Method for producing polymer, polymer, and composition

Abstract

To provide a method for producing a polymer capable of suppressing heat generation during polymerization, and a novel polymer and composition.SOLUTION: A method for producing a polymer comprises polymerizing a radically polymerizable monomer component (M) in the presence of a non-conjugated olefin. A polymer has a structural unit (i) derived from a monomer (1) represented by formula (1) in the figure and a structural unit (v) derived from a non-conjugated olefin. A composition comprises a polymer having a structural unit (i) derived from a monomer (1) represented by formula (1), and a non-conjugated olefin. (In formula (1), j is an integer from 1 to 5.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polymer, a polymer, and a composition. [Background technology]

[0002] Modifiers are sometimes used in components for electronic devices, electrical devices, office automation equipment, automobile components, building components, and other resins to improve their impact strength. As a modifier, for example, Patent Document 1 discloses an acrylic rubber graft copolymer obtained by emulsion polymerization of a vinyl monomer such as methyl methacrylate in the presence of an acrylic rubber component. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-319482 Summary of the Invention [Problem to be solved by the invention]

[0004] However, in the polymerization method described in Patent Document 1, heat may be generated during polymerization. Heat generated during polymerization may make the polymerization unstable. In addition, a large amount of cooling water may be required. Therefore, from the viewpoint of stable production of a polymer and reducing the use of cooling water, it is necessary to suppress heat generation during polymerization.

[0005] An object of the present invention is to provide a method for producing a polymer that can suppress heat generation during polymerization. Another object of the present invention is to provide novel polymers and compositions. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] A method for producing a polymer, comprising polymerizing a radically polymerizable monomer component (M) in the presence of a non-conjugated olefin. [2] The method for producing a polymer according to [1] above, wherein the proportion of the non-conjugated olefin is 1 to 25 parts by mass per 100 parts by mass of the radically polymerizable monomer component (M). [3] The method for producing a polymer according to [1] or [2] above, wherein the radical polymerizable monomer component (M) comprises at least one selected from the group consisting of a monomer (1) represented by the following formula (1) and an alkyl(meth)acrylate:

[0007] [ka]

[0008] In formula (1), j is an integer of 1 to 5.

[0009] [4] The method for producing a polymer according to [3] above, wherein the monomer (1) contains myrcene. [5] The method for producing a polymer according to any one of [1] to [4] above, wherein the non-conjugated olefin comprises a cyclic monoterpene. [6] The method for producing a polymer according to [5] above, wherein the cyclic monoterpene comprises one or more selected from the group consisting of limonene, camphene, and β-pinene. [7] A polymer having a structural unit (i) derived from a monomer (1) represented by the following formula (1) and a structural unit (v) derived from a non-conjugated olefin:

[0010] [ka]

[0011] In formula (1), j is an integer of 1 to 5.

[0012] [8] The polymer is a polymer obtained by polymerizing the monomer (1) and the non-conjugated olefin, The polymer of [7] above, wherein the proportion of the monomer (1) is 80 to 99 mass % when the total of the monomer (1) and the non-conjugated olefin is 100 mass %. [9] The polymer according to [7] or [8] above, further comprising a structural unit (ii) derived from an alkyl(meth)acrylate.

[10] The polymer according to any one of [7] to [9] above, wherein the monomer (1) contains myrcene.

[11] The polymer according to any one of [7] to

[10] above, wherein the non-conjugated olefin comprises a cyclic monoterpene.

[12] The polymer according to

[11] , wherein the cyclic monoterpene includes one or more selected from limonene, camphene, and β-pinene.

[13] A composition comprising a polymer having a structural unit (i) derived from a monomer (1) represented by the following formula (1) and a non-conjugated olefin:

[0013] [ka]

[0014] In formula (1), j is an integer of 1 to 5.

[0015]

[14] The composition according to

[13] , wherein the polymer further comprises a structural unit (ii) derived from an alkyl(meth)acrylate.

[15] The composition according to

[13] or

[14] , wherein the monomer comprises myrcene.

[16] The composition according to any one of

[13] to

[15] above, wherein the non-conjugated olefin comprises a cyclic monoterpene.

[17] The composition according to

[16] , wherein the cyclic monoterpene comprises one or more selected from limonene, camphene, and β-pinene. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a method for producing a polymer that can suppress heat generation during polymerization. Furthermore, the present invention can provide novel polymers and compositions. DETAILED DESCRIPTION OF THE INVENTION

[0017] The following definitions of terms are used herein: The term "structural unit" refers to a structural unit derived from a monomer, i.e., a structural unit formed by polymerizing a monomer, or a structural unit in which a portion of the structural unit is converted into a different structure by treating the polymer. Alkyl acrylate and alkyl methacrylate are collectively referred to as "alkyl (meth)acrylate." A numerical range indicated by "to" means a numerical range that includes the numbers before and after "to" as the lower and upper limits. The numerical ranges of the contents, various physical property values, and property values disclosed in this specification can be arbitrarily combined with the lower and upper limits to form new numerical ranges.

[0018] [Polymer manufacturing method] The method for producing a polymer according to the first aspect of the present invention is a method for obtaining a polymer (P) by polymerizing a radically polymerizable monomer component (M) in the presence of a non-conjugated olefin.

[0019] <Non-conjugated olefin> Examples of non-conjugated olefins include cyclic monoterpenes, α-olefins, etc. Among these, cyclic monoterpenes are preferred from the viewpoint of further suppressing heat generation during polymerization. These non-conjugated olefins may be used alone or in combination of two or more.

[0020] Examples of cyclic monoterpenes include limonene, camphene, α-pinene, β-pinene, sabinene, etc. Among these, from the viewpoint of further suppressing heat generation during polymerization, limonene, camphene, and β-pinene are preferred, and limonene is more preferred. These cyclic monoterpenes may be used alone or in combination of two or more.

[0021] <Radical polymerizable monomer component (M)> The radically polymerizable monomer component (M) (hereinafter also referred to as "monomer component (M)") is not particularly limited as long as it is a monomer having radical polymerizability, and examples thereof include a monomer (1) (hereinafter also referred to as "monomer (1)") represented by the following formula (1), an alkyl(meth)acrylate (hereinafter also referred to as "monomer (2)"), a monofunctional monomer (3) other than the monomer (1) and the monomer (2) (hereinafter also referred to as "monomer (3)"), and a polyfunctional monomer (4) (hereinafter also referred to as "monomer (4)"). These monomers may be used alone or in combination of two or more kinds. That is, the monomer component (M) may consist of only one kind of monomer, or may contain two or more kinds of monomers.

[0022] The monomer (1) is a monomer represented by the following formula (1).

[0023] [ka]

[0024] In formula (1), j is an integer of 1 to 5, preferably an integer of 1 or 2, and more preferably 1. Monomer (1) is myrcene when j=1 and farnesene when j=2. The monomer (1) is preferably a plant-derived monomer. When the monomer (1) is plant-derived, the resulting polymer (P) contributes to a carbon-recycling society. In particular, myrcene is preferred as the monomer (1). These monomers (1) may be used alone or in combination of two or more. That is, the polymer (P) obtained by the method for producing a polymer according to the first aspect of the present invention may be a homopolymer, a copolymer, or a graft copolymer.

[0025] Examples of the monomer (2) include alkyl (meth)acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, octyl acrylate, phenyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, p-diphenyl acrylate, o-diphenyl acrylate, o-chlorophenyl acrylate, 4-methoxyphenyl acrylate, 4-chlorophenyl acrylate, 2,4,6-trichlorophenyl acrylate, 4-tert-butylphenyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, and stearyl methacrylate. Of these, methyl methacrylate, n-butyl acrylate, and 2-ethylhexyl acrylate are more preferred. These monomers (2) may be used alone or in combination of two or more.

[0026] Examples of the monomer (3) include acrylate monomers other than alkyl (meth)acrylates, such as glycidyl acrylate, phenyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, p-diphenyl acrylate, o-diphenyl acrylate, o-chlorophenyl acrylate, 4-methoxyphenyl acrylate, 4-chlorophenyl acrylate, 2,4,trichlorophenyl acrylate, and 4-tert-butylphenyl acrylate; and aromatic vinyl monomers, such as styrene, α-methylstyrene, and vinyl toluene. Monomers include diene monomers such as 1,3-butadiene and isoprene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; carboxylic acid vinyl monomers such as vinyl acetate and vinyl butyrate; olefin monomers such as ethylene, propylene, and isobutylene; halogenated vinyl monomers such as vinyl chloride and vinylidene chloride; and maleimide monomers such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and N-methylmaleimide. These monomers (3) may be used alone or in combination of two or more.

[0027] Examples of the monomer (4) include crosslinking agents such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and divinylbenzene; and grafting agents such as allyl acrylate, allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate. Of these, allyl acrylate and allyl methacrylate are preferred. These monomers (4) may be used alone or in combination of two or more.

[0028] The proportions of the monomers (1), (2), (3) and (4) in 100% by mass of the monomer component (M) are not particularly limited and may be appropriately adjusted according to the target polymer, for example as follows: When the total of the monomer component (M) and the non-conjugated olefin is taken as 100% by mass, the content of the monomer (1) in the monomer component (Ma1) is preferably 0 to 99% by mass, more preferably 0 to 90% by mass, and even more preferably 20 to 80% by mass. When the total of the monomer component (M) and the non-conjugated olefin is taken as 100% by mass, the content of the monomer (2) in the monomer component (Ma1) is preferably 0 to 99% by mass, more preferably 0 to 95% by mass, and even more preferably 25 to 95% by mass. When the total of the monomer component (M) and the non-conjugated olefin is taken as 100% by mass, the content of the monomer (3) in the monomer component (Ma1) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 1 to 3% by mass. When the total of the monomer component (M) and the non-conjugated olefin is taken as 100% by mass, the content of the monomer (4) in the monomer component (Ma1) is preferably 0 to 5% by mass, more preferably 0.1 to 4% by mass, and even more preferably 0.5 to 3% by mass.

[0029] <Polymerization of monomer component (M)> (First embodiment) When producing a polymer (P) that is a homopolymer or a copolymer (excluding graft copolymers), the polymer (P) is obtained by polymerizing a monomer component (M) in the presence of a non-conjugated olefin. The monomer component (M) and the non-conjugated olefin may be added to the reaction system all at once or continuously. The proportion of the non-conjugated olefin is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, even more preferably 1 to 25 parts by mass, even more preferably 1 to 20 parts by mass, particularly preferably 1 to 15 parts by mass, and most preferably 1 to 10 parts by mass, per 100 parts by mass of the monomer component (M). When the proportion of the non-conjugated olefin is equal to or greater than the lower limit, heat generation during polymerization can be further suppressed. When the proportion of the non-conjugated olefin is equal to or less than the upper limit, polymerization proceeds easily, and the polymerization conversion rate of the monomer component (M) can be maintained at a good level, so that the powder properties of the resulting polymer (P) tend to be good. The ratio of non-conjugated olefins herein refers to the total amount of non-conjugated olefins used throughout the polymerization reaction of the monomer component (M), i.e., the total amount of non-conjugated olefins used relative to 100 parts by mass of the total amount (total added amount) of the monomer component (M) used until the polymerization reaction is completed.

[0030] The polymer (P) has structural units derived from the monomer component (M), and when the monomer component (M) is polymerized, a portion of the non-conjugated olefin may polymerize with the monomer component (M). That is, the polymer (P) may further have structural units derived from the non-conjugated olefin in addition to the structural units derived from the monomer component (M). For example, when the monomer component (M) contains the monomer (1), the polymer (P) has a structural unit (i) (hereinafter also referred to as "structural unit (i)") derived from the monomer (1). Furthermore, the polymer (P) may further have a structural unit (v) (hereinafter also referred to as "structural unit (v)") derived from a non-conjugated olefin, in addition to the structural unit derived from the monomer (1).

[0031] The method for polymerizing the monomer component (M) is not particularly limited, as long as the monomer component (M) is polymerized in the presence of a non-conjugated olefin. Examples of the method include a method in which the monomer component (M) is polymerized using an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, etc.

[0032] Among these, emulsion polymerization is preferred from the viewpoint of ease of controlling the particle size of the resulting polymer (P). Hereinafter, a method for producing polymer (P) by polymerizing monomer component (M) by emulsion polymerization will be described in detail. As the emulsion polymerization method, commonly known methods such as batch addition polymerization of monomers, continuous addition polymerization, and multi-stage polymerization can be used. When the emulsion polymerization method is used, the polymer (P) can be obtained as a latex dispersed in water (hereinafter also referred to as "polymer (P) latex"). The polymer (P) latex contains unreacted non-conjugated olefin. In other words, the polymer (P) latex can be said to be a composition containing the polymer (P), the non-conjugated olefin, and water.

[0033] The emulsifier used in emulsion polymerization may be an emulsifier having an ionic hydrophilic moiety and a nonionic hydrophilic moiety in the same molecule, or may be a nonionic emulsifier. Examples of emulsifiers having an ionic hydrophilic moiety and a nonionic hydrophilic moiety in the same molecule include carboxylic acid-based emulsifiers, phosphoric acid-based emulsifiers, and sulfonic acid-based emulsifiers. These emulsifiers may be used alone or in combination of two or more.

[0034] Examples of carboxylic acid emulsifiers include caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, ricinoleic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, and eleostearic acid. Examples of metal salts include metal salts of saturated or unsaturated fatty acids having an alkyl group having 8 to 28 carbon atoms, such as sarcosine, mead acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, bosseopentaenoic acid, eicosapentaenoic acid, osbondo acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, and nisinic acid; metal salts of oligocarboxylic acid compounds such as alkenylsuccinic acid; and metal salts of sarcosine derivatives such as N-lauroylsarcosine and N-cocoylsarcosine. These carboxylic acid emulsifiers may be used alone or in combination of two or more.

[0035] Examples of the phosphoric acid emulsifier include polyoxyethylene phenyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, polyoxyethylene alkyl ether phosphate, and alkyl phosphate. These phosphoric acid-based emulsifiers may be used alone or in combination of two or more.

[0036] Examples of sulfonic acid emulsifiers include polyoxyalkylene alkyl ether sulfonates, alkylbenzene sulfonates, α-sulfofatty acid methyl ester salts, and α-olefin sulfonates. These sulfonic acid emulsifiers may be used alone or in combination of two or more.

[0037] Examples of nonionic emulsifiers include polyoxyalkylene alkyl ethers, polyoxyethylene alkylene alkyl ethers, polyoxyethylene distyrenated phenyl ethers, polyoxyethylene tribenzyl phenyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene fatty acid esters. These nonionic emulsifiers may be used alone or in combination of two or more.

[0038] The amount of emulsifier used is preferably 0.1 to 20 parts by mass per 100 parts by mass of the total of the monomer component (M) and the non-conjugated olefin. When the amount of emulsifier used is equal to or greater than the above lower limit, emulsion stability is likely to be improved. When the amount of emulsifier used is equal to or less than the above upper limit, coagulation of the polymer (P) latex is facilitated, and the polymer (P) is easily recovered. The amount of emulsifier used here refers to the total amount of emulsifier used throughout the polymerization reaction of the monomer component (M). That is, it refers to the total amount of emulsifier used per 100 parts by mass of the total amount (total added amount) of the monomer component (M) and the non-conjugated olefin used until the polymerization reaction is completed. The same applies to the amounts of polymerization initiator, reducing agent, and water used, which will be described later.

[0039] The polymerization initiator used in the emulsion polymerization is not particularly limited, but examples thereof include azo-based initiators and peroxide-based initiators. These polymerization initiators may be used alone or in combination of two or more.

[0040] The amount of the polymerization initiator used is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of the monomer component (M) and the non-conjugated olefin. When a peroxide-based initiator is used, it can be used in combination with a reducing agent as a redox-based initiator. The amount of the reducing agent used is preferably 0.0001 to 1 part by mass per 100 parts by mass of the total of the monomer component (M) and the non-conjugated olefin.

[0041] In emulsion polymerization, water is usually used as the solvent. The amount of water used is preferably 100 to 700 parts by mass, more preferably 400 to 600 parts by mass, per 100 parts by mass of the total of the monomer component (M) and the non-conjugated olefin.

[0042] As described above, the polymer (P) is obtained as a latex dispersed in water. The method for recovering the polymer (P) from the polymer (P) latex is not particularly limited, but for example, the polymer (P) can be obtained as a powder by drying the polymer (P) latex by a spray drying method or a freeze drying method, or by coagulation. Among these, drying or coagulation by a spray drying method is preferred. Drying the polymer (P) latex by spray drying tends to improve the dispersibility of the polymer (P) powder when it is added to, for example, a resin material. By coagulating the polymer (P) latex, impurities such as the emulsifier used in the emulsion polymerization can be easily removed, and therefore a powder of the polymer (P) with high purity can be easily obtained.

[0043] In the case of drying by the spray drying method, for example, the polymer (P) latex is sprayed onto fine droplets and then dried by applying hot air to them. Examples of the device for generating droplets include a rotating disk type, a pressure nozzle type, and a two-fluid nozzle type. The hot air temperature is preferably 100 to 200° C. If the hot air temperature is equal to or higher than the lower limit, the polymer (P) latex can be easily dried sufficiently. If the hot air temperature is equal to or lower than the upper limit, thermal decomposition of the powder can be easily suppressed.

[0044] When coagulation is performed, for example, the polymer (P) latex is introduced into hot water in which a coagulant has been dissolved, and the polymer (P) is separated and purified by salting out, and the coagulated, wet product is dehydrated and dried. Examples of the coagulant include inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, sodium nitrate, and calcium acetate; and acids such as sulfuric acid. Among these, calcium acetate is particularly preferred. The coagulant may be used alone or in combination of two or more kinds, but when used in combination, it is necessary to select a combination that does not form a water-insoluble salt. For example, when calcium acetate is used in combination with sulfuric acid or its sodium salt, a water-insoluble calcium salt may be formed, and it is difficult to separate this calcium salt from the polymer (P) powder.

[0045] The volume average particle size (Dv) of the polymer (P) thus obtained is preferably from 50 to 1000 nm, more preferably from 70 to 500 nm. The volume average particle size (Dv) of the polymer (P) can be controlled by adding an enlargement agent to the polymer (P) latex. Various thickening agents can be used, including, for example, acid group-containing copolymers and oxyacid salts. Examples of acid group-containing copolymers include copolymers having acrylic acid, methacrylic acid, itaconic acid, or the like as constituent elements. Examples of oxyacid salts include alkali metal salts or alkaline earth metal salts of oxyacids, or at least one oxyacid salt selected from zinc, nickel, and aluminum salts. Specific examples of oxyacid salts include potassium salts, sodium salts, magnesium salts, calcium salts, nickel salts, and aluminum salts of oxyacids such as sulfuric acid, nitric acid, and phosphoric acid. In this specification, the volume-based particle size distribution is measured using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is taken as the volume-average particle size (Dv).

[0046] The polymer (P) thus obtained is a homopolymer or a copolymer, but the method for producing a polymer according to the first aspect of the present invention may be, for example, a method for producing a graft copolymer in which the polymer chain (A) is a rubber portion (core portion) and the polymer chain (B) is a graft portion (shell portion). In this specification, the graft portion is also referred to as a "graft chain." An example of a method for producing the polymer (P), which is a graft copolymer, will be described below.

[0047] Second Embodiment The method for producing polymer (P) of the second embodiment involves polymerizing a radically polymerizable monomer component (Ma) (hereinafter also referred to as "monomer component (Ma)") that constitutes polymer chain (A) to produce polymer chain (A), and then polymerizing a radically polymerizable monomer component (Mb) (hereinafter also referred to as "monomer component (Mb)") that constitutes polymer chain (B) in the presence of the resulting polymer chain (A) to produce polymer (P). The polymer (P) thus obtained is a graft copolymer in which a graft chain is introduced into the polymer chain (A), and the graft chain is polymer chain (B). In the following description, the polymerization of the monomer component (Ma) is also referred to as the "first polymerization reaction," and the polymerization of the monomer component (Mb) is also referred to as the "second polymerization reaction."

[0048] In the second embodiment, at least one of the first polymerization reaction and the second polymerization reaction is carried out in the presence of a non-conjugated olefin. That is, one of the first polymerization reaction and the second polymerization reaction may be carried out in the presence of a non-conjugated olefin and the other in the absence of a non-conjugated olefin, or both the first polymerization reaction and the second polymerization reaction may be carried out in the presence of a non-conjugated olefin. Among these, it is preferable to carry out both the first polymerization reaction and the second polymerization reaction in the presence of a non-conjugated olefin. Specific aspects of the second embodiment include α to γ shown below. α: A monomer component (Ma) constituting a polymer chain (A) is polymerized in the presence of a non-conjugated olefin to produce a polymer chain (A), and a monomer component (Mb) constituting a polymer chain (B) is polymerized in the presence of the obtained polymer chain (A) and the non-conjugated olefin to produce a polymer (P) that is a graft copolymer. β: A polymer chain (A) is produced by polymerizing a monomer component (Ma) that constitutes the polymer chain (A) in the presence of a non-conjugated olefin, and a monomer component (Mb) that constitutes the polymer chain (B) is polymerized in the presence of the obtained polymer chain (A) and in the absence of a non-conjugated olefin to produce a polymer (P) that is a graft copolymer. γ: A polymer chain (A) is produced by polymerizing a monomer component (Ma) that constitutes the polymer chain (A) in the absence of a non-conjugated olefin, and a monomer component (Mb) that constitutes the polymer chain (B) is polymerized in the presence of the obtained polymer chain (A) and in the presence of a non-conjugated olefin to produce a polymer (P) that is a graft copolymer.

[0049] The monomer component (Ma) preferably contains at least one of the monomer (1) and the monomer (2). The monomer component (Ma) may further contain at least one of the monomer (3) and the monomer (4) in addition to at least one of the monomer (1) and the monomer (2). That is, the polymer chain (A) preferably has at least one of a structural unit derived from the monomer (1) (structural unit (i)) and a structural unit (ii) derived from the monomer (2) (hereinafter also referred to as "structural unit (ii)"). In addition to at least one of the structural unit (i) and the structural unit (ii), the polymer chain (A) may further have at least one of a structural unit (iii) derived from the monomer (3) (hereinafter also referred to as "structural unit (iii)") and a structural unit (iv) derived from the monomer (4) (hereinafter also referred to as "structural unit (iv)").

[0050] The total proportion of the monomer (1) and the monomer (2) for obtaining the polymer chain (A) is preferably 80 to 99.9 mass %, more preferably 90 to 99 mass %, based on the total mass of the monomer component (Ma). The proportion of the monomer (3) for obtaining the polymer chain (A) is preferably 0 to 10 mass %, more preferably 0 to 5 mass %, based on the total mass of the monomer components (Ma). The proportion of the monomer (4) for obtaining the polymer chain (A) is preferably 0.1 to 10 mass %, more preferably 0.1 to 5 mass %, based on the total mass of the monomer component (Ma).

[0051] The monomer component (Mb) preferably has a different composition from the monomer component (Ma). It is preferred that the monomer component (Mb) is substantially free of the monomer (1). The monomer component (Mb) preferably contains the monomer (2). The monomer component (Mb) may further contain at least one of the monomer (3) and the monomer (4) in addition to the monomer (2). That is, the polymer chain (B) preferably has the structural unit (ii). Furthermore, the polymer chain (B) may further have at least one of the structural unit (iii) and the structural unit (iv) in addition to the structural unit (ii). Furthermore, the polymer chain (B) preferably does not substantially have the structural unit (i). Here, "substantially free of structural unit (i)" means that the content of structural unit (i) in the polymer chain (B) is 0 to 1 mass% relative to 100 mass% of all structural units constituting the polymer chain (B). The content of structural unit (i) in the polymer chain (B) is preferably 0 to 1 mass%, more preferably 0 to 0.8 mass%, even more preferably 0 to 0.5 mass%, particularly preferably 0 to 0.1 mass%, and most preferably 0 to 0.01 mass%, relative to 100 mass% of all structural units constituting the polymer chain (B).

[0052] The total proportion of the monomer (1) for obtaining the polymer chain (B) is preferably 0 to 1 mass %, more preferably 0 to 0.8 mass %, even more preferably 0 to 0.5 mass %, particularly preferably 0 to 0.1 mass %, and most preferably 0 to 0.01 mass %, based on the total mass of the monomer component (Mb). The total proportion of the monomers (2) for obtaining the polymer chain (B) is preferably 90 to 100 mass %, more preferably 95 to 100 mass %, based on the total mass of the monomer components (Mb). The proportion of the monomer (3) for obtaining the polymer chain (B) is preferably 0 to 5 mass %, more preferably 0 to 1 mass %, based on the total mass of the monomer component (Mb). The proportion of the monomer (4) for obtaining the polymer chain (B) is preferably 0 to 5 mass %, more preferably 0 to 1 mass %, based on the total mass of the monomer component (Mb).

[0053] The polymer chain (A) is obtained by polymerizing the monomer component (Ma). The polymerization of the monomer component (Ma) may be carried out in the presence or absence of a non-conjugated olefin. Examples of the method for polymerizing the monomer component (Ma) include methods of polymerizing the monomer component (Ma) using emulsion polymerization, suspension polymerization, solution polymerization, etc. Among these, emulsion polymerization is preferred from the viewpoint of ease of controlling the particle size of the resulting polymer chain (A). Examples of the emulsifier and polymerization initiator used in the polymerization method and emulsion polymerization include those exemplified above in the description of the first embodiment.

[0054] The amount of the emulsifier used is preferably 0.1 to 20 parts by mass per 100 parts by mass of the total of the monomer component (Ma) and the non-conjugated olefin. The amount of the polymerization initiator used is preferably 0.05 to 2.0 parts by mass, more preferably 0.1 to 1.5 parts by mass, per 100 parts by mass of the total of the monomer component (Ma) and the non-conjugated olefin. When a peroxide-based initiator is used, it can be used in combination with a reducing agent as a redox-based initiator. The amount of the reducing agent used is preferably 0.0001 to 1 part by mass per 100 parts by mass of the total of the monomer component (Ma) and the non-conjugated olefin. The amount of water used is preferably 600 to 1400 parts by mass, more preferably 800 to 1200 parts by mass, per 100 parts by mass of the total of the monomer component (Ma) and the non-conjugated olefin. The amount of emulsifier used here refers to the total amount of emulsifier used throughout the first polymerization reaction. That is, it refers to the total amount of emulsifier used per 100 parts by mass of the total amount (total added amount) of the monomer component (Ma) and non-conjugated olefin used until the first polymerization reaction is completed. The same applies to the amounts of polymerization initiator, reducing agent, and water used.

[0055] When the first polymerization reaction is carried out in the presence of a non-conjugated olefin, the proportion of the non-conjugated olefin is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, even more preferably 1 to 25 parts by mass, even more preferably 1 to 20 parts by mass, particularly preferably 1 to 15 parts by mass, and most preferably 1 to 10 parts by mass, per 100 parts by mass of the monomer component (Ma). When the proportion of the non-conjugated olefin is equal to or greater than the above lower limit, heat generation during polymerization can be further suppressed. When the proportion of the non-conjugated olefin is equal to or less than the above upper limit, polymerization proceeds easily, and the polymerization conversion rate of the monomer component (Ma) can be maintained at a good level. The ratio of non-conjugated olefins herein refers to the total amount of non-conjugated olefins used throughout the first polymerization reaction, i.e., the total amount of non-conjugated olefins used relative to 100 parts by mass of the total amount (total added amount) of monomer components (Ma) used until the first polymerization reaction is completed.

[0056] When the second polymerization reaction is carried out in the presence of a non-conjugated olefin, the proportion of the non-conjugated olefin is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, even more preferably 1 to 25 parts by mass, even more preferably 1 to 20 parts by mass, particularly preferably 1 to 15 parts by mass, and most preferably 1 to 10 parts by mass, per 100 parts by mass of the monomer component (Mb). When the proportion of the non-conjugated olefin is equal to or greater than the above lower limit, heat generation during polymerization can be further suppressed. When the proportion of the non-conjugated olefin is equal to or less than the above upper limit, polymerization proceeds easily, and the polymerization conversion rate of the monomer component (Mb) can be maintained at a good level. The ratio of non-conjugated olefins herein refers to the total amount of non-conjugated olefins used throughout the second polymerization reaction, i.e., the total amount of non-conjugated olefins used relative to 100 parts by mass of the total amount (total added amount) of monomer components (Mb) used until the second polymerization reaction is completed.

[0057] As mentioned above, only one of the first and second polymerization reactions may be carried out in the presence of a non-conjugated olefin, but it is preferable to carry out both the first and second polymerization reactions in the presence of a non-conjugated olefin. In this case, the ratio of the non-conjugated olefin to each radically polymerizable monomer component in each polymerization reaction is preferably within the above-mentioned range. However, the ratio of the non-conjugated olefin to the total amount (total added amount) of the monomer component (Ma) used until the completion of the first polymerization reaction and the total amount (total added amount) of the monomer component (Mb) used until the completion of the second polymerization reaction is 100 parts by mass is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, even more preferably 1 to 25 parts by mass, even more preferably 1 to 20 parts by mass, particularly preferably 1 to 15 parts by mass, and most preferably 1 to 10 parts by mass. When the ratio of the non-conjugated olefin is equal to or greater than the lower limit, heat generation during polymerization can be further suppressed.

[0058] The polymer chain (A) has a structural unit derived from the monomer component (Ma). When the first polymerization reaction is carried out in the presence of a non-conjugated olefin, a portion of the non-conjugated olefin may polymerize with the monomer component (Ma) during polymerization of the monomer component (Ma). That is, when the first polymerization reaction is carried out in the presence of a non-conjugated olefin, the polymer chain (A) may further have a structural unit derived from the non-conjugated olefin (structural unit (v)) in addition to the structural unit derived from the monomer component (Ma). For example, when the monomer component (Ma) contains at least one of the monomer (1) and the monomer (2), the polymer chain (A) contains at least one of the structural unit (i) and the structural unit (ii). Furthermore, the polymer chain (A) may further contain the structural unit (v) in addition to at least one of the structural unit (i) and the structural unit (ii).

[0059] The volume average particle size (Dv) of the polymer chains (A) is preferably from 50 to 1000 nm, more preferably from 70 to 500 nm.

[0060] The polymer chain (A) is obtained as a latex dispersed in water (hereinafter also referred to as "polymer chain (A) latex"). The second polymerization reaction, that is, polymerization of the monomer component (Mb), can be carried out in the polymer chain (A) latex. Polymerization of the monomer component (Mb) in the polymer chain (A) latex can produce a graft copolymer (P) (hereinafter simply referred to as a "graft copolymer") having the polymer chain (A) as the rubber portion (core portion) and the polymer chain (B) as the graft portion (shell portion). Specifically, the monomer component (Mb) is added to the polymer chain (A) latex and impregnated, and then various radical polymerization initiators are reacted to polymerize the monomer component (Mb). Methods for adding the radical polymerization initiator include adding the entire amount to the polymer chain (A) latex all at once and adding it dropwise at a constant rate to the polymer chain (A) latex.

[0061] The amount of monomer component (Mb) added is not particularly limited, but is preferably 50 to 90 mass% of the total amount of monomer component (Ma) added and the total amount of monomer component (Mb) added, with the total amount being 100 mass%. The amount of monomer component (Ma) added is preferably 55 to 80 mass%, more preferably 60 to 75 mass%. If the total amount of monomer component (Ma) added is equal to or greater than the lower limit, excellent low-temperature impact properties are likely to be obtained when the resulting graft copolymer is added to, for example, a resin material. If the total amount of monomer component (Ma) added is equal to or less than the upper limit, the resulting graft copolymer exhibits good dispersibility when added to, for example, a resin material. The total amount of monomer component (Ma) used here refers to the total amount (total added amount) of monomer component (Ma) used until the first polymerization reaction is completed. The total amount of monomer component (Mb) used refers to the total amount (total added amount) of monomer component (Mb) used until the second polymerization reaction is completed.

[0062] The method for polymerizing the monomer component (Mb) is not particularly limited, and examples thereof include methods in which the monomer component (Mb) is polymerized using an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, etc. Among these, the emulsion polymerization method is preferred from the viewpoint of easy control of the particle size of the resulting graft copolymer. Examples of the emulsifier and polymerization initiator used in the polymerisation method and emulsion polymerization include those exemplified above. The emulsifier used in producing the polymer chain (A) may be used as it is as the emulsifier used in polymerizing the monomer component (Mb), or may be added separately.

[0063] When an emulsifier is separately added in the polymerization of the monomer component (Mb), the amount of the emulsifier used is preferably 0.1 to 20 parts by mass per 100 parts by mass of the total of the monomer component (Mb) and the non-conjugated olefin. When a polymerization initiator is used for polymerizing the monomer component (Mb), the amount of the polymerization initiator used is preferably 0.05 to 1.0 part by mass per 100 parts by mass of the total of the monomer component (Mb) and the non-conjugated olefin. The amount of emulsifier used here refers to the total amount of emulsifier used throughout the entire second polymerization reaction. That is, it is the total amount of emulsifier used per 100 parts by mass of the total amount (total added amount) of the monomer component (Mb) and the non-conjugated olefin used until the second polymerization reaction is completed. The same applies to the amount of polymerization initiator used.

[0064] When the first polymerization reaction is carried out in the presence of a non-conjugated olefin, the polymer chain (A) latex obtained in the first polymerization reaction may contain unreacted non-conjugated olefin in addition to the polymer chain (A). Polymerizing the monomer component (Mb) in the polymer chain (A) latex containing unreacted non-conjugated olefin means that the second polymerization reaction is also carried out in the presence of a non-conjugated olefin.

[0065] When the first polymerization reaction is carried out in the presence of a non-conjugated olefin and the second polymerization reaction is carried out in the absence of a non-conjugated olefin, the polymer chain (A) is first recovered from the polymer chain (A) latex obtained in the first polymerization reaction, water is added to the recovered polymer chain (A) to make it into a latex again, and then the monomer component (Mb) and the like are added to carry out the second polymerization reaction. The method for recovering the polymer chains (A) from the polymer chain (A) latex is not particularly limited. For example, the polymer chains (A) can be obtained as a powder by drying the polymer chain (A) latex using a spray drying method or a freeze drying method, or by coagulation. Among these, drying or coagulation using a spray drying method is preferred. Furthermore, when coagulation is performed, impurities such as the emulsifier used in the emulsion polymerization can be easily removed, making it easy to obtain a powder of the polymer chains (A) with high purity. The conditions for the spray drying method and the coagulation method are the same as those previously described in the first embodiment.

[0066] When the first polymerization reaction is carried out in the absence of a non-conjugated olefin and the second polymerization reaction is carried out in the presence of a non-conjugated olefin, the non-conjugated olefin, the monomer component (Mb), etc. may be added to the polymer chain (A) latex obtained in the first polymerization reaction, and then the second polymerization reaction may be carried out. When only the second polymerization reaction is carried out in the presence of a non-conjugated olefin, the proportion of the non-conjugated olefin is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, even more preferably 1 to 25 parts by mass, even more preferably 1 to 20 parts by mass, particularly preferably 1 to 15 parts by mass, and most preferably 1 to 10 parts by mass, per 100 parts by mass of the monomer component (Mb). When the proportion of the non-conjugated olefin is equal to or greater than the above lower limit, heat generation during polymerization can be further suppressed. When the proportion of the non-conjugated olefin is equal to or less than the above upper limit, polymerization proceeds easily, and the polymerization conversion rate of the monomer component (Mb) can be maintained at a good level. The ratio of non-conjugated olefins herein refers to the total amount of non-conjugated olefins used throughout the second polymerization reaction, i.e., the total amount of non-conjugated olefins used relative to 100 parts by mass of the total amount (total added amount) of monomer components (Mb) used until the second polymerization reaction is completed.

[0067] The polymer chain (B) has a structural unit derived from the monomer component (Mb), but when the second polymerization reaction is carried out in the presence of a non-conjugated olefin, a portion of the non-conjugated olefin may polymerize with the monomer component (Mb) during polymerization of the monomer component (Mb). That is, the polymer chain (B) may further have a structural unit (structural unit (v)) derived from the non-conjugated olefin in addition to the structural unit derived from the monomer component (Mb). For example, when the monomer component (Mb) contains the monomer (2), the polymer chain (B) contains the structural unit (ii). In addition to the structural unit (ii), the polymer chain (B) may further contain the structural unit (v).

[0068] The polymer (P), which is a graft copolymer, is obtained as a latex dispersed in water (hereinafter also referred to as "graft copolymer latex"). The graft copolymer latex obtained by emulsion polymerization may be blended with additives such as an antioxidant, if necessary. The graft copolymer latex may be produced by blending the antioxidant in advance and then carrying out emulsion polymerization. Examples of the antioxidant include phenol-based antioxidants, thioether-based antioxidants, phosphite-based antioxidants, etc. These antioxidants may be used alone or in combination of two or more. The antioxidant may be blended as a powder or tablet, or may be blended in a state of being dispersed in water. However, a method of blending the antioxidant in a state of being dispersed in water into the graft copolymer latex is preferred. This allows the antioxidant to be added more uniformly, making it easier to suppress oxidative degradation of the graft copolymer. When an antioxidant is added to the graft copolymer latex, the amount of the antioxidant used is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 6 parts by mass, and even more preferably 0.01 to 3 parts by mass, per 100 parts by mass of the total of the monomer components (Ma) and (Mb). The amount of antioxidant used here refers to the total amount of antioxidant used relative to 100 parts by mass of the total amount (total added amount) of the monomer component (Ma) and the total amount (total added amount) of the monomer component (Mb) used until the first polymerization reaction and the second polymerization reaction are completed.

[0069] The method for recovering the graft copolymer from the graft copolymer latex is not particularly limited. For example, the graft copolymer can be obtained as a powder by drying the graft copolymer latex using a spray drying method or a freeze drying method, or by coagulation. Among these, drying or coagulation using a spray drying method is preferred. When drying is performed using a spray drying method, the dispersibility of the graft copolymer powder when added to a resin material is likely to be improved. Furthermore, when coagulation is performed, impurities such as the emulsifier used in the emulsion polymerization can be easily removed, making it easy to obtain a highly pure graft copolymer powder. The conditions for the spray drying method and the coagulation method are the same as those previously described in the first embodiment.

[0070] The volume average particle size (Dv) of the thus obtained graft copolymer is preferably from 60 to 1100 nm, more preferably from 80 to 600 nm. The number average particle size (Dn) of the graft copolymer is preferably from 30 to 600 nm, more preferably from 50 to 400 nm. In this specification, the number-based particle size distribution is measured using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is taken as the number-average particle diameter (Dn).

[0071] <Action and effect> According to the method for producing a polymer of the first aspect of the present invention, a polymer is produced by polymerizing the monomer component (M) in the presence of a non-conjugated olefin, so that heat generation during polymerization can be suppressed. Therefore, according to the method for producing a polymer of the first aspect of the present invention, a polymer can be produced stably, and the amount of cooling water used can be reduced.

[0072] [Polymer] The polymer according to the second aspect of the present invention (hereinafter also referred to as "polymer (P1)") has a structural unit (structural unit (i)) derived from the monomer (1) represented by the formula (1) above, and a structural unit (structural unit (v)) derived from a non-conjugated olefin. In other words, the polymer (P1) is a polymer obtained by polymerizing the monomer (1) and a non-conjugated olefin. The monomer (1) and the non-conjugated olefin are the same as the monomer (1) and the non-conjugated olefin exemplified above in the description of the method for producing the polymer of the first embodiment of the present invention, and therefore, description thereof will be omitted.

[0073] The monomer (1) preferably contains myrcene, that is, the polymer (P1) preferably has a structural unit derived from myrcene. The non-conjugated olefin preferably contains a cyclic monoterpene, and more preferably contains one or more selected from limonene, camphene, and β-pinene. That is, the polymer (P1) preferably contains a structural unit (v-1) (hereinafter also referred to as "structural unit (v-1)") derived from one or more compounds selected from limonene, camphene, and β-pinene. The polymer (P1) more preferably has a structural unit derived from myrcene and the structural unit (v-1).

[0074] The polymer (P1) may further have structural units derived from monomers other than the monomer (1) and the non-conjugated olefin (hereinafter also referred to as "other monomers"). Examples of other monomers include the monomers (2), (3), and (4) exemplified above in the description of the method for producing the polymer according to the first embodiment of the present invention. That is, in addition to the structural units (i) and (v), the polymer (P1) may further contain one or more structural units selected from the group consisting of a structural unit derived from the monomer (2) (structural unit (ii)), a structural unit derived from the monomer (3) (structural unit (iii)), and a structural unit derived from the monomer (4) (structural unit (iv)). In particular, the polymer (P1) preferably contains the structural unit (ii) in addition to the structural units (i) and (v).

[0075] A preferred embodiment of the polymer (P1) is a copolymer having a polymer chain (A1) and a polymer chain (B1). In particular, a graft copolymer (graft copolymer (1)) in which the polymer chain (A1) is the rubber portion (core portion) and the polymer chain (B1) is the graft portion (shell portion) is preferred. That is, the graft copolymer (1) is a graft copolymer in which a graft chain is introduced into the polymer chain (A1), and the graft chain is the polymer chain (B1). The polymer chain (A1) preferably has the structural unit (i) and the structural unit (v). In addition to the structural unit (i) and the structural unit (v), the polymer chain (A1) may further have one or more structural units selected from the structural unit (ii), the structural unit (iii), and the structural unit (iv).

[0076] The proportion of the polymer chain (A1) is preferably 50 to 90% by mass, more preferably 55 to 80% by mass, and even more preferably 60 to 75% by mass, when the total of the polymer chain (A1) and the polymer chain (B1) is taken as 100% by mass. If the proportion of the polymer chain (A1) is equal to or greater than the above lower limit, excellent low-temperature impact properties are likely to be obtained when the graft copolymer (1) is added to, for example, a resin material. If the proportion of the polymer chain (A1) is equal to or less than the above upper limit, good dispersibility is achieved when the graft copolymer (1) is added to, for example, a resin material.

[0077] The polymer chain (B1) preferably has a composition different from that of the polymer chain (A1). It is preferable that the polymer chain (B1) is substantially free of the structural unit (i). The polymer chain (B1) preferably has the structural unit (ii). In addition to the structural unit (ii), the polymer chain (B1) may further include at least one of the structural unit (iii) and the structural unit (iv). The polymer chain (B1) may further include a structural unit (v) in addition to the structural unit (ii).

[0078] The polymer (P1) is a polymer obtained by polymerizing the monomer (1) and a non-conjugated olefin, and can be obtained, for example, by polymerizing a radically polymerizable monomer component (M1) (hereinafter also referred to as "monomer component (M1)") containing the monomer (1) in the presence of the non-conjugated olefin. The monomer component (M1) may contain, in addition to the monomer (1), one or more monomers selected from the group consisting of the monomer (2), the monomer (3) and the monomer (4). The method for polymerizing the monomer component (M1) is the same as the method for polymerizing the monomer component (M) exemplified above in the description of the first embodiment of the method for producing a polymer according to the first aspect of the present invention, and therefore a description thereof will be omitted. When the monomer component (M1) is emulsion polymerized, the polymer (P1) is obtained as a latex (hereinafter also referred to as "polymer (P1) latex"). Therefore, the powdery polymer (P1) can be recovered from the polymer (P1) latex by drying, for example, by spray drying or freeze drying, or by coagulation.

[0079] When the total of the monomer (1) and the non-conjugated olefin is taken as 100% by mass, the proportion of the monomer (1) is preferably 80 to 99.99% by mass, more preferably 80 to 99% by mass, even more preferably 85 to 99% by mass, and particularly preferably 90 to 99% by mass. If the proportion of the monomer (1) is equal to or greater than the above lower limit, low-temperature impact properties are likely to be obtained when the polymer (P1) is added to, for example, a resin material. If the proportion of the monomer (1) is equal to or less than the above lower limit, coloration can be suppressed when the polymer (P1) is added to, for example, a resin material. When the total of the monomer (1) and the non-conjugated olefin is taken as 100% by mass, the proportion of the non-conjugated olefin is preferably 0.01 to 20% by mass, more preferably 1 to 20% by mass, and even more preferably 1 to 10% by mass.

[0080] Furthermore, when the total of the monomer component (M1) and the non-conjugated olefin is taken as 100% by mass, the proportion of the monomer (1) in the monomer component (M1) is preferably 50 to 99.99% by mass, more preferably 70 to 99.9% by mass. If the proportion of the monomer (1) is equal to or greater than the above lower limit, low-temperature impact properties are easily obtained when the polymer (P1) is added to, for example, a resin material. If the proportion of the monomer (1) is equal to or less than the above lower limit, yellowing can be suppressed when the polymer (P1) is added to, for example, a resin material. When the total of the monomer component (M1) and the non-conjugated olefin is taken as 100% by mass, the proportion of the monomer (2) in the monomer component (M1) is preferably 1 to 50% by mass, more preferably 10 to 40% by mass. When the total of the monomer component (M1) and the non-conjugated olefin is taken as 100% by mass, the total proportion of the monomer (3) and the monomer (4) in the monomer component (M1) is preferably 1 to 15% by mass, more preferably 1 to 10% by mass. When the total of the monomer component (M1) and the non-conjugated olefin is taken as 100% by mass, the proportion of the non-conjugated olefin is preferably 0.01 to 10% by mass. The content of the structural units constituting the polymer (P1) can be calculated from the charged amounts.

[0081] When the polymer (P1) is a graft copolymer (1), the polymer (P1) can be obtained by, for example, polymerizing a radically polymerizable monomer component (Ma1) (hereinafter also referred to as "monomer component (Ma1)") containing the monomer (1) to produce a polymer chain (A1) (first polymerization reaction), and then polymerizing a radically polymerizable monomer component (Mb1) (hereinafter also referred to as "monomer component (Mb1)") in the presence of the resulting polymer chain (A1) (second polymerization reaction). Note that at least one of the first and second polymerization reactions is carried out in the presence of a non-conjugated olefin. That is, one of the first and second polymerization reactions may be carried out in the presence of a non-conjugated olefin, and the other may be carried out in the absence of a non-conjugated olefin. Alternatively, both the first and second polymerization reactions may be carried out in the presence of a non-conjugated olefin. It is preferred that both the first and second polymerization reactions be carried out in the presence of a non-conjugated olefin.

[0082] The monomer component (Ma1) may contain, in addition to the monomer (1), one or more monomers selected from the group consisting of the monomer (2), the monomer (3) and the monomer (4). The polymerization method of the monomer component (Ma1), and the monomer component (Mb1) and its polymerization method are the same as those exemplified above in the description of the second embodiment of the polymer production method of the first aspect of the present invention, and therefore their description will be omitted. When the monomer component (Ma1) and the monomer component (Mb1) are emulsion-polymerized, the graft copolymer (1) is obtained as a latex (graft copolymer (1) latex). Therefore, the powdery graft copolymer (1) can be recovered from the graft copolymer latex by drying, for example, by spray drying or freeze drying, or by coagulation.

[0083] When the total of the monomer component (Ma1), the monomer component (Mb1), and the non-conjugated olefin is taken as 100% by mass, the proportion of the monomer (1) in the monomer component (Ma1) is preferably 10 to 99% by mass, more preferably 50 to 99% by mass, even more preferably 50 to 95% by mass, and particularly preferably 60 to 90% by mass. If the proportion of the monomer (1) is equal to or greater than the above lower limit, low-temperature impact properties are likely to be obtained when the graft copolymer (1) is added to, for example, a resin material. If the proportion of the monomer (1) is equal to or less than the above lower limit, optical properties are likely to be improved when the graft copolymer (1) is added to, for example, a resin material. When the total of the monomer component (Ma1), the monomer component (Mb1) and the non-conjugated olefin is taken as 100% by mass, the proportion of the monomer (2) in the monomer component (Ma1) is preferably 0 to 90% by mass, more preferably 0 to 80% by mass, even more preferably 10 to 60% by mass, particularly preferably 10 to 50% by mass, and most preferably 10 to 40% by mass. When the total of the monomer component (Ma1), the monomer component (Mb1) and the non-conjugated olefin is taken as 100% by mass, the proportion of the monomer (3) in the monomer component (Ma1) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 1 to 3% by mass. When the total of the monomer component (Ma1), the monomer component (Mb1) and the non-conjugated olefin is taken as 100% by mass, the proportion of the monomer (4) in the monomer component (Ma1) is preferably 0 to 5% by mass, more preferably 0.1 to 4% by mass, and even more preferably 0.5 to 3% by mass.

[0084] When the total of the monomer component (Ma1), the monomer component (Mb1) and the non-conjugated olefin is taken as 100% by mass, the proportion of the monomer (1) in the monomer component (Mb1) is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and even more preferably substantially none. When the total of the monomer component (Ma1), the monomer component (Mb1) and the non-conjugated olefin is taken as 100% by mass, the proportion of the monomer (2) in the monomer component (Mb1) is preferably 1 to 50% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 40% by mass. When the total of the monomer component (Ma1), the monomer component (Mb1) and the non-conjugated olefin is taken as 100% by mass, the proportion of the monomer (3) in the monomer component (Mb1) is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass. When the total of the monomer component (Ma1), the monomer component (Mb1) and the non-conjugated olefin is taken as 100% by mass, the proportion of the monomer (4) in the monomer component (Mb1) is preferably 0 to 5% by mass, more preferably 0 to 2% by mass, and even more preferably 0 to 0.5% by mass.

[0085] When the total of the monomer component (Ma1), the monomer component (Mb1) and the non-conjugated olefin is taken as 100% by mass, the proportion of the non-conjugated olefin is preferably 0.01 to 20% by mass, more preferably 0.1 to 18% by mass, and even more preferably 1 to 15% by mass.

[0086] The proportion of the structural unit (i) in the polymer chain (A1) is preferably 30 to 99.99 mass%, more preferably 40 to 99.9 mass%, and even more preferably 45 to 99.8 mass%, based on 100 mass% of the total of all structural units in the polymer chain (A1). If the proportion of the structural unit (i) is at least the above lower limit, low-temperature impact properties are likely to be obtained when the graft copolymer (1) is added to, for example, a resin material. If the proportion of the structural unit (i) is at most the above lower limit, optical properties are likely to be improved when the graft copolymer (1) is added to, for example, a resin material. The proportion of the structural unit (v) in the polymer chain (A1) is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 0.2 to 1 mass%, relative to 100 mass% of the total of all structural units in the polymer chain (A1). The total proportion of the structural unit (ii) in the polymer chain (A1) is preferably from 0 to 69.99 mass%, and more preferably from 0 to 55 mass%, relative to 100 mass% of the total of all structural units in the polymer chain (A1). The proportion of the structural unit (iii) in the polymer chain (A1) is preferably from 0 to 10 mass %, and more preferably from 0.1 to 5 mass %, relative to 100 mass % of the total of all structural units in the polymer chain (A1). The proportion of the structural unit (iv) in the polymer chain (A1) is preferably from 0 to 10 mass %, and more preferably from 0.1 to 5 mass %, relative to 100 mass % of the total of all structural units in the polymer chain (A1).

[0087] The total proportion of the structural unit (i) in the polymer chain (B1) is preferably 0 to 1 mass%, more preferably 0 to 0.8 mass%, even more preferably 0 to 0.5 mass%, particularly preferably 0 to 0.1 mass%, and most preferably 0 to 0.01 mass%, relative to 100 mass% of all structural units in the polymer chain (B1). The total proportion of the structural unit (ii) in the polymer chain (B1) is preferably 90 to 100 mass %, and more preferably 95 to 100 mass %, relative to 100 mass % of the total of all structural units in the polymer chain (B1). The proportion of the structural unit (iii) in the polymer chain (B1) is preferably from 0 to 5 mass %, and more preferably from 0 to 1 mass %, relative to 100 mass % of the total of all structural units in the polymer chain (B1). The proportion of the structural unit (iv) in the polymer chain (B1) is preferably from 0 to 5 mass %, and more preferably from 0 to 1 mass %, relative to 100 mass % of the total of all structural units in the polymer chain (B1). The proportion of the structural unit (v) in the polymer chain (B1) is preferably from 0 to 5 mass %, and more preferably from 0 to 1 mass %, relative to 100 mass % of the total of all structural units in the polymer chain (B1).

[0088] The polymer (P1) of this embodiment is suitable as a resin additive such as a modifier for improving the impact strength of resins.

[0089] [Composition] The composition according to the third aspect of the present invention (hereinafter also referred to as "composition (X)") comprises a polymer (hereinafter also referred to as "polymer (P2)") having a structural unit (structural unit (i)) derived from the monomer (1) represented by the formula (1) above, and a non-conjugated olefin. The monomer (1) and the non-conjugated olefin are the same as the monomer (1) and the non-conjugated olefin exemplified above in the description of the method for producing the polymer of the first embodiment of the present invention, and therefore, description thereof will be omitted.

[0090] The monomer (1) preferably contains myrcene, that is, the polymer (P2) preferably has a structural unit derived from myrcene. The non-conjugated olefin preferably contains a cyclic monoterpene, and more preferably contains one or more selected from limonene, camphene, and β-pinene.

[0091] Polymer (P2) is the same as polymer (P1) of the second aspect of the present invention, except that polymer (P2) does not contain a structural unit derived from a non-conjugated olefin (structural unit (v)) as an essential structural unit. Furthermore, the polymer (P2) may further include a structural unit (v) in addition to the structural unit (i). The polymer (P2) preferably further contains the structural unit (ii) in addition to the structural unit (i).

[0092] A preferred embodiment of the polymer (P2) is a copolymer having a polymer chain (A2) and a polymer chain (B2). In particular, a graft copolymer (graft copolymer (2)) in which the polymer chain (A2) is the rubber portion (core portion) and the polymer chain (B2) is the graft portion (shell portion) is preferred. That is, the graft copolymer (2) is a graft copolymer in which a graft chain is introduced into the polymer chain (A2), and the graft chain is the polymer chain (B2). The polymer chain (A2) preferably contains the structural unit (i). In addition to the structural unit (i), the polymer chain (A2) may further contain one or more structural units selected from the structural unit (ii), the structural unit (iii), and the structural unit (iv). Furthermore, in addition to the structural unit (i), the polymer chain (A2) may further contain the structural unit (v). The polymer chain (B2) may be the polymer chain (B1) exemplified above in the description of the polymer (P1) of the second aspect of the present invention. The polymer chain (B2) preferably has a different composition from the polymer chain (A2). The polymer chain (B2) preferably has the structural unit (ii).

[0093] The proportion of the polymer chain (A2) when the total of the polymer chain (A1) and the polymer chain (B1) is taken as 100% by mass is the same as that of the polymer chain (A1) exemplified above in the description of the polymer (P1) of the second embodiment of the present invention.

[0094] The content of the polymer (P2) is preferably from 90 to 99.99 mass %, more preferably from 95 to 99.5 mass %, based on the total mass of the solid contents of the composition (X). The content of the non-conjugated olefin is preferably from 0.01 to 10 mass %, more preferably from 0.5 to 5 mass %, based on the total mass of the solid contents of the composition (X). Here, "solid content of composition (X)" refers to components other than volatile components contained in the composition, i.e., so-called pure components. "Volatile components" refer to components that volatilize at 150°C or higher.

[0095] The composition (X) may further contain components other than the polymer (P2) and the non-conjugated olefin (hereinafter also referred to as "optional components"). Optional components include additives such as antioxidants, ultraviolet absorbers, dyes, and pigments.

[0096] Composition (X) can be prepared, for example, by polymerizing a radically polymerizable monomer component (M2) (hereinafter also referred to as "monomer component (M2)") containing monomer (1) in the presence of a non-conjugated olefin, thereby obtaining a composition containing polymer (P2) having structural unit (i) and unreacted non-conjugated olefin. The monomer component (M2) preferably further contains a monomer (2) in addition to the monomer (1). The monomer component (M2) may further contain, in addition to the monomer (1), one or more monomers selected from the monomer (3) and the monomer (4). The polymerization method for the monomer component (M2) is the same as the polymerization method exemplified above in the description of the first embodiment of the method for producing a polymer according to the first aspect of the present invention, and therefore a description thereof will be omitted. When the monomer component (M2) is emulsion polymerized, the polymer (P2) is obtained as a latex (hereinafter also referred to as "polymer (P2) latex"). The polymer (P2) latex contains the polymer (P2) as well as unreacted non-conjugated olefin and water.

[0097] The proportion of monomer (1) when the total of monomer (1) and non-conjugated olefin is taken as 100% by mass, and the proportion of each monomer in monomer component (M2) and the proportion of non-conjugated olefin when the total of monomer component (M2) and non-conjugated olefin is taken as 100% by mass, are the same as in the case of polymer (P1) of the second embodiment of the present invention.

[0098] When the polymer (P2) is a graft copolymer (2), a composition (X) containing the graft copolymer (2) can be produced by, for example, polymerizing a radically polymerizable monomer component (Ma2) (hereinafter also referred to as "monomer component (Ma2)") containing the monomer (1) to produce a polymer chain (A2) (first polymerization reaction), and then polymerizing a radically polymerizable monomer component (Mb2) (hereinafter also referred to as "monomer component (Mb2)") in the presence of the resulting polymer chain (A2) (second polymerization reaction). However, at least one of the first and second polymerization reactions is carried out in the presence of a non-conjugated olefin. That is, one of the first and second polymerization reactions may be carried out in the presence of a non-conjugated olefin, and the other may be carried out in the absence of a non-conjugated olefin. Alternatively, both the first and second polymerization reactions may be carried out in the presence of a non-conjugated olefin. It is preferred that both the first and second polymerization reactions be carried out in the presence of a non-conjugated olefin. By doing so, a composition containing the polymer (P2), which is the graft copolymer (2) having the polymer chain (A2) and the polymer chain (B2), and the unreacted non-conjugated olefin is obtained.

[0099] The monomer component (Ma2) may contain, in addition to the monomer (1), one or more monomers selected from the monomer (2), the monomer (3) and the monomer (4). The polymerization method of the monomer component (Ma2), and the monomer component (Mb2) and its polymerization method are the same as those exemplified above in the description of the second embodiment of the polymer production method of the first aspect of the present invention, and therefore their description will be omitted. When the monomer component (Ma2) and the monomer component (Mb2) are emulsion polymerized, the graft copolymer (2) is obtained as a latex (graft copolymer (2) latex). The graft copolymer (2) latex contains unreacted non-conjugated olefin and water in addition to the graft copolymer (2). Therefore, the obtained graft copolymer (2) latex may be used as the composition (X) as it is.

[0100] When the total of the monomer component (Ma2), the monomer component (Mb2) and the non-conjugated olefin is taken as 100% by mass, the proportion of each monomer in the monomer component (Ma2) and the monomer component (Mb2) and the proportion of the non-conjugated olefin are the same as in the case of the polymer (P1) of the second embodiment of the present invention. The proportions of the structural units in the polymer chain (A2) and the structural units in the polymer chain (B2) are the same as those in the polymer (P1) of the second aspect of the present invention.

[0101] The composition (X) of this embodiment is suitable as, for example, an adhesive, a primer, or a paint in the form of an aqueous emulsion.

[0102] Among the above-mentioned polymers, polymer (P), which is a graft copolymer, polymer (P1), which is a graft copolymer (1), and polymer (P2), which is a graft copolymer (2), can function as a resin modifier when added to a matrix resin. There are no particular limitations on the matrix resin, and examples thereof include polylactic acid, polycarbonate, polymethyl methacrylate, polystyrene, polyolefin, and polyester. Hereinafter, a composition containing one or more polymers selected from polymer (P), polymer (P1), and polymer (P2) according to this embodiment and a matrix resin will also be referred to as "resin composition (E)." It is preferable that resin composition (E) further contains a non-conjugated olefin. A molded article can be obtained by molding resin composition (E). There are no particular limitations on the molding method, and known methods can be used. [Example]

[0103] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following descriptions. In the following, "parts" means "parts by mass" unless otherwise specified.

[0104] [Measurement and Evaluation] <Calculation method of polymerization conversion rate> After the polymerization was completed, a portion of the graft copolymer latex was sampled and its weight (w1) was measured, and then it was placed in a nitrogen-circulating hot air dryer at 150°C for 30 minutes to volatilize the water, after which the amount of solids remaining (w2) was measured. The total weight of the monomer and non-conjugated olefin used in the polymerization was defined as w3, and the total weight of the monomer, non-conjugated olefin, emulsifier, polymerization initiator, and water used in the polymerization was defined as w4, and the polymerization conversion rate was calculated using the following formula (I): Polymerization conversion rate = (w2 / w1) × (w4 / w3) × 100 Equation (I)

[0105] <Evaluation of powder properties> The powder properties of the graft copolymer were evaluated based on the following evaluation criteria regarding passability when the entire powder amount of the graft copolymer was passed through an 8-mesh sieve (opening size 2.36 mm) specified in JIS Z 8801-1:2019 for 30 seconds. ○: The entire amount of the graft copolymer powder passes through an 8-mesh sieve. ×: The graft copolymer cannot be recovered as a powder and cannot be sieved through an 8-mesh sieve.

[0106] [Example 1] <Production of polymer chain (A)> As the monomer component (Ma), 54.8 parts of n-butyl acrylate (manufactured by Mitsubishi Chemical Corporation) as the monomer (2), 0.9 parts of allyl methacrylate (manufactured by Mitsubishi Chemical Corporation) as the monomer (4), 7.2 parts of limonene as the non-conjugated olefin, and 1.2 parts of sodium dodecylbenzenesulfonate as the emulsifier were used. These were added to 100 parts of deionized water and stirred at 15,000 rpm for 5 minutes to obtain a stable premixed emulsion.

[0107] The resulting premixed emulsion was placed in a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer. The atmosphere inside the polymerization apparatus was thoroughly purged with nitrogen, and the temperature was then raised to 60°C. Next, 1.0 part of diisopropylbenzene hydroperoxide (NOF Corporation, trade name "Percumyl P") as a polymerization initiator and 0.002 parts of ferrous sulfate, 0.006 parts of disodium ethylenediaminetetraacetate, and 0.3 parts of sodium formaldehyde sulfoxylate as reducing agents were added to initiate polymerization. Stirring was continued for 360 minutes, yielding a polymer chain (A) latex. The proportion of the non-conjugated olefin-derived structural unit (structural unit (v)) in the total structural units constituting the polymer chain (A) was 0.01 to 10% by mass.

[0108] <Production of Graft Copolymer> In the obtained polymer chain (A) latex, methyl methacrylate, which is the monomer (2), was polymerized as the monomer component (Mb) as follows to produce a graft copolymer. 0.1 parts of t-butyl hydroperoxide was added as a polymerization initiator to 37.1 parts of methyl methacrylate (manufactured by Mitsubishi Chemical Corporation), and the resulting solution was continuously added dropwise to the polymer chain (A) latex over 60 minutes to polymerize. The temperature inside the polymerization apparatus was then raised to 70°C, and stirring was continued for 120 minutes to obtain a graft copolymer latex. The proportion of the structural unit (v) in the total structural units constituting the obtained graft copolymer was 0.01 to 10% by mass. In the production of the polymer chain (A) latex and the production of the graft copolymer, the difference between the set temperature in the polymerization apparatus and the maximum temperature in the system was defined as the polymerization heat temperature, and this temperature was monitored. The results are shown in Table 1. The polymerization conversion rate was also calculated, and the results are shown in Table 1.

[0109] <Recovery of graft copolymer> To the obtained graft copolymer latex, 0.25 parts of n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate (manufactured by BASF Japan Ltd., trade name "Irganox 1076") as a phenolic antioxidant and 0.75 parts of didodecyl 3,3'-thiodipropionate (manufactured by Bayer, trade name "DLDTP") as a thioether antioxidant were added. This was added to 460 parts of deionized water containing 5 parts by mass of calcium acetate to cause coagulation, followed by washing with water, dehydration, and drying to obtain the graft copolymer in powder form. The powder properties of the obtained graft copolymer were evaluated, and the results are shown in Table 1.

[0110] [Example 2] A graft copolymer was produced in the same manner as in Example 1, except that the composition of the monomer component (Ma), the amount of methyl methacrylate used as the monomer component (Mb), and the amount of limonene used as the non-conjugated olefin were changed to the values shown in Table 1, and measurements and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1. In Example 2, the proportion of the structural unit (v) in all structural units constituting the polymer chain A is 0.01 to 10 mass %, and the proportion of the structural unit (v) in all structural units constituting the graft copolymer is 0.01 to 10 mass %.

[0111] [Example 3] A graft copolymer was produced in the same manner as in Example 1, except that the polymer chain (A) latex was produced by changing the composition of the monomer component (Ma) and the amount of limonene used as the non-conjugated olefin as shown in Table 1, and measurements and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1. In Example 3, the proportion of the structural unit (v) in all structural units constituting the polymer chain A is 0.01 to 10 mass %, and the proportion of the structural unit (v) in all structural units constituting the graft copolymer is 0.01 to 10 mass %.

[0112] [Example 4] A premixed emulsion was obtained in the same manner as in Example 1, except that the compositions of the monomer component (Ma) and the non-conjugated olefin were changed as shown in Table 1. Using the obtained premixed emulsion, a polymer chain (A) latex was produced in the same manner as in Example 1, except that the stirring time after adding the polymerization initiator was changed from 360 minutes to 240 minutes. Using the obtained polymer chain (A) latex, a graft copolymer was produced in the same manner as in Example 1, except that the amount of methyl methacrylate used as the monomer component (Mb) was changed to the value shown in Table 1, and measurements and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1. In Example 4, the proportion of the structural unit (v) in all structural units constituting the polymer chain A is 0.01 to 10 mass %, and the proportion of the structural unit (v) in all structural units constituting the graft copolymer is 0.01 to 10 mass %.

[0113] [Example 5] A premixed emulsion was obtained in the same manner as in Example 1, except that the compositions of the monomer component (Ma) and the non-conjugated olefin were changed as shown in Table 1. Using the obtained premixed emulsion, a polymer chain (A) latex was produced in the same manner as in Example 1, except that the stirring time after adding the polymerization initiator was changed from 360 minutes to 240 minutes. Using the obtained polymer chain (A) latex, a graft copolymer was produced in the same manner as in Example 1, except that the amount of methyl methacrylate used as the monomer component (Mb) was changed to the value shown in Table 1, and measurements and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1. In Example 5, the proportion of the structural unit (v) in all structural units constituting the polymer chain A is 0.01 to 10 mass %, and the proportion of the structural unit (v) in all structural units constituting the graft copolymer is 0.01 to 10 mass %.

[0114] [Comparative Example 1] A polymer chain (A) latex was produced in the same manner as in Example 1, except that the composition of the monomer component (Ma) was changed to the values shown in Table 1 and no non-conjugated olefin was used. Using the obtained polymer chain (A) latex, a graft copolymer was produced in the same manner as in Example 1, except that the amount of methyl methacrylate used as the monomer component (Mb) was changed to the value shown in Table 1, and measurements and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0115] Comparative Example 2 A polymer chain (A) latex was produced in the same manner as in Example 1, except that the composition of the monomer component (Ma) was changed to the values shown in Table 1 and no non-conjugated olefin was used. Using the obtained polymer chain (A) latex, a graft copolymer was produced in the same manner as in Example 1, except that the amount of methyl methacrylate used as the monomer component (Mb) was changed to the value shown in Table 1, and measurements and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0116] [Table 1]

[0117] The abbreviations in the table are as follows: "Ratio of non-conjugated olefin to 100 parts by mass of monomer component (M)" is the ratio (parts by mass) of non-conjugated olefin when the total of monomer component (Ma) and monomer component (Mb) is 100 parts by mass. ·BA: n-butyl acrylate. · AMA: Allyl methacrylate. · MMA: Methyl methacrylate. · 2EHA: 2-ethylhexyl acrylate.

[0118] As is clear from the results shown in Table 1, heat generation during polymerization could be suppressed by polymerizing the radically polymerizable monomer component in the presence of a non-conjugated olefin. In particular, the results of Examples 1 to 5 show that by setting the amount of the non-conjugated olefin to a specific amount or less, a higher polymerization conversion rate could be maintained and excellent powder properties were also achieved.

Claims

1. A method for producing a polymer, comprising polymerizing a radically polymerizable monomer component (M) in the presence of a non-conjugated olefin.

2. 2. The method for producing a polymer according to claim 1, wherein the proportion of the non-conjugated olefin is 1 to 25 parts by mass per 100 parts by mass of the radically polymerizable monomer component (M).

3. The method for producing a polymer according to claim 1 or 2, wherein the radical polymerizable monomer component (M) comprises at least one selected from the group consisting of a monomer (1) represented by the following formula (1) and an alkyl (meth)acrylate: 【Chemical 1】 (In formula (1), j is an integer of 1 to 5.)

4. The method for producing a polymer according to claim 3, wherein the monomer (1) comprises myrcene.

5. The method for producing a polymer according to claim 1 or 2, wherein the non-conjugated olefin comprises a cyclic monoterpene.

6. The method for producing a polymer according to claim 5, wherein the cyclic monoterpene includes one or more selected from limonene, camphene, and β-pinene.

7. A polymer having a structural unit (i) derived from a monomer (1) represented by the following formula (1) and a structural unit (v) derived from a non-conjugated olefin: 【Chemistry 2】 (In formula (1), j is an integer of 1 to 5.)

8. the polymer is a polymer obtained by polymerizing the monomer (1) and the non-conjugated olefin, 8. The polymer according to claim 7, wherein the proportion of the monomer (1) is 80 to 99% by mass when the total of the monomer (1) and the non-conjugated olefin is 100% by mass.

9. The polymer according to claim 7 or 8, further comprising a structural unit (ii) derived from an alkyl (meth)acrylate.

10. 9. The polymer of claim 7 or 8, wherein the monomer (1) comprises myrcene.

11. 9. The polymer of claim 7 or 8, wherein the non-conjugated olefin comprises a cyclic monoterpene.

12. The polymer according to claim 11, wherein the cyclic monoterpene comprises one or more selected from limonene, camphene, and β-pinene.

13. A composition comprising a polymer having a structural unit (i) derived from a monomer (1) represented by the following formula (1), and a non-conjugated olefin: 【Chemistry 3】 (In formula (1), j is an integer of 1 to 5.)

14. The composition according to claim 13, wherein the polymer further comprises a structural unit (ii) derived from an alkyl (meth)acrylate.

15. 15. The composition of claim 13 or 14, wherein the monomer (1) comprises myrcene.

16. 15. The composition of claim 13 or 14, wherein the non-conjugated olefin comprises a cyclic monoterpene.

17. The composition of claim 16, wherein the cyclic monoterpene comprises one or more selected from limonene, camphene, and β-pinene.

Images