Additives for the emulsion polymerization of polyalkylene oxides and olefins, emulsion polymerization compositions, methods for producing polyalkylene oxides, methods for producing olefin polymers, olefin polymers, methods for producing films, films

Abstract

This invention provides a polyalkylene oxide that allows for the simple production of highly transparent resin films, and a method for producing the same. [Solution] The polyalkylene oxide is a random copolymer of a monomer composition containing a hydrophilic oxirane monomer and a hydrophobic oxirane monomer, wherein the copolymerization ratio of the hydrophobic oxirane monomer is 28 to 45 mol%, and the hydrophobic oxirane monomer contains at least one oxirane monomer having a radical reactive group in its side chain.

Description

[Technical Field]

[0001] This invention relates to polyalkylene oxides, additives for emulsion polymerization of olefins, emulsion polymerization compositions, methods for producing polyalkylene oxides, methods for producing olefin polymers, olefin polymers, methods for producing films, and films. [Background technology]

[0002] Resin films are used in a wide range of technical fields.

[0003] High transparency is sometimes required for resin films. For example, when using a resin film to protect the surface of a display, the transparency of the resin film is related to hue and light energy loss, so a resin film with a low haze value (i.e., high transparency) is required. Note that "haze" can also be pronounced "haze" or "haze value".

[0004] Acrylic resins, which have excellent transparency, are one example of materials for resin films. However, the transparency of acrylic resins may decrease depending on the manufacturing conditions and additives used during manufacturing. As a way to solve this problem, a processing method that makes the front and back of the film different during film formation (Patent Document 1) and a manufacturing method that suppresses the aggregation of polymer chains by incorporating unsaturated monomers into the polymer chains (Patent Document 2) have been proposed. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2019-014047 [Patent Document 2] WO2015 / 159829A1 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, in the methods of Patent Documents 1 and 2, in order to enhance the transparency of the produced resin film, it is necessary to use special equipment or raw materials.

[0007] Therefore, the present disclosure aims to provide a polyalkylene oxide, an additive for emulsion polymerization of olefins, an emulsion polymerization composition, a method for producing a polyalkylene oxide, a method for producing an olefin polymer, an olefin polymer, a method for producing a film, and a film, which can easily produce a resin film with high transparency.

Means for Solving the Problems

[0008] In order to achieve the above object, the polyalkylene oxide of the present disclosure is a polyalkylene oxide, wherein the polyalkylene oxide is a random copolymer of a monomer composition containing a hydrophilic oxirane monomer and a hydrophobic oxirane monomer, the copolymerization ratio of the hydrophobic oxirane monomer is 28 to 45 mol%, and the hydrophobic oxirane monomer contains at least one kind of oxirane monomer having a radical-reactive group in the side chain.

[0009] The additive for emulsion polymerization of olefins of the present disclosure is characterized by containing the polyalkylene oxide of the present disclosure.

[0010] The emulsion polymerization composition of the present disclosure is characterized by containing the additive for emulsion polymerization of olefins of the present disclosure and an olefin which is a raw material for emulsion polymerization.

[0011] The method for producing the polyalkylene oxide of the present disclosure is the method for producing the polyalkylene oxide of the present disclosure, which is characterized by randomly copolymerizing the monomer composition containing the hydrophilic oxirane monomer and the hydrophobic oxirane monomer.

[0012] A method for producing an olefin polymer according to the present disclosure is characterized by copolymerizing the olefin in the emulsion polymerization composition according to the present disclosure with a polyalkylene oxide according to the present disclosure.

[0013] The olefin polymer of this disclosure is characterized by being produced by the method for producing the olefin polymer of this disclosure.

[0014] The method for manufacturing the film disclosed herein is: An olefin polymer manufacturing step for manufacturing an olefin polymer by the method for manufacturing an olefin polymer described herein, A molding step of forming the composition containing the olefin polymer into a film, A method for producing a film containing the olefin polymer, characterized by including the following:

[0015] The film of this disclosure is a film comprising the olefin polymer, characterized by being manufactured by the method for manufacturing the film of this disclosure. [Effects of the Invention]

[0016] According to this disclosure, it is possible to provide a polyalkylene oxide, an additive for emulsion polymerization of olefins, an emulsion polymerization composition, a method for producing polyalkylene oxide, a method for producing olefin polymers, an olefin polymer, a method for producing a film, and a film, which can be easily produced as a resin film with high transparency. [Brief explanation of the drawing]

[0017] [Figure 1] Figure 1 is a diagram illustrating the method for calculating the copolymerization ratio of each monomer component in the examples, and is a 1H-NMR chart of the polyalkylene oxide produced in Example 1. [Figure 2] Figure 2 shows the 1H-NMR chart of the polyalkylene oxide produced in Example 1. [Figure 3] Figure 3 shows the 1H-NMR chart of the polyalkylene oxide prepared in Example 2. [Figure 4] Figure 4 shows the 1H-NMR chart of the polyalkylene oxide prepared in Example 3. [Figure 5] Figure 5 shows the 1H-NMR chart of the polyalkylene oxide produced in Example 4. [Figure 6] Figure 6 shows the 1H-NMR chart of the polyalkylene oxide produced in Comparative Example 1. [Figure 7] Figure 7 shows the 1H-NMR chart of the polyalkylene oxide produced in Comparative Example 2. [Figure 8] Figure 8 shows the 1H-NMR chart of the polyalkylene oxide produced in Comparative Example 4. [Modes for carrying out the invention]

[0018] The following provides an example of this disclosure. However, this disclosure is not limited to the following description.

[0019] [1. Polyalkylene oxides] The polyalkylene oxide of this disclosure is a random copolymer of a monomer composition comprising a hydrophilic oxirane monomer and a hydrophobic oxirane monomer, wherein the copolymerization ratio of the hydrophobic oxirane monomer is 28 to 45 mol%, and the hydrophobic oxirane monomer comprises at least one oxirane monomer having a radical-reactive group in its side chain.

[0020] As a result of their investigations, the present inventors have found that a highly transparent resin film can be easily manufactured by using the polyalkylene oxide of the present disclosure, which is a random copolymer of a monomer composition containing a hydrophilic oxirane monomer and a hydrophobic oxirane monomer, wherein the copolymerization ratio of the hydrophobic oxirane monomer is within the range described above.

[0021] Specifically, in the emulsion polymerization of olefins, by adding the polyalkylene oxide of the present disclosure as a prepolymer and copolymerizing the olefin with the polyalkylene oxide of the present disclosure to produce a film, the transparency of the produced film can be easily improved without using special equipment or monomers.

[0022] The weight average molecular weight of the polyalkylene oxide of the present disclosure is not particularly limited, but it is preferably larger from the viewpoint of transparency. For example, 2.0×10 4 or more is preferable. Also, from the viewpoint of reducing the viscosity and facilitating handling, the weight average molecular weight is preferably smaller. For example, 2.0×10 5 or less. The weight average molecular weight of the polyalkylene oxide of the present disclosure is, for example, 2.0×10 3 or more, 2.5×10 3 or more, 3.0×10 3 or more, 3.5×10 3 or more, or 4.0×10 3 or more may be used. For example, 2.0×10 5 or less, 1.5×10 5 or less, 1.0×10 5 or less, 5.0×10 4 or less, or 4.5×10 4 or less may be used. For example, 2.0×10 3 ~2.0×10 5 、2.5×10 3 ~1.5×10 5 、3.0×10 3 ~1.0×10 5 、3.5×10 3 ~5.0×10 4 、or 4.0×10 3 ~5.0×10 4 may be used. When the numerical value of the weight average molecular weight can be measured by the measurement method described in the examples below, it is the measured value by that measurement method. However, the measurement method of the weight average molecular weight is not particularly limited, and it may be measured by any measurement method.

[0023] [1-1. Hydrophilic Oxirane Monomer] In this disclosure, "hydrophilic oxirane monomer" refers to an oxirane monomer whose structure, after ring-opening polymerization at a degree of polymerization of 30, is miscible with water in any ratio. Note that "oxirane" and "epoxide" are synonymous.

[0024] In this disclosure, examples of the hydrophilic oxirane monomer include ethylene oxide (also known as ethylene oxide, and hereinafter sometimes referred to as "EO"), glycidol, oxirane-2-carboxylic acid, glycidamine, and the like.

[0025] In the polyalkylene oxide of this disclosure, the copolymerization ratio of the hydrophilic oxirane monomer may be, for example, 55 mol% or more, 56 mol% or more, 57 mol% or more, 58 mol% or more, or 59 mol% or more, for example, 72 mol% or less, 71 mol% or less, 70 mol% or less, 69 mol% or less, or 68 mol% or less, for example, 55-72 mol%, 56-72 mol%, 55-71 mol%, 57-72 mol%, or 56-71 mol%.

[0026] In the polyalkylene oxide of this disclosure, the method for measuring the copolymerization ratio of each monomer component, such as the hydrophilic oxirane monomer and the hydrophobic oxirane monomer, is not particularly limited and can be measured by any method. However, the numerical values ​​of the copolymerization ratio of each monomer component shall be obtained by the measurement and calculation methods described in the examples below. 1 If measurement and calculation are possible using 1H-NMR, the value shall be the value calculated from the measurement value obtained by that method.

[0027] [1-2. Hydrophobic oxilan monomers] In this disclosure, "hydrophobic oxirane monomer" refers to an oxirane monomer other than a hydrophilic oxirane monomer, that is, an oxirane monomer whose structure after ring-opening polymerization at a degree of polymerization of 30 is not miscible with water in any ratio. As stated above, "oxirane" and "epoxide" are synonymous.

[0028] In this disclosure, the type of hydrophobic oxirane monomer is not particularly limited. However, in order for the polyalkylene oxide of this disclosure to copolymerize with an olefin, which is a raw material for emulsion polymerization described later, as described above, the hydrophobic oxirane monomer must contain at least one oxirane monomer having a radical reactive group in its side chain.

[0029] In this disclosure, examples of the hydrophobic oxirane monomer include propylene oxide (also known as propylene oxide, and hereinafter sometimes referred to as "PO"), allyl glycidyl ether (hereinafter sometimes referred to as "AGE"), butylene oxide, phenyl glycidyl ether, alkyl monoglycidyl ether, epihalohydrin, and the like.

[0030] In the polyalkylene oxides of this disclosure, the copolymerization ratio of the hydrophobic oxirane monomer is 28 to 45 mol%, as described above. If the copolymerization ratio of the hydrophobic oxirane monomer is too high or too low compared to this range, the transparency of the film produced using the polyalkylene oxides of this disclosure will be reduced or the appearance will be poor. The copolymerization ratio of the hydrophobic oxirane monomer may be, for example, 28 mol% or more, 29 mol% or more, 30 mol% or more, 31 mol% or more, or 32 mol% or more, and may also be, for example, 45 mol% or less, 44 mol% or less, 43 mol% or less, 42 mol% or less, or 41 mol% or less, and may also be, for example, 28 to 45 mol%, 28 to 44 mol%, 29 to 45 mol%, 30 to 45 mol%, or 29 to 44 mol%.

[0031] In the polyalkylene oxide of this disclosure, the method for measuring the copolymerization ratio of each monomer component, such as the hydrophobic oxirane monomer, is as described above, for example, by the measurement method described in the examples below. 1 It can be measured and calculated using 1H-NMR.

[0032] [1-3. Other monomer components] The polyalkylene oxides of this disclosure may or may not contain other monomer components other than the hydrophilic oxirane monomer and the hydrophobic oxirane monomer (i.e., monomer components other than the oxirane monomer) as copolymer components. The other monomer components are not particularly limited, but examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, glycerol, and the like. When the polyalkylene oxides of this disclosure contain the other monomers as copolymer components, the copolymerization ratio of the other monomers may be, for example, 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, or 5 mol% or more, for example, 15 mol% or less, 14 mol% or less, 13 mol% or less, 12 mol% or less, or 11 mol% or less, for example, 1 to 15 mol%, 2 to 15 mol%, 1 to 14 mol%, 3 to 15 mol%, or 2 to 14 mol%.

[0033] [2. Method for producing polyalkylene oxides] The method for producing the polyalkylene oxide of this disclosure is not particularly limited, but for example, it can be produced by the method for producing the polyalkylene oxide of this disclosure, which involves random copolymerizing the monomer composition comprising the hydrophilic oxirane monomer and the hydrophobic oxirane monomer. The monomer composition may or may not contain the other monomer components mentioned above, in addition to the hydrophilic oxirane monomer and the hydrophobic oxirane monomer.

[0034] The method and reaction conditions for random copolymerization are not particularly limited and may be the same as or similar to those of a general polymerization reaction. In the random copolymerization, for example, a solvent, a reaction initiator (nucleophile), a catalyst, etc. may be used. The solvent is not particularly limited but may include aromatic hydrocarbons such as toluene and benzene, and n-butane, isobutane, n-pentane, cyclopentane, industrial hexane, n-hexane, isohexane, cyclohexane, n-heptane, n-octane, isooctane, acetonitrile, etc., and may be used alone or in any proportion. The reaction initiator is not particularly limited but may include potassium t-butoxide, sodium ethoxide, sodium methoxide, etc., and may be used alone or in any proportion. The catalyst is not particularly limited, but examples include alkylaluminum (e.g., triisobutylaluminum, trimethylaluminum, triethylaluminum, triphenylaluminum, diphenylisobutylaluminum, monophenyldiisobutylaluminum, etc.), and only one type may be used, or multiple types may be used in any ratio. The ratio of amounts and concentrations of each substance used are not particularly limited and can be set as appropriate. The reaction temperature for the random copolymerization is not particularly limited, but may be, for example, 5°C or higher, 10°C or higher, 15°C or higher, 20°C or higher, or 25°C or higher, or for example, 50°C or lower, 45°C or lower, 40°C or lower, 35°C or lower, or 30°C or lower, or for example, 5-50°C, 10-50°C, 5-45°C, 10-45°C, or 15-50°C. The reaction time for the random copolymerization is not particularly limited, but may be, for example, 8.0 hr or more, 8.5 hr or more, 9.0 hr or more, 9.5 hr or more, or 10.0 hr or more. It may also be, for example, 24.0 hr or less, 20.0 hr or less, 17.0 hr or less, 15.0 hr or less, or 13.0 hr or less. For example, it may be 8.0 to 24.0 hr, 8.5 to 24.0 hr, 8.0 to 20.0 hr, 9.0 to 24.0 hr, or 9.0 to 20.0 hr.

[0035] [3. Additives for emulsion polymerization of olefins] The additives for emulsion polymerization of olefins according to this disclosure are not particularly limited except that they include the polyalkylene oxide according to this disclosure. The additives for emulsion polymerization of olefins according to this disclosure may or may not contain other components other than the polyalkylene oxide according to this disclosure.

[0036] [4. Emulsion polymerization composition] As described above, the emulsion polymerization composition of the present disclosure is characterized by comprising an additive for emulsion polymerization of the olefin of the present disclosure and an olefin that is a raw material for emulsion polymerization.

[0037] In the emulsion polymerization composition of the present disclosure, the ratio of the polyalkylene oxide of the present disclosure to the total amount (mol) of the polyalkylene oxide of the present disclosure and the olefin that is a raw material for the emulsion polymerization is, for example, 2.5 × 10 -3 mol% or more, 3.0×10 -3 mol% or more, 3.5×10 -3 mol% or more, 4.5×10 -3 mol% or more, or 5.0 × 10 -3 It may be mol% or more, for example, 1.0 × 10 2 mol% or less, 10mol% or less, 1.0mol% or less, 1.0×10 -1 mol% or less, or 1.0 × 10⁻⁶ -2 It may be less than mol%, for example, 2.5 × 10 -3 ~1.0×10 2 mol%, 3.0 × 10 -3 ~1.0×10 2 mol%, 3.5 × 10 -3 ~1.0×10 2 mol%, 4.0 × 10 -3 ~1.0×10 2 mol%, or 4.5 × 10 -3 ~1.0×10 2It may be mol%. The ratio of the olefin raw material for emulsion polymerization to the total amount (mol) of the polyalkylene oxide and the olefin raw material for emulsion polymerization of the present disclosure is not particularly limited, but is the remaining ratio after subtracting the ratio (mol%) of the polyalkylene oxide of the present disclosure from 100% (100 mol%).

[0038] The olefin used as a raw material for the emulsion polymerization is not particularly limited, and any olefin that is a common raw material for emulsion polymerization can be used. Only one type may be used, or multiple types may be used in any ratio. Examples of the olefin used as a raw material for emulsion polymerization include (meth)acrylic acid derivatives. Examples of (meth)acrylic acid derivatives include (meth)acrylate alkyl esters. Examples of (meth)acrylate alkyl esters include ethyl methacrylate, butyl methacrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, etc. In this disclosure, "(meth)acrylic" means at least one of "acrylic" and "methacrylic". For example, in this disclosure, "(meth)acrylic acid derivative" represents at least one of acrylic acid derivatives and methacrylic acid derivatives. Also, in this disclosure, "(meth)acrylate alkyl ester" represents at least one of acrylate alkyl esters and methacrylate alkyl esters.

[0039] The emulsion polymerization composition of the present disclosure may contain, or may not contain, other components besides the additive for emulsion polymerization of the olefin of the present disclosure and the olefin, which is a raw material for emulsion polymerization. The other components are not particularly limited, but may be components commonly used in emulsion polymerization, such as solvents (dispersion media), surfactants, polymerization initiators, etc. The solvent (dispersion media) is not particularly limited, but may be water, water-soluble organic solvents, etc., and may be used alone or in any ratio of multiple types. Examples of water-soluble organic solvents include alcohols, ketones, nitriles, etc. The alcohol may be monohydric or polyhydric, such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, diethylene glycol, etc. Examples of ketones include acetone, etc. Examples of nitriles include acetonitrile, etc. The surfactant is not particularly limited, but may be a general surfactant, such as polyoxyethylene alkyl ethers, sulfate ester salts of higher alcohols, or quaternary ammonium salts. Only one type may be used, or multiple types may be used in any ratio. The polymerization initiator is not particularly limited, but may be a general polymerization initiator, such as azo initiators, peroxide initiators, or redox initiators. Only one type may be used, or multiple types may be used in any ratio. The ratio of amounts and concentrations of each substance used are not particularly limited and can be set as appropriate.

[0040] The method for producing the emulsion polymerization composition of this disclosure is not particularly limited, and for example, it may simply involve mixing all the components constituting the emulsion polymerization composition of this disclosure.

[0041] [5. Method for producing olefin polymers] As described above, the method for producing the olefin polymer of the present disclosure is characterized by copolymerizing the olefin in the emulsion polymerization composition of the present disclosure with the polyalkylene oxide of the present disclosure. The copolymerization method is not particularly limited and may be the same as or similar to general copolymerization methods. Specifically, for example, the emulsion polymerization composition of the present disclosure may be simply heated to cause a copolymerization reaction. The reaction temperature of the copolymerization reaction is not particularly limited, but may be, for example, 45°C or higher, 50°C or higher, 55°C or higher, 60°C or higher, or 65°C or higher, or for example, 95°C or lower, 90°C or lower, 85°C or lower, 80°C or lower, 75 or 70°C or lower, or for example, 45-95°C, 45-90°C, 50-95°C, 50-90°C, or 55-90°C. The reaction time for the copolymerization reaction is not particularly limited, but may be, for example, 8 hours or more, 9 hours or more, 10 hours or more, 11 hours or more, or 12 hours or more, or for example, 24 hours or less, 23 hours or less, 22 hours or less, 21 hours or less, or 20 hours or less, or for example, 8 to 24 hours, 9 to 24 hours, 10 to 24 hours, 11 to 24 hours, or 12 to 24 hours.

[0042] [6. Olefin Polymer] The olefin polymer of this disclosure is characterized by being produced by the method for producing the olefin polymer of this disclosure, as described above. By producing the olefin polymer of this disclosure by the method for producing the olefin polymer of this disclosure, for example, a highly transparent resin film can be easily produced.

[0043] [7. Film manufacturing method] As described above, the method for manufacturing a film according to the present disclosure is a method for manufacturing a film containing an olefin polymer, characterized by comprising an olefin polymer manufacturing step of manufacturing an olefin polymer by the method for manufacturing an olefin polymer according to the present disclosure, and a molding step of forming a composition containing the olefin polymer into a film.

[0044] The olefin polymer manufacturing process for producing an olefin polymer by the method for producing an olefin polymer described herein is not particularly limited, but may include, for example, the steps described above.

[0045] The molding process for forming the composition containing the olefin polymer into a film is not particularly limited. For example, after the olefin polymer manufacturing process, the emulsion or solution containing the olefin polymer may be spread thinly and dried to form a film. The film (resin film) produced in this way is sometimes called a "dried film." The drying temperature and drying time are not particularly limited and can be set as appropriate. The drying temperature is not particularly limited, but may be, for example, 35°C or higher, 40°C or higher, 45°C or higher, 50°C or higher, or 55°C or higher, or for example, 95°C or lower, 90°C or lower, 85°C or lower, 80°C or lower, or 75°C or lower, or for example, 35-95°C, 40-95°C, 35-90°C, 40-90°C, or 45-85°C. The drying time is not particularly limited, but may be, for example, 12 hours or more, 13 hours or more, 14 hours or more, 15 hours or more, or 16 hours or more, or for example, 36 hours or less, 35 hours or less, 34 hours or less, 33 hours or less, or 32 hours or less, or for example, 12 to 36 hours, 13 to 36 hours, 12 to 35 hours, 13 to 35 hours, or 14 to 36 hours. The drying may also be a two-stage (or more multi-stage) drying, for example, drying at a low temperature followed by drying at a high temperature. In this case, the drying temperature at the low temperature is not particularly limited, but may be, for example, 35°C or higher, 40°C or higher, 45°C or higher, 50°C or higher, or 55°C or higher, or for example, 95°C or lower, 90°C or lower, 85°C or lower, 80°C or lower, or 75°C or lower, or for example, 35 to 95°C, 40 to 95°C, 35 to 90°C, 40 to 90°C, or 45 to 85°C. The drying time at low temperatures is not particularly limited, but may be, for example, 8 hours or more, 9 hours or more, 10 hours or more, 11 hours or more, or 12 hours or more, or for example, 24 hours or less, 23 hours or less, 22 hours or less, 21 hours or less, or 20 hours or less, or for example, 8 to 24 hours, 9 to 24 hours, 8 to 23 hours, 9 to 23 hours, or 10 to 24 hours.The drying temperature at the high temperature is not particularly limited, but may be, for example, 100°C or higher, 105°C or higher, 110°C or higher, 115°C or higher, or 120°C or higher, and may also be, for example, 200°C or lower, 195°C or lower, 190°C or lower, 185°C or lower, or 180°C or lower, and may also be, for example, 100-200°C, 105-200°C, 100-195°C, 105-195°C, or 110-200°C. The drying time at high temperature is not particularly limited, but may be, for example, 1.0 hr or more, 1.5 hr or more, 2.0 hr or more, 2.5 hr or more, or 3.0 hr or more, or for example, 6.0 hr or less, 5.5 hr or less, 5.0 hr or less, 4.5 hr or less, or 4.0 hr or less, or for example, 1.0 to 6.0 hr, 1.5 to 6.0 hr, 1.0 to 5.5 hr, 1.5 to 5.5 hr, or 2.0 to 6.0 hr.

[0046] Furthermore, after the drying process, other treatments such as stretching may or may not be performed as appropriate.

[0047] [8. Film] The film of this disclosure is a film containing the olefin polymer, characterized in that it is manufactured by the method for manufacturing the film of this disclosure, as described above. The film of this disclosure has high transparency because it is manufactured by the method for manufacturing the film of this disclosure. The method for measuring the haze value (also called haze value, total haze value, or total haze value), which is an indicator of high transparency, is not particularly limited, but can be measured by the measurement method of the examples described later. The haze value (total haze value) of the film of this disclosure is not particularly limited, but may be, for example, 20% or less, 19% or less, 18% or less, 17% or less, or 16% or less, and the lower limit is not particularly limited, but may be, for example, 0% or more or a value greater than 0%.

[0048] The film disclosed herein is a highly transparent resin film and is therefore applicable, for example, to the field of resin films for surface protection of displays. Furthermore, the film disclosed herein is not limited to this and is applicable to all technical fields related to resin films, specifically, for example, to the interior and exterior of personal computers, the interior and exterior of mobile phones, automotive headlights, films for liquid crystal displays, films for organic EL displays, and the like. [Examples]

[0049] Examples and comparative examples of the present invention are described below. However, the present invention is not limited to these examples. Furthermore, in the following, "parts" refers to parts by weight, and "%" refers to "weight percent".

[0050] [Weight-average molecular weight (Mw) of polyalkylene oxides] The weight-average molecular weight (Mw) of each polymer (polyalkylene oxide) synthesized according to the examples and comparative examples described below was measured by GPC (gel permeation chromatography) using the following apparatus and under the following measurement conditions. Polyethylene oxide was used as the conversion standard as described below. Device: Product name "LC-10AD (manufactured by Shimadzu Corporation)" Detector: Differential refractive index detector (RID) Column: Product name "SHODEX LF-804 (manufactured by Showa Denko Corporation)" Measurement temperature: 33℃ Eluent:THF Flow rate: 1.0mL / min Sample concentration: 0.2 wt% (THF) Sample injection volume: 100 μL Conversion standard: Polyethylene oxide

[0051] [Copolymerization ratio of polyalkylene oxides] The copolymerization ratio of each polymer (polyalkylene oxide) in the examples and comparative examples described below was measured as follows: 1The measurement was performed by 1H-NMR under the following conditions. However, as will be described later, Comparative Example 3 is a homopolymer of ethylene oxide, 1 1H-NMR was not performed. <Measurement conditions> Equipment: Product name "JNM-ECZL400S (manufactured by JEOL Ltd.)" Observed nuclei: 1 H Observation range: 7507.50Hz Number of data points: 65536 Pulse width: 3.415 μsec Waiting time: 5 seconds Total count: 128 Measurement temperature: 25℃ Measurement solvent: Deuterated chloroform Sample concentration: 0.01 g / ml

[0052] Polyalkylene oxide 1 The copolymerization ratio of each monomer was calculated from 1H-NMR using the method described below. This will be explained using Figure 1 as an example, with reference to Example 1. Figure 1 shows the polyalkylene oxide produced in Example 1. 1 This is an H-NMR chart. In addition to Example 1, the copolymerization ratio of each monomer was calculated in each example and comparative example using the same method as described below. (a) The relative number of allyl glycidyl ether moieties (AGEs) in a polyalkylene oxide molecule is defined as the peak intensity of j in Figure 1 divided by the number of hydrogen atoms in j (i.e., 1). (b) The relative number of propylene oxide (PO) moieties in a polyalkylene oxide molecule is defined as the peak intensity of e in Figure 1 divided by the number of hydrogen atoms in e (i.e., 3). (c) Since the peaks a and b in Figure 1 overlap with the peaks c, d, f, g, h, and i in the same figure, the sum of the peak intensities of a and b, "a+b", is calculated using the following formula (1).

number

number

number

[0053] [Examples 1-4 and Comparative Examples 1-4: Polyalkylene Oxides] The monomers in a monomer composition containing a hydrophilic oxirane monomer and a hydrophobic oxirane monomer were randomly copolymerized as described below to produce the polyalkylene oxides of the present disclosure in Examples 1 to 4 or the polyalkylene oxides of Comparative Examples 1 to 2. Furthermore, the polyalkylene oxides of Comparative Examples 3 to 4, described later, were used as comparison subjects with the polyalkylene oxides of the present disclosure.

[0054] [Example 1] In a 1 L autoclave, 165 parts by weight of toluene and 0.84 parts by weight of potassium t-butoxide were added and nitrogen purged. Then, 39 parts by weight of triisobutylaluminum were added and nitrogen purged again. This reaction solution was stirred while cooling the outside of the autoclave with cooling water below 10°C. While continuing this cooling and stirring, a mixture of ethylene oxide, propylene oxide, and allyl glycidyl ether was added dropwise to the reaction solution over 8 hours. The charging ratio of the monomers was adjusted as appropriate so that copolymerization could be achieved in the proportions described in Example 1 (A-1) in Table 1 below. Note that ethylene oxide corresponds to a "hydrophilic oxirane monomer," and both propylene oxide and allyl glycidyl ether correspond to "hydrophobic oxirane monomers." After the dropwise addition was completed, stirring was continued for a further 13 hours while cooling was continued. In this way, the monomers in the monomer composition were randomly copolymerized. Thereafter, the reaction was stopped by adding 4.1 parts by weight of water and stirring for 1 hour to produce the polyalkylene oxide of this disclosure. The polyalkylene oxide produced in this manner in this example is designated as copolymer A-1. The copolymerization ratio of the hydrophobic oxirane monomer in copolymer A-1 was calculated to be 28.6 mol%, as will be described later.

[0055] Copolymer A-1 1 Figure 2 shows a chart of the 1H-NMR measurement results. The analysis results (copolymerization ratios of each monomer in copolymer A-1) are shown below. EO:PO:AGE=71.4:25.5:3.1

[0056] [Example 2] The same procedure as in Example 1 was performed to produce the polyalkylene oxide of this disclosure, except that the composition of the monomer composition was adjusted so that the charging ratios of ethylene oxide, propylene oxide, and allyl glycidyl ether were copolymerized in the proportions described in Example 2 (A-2) in Table 1 below. The polyalkylene oxide of this example produced in this way is designated as copolymer A-2. The copolymerization ratio of the hydrophobic oxirane monomer in copolymer A-2 was calculated to be 33.2 mol%, as will be described later.

[0057] Copolymer A-2 1 Figure 3 shows a chart of the 1H-NMR measurement results. The analysis results (copolymerization ratios of each monomer in copolymer A-2) are shown below. EO:PO:AGE=66.8:29.6:3.6

[0058] [Example 3] The same procedure as in Example 1 was performed to produce the polyalkylene oxide of this disclosure, except that the composition of the monomer composition was adjusted so that the charging ratios of ethylene oxide, propylene oxide, and allyl glycidyl ether were copolymerized in the proportions described in Example 3 (A-3) in Table 1 below. The polyalkylene oxide of this example produced in this way is designated as copolymer A-3. The copolymerization ratio of the hydrophobic oxirane monomer in copolymer A-3 was calculated to be 40.6 mol%, as will be described later.

[0059] Copolymer A-3 1 The chart of the 1H-NMR measurement results is shown in Figure 4. The analysis results (copolymerization ratio of each monomer in copolymer A-3) are shown below. EO:PO:AGE=59.4:36.0:4.6

[0060] [Example 4] The same procedure as in Example 1 was performed to produce the polyalkylene oxide of the present disclosure, except that the composition of the monomer composition was adjusted so that the charging ratios of ethylene oxide, propylene oxide, and allyl glycidyl ether were copolymerized in the proportions described in Example 4 (A-4) in Table 1 below. The polyalkylene oxide of this example produced in this way is designated as copolymer A-4. The copolymerization ratio of the hydrophobic oxirane monomer in copolymer A-4 was calculated to be 43.7 mol%, as will be described later.

[0061] Copolymer A-4 1 The chart of the 1H-NMR measurement results is shown in Figure 5. The analysis results (copolymerization ratio of each monomer in copolymer A-4) are shown below. EO:PO:AGE=56.3:39.0:4.7

[0062] [Comparative Example 1] The same procedure as in Example 1 was followed to produce the polyalkylene oxide of this comparative example, except that the composition of the monomer composition was adjusted so that the charging ratios of ethylene oxide, propylene oxide, and allyl glycidyl ether were copolymerized in the proportions described in Comparative Example 1 (B-1) in Table 1 below. The polyalkylene oxide of this comparative example produced in this way was designated as copolymer B-1. The copolymerization ratio of the hydrophobic oxirane monomer in copolymer B-1 was calculated to be 26.1 mol%, as described later.

[0063] Copolymer B-1 1 The chart of the 1H-NMR measurement results is shown in Figure 6. The analysis results (copolymerization ratio of each monomer in copolymer B-1) are shown below. EO:PO:AGE=73.9:23.3:2.8

[0064] [Comparative Example 2] The same procedure as in Example 1 was followed to produce the polyalkylene oxide of this comparative example, except that the composition of the monomer composition was adjusted so that the charging ratios of ethylene oxide, propylene oxide, and allyl glycidyl ether were copolymerized in the proportions described in Comparative Example 2 (B-2) in Table 1 below. The polyalkylene oxide of this comparative example produced in this way was designated as copolymer B-2. The copolymerization ratio of the hydrophobic oxirane monomer in copolymer B-2 was calculated to be 47.9 mol%, as described later.

[0065] Copolymer B-2 1 Figure 7 shows a chart of the 1H-NMR measurement results. The analysis results (copolymerization ratios of each monomer in copolymer B-2) are shown below. EO:PO:AGE=52.2:42.7:5.2

[0066] [Comparative Example 3] The same procedure as in Example 1 was followed to produce the polyalkylene oxide of this comparative example, except that the composition of the monomer composition was adjusted so that the charging ratios of ethylene oxide, propylene oxide, and allyl glycidyl ether were copolymerized in the proportions shown in Comparative Example 3 (B-3) in Table 1 below. The polyalkylene oxide of this comparative example produced in this manner is designated as polymer B-3. The copolymerization ratio of hydrophobic oxirane monomers in polymer B-3 is 0%.

[0067] [Comparative Example 4] The same procedure as in Example 1 was followed to produce the polyalkylene oxide of this comparative example, except that the composition of the monomer composition was adjusted so that the charging ratios of ethylene oxide, propylene oxide, and allyl glycidyl ether were copolymerized in the proportions described in Comparative Example 4 (B-4) in Table 1 below. The polyalkylene oxide of this comparative example produced in this way was designated as copolymer B-4. The copolymerization ratio of the hydrophobic oxirane monomer in copolymer B-4 was calculated to be 7.6 mol%, as described later.

[0068] Copolymer B-4 1 Figure 8 shows a chart of the 1H-NMR measurement results. The analysis results (copolymerization ratios of each monomer in copolymer B-4) are shown below. EO:PO:AGE=92.4:5.4:2.2

[0069] The measured weight-average molecular weight and copolymerization rate of the polyalkylene oxides in the examples and comparative examples are shown in Table 1 below. As mentioned above, EO (ethylene oxide) is a hydrophilic oxirane monomer, while PO (propylene oxide) and AGE (allyl glycidyl ether) are hydrophobic oxirane monomers. In other words, the sum of the copolymerization rates of PO and AGE represents the copolymerization ratio of hydrophobic oxirane monomers in the polyalkylene oxide.

[0070] [Table 1]

[0071] <Manufacturing of water-based acrylic resin emulsions and films (evaluation examples 1-8)> In a separable flask equipped with a stirrer, condenser, and thermometer, 0.33 parts by weight of any polyalkylene oxide from Examples 1-4 and Comparative Examples 1-4, 1.58 parts by weight of trade name Cotamine 86W (surfactant manufactured by Kao Corporation), 14.7 parts by weight of butyl acrylate, 14.6 parts by weight of methyl methacrylate, and 237.3 parts by weight of distilled water were charged, and the mixture was mixed at room temperature after nitrogen purging. Furthermore, an aqueous solution of 0.033 parts by weight of an azo polymerization initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "VA-044") and 30 parts by weight of distilled water was added to prepare (manufacture) an emulsion polymer. Of these emulsion polymers, the emulsion polymer containing any polyalkylene oxide from Examples 1-4 corresponds to the emulsion polymer of the examples in this disclosure. The emulsion polymer containing any polyalkylene oxide from Comparative Examples 1-4 corresponds to the emulsion polymer of the comparative examples. Both butyl acrylate and methyl methacrylate fall under the category of "olefins used as raw materials for emulsion polymerization." This emulsion polymer was reacted at a liquid temperature of 60°C with stirring for 20 hours to obtain an aqueous acrylic resin emulsion. These aqueous acrylic resin emulsions are designated as Evaluation Examples 1 to 8. As shown in Table 2 below, Evaluation Examples 1 to 4 correspond to Examples 1 to 4, respectively, and Evaluation Examples 5 to 8 correspond to Comparative Examples 1 to 4, respectively.

[0072] Furthermore, the aqueous acrylic resin emulsions obtained in Evaluation Examples 1 to 8 were first dried overnight in a 40°C dryer, then for 1 hour in a 110°C dryer, and then left to stand overnight in a 25°C incubator to produce films (dried films). Of the films produced, Evaluation Examples 1 to 4 correspond to the films of the examples of this disclosure, and Evaluation Examples 5 to 8 correspond to the films of the comparative examples.

[0073] <Production of water-based acrylic resin emulsion (Evaluation example 9: without polyalkylene oxide polymer)> In a separable flask equipped with a stirrer, condenser, and thermometer, 1.58 parts by weight of trade name Cotamin 86W (a surfactant manufactured by Kao Corporation), 14.7 parts by weight of butyl acrylate, 14.6 parts by weight of methyl methacrylate, and 237.3 parts by weight of distilled water were charged and mixed at room temperature after nitrogen purging. Furthermore, an aqueous solution of 0.033 parts by weight of an azo polymerization initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "VA-044") and 30 parts by weight of distilled water was added to prepare (manufacture) an emulsion polymer. This emulsion polymer corresponds to the emulsion polymer of the comparative example. This emulsion polymer was reacted with stirring at a liquid temperature of 60°C for 20 hours to obtain an aqueous acrylic resin emulsion. This aqueous acrylic resin emulsion is designated as Evaluation Example 9 (Comparative Example 5). The aqueous acrylic resin emulsion of Evaluation Example 9 was dried overnight in a 40°C dryer, then in a 110°C dryer for 1 hour, and then left to stand overnight in a 25°C incubator to obtain the film (dried film) of Evaluation Example 9 (Comparative Example 5).

[0074] The haze values ​​of the dried films in Evaluation Examples 1-9 were measured using the measurement method described below. Furthermore, the appearance of the dried films in Evaluation Examples 1-9 was visually evaluated using the method described below.

[0075] <Method for measuring haze in dried film> The haze values ​​of the dry films (acrylic resin films) in evaluation examples 1-9 were measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: NDH4000) in accordance with JIS-K 7136 (2000 edition).

[0076] <Visual evaluation method for the appearance of dried film> When the dried films of evaluation examples 1-9 were held up to the light, the degree to which lines were visible or the films appeared cloudy was visually evaluated. The evaluation criteria are described below. About "lines" A: I can't see the line. B: The lines are mostly invisible, but the pattern is partially visible. C: The lines are clearly visible. About "White" A: It's cloudy and I can't see. B: It is not generally cloudy white, but there are some areas with a faint whiteness. C: Appears cloudy white.

[0077] These measurement and evaluation results, along with the copolymerization ratio (hydrophobic portion mol%) of the hydrophobic oxirane monomer in the polyalkylene oxide, are shown in Table 2 below. In Table 2 below, "HAZE" is the haze value (total haze value) measured by the method described above, and a lower value indicates higher transparency of the film. "TT", "PT", and "Dif." are all values ​​measured simultaneously when measuring the haze value as described above. "TT" is the total light transmittance, and a higher value indicates higher transparency of the film. "PT" is the transmittance of light that passes through the film without refraction or scattering. "Dif." is the transmittance of light that passes through the film with refraction or scattering. The sum of the "PT" and "Dif." values ​​equals the "TT" value.

[0078] [Table 2]

[0079] As shown in Table 2 above, the films of Evaluation Examples 1-4 (Examples 1-4), in which the copolymerization ratio (hydrophobic portion mol%) of the hydrophobic oxirane monomer in the polyalkylene oxide was within the range of this disclosure, all showed excellent transparency. In contrast, Evaluation Examples 5 and 6 (Comparative Examples 1 and 2), in which the copolymerization ratio (hydrophobic portion mol%) of the hydrophobic oxirane monomer in the polyalkylene oxide was outside the range of this disclosure, both showed high haze values, confirming that they were less transparent than the films of the Examples. In particular, Evaluation Example 5 (Comparative Example 1) had a haze value equivalent to Evaluation Example 9 (Comparative Example 5), in which no polyalkylene oxide was added, and Evaluation Example 6 had an even higher haze value, resulting in lower transparency than the films of the Examples. Furthermore, in Evaluation Example 7 (Comparative Example 3), which used EO homopolymer L-11 as the polyalkylene oxide, although the haze value improved compared to Evaluation Example 9 (Comparative Example 5), the dried film appeared to have a pattern. Furthermore, in Evaluation Example 8 (Comparative Example 4), which used the polyalkylene oxide copolymer CP-A13H in which the copolymerization ratio (hydrophobic portion mol%) of the hydrophobic oxirane monomer in the polyalkylene oxide was significantly outside the scope of this disclosure, the haze value did not decrease (improve) significantly, and the dried film appeared to have a pattern.

[0080] This disclosure may also be presented as follows; however, this disclosure is not limited to these.

[0081] (Note 1) It is a polyalkylene oxide, The polyalkylene oxide is a random copolymer of a monomer composition containing a hydrophilic oxirane monomer and a hydrophobic oxirane monomer. The copolymerization ratio of the hydrophobic oxirane monomer is 28-45 mol%, The polyalkylene oxide is characterized in that the hydrophobic oxirane monomer contains at least one oxirane monomer having a radical-reactive group in its side chain. (Note 2) The weight-average molecular weight is 2.0 × 10⁻⁶.3 ~2.0×10 5 Polyalkylene oxides as described in Appendix 1, within the range specified. (Note 3) An additive for emulsion polymerization of olefins, characterized by containing the polyalkylene oxide described in Appendix 1 or 2. (Note 4) An emulsion polymerization composition characterized by containing the additive described in Appendix 3 and an olefin, which is a raw material for emulsion polymerization. (Note 5) A method for producing a polyalkylene oxide according to Appendix 1 or 2, characterized by random copolymerizing the monomer composition comprising the hydrophilic oxirane monomer and the hydrophobic oxirane monomer. (Note 6) The manufacturing method according to Appendix 5, wherein alkylaluminum is used as a polymerization catalyst in the polymerization step. (Note 7) A method for producing an olefin polymer, characterized by copolymerizing the olefin in the emulsion polymerization composition described in Appendix 4 with the polyalkylene oxide described in Appendix 1 or 2. (Note 8) An olefin polymer characterized by being produced by the manufacturing method described in Appendix 7. (Note 9) An olefin polymer manufacturing process for producing an olefin polymer by the manufacturing method described in Appendix 7, A molding step of forming the composition containing the olefin polymer into a film, A method for producing a film containing the olefin polymer, characterized by including the above. (Note 10) A film containing the olefin polymer, characterized by being manufactured by the manufacturing method described in Appendix 9. [Industrial applicability]

[0082] As described above, this disclosure provides a polyalkylene oxide, an additive for emulsion polymerization of olefins, an emulsion polymerization composition, a method for producing polyalkylene oxide, a method for producing olefin polymers, an olefin polymer, a method for producing a film, and a film, which can be easily manufactured in a highly transparent resin film. Since this disclosure can provide a highly transparent resin film, it is applicable, for example, to the field of resin films for surface protection of displays. Furthermore, this disclosure is not limited to this and is applicable to any technical field related to resin films, specifically, for example, to the interior and exterior of personal computers, the interior and exterior of mobile phones, automobile headlights, films for liquid crystal displays, films for organic EL displays, etc. Moreover, the polyalkylene oxide, the additive for emulsion polymerization of olefins, the emulsion polymerization composition, the method for producing polyalkylene oxide, the method for producing olefin polymers, and the olefin polymer of this disclosure are not limited to the technical field of films but are applicable to any technical field, specifically, for example, to lighting fixture covers, coatings, sunglasses, aquariums, bathtubs, tableware containers, windows, automobile interior parts, etc.

Claims

1. It is a polyalkylene oxide, The polyalkylene oxide is a random copolymer of a monomer composition containing a hydrophilic oxirane monomer and a hydrophobic oxirane monomer. The copolymerization ratio of the hydrophobic oxirane monomer is 28 to 45 mol%, The polyalkylene oxide is characterized in that the hydrophobic oxirane monomer contains at least one oxirane monomer having a radical-reactive group in its side chain.

2. The weight-average molecular weight is 2.0 × 10⁻⁶. ３ ~2.0 x 10 ５ A polyalkylene oxide according to claim 1, which is within the range of claim 1.

3. An additive for emulsion polymerization of olefins, characterized by containing the polyalkylene oxide described in claim 1.

4. An emulsion polymerization composition characterized by comprising the additive described in claim 3 and an olefin, which is a raw material for emulsion polymerization.

5. A method for producing a polyalkylene oxide according to claim 1, characterized by random copolymerizing the monomer composition comprising the hydrophilic oxirane monomer and the hydrophobic oxirane monomer.

6. The manufacturing method according to claim 5, wherein alkylaluminum is used as a polymerization catalyst in the polymerization step.

7. A method for producing an olefin polymer, characterized by copolymerizing the olefin in the emulsion polymerization composition according to claim 4 with the polyalkylene oxide according to claim 1.

8. An olefin polymer characterized by being produced by the manufacturing method of claim 7.

9. An olefin polymer manufacturing step for manufacturing an olefin polymer by the manufacturing method of claim 7, A molding step of forming the composition containing the olefin polymer into a film, A method for producing a film containing the olefin polymer, characterized by including the above.

10. A film comprising the olefin polymer, characterized by being manufactured by the manufacturing method of claim 9.

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