Macropolymerization initiator and method for producing macropolymerization initiator

Abstract

Provided is a macro-polymerization initiator represented by general formula (1).　General formula (1): (In general formula (1), P1 represents polyolefin. R1 represents any one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group. R2 represents any one of a carbonyloxy group, an alkylene group, and a phenylene group. Two R1's may be the same or different from each other. n is an integer of 1 or more.)

Description

[Technical Field]

[0001] The present invention relates to a macropolymerization initiator and a method for producing the macropolymerization initiator. [Background technology]

[0002] Conventionally, a laminate of a layer containing a polyolefin adhesive resin and a layer containing a polar adhesive resin has been proposed as an adhesive layer for bonding a polyolefin substrate and a polar resin material (acrylic, PET) (see, for example, Patent Document 1).

[0003] The polyolefin adhesive resin has adhesive properties to polyolefin substrates. The polar adhesive resin has adhesive properties to polar resin materials. A preferred example of the polyolefin adhesive resin is a maleic anhydride-modified propylene-1-butene copolymer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-8694 Summary of the Invention [Problem to be solved by the invention]

[0005] The polyolefin adhesive resin described in Patent Document 1 may have insufficient adhesion to polyolefin substrates.

[0006] The present invention provides a macropolymerization initiator that can easily produce a block polymer that can improve adhesion to a polyolefin substrate, and a method for producing the macropolymerization initiator. [Means for solving the problem]

[0007] The present invention [1] includes a macropolymerization initiator represented by the following general formula (1).

[0008] General formula (1):

[0009] [ka]

[0010] (In the general formula (1), P1 represents a polyolefin. R 1 represents one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group. 2 represents one of a carbonyloxy group, an alkylene group, and a phenylene group. 1 may be the same or different from each other, and n is an integer of 1 or more. The present invention [2] is a compound in which, in the general formula (1), R 1 is a methyl group, and R 2 is a carbonyloxy group.

[0011] The present invention [3] is a method for producing the macropolymerization initiator of the above [1] or [2], which includes a preparation step of preparing a polyolefin and an introduction step of introducing a terminal structure represented by the following general formula (2) into the polyolefin:

[0012] General formula (2)

[0013] [ka]

[0014] (In general formula (2), R 1 represents one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group. 1 may be the same or different from each other.) The present invention [4] includes a method for producing the macropolymerization initiator according to the above [3], in which, in the preparation step, a hydroxypolyolefin, which is a polyolefin having a hydroxy group, is prepared, and in the introduction step, the hydroxypolyolefin is reacted with a compound represented by the following general formula (3):

[0015] General formula (3):

[0016] [ka]

[0017] (In general formula (3), R 1 represents one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group. 1 may be the same or different from each other. 3 represents one of a hydroxy group, an alkoxy group, and a halogen atom. Claim [5] includes the method for producing the macropolymerization initiator of the above [4], wherein in the preparation step, the ethylenically unsaturated group of a polyolefin having an ethylenically unsaturated group is hydroborated and oxidized to obtain the hydroxypolyolefin. [Effects of the Invention]

[0018] According to the macropolymerization initiator of the present invention, the macropolymerization initiator has a portion made of a polyolefin.

[0019] Therefore, by using a macropolymerization initiator, a block polymer having a block made of polyolefin can be easily produced.

[0020] The resulting block polymer has blocks made of polyolefin, and therefore, can improve adhesion to polyolefin substrates.

[0021] According to the method for producing a macropolymerization initiator of the present invention, the macropolymerization initiator can be easily produced by introducing the terminal structure represented by the above general formula (2) into a polyolefin. [Brief explanation of the drawings]

[0022] [Figure 1] FIG. 1 is a graph showing the change in GPC peak of a block polymer with the passage of polymerization time in the production of the block polymer. DETAILED DESCRIPTION OF THE INVENTION

[0023] 1. Macropolymerization initiator The macropolymerization initiator can be used for living radical polymerization. The macropolymerization initiator has a main chain made of a polyolefin and has an iodine atom as a protecting group at the end. The macropolymerization initiator may have an iodine atom in a side chain of the polyolefin.

[0024] Specifically, the macropolymerization initiator is represented by the following general formula (1): The macropolymerization initiator generates radicals by cleavage of the bond between an iodine atom and a carbon atom.

[0025] General formula (1):

[0026] [ka]

[0027] In the general formula (1), P1 represents a polyolefin.

[0028] Examples of polyolefins include polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, α-olefin copolymers, ethylene-propylene-diene copolymers, cyclic olefin copolymers, conjugated diene copolymers, and modified products thereof.

[0029] Examples of the α-olefin copolymer include an ethylene-propylene copolymer, an ethylene-propylene-1-butene copolymer, and a propylene-1-butene copolymer.

[0030] Examples of the modified products include graft modified products, and examples of the graft modified products include maleic anhydride modified products.

[0031] As the polyolefin, preferably, polybutadiene and an α-olefin copolymer are used, and more preferably, hydrogenated polybutadiene and a propylene-1-butene copolymer are used.

[0032] In general formula (1), R 1 represents any one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group.

[0033] Examples of the aliphatic group include a linear alkyl group having 1 to 12 carbon atoms and a branched alkyl group having 3 to 12 carbon atoms.

[0034] Examples of the linear alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl 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, and an n-dodecyl group.

[0035] Examples of the branched alkyl group having 3 to 12 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a 2-ethylhexyl group.

[0036] The aliphatic group may be substituted. The aliphatic group is preferably unsubstituted.

[0037] When the aliphatic group is substituted, the number of substituents is not limited, and the aliphatic group may have one or more substituents.

[0038] Examples of the substituent include a halogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aromatic hydrocarbon group, a non-aromatic heterocyclic group, a linear or branched alkoxy group having 1 to 12 carbon atoms, a cyano group, and a nitro group. The alkyl group, aromatic hydrocarbon group, and non-aromatic heterocyclic group as the substituent may also be substituted.

[0039] Examples of the aromatic group include an aromatic hydrocarbon group and an aromatic heterocyclic group.

[0040] Examples of aromatic hydrocarbon groups include phenyl, biphenylyl, terphenylyl, naphthyl, binaphthyl, azulenyl, anthracenyl, and phenanthrenyl groups.

[0041] Examples of aromatic heterocyclic groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuryl, indolyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, benzothiazolyl, carbazolyl, phenanthridinyl, phenazinyl, phenoxazinyl, and phenothiazinyl groups.

[0042] The Two R's 1 may be the same or different from each other. Preferably, two R 1 are both unsubstituted methyl groups.

[0043] In general formula (1), R 2 represents any one of a carbonyloxy group, an alkylene group, and a phenylene group.

[0044] Examples of the alkylene group include a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 2 to 12 carbon atoms, and a cycloalkylene group having 3 to 12 carbon atoms.

[0045] Examples of linear alkylene groups having 1 to 12 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, and 1,12-dodecylene.

[0046] Examples of branched alkylene groups having 2 to 12 carbon atoms include a 1,1-ethylene group, a 1,1-propylene group, a 1,2-propylene group, a 2,2-propylene group, a 1,1-butylene group, a 1,2-butylene group, a 1,3-butylene group, a 2,2-butylene group, and a 2,3-butylene group.

[0047] Examples of cycloalkylene groups having 4 to 12 carbon atoms include a 1,1-cyclopropyl group, a 1,2-cyclopropyl group, a 1,1-cyclobutyl group, a 1,2-cyclobutyl group, a 1,3-cyclobutyl group, a 1,1-cyclopentyl group, a 1,2-cyclopentyl group, and a 1,3-cyclopentyl group.

[0048] Preferably, R 2 is a carbonyloxy group.

[0049] In general formula (1), n ​​is an integer of 1 or more. n is, for example, 10 or less, preferably 2 or less.

[0050] 2. Effects of macropolymerization initiators The macropolymerization initiator represented by general formula (1) has a moiety made of polyolefin.

[0051] Therefore, by using a macropolymerization initiator, a block polymer having a block made of polyolefin can be easily produced.

[0052] 3. Manufacturing method of macropolymerization initiator Next, an example of a method for producing the macropolymerization initiator will be described.

[0053] The method for producing the macropolymerization initiator includes a preparation step and an introduction step.

[0054] (1) Preparation process In the preparation step, a hydroxypolyolefin is prepared. Hydroxypolyolefin is a polyolefin having a hydroxy group. The preparation step includes a first preparation step, a second preparation step, and a third preparation step. In the preparation step, a commercially available hydroxypolyolefin may be purchased.

[0055] (1-1) First preparation process In the first preparation step, a polyolefin is prepared. To prepare the polyolefin, a commercially available polyolefin may be purchased, or the polyolefin may be synthesized. The polyolefin prepared in the first preparation step does not have a polar group or a polar bond. Examples of polar groups include a hydroxy group, a carboxy group, and an alkoxy group. Examples of polar bonds include an ether bond and an ester bond.

[0056] Polyolefins can be synthesized, for example, by polymerizing olefin monomers in the presence of known metallocene catalysts.

[0057] Examples of the metallocene catalyst include a combination of dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride as the metallocene and methylaluminoxane and triisobutylaluminum as cocatalysts.

[0058] Examples of olefin monomers include α-olefins, cyclic olefins, and conjugated dienes.

[0059] Examples of the α-olefin include linear or branched α-olefins having 2 to 20 carbon atoms. Examples of the linear or branched α-olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0060] Examples of the cyclic olefin include cyclic olefins having 4 to 20 carbon atoms. Examples of the cyclic olefins having 4 to 20 carbon atoms include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, and tetracyclododecene.

[0061] Examples of conjugated dienes include aliphatic conjugated dienes having 4 to 20 carbon atoms. Examples of aliphatic conjugated dienes having 4 to 20 carbon atoms include 1,3-butadiene, isoprene, chloroprene, 1,3-cyclohexadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, and 1,3-octadiene.

[0062] (1-2) Second preparation process In the second preparation step, an ethylenically unsaturated group is introduced into the polyolefin prepared in the first preparation step.

[0063] Examples of methods for introducing an ethylenically unsaturated group include a thermal decomposition method, a high-pressure method, and a method of polymerizing a compound having an ethylenically unsaturated group using a Ziegler catalyst or a metallocene catalyst.

[0064] Examples of Ziegler catalysts include magnesium-supported titanium catalysts described in JP-A-57-63310, JP-A-58-83006, JP-A-3-706, Japanese Patent No. 3476793, JP-A-4-218508, and JP-A-2003-105022.

[0065] Examples of the metallocene catalyst include those described in WO 01 / 53369, WO 01 / 27124, WO 2004 / 087775, JP-A 3-193796 and JP-A 02-41303.

[0066] Preferably, the ethylenically unsaturated groups are introduced into the polyolefin by a pyrolysis method.

[0067] In the thermal decomposition method, a polyolefin is heated in a thermal decomposition device and thermally decomposed, thereby introducing a vinylidene group, which is an example of an ethylenically unsaturated group, into the polyolefin.

[0068] The heating temperature in the pyrolysis device is, for example, 300°C or more, preferably 350°C or more, and for example, 500°C or less, preferably 450°C or less.

[0069] The heating time in the pyrolysis device is, for example, 1 hour or more, preferably 3 hours or more, and for example, 8 hours or less, preferably 5 hours or less.

[0070] The functional group equivalent weight of the vinylidene group can be adjusted by adjusting the heating temperature and heating time.

[0071] (1-3) Third preparation process In the third preparation step, the ethylenically unsaturated group introduced in the second preparation step is substituted with a hydroxy group.

[0072] To substitute an ethylenically unsaturated group introduced into a polyolefin with a hydroxy group, for example, the ethylenically unsaturated group is subjected to hydroboration and oxidation.

[0073] Specifically, first, an ethylenically unsaturated group is reacted with an alkylborane to introduce boron into the polyolefin.

[0074] Examples of alkylboranes include 9-borabicyclo[3.3.1]nonane, disiamylborane, thexylborane, dicyclohexylborane, catecholborane, pinacolborane, and diisopinocampheylborane.

[0075] Next, the polyolefin with boron introduced therein is reacted with hydrogen peroxide in the presence of a base to convert the boron introduced into a hydroxy group, thereby obtaining a hydroxypolyolefin. Examples of the base include sodium hydroxide.

[0076] Specifically, first, a polyolefin having an ethylenically unsaturated group introduced therein is dissolved in a solvent, and then an alkylborane is added to the resulting solution, followed by stirring for, for example, 30 minutes or more, preferably 1 hour or more, for example, 5 hours or less, preferably 3 hours or less.

[0077] As a result, the alkylborane reacts with the ethylenically unsaturated group of the polyolefin, and boron is introduced into the polyolefin.

[0078] Subsequently, a base and hydrogen peroxide are added to the solution, and the mixture is stirred for, for example, 12 hours or more, preferably 20 hours or more, for example, 48 hours or less, preferably 30 hours or less.

[0079] As a result, the boron introduced into the polyolefin is substituted with a hydroxy group.

[0080] Thereafter, washing is carried out to obtain the hydroxypolyolefin.

[0081] If necessary, the resulting hydroxypolyolefin may be modified (for example, modified with maleic anhydride).

[0082] (2) Introduction process In the introduction step, a terminal structure represented by the following general formula (2) is introduced into the polyolefin.

[0083] General formula (2):

[0084] [ka]

[0085] In general formula (2), R 1 is R in the above general formula (1). 1 That is, in the general formula (2), R 1 represents one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group. 1 may be the same or different from each other.

[0086] Specifically, in the introduction step, the hydroxypolyolefin obtained in the preparation step is reacted with a compound represented by the following general formula (3).

[0087] General formula (3):

[0088] [ka]

[0089] In general formula (3), R 1 is R in the above general formula (1). 1 That is, in the general formula (3), R 1 represents one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group. 1 may be the same or different from each other.

[0090] In general formula (3), R 3 represents any one of a hydroxy group, an alkoxy group, and a halogen atom.

[0091] In the introduction step, for example, as shown in the following reaction formula (A), a hydroxy polyolefin (P1-OH) is dissolved or suspended in a solvent, and an α-iodocarboxylic acid (I-CR 1 2-COOH) and condensation reaction.

[0092] Reaction scheme (A):

[0093] [ka]

[0094] In reaction formula (A), R 1 is R in the above general formula (1). 1 is the same as

[0095] Specifically, in the introduction step, the hydroxypolyolefin is first dissolved or suspended in a solvent. Next, an α-iodocarboxylic acid and a condensing agent are added to the resulting solution or suspension. If necessary, a nucleophilic compound may be added to the solution or suspension.

[0096] The amount of α-iodocarboxylic acid added is, for example, 1 equivalent or more, for example, 10 equivalents or less, preferably 3 equivalents or less, relative to the hydroxy groups of the hydroxypolyolefin.

[0097] The amount of the condensing agent added is, for example, 1 equivalent or more, for example, 10 equivalents or less, preferably 3 equivalents or less, relative to the hydroxy groups of the hydroxypolyolefin.

[0098] When a nucleophilic compound is added, the amount of the nucleophilic compound added is, for example, 0.01 equivalents or more, preferably 0.05 equivalents or more, and for example, 5 equivalents or less, preferably 2 equivalents or less, relative to the hydroxy groups of the hydroxypolyolefin.

[0099] Next, the solution or suspension is stirred, for example, at -40°C or higher, preferably -20°C or higher, for example, 150°C or lower, preferably 100°C or lower, for example, 5 minutes or more, preferably 15 minutes or more, for example, 48 hours or less, preferably 24 hours or less.

[0100] This causes a condensation reaction between the hydroxy group of the hydroxypolyolefin and the carboxy group of the α-iodocarboxylic acid.

[0101] Examples of the condensing agent include carbodiimide, carbodiimidazole, phosgene derivatives, phosphonium, uronium, and triflate reagents.

[0102] Examples of carbodiimides include N,N-dicyclohexylcarbodiimide, N,N-diisopropylcarbodiimide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide.

[0103] Examples of carbodiimidazoles include carbonyldiimidazole and 1,1'-carbonyldi(1,2,4-triazole).

[0104] Examples of phosgene derivatives include triphosgene, thiophosgene, and di(N-succinimidyl) carbonate.

[0105] Examples of phosphonium include BOP and BroP.

[0106] Examples of uronium include HATU and TATU.

[0107] Examples of the triflate reagent include 4-nitrophenyl trifluoromethanesulfonate and trifluoromethanesulfonyl chloride.

[0108] Furthermore, examples of the condensing agent include chloroformate, p-toluenesulfonic acid chloride, 2,4,6-trichlorobenzoic acid chloride, and 2-chloro-1-methylpyridinium iodide.

[0109] Examples of nucleophilic compounds include pyridine compounds, imidazole compounds, amine compounds, N-hydroxysuccinimide, and 1-hydroxybenzotriazole. Examples of pyridine compounds include pyridine, N,N-dimethyl-4-aminopyridine, and 4-pyrrolidinopyridine. Examples of imidazole compounds include imidazole and 1-methylimidazole. Examples of amine compounds include triethylamine.

[0110] The solvent is not limited as long as it is a solvent that can be used in a condensation reaction. Examples of the solvent include halogenated solvents, ether solvents, hydrocarbon solvents, and aprotic polar solvents. Examples of halogenated solvents include dichloromethane and chloroform. Examples of ether solvents include tetrahydrofuran and diethyl ether. Examples of hydrocarbon solvents include toluene and benzene. Examples of aprotic polar solvents include acetonitrile and dimethylformamide.

[0111] This makes it possible to obtain a macropolymerization initiator.

[0112] In the introduction step, as shown in the following reaction formula (B), hydroxypolyolefin (P1-OH) and α-halogenated carboxylic acid (X-CR 1 2-COOH) to produce the precursor of macropolymerization initiator (X-CR 1 2-COO-P1), and then the halogen atom (X) of the resulting macropolymerization initiator precursor can be replaced with an iodine atom by a halogen exchange reaction such as the Finkelstein reaction to obtain the macropolymerization initiator.

[0113] Reaction scheme (B):

[0114] [ka]

[0115] In reaction formula (B), R1 is R in the above general formula (1). 1 X is a halogen atom other than iodine. Examples of halogen atoms include chlorine and bromine.

[0116] In the introduction step, as shown in the following reaction formula (C), hydroxy polyolefin (P1-OH) and α-iodo ester (I-CR 1 2-COOR 4 ) can also be used to obtain a macropolymerization initiator.

[0117] Reaction scheme (C):

[0118] [ka]

[0119] In reaction formula (C), R 1 is R in the above general formula (1). 1 is the same as R 4 is an alkyl group.

[0120] In the introduction step, as shown in the following reaction formula (D), a hydroxy polyolefin (P1-OH) and an α-halogenated ester (X-CR 1 2-COOR 4 ) to form a macropolymerization initiator precursor (X-CR 1 2-COO-P1), and then the halogen atom (X) of the obtained precursor of the macropolymerization initiator is substituted with an iodine atom by a halogen exchange reaction to obtain the macropolymerization initiator.

[0121] Reaction scheme (D):

[0122] [ka]

[0123] In reaction formula (D), R 1 is R in the above general formula (1). 1X is the same as X in the above reaction formula (B). R 4 is R in the above reaction formula (C) 4 is the same as

[0124] In the introduction step, as shown in the following reaction formula (E), hydroxypolyolefin (P1-OH) and α-iodocarboxylic acid halide (I-CR 1 2-CO-X') to obtain a macropolymerization initiator. In this case, a condensing agent is not required.

[0125] Reaction scheme (E):

[0126] [ka]

[0127] In reaction formula (E), R 1 is R in the above general formula (1). 1 X' is a halogen atom. Examples of halogen atoms include chlorine and bromine.

[0128] In the introduction step, as shown in the following reaction formula (F), hydroxy polyolefin (P1-OH) and α-halogenated carboxylic acid halide (X-CR 1 2-CO-X') to obtain the precursor of macropolymerization initiator (X-CR 1 The macropolymerization initiator can also be obtained by synthesizing 2-COO-P1) and then substituting the halogen atom (X) of the resulting macropolymerization initiator precursor with an iodine atom through a halogen exchange reaction. In this case, a condensing agent is also not required.

[0129] Reaction equation (F):

[0130] [ka]

[0131] In reaction formula (F), R 1 is R in the above general formula (1).1 X is the same as X in the above reaction formula (B). X' is the same as X' in the above reaction formula (E).

[0132] 4. Effects of the manufacturing method of macropolymerization initiator According to the method for producing a macropolymerization initiator, the macropolymerization initiator represented by general formula (1) can be easily produced by introducing a terminal structure represented by general formula (2) into a polyolefin.

[0133] 5. Modified Method for Producing Macropolymerization Initiator R in general formula (1) 2 The macropolymerization initiator in which is an alkylene group can be produced, for example, by reacting the ethylenically unsaturated group of the polyolefin obtained in the second preparation step with hydrogen iodide to iodinate it.

[0134] R in general formula (1) 2 The macropolymerization initiator in which R is a phenylene group can be prepared by, for example, firstly reacting R 2 A macropolymerization initiator in which the alkylene group is present is subjected to a nucleophilic substitution reaction with 4-methylphenylmagnesium bromide.

[0135] Next, the methyl group on the introduced phenyl group is iodinated by a method such as the Wohl-Ziegler reaction, thereby completing the production.

[0136] 6. Block polymers Next, a block polymer produced using the above-mentioned macropolymerization initiator will be described.

[0137] The block polymer has a first block (a block represented by P1 in the following general formula (4)) and a second block (a block represented by P2 in the following general formula (4)). The first block is made of the above-mentioned polyolefin. The second block is made of a polymer of a radically polymerizable monomer. The block polymer has an iodine atom. The block polymer may have an iodine atom at the end of the second block.

[0138] Specifically, the block polymer is represented by the following general formula (4).

[0139] General formula (4):

[0140] [ka]

[0141] In general formula (4), P1, R 1 , R 2 and n is P1, R in the above general formula (1). 1 , R 2 and n.

[0142] In general formula (4), P2 is a polymer of a radically polymerizable monomer. The radically polymerizable monomer is a monomer capable of undergoing radical polymerization. Examples of the radically polymerizable monomer include ethylenically unsaturated carboxylic acids, anhydrides of ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid esters, aromatic vinyls, and conjugated dienes.

[0143] Examples of ethylenically unsaturated carboxylic acids include monocarboxylic acids and dicarboxylic acids. Examples of monocarboxylic acids include acrylic acid and methacrylic acid. Examples of dicarboxylic acids include fumaric acid, maleic acid, and itaconic acid.

[0144] Examples of the anhydrides of ethylenically unsaturated carboxylic acids include maleic anhydride and itaconic anhydride.

[0145] Ethylenically unsaturated carboxylic acid esters include, for example, acrylic acid esters and methacrylic acid esters.

[0146] Examples of acrylic acid esters include alkyl acrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate.

[0147] Examples of methacrylic acid esters include alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate.

[0148] An example of the aromatic vinyl is styrene.

[0149] Examples of the conjugated diene include the conjugated dienes described above.

[0150] The radical polymerizable monomer preferably has an acrylic group or a methacrylic group. Preferred examples of the radical polymerizable monomer include acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters.

[0151] The weight average molecular weight (Mw) of the block polymer is, for example, 1,000 or more, or preferably 2,000 or more. The weight average molecular weight (Mw) of the block polymer is, for example, 2,000,000 or less, or preferably 200,000 or less.

[0152] The number average molecular weight (Mn) of the block polymer is, for example, 1,000 or more, preferably 2,000 or more. The number average molecular weight (Mn) of the block polymer is, for example, 1,000,000 or less, preferably 100,000 or less.

[0153] The weight average molecular weight and number average molecular weight are measured by GPC (gel permeation chromatography) under the conditions described in the Examples below, and are polystyrene equivalent values ​​(PS equivalent values) determined by a general-purpose calibration method.

[0154] The dispersity (Mw / Mn) of the block polymer is, for example, 1 or more, or preferably 1.05 or more. The dispersity (Mw / Mn) of the block polymer is, for example, 5 or less, or preferably 2 or less.

[0155] 7. Effects of block polymers The block polymer represented by the general formula (4) has a first block made of polyolefin.

[0156] Therefore, the adhesion to the polyolefin substrate can be improved.

[0157] Furthermore, the second block made of a polymer of a radically polymerizable monomer can improve adhesion to substrates having a polarity different from that of the polyolefin substrate.

[0158] As a result, it is possible to improve the adhesion between the polyolefin substrate and a substrate having a polarity different from that of the polyolefin substrate.

[0159] 8. Block polymer manufacturing method Next, a method for producing a block polymer using a macropolymerization initiator will be described.

[0160] To produce the block polymer, radically polymerizable monomers are polymerized using the macropolymerization initiator described above in the presence of iodine (I2) and a catalyst.

[0161] By carrying out the polymerization in the presence of iodine, it is possible to prevent the macropolymerization initiator from remaining unreacted.

[0162] The proportion of iodine relative to 1 mole of the macropolymerization initiator is, for example, 0.01 mole or more, preferably 0.02 mole or more, and for example, 0.05 mole or less, preferably 0.03 mole or less.

[0163] The catalyst does not contain a transition metal, and examples of the catalyst include tributylmethylphosphonium iodide, tetrabutylammonium iodide, and tetraoctylammonium iodide.

[0164] Specifically, to produce a block polymer, a macropolymerization initiator, a radical polymerizable monomer, a catalyst, iodine, and a reaction solvent are placed in a nitrogen-substituted reaction vessel, and the mixture is heated with stirring.

[0165] If necessary, iodine may be eliminated by a known method as a post-treatment after the completion of the reaction.

[0166] As a result, the radical polymerizable monomer is polymerized (living radical polymerization) with the macropolymerization initiator, and a block polymer represented by the above general formula (4) is obtained.

[0167] Specifically, the bond between the iodine atom and the carbon atom of the macropolymerization initiator (carbon-iodine bond) is cleaved, causing the iodine atom to leave the macropolymerization initiator and generate a carbon radical. A radical polymerizable monomer reacts with the generated carbon radical, generating a growing species, which is the reaction product between the macropolymerization initiator and the radical polymerizable monomer. A chain reaction occurs between the carbon radical at the end of the growing species and the radical polymerizable monomer, resulting in the growth of P2 (the second block) in the general formula (4) above. When an iodine atom bonds to the carbon radical at the end of the growing species, the growing species is inactivated. The carbon-iodine bond at the inactivated end of the growing species is cleaved, generating another carbon radical at the end of the growing species. A chain reaction occurs between the generated carbon radical and the radical polymerizable monomer, causing the growth of P2 (the second block) in the general formula (4) above. This results in the production of a block polymer represented by the general formula (4) above.

[0168] The heating temperature is, for example, 50°C or more, preferably 60°C or more, and for example, 100°C or less, preferably 90°C or less.

[0169] The polymerization time is, for example, 8 hours or more, preferably 20 hours or more, and for example, 48 hours or less, preferably 30 hours or less.

[0170] 9. Effects of the block polymer manufacturing method According to the method for producing a block polymer, by polymerizing a radical polymerizable monomer in the presence of iodine using a macropolymerization initiator represented by general formula (1), it is possible to reliably react the macropolymerization initiator with the radical polymerizable monomer.

[0171] As a result, the block polymer represented by the general formula (4) can be stably produced while preventing the macropolymerization initiator from remaining unreacted.

[0172] 10. Applications of block polymers The block polymer represented by general formula (4) is incorporated into, for example, a coating agent for covering a polyolefin substrate. The coating agent may be an adhesive layer for bonding a polyolefin substrate to a substrate having a polarity different from that of the polyolefin substrate. For example, the coating agent can be used as an adhesive layer for a decorative film.

[0173] The coating agent contains, as an essential component, a block polymer represented by general formula (4).

[0174] The block polymer is blended in the coating agent in an amount, calculated as solid content, of, for example, 5 mass % or more, preferably 7 mass % or more, for example, 20 mass % or less, preferably 15 mass % or less.

[0175] The formulation of the coating agent is not limited. The coating agent may be, for example, a coating liquid or a film such as a hot-melt adhesive film (heat-seal film).

[0176] When the coating agent is a coating liquid, the coating agent may contain, as necessary, within a range that does not impair the effects, for example, a solvent, a surfactant, a polar resin, a curing agent, a curing catalyst, a leveling agent, an antifoaming agent, an antioxidant, a heat stabilizer, a light stabilizer (such as an ultraviolet absorber), a plasticizer, a pigment (such as rutile titanium oxide, zinc oxide, or carbon black), a thixotropic agent, a thickener, a tackifier (such as a rosin resin or a terpene resin), a surface conditioner, an antisettling agent, a weathering agent, a pigment dispersant, an antistatic agent, a filler, organic or inorganic fine particles, an antifungal agent, or a silane coupling agent.

[0177] When the coating agent is in the form of a film, the coating agent can be obtained, for example, by printing and applying a varnish containing a block polymer and drying it, or by forming the block polymer into a film. The varnish may be the above-mentioned coating liquid. [Example]

[0178] The present invention will be described in more detail below with reference to examples, but is not limited thereto. Specific numerical values ​​of the blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values ​​(numeric values ​​defined as "not more than" or "less than") or lower limit values ​​(numeric values ​​defined as "not less than" or "exceeding") of the corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the above "Form for Carrying Out the Invention." Note that "parts" and "%" are based on mass unless otherwise specified.

[0179] 1. Preparation of macropolymerization initiator (1) Preparation process (1-1) Production of polyolefin (first preparation step) A 2000 ml polymerization reactor purged with nitrogen was charged with 900 ml of dry hexane (solvent), 30 g of 1-butene, and 1.0 mmol of triisobutylaluminum at room temperature.

[0180] Next, the internal temperature of the polymerization apparatus was raised to 70° C., and propylene gas was introduced into the polymerization apparatus so that the internal pressure of the polymerization apparatus became 0.7 MPa.

[0181] Next, a toluene solution containing 0.002 mmol of dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride and 0.6 mmol of methylaluminoxane (manufactured by Tosoh Finechem Co., Ltd.) in terms of aluminum was added to the polymerization reactor, and polymerization was carried out for 30 minutes while maintaining the internal temperature at 62°C and the internal pressure at 0.7 MPa.

[0182] Then, 20 ml of methanol was added to terminate the polymerization, yielding a polymerization solution containing propylene-1-butene copolymer (an example of polyolefin).

[0183] After depressurizing the inside of the polymerization reactor, the obtained polymerization solution was mixed with 2 L of methanol to precipitate a propylene-1-butene copolymer from the polymerization solution.

[0184] The precipitated propylene-1-butene copolymer was dried under vacuum at 130°C for 12 hours.

[0185] (1-2) Introduction of vinylidene groups (second preparation step) 200 g of propylene-1-butene copolymer was placed in a 1.5 L stainless steel pyrolysis apparatus equipped with a stirrer, a nitrogen inlet tube, and a condenser, and the atmosphere inside the pyrolysis apparatus was replaced with nitrogen.

[0186] Next, the internal temperature of the pyrolysis reactor was raised to 380°C while nitrogen was still flowing in, and the propylene-1-butene copolymer was melted.

[0187] Next, stirring was started, and after the temperature of the propylene-1-butene copolymer in the pyrolysis apparatus reached a predetermined temperature, heating was continued for 4.5 hours to pyrolyze the propylene-1-butene copolymer.

[0188] After that, the mixture was cooled to room temperature to obtain a propylene-1-butene copolymer having terminal vinylidene groups.

[0189] (1-3) Introduction of a hydroxy group (third preparation step) In a nitrogen-purged 1000 mL eggplant-shaped flask, 20 g (156 mmol) of propylene-1-butene copolymer having a vinylidene group at the end and 200 g of methylcyclohexane as a solvent were placed, heated to 50°C, and stirred.

[0190] Propylene-1-butene copolymers having vinylidene groups at the terminals were dissolved homogeneously in methylcyclohexane and then cooled to room temperature.

[0191] Next, 31 mL of a THF solution of 9-borabicyclo[3.3.1]nonane (9-BBN) (15 mmol, 0.50 mol / L) was added to the eggplant-shaped flask and stirred. This allowed the 9-borabicyclo[3.3.1]nonane to react with the vinylidene groups at the terminals of the propylene-1-butene copolymer (a hydroboration reaction), introducing boron to the terminals of the copolymer.

[0192] After 2 hours, the solution in the eggplant-shaped flask was cooled to 0°C, and 15 mL of a mixed solution of NaOH in methanol / water (1 / 4) (62 mmol, 4.0 mol / L) and 5.0 mL of an aqueous solution of H2O2 (52 mmol, 35%) were added to the eggplant-shaped flask. After 10 minutes, the temperature was raised to room temperature.

[0193] The mixture was then stirred for 24 hours to replace the terminal boron of the propylene-1-butene copolymer with a hydroxyl group (oxidation reaction).

[0194] Next, the resulting reaction product was washed. Specifically, 100 mL of methylcyclohexane and 100 mL of distilled water were added to the solution containing the reaction product, and the mixture was extracted and washed using a separatory funnel. 50 mL of 10% hydrochloric acid was then added to the solution containing the reaction product for extraction and washing, and 50 mL of distilled water was added for washing. 50 mL of saturated aqueous sodium bicarbonate solution was then added to the solution containing the reaction product for extraction and washing, and 50 mL of distilled water was added for washing. 50 mL of saturated saline solution was then added for washing, and the resulting organic layer was dried over magnesium sulfate and then reprecipitated in methanol.

[0195] This resulted in the production of a propylene-1-butene copolymer with terminal hydroxy groups (an example of a hydroxypolyolefin, XKP-001).

[0196] (2) Introduction process Manufacturing Example 1-1 A macropolymerization initiator was produced by the following steps using a 300 mL four-necked glass flask purged with argon gas.

[0197] First, 25 g of hydroxypolyolefin (XKP-001, number average molecular weight (Mn): 10260, dispersity (Mw / Mn): 1.95, hydroxy group amount: 3.3 / 1000C) was suspended in chlorobenzene to obtain 140 mL of suspension. The hydroxy group amount was measured by the method described in the Reference Example below.

[0198] While the resulting suspension was cooled on ice, 2.35 g (11.0 mmol) of 2-iodoisobutyric acid (an example of the compound represented by the above general formula (3)) and 122 mg (1.0 mmol) of N,N-dimethyl-4-aminopyridine (an example of a nucleophilic compound) were added to the suspension, and further, a 10 mL solution of 1.39 g (11.0 mmol) of N,N'-diisopropylcarbodiimide (an example of a condensing agent) in chlorobenzene was added.

[0199] Thereafter, the mixture was stirred for 30 minutes while cooling on ice, and then stirred for a further 2 hours at 25° C. This resulted in the synthesis of a condensation product of hydroxypolyolefin (XKP-001) and 2-iodoisobutyric acid.

[0200] The synthesized condensation product is represented by the general formula (1), where P1 is a propylene-1-butene copolymer and two R 1 are both methyl groups, and R 2 is a macropolymerization initiator in which the carbonyloxy group is

[0201] Next, 10 mL of methanol was added to decompose unreacted N,N'-diisopropylcarbodiimide.

[0202] After the addition, the mixture was filtered, and the resulting filter residue was washed with methanol and then dried in vacuo.

[0203] As a result, 26 g of a macropolymerization initiator was obtained as a white powder.

[0204] The obtained macropolymerization initiator was pretreated by oxygen flask combustion method, and the proportion of iodine in the macropolymerization initiator (iodine content) was measured by ion chromatography. The iodine content was 2.4 mass %.

[0205] The introduction rate (introduced amount / 1000C) of the iodine initiating group (terminal structure represented by the above general formula (2)) of the macropolymerization initiator was measured using a nuclear magnetic resonance spectrometer. 1 The ratio of the integrated intensity from 2.2 to 2.0 ppm to the integrated intensity from 2.0 to 0.5 ppm in H-NMR measurements was used for calculation. The calculated "amount introduced / 1000C" is shown in Table 1.

[0206] In addition, the macropolymerization initiator 1 The H-NMR spectrum has a peak at 2.1 ppm corresponding to the iodine initiator group, and the peak intensity corresponds to the amount of iodine initiator group introduced. The signal intensity from 2.0 to 0.5 ppm corresponds to the main skeleton of the macropolymerization initiator (the portion corresponding to P1 in the general formula (1) above).

[0207] Acyclic saturated aliphatic is C n H 2n+1 Therefore, if n is large enough, the number of carbon atoms in the polymer will be half the number of hydrogen atoms. Therefore, the "amount introduced / 1000C" in Table 1 can be calculated using the following formula:

[0208] Formula: Introduced amount / 1000C = (integral intensity of 2.2-2.0 ppm) / (integral intensity of 2.0-0.5 ppm) × 2000 / 6 Manufacturing Examples 1-2 to 1-7 Macropolymerization initiators were obtained in the same manner as in Production Example 1-1, except that chlorobenzene was changed to a solvent shown in Table 1. The "amount introduced / 1000C" of the obtained macropolymerization initiators is shown in Table 1.

[0209] Manufacturing Example 1-8 Using a Schlenk flask purged with argon gas, a macropolymerization initiator was produced by the following steps.

[0210] 0.5 mL of chlorobenzene and 19 mg (0.1 mmol) of p-toluenesulfonic acid chloride (an example of a condensing agent) were added to 21 mg (0.1 mmol) of 2-iodoisobutyric acid (a compound represented by the above general formula (3)), and the mixture was cooled in an ice bath.

[0211] Next, 8 μL (0.1 mmol) of 1-methylimidazole (an example of a nucleophilic compound) was added using a microsyringe, and the mixture was stirred at ice bath temperature for 1 hour to activate 2-iodoisobutyric acid.

[0212] Next, 230 mg of hydroxypolyolefin (XKP-001) and 8 μL (0.1 mmol) of 1-methylimidazole (nucleophilic compound) were added, and the 2-iodoisobutyric acid and hydroxypolyolefin (XKP-001) were reacted for 3 hours at 25° C. This resulted in the synthesis of a condensation product (macropolymerization initiator) of hydroxypolyolefin (XKP-001) and 2-iodoisobutyric acid.

[0213] Unreacted condensing agent (p-toluenesulfonic acid chloride) or activated 2-iodoisobutyric acid was decomposed with 1 mL of methanol and then filtered. The resulting filter residue was washed with methanol and then vacuum dried. This yielded a macropolymerization initiator. The "introduced amount / 1000C" of the resulting macropolymerization initiator is shown in Table 1.

[0214] Manufacturing Example 1-9 A macropolymerization initiator was obtained in the same manner as in Production Example 1-8, except that mesitylene was used instead of chlorobenzene. The "amount introduced / 1000C" of the obtained macropolymerization initiator is shown in Table 1.

[0215] Reference example In a reference example, the amount of hydroxy groups in hydroxypolyolefin (XKP-001) was measured.

[0216] While argon gas was flowing into a Schlenk tube, 92 mg of hydroxypolyolefin (XKP-001), 0.5 mL of tetrahydrofuran, and 60 mg (0.6 mmol) of acetic anhydride were mixed, and then 12 mg (0.1 mmol) of N,N-dimethyl-4-aminopyridine (nucleophilic compound) was added.

[0217] The obtained slurry solution was heated to 50°C while stirring to dissolve the hydroxypolyolefin in tetrahydrofuran, and the hydroxypolyolefin was reacted with acetic anhydride for 2.5 hours, whereby the hydrogen atoms of the hydroxy groups in the hydroxypolyolefin were substituted with acetyl groups.

[0218] Next, 1 mL of methanol was mixed with the reaction solution and then filtered to obtain a polyolefin having an acetyl group introduced therein as a residue. The residue was washed with methanol and the 1 The amount of acetyl groups introduced into the polyolefin (amount introduced / 1000C) was calculated from the H-NMR spectrum. The results are shown in Table 1.

[0219] By substituting all hydrogen atoms of the hydroxy groups in the hydroxypolyolefin (XKP-001) with acetyl groups, the amount of acetyl groups introduced can be considered to be the same as the amount of hydroxy groups in the hydroxypolyolefin (XKP-001). Therefore, the amount of acetyl groups introduced corresponds to the amount of hydroxy groups in the hydroxypolyolefin (XKP-001).

[0220] [Table 1]

[0221] The abbreviations in Table 1 are explained below.

[0222] THF: tetrahydrofuran MCH / MIBK: A mixture of methylcyclohexane (MCH) and methyl isobutyl ketone (MIBK) (volume ratio of methylcyclohexane to methyl isobutyl ketone (MCH / MIBK) = 4 / 1) DIC: N,N'-diisopropylcarbodiimide DMAP: N,N-dimethyl-4-aminopyridine TsCl: p-toluenesulfonic acid chloride NMI: 1-methylimidazole Ac2O: acetic anhydride Manufacturing Example 2-1 A macropolymerization initiator was produced by the following steps using a 300 mL four-necked glass flask purged with argon gas.

[0223] 15.4 g (7.2 mmol) of 2-iodoisobutyric acid (the compound represented by the above general formula (3)) and 13.4 g (7.0 mmol) of p-toluenesulfonic acid chloride (condensing agent) were mixed in 30 mL of methylene chloride and cooled on ice.

[0224] Next, a solution of 5.9 g (7.2 mmol) of 1-methylimidazole (nucleophilic compound) in 5 mL of methylene chloride was added over 5 minutes, and after the addition was completed, the mixture was stirred for 30 minutes.

[0225] Next, a mixture of 50 mL of methylene chloride and 50 g of hydrogenated polybutadiene glycol (hydroxypolyolefin, manufactured by Nippon Soda Co., Ltd., product name: NISSO PB GI-1000, Mn: 2080, Mw / Mn: 3.58, hydroxyl value (KOH mg / g): 60-75) was added to the reactor. Furthermore, a solution of 5.9 g (7.2 mmol) of 1-methylimidazole (nucleophilic compound) in 5 mL of methylene chloride was added over 5 minutes, and the mixture was stirred for 1 hour while cooling with ice.

[0226] This resulted in the synthesis of a condensation product (macropolymerization initiator) of hydrogenated polybutadiene glycol and 2-iodoisobutyric acid.

[0227] 1 After confirming the completion of the reaction by H-NMR, 200 mL of hexane was added to the reaction solution. The resulting mixture was washed three times with 100 mL of methanol, and then the solvent was distilled off under reduced pressure for purification. This yielded 49 g of a macropolymerization initiator as a pale yellow-yellow viscous liquid.

[0228] The obtained macropolymerization initiator was pretreated by oxygen flask combustion, and the iodine content of the macropolymerization initiator was measured by ion chromatography of the combustion gas absorption liquid, which was found to be 9.7% by mass.

[0229] Manufacturing Example 2-2 35 g of a pale yellow-yellow viscous liquid macropolymerization initiator was obtained in the same manner as in Production Example 2-1, except that 36 g of hydrogenated polybutadiene glycol (manufactured by Nippon Soda Co., Ltd., product name: NISSO PB GI-2000, Mn: 2394, Mw / Mn: 1.92, hydroxyl value (KOH mg / g): 40-55) was used as the hydroxypolyolefin. The iodine content of the obtained macropolymerization initiator was 8.0 mass%.

[0230] Manufacturing Example 2-3 As the hydroxy polyolefin, 60 g of hydrogenated polybutadiene glycol (manufactured by Nippon Soda Co., Ltd., product name: NISSO PB GI-3000, Mn: 4573, Mw / Mn: 1.32, hydroxyl value (KOHmg / g): 25 - 35) was used, and in the same manner as in Production Example 2-1, 58 g of a pale yellow - yellow viscous liquid macro polymerization initiator was obtained. The iodine content of the obtained macro polymerization initiator was 5.1 mass%.

[0231] 2. Production of block polymer Example 1 After replacing the nitrogen in a 100 mL test tube, 2.0 g (20 mmol) of methyl methacrylate, 1.8 g (0.20 mmol) of the macro polymerization initiator, 69 mg (0.20 mmol) of tributylmethylphosphonium iodide, 1.3 mg (0.0050 mmol) of iodine, and 18 g of toluene as the organic solvent were blended, heated to 80°C, and heated for 24 hours.

[0232] As a result, methyl methacrylate polymerizes at the terminal of the macro polymerization initiator, and a block polymer of a propylene·1-butene copolymer and polymethyl methacrylate is formed.

[0233] When the internal temperature reached 80°C (polymerization time 0 hours), 1 hour after the internal temperature reached 80°C (polymerization time 1 hour), 8 hours after (polymerization time 8 hours), and 24 hours after (polymerization time 24 hours), the molecular weight distribution was measured by GPC (gel permeation chromatography) under the following measurement conditions. The results are shown in Figure 1.

[0234] <GPC measurement conditions> Apparatus; Gel permeation chromatograph Shodex GPC-101 (manufactured by Showa Denko KK) Mobile phase; THF (tetrahydrofuran) Column; GPC KF804L×3 (manufactured by Showa Denko KK) Flow rate; 1.0 ml / min Sample; 0.15 mg / mL THF solution Temperature; 40°C Detector; Differential refractometer RI-71S Calibration curve: Commercially available monodisperse standard polystyrene (PS) From FIG. 1, it is believed that no homopolymer of polymethyl methacrylate is produced, since the peak of the block polymer remains single-peaked even with the progress of polymerization time.

[0235] The reaction solution in the test tube was then mixed with 200 g of methanol to precipitate the block polymer. The resulting precipitate was then collected by filtration and dried under reduced pressure, yielding a dried block polymer.

[0236] Example 2 A block polymer was obtained in the same manner as in Example 1, except that the amount of methyl methacrylate was changed to 1.0 g (10 mmol).

[0237] Example 3 A block polymer was obtained in the same manner as in Example 1, except that the amount of methyl methacrylate was changed to 0.40 g (4.0 mmol).

[0238] Comparative Example A propylene-1-butene copolymer was obtained in the same manner as in "(1-1) Production of polyolefin (first preparatory step)" in "1. Production of macropolymerization initiator" above.

[0239] Next, 3 kg of the obtained propylene-1-butene copolymer was added to 10 L of toluene, and the temperature was raised to 145°C under a nitrogen atmosphere to dissolve the propylene-1-butene copolymer in the toluene.

[0240] Next, 382 g of maleic anhydride as a monomer and 175 g of di-tert-butyl peroxide as a polymerization initiator were fed into the system over 4 hours with stirring.

[0241] The mixture was then stirred at 145°C for 2 hours to produce a maleic anhydride-modified propylene-1-butene copolymer.

[0242] After cooling, a large amount of acetone was added to precipitate the maleic anhydride-modified propylene-1-butene copolymer. The resulting precipitate was filtered, washed with acetone, and then dried in vacuum.

[0243] 3. Evaluation (1) Preparation of test specimens The block polymers obtained in Examples 1 to 3 and the maleic anhydride-modified propylene-1-butene copolymer obtained in the Comparative Example were each dissolved in toluene to prepare a coating agent with a solids concentration of 10% by mass (specifically, (mass after drying) / (mass before drying) × 100).

[0244] Each of the obtained coating agents was applied to a polypropylene plate and a TSOP (Toyota Super Olefin Polymer (registered trademark): a thermoplastic resin containing PP (polypropylene) and EPDM (ethylene-propylene-diene rubber)) plate using a No. 14 bar coater.

[0245] Next, the resulting coating film was left standing at room temperature for 20 minutes, and then at 120°C for a further 20 minutes.

[0246] This gave a test piece having a dry coating film of the coating agent.

[0247] (2) Adhesion to the substrate (substrate adhesion) The adhesion of the dried coating film of the coating agent to a polypropylene plate or TSOP plate (substrate) was evaluated using the cross-cut method in accordance with JIS K 5600-5-6 (1999) "General test methods for paints - Part 5: Mechanical properties of coating films - Section 6: Adhesion (cross-cut method)".

[0248] Specifically, the dried coating film of the above test piece was cross-cut into a grid of 1 x 1 mm (100 squares) using a cutter knife.

[0249] Next, a 24 mm wide adhesive tape (manufactured by Nichiban) was attached onto the grid, and the adhesive tape was pressed down so that the dried coating film could be seen through it.

[0250] The adhesive tape was then peeled off at an angle of 60° to the coating film in 0.5 seconds, and the adhesion was evaluated based on the number of squares remaining. The number of squares remaining is shown in Table 2.

[0251] (3) Topcoat properties A UV-curable acrylic top coating agent was applied onto the dried coating film of the above coating agent using a No. 14 bar coater, and then allowed to stand at 60°C for 3 minutes to dry.

[0252] Next, the applied UV-curable acrylic top coat agent was irradiated with 80 mW / cm 2 The UV-curable acrylic top coating agent was cured by irradiating it with ultraviolet light at an irradiation distance of 8.5 cm and a line speed of 1.2 m / min using an ultraviolet irradiation device equipped with a high-pressure mercury lamp. This formed an acrylic resin layer on top of the dried coating film of the coating agent.

[0253] Next, in accordance with JIS K 5600-5-6 (1999) "General Test Methods for Paints - Part 5: Mechanical Properties of Coatings - Section 6: Adhesion (Cross-Cut Method)", the adhesion of the dried coating film of the coating to the TSOP board (substrate) was evaluated using the cross-cut method (100 squares) with an acrylic resin layer formed on top of the dried coating film of the coating. The number of remaining squares is shown in Table 2.

[0254] In the comparative example, all squares that remained in the evaluation of substrate adhesion to TSOP were peeled off in the evaluation of topcoat properties. This is thought to be because film shrinkage accompanying the curing of the acrylic topcoat agent applied stress to the dried coating film of the coating agent, making it more likely to peel off from the substrate.

[0255] In this regard, in the evaluation of the topcoat properties, more mass remained in each of the Examples than in the Comparative Examples. Therefore, the block polymers of each Example have superior adhesion to polyolefin substrates compared to the maleic anhydride modified polymer of the Comparative Examples, even when an acrylic resin layer is formed on the dried coating film of the coating agent.

[0256] [Table 2] The above invention is provided as an exemplary embodiment of the present invention, but it is merely an example and should not be interpreted as being limiting. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the following claims. [Industrial Applicability]

[0257] The macropolymerization initiator of the present invention can be used to produce a block polymer. The method for producing a macropolymerization initiator of the present invention can produce a macropolymerization initiator that can be used to produce a block polymer.

Claims

1. A macropolymerization initiator represented by the following general formula (1): General formula (1): 【Chemistry 1】 (In the general formula (1), P1 represents a polymer of at least one olefin monomer selected from linear or branched α-olefins having 3 to 20 carbon atoms, cyclic olefins having 4 to 20 carbon atoms, and aliphatic conjugated dienes having 4 to 20 carbon atoms, and modified products thereof. R １ represents any one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group. ２ represents either a carbonyloxy group or a phenylene group. １ may be the same or different from each other, and n is an integer of 1 or more.

2. In the general formula (1), R １ is a methyl group, and R ２ The macropolymerization initiator according to claim 1 , wherein is a carbonyloxy group.

3. A method for producing the macropolymerization initiator according to claim 1, comprising: a preparation step of preparing a polyolefin; an introduction step of introducing a terminal structure represented by the following general formula (2) into the polyolefin; A method for producing a macropolymerization initiator, comprising: General formula (2) 【Chemistry 2】 (In general formula (2), R １ represents one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group. R 2 represents one of a carbonyloxy group and a phenylene group. １ may be the same or different from each other.)

4. In the preparation step, a hydroxypolyolefin, which is a polyolefin having a hydroxy group, is prepared; The method for producing a macropolymerization initiator according to claim 3 , wherein the introducing step comprises reacting the hydroxypolyolefin with a compound represented by the following general formula (3): General formula (3): 【Transformation 3】 (In general formula (3), R １ represents any one of a hydrogen atom, an aliphatic group, an aromatic group, an alkoxycarbonyl group, and a nitrile group. １ may be the same or different from each other. ３ represents any one of a hydroxy group, an alkoxy group, and a halogen atom.

5. 5. The method for producing a macropolymerization initiator according to claim 4, wherein the hydroxypolyolefin is obtained in the preparation step by hydroborating and oxidizing the ethylenically unsaturated group of a polyolefin having an ethylenically unsaturated group.

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