Polyalkylene oxide composition and building material using same

Abstract

To provide a polyalkylene oxide composition that exhibits low contamination, high lipophilicity, good plasticizing effect, and compatibility, and to obtain a building material using the same and having excellent bleeding resistance and flexibility.SOLUTION: A polyalkylene oxide composition includes: a polyalkylene oxide (A1) having a propylene oxide residue and 2 to 8 hydroxyl groups; and a polyalkylene oxide (A2) having one hydroxyl group and a hydrocarbon group having a carbon number of 1 to 100 at the end, wherein an unsaturation degree of the polyalkylene oxide composition (A) is less than 0.07 meq / g, and a molar ratio of polyalkylene oxide (A1) and polyalkylene oxide (A2) is in the range of 86 / 14 to 99.99 / 0.01.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a polyalkylene oxide composition and a building material using the same that has good bleeding resistance and flexibility. [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.

[0003] When such highly unsaturated polyalkylene oxides are used as plasticizers for building materials such as modified silicone sealants and urethane sealants, they contain a large amount of low-molecular-weight components and tend to bleed over time. In addition, because they have allyl groups at the molecular terminals, they have insufficient fat solubility and are not sufficiently compatible with building materials.

[0004] 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 their compatibility with building materials is insufficient, resulting in insufficient plasticizing effect during application and poor handleability. 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.

[0005] That is, there has been a demand for a polyalkylene oxide composition that has a low degree of unsaturation, low staining properties, high fat solubility, and good plasticizing effect and compatibility. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 6878765 Summary of the Invention [Problem to be solved by the invention]

[0007] One aspect of the present invention is to provide a polyalkylene oxide composition that is low-staining, highly fat-soluble, and exhibits good plasticizing effect and compatibility, and a building material that uses the same and has good bleeding resistance and flexibility. [Means for solving the problem]

[0008] The embodiments of the present invention are [1] to [9] shown below. [1] A polyalkylene oxide composition (A) comprising a polyalkylene oxide (A1) having a propylene oxide residue and 2 to 8 hydroxyl groups, and a polyalkylene oxide (A2) having a saturated hydrocarbon group having 1 to 100 carbon atoms at its terminal and one hydroxyl group, 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 (A2) is in the range of 86 / 14 to 99.99 / 0.01. [2] The polyalkylene oxide (A1) has three or more hydroxyl groups, The polyalkylene oxide composition (A) according to [1], further comprising 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. [3] The polyalkylene oxide composition (A) according to [1] or [2], wherein the molar ratio of the polyalkylene oxide (A1) to the polyalkylene oxide (A3) in the polyalkylene oxide composition (A) is in the range of 86 / 14 to 99.99 / 0.01. [4] The polyalkylene oxide composition (A) according to any one of [1] to [3], characterized in that the polyalkylene oxide (A2) contains at least one type of residue selected from the group consisting of an ethyl group, a propyl group, and a butyl group at a molecular terminal. [5] The polyalkylene oxide composition (A) according to any one of [1] to [4], wherein the molecular weight of the polyalkylene oxide (A2) 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. [6] The polyalkylene oxide composition (A) according to any one of [1] to [5], wherein the number average molecular weight of the polyalkylene oxide composition (A) calculated by gel permeation chromatography (GPC) is 2,000 or more and less than 20,000. [7] A plasticizer comprising the polyalkylene oxide composition (A) according to any one of [1] to [6]. [8] A building material containing the plasticizer described in [7]. [9] The building material according to [8], which comprises a polymer having an alkylene oxide residue, and the polymer is a modified silicone or polyurethane. [Effects of the Invention]

[0009] The polyalkylene oxide composition according to one embodiment of the present invention exhibits low staining properties, high fat solubility, and good plasticizing effect and compatibility. Furthermore, by using the polyalkylene oxide composition as a plasticizer for building materials and the like, building materials that combine high bleed resistance and flexibility can be formed. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is an analytical diagram of the polyalkylene oxide composition (AA20) of Example 20 by MALDI-TOF-MS. [Figure 2] FIG. 1 is an analytical diagram of the polyalkylene oxide composition (AA21) of Example 21 by MALDI-TOF-MS. DETAILED DESCRIPTION OF THE INVENTION

[0011] 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 2 to 8 hydroxyl groups, and a polyalkylene oxide (A2) having a saturated hydrocarbon group having 1 to 100 carbon atoms at its terminal and one hydroxyl group, wherein the polyalkylene oxide composition (A) has a degree of unsaturation of less than 0.07 meq / g and a molar ratio of the polyalkylene oxide (A1) to the polyalkylene oxide (A2) in the range of 86 / 14 to 99.99 / 0.01.

[0012] 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.

[0013] 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 plasticizing effect, 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.

[0014] 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 (A2). 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 be used to further reduce monools having unsaturated groups, thereby improving stain resistance at the expense of reduced plasticizing effect.

[0015] 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.

[0016] 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.

[0017] The molar ratio of polyalkylene oxide (A1) to polyalkylene oxide (A2) in the polyalkylene oxide composition (A) is in the range of 86 / 14 to 99.99 / 0.01. If the polyalkylene oxide (A2) is not contained in addition to the polyalkylene oxide (A1), the composition will be difficult to use due to insufficient fat solubility and poor compatibility with building materials, etc., and if the content of polyalkylene oxide (A2) relative to polyalkylene oxide (A1) exceeds 14% in molar ratio (molar ratio: less than 86 / more than 14), the composition will be difficult to use due to insufficient stain resistance.

[0018] In particular, the molar ratio of polyalkylene oxide (A1) to polyalkylene oxide (A2) 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 contamination resistance and good compatibility. The method for calculating the molar ratio of polyalkylene oxide (A1) to polyalkylene oxide (A2) in the polyalkylene oxide composition (A) is not particularly limited, and can be calculated by, for example, analyzing the molecular terminal structure by H-NMR. Furthermore, when the ratio of initiators used as raw materials is known, the approximate ratio may be calculated using the charge ratio.

[0019] The polyalkylene oxide composition (A) may contain other components in addition to the polyalkylene oxide (A1) and polyalkylene oxide (A2) described above. Among these, the polyalkylene oxide composition (A) is improved in stain resistance, and affinity with building materials and the like is likely to be improved, resulting in excellent compatibility and plasticizing effect. Therefore, it is preferred that the polyalkylene oxide (A1) contains a polyalkylene oxide (A3) having three or more hydroxyl groups, a propylene oxide residue and / or an ethylene oxide residue and two hydroxyl groups, and the total content of these is 80% by weight or more, and the molar ratio of the polyalkylene oxide (A1) to the polyalkylene oxide (A3) is preferably in the range of 86 / 14 to 99.99 / 0.01.

[0020] That is, by including a polyalkylene oxide (A2) having a terminal saturated hydrocarbon group and a polyalkylene oxide (A3) with a low functionality and a high content of alkylene oxide residues in a specific ratio relative to the polyalkylene oxide (A1), the lipophilicity derived from the polyalkylene oxide (A2) and the affinity for building materials, etc., derived from the polyalkylene oxide (A3) are likely to reduce staining while exhibiting higher compatibility and plasticizing effects. In particular, when the amount of polyalkylene oxide (A2) is small, the inclusion of the highly compatible polyalkylene oxide (A3) acts as an auxiliary compatibilizer, making it easy to exhibit high plasticizing effects and compatibility even with a small amount of monofunctional polyalkylene oxide (A2). Furthermore, even when using a polyalkylene oxide (A1) with a high number of hydroxyl groups (3 or more) that has a high plasticizing effect, it is easy to adjust and reduce hydrophilicity and exhibit high compatibility.

[0021] In particular, the molar ratio of polyalkylene oxide (A1) to polyalkylene oxide (A3) is preferably in the range of 95 / 5 to 99.99 / 0.01, more preferably in the range of 97 / 3 to 99.8 / 0.2, and most preferably in the range of 97 / 3 to 99 / 1.

[0022] The molar ratio of polyalkylene oxide (A2) to polyalkylene oxide (A3) is preferably in the range of 30 / 70 to 90 / 10, more preferably 35 / 65 to 85 / 15, and most preferably 40 / 60 to 80 / 20, since this tends to provide higher stain resistance. By including polyalkylene oxide (A3), which has properties intermediate between polyalkylene oxide (A2) and polyalkylene oxide (A1), in a predetermined ratio, the compatibility between polyalkylene oxide (A2) and polyalkylene oxide (A1) is improved, and bleeding of polyalkylene oxide (A2) in the building material is more unlikely, making it easier to provide higher stain resistance.

[0023] The method for calculating the molar ratio of polyalkylene oxide (A2) to polyalkylene oxide (A3) is not particularly limited, but in the present invention, when the charge ratio or initiator ratio was known, the calculation was performed using those values. In addition, after collecting the target components over a wide molecular weight range, the approximate ratio was calculated from the peak intensity and distribution derived from polyalkylene oxide (A2) and polyalkylene oxide (A3) by MALDI-TOF-MS.

[0024] The peak top molecular weights (M) of the polyalkylene oxide (A1) and the polyalkylene oxide (A2) in the polyalkylene oxide composition (A) calculated by MALDI-TOF-MS preferably satisfy the following relational expression:

[0025] Peak top molecular weight of (A2) × 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 (A2) according to the above formula, because the polyalkylene oxide (A2) is more likely to act stably as a compatibilizer between the building material and the polyalkylene oxide (A1), and is more likely to exhibit higher compatibility and stain resistance.

[0026] In particular, it is preferable that the peak top molecular weight of the polyalkylene oxide (A1) is higher than the peak top molecular weight of the polyalkylene oxide (A2), 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:

[0027] Peak top molecular weight of (A2) × 4 > Peak top molecular weight of (A1) > Peak top molecular weight of (A2) In addition, the peak top molecular weight (M A3) exhibits higher stain resistance and acts more easily as a compatibilizer, so it is preferable that the following relational expression be satisfied.

[0028] Peak top molecular weight of (A3) × 6 > Peak top molecular weight of (A1) 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.

[0029] 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 deterioration 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] Examples of the leveling agent include an acrylic leveling agent, a fluorine-based leveling agent, and a silicone-based leveling agent.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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 2 to 8 hydroxyl groups.

[0043] 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.

[0044] 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 3 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.

[0045] 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:

[0046] [ka]

[0047] [In the above general formula (1), R represents an active hydrogen-containing compound (R[-H] m ) by removing m active hydrogen atoms, 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 2 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 2 to 4, more preferably 2 to 3, and most preferably 3, because this tends to improve compatibility with the main chain polymer of the building material.

[0048] 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 2 to 8 hydroxyl groups per molecule, and more preferably a residue of a polyether polyol having a molecular weight of 200 to 3,000, due to its versatility, high compatibility, and tendency to produce low coloration. These active hydrogen-containing compounds may be used alone or in combination.

[0049] The polyalkylene oxide (A1) has 2 to 8 hydroxyl groups per molecule. If the number of hydroxyl groups per molecule of the polyalkylene oxide (A1) exceeds 8, the hydrophilicity increases, the compatibility with building materials deteriorates, and the building materials become prone to moisture absorption, making them difficult to use. If the number of hydroxyl groups per molecule is less than 2, the productivity during alkylene oxide addition decreases, making them difficult to use. In particular, the number of hydroxyl groups per molecule is preferably in the range of 2 to 4, more preferably 3 to 4, in order to easily achieve both a high plasticizing effect and compatibility with building materials. Most preferably, the number of hydroxyl groups per molecule is 3, in order to achieve a higher plasticizing effect while maintaining high compatibility. 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 the unsaturated monool.

[0050] Furthermore, when polyalkylene oxide (A3) is contained in order to improve stain resistance and affinity with building materials, etc., the number of hydroxyl groups in one molecule of polyalkylene oxide (A1) is preferably 3 or more in order to enhance the plasticizing effect. More preferably, the number of hydroxyl groups in one molecule is in the range of 3 to 4, and most preferably 3, in order to reduce hydrophilicity and the hygroscopicity of building materials.

[0051] 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).

[0052] 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.

[0053] 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).

[0054] 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 (A2)> The polyalkylene oxide composition (A) is characterized by containing, as an essential component, a polyalkylene oxide (A2) having a saturated hydrocarbon group having 1 to 100 carbon atoms at its terminal and one hydroxyl group. By containing the polyalkylene oxide (A2) having a saturated hydrocarbon group with high fat solubility and one hydrophilic hydroxyl group in the polyalkylene oxide composition (A), a high plasticizing effect and high compatibility with building materials having alkylene oxide residues are exhibited, resulting in a building material with excellent stain resistance.

[0055] If the polyalkylene oxide (A2) does not have a saturated hydrocarbon group at its terminal or if it has two or more hydrophilic hydroxyl groups, it is difficult to impart fat solubility to the polyalkylene oxide composition, resulting in insufficient improvement in compatibility with building materials, etc., making it difficult to use. Furthermore, if it does not have a hydrophilic hydroxyl group, fat solubility tends to improve, it does not react with urethane-based building materials, and the plasticizing effect tends to be large, but a sealing reaction, etc. is required, which tends to be economical.

[0056] The saturated hydrocarbon group having 1 to 100 carbon atoms contained in the polyalkylene oxide (A2) is not particularly limited, but among them, a residue having a saturated hydrocarbon structure having 2 to 100 carbon atoms is preferred because it has higher fat solubility and is likely to further improve compatibility with building materials, and a residue having a saturated hydrocarbon structure having 2 to 8 carbon atoms is more preferred because it is less likely to precipitate or solidify at low temperatures in the polyalkylene oxide composition (A) and provides good handleability, and most preferably it contains one or more of an ethyl group, a propyl group, or a butyl group, which have a higher plasticizing effect and are highly versatile. Note that propyl and butyl groups, including their isomers, can be suitably used, but normal propyl and normal butyl groups, which tend to have higher fat solubility, are more preferred.

[0057] The polyalkylene oxide (A2) is not particularly limited as long as it contains an alkylene oxide residue, but preferably contains an alkylene oxide residue having 3 or more carbon atoms. The alkylene oxide residue having 3 or more carbon atoms is not particularly limited, and examples thereof include alkylene oxide residues having 3 to 20 carbon atoms. Specific examples include propylene 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, propylene oxide residue is preferred because the raw materials for obtaining the polyalkylene oxide (A2) are easily available and have high industrial value.

[0058] Furthermore, the polyalkylene oxide (A2) may contain only a single alkylene oxide residue as the alkylene oxide residue having 3 or more carbon atoms, or may contain two or more types of alkylene oxide residues. 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. Furthermore, the polyalkylene oxide (A2) may contain an ethylene oxide residue having 2 carbon atoms in addition to the alkylene oxide residue having 3 or more carbon atoms, which is a preferred alkylene oxide residue.

[0059] The polyalkylene oxide (A2) may contain an initiator residue. The initiator residue is not particularly limited, but preferably contains a residue of a monol or the like having a saturated hydrocarbon structure with 1 to 100 carbon atoms, since it is easy to introduce a saturated hydrocarbon group to the molecular end. Among them, a residue of a monol having a saturated hydrocarbon structure with the carbon number exemplified as a preferred saturated hydrocarbon group is preferred, and the reasons for this preference are the same. Note that, as long as a saturated hydrocarbon group can be introduced to the molecular end, methods other than the method of introduction as an initiator can also be suitably used, and are not particularly limited.

[0060] 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. The polyalkylene oxide (A2) can be identified by the initiator structure and the alkylene oxide structural unit by MALDI-TOF-MS, and since this easily achieves both a higher plasticizing effect and compatibility, the molecular weight at which the peak intensity of the polyalkylene oxide (A2) is highest (peak top molecular weight) measured by MALDI-TOF-MS is preferably in the range of 1000 or more and less than 5500. In particular, the peak top molecular weight of the polyalkylene oxide (A2) measured by MALDI-TOF-MS is preferably 1500 or more and less than 4500, and most preferably 1900 or more and less than 4000, since this easily achieves low contamination, a more excellent plasticizing effect, and improved compatibility.

[0061] The number average molecular weight of the polyalkylene oxide (A2) before mixing can be calculated from the hydroxyl value of the polyalkylene oxide (A2) calculated by the method described in JIS K-1557-1 and the number of hydroxyl groups per molecule of the polyalkylene oxide (A2), which is 1.

[0062] The number average molecular weight of the polyalkylene oxide (A2) 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 (A2) measured from the polyalkylene oxide (A1) by MALDI-TOF-MS.

[0063] The method for producing such polyalkylene oxide (A2) is not particularly limited, but it can be obtained by adding an alkylene oxide to a monool having a saturated hydrocarbon structure of 1 to 100 carbon atoms as an initiator. Furthermore, when a monool having a saturated hydrocarbon structure of 2 to 8 carbon atoms is used as the initiator, it may volatilize during synthesis. Therefore, it is preferable to use a monool initiator to which a small amount of alkylene oxide has been added, such as tripropylene glycol monobutyl ether (Dowanol TPnB manufactured by DOW) or dipropylene glycol monopropyl ether (PFDG-SS manufactured by Nippon Nyukazai Co., Ltd.), but this is not particularly limited. Furthermore, when producing using a combination initiator system, it is also possible to alcoholate the other initiator with an alkylene oxide polymerization catalyst, and then add and react the monool having a saturated hydrocarbon structure of 1 to 100 carbon atoms immediately before the reaction. <Polyalkylene oxide (A3)> The polyalkylene oxide composition (A) may contain other components in addition to the polyalkylene oxides (A1) and (A2), and since this improves the stain resistance of the polyalkylene oxide composition (A), and also tends to improve affinity with building materials and the like, and tends to provide excellent compatibility and plasticizing effect, it is preferred that the polyalkylene oxide (A1) contains three or more hydroxyl groups, and that the polyalkylene oxide (A2) also contains a polyalkylene oxide (A3) having propylene oxide residues and / or ethylene oxide residues and two hydroxyl groups in a total content of 80% by weight or more. That is, it is preferred that the polyalkylene oxide composition (A) contains a diol in which the total content of propylene oxide residues, ethylene oxide residues, and two hydroxyl groups is 80% by weight or more.

[0064] The inclusion of a small amount of a diol of intermediate properties, such as polyalkylene oxide (A3), which has a relatively low molecular weight and contains many propylene oxide residues and ethylene oxide residues in the molecular chain, acts as a compatibilizer, making the relatively low molecular weight polyalkylene oxide (A2) and monools with unsaturated terminals 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, which tends to improve the compatibility of the polyalkylene oxide composition (A) with building materials.

[0065] 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.

[0066] The method for producing such polyalkylene oxide (A3) is not particularly limited, but can be achieved by adding propylene oxide and / or ethylene oxide as the alkylene oxide to an initiator consisting only of propylene oxide residues, ethylene oxide residues, and hydroxyl groups, an initiator with a high content of such residues, or a low-molecular-weight initiator. Furthermore, when using a low-boiling initiator such as propylene glycol, ethylene glycol, or water, volatilization may occur during synthesis. Therefore, it is preferable to use a diol initiator to which a small amount of alkylene oxide, such as dipropylene glycol, tripropylene glycol, or tetraethylene glycol, has been added, but this is not particularly limited. For example, when producing using a combined initiator system, the other initiator can be alcoholated with an alkylene oxide polymerization catalyst, and an initiator consisting only of propylene oxide residues, ethylene oxide residues, and hydroxyl groups can be added and reacted immediately before the reaction.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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> 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.

[0071] 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.

[0072] 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.

[0073] Among these, the polyalkylene oxide composition (A) has a low degree of unsaturation (low unsaturated monool content) and contains a polyalkylene oxide (A2) having a terminal saturated hydrocarbon group, and therefore has low staining properties, high fat solubility, and excellent plasticizing effect and compatibility, making it suitable for use as a plasticizer. Furthermore, the low content of unsaturated groups provides excellent chemical stability and low coloring, and the high fat solubility provides good wetting properties and few impurities, making it suitable for use as a moisturizing component in cosmetics.

[0074] Furthermore, the polyalkylene oxide composition (A) has remarkably good compatibility with polymers containing alkylene oxide residues, is less likely to bleed, and is likely to exhibit a high plasticizing effect, making it particularly suitable for use as a plasticizer for building materials, and is most preferably used for building materials containing a polymer having alkylene oxide residues, where the polymer is a modified silicone or polyurethane.

[0075] 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, flexibility, low coloration, and low odor can be easily obtained, and can be suitably used.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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]

[0080] 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 bifunctional polypropylene glycol initiator having a molecular weight of 400, and then removing water by dehydration under reduced pressure at 100°C for at least 3 hours. After that, propylene oxide was continuously supplied at a reaction temperature of 90°C and 0.3 MPa to carry out the reaction. Subsequently, residual monomers and catalyst were removed by conventional methods to obtain a bifunctional polyalkylene oxide having a molecular weight of 4000 and an unsaturated group monool content of 0.028 meq / g.

[0081] Polyalkylene oxide (A1-2) was prepared by mixing an aqueous IPZ catalyst solution with a trifunctional glycerin-propylene oxide adduct initiator having a molecular weight of 600, dehydrating the mixture under reduced pressure at 100°C for more than 3 hours to remove water, and then continuously feeding propylene oxide at a reaction temperature of 90°C and 0.3 MPa to carry out the reaction. After removing the remaining propylene oxide, the reaction was carried out by continuously feeding ethylene oxide at a reaction temperature of 130°C and 0.4 MPa or less. The remaining monomer and catalyst were then removed by conventional methods to produce a trifunctional polyalkylene oxide having a molecular weight of 7000 and an unsaturated group monool content of 0.032 meq / g.

[0082] 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 (A1-2). 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.

[0083] Polyalkylene oxide (A1-5) is a trifunctional polyalkylene oxide having a molecular weight of 7000 and an unsaturated group monool content of 0.002 meq / g, synthesized under similar conditions using the same catalyst system as (A1-4), the same initiator as (A1-2), and the same alkylene oxide.

[0084] The polyalkylene oxide (AC1-1) is a bifunctional polypropylene oxide having an unsaturation degree of more than 0.07 meq / g, synthesized by a conventional method.

[0085] Poly(alkylene oxide) (AC1-2) is a trifunctional poly(propylene oxide)-poly(ethylene oxide) block copolymer with an unsaturation level exceeding 0.07 meq / g, synthesized by conventional methods.

[0086] The properties of the polyalkylene oxides (A1) and (AC1) are summarized in the table below.

[0087] [Table 1]

[0088] (Raw Material 1-2) Monofunctional Polyalkylene Oxide (A2) Having a Saturated Hydrocarbon Group at the Terminal or Monofunctional Polyalkylene Oxide (AC2) Not Having a Saturated Hydrocarbon Group at the Terminal Polyalkylene oxides (A2-1) and (A2-2) are monofunctional polyalkylene oxides having normal butyl groups at the molecular terminals, synthesized under the same conditions as polyalkylene oxide (A1-1) using tripropylene glycol monobutyl ether (Dowanol TPnB, manufactured by DOW) as an initiator.

[0089] The polyalkylene oxide (A2-3) is a monofunctional polyalkylene oxide synthesized by a conventional method and having a 2-ethylhexyl group, which is a saturated hydrocarbon group having 8 carbon atoms, at the molecular terminal.

[0090] The polyalkylene oxide (AC2-1) is a monofunctional polyalkylene oxide synthesized by a conventional method, which does not have a saturated hydrocarbon group at the molecular end, but instead has an allyl group, which is an unsaturated group.

[0091] The properties of the polyalkylene oxides (A2) and (AC2) are summarized in the table below.

[0092] [Table 2]

[0093] (Raw material 1-3) Bifunctional polyalkylene oxide (A3) consisting of propylene oxide residues, ethylene oxide residues, and hydroxyl groups, and bifunctional polyol (AC3) having a total content of propylene oxide residues, ethylene oxide residues, and hydroxyl groups 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 (A1-1) using tripropylene glycol (a reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as an initiator, excluding the by-product unsaturated monool.

[0094] The polyol (AC3-1) is a commercially available bifunctional polyoxytetramethylene glycol (PTG2000SN manufactured by Hodogaya Chemical Co., Ltd.) 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%.

[0095] The properties of the polyalkylene oxide (A3) and polyol (AC3) are summarized in the table below.

[0096] [Table 3]

[0097] (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 (AA21) and (AC1) to (AC19)) The polyalkylene oxide compositions (AA1) to (AA19) and (AC1) to (AC18) of the Examples and Comparative Examples were obtained by placing the raw materials listed in Tables 4 to 6 in a mayonnaise bottle and stirring and degassing the mixture at room temperature using a disper.

[0098] Polyalkylene oxide composition (AA20) was prepared by mixing a trifunctional glycerin-propylene oxide adduct with a molecular weight of 600, monofunctional tripropylene glycol monopropyl ether, and difunctional tripropylene glycol in a molar ratio of 97:2:1. The resulting initiator mixture was mixed with an aqueous IPZ catalyst solution and dehydrated under reduced pressure at 100°C for more than three hours to remove water. Propylene oxide was then continuously supplied at a reaction temperature of 90°C and 0.3 MPa to react with each initiator. Subsequently, residual monomers and catalyst were removed by standard methods, and an antioxidant was added to obtain a polyalkylene oxide composition with a total unsaturation content of 0.035 meq / g. MALDI-TOF-MS analysis of the polyalkylene oxide composition (AA20) revealed a mixture of a small amount of unsaturated monool and a chain-extended structure of each initiator with propylene oxide.

[0099] Polyalkylene oxide composition (AA21) was synthesized under the same conditions as in the production method for (AA20), except that an aqueous solution of IPZ catalyst was mixed with an initiator, dehydrated, and then a toluene solution of triisobutylaluminum was added and mixed, and toluene and by-products such as isobutane were removed under reduced pressure at 100°C for 3 hours or more, and then propylene oxide was reacted at a reaction temperature of 110°C and 0.3 MPa. This polyalkylene oxide composition had a total unsaturation of 0.002 meq / g, and the analyzed structure was a mixture of a trace amount of unsaturated monool and a structure in which propylene oxide was added to each initiator to extend the chain.

[0100] Polyalkylene oxide composition (AC19) is produced by the production method of (AA20), using an aqueous potassium hydroxide catalyst solution instead of an aqueous IPZ catalyst solution, and removing water by dehydration under reduced pressure at 100°C for 3 hours or more. Propylene oxide is then continuously supplied at a reaction temperature of 130°C and 0.3 MPa, and each initiator is reacted in a controlled manner. Subsequently, residual monomers and catalyst are removed by conventional methods, and an antioxidant is added to obtain a polyalkylene oxide composition with a total unsaturation level exceeding 0.07 meq / g. (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.

[0101] The prepared building material composition was filled into a metal mold with a depth of 2 mm by leveling it with a spatula, and then left to stand at room temperature for 1 week to harden, forming 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.

[0102] 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. <Plasticization effect> A building material composition containing a polyalkylene oxide composition was cured, and a commercially available one-component modified silicone sealant containing no polyalkylene oxide composition was cured according to the method for producing the cured product.

[0103] Compared to a composition that did not contain a polyalkylene oxide composition, the polyalkylene oxide compositions (A) and (AC) were evaluated according to the following criteria based on their effect of improving the handleability (reducing viscosity / improving flexibility) of the composition before curing and their effect of improving the flexibility of the resulting cured product. ◎ (Passed plasticizing effect): The plasticizing effect of the building material composition before hardening is noticeable, making it clearly easier to handle when filling and molding, and the building material after hardening has a noticeable plasticizing effect that can be felt by touch (both before hardening and hardened material are soft). ○ (Passed plasticizing effect): When the building material after hardening does not have a noticeable plasticizing effect that can be detected by touch evaluation, but the plasticizing effect of the building material composition before hardening can be felt and handling for filling and molding into molds is clearly easy (the composition before hardening is flexible and handleability is improved). △ (Failed plasticizing effect): When the hardened building material has a plasticizing effect when touched, but the building material composition before hardening does not have a plasticizing effect, and handling for filling and molding into molds is not improved. (Only flexible after hardening, insufficient improvement in handling) × (Failed plasticizing effect): When no clear plasticizing effect is felt in the composition for building materials before hardening, and when the building material after hardening is evaluated by touching, no plasticizing effect is felt. <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 seen as uniform after 7 minutes of mixing, and no separation or non-uniformity occurs when left to stand at room temperature. Good (compatible): When the mixture can be visually seen to be uniform 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 of 10 or more or Hazen color number of 200 or more after storage at 50°C for 18 hours.

[0104] Those that passed the tests for stain resistance, plasticizing effect, and compatibility were judged to be polyalkylene oxide compositions that have low staining properties, high fat solubility, and good plasticizing effect and compatibility, and that contribute to the formation of building materials with good bleeding resistance and flexibility (passed).

[0105] 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 95 parts by weight of polyalkylene oxide (A1-1), 5 parts by weight of monofunctional polyalkylene oxide (A2-1) having a saturated hydrocarbon group, and 700 ppm of Irganox 1098 as a hindered phenol-based antioxidant with a molecular weight of 300 or more. Table 4 shows the results of Example 1. The composition has excellent stain resistance and stability due to its low content of monool having an unsaturated group, and has a remarkably good plasticizing effect and excellent compatibility with building materials due to the inclusion of monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group, and is a composition that contributes to the formation of building materials with good bleed resistance, flexibility, and stability.

[0106] The compositions in Examples 2 to 4 were prepared by varying the ratio of polyalkylene oxide (A1-1) to polyalkylene oxide (A2-1) having a saturated hydrocarbon group. Table 4 shows the results of Examples 2 to 4. Since the content of polyalkylene oxide (A2-1) was 10 parts by weight or less, all of the compositions were excellent in stain resistance, stability, and plasticizing effect, and were useful for forming building materials with good bleeding resistance, flexibility, and stability.

[0107] In Example 5, the hindered phenol antioxidant with a molecular weight of 300 or more was omitted from Example 2, and the difunctional polyalkylene oxide (A1-1) without an ethylene oxide residue was replaced with a trifunctional polyalkylene oxide (A1-2) with a high molecular weight ethylene oxide residue. This polyalkylene oxide composition (AA5) was obtained by replacing the difunctional polyalkylene oxide (A1-1) with a trifunctional polyalkylene oxide (A1-2) with a high molecular weight ethylene oxide residue. Table 4 shows the results of Example 5. The polyalkylene oxide composition (AA5) exhibited good results despite its low oil solubility and low compatibility due to the trifunctional polyalkylene oxide (A1-2) and high hydroxyl group content. Furthermore, the presence of ethylene oxide residues resulted in high dispersibility and a high plasticizing effect, even at a high molecular weight. This composition was excellent in stain resistance, stability, and plasticizing effect, and was suitable for the formation of building materials with excellent bleed resistance, flexibility, and stability.

[0108] In Examples 6 and 7, a hindered phenol-based antioxidant was added to Example 5, resulting in polyalkylene oxide compositions (AA6) and (AA7) containing a difunctional polyalkylene oxide (A3) consisting only of propylene oxide residues and hydroxyl groups in addition to the monofunctional polyalkylene oxide (A2). Table 4 shows the results of Examples 6 and 7. Because they contain the difunctional polyalkylene oxide (A3) consisting only of propylene oxide residues and hydroxyl groups, they act as a compatibilizer, and even when a trifunctional polyalkylene oxide (A1-2) with many hydroxyl groups is used, the compositions are more compatible with building materials and have significantly superior stain resistance, stability, and plasticizing effect, and are useful for forming building materials with significantly excellent bleed resistance, flexibility, and stability.

[0109] Example 8 is a polyalkylene oxide composition (AA8) in which the amount of polyalkylene oxide (A2) added was 0.2 parts by weight and the amount of polyalkylene oxide (A3) added was 0.3 parts by weight. Table 4 shows the results of Example 8. Because the polyalkylene oxide composition (AA8) contains polyalkylene oxide (A2), it is a composition that is excellent in stain resistance, stability, and plasticizing effect, and is useful for forming building materials with good bleeding resistance, flexibility, and stability.

[0110] Example 9 is a polyalkylene oxide composition (AA9) in which the molecular weight of the main component polyalkylene oxide (A1) was reduced to 2900 to enhance the plasticizing effect, and the amount of polyalkylene oxide (A3) added was 0.49 parts by weight and the amount of polyalkylene oxide (A2) added was 0.01 parts by weight. Table 4 shows the results of Example 9. Because polyalkylene oxide composition (AA9) contains polyalkylene oxide (A2), it was a composition that was excellent in stain resistance, stability, and plasticizing effect, and was useful for forming building materials with good bleeding resistance, flexibility, and stability.

[0111] Comparative Example 1 is a polyalkylene oxide composition (AC1) that does not contain a monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group, as opposed to Examples 1 to 4. Table 4 shows the results of Comparative Example 1. This composition had good stain resistance due to the low content of monools having unsaturated groups, but because it did not contain a monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group, it had poor compatibility with building materials, and the plasticizing effect of the composition before curing was insufficient, resulting in poor workability. The composition was poor in handleability and difficult to use as a plasticizer for building materials, and the plasticizing effect on building materials after curing was also small.

[0112] In Comparative Example 2, a polyalkylene oxide composition (AC2) containing a large amount of monofunctional polyalkylene oxide (A2-1) having a saturated hydrocarbon group (15 parts) was used, compared to Examples 1 to 4. Table 4 shows the results of Comparative Example 2. This composition contained a small amount of monool containing an unsaturated group, but a large amount of monofunctional, relatively low-molecular-weight polyalkylene oxide (A2). 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 the increase in low-molecular-weight components, and the composition was also relatively unstable.

[0113] In Comparative Example 3, a polyalkylene oxide composition (AC3) was prepared by adding a bifunctional polyalkylene oxide (A3) with an intermediate structure and a high alkylene oxide content to suppress bleeding of the polyalkylene oxide composition (AC2) contained in a large amount, in comparison with Comparative Example 2. Table 4 shows the results of Comparative Example 3. Because this composition contained a large amount of the monofunctional, relatively low-molecular-weight polyalkylene oxide composition (A2), bleeding occurred even when the highly compatible polyalkylene oxide (A3) was added, and the composition had low 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.

[0114] Comparative Example 4 is a polyalkylene oxide composition (AC4) that does not contain a monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group, unlike Examples 5 to 8. Table 4 shows the results of Comparative Example 4. This composition had good stain resistance due to the low content of monools having unsaturated groups, but did not contain a monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group, resulting in poor compatibility with building materials, insufficient plasticizing effect on the composition before curing, and poor workability. It was a composition that was poor in handleability and difficult to use as a plasticizer for building materials, and also had a small plasticizing effect on building materials after curing.

[0115] Comparative Example 5 is a polyalkylene oxide composition (AC5) in which the amount of monofunctional polyalkylene oxide (A2-1) having a saturated hydrocarbon group was increased to 19 parts, compared to Example 6, which showed the best plasticizing effect and compatibility and also remarkably good stain resistance. Table 4 shows the results of Comparative Example 5. This composition contains a small amount of monool containing an unsaturated group, but a large amount of monofunctional, relatively low-molecular-weight polyalkylene oxide (A2). This composition therefore 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.

[0116] In Comparative Example 6, a polyalkylene oxide composition (AC6) was used, which, unlike Example 9, did not contain polyalkylene oxide (A2) or polyalkylene oxide (A3), which acts as a compatibilizer. Table 4 shows the results of Comparative Example 6. Although the molecular weight of the polyalkylene oxide (A1) in this composition was low and it had a plasticizing effect on building materials before hardening, the lack of a monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group resulted in poor compatibility with building materials. This resulted in poor workability due to the time required for dispersion and plasticization, making it difficult to use as a plasticizer for building materials. Furthermore, because the composition did not contain polyalkylene oxide (A2) or polyalkylene oxide (A3), which acts as a compatibilizer, the relatively low-molecular-weight polyalkylene oxide (A1), polyalkylene oxide (A2), and unsaturated monool were prone to bleeding, resulting in slightly inferior stain resistance compared to Example 9.

[0117] Comparative Example 7 is a polyalkylene oxide composition (AC6) in which the trifunctional polyalkylene oxide (A1-3) in Comparative Example 6 was completely replaced with a monofunctional polyalkylene oxide (A2-1) having a saturated hydrocarbon group. Table 4 shows the results of Comparative Example 7. Although the composition contained a small amount of monool containing an unsaturated group, it did not contain a bifunctional or higher functional, relatively high molecular weight polyalkylene oxide (A1) as a main component, and therefore had insufficient stain resistance and was difficult to use. It also showed a deterioration in the odor index when stored at 50°C, which is thought to be due to an increase in low molecular weight components, and was a composition with low stability.

[0118] [Table 4]

[0119] Example 10 is a polyalkylene oxide composition (AA10) obtained by changing the polyalkylene oxide (A1-1) having an unsaturation degree of 0.028 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 5 shows the results of Example 10. Since the amount of unsaturated monool was significantly lower and the viscosity of the polyalkylene oxide composition was higher, the plasticizing effect and compatibility were slightly lower compared to Example 1, but were still good, and the composition was remarkably excellent in stain resistance and stability, and was useful for forming building materials with good bleed resistance, flexibility, and stability.

[0120] Example 11 is a polyalkylene oxide composition (AA11) in which the amount of unsaturated monool was changed to a trifunctional polyalkylene oxide (A1-5) with a significantly lower amount of unsaturated monool compared to Example 2. Table 5 shows the results of Example 11. Because the amount of unsaturated monool was significantly lower and the viscosity of the polyalkylene oxide composition was higher, the plasticizing effect and compatibility were slightly lower than those of Example 2, but were still good, and the composition was significantly excellent in stain resistance and was useful for forming building materials with good bleed resistance, flexibility, and stability.

[0121] Examples 12 and 13 are polyalkylene oxide compositions (AA12) and (AA13), which were prepared by adding a bifunctional polyalkylene oxide (A3) with a high content of propylene oxide residues in order to improve compatibility and plasticizing effect compared to Example 11. Table 5 shows the results of Examples 12 and 13. Because they contain polyalkylene oxide (A3) in addition to polyalkylene oxide (A2), they have better compatibility with building materials than Example 11, and are compositions that are excellent in stain resistance, stability, and plasticizing effect, and are useful for forming building materials with good bleed resistance, flexibility, and stability.

[0122] Comparative Example 8 is a polyalkylene oxide composition (AC8) that does not contain the monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group, as opposed to Example 10. Table 5 shows the results of Comparative Example 8. This composition had significantly less monool containing an unsaturated group, and therefore had significantly better stain resistance and stability. However, since it did not contain the monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group, it had poor compatibility with building materials, and the plasticizing effect of the composition before curing was insufficient, resulting in poor workability. It was a composition that was poor in handleability and difficult to use as a plasticizer for building materials, and its plasticizing effect on building materials after curing was also relatively small.

[0123] Comparative Examples 9 and 10 are polyalkylene oxide compositions (AC9) and (AC10), which contain a large amount (15 parts) of monofunctional polyalkylene oxide (A2-1) having a saturated hydrocarbon group, and have an adjusted composition. Table 5 shows the results of Comparative Examples 9 and 10. These compositions contain significantly less monool containing an unsaturated group, but contain a large amount of monofunctional, relatively low-molecular-weight polyalkylene oxide (A2). As a result, they have poor stain resistance and are difficult to use. In addition, 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 compositions were also relatively unstable.

[0124] Comparative Example 11 is a polyalkylene oxide composition (AC11) that does not contain the monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group, as compared with Example 11. Table 5 shows the results of Comparative Example 11. This composition had significantly less monool having an unsaturated group, and therefore had significantly better stain resistance and stability. However, since it did not contain the monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group, it had poor compatibility with building materials, and the plasticizing effect of the composition before curing was insufficient, resulting in poor workability. The composition was also poor in handleability, making it difficult to use as a plasticizer for building materials, and its plasticizing effect on building materials after curing was also relatively small.

[0125] Comparative Example 12 is a polyalkylene oxide composition (AC12) in which the amount of monofunctional polyalkylene oxide (A2-1) having a saturated hydrocarbon group was increased to 19 parts compared to Example 12. Table 5 shows the results of Comparative Example 12. This composition contained significantly less monool containing an unsaturated group, but a large amount of monofunctional, relatively low-molecular-weight polyalkylene oxide (A2), resulting in poor stain resistance and difficulty in use. In addition, 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 poor in stability.

[0126] [Table 5]

[0127] Example 14 is a polyalkylene oxide composition (AA14) in which the composition was adjusted by changing the monofunctional polyalkylene oxide (A2-1) having a saturated hydrocarbon group to a polyalkylene oxide (A2-2) having a higher molecular weight in comparison with Example 2. The results of Example 14 are shown in Table 6. The composition was excellent in stain resistance, stability, and plasticizing effect, and was a composition that contributed to the formation of a building material with good bleeding resistance, flexibility, and stability.

[0128] Example 15 is a polyalkylene oxide composition (AA14) obtained by changing the monofunctional polyalkylene oxide (A2-1) having a saturated hydrocarbon group to a polyalkylene oxide (A2-2) having a higher molecular weight, thereby adjusting the composition compared to Example 6. Table 6 shows the results of Example 15. This composition contains a trifunctional polyalkylene oxide (A1-2) with a small amount of unsaturated monool and many hydroxyl groups, and a polyalkylene oxide (A3) with many highly compatible polyalkylene oxide residues and only two hydroxyl groups. Therefore, the composition has remarkably excellent stain resistance, plasticizing effect, and compatibility, and is a composition that contributes to the formation of building materials with good bleed resistance, flexibility, and stability.

[0129] Examples 16 and 17 are polyalkylene oxide compositions (AA16) and (AA17), in which the polyalkylene oxide (A2-2) having a butyl group at the end as the saturated hydrocarbon group in Example 15 was changed to a polyalkylene oxide (A2-3) having an ethylhexyl group, a saturated hydrocarbon group having 8 carbon atoms, at the end. Table 6 shows the results of Examples 16 and 17, and these compositions were excellent in stain resistance, stability, and plasticizing effect, and were useful for forming building materials with good bleeding resistance, flexibility, and stability.

[0130] Example 18 is a polyalkylene oxide composition (AA18) in which the bifunctional polyalkylene oxide (A3-1) acting as a compatibilizer was replaced with a bifunctional polyalkylene oxide (A3-2) having a slightly higher molecular weight compared to Example 17. Table 6 shows the results of Example 18. This composition was excellent in stain resistance, stability, and plasticizing effect, and was a composition that contributed to the formation of building materials with good bleed resistance, flexibility, and stability.

[0131] Example 19 is a polyalkylene oxide composition (AA19) in which the bifunctional polyalkylene oxide (A3-2), which has a high content of alkylene oxide residues and high compatibility, was replaced with a bifunctional polytetramethylene glycol polyol (AC3-1) containing no alkylene oxide residues, as compared to Example 18. Table 6 shows the results of Example 19. Although the composition exhibits a slight decrease in plasticizing effect and compatibility compared to Example 18 because the bifunctional polyol does not contain alkylene oxide residues, the composition contains a monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group, resulting in good plasticizing effect and compatibility, making it a composition useful for forming building materials with good bleed resistance, flexibility, and stability.

[0132] In Comparative Example 13, the polyalkylene oxide composition (AC13) was prepared by replacing the polyalkylene oxide (A1-1) with a low unsaturated monool content (0.028 meq / g) with a general-purpose polyalkylene oxide (AC1-1) with a high unsaturation level of 0.103 meq / g and containing a large amount of monools having terminal unsaturated groups, as compared to Example 14. The total unsaturation level in the composition exceeded 0.07 meq / g. The results of Comparative Example 13 are shown in Table 6. Because the composition contained a large amount of monools containing unsaturated groups with insufficient fat solubility, it had poor stain resistance and was difficult to use. Furthermore, the odor index deteriorated when stored at 50°C, likely due to an increase in low-molecular-weight components, and the composition was also relatively unstable.

[0133] Comparative Example 14 is a polyalkylene oxide composition (AC14) obtained by replacing a general-purpose polyalkylene oxide (AC1-1) containing a large amount of bifunctional unsaturated monool with a general-purpose polyalkylene oxide (AC1-2) containing a large amount of trifunctional unsaturated monool in Comparative Example 13, and the total unsaturation level in the composition exceeds 0.07 meq / g. Table 6 shows the results of Comparative Example 14. As with Comparative Example 13, this composition contains a large amount of monools containing unsaturated groups with insufficient fat solubility, and therefore, even when a trifunctional polyalkylene oxide with many hydroxyl groups was used, the composition 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 unstable.

[0134] In Comparative Example 15, a polyalkylene oxide composition (AC14) containing a polyalkylene oxide (A3-2) with a relatively low molecular weight, a high content of bifunctional alkylene oxide residues, and high compatibility, as compared to Comparative Example 14, was used. The total unsaturation level in the composition exceeded 0.07 meq / g. Table 6 shows the results of Comparative Example 15. Similar to Comparative Example 14, this composition contained a large amount of monool containing an unsaturated group with insufficient fat solubility. Therefore, even when a polyalkylene oxide consisting only of a highly compatible bifunctional propylene oxide residue and a hydroxyl group was used, the composition exhibited 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.

[0135] Comparative Example 16 is a polyalkylene oxide composition (AC16) obtained by replacing the monofunctional polyalkylene oxide (A2-2) having a butyl group, a saturated hydrocarbon group, at the molecular end with a monofunctional polyalkylene oxide (AC2-1) having an allyl group, an unsaturated group, at the molecular end, with the monofunctional polyalkylene oxide (AC2-1) of Example 14. The total unsaturation level in the composition is less than 0.07 meq / g, but the composition does not contain a monool having a saturated hydrocarbon group at the molecular end. Table 6 shows the results of Comparative Example 16. The composition did not contain the monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group, so it had poor compatibility with building materials, insufficient plasticization effect on the composition before hardening, poor workability, and poor handleability, making it difficult to use as a plasticizer for building materials.

[0136] In Comparative Example 17, the polyalkylene oxide composition (AC17) was prepared by increasing the amount of monofunctional polyalkylene oxide (AC2-1) having an unsaturated terminal allyl group to enhance the plasticizing effect and adding bifunctional polyalkylene oxide (A3-2) with a high content of alkylene oxide residues to enhance compatibility, resulting in a total unsaturation level of more than 0.07 meq / g. Table 6 shows the results of Comparative Example 17. This composition contained a large amount of monools having allyl groups, which are poorly fat-soluble, and did not contain monools having saturated hydrocarbon groups, which are highly fat-soluble. Therefore, even when the highly compatible bifunctional polyalkylene oxide (A3-2) with a high content of alkylene oxide residues was added, the compatibility was insufficient, resulting in poor handleability and poor stain resistance, making it difficult to use as a plasticizer for building materials.

[0137] Comparative Example 18 is a polyalkylene oxide composition (AC18) in which the bifunctional polyalkylene oxide (A1-1) in Comparative Example 17 was changed to a trifunctional polyalkylene oxide (A1-2), and the total degree of unsaturation in the composition exceeded 0.07 meq / g. Table 6 shows the results of Comparative Example 18. This composition contained a large amount of monool having an allyl group, which is poorly fat-soluble, and did not contain a monool having a saturated hydrocarbon group, which is highly fat-soluble. Therefore, even when a highly compatible bifunctional polyalkylene oxide (A3-2) with a high content of alkylene oxide residues was added, the compatibility was insufficient, and the composition was poor in handleability and contamination resistance, making it difficult to use as a plasticizer for building materials.

[0138] [Table 6]

[0139] In Example 20, unlike the method of mixing the polyalkylene oxides (A1), (A2), and (A3) of Example 6 to form a polyalkylene oxide composition, an initiator mixture was prepared by mixing GP600 manufactured by Sanyo Chemical Industries, Ltd., a trifunctional glycerin-initiated low-molecular-weight polypropylene oxide serving as the polyalkylene oxide (A1) initiator, tripropylene glycol monopropyl ether serving as the polyalkylene oxide (A2) initiator, and tripropylene glycol serving as the polyalkylene oxide (A3) initiator, in the molar ratios shown in Table 7. This is polyalkylene oxide composition (AA20), which was synthesized in one shot according to the method for preparing a polyalkylene oxide composition using an IPZ catalyst as the mixed initiator.

[0140] Analysis by MALDI-TOF-MS confirmed that this composition contained polyalkylene oxides (A1), (A2), and (A3), and when fractions containing polyalkylene oxides (A2) and (A3) were collected, the peak top molecular weights of each were 1000 or more, and approximately 1850, respectively (Figure 1). Note that the peak with the greatest intensity in Figure 1 is the allyl-terminated monool, with (A2) adjacent to it and the distant peak coming from (A3).

[0141] Furthermore, analysis of the initiator residues revealed that the molar ratio of polyalkylene oxides (A1) and (A2) roughly correlated with the molar ratio of the initiators in the mixed initiator.

[0142] The results of Example 20 are shown in Table 7. The composition exhibited excellent stain resistance and stability due to its low content of monools having unsaturated groups, a remarkably good plasticizing effect due to the inclusion of a monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group, and outstanding compatibility with building materials due to the inclusion of a bifunctional polyalkylene oxide (A3) consisting only of propylene oxide residues and hydroxyl groups. This composition was useful for forming building materials with excellent bleed resistance, flexibility, and stability. Furthermore, when used with a commercially available one-component urethane sealant whose main polymer component is polypropylene oxide residues, the composition also exhibited high compatibility and a high plasticizing effect, and functioned as a reactive plasticizer with good handleability, stain resistance, and minimal contamination.

[0143] In Example 21, unlike the method of forming a polyalkylene oxide composition by mixing the polyalkylene oxides (A1), (A2), and (A3) of Example 12, which used polyalkylene oxides with significantly lower degrees of unsaturation, an initiator mixture was prepared by mixing GP600 manufactured by Sanyo Chemical Industries, Ltd., a trifunctional glycerin-initiated low-molecular-weight polypropylene oxide equivalent to the polyalkylene oxide (A1) initiator, tripropylene glycol monopropyl ether equivalent to the polyalkylene oxide (A2) initiator, and tripropylene glycol equivalent to the polyalkylene oxide (A3) initiator, in the molar ratios shown in Table 7. This polyalkylene oxide composition (AA21) had significantly less unsaturated monool and was synthesized in one shot according to the method for preparing a polyalkylene oxide composition using IPZ catalyst and a triisobutylaluminum / toluene solution as the mixed initiator.

[0144] MALDI-TOF-MS analysis of this composition confirmed that it contained polyalkylene oxides (A1), (A2), and (A3). When fractions containing polyalkylene oxides (A2) and (A3) were collected, the peak top molecular weights were over 1000, with each peak being approximately 1630 (Figure 2). Unlike Figure 1, the peak with the highest intensity in Figure 2 is polyalkylene oxide (A2), and the peak adjacent to and distant from it, which is derived from allyl-terminated monool, is derived from (A3). Analysis of initiator residues also revealed that the molar ratio of polyalkylene oxides (A1) and (A2) generally correlated with the molar ratio of the initiators in the mixed initiator.

[0145] The results of Example 21 are shown in Table 7. Although the plasticizing effect of the cured product was lower than that of Example 20 due to the significantly lower content of monools having unsaturated groups, it was still good and exhibited significantly superior stain resistance and stability. The monofunctional polyalkylene oxide (A2) having a saturated hydrocarbon group provided a good plasticizing effect before curing and excellent handleability. The bifunctional polyalkylene oxide (A3) consisting only of propylene oxide residues and hydroxyl groups provided a composition with significantly superior compatibility with building materials, contributing to the formation of building materials with excellent bleed resistance, flexibility, and stability. Furthermore, when used with a commercially available one-component urethane sealant containing polypropylene oxide residues as the main polymer component, the composition also exhibited high compatibility and a high plasticizing effect, and functioned as a reactive plasticizer with good handleability, stain resistance, and minimal contamination.

[0146] In Comparative Example 19, in contrast to the method of forming a polyalkylene oxide composition by mixing the polyalkylene oxides (AC1), (A2), and (A3) of Comparative Example 15, an initiator mixture was prepared by mixing GP600 manufactured by Sanyo Chemical Industries, Ltd., a trifunctional glycerin-initiated low-molecular-weight polypropylene oxide equivalent to the polyalkylene oxide (AC1) initiator, tripropylene glycol monopropyl ether equivalent to the polyalkylene oxide (A2) initiator, and tripropylene glycol equivalent to the polyalkylene oxide (A3) initiator, in the molar ratios shown in Table 7. This polyalkylene oxide composition (AC21) was synthesized in one shot according to the method for preparing a polyalkylene oxide composition using aqueous potassium hydroxide, a general-purpose alkylene oxide addition catalyst, as the mixed initiator, with an unsaturated monool by-product exceeding 0.07 meq / g. The results of Comparative Example 19 are shown in Table 7. This composition contained a large amount of monool containing an unsaturated group with insufficient fat solubility, and therefore had poor stain resistance and was difficult to use, similar to Comparative Example 15. In addition, the odor index deteriorated when stored at 50°C, which is thought to be due to the influence of an increase in low-molecular-weight components, and the composition was also relatively poor in stability.

[0147] The polyalkylene oxide (A1-1) used in Comparative Example 1 was prepared using an aqueous solution of IPZ catalyst as a catalyst, and the polyalkylene oxide (A1-4) used in Comparative Example 8 was prepared using an aqueous solution of IPZ catalyst and a toluene solution of triisobutylaluminum as catalysts, followed by the addition of alkylene oxide after removing the solvent; these products did not contain any aliphatic alcohol that acts as an initiator during production.

[0148] [Table 7]

[0149] The polyalkylene oxide compositions (A) described in the examples, including Example 9, which used polyalkylene oxide (A1-3) with a molecular weight of 2900 calculated from the hydroxyl value, all had number average molecular weights of 3000 or more and less than 10000, calculated by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and polystyrene as a standard substance, and exhibited appropriate handleability.

[0150] As shown above in the Examples, the polyalkylene oxide composition (A) is a composition that exhibits low staining properties, high fat solubility, and good plasticizing effect and compatibility, 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.

[0151] In particular, it was shown that the building materials obtained using the composition have good bleeding resistance and flexibility, 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; a polyalkylene oxide (A2) having a saturated hydrocarbon group having 1 to 100 carbon atoms at its terminal and having one hydroxyl group; and a polyalkylene oxide (A3) having a propylene oxide residue and / or ethylene oxide residue and two hydroxyl groups, the total content of which is 80% by weight or more; the polyalkylene oxide composition (A) has an unsaturation degree of less than 0.07 meq / g, the molar ratio of the polyalkylene oxide (A1) to the polyalkylene oxide (A2) is in the range of 86 / 14 to 99.99 / 0.01; A polyalkylene oxide composition (A) in which the molar ratio of the polyalkylene oxide (A1) to the polyalkylene oxide (A3) is in the range of 95 / 5 to 99.99 / 0.

01.

2. The polyalkylene oxide composition (A) according to claim 1, wherein the polyalkylene oxide (A2) contains at least one group selected from the group consisting of an ethyl group, a propyl group, and a butyl group at a molecular terminal.

3. The polyalkylene oxide composition (A) according to claim 1 or claim 2, wherein the molecular weight of the polyalkylene oxide (A2) 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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