

[0077] Polyol (AC3-2) is a bifunctional polypropylene oxide containing an aniline residue in the initiator residue, synthesized by a conventional method, and is a bifunctional polyalkylene oxide with a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of 64%.

[0078] Polyol (AC3-3) is a bifunctional polypropylene oxide containing bisphenol A residues as initiator residues, synthesized by a conventional method, and is a bifunctional polyalkylene oxide with a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of 57%.

[0079] Polyol (AC3-4) is a commercially available bifunctional polyoxytetramethylene glycol (PTG2000SN manufactured by Hodogaya Chemical) that does not contain propylene oxide residues or ethylene oxide residues and has a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of less than 80%.

[0080] The properties of the polyalkylene oxide (A3) and polyol (AC3) are summarized in the table below.

[0081] [Table 2]

[0082] (Raw material 2) Additives In the examples and comparative examples, Irganox 1098 (manufactured by BASF Japan Ltd.) was used as the antioxidant and coloring inhibitor. (Method for producing polyalkylene oxide compositions (AA1) to (AA13) and (AC1) to (AC12)) The polyalkylene oxide compositions (AA1) to (AA13) and (AC1) to (AC12) of the Examples and Comparative Examples were obtained by placing the raw materials listed in Tables 3 to 5 in a mayonnaise bottle and stirring and degassing the mixture at room temperature using a disper. (Preparation of a cured product of a building material composition containing a polyalkylene oxide composition) A paste-like composition for building materials was prepared by mixing 100 parts by weight of a commercially available one-component modified silicone sealant having polypropylene oxide residues as the main polymer component with 7 parts by weight of the polyalkylene oxide composition for 15 minutes using a heated mixer 1636 manufactured by Imoto Machinery Works.

[0083] The prepared building material composition was filled into a metal mold with a depth of 2 mm, leveled with a spatula, and left to harden at room temperature for 1 week to form a hardened product. (Performance Evaluation of Polyalkylene Oxide Compositions (A) and (AC)) Cured products were prepared using the polyalkylene oxide compositions (A) and (AC) by the above-mentioned method, and the stain resistance, plasticizing effect, and compatibility were evaluated during the process.

[0084] In addition, polyalkylene oxide compositions (A) and (AC) were added alone to a sample bottle so that the ratio with the air layer was 1:1, and the bottle was sealed. The bottle was heated at 50°C for 18 hours, and the air layer was diluted 5 times and 10 times with fresh air, and the odor index and the color number of the remaining composition were evaluated. <Stain resistance> ◎ (Passed stain resistance): After leaving it at room temperature for one week, there is absolutely no tackiness (stickiness) when touched with the fingers. Good (stain resistance passed): After leaving the product at room temperature for one week, it feels slightly tacky (sticky) to the touch, but no obvious residue remains on the finger that touches it. △ (Failed stain resistance): After leaving the product at room temperature for one week, there is a clear tackiness (stickiness) when touched with the finger, but no clear residue remains on the finger that comes into contact with the product. × (failed contamination resistance): After leaving the product at room temperature for one week, there is a clear tacky (sticky) feeling when touched with the fingers, and residue adheres to the fingers that come into contact with the product. <compatibility> When a commercially available one-component modified silicone sealant and a polyalkylene oxide composition were mixed using the heated mixer 1636, the compatibility was evaluated according to the following criteria. ◎ (Passed compatibility): When the mixture can be visually mixed uniformly after 7 minutes of mixing, and no separation or non-uniformity occurs when left to stand at room temperature. ○ (Compatibility passed): When the mixture can be visually mixed uniformly after 7 to 10 minutes of mixing, and no separation or non-uniformity occurs when left to stand at room temperature. △ (Failed compatibility): When the mixture can be visually mixed uniformly after 10 to 15 minutes of mixing, and no separation or non-uniformity occurs when left standing at room temperature. (Insufficient compatibility) × (Failed compatibility): When the mixture is not visually uniform after 15 minutes of mixing, or when partial separation or non-uniformity occurs after leaving the mixture at room temperature. <Color number and odor index after storage at 50°C> ◎ (Passing stability): After storage at 50°C for 18 hours, the odor index is less than 5 and the Hazen color number is less than 100. ○ (Passed stability): Odor index is 5 or more but less than 10 or Hazen color number is 100 or more but less than 200 after storage at 50°C for 18 hours. × (Failed stability): Odor index is 10 or more or Hazen color number is 200 or more after storage at 50°C for 18 hours.

[0085] Those that passed both the stain resistance and compatibility were judged to be polyalkylene oxide compositions that exhibit low staining properties and good compatibility, and that contribute to the formation of building materials with good bleeding resistance (passed).

[0086] Furthermore, compositions that passed the color number and odor index test at 50°C were judged to have significantly superior stability, compositions that passed the test were judged to have excellent stability and contribute to the formation of more durable building materials, and compositions that passed the test were judged to have ordinary durability. <Examples and Comparative Examples> Example 1 is a polyalkylene oxide composition (AA1) containing 97 parts by weight of polyalkylene oxide (A1-1), 3 parts by weight of a bifunctional polyalkylene oxide (A3-1) consisting only of propylene oxide residues and hydroxyl groups, and 700 ppm of Irganox 1098 as a hindered phenol-based antioxidant with a molecular weight of 300 or more. Table 3 shows the results of Example 1. The composition has excellent stain resistance and stability due to its low content of monools having unsaturated groups, and is remarkably compatible with building materials due to the inclusion of bifunctional polyalkylene oxide (A3) with a high total content of propylene oxide residues and hydroxyl groups, and is a composition that contributes to the formation of building materials with good bleed resistance and stability.

[0087] Example 2 is a polyalkylene oxide composition (AA2) in which the composition ratio of polyalkylene oxide (A1-1) and polyalkylene oxide (A3-1) was changed. Table 3 shows the results of Example 2. Even when the content of polyalkylene oxide (A3-1) was 0.5 parts by weight, the composition exhibited significantly good compatibility, and was excellent in handleability and productivity, as well as in stain resistance and stability. The composition was useful for forming building materials with good bleeding resistance and stability.

[0088] In Example 3, the hindered phenol-based antioxidant having a molecular weight of 300 or more was not added compared to Example 1, and the trifunctional polyalkylene oxide (A1-1) having an ethylene oxide residue was replaced with a tetrafunctional, high-molecular-weight polyalkylene oxide (A1-2) having no ethylene oxide residue. This polyalkylene oxide composition (AA3) was obtained by changing the polyalkylene oxide (A1-2) from trifunctional and having an ethylene oxide residue to a high-molecular-weight polyalkylene oxide (A1-2) having no ethylene oxide residue. The results of Example 3 are shown in Table 3. Although the polyalkylene oxide composition (AA3) contains tetrafunctional polyalkylene oxide (A1-2) with a large number of hydroxyl groups, it exhibits remarkably good compatibility due to the inclusion of 3 parts by weight of the highly compatible polyalkylene oxide (A3-1). Furthermore, the composition exhibited excellent stain resistance and stability, making it a composition useful for forming building materials with good bleed resistance and stability.

[0089] Examples 4 and 5 are compositions obtained by adding a hindered phenol-based antioxidant to Example 3 and changing the composition ratio of polyalkylene oxide (A1-2) and polyalkylene oxide (A3-1). Table 3 shows the results of Examples 4 and 5. When the polyalkylene oxide (A3-1) was in the range of 0.2 to 10 parts by weight, the compositions exhibited good stain resistance and compatibility and were also excellent in stability, and were compositions that contributed to the formation of building materials with good bleeding resistance and stability.

[0090] Example 6 is a polyalkylene oxide composition (AA6) in which the amount of polyalkylene oxide (A3-1) was reduced compared to Example 2, but instead, in order to improve compatibility with building materials, the polyalkylene oxide (A1-1) with a molecular weight of 7000 was replaced with a polyalkylene oxide (A1-3) with a lower molecular weight of 2900. The results of Example 6 are shown in Table 3. The composition containing the polyalkylene oxide (A1-3) with a lower molecular weight of 2900 and a reduced amount of polyalkylene oxide (A3-1) showed improved compatibility and a bleeding-inhibiting effect of low-molecular-weight components compared to Comparative Example 5, which does not contain polyalkylene oxide (A3-1), as described below. This composition exhibited significantly good stain resistance and good compatibility, and was a composition that contributed to the formation of building materials with good bleeding resistance and stability. In Comparative Example 1, in contrast to Examples 1 and 2, the polyalkylene oxide composition (AC1) does not contain a bifunctional polyalkylene oxide (A3) having a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of 80% or more. The results of Comparative Example 1 are shown in Table 3. This composition had good stain resistance because it contained a small amount of monools containing unsaturated groups, but it did not contain a bifunctional polyalkylene oxide (A3) with a relatively low molecular weight and a high content of highly compatible alkylene oxide residues, and therefore had poor compatibility with building materials. Therefore, it took a long time to prepare the composition, and it was a composition that was difficult to use as a plasticizer for building materials due to its poor handleability and productivity.

[0091] In Comparative Example 2, a polyalkylene oxide composition (AC2) containing a large amount (15 parts by weight) of a bifunctional polyalkylene oxide (A3) having a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of 80% or more, compared to Examples 1 and 2. Table 3 shows the results of Comparative Example 2. This composition contained a small amount of monool containing an unsaturated group, but a large amount of bifunctional, relatively low-molecular-weight polyalkylene oxide (A3). This composition had poor stain resistance and was difficult to use. Furthermore, the odor index deteriorated when stored at 50°C, which is thought to be due to the increase in low-molecular-weight components, and the composition was also relatively unstable.

[0092] In Comparative Example 3, in contrast to Examples 4 and 5, the polyalkylene oxide composition (AC3) did not contain a bifunctional polyalkylene oxide (A3) having a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of 80% or more. Table 3 shows the results of Comparative Example 3. This composition had good stain resistance because it contained a small amount of monools containing unsaturated groups, but it did not contain a bifunctional polyalkylene oxide (A3) with a relatively low molecular weight and a high content of highly compatible alkylene oxide residues, and therefore had poor compatibility with building materials. Therefore, it took a long time to prepare the composition, and it was a composition that was difficult to use as a plasticizer for building materials due to its poor handleability and productivity.

[0093] In Comparative Example 4, compared to Examples 4 and 5, a polyalkylene oxide composition (AC4) was used, which contained a large amount (15 parts by weight) of a bifunctional polyalkylene oxide (A3) having a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of 80% or more. The results of Comparative Example 4 are shown in Table 3. This composition contained a small amount of monools containing unsaturated groups, but a large amount of bifunctional, relatively low-molecular-weight polyalkylene oxide (A3). This resulted in poor stain resistance and made the composition difficult to use. Furthermore, the odor index deteriorated when stored at 50°C, which is thought to be due to an increase in low-molecular-weight components, and the composition was also relatively unstable.

[0094] Comparative Example 5 is a polyalkylene oxide composition (AC5) that does not contain a bifunctional polyalkylene oxide (A3) having a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of 80% or more, in which a polyalkylene oxide (A1-1) with a molecular weight of 7000 was replaced with a polyalkylene oxide (A1-3) with a lower molecular weight of 2900 in order to improve compatibility compared to Comparative Example 1. Table 3 shows the results of Comparative Example 5. Since the molecular weight of the polyalkylene oxide (A1) was somewhat low, the composition exhibited a tendency toward worsening stain resistance, and although an improvement in compatibility was observed, it was insufficient. Furthermore, due to poor compatibility with building materials, the composition required time for preparation, and was poor in handleability and productivity, making it difficult to use as a plasticizer for building materials.

[0095] [Table 3]

[0096] Example 7 is a polyalkylene oxide composition (AA7) obtained by changing the polyalkylene oxide (A1-1) having an unsaturation degree of 0.032 meq / g to a polyalkylene oxide (A1-4) having an unsaturation degree of 0.002 meq / g and a significantly lower amount of unsaturated monool compared to Example 1. Table 4 shows the results of Example 7. Although there is a slight decrease in compatibility compared to Example 1 due to the significantly lower amount of unsaturated monool, the composition has good compatibility due to the inclusion of a bifunctional polyalkylene oxide (A3) having a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of 80% or more, and is a composition that is significantly excellent in stain resistance and stability and contributes to the formation of building materials with good bleed resistance and stability.

[0097] Example 8 is a polyalkylene oxide composition (AA8) prepared by using a polyalkylene oxide (A1-4) having a significantly lower amount of unsaturated monool as in Example 7, but changing the bifunctional polyalkylene oxide (A3-1) having a molecular weight of 1900 to a bifunctional polyalkylene oxide (A3-2) having a molecular weight of 3500, and increasing the amount used to 10 parts by weight. Table 4 shows the results of Example 8. Although the amount of bifunctional polyalkylene oxide (A3-2) was slightly high at 10 parts by weight, which tended to slightly worsen the stain resistance, the composition was good and had excellent compatibility and stability, and was a composition useful for forming building materials with good bleed resistance and stability.

[0098] Comparative Example 6 is a polyalkylene oxide composition (AC6) that does not contain a hindered phenol-based antioxidant with a molecular weight of 300 or more, and does not contain a bifunctional polyalkylene oxide (A3) with a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of 80% or more, as compared to Examples 7 and 8. Table 4 shows the results of Comparative Example 6. This composition had good stain resistance due to the low content of monools containing unsaturated groups, but did not contain a bifunctional polyalkylene oxide (A3) with a relatively low molecular weight and a high content of highly compatible alkylene oxide residues, resulting in poor compatibility with building materials. Therefore, the composition required a long time to prepare, and was poor in handleability and productivity, making it difficult to use as a plasticizer for building materials.

[0099] In Comparative Example 7, the polyalkylene oxide composition (AC7) was prepared by replacing the polyalkylene oxide (A1-1) having an unsaturation degree of 0.032 meq / g with a general-purpose polyalkylene oxide (AC1-1) having an unsaturation degree of 0.091 meq / g and containing a large amount of monool having an unsaturated group at the end, as compared to Example 1. The total unsaturation degree in the composition exceeded 0.07 meq / g. Table 4 shows the results of Comparative Example 7. Because the composition contained a large amount of monool containing an unsaturated group with insufficient fat solubility, it was prone to bleeding, had poor stain resistance, and was difficult to use. In addition, the odor index deteriorated when stored at 50°C, which is thought to be due to an increase in low-molecular-weight components, and the composition was also relatively unstable.

[0100] Comparative Example 8 is a polyalkylene oxide composition (AC8) in which the general-purpose polyalkylene oxide (AC1-1) containing a large amount of trifunctional unsaturated monool was replaced with a general-purpose polyalkylene oxide (AC1-2) containing a large amount of tetrafunctional unsaturated monool, as compared to Comparative Example 7. The total unsaturation level in the composition was greater than 0.07 meq / g. Table 4 shows the results of Comparative Example 8. As with Comparative Example 7, this composition contained a large amount of monool containing an unsaturated group with insufficient fat solubility. Therefore, even when a polyalkylene oxide with tetrafunctionality and many hydroxyl groups was used, the composition was prone to bleeding, had poor stain resistance, and was difficult to use. In addition, the odor index when stored at 50°C deteriorated, which is thought to be due to an increase in low-molecular-weight components, and the composition was also relatively poorly stable.

[0101] [Table 4]

[0102] Example 9 is a polyalkylene oxide composition (AA9) prepared by adding a hindered phenol-based antioxidant having a molecular weight of 300 or more to Example 3 and changing the bifunctional polyalkylene oxide (A3-1) having a molecular weight of 1900 to a bifunctional polyalkylene oxide (A3-2) having a molecular weight of 3500. Table 5 shows the results of Example 9. Polyalkylene oxide composition (AA9) exhibits significantly good compatibility because it contains 3 parts by weight of highly compatible polyalkylene oxide (A3-2) consisting only of propylene oxide residues, ethylene oxide residues, and hydroxyl groups. Furthermore, since the polyalkylene oxide (A3) has a higher molecular weight than Example 3 and is closer in molecular weight to (A1-2), it is a composition that exhibits significantly good stain resistance and stability, and is a composition that contributes to the formation of building materials with significantly good bleed resistance and stability.

[0103] Example 10 is a polyalkylene oxide composition (AA10) in which the bifunctional polyalkylene oxide (A3-1) consisting only of propylene oxide residues, ethylene oxide residues, and hydroxyl groups was replaced with a bifunctional polyalkylene oxide (A3-3) having a hexanediol residue in the molecular chain and a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of 97% compared to Example 1. Table 5 shows the results of Example 10. Polyalkylene oxide composition (AA10) contains 3 parts by weight of bifunctional polyalkylene oxide (A3-3) having a high total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups, and therefore exhibits remarkably good compatibility and exhibits good stain resistance and stability, making it a composition useful for forming building materials with good bleed resistance and stability.

[0104] Example 11 is a polyalkylene oxide composition (AA11) obtained by replacing the bifunctional polyalkylene oxide (A3-1) consisting only of propylene oxide residues, ethylene oxide residues, and hydroxyl groups in Example 1 with a bifunctional polyalkylene oxide (A3-3) having a highly lipophilic, C9 nonanediol residue in the molecular chain and a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups of 92%. Table 5 shows the results of Example 11. Although polyalkylene oxide composition (AA11) contains a more lipophilic, C9 nonanediol residue than Example 1, it still contains the more lipophilic C9 nonanediol residue in the molecular chain and has a slightly lower total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups, resulting in a slightly reduced compatibility. However, the polyalkylene oxide composition exhibited good stain resistance and stability, and was a composition useful for forming building materials with good bleed resistance and stability.

[0105] Examples 12 and 13 are polyalkylene oxide compositions (AA12) and (AA13) obtained by changing the trifunctional polyalkylene oxide (A1-1) having ethylene oxide residues to a tetrafunctional, high-molecular-weight polyalkylene oxide (A1-2) having no ethylene oxide residues compared to Examples 10 and 11. Table 5 shows the results of Examples 12 and 13. Although the polyalkylene oxide (A1-2) is tetrafunctional and has a large number of hydroxyl groups, the polyalkylene oxide compositions (AA12) and (AA13) contain 3 parts by weight of polyalkylene oxide (A3) having a high total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups, and therefore exhibit remarkably good compatibility. They are also compositions with excellent stain resistance and stability, and are useful for forming building materials with good bleed resistance and stability.

[0106] Comparative Example 9 is a polyalkylene oxide composition (AC9) in which a trifunctional polyalkylene oxide (AC3-1) with a large number of hydroxyl groups and high hydrophilicity was used instead of the difunctional polyalkylene oxide (A3-1) in Example 1. Table 5 shows the results of Comparative Example 9. Although the polyalkylene oxide composition (AC9) contains the same trifunctional polyalkylene oxide as the polyalkylene oxide (A1-1), it does not contain the bifunctional polyalkylene oxide (A3) with few hydrophilic hydroxyl groups, and therefore no compatibility-improving effect was observed. Furthermore, the poor compatibility with building materials meant that the composition preparation required a long time, and the composition was difficult to use as a plasticizer for building materials due to its poor handleability and productivity.

[0107] In Comparative Examples 10 and 11, the polyalkylene oxide compositions (AC10) and (AC11) used in Examples 1 and 9 were polyalkylene oxide compositions (AC3-2) and (AC3-3) containing aniline or bisphenol A residues and having a total content of propylene oxide, ethylene oxide, and hydroxyl groups of less than 80% by weight, instead of the bifunctional polyalkylene oxide (A3-1) consisting only of propylene oxide, ethylene oxide, and hydroxyl groups. Table 5 shows the results of Comparative Examples 10 and 11. Because the polyalkylene oxide compositions (AC10) and (AC11) did not contain the polyalkylene oxide (A3) with a high content of propylene oxide, ethylene oxide, and hydroxyl groups, they did not exhibit any effect in improving the compatibility of the polyalkylene oxide (A1) with building materials. Furthermore, due to their poor compatibility with building materials, the preparation of the compositions required a long time, and they were difficult to use as plasticizers for building materials due to their poor handleability and productivity.

[0108] Comparative Example 12 is a polyalkylene oxide composition (AC12) containing a polyol (AC3-4), which is a polyoxytetramethylene glycol having a similar molecular weight but no propylene oxide or ethylene oxide residues, instead of the bifunctional polyalkylene oxide (A3-1) consisting only of propylene oxide residues, ethylene oxide residues, and hydroxyl groups, as in Example 1. Table 5 shows the results of Comparative Example 12. Since the polyalkylene oxide composition (AC12) does not contain the polyalkylene oxide (A3) having a high content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups, it did not exhibit any effect of improving the compatibility of the polyalkylene oxide (A1) with building materials. Due to its poor compatibility with building materials, the composition required a long time to prepare, and it was difficult to use as a plasticizer for building materials due to its poor handleability and productivity.

[0109] [Table 5]

[0110] The polyalkylene oxide compositions (A) described in the examples all had number average molecular weights of 2,500 or more and less than 13,000, as calculated by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and polystyrene as a standard substance, and exhibited appropriate handleability.

[0111] As shown above in the Examples, the polyalkylene oxide composition (A) is a composition that exhibits low contamination, good compatibility, and excellent handling properties, and it has been shown that it can be suitably used in applications requiring the above properties, such as building materials, cosmetics, and urethane-based products.

[0112] In particular, it was shown that the building materials obtained using the composition have good bleeding resistance and excellent productivity, and can be suitably used as plasticizers for building materials.

Claims

1. A polyalkylene oxide composition (A) comprising a polyalkylene oxide (A1) having a propylene oxide residue and 3 to 8 hydroxyl groups, and a polyalkylene oxide (A3) having a propylene oxide residue and / or an ethylene oxide residue and two hydroxyl groups, the total content of which is 80% by weight or more, The polyalkylene oxide composition (A) has a degree of unsaturation of 0.04 meq / g or less, and the molar ratio of the polyalkylene oxide (A1) to the polyalkylene oxide (A3) is in the range of 86 / 14 to 99.99 / 0.

01.

2. The polyalkylene oxide composition (A) according to claim 1, wherein the polyalkylene oxide (A3) consists of only propylene oxide residues and / or ethylene oxide residues and two hydroxyl groups.

3. The polyalkylene oxide composition (A) according to claim 1 or claim 2, wherein the molecular weight of the polyalkylene oxide (A3) at which the peak intensity is highest as measured by MALDI-TOF-MS is in the range of 1,000 or more and less than 5,500.

4. The polyalkylene oxide composition (A) according to any one of claims 1 to 3, wherein the polyalkylene oxide composition (A) has a number average molecular weight calculated by gel permeation chromatography (GPC) of 2,000 or more and less than 20,000.

5. A plasticizer comprising the polyalkylene oxide composition (A) according to any one of claims 1 to 4.

6. A building material comprising the plasticizer of claim 5.

7. 7. The building material of claim 6, comprising a polymer having alkylene oxide residues, said polymer being a modified silicone or polyurethane.

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