Polymer composition containing siloxane, method for identifying chemical structure of siloxane, and method for individual management of polymer article containing siloxane

Abstract

Disclosed is a polymer composition which contains a base polymer and a siloxane, wherein: the siloxane is a linear siloxane that is composed of n D units (n is an integer of 0 or more) and two M units; and the content of the siloxane is 1 ppm by mass to 3,000 ppm by mass inclusive.

Description

Polymer composition containing siloxane, method for identifying the chemical structure of siloxane, and method for managing individual polymer articles containing siloxane

[0001] The present disclosure relates to polymer compositions containing siloxanes, methods for identifying the chemical structure of siloxanes, and methods for the individual control of polymer articles containing siloxanes.

[0002] In order to ensure the safety or reliability of products, it is becoming increasingly important to record and trace information about the raw materials, manufacturers, transporters, etc. of products. In recent years, technology has become widely used to identify and manage individuals by attaching an integrated circuit (IC) tag to an individual and reading the data on this IC tag with a radio frequency identification (RFID) reader.

[0003] For example, Patent Document 1 discloses a technology that enables tracking of goods placed on a synthetic resin pallet by using the synthetic resin pallet with a built-in IC tag.

[0004] JP 2008-087839 A

[0005] However, typical IC tags have a heat resistance temperature of around 85°C and may not function in high-temperature environments. Furthermore, IC tags may deteriorate over time due to ultraviolet rays, malfunction due to contact with water, or be damaged by external impact, making the data unreadable. Therefore, they are unsuitable for identifying and managing resin products, such as synthetic resin pallets, which are expected to be exposed to high-temperature environments, ultraviolet rays, water, or external impacts. Therefore, there is a need for the development of technology that can identify and manage individual items using tags that can replace IC tags.

[0006] An object of the present disclosure is to provide a polymer composition containing a molecule that can function as a tag, which has excellent resistance to at least one of high temperature environments, ultraviolet light, water, and external impact.

[0007] As a result of extensive research, the inventors of the present disclosure have found that sequence-controlled siloxanes can function as molecular tags.

[0008] [1] A polymer composition comprising a base polymer and a siloxane, wherein the siloxane is a linear siloxane consisting of n D units (n is an integer of 0 or more) and two M units, and wherein the content of the siloxane is 1 ppm by mass or more and 3,000 ppm by mass or less. [2] The composition according to [1], wherein the polymer composition comprises two or more types of siloxanes, and wherein the mass ratio of the siloxane with the largest content among the siloxanes to the siloxane with the smallest content among the siloxanes is 4 or less. [3] The polymer composition according to [1] or [2], wherein the M units are each independently a unit represented by formula (I). *—OSi(R １ ) ３ (I) (wherein, R １ is an alkyl group, an aryl group, an alkoxy group, or a hydrogen atom; １ may be the same or different from each other.) [4] R １ is a methyl group or a phenyl group. [5] The polymer composition according to any one of [1] to [4], wherein the D units are each independently a unit represented by formula (II): *—OSi(R ２ ) ２ O-* (II) (wherein, R ２ is an alkyl group, an aryl group, an alkoxy group, or a hydrogen atom; ２ may be the same or different from each other.) [6] The polymer composition according to any one of [1] to [5], wherein the D units are each independently a unit represented by formula (II-1) to formula (II-4). ２ O-* (II-1) *-OSiEt ２ O-* (II-2) *-OSiPh ２ O-* (II-3) *-OSiMePhO-* (II-4) [7] The polymer composition according to any one of [1] to [6], wherein n is an integer of 2 or more and 8 or less. [8] The polymer composition according to any one of [1] to [7], wherein the siloxane is a compound represented by any one of formulas (1) to (22). [9] The polymer composition according to any one of [1] to [8], wherein the base polymer is at least one selected from the group consisting of a polystyrene resin, a polyolefin resin, a polyamide resin, a vinyl chloride resin, and a silicone resin.

[10] A method for producing the polymer composition according to any one of [1] to [9], comprising a mixing step of mixing the base polymer with a high-purity siloxane having a purity of 95% by mass or more.

[11] A method for identifying the chemical structure of a siloxane contained in a polymer composition, comprising: a mass analysis step of performing mass analysis of the siloxane to obtain a mass spectrum; and an identification step of identifying the chemical structure of the siloxane based on a search result of the mass spectrum in a mass spectrum database in which mass spectra of the siloxanes are registered, wherein the polymer composition comprises a base polymer and the siloxane, the siloxane is a linear siloxane consisting of n D units (n is an integer of 0 or more) and two M units, and the content of the siloxane in the polymer composition is 1 ppm by mass or more and 3,000 ppm by mass or less.

[12] The method for identifying the chemical structure of a siloxane according to

[11] , wherein the M units are each independently a unit represented by formula (I). *—OSi(R １ ) ３ (I) (wherein, R １ is an alkyl group, an aryl group, an alkoxy group, or a hydrogen atom;１may be the same or different.)

[13] The method for identifying the chemical structure of a siloxane according to

[11] or

[12] , wherein the polymer composition contains two or more of the siloxanes, and the mass ratio of the siloxane with the largest content among the siloxanes to the siloxane with the smallest content among the siloxanes is 4 or less.

[14] The method for identifying the chemical structure of a siloxane according to any of

[11] to

[13] , wherein the mass analysis is performed by chromatography-mass spectrometry, and the ionization method in the mass analysis is photoionization or electron ionization.

[15] The method for identifying the chemical structure of a siloxane according to any one of

[11] to

[13] , wherein the mass analysis is chromatography-mass analysis, and the identification step identifies the chemical structure of the siloxane based on the results of searching the mass spectrum database and the results of searching the retention time of the siloxane determined from the chromatography in the chromatography-mass analysis in a retention time database in which the retention times of the siloxane are registered.

[16] The method for identifying the chemical structure of a siloxane according to any one of

[11] to

[15] , comprising a mass spectrum database creation step of creating the mass spectrum database by acquiring and accumulating mass spectra of the siloxane.

[17] A method for managing individual polymer articles, wherein the polymer article comprises a base polymer and a siloxane, the siloxane is a linear siloxane consisting of n D units (n is an integer of 0 or more) and two M units, and the content of the siloxane in the polymer article is 1 ppm by mass or more and 3,000 ppm by mass or less, the method comprising: a registration step of linking management information of the polymer article to the chemical structure of the siloxane and registering the linked information in a management information database; a chemical structure identification step of identifying the chemical structure of the siloxane in the polymer article; and an information extraction step of extracting, from the management information database, the management information linked to the chemical structure of the siloxane identified in the chemical structure identification step.

[18] The method for managing individual polymer articles according to

[17] , wherein the chemical structure identification step is carried out by the method for identifying the chemical structure of siloxane according to any one of

[11] to

[16] , and the polymer article is formed from the polymer composition.

[0009] According to the present disclosure, it is possible to provide a polymer composition including a tag that has excellent resistance to at least one of high temperature environments, ultraviolet light, water, and external impacts.

[0010] Total ion chromatogram of siloxane represented by formula (1). Photoionization mass spectrum of siloxane represented by formula (1). Photoionization mass spectrum of siloxane represented by formula (2). Photoionization mass spectrum of siloxane represented by formula (3). Photoionization mass spectrum of siloxane represented by formula (4). Photoionization mass spectrum of siloxane represented by formula (5). Photoionization mass spectrum of siloxane represented by formula (6). Photoionization mass spectrum of siloxane represented by formula (7). Photoionization mass spectrum of siloxane represented by formula (8). Photoionization mass spectrum of siloxane represented by formula (9). Photoionization mass spectrum of siloxane represented by formula (10). Photoionization mass spectrum of siloxane represented by formula (11). Photoionization mass spectrum of siloxane represented by formula (12). Photoionization mass spectrum of siloxane represented by formula (13). FIG. 1 shows a photoionization mass spectrum of a siloxane represented by formula (14). FIG. 2 shows a photoionization mass spectrum of a siloxane represented by formula (15). FIG. 3 shows a photoionization mass spectrum of a siloxane represented by formula (16). FIG. 4 shows a photoionization mass spectrum of a siloxane represented by formula (17). FIG. 5 shows a photoionization mass spectrum of a siloxane represented by formula (18). FIG. 6 shows a photoionization mass spectrum of a siloxane represented by formula (19). FIG. 7 shows a photoionization mass spectrum of a siloxane represented by formula (20). FIG. 8 shows a photoionization mass spectrum of a siloxane represented by formula (21). FIG. 9 shows a photoionization mass spectrum of a siloxane represented by formula (22). FIG. 10 shows gas chromatograms of a siloxane represented by formula (21), a siloxane represented by formula (22), and a mixture thereof. FIG. 11 shows electron ionization mass spectra of a siloxane represented by formula (1) and a siloxane represented by formula (2) at an ionization voltage of 70 V. Electron ionization mass spectra of the siloxane represented by formula (1) at ionization voltages of 70 V, 30 V, 25 V, 20 V, and 15 V. Electron ionization mass spectra of the siloxane represented by formula (2) at ionization voltages of 70 V, 30 V, 25 V, 20 V, and 15 V. Electron ionization mass spectra of the siloxane represented by formula (1) at an ionization voltage of 20 V.Electron ionization mass spectrum of a siloxane represented by formula (2) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (3) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (4) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (5) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (6) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (7) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (8) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (9) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (10) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (11) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (12) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (13) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (14) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (15) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (16) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (17) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (18) at an ionization voltage of 20 V. Electron ionization mass spectrum of a siloxane represented by formula (19) at an ionization voltage of 20 V. 50 is an electron ionization mass spectrum of the siloxane represented by formula (20) at an ionization voltage of 20 V. 51 is an electron ionization mass spectrum of the siloxane represented by formula (21) at an ionization voltage of 20 V. 52 is an electron ionization mass spectrum of the siloxane represented by formula (22) at an ionization voltage of 20 V. 53 is a total ion chromatogram of the siloxane represented by formula (1). 54 is an extracted ion chromatogram of m / z=978.3 drawn from the total ion chromatogram of FIG. 50.Fig. 52 is a mass spectrum of the siloxane eluted at 30.6 minutes in Fig. 51. Fig. 53 is a flowchart showing a preferred example of a method for identifying the chemical structure of a siloxane according to an embodiment of the present disclosure.

[0011] The present disclosure will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present disclosure, and the present disclosure is not limited to these contents, and can be implemented in various modifications within the scope of its gist.

[0012] In the present disclosure, the range "X to Y" means "X or more and Y or less." Furthermore, when a numerical range expressed as "X to Y" or "X or more and Y or less" is described in stages (for example, in order of preference), the upper and lower limits of each numerical range can be combined in any way.

[0013] In the present disclosure, a description such as "X such as x1, x2, and x3" lists x1, x2, and x3 as examples of X, and does not mean that X is limited to x1, x2, x3, and the like.

[0014] 1. Polymer Composition The polymer composition according to the first embodiment of the present disclosure includes a base polymer and a siloxane. The siloxane is a linear siloxane consisting of n D units and two M units. The content of the siloxane in the polymer composition is 1 ppm by mass or more and 3,000 ppm by mass or less. Such a polymer composition is sometimes called a "composite."

[0015] 1-1. Base Polymer The base polymer is not particularly limited and may be any polymer. The any polymer may be a crosslinkable polymer (uncured product), a crosslinked polymer (cured product), or a non-crosslinkable polymer. The base polymer is preferably a high molecular weight compound (polymer) that can be uniformly mixed with siloxane, and is also preferably a thermoplastic resin. The polymer composition may contain one type of base polymer alone, or two or more types in any combination and ratio.

[0016] Examples of the base polymer include polystyrene resin, polyolefin resin such as polyethylene and polypropylene, polyamide resin such as nylon 6 and nylon 66, vinyl chloride resin, silicone resin such as polydimethylsiloxane, polycarbonate resin, (meth)acrylic resin such as polymethyl acrylate and polymethyl methacrylate, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyurethane resin, epoxy resin, and polyimide resin. In view of excellent compatibility with siloxane, the base polymer is preferably one or more selected from the group consisting of polystyrene resin, polyolefin resin, polyamide resin, vinyl chloride resin, and silicone resin, and more preferably silicone resin.

[0017] The weight-average molecular weight of the base polymer is not particularly limited, but is preferably 10,000 to 1,000,000. The number-average molecular weight of the base polymer is not particularly limited, but is preferably 1,000 to 500,000. When the base polymer is a cured product, the weight-average molecular weight of the cured product may be infinite.

[0018] The siloxane is a linear siloxane consisting of n D units and two M units. The siloxane is preferably a sequence-controlled siloxane, since it can function as a molecular tag.

[0019] The M unit is a unit at the end of the siloxane (hereinafter, sometimes referred to as an "end group"). The two M units may be the same or different from each other, but from the viewpoint of ease of synthesis of the siloxane, it is preferable that they are the same.

[0020] The M unit is preferably a substituted silyloxy group in which one or more hydrogen atoms bonded to the silicon atom of the trihydrosilyloxy group have been substituted with any functional group, more preferably a substituted silyloxy group in which two or more hydrogen atoms bonded to the silicon atom of the trihydrosilyloxy group have been substituted with any functional group, and even more preferably a substituted silyloxy group in which all three hydrogen atoms bonded to the silicon atom of the trihydrosilyloxy group have been substituted with any functional group. When there is a plurality of optional functional groups, the multiple optional functional groups may be the same or different from each other.

[0021] More specifically, a preferred embodiment of the M unit is a substituted silyloxy group represented by formula (I): *—OSi(R １ ) ３ (I)

[0022] In formula (I), R １ is an alkyl group, an aryl group, an alkoxy group, or a hydrogen atom. １ may be the same or different from each other. １ Among them, two or three R １ are each preferably an alkyl group, an aryl group, or an alkoxy group, and two or three R １ and are more preferably alkyl groups or aryl groups, respectively.

[0023] R １ The number of carbon atoms in the alkyl group represented by the formula (I) is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 2 or more and 6 or less.

[0024] R １Specific examples of the alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-docosyl group, among which a methyl group, an ethyl group, or an n-hexyl group is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is even more preferred.

[0025] R １ The number of carbon atoms of the aryl group represented by the formula (I) is preferably 6 or more and 20 or less, more preferably 6 or more and 16 or less, and even more preferably 6 or more and 12 or less.

[0026] R １ Specific examples of the aryl group represented by the formula (I) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a 2,6-xylyl group, a 3,4-xylyl group, a mesityl group, a 9-phenanthrenyl group, a 2-anthracenyl group, and a 9-anthracenyl group, and the like, and a phenyl group is preferred.

[0027] R １ The number of carbon atoms of the alkoxy group represented by the formula (I) is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 2 or more and 6 or less.

[0028] R １Specific examples of the alkoxy group represented by the formula (I) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an isobutoxy group, an n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, an n-undecyloxy group, and an n-dodecyloxy group, among which a methoxy group, an ethoxy group, an n-propoxy group, or an isopropoxy group is preferred, and an isopropoxy group is more preferred.

[0029] Among the above groups, R １ is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, or a phenyl group, even more preferably a hydrogen atom, a methyl group, an ethyl group, an n-hexyl group, or a phenyl group, and from the viewpoint of ease of synthesis, even more preferably a methyl group or a phenyl group.

[0030] Specific examples of the M unit include a trimethylsilyloxy group, a dimethylhydrosilyloxy group, a dimethylethylsilyloxy group, a dimethylpropylsilyloxy group, a dimethylisopropylsilyloxy group, a dimethylbutylsilyloxy group, a dimethylpentylsilyloxy group, a dimethylhexylsilyloxy group, a triethylsilyloxy group, a diethylhydrosilyloxy group, a diethylhexylsilyloxy group, a triphenylsilyloxy group, a diphenylsilyloxy group, a diphenylisopropoxysilyloxy group, a trimethoxysilyloxy group, and a triethoxysilyloxy group, and preferably a trimethylsilyloxy group, a diethylhydrosilyloxy group, a diethylhexylsilyloxy group, a diphenylsilyloxy group, or a diphenylisopropoxysilyloxy group.

[0031] The D unit is a unit that forms the main chain portion sandwiched between two M units of the linear siloxane. When there are multiple D units, the multiple D units may be the same or different from each other.

[0032] The D unit is preferably a group in which one or two hydrogen atoms bonded to the silicon atom of an oxydihydrosiloxy group have been substituted with an arbitrary functional group, and more preferably a group in which all two hydrogen atoms bonded to the silicon atom of an oxydihydrosiloxy group have been substituted with an arbitrary functional group. When there are a plurality of arbitrary functional groups, the plurality of arbitrary functional groups may be the same or different from each other.

[0033] More specifically, a preferred embodiment of the D unit is a group represented by formula (II): *—OSi(R ２ ) ２ O-* (II)

[0034] In formula (I), R ２ is an alkyl group, an aryl group, an alkoxy group, or a hydrogen atom, and is preferably an alkyl group or an aryl group. ２ may be the same or different, but are preferably the same. ２ The alkyl group, aryl group, and alkoxy group represented by R １ The meanings and preferred embodiments thereof are the same as those of the alkyl group, aryl group, and alkoxy group represented by the following formula:

[0035] n is the number of D units and is an integer of 0 or more. In terms of excellent functionality as a molecular tag, which will be described later, n is preferably an integer of 0 or more and 20 or less, more preferably an integer of 1 or more and 12 or less, even more preferably an integer of 2 or more and 8 or less, and even more preferably an integer of 4 or more and 8 or less.

[0036] As shown in the examples below, by setting n to an integer of 2 or more, the thermal stability of the siloxane can be improved, and the chemical structure can be maintained without decomposition even under high-temperature conditions, for example, at around 200°C. Considering that the heat resistance temperature of tags such as IC tags and conventional molecular tags such as DNA is around 150°C, siloxanes with n of 2 or more are expected to be developed as molecular tags that can be used under high-temperature conditions. Furthermore, as shown in the examples below, by setting n to an integer of 2 or more, photodegradation and hydrolysis of the siloxane in the polymer composition are suppressed. Therefore, siloxanes with n of 2 or more are expected to be developed as molecular tags that can be used in environments exposed to ultraviolet light, water, etc.

[0037] Specific examples of D units include oxydimethylsiloxy groups (*-OSiMe ２ O-*), oxydiethylsiloxy group (*-OSiEt ２ O-*), oxydiphenylsiloxy group (*-OSiPh ２ Examples of the siloxy group include an oxydimethylsiloxy group, an oxydiphenylsiloxy group, and an oxymethylphenylsiloxy group (*-OSiMePhO-*), and an oxymethylphenylsiloxy group (*-OSiMePhO-*). Preferred are an oxydimethylsiloxy group, an oxydiphenylsiloxy group, and an oxymethylphenylsiloxy group.

[0038] From the viewpoint of ease of synthesis, preferred siloxanes include, for example, siloxanes having as M units substituted silyloxy groups in which three hydrogen atoms bonded to the silicon atom of a trihydrosilyloxy group have been substituted with the same functional group, two M units being the same unit, and having as D units groups in which two hydrogen atoms bonded to the silicon atom of an oxydihydrosiloxy group have been substituted with the same functional group.

[0039] Considering the above, the siloxane is preferably a compound represented by formula (III). １ is R in formula (I). １ is synonymous with R ２ is R in formula (II). ２ and n is as defined above.

[0040]

[0041] Specific examples of suitable siloxanes include compounds represented by formulas (1) to (22).

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064] Siloxane can be synthesized by the method described in Angew. Chem. Int. Ed., 2018, 57, 4637-4641, Kawatsu, T. et al., Macromol. Rapid Commun., 2021, 42, 2000593, or WO 2018 / 159756, or a method similar thereto. By adopting these methods, high-purity siloxane with few impurities can be obtained.

[0065] The content of siloxane in the polymer composition (total content when multiple types of siloxanes are contained in the polymer composition) is usually 1 ppm by mass or more and 3,000 ppm by mass or less, preferably 10 ppm by mass or more and 1,000 ppm by mass or less, more preferably 12 ppm by mass or more and 500 ppm by mass or less, and even more preferably 100 ppm by mass or more and 300 ppm by mass or less. When multiple types of siloxanes are contained in the polymer composition, the content of each type of siloxane is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, and even more preferably 12 ppm by mass or more.

[0066] If the siloxane content is equal to or greater than the lower limit, a sufficient amount of siloxane can be ensured when analyzing the polymer composition to identify the chemical structure of the siloxane. However, as shown in the examples described below, even if the siloxane content is low, the chemical structure of the siloxane can be identified by increasing the siloxane content in the polymer composition through an extraction operation and preparing a measurement sample with a high siloxane content. The siloxane content is not particularly limited, but by keeping it equal to or less than the upper limit, the increase in cost due to the use of siloxane can be suppressed.

[0067] The polymer composition may contain one type of siloxane alone, or two or more types in any combination and ratio. When the polymer composition contains two or more types of siloxanes, the mass ratio of the siloxane with the largest content to the siloxane with the smallest content (the siloxane with the largest content / the siloxane with the smallest content) is not particularly limited, but is preferably more than 1 and not more than 4, more preferably more than 1 and not more than 3, and even more preferably more than 1 and not more than 2. By keeping this ratio within the above range, excessive variation in the content of multiple types of siloxanes can be suppressed, making it easier to identify the chemical structure of the siloxane in the polymer composition.

[0068] 1-3. Method for Producing Polymer Composition The method for producing the polymer composition according to this embodiment is not particularly limited, but preferably includes a mixing step of mixing a base polymer and a siloxane. More specifically, methods including a mixing step include a method of mixing a base polymer, a siloxane, and other components as needed; a method of mixing a base polymer, a siloxane, a solvent, and other components as needed and removing the solvent; and a method of preparing a composition containing a crosslinkable base polymer precursor (when the base polymer is a cured product), a curing agent, a siloxane, and other components as needed, and curing the crosslinkable base polymer precursor in the composition to convert it into a base polymer (cured product). Examples of methods including a mixing step include, but are not limited to, a method of mixing a base polymer, a siloxane, a solvent, and other components as needed and removing the solvent.

[0069] It is preferable to use high-purity siloxane as the siloxane to be mixed. The purity of the high-purity siloxane is preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 99% by mass or more. When mixing multiple types of siloxane, it is preferable that the purity of each siloxane is within the above range. The high-purity siloxane can be prepared by the above-mentioned synthesis method.

[0070] When multiple types of siloxanes are mixed with the base polymer in the mixing step, the purity of one siloxane is calculated using the following formula: In other words, the other siloxanes are not treated as impurities of the one siloxane. Purity of high-purity siloxane (%) = [(mass of one siloxane) / (mass obtained by subtracting the total mass of other siloxanes from the total mass of all siloxanes)] × 100

[0071] In the mixing step, when multiple types of siloxanes are mixed with the base polymer, each siloxane is assumed to be a high-purity siloxane. For example, when mixing a base polymer, siloxane A, and siloxane B, "mixing the base polymer and high-purity siloxane" means "mixing the base polymer with a reagent whose siloxane A purity falls within the above range and a reagent whose siloxane B purity falls within the above range."

[0072] During mixing, it is preferable to use a kneader to disperse the siloxane in the base polymer.

[0073] The other components are not particularly limited as long as they do not impair the effects of the present disclosure, and examples thereof include various additives such as antioxidants, ultraviolet absorbers, fillers, release agents, and foaming agents. The solvent is not particularly limited as long as it can dissolve the base polymer and siloxane, and examples thereof include ether solvents such as tetrahydrofuran and diethyl ether; hydrocarbon solvents such as benzene, toluene, and xylene; and alcohol solvents such as ethanol and hexafluoroisopropanol.

[0074] The polymer composition may be a molded article formed into the shape of a film, a sheet, a three-dimensional object, etc. Therefore, the method for producing a polymer composition may include a step of curing and / or molding the polymer composition or a composition obtained by changing the base polymer in the polymer composition to a crosslinkable base polymer precursor (when the base polymer is a cured product).

[0075] 2. Method for Identifying the Chemical Structure of Siloxane A method for identifying the chemical structure of a siloxane according to a second embodiment of the present disclosure is a method for identifying the chemical structure of a siloxane contained in the polymer composition according to the first embodiment of the present disclosure. This method for identifying the chemical structure of a siloxane according to this embodiment includes a mass analysis step of performing mass analysis of the siloxane to obtain a mass spectrum, and an identification step of identifying the chemical structure of the siloxane based on the results of searching the mass spectrum in a mass spectrum database in which mass spectra of the siloxanes are registered.

[0076] 2-1 Mass Analysis Step In the mass analysis step, a mass spectrum of the siloxane is obtained by subjecting a polymer composition containing the siloxane to mass analysis.

[0077] The mass spectrometry method is not particularly limited, and any known mass spectrometry method, such as a known method or a method based thereon, can be used. Separation modes in mass spectrometry include time-of-flight, magnetic sector, quadrupole, and ion trap, with time-of-flight being preferred.

[0078] Examples of ionization methods used in mass spectrometry include photoionization, electron ionization, chemical ionization, electrospray ionization, atmospheric pressure chemical ionization, and matrix-assisted laser desorption ionization. Photoionization or electron ionization is preferred because it allows for more accurate determination of the chemical structure (sequence) of siloxane.

[0079] When the ionization method in mass spectrometry is electron ionization, the ionization voltage is preferably 70 V or less, more preferably 10 V to 70 V, even more preferably 10 V to 40 V, still more preferably 15 V to 30 V, and particularly preferably 20 V to 25 V. By setting the ionization voltage within the above range, differences in the chemical structures of siloxanes become more clearly apparent in the mass spectrum, making it possible to more accurately and easily identify the chemical structures of siloxanes.

[0080] The mass analysis of the siloxane is preferably performed by chromatography-mass spectrometry. That is, the mass analysis in this step is preferably chromatography-mass spectrometry. By separating the siloxane from the polymer composition by chromatography prior to mass analysis, the mass spectrum of the siloxane alone can be easily obtained. By obtaining the mass spectrum of the siloxane alone by chromatography-mass spectrometry, even if it is difficult to extract only the peaks derived from the siloxane from the mass spectrum, the chemical structure of the siloxane can be more easily and accurately identified in the identification step. Note that, when it is easy to extract only the peaks derived from the siloxane from the mass spectrum (for example, when accurate mass analysis is performed using a time-of-flight mass spectrometer or the like and the base polymer does not contain silicon atoms), it is possible to easily compare the mass spectra without separating the siloxane from the polymer composition. Furthermore, when the polymer composition contains two or more types of siloxane, it is preferable to separate the two or more types of siloxane into individual siloxanes by chromatography prior to mass analysis, so that the mass spectrum of each siloxane can be easily obtained in the subsequent mass analysis.

[0081] The chromatography mass spectrometry is preferably gas chromatography mass spectrometry (GC / MS) or liquid chromatography mass spectrometry (LC / MS), more preferably GC / MS, and even more preferably GC / MS using photoionization as the ionization method in mass spectrometry. In particular, in the mass analysis of siloxanes, it is preferable to obtain a total ion chromatogram in GC / MS and then obtain the mass spectrum of the siloxane peak in this total ion chromatogram. Specific techniques are as shown in the examples.

[0082] 2-2. Chromatography Step The method for identifying the chemical structure of a siloxane according to this embodiment may include a chromatography step in which the siloxane is subjected to chromatography to obtain a chromatogram of the siloxane. When the mass spectrometry step is performed by chromatography-mass spectrometry, the chromatography step may be chromatography in chromatography-mass spectrometry. In other words, if the mass spectrometry step is performed by chromatography-mass spectrometry, the chromatography step can be omitted. However, the chromatography step may be performed separately from the chromatography-mass spectrometry of the siloxane.

[0083] Siloxanes such as multiple siloxanes having the same molecular weight, or multiple siloxanes having the same type and number of functional groups but different arrangements often give very similar mass spectra due to their similar chemical structures. Even in such cases, these siloxanes may show different retention times in chromatography. Therefore, in the identification step described below, by performing analysis based on the retention times of the siloxanes in addition to the results of comparing the mass spectra, it is possible to increase the number of siloxanes whose chemical structures can be identified. In particular, when a siloxane is represented by formula (II) and has two R ２ When siloxanes have different D units, their mass spectra tend to be very similar to those of siloxanes having similar D units, and therefore, when identifying the chemical structure of such siloxanes, it is effective to perform a chromatography step.

[0084] The chromatography is not particularly limited, but is preferably gas chromatography or liquid chromatography, more preferably gas chromatography. Specific techniques are as shown in the Examples.

[0085] In the identification step, the mass spectrum of the siloxane in the polymer composition is searched in a mass spectrum database and compared with the mass spectra of siloxanes registered in the mass spectrum database, thereby identifying the chemical structure of the siloxane in the polymer composition.

[0086] If the search results in multiple mass spectra that are similar to the mass spectrum of the siloxane in the polymer composition, the retention times obtained in the chromatography step are compared with the retention times of each siloxane that gives the multiple searched mass spectra to identify the chemical structure of the siloxane in the polymer composition. The retention time comparison is performed by searching a retention time database in which the retention times of siloxanes are registered. As described below, by combining the results of the mass spectrum search and the retention time search, it becomes possible to identify the chemical structures of a greater number of siloxanes.

[0087] In the present disclosure, the term "retention time" in the retention time collation and retention time database refers to the retention time itself or a retention index, which is an index of the retention time. While the retention time is susceptible to the influence of analytical conditions such as the column length, the column temperature, and the carrier flow rate, the retention index is not influenced by these conditions. Therefore, in this embodiment, it is preferable to use the retention index as the retention time.

[0088] The mass spectral database in which the mass spectra of siloxanes are registered may be an existing mass spectral database, a mass spectral database created in the mass spectral database creation step described below, or a combination of these mass spectral databases. The existing mass spectral database may be a mass spectral database (National Institute of Standards and Technology (NIST), NIST / EPA / NIH Mass Spectral Library).

[0089] Furthermore, in the identification step, it is preferable to perform a mass spectral similarity search prior to comparing the mass spectra, and extract mass spectra that are highly similar to the mass spectrum of the siloxane in the polymer composition from the mass spectra registered in the mass spectrum database. Narrowing down the mass spectra to be compared through the similarity search can significantly reduce the effort required for comparison. For example, library search software (US National Institute of Standards and Technology (NIST), MS search) can be used for the similarity search of the mass spectra of siloxanes.

[0090] The retention time database in which the retention times of siloxanes are registered may be an existing retention time database, a retention time database created in the retention time database creation process described below, or a combination of these retention time databases.

[0091] 2-4. Mass Spectrum Database Creation Step The method for identifying the chemical structure of siloxane according to this embodiment may include a mass spectrum database creation step of creating a database of mass spectra of siloxanes. The mass spectrum database can be created by acquiring mass spectra of siloxanes and storing the mass spectra. For example, as shown in the examples described below, a user library can be created by registering the acquired mass spectra in library search software (MS search, National Institute of Standards and Technology (NIST)). Note that the method for acquiring mass spectra of siloxanes is not particularly limited, and the method described in "2-1. Mass Analysis Step" can be used, for example.

[0092] Even if the mass spectrum of the siloxane to be contained in the polymer composition is not registered in an existing mass spectrum database, or if the mass spectrum registered in the existing mass spectrum database is of low quality, by creating a mass spectrum database containing the necessary data, the chemical structure of the siloxane in the polymer composition can be accurately identified using the created mass spectrum database.

[0093] The method for identifying the chemical structure of a siloxane according to this embodiment may include a retention time database creation step of creating a database in which the retention times of siloxanes in chromatography are registered. The retention time database can be created by acquiring a chromatogram of the siloxane and accumulating the retention times and / or retention indices calculated from the retention times.

[0094] 2-6. Preferred Mode of Method for Identifying the Chemical Structure of Siloxane Figure 53 is a flowchart showing a preferred mode of the method for identifying the chemical structure of siloxane according to this embodiment.

[0095] In the flow shown in Figure 53, first, in step S11, a mass spectrum of the siloxane in the polymer composition is obtained by chromatography-mass spectrometry. Next, in step S12, the mass spectrum obtained by chromatography-mass spectrometry is searched in a mass spectrum database. If the search results in only one mass spectrum corresponding to the mass spectrum of the siloxane in the polymer composition (YES in step S13), in step S15, the chemical structure of the siloxane giving the hit mass spectrum is determined to be the chemical structure of the siloxane in the polymer composition. On the other hand, if the search results in two or more mass spectra having a similar degree of similarity to the mass spectrum of the siloxane in the polymer composition (NO in step S13), in step S14, the retention times of each siloxane giving these mass spectra are determined from the chromatography in the chromatography-mass spectrometry, and this retention time is searched in the retention time database. Then, in step S15, among the siloxanes that give two or more mass spectra hit in the mass spectrum database search, the chemical structure of the siloxane that shows a retention time similar to that of the siloxane in the polymer composition is determined to be the chemical structure of the siloxane in the polymer composition.

[0096] 3. Individual Management Method for Polymer Articles A method for individual management of polymer articles according to a third embodiment of the present disclosure is a method for managing individual polymer articles comprising a base polymer and a siloxane. The siloxane is a linear siloxane consisting of n D units (n is an integer equal to or greater than 0) and two M units, and is contained in the polymer article at 1 ppm by mass or more and 3,000 ppm by mass or less. This method for individual management of polymer articles according to this embodiment includes a registration step of linking management information of the polymer article to the chemical structure of the siloxane and registering the linked information in a management information database; a chemical structure identification step of identifying the chemical structure of the siloxane in the polymer article; and an information extraction step of extracting the management information linked to the chemical structure of the siloxane identified in the chemical structure identification step from the management information database.

[0097] In this embodiment, a linear siloxane consisting of n D units and two M units is used as a molecular tag, and information used for individual management of polymer articles is linked to this siloxane. As described above, such siloxane is a molecule itself, and therefore, unlike IC tags, is less likely to be damaged by external impact. Furthermore, as described above, it is resistant to photodegradation and hydrolysis and has high thermal stability. Therefore, it is possible to extract management information from a polymer article even after the polymer article has been exposed to a high-temperature environment, ultraviolet light, water, external impact, or the like.

[0098] Furthermore, in this embodiment, since the control information is linked to the chemical structure of the siloxane distributed in the polymer article, tampering is extremely difficult, which makes it possible to achieve more reliable control and determine the authenticity of polymer products based on the extracted control information and whether or not the control information can be extracted.

[0099] In the chemical structure identification step, the method for identifying the chemical structure of the siloxane is not particularly limited and may be any method used in the field of analytical chemistry, but is preferably the method for identifying the chemical structure of a siloxane according to the second embodiment of the present disclosure. That is, the method for managing individual polymer articles according to this embodiment is preferably a method for managing individual polymer articles using the method for identifying the chemical structure of a siloxane according to the second embodiment of the present disclosure. In this preferred embodiment, the polymer article is formed from the polymer composition according to the first embodiment of the present disclosure. Therefore, the polymer composition, base polymer, and siloxane in the first embodiment of the present disclosure correspond to the polymer article, base polymer, and siloxane in this embodiment, respectively. Details of the polymer composition are as described in the section "2. Method for identifying the chemical structure of a siloxane." Below, the method for managing individual polymer articles using the method for identifying the chemical structure of a siloxane according to the second embodiment of the present disclosure is described.

[0100] In the registration process, management information related to the individual management of polymer articles is linked to siloxanes and registered in a management information database. By linking management information to each siloxane, which is a molecular tag, once the chemical structure of the siloxane is identified in the chemical structure identification process, the management information corresponding to that chemical structure can be extracted in the information extraction process.

[0101] The polymer article is formed from the polymer composition according to the first embodiment of the present disclosure (hereinafter, sometimes simply referred to as the "polymer composition"), and may have the form of a film, a sheet, a three-dimensional object, or the like, as described above. Examples of management information related to the individual management of polymer articles include information according to management purposes, such as tracing the manufacturing process of the polymer article, tracking the distribution process, tracking the usage environment, and determining whether or not it can be recycled. More specifically, examples of the management information include the raw materials, manufacturer, manufacturing conditions, lot number, manufacturing date, product name, transporter, seller, recycling history, chemical analysis information, and physical property values ​​of the polymer article.

[0102] In this embodiment, the chemical structure of the siloxane functions as an identification code for identifying the management information. When linking the management information to the chemical structure of the siloxane and registering it in the management information database, the management information may be linked to the chemical structure of the entire siloxane molecule, or may be linked to a portion of the chemical structure of the siloxane molecule. Furthermore, the M units and D units in the chemical structure of the siloxane may be replaced with numbers or letters. For example, combinations of M units may be replaced with letters such as P, Q, and R, and D units may be represented by numbers such as 0 and 1.

[0103] When linking management information to a portion of the chemical structure of one siloxane molecule, the portion can be the chemical structure of the D unit portion (partial structure other than the M unit). To give a more specific example, if the oxydimethylsiloxy group, which is the D unit, is replaced with "0" and the oxydiphenylsiloxy group is replaced with "1," the chemical structure of the D unit portion of the siloxane represented by formula (1) is represented by "101010," the chemical structure of the D unit portion of the siloxane represented by formula (2) is represented by "111000," and the chemical structure of the D unit portion of the siloxane represented by formula (3) is represented by "110100." In this way, even if the chemical structure of the M unit is not included, if it can be recognized as a separate identification code, it is possible to link management information to the chemical structure of the D unit portion.

[0104] On the other hand, if the molecular weight of each siloxane is varied by selecting the type of M unit, and the chemical structure of the entire siloxane molecule, including the M unit, is made to function as an identification code, management information can be linked to the chemical structure of the entire siloxane molecule. To give a more specific example, if the oxydimethylsiloxy group, which is a D unit, is replaced with "0," the oxydiphenylsiloxy group is replaced with "1," and the combination of trimethylsilyloxy and diethylhydrosilyloxy groups, which are M units, is replaced with "P," and the combination of trimethylsilyloxy and diethylhexylsilyloxy groups, which are M units, is replaced with "Q," then the chemical structure of the entire siloxane represented by formula (11) is represented by "P011," and the chemical structure of the entire siloxane represented by formula (13) is represented by "Q011." In these cases, even if the chemical structure of the D unit portion is the same, if the chemical structure or molecular weight differs due to the inclusion of the chemical structure of the M unit, and each chemical structure can be recognized as a separate identification code, then the management information can be linked to the chemical structure of the entire siloxane molecule.

[0105] In this embodiment, it is preferable to increase the molecular weight of the siloxane or to include multiple types of siloxane in the polymer composition, since this makes it possible to obtain a large number of identification code patterns.

[0106] 3-2. Chemical Structure Identification Method In the chemical structure identification step, the chemical structure of the siloxane in the polymer article is identified by the method for identifying the chemical structure of a siloxane according to the second embodiment of the present disclosure. The method for identifying the chemical structure of a siloxane according to the second embodiment of the present disclosure is as described above.

[0107] In the information extraction process, the chemical structure of the siloxane identified in the chemical structure identification process is searched in a management information database, and management information linked to the chemical structure of the siloxane is extracted from the management information database. This makes it possible to obtain the management information of the polymer article registered in the management information database in the registration process, thereby enabling appropriate management of the polymer article.

[0108] [Synthesis Example: Synthesis of Sequence-Controlled Siloxanes] Octasiloxanes represented by formulas (1) to (10), pentasiloxanes represented by formulas (11) to (16), hexasiloxanes represented by formulas (17) to (18), decasiloxanes represented by formulas (19) to (20), and heptasiloxanes represented by formulas (21) to (22) were synthesized according to the methods described in Angew. Chem. Int. Ed., 2018, 57, 4637-4641, Kawatsu, T. et al., Macromol. Rapid Commun., 2021, 42, 2000593, or WO 2018 / 159756. During the synthesis of each siloxane, the formation of the target compound was confirmed by nuclear magnetic resonance spectroscopy (NMR), and the product was purified by preparative chromatography. For this reason, the chemical structure (sequence) of each siloxane was strictly controlled, and all siloxanes were obtained with a purity of 95% or higher.

[0109] The octasiloxanes represented by formulas (1) to (10) have trimethylsilyloxy groups (M units (R １ =Me)) and have the same composition formula and molecular weight, but the arrangement of D units is different from each other.

[0110] The pentasiloxane represented by formula (11) and the pentasiloxane represented by formula (12) both have a trimethylsilyloxy group at one end and have the same composition formula and molecular weight, but differ from each other in the other end and the arrangement of D units.

[0111] The pentasiloxane represented by formula (13) and the pentasiloxane represented by formula (14) both have a trimethylsilyloxy group at one end and have the same composition formula and molecular weight, but differ from each other in the other end and the arrangement of D units.

[0112] The pentasiloxane represented by formula (15) and the pentasiloxane represented by formula (16) both have a trimethylsilyloxy group at one end and a diphenylisopropoxysilyloxy group at the other end, and have the same composition formula and molecular weight, but the arrangement of D units is different.

[0113] The hexasiloxane represented by formula (17) and the hexasiloxane represented by formula (18) both have trimethylsilyloxy groups at both ends and have the same composition formula and molecular weight, but the arrangement of D units is different from each other.

[0114] The decasiloxane represented by formula (19) and the decasiloxane represented by formula (20) both have trimethylsilyloxy groups at both ends and have the same composition formula and molecular weight, but differ in the arrangement of D units.

[0115] The heptasiloxane represented by formula (21) and the heptasiloxane represented by formula (22) both have trimethylsilyloxy groups at both ends and have the same composition formula and molecular weight, but the arrangement of D units is different from each other.

[0116] The pentasiloxanes represented by formulas (11) to (16) all have M units (R １ The siloxanes represented by formulas (1) to (10) have the same composition formula and molecular weight, but differ from one another in the arrangement of D units.

[0117] Example 1-1: Creation of a mass spectrum database by photoionization mass spectrometry and identification of the chemical structure of siloxane using the mass spectrum database 0.105 mg of siloxane represented by formula (1) was placed in a sample cup (Frontier Labs, Inc., PY1-EC50F (same hereinafter)) and heated from 300°C to 700°C at a rate of 20°C / min in a helium stream in a pyrolysis furnace (Frontier Labs, Inc., EGA / PY-3030D (same hereinafter)). The vaporized compounds were passed through a deactivated tube (Frontier Labs, UADTM-2.5N) maintained at 320°C in a gas chromatograph (Agilent Technologies, GC7890B), and mass spectra were obtained using a time-of-flight mass spectrometer (JEOL, JMS-T200GC) equipped with a photoionization ion source. The data were analyzed using the software provided with the mass spectrometer (JEOL, MsAxel v3.0). The resulting total ion chromatogram is shown in Figure 1.

[0118] The photoionization mass spectrum of the siloxane represented by formula (1) was obtained by adding up the mass spectra of the peaks from 1.8 to 8.0 minutes in the total ion chromatogram shown in Figure 1. The peak from 0.2 to 1.0 minutes in Figure 1 is derived from an internal standard substance used for mass calibration. The obtained photoionization mass spectrum is shown in Figure 2. The composition formula C was estimated from the peak with a mass-to-charge ratio (m / z) of 978.2957. ４８ H ６６ Si ８ O ７ is the composition formula C of the siloxane represented by formula (1). ４８ H ６６ Si ８ O ７ The mass of the siloxane in Figure 2 coincided with that of the monoisotopic siloxane (monoisotopic mass 978.2957). Therefore, it was determined that Figure 2 is the photoionization mass spectrum of the siloxane represented by formula (1). Note that peaks in Figure 2 with mass-to-charge ratios less than 978 correspond to fragment ions, and contain the partial structure of the siloxane, i.e., sequence information.

[0119] In the same manner as above, mass analysis was performed three times for each compound of the siloxanes represented by formulas (1) to (22), and photoionization mass spectra were obtained (the photoionization mass spectra obtained in the first to third mass analyses are referred to as photoionization mass spectra 1 to 3, respectively). However, in the mass analysis of the siloxanes represented by formulas (19) to (20), the temperature of the deactivation tube was changed to 400°C. Photoionization mass spectra 1 of the siloxanes represented by formulas (2) to (22) are shown in Figures 3 to 23, respectively.

[0120] A mass spectrum database was created by registering the photoionization mass spectra 1 of the siloxanes represented by formulas (1) to (22) as a user library in library search software (National Institute of Standards and Technology (NIST), MS search v2.4).

[0121] For the siloxanes represented by formulas (1) to (20), a user library was searched for photoionization mass spectrum 2 and photoionization mass spectrum 3, which were not registered in the library. Table 1 shows the order in which the siloxanes represented by formulas (1) to (20) were listed as candidates for compounds that give photoionization mass spectrum 2 and photoionization mass spectrum 3.

[0122]

[0123] As can be seen from Table 1, a total of 40 photoionization mass spectra for siloxanes represented by formulas (1) to (20) were searched in the user library. As a result, for 37 photoionization mass spectra, the siloxane actually being measured was selected as the first candidate for the siloxane that gave the photoionization mass spectrum. In a search for photoionization mass spectra 3 for siloxanes represented by formulas (7) and (10), the siloxanes actually being measured were not selected as the first candidate, but were selected as the second or third candidate. By visually comparing the photoionization mass spectra 3 of these siloxanes with the photoionization mass spectra registered in the user library, it was possible to determine that the siloxanes being measured were the siloxanes represented by formula (7) and formula (10).

[0124] From the above, it has been demonstrated that the chemical structures of siloxanes represented by formulas (1) to (20) can be identified by searching photoionization mass spectra against a mass spectral database. In particular, it has traditionally been difficult to distinguish between the hexasiloxane represented by formula (17) and the hexasiloxane represented by formula (18), and between the decasiloxane represented by formula (19) and the decasiloxane represented by formula (20). However, it has been found that by searching photoionization mass spectra against a mass spectral database, it is possible to accurately identify the chemical structures, including the differences in the sequences. Furthermore, pentasiloxanes represented by formulas (11) to (16) have two different terminal groups, and it has traditionally been difficult to accurately distinguish between the two terminal groups. However, it has been found that by searching photoionization mass spectra against a mass spectral database, it is possible to accurately identify the chemical structures, including not only the sequences but also both terminal groups.

[0125] The siloxane represented by formula (21), the siloxane represented by formula (22), and a mixture thereof were each subjected to gas chromatography mass spectrometry. The resulting gas chromatogram is shown in Figure 24. A gas chromatograph (Frontier Labs, Inc., UA5 (MS / HT), inner diameter 0.25 mm, film thickness 0.25 μm, length 30 m) was used for the gas chromatography, and the split ratio was adjusted from splitless to 50 depending on the siloxane concentration in the sample. The temperature program was set to hold the temperature at 50°C for 2 minutes, increase the temperature at 2°C / min, and then hold the temperature at 320°C for 44.5 minutes. The measurement conditions for mass spectrometry were the same as those described above.

[0126] The siloxane represented by formula (21) and the siloxane represented by formula (22) have the same terminal group and very similar sequences, so their photoionization mass spectra are also very similar. Therefore, when the mass spectrum of the siloxane represented by formula (21) was searched in the user library, the mass spectrum of the siloxane represented by formula (21) and the mass spectrum of the siloxane represented by formula (22) were hit with no significant difference. Similarly, when the mass spectrum of the siloxane represented by formula (22) was searched in the user library, the two mass spectra were hit with no significant difference. Meanwhile, in gas chromatography, the retention time of the siloxane represented by formula (21) was 107.75 minutes, and the retention time of the siloxane represented by formula (22) was 107.90 minutes. From this, it was found that slight differences in sequence cause differences in retention time, and the two can be distinguished as different compounds. Furthermore, the photoionization mass spectra of the siloxanes represented by formulas (21) to (22) were significantly different from the photoionization mass spectra of the siloxanes represented by formulas (1) to (20).

[0127] From the above, it was found that even if the chemical structures are very similar, the chemical structure of a siloxane can be identified based on the chromatographic retention time and photoionization mass spectrum.

[0128] Example 1-2: Creation of a mass spectrum database by electron ionization mass spectrometry and identification of the chemical structure of siloxanes using the mass spectrum database. Electron ionization mass spectra of siloxanes represented by formulas (1) and (2) were obtained in the same manner as in Example 1-1, except that the photoionization ion source was changed to a dedicated electron ionization ion source (JEOL Ltd.). First, ionization (fragmentation) was controlled by changing the ionization voltage of the dedicated electron ionization ion source, and it was investigated whether it was possible to distinguish between siloxanes represented by formula (1) and siloxanes represented by formula (2). In the electron ionization mass spectrum measured at a commonly used ionization voltage of 70 V, molecular ions (m / z 978.3) and fragment ions (m / z < 978.3) were observed. As fragment ions based on the sequence, a relatively strong peak at m / z 345.1 was observed in the electron ionization mass spectrum of the siloxane represented by formula (1), while a relatively strong peak at m / z 221.1 was observed in the electron ionization mass spectrum of the siloxane represented by formula (2). Peaks characteristic of each siloxane sequence were more clearly observed in the electron ionization mass spectra measured at ionization voltages of 30 V, 25 V, 20 V, or 15 V. The electron ionization mass spectra of the siloxane represented by formula (1) and the siloxane represented by formula (2), measured at an ionization voltage of 70 V, are shown in FIG. 25. For a series of measurements performed at different ionization voltages, the electron ionization mass spectrum of the siloxane represented by formula (1) is shown in FIG. 26, and the electron ionization mass spectrum of the siloxane represented by formula (2) is shown in FIG. 27. The electron ionization mass spectra were able to be distinguished from each other at any ionization voltage. In particular, by suppressing fragmentation by lowering the ionization voltage, it was possible to obtain an electron ionization mass spectrum in which peaks derived from siloxane sequences were strongly observed, making identification easier. Note that to compensate for the decrease in peak intensity in the mass spectrum due to the lowering of the ionization voltage, measurements were taken by appropriately setting the detector voltage in the range of 2250 V to 2500 V.

[0129] In the same manner as above, mass analysis was performed three times for each compound of the siloxanes represented by formulas (1) to (22) at an ionization voltage of 20 V to obtain electron ionization mass spectra (the electron ionization mass spectra obtained in the first to third mass analyses are referred to as electron ionization mass spectra 4 to 6, respectively). Electron ionization mass spectra 4 of the siloxanes represented by formulas (1) to (22) are shown in Figures 28 to 49, respectively.

[0130] A mass spectrum database was created by registering the electron ionization mass spectra 4 of the siloxanes represented by formulas (1) to (22) as a user library in library search software (National Institute of Standards and Technology (NIST), MS search v2.4).

[0131] For the siloxanes represented by formulas (1) to (20), electron ionization mass spectrum 5 and electron ionization mass spectrum 6, which were not registered in the library, were searched in a user library. Table 2 shows the order in which the siloxanes represented by formulas (1) to (20) were listed as candidates for compounds that give electron ionization mass spectrum 5 and electron ionization mass spectrum 6.

[0132]

[0133] As can be seen from Table 2, a total of 40 electron ionization mass spectra for the siloxanes represented by formulas (1) to (20) were searched in the user library. As a result, in all of the electron ionization mass spectra, the siloxane that was actually being measured was ranked as the first candidate for the siloxane that gave the electron ionization mass spectrum.

[0134] From the above, it was demonstrated that the siloxanes represented by formulas (1) to (20) can be identified by searching the electron ionization mass spectrum in a mass spectrum database.

[0135] The electron ionization mass spectra of the siloxanes represented by formulas (21) to (22) were significantly different from the electron ionization mass spectra of the siloxanes represented by formulas (1) to (20). Furthermore, as shown in Example 1-1, it has been found that slight differences in sequence result in differences in retention time in gas chromatography, allowing the two compounds to be distinguished as different compounds. From these findings, it was found that the siloxanes represented by formulas (21) and (22) have the same terminal group and very similar sequences, and therefore their electron ionization mass spectra were very similar, but they could be distinguished as different compounds based on the electron ionization mass spectra and retention times in gas chromatography.

[0136] Example 2-1 Identification of Chemical Structure of Siloxane in Polymer Composition (Production of Polymer Composition) Approximately 500 mg of polystyrene (FUJIFILM Wako Pure Chemical Industries, Ltd., 198-12805) as a base polymer and approximately 0.5 mg of the siloxane represented by formula (1) were dissolved in tetrahydrofuran (THF) to obtain a solution. This solution was poured into a glass Petri dish, and the THF was evaporated at room temperature to obtain a polymer film made of a polymer composition containing approximately 1000 ppm by mass of the siloxane represented by formula (1).

[0137] (Identification of the Chemical Structure of Siloxane in the Polymer Composition) 1.33 mg of this polymer film was placed in a sample cup and vaporized in a pyrolysis furnace at 600°C under a helium stream. The resulting gas was separated using a gas chromatograph (Frontier Labs, Inc., UA5 (MS / HT), inner diameter 0.25 mm, film thickness 0.25 μm, length 30 m), and a photoionization mass spectrum was obtained. The gas chromatograph was adjusted from splitless to a split ratio of 50 depending on the concentration of siloxane in the sample. The temperature program was set to hold at 50°C for 2 minutes, increase the temperature at 20°C / min, and then hold at 320°C for 44.5 minutes. The resulting total ion chromatogram is shown in Figure 50. An extracted ion chromatogram of m / z = 978.3 drawn from this total ion chromatogram is shown in Figure 51.

[0138] As shown in Figure 51, the siloxane represented by formula (1) eluted at 30.6 minutes. Mass analysis of the eluted siloxane represented by formula (1) was performed. The resulting photoionization mass spectrum is shown in Figure 52. When the photoionization mass spectrum shown in Figure 52 was searched using the above-mentioned user library, siloxane represented by formula (1) was identified as the first candidate compound that would give the photoionization mass spectrum shown in Figure 52. This demonstrates that the chemical structure of siloxanes contained in polymer films can be identified using the method for identifying the chemical structure of siloxanes disclosed herein.

[0139] [Examples 2-2 to 2-16: Identification of Chemical Structure of Siloxane in Polymer Composition] (Production of Polymer Composition) In Examples 2-1 to 2-7 and Examples 2-10 to 2-15, polymer films composed of polymer compositions were obtained in the same manner as in Example 2-1, except that the base polymer, siloxane, and solvent were changed as shown in Table 3 or Table 4. In Examples 2-8, 2-9, and 2-16, which used silicone as the base polymer, a composition was obtained by adding a curing agent (CAT-RC, Shin-Etsu Chemical Co., Ltd.) and siloxane to a main component of a two-component room temperature curing silicone rubber (KE66, Shin-Etsu Chemical Co., Ltd.), and the resulting composition was poured into a glass Petri dish and allowed to stand at room temperature for one day to obtain a polymer film. Siloxane dispersed well in both relatively low-polarity polystyrene, silicone, and polypropylene, as well as highly polar polyvinyl chloride and nylon 6.

[0140] (Identification of Chemical Structure of Siloxane in Polymer Composition) Photoionization mass spectra were obtained in the same manner as in Example 2-1, and the chemical structure of siloxane in the polymer film was identified using the above-mentioned user library (Examples 2-2 to 2-15) or library search software (Example 2-16). However, in Example 2-9, the polymer film was heated in an air atmosphere at 200°C for 7 days, in Example 2-14, the polymer film was immersed in water at 80°C for 24 hours, and in Example 2-15, the polymer film was irradiated with ultraviolet light for 24 hours (wavelength 365 nm, intensity 100 mW / cm). －２In Examples 2-16, the polymer film was heated in an air atmosphere at 200° C. for 24 hours before analysis. The results are shown in Tables 3 and 4.

[0141]

[0142]

[0143] The above examples have demonstrated that the chemical structure of siloxanes can be identified by comparing mass spectra or comparing mass spectra and retention times. Furthermore, even if siloxanes have the same molecular weight, if their sequences are different, their retention times in chromatography will be different. Therefore, by using the retention times in chromatography in addition to the photoionization mass spectra in the analysis, it has been demonstrated that the variety of siloxanes whose chemical structures can be identified can be increased.

[0144] In Example 2-4, the siloxane content in the polymer composition was as low as 12 ppm by mass, but by increasing the siloxane concentration in the sample by extraction, the chemical structure of the siloxane could be accurately identified. The mass spectrometer used in Example 2-4 had an S / N ratio of 100 or higher for the benzophenone (10 ng) peak. The siloxane content in the sample used to identify the chemical structure of the siloxane was 660 nm (55 mg x 12 ppm by mass). From the above, it is believed that by using a mass spectrometer with the same detection sensitivity as above, it is possible to identify the chemical structure of the siloxane even when the siloxane content is as low as 1 ppm by mass.

[0145] Examples 2-1 to 2-8 demonstrated that the chemical structure of siloxane can be identified by searching a mass spectrum database, regardless of the type of base polymer in the polymer composition.

[0146] Examples 2-9 to 2-16 demonstrated that the chemical structure of siloxanes can be identified without decomposition of the siloxanes even after the polymer film was heated in an air atmosphere, immersed in warm water, or exposed to ultraviolet light. Furthermore, Example 2-16, which used decamethyltetrasiloxane, which has a boiling point of 195°C, also demonstrated that the chemical structure of siloxanes in the polymer film could be identified after heating the polymer film at 200°C for 24 hours.

[0147] From the above results, it was confirmed that the above siloxane has high chemical and thermal stability and can maintain its chemical structure without decomposition or denaturation even when the polymer composition is exposed to high temperature environments, ultraviolet light, water, etc. Therefore, the above siloxane is considered to be useful as a molecular tag that is highly resistant to high temperature environments, ultraviolet light, water, etc.

Claims

1. A polymer composition comprising a base polymer and a siloxane, the siloxane being a linear siloxane consisting of n D units (n is an integer of 0 or more) and two M units, and the content of the siloxane being 1 ppm by mass or more and 3,000 ppm by mass or less.

2. The composition according to claim 1, wherein the polymer composition contains two or more of the siloxanes, and the ratio by mass of the siloxane contained at the maximum amount among the siloxanes to the siloxane contained at the minimum amount among the siloxanes is 4 or less.

3. The polymer composition according to claim 1, wherein each of the M units is independently a unit represented by formula (I). １ ) ３ (I) (wherein, R １ is an alkyl group, an aryl group, an alkoxy group, or a hydrogen atom; １ may be the same or different.) 4. R １ The polymer composition of claim 3 , wherein is a methyl group or a phenyl group.

5. The polymer composition according to claim 3, wherein each of the D units is independently a unit represented by formula (II): *-OSi(R ２ ) ２ O-* (II) (wherein, R ２ is an alkyl group, an aryl group, an alkoxy group, or a hydrogen atom; ２ may be the same or different.) 6. The polymer composition according to claim 3, wherein the D units are each independently a unit represented by formula (II-1) to formula (II-4). ２ O-* (II-1) *-OSiEt ２ O-* (II-2) *-OSiPh ２ O-* (II-3) *-OSiMePhO-* (II-4) 7. The polymer composition of claim 1, wherein n is an integer between 2 and 8.

8. The polymer composition according to claim 1, wherein the siloxane is a compound represented by any one of formulas (1) to (22).

9. The polymer composition according to claim 1, wherein the base polymer is at least one selected from the group consisting of polystyrene resins, polyolefin resins, polyamide resins, vinyl chloride resins, and silicone resins.

10. A method for producing a polymer composition according to any one of claims 1 to 9, comprising a mixing step of mixing the base polymer with a high-purity siloxane having a purity of 95% by mass or more.

11. A method for identifying the chemical structure of a siloxane contained in a polymer composition, comprising: a mass spectrometry step of performing mass analysis of the siloxane to obtain a mass spectrum; and an identification step of identifying the chemical structure of the siloxane based on a result of searching the mass spectrum in a mass spectrum database in which the mass spectrum of the siloxane is registered; wherein the polymer composition comprises a base polymer and the siloxane; the siloxane is a linear siloxane consisting of n D units (n is an integer of 0 or more) and two M units; and the content of the siloxane in the polymer composition is 1 ppm by mass or more and 3,000 ppm by mass or less.

12. The method for identifying the chemical structure of a siloxane according to claim 11, wherein each of the M units is independently a unit represented by formula (I). １ ) ３ (I) (wherein, R １ is an alkyl group, an aryl group, an alkoxy group, or a hydrogen atom; １ may be the same or different.) 13. The method for identifying the chemical structure of a siloxane according to claim 11, wherein the polymer composition contains two or more types of siloxanes, and the ratio by mass of the siloxane that is contained the largest amount among the siloxanes to the siloxane that is contained the smallest amount among the siloxanes is 4 or less.

14. The method for identifying the chemical structure of a siloxane according to claim 11, wherein the mass spectrometry is carried out by chromatography-mass spectrometry, and the ionization method in the mass spectrometry is photoionization or electron ionization.

15. A method for identifying the chemical structure of a siloxane according to claim 11, wherein the mass spectrometry is chromatography-mass spectrometry, and the identification step identifies the chemical structure of the siloxane based on a result of searching the mass spectrum database and a result of searching a retention time database in which the retention times of the siloxanes are registered, using the retention time of the siloxane determined from the chromatography in the chromatography-mass spectrometry.

16. A method for identifying the chemical structure of a siloxane according to any one of claims 11 to 15, further comprising a mass spectrum database creation step of acquiring and storing mass spectra of the siloxane to create the mass spectrum database.

17. A method for managing individual polymer articles, the polymer article comprising a base polymer and a siloxane, the siloxane being a linear siloxane consisting of n D units (n is an integer equal to or greater than 0) and two M units, the content of the siloxane in the polymer article being 1 ppm by mass or more and 3,000 ppm by mass or less, the method comprising: a registration step of linking management information of the polymer article to a chemical structure of the siloxane and registering the information in a management information database; a chemical structure identification step of identifying the chemical structure of the siloxane in the polymer article; and an information extraction step of extracting, from the management information database, the management information linked to the chemical structure of the siloxane identified in the chemical structure identification step.

18. The method for individual management of polymer articles according to claim 17, wherein the chemical structure identification step is carried out by the method for identifying the chemical structure of siloxane according to claim 11, and the polymer article is formed from the polymer composition.

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