Modified styrene elastomer

Abstract

One embodiment of the present invention relates to a modified styrene-based elastomer having, in a side chain, an N-substituted succinimide group including a phenolic hydroxyl group, an isocyanate group, a blocked isocyanate group, a maleimide group, or a benzoxazine group.

Description

Technical Field

[0001] The invention relates to a modified styrene elastomer. Background Art

[0002] Styrene elastomers composed of copolymers of aromatic vinyl compounds and conjugated diene compounds and hydrogenated products thereof are used in various applications. It is known to modify styrene elastomers with maleic anhydride or the like in order to impart properties such as adhesion and affinity (for example, see Patent Document 1).

[0003] Previous technical literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2013-028761 Summary of the invention

[0006] Technical issues to be solved by the invention

[0007] An object of the present invention is to provide a novel modified styrene elastomer modified with a group having a specific structure.

[0008] Means for solving technical problems

[0009] One embodiment of the present invention relates to the following modified styrene-based elastomer.

[0010] [1] A modified styrene-based elastomer having an N-substituted succinimide group containing a phenolic hydroxyl group, an isocyanate group, a blocked isocyanate group, a maleimide group or a benzoxazine group in a side chain.

[0011] [2] The modified styrene-based elastomer according to [1] above, wherein

[0012] The N-substituted succinimide group has a structure represented by the following formula (1).

[0013]

[0014] [In formula (1), X represents a monovalent organic group having a phenolic hydroxyl group, an isocyanate group, a blocked isocyanate group, a maleimide group or a benzoxazine group, and * represents a bonding portion.]

[0015] [3] The modified styrene-based elastomer according to [1] or [2] above, wherein

[0016] The N-substituted succinimide group containing a phenolic hydroxyl group has a structure represented by the following formula (2).

[0017]

[0018] [In formula (2), R 1 represents an alkylene group or a single bond, R 2 represents an alkyl group, m is 0 or 1, n is 1 or 2, and * represents a bonding portion.]

[0019] [4] The modified styrene-based elastomer according to [1] or [2] above, wherein

[0020] The N-substituted succinimide group containing an isocyanate group has a structure represented by the following formula (3).

[0021]

[0022] [In formula (3), R 3 represents an aliphatic hydrocarbon group, a hydrocarbon group having an aromatic ring, or an organic group having a urethane bond, and * represents a bonding portion.]

[0023] [5] The modified styrene-based elastomer according to [1] or [2] above, wherein

[0024] The N-substituted succinimide group containing a blocked isocyanate group has a structure represented by the following formula (4).

[0025]

[0026] [In formula (4), R 4 represents the residue of a diisocyanate compound, R 5 represents the residue of the blocking agent, and * represents the bonding part. ]

[0027] [6] The modified styrene-based elastomer according to [1] or [2] above, wherein

[0028] The N-substituted succinimide group containing a maleimide group has a structure represented by the following formula (5).

[0029]

[0030] [In formula (5), R 6 represents the residue of a diamine compound.]

[0031] [7] The styrene-based elastomer according to [1] or [2] above, wherein

[0032] The N-substituted succinimide group containing a benzoxazine group has a structure represented by the following formula (6).

[0033]

[0034] [In formula (6), R 7 represents an alkylene group, R8 represents an alkyl group, a phenyl group or an allyl group, and * represents a bonding part. ] Effect of the Invention

[0035] According to the present invention, there can be provided a novel modified styrene-based elastomer modified with a group having a specific structure. DETAILED DESCRIPTION

[0036] The preferred embodiments of the present invention are described in detail below. However, the present invention is not limited to the following embodiments. In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved. In this specification, the term "layer" includes not only structures of shapes formed on the entire surface, but also structures of shapes formed on a portion of the surface when viewed in a plan view.

[0037] In this specification, the numerical range represented by "~" indicates a range that includes the numerical values ​​recorded before and after "~" as the minimum and maximum values, respectively. In the numerical range recorded in stages in this specification, the upper limit or lower limit of the numerical range of any stage can also be replaced by the upper limit or lower limit of the numerical range of other stages. In addition, in the numerical range recorded in this specification, the upper limit or lower limit of its numerical range can be replaced by the value shown in the embodiment. In this specification, when the amount of each component in the composition is mentioned, and when there are multiple substances equivalent to each component in the composition, unless otherwise specified, it refers to the total amount of the multiple substances present in the composition. "A or B" includes either A and B, or both. "Solid content" refers to non-volatile components in the resin composition other than volatile substances (water, solvent, etc.). That is, "solid content" refers to components other than the solvent that does not volatilize and remain during the drying of the resin composition described later, and also includes liquid, syrupy or waxy components at room temperature (25°C).

[0038] [Modified styrene elastomer)

[0039] The modified styrene-based elastomer according to the present embodiment has an N-substituted succinimide group containing a phenolic hydroxyl group, an isocyanate group, a blocked isocyanate group, a maleimide group, or a benzoxazine group in a side chain. It is believed that the modified styrene-based elastomer has an N-substituted succinimide group, which makes it difficult to be hydrolyzed by moisture in the air, and thus has excellent stability, and furthermore, it has reactivity by containing at least one functional group selected from the group consisting of a phenolic hydroxyl group, an isocyanate group, a blocked isocyanate group, a maleimide group, and a benzoxazine group, and thus can improve the heat resistance, strength, and other properties of the cured product.

[0040] The N-substituted succinimide group can be introduced by reacting a compound having a reactive group such as an amino group or an isocyanate group with an acid anhydride group of a styrene elastomer modified with maleic anhydride. The styrene elastomer may be a copolymer having a structural unit derived from a styrene compound and a structural unit derived from a conjugated diene compound.

[0041] Examples of the styrene-based compound include styrene, α-methylstyrene, p-methylstyrene, and p-tert-butylstyrene. Among them, styrene, α-methylstyrene, and 4-methylstyrene are preferred from the viewpoint of availability and productivity, and styrene is more preferred.

[0042] Examples of the conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene (piperylene), 1-phenyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3,4-dimethyl-1,3-hexadiene, and 4,5-diethyl-1,3-octadiene. Among them, 1,3-butadiene and isoprene are preferred from the viewpoint of availability and productivity.

[0043] The styrene-based elastomer may also be a hydrogenated styrene-based elastomer in which at least a portion of the structural unit derived from the conjugated diene compound is hydrogenated. As hydrogenated styrene-based elastomers, for example, hydrogenated products of styrene-butadiene-styrene block copolymers (SEBS) and hydrogenated products of styrene-isoprene-styrene block copolymers can be cited. As commercially available products of SEBS, for example, Tuftec (registered trademark) H series and M series manufactured by Asahi Kasei Corporation, SEPTON (registered trademark) series manufactured by KURARAY CO., LTD., Kraton (registered trademark) G polymer series manufactured by Kraton Polymers Japan Ltd., etc. can be cited.

[0044] The styrene elastomer or hydrogenated styrene elastomer modified with maleic anhydride (hereinafter referred to as "maleic anhydride-modified styrene elastomer") can be prepared by reacting maleic anhydride with a styrene or hydrogenated styrene elastomer, or a commercially available product can be used.

[0045] The maleic anhydride-modified styrene elastomer can be prepared, for example, by adding a free radical initiator to a mixed solution obtained by dissolving a styrene elastomer and maleic anhydride in a solvent under a nitrogen atmosphere, and reacting the maleic anhydride with the styrene elastomer. The reaction temperature can be 20 to 150° C. After the reaction, it is preferred to remove unreacted maleic anhydride by extraction from the viewpoint of suppressing side reactions.

[0046] As the free radical initiator, for example, organic peroxides and azo compounds can be used. As the organic peroxide, for example, dicumyl peroxide, benzoyl peroxide, 2-butanone peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, bis(tert-butylperoxyisopropyl)benzene and tert-butyl hydroperoxide can be mentioned. As the azo compound, for example, 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile) and 1,1'-azobis(cyclohexanecarbonitrile) can be mentioned.

[0047] As the solvent, for example, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, mesitylene, methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate and ethyl acetate can be cited. These can be used alone or in combination of two or more. Among them, toluene, xylene and propylene glycol monomethyl ether are preferred from the viewpoint of solubility.

[0048] The N-substituted succinimide group may be a group having a structure represented by the following formula (1).

[0049]

[0050] In formula (1), X represents a monovalent organic group having a phenolic hydroxyl group, an isocyanate group, a blocked isocyanate group, a maleimide group or a benzoxazine group, and * represents a bonding portion.

[0051] The N-substituted succinimide group containing a phenolic hydroxyl group may be a group having a structure represented by the following formula (2).

[0052]

[0053] In formula (2), R 1 represents an alkylene group or a single bond, R 2 represents an alkyl group, m is 0 or 1, n is 1 or 2, and * represents a bonding portion. 1 Examples of the alkylene group include methylene, ethylene and propylene. 2 Examples of the alkyl group include a methyl group, an ethyl group and a propyl group.

[0054] The modified styrene elastomer having an N-substituted succinimide group containing a phenolic hydroxyl group in a side chain (hereinafter referred to as "phenolic hydroxyl group-containing succinimide-modified styrene elastomer") can be a reaction product of a maleic anhydride-modified styrene elastomer and an amine compound having a phenolic hydroxyl group. Examples of the amine compound having a phenolic hydroxyl group include tyramine, dopamine, 4-aminophenol, and 5-amino-o-cresol.

[0055] The N-substituted succinimide group containing an isocyanate group may be a group having a structure represented by the following formula (3).

[0056]

[0057] In formula (3), R 3 represents an aliphatic hydrocarbon group, a hydrocarbon group having an aromatic ring, or an organic group having a urethane bond, and * represents a bonding portion.

[0058] The modified styrene elastomer having an N-substituted succinimide group containing an isocyanate group in the side chain (hereinafter referred to as "succinimide-modified styrene elastomer containing an isocyanate group") can be a reaction product of a maleic anhydride-modified styrene elastomer and a diisocyanate compound or a reaction product of a maleic anhydride-modified styrene elastomer, an amine compound having an alcoholic hydroxyl group and a diisocyanate compound.

[0059] Examples of the diisocyanate compound include diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and hexamethylene diisocyanate having a urethane bond. Examples of the amine compound having an alcoholic hydroxyl group include hydroxyethylamine.

[0060] The N-substituted succinimide group containing a blocked isocyanate group may be a group having a structure represented by the following formula (4).

[0061]

[0062] In formula (4), R 4 represents the residue of a diisocyanate compound, R 5 represents the residue of the blocking agent, and * represents the bonding part. In addition, the residue refers to the structure of the part in which the functional group for bonding is removed from the raw material component.

[0063] In a modified styrene elastomer having an N-substituted succinimide group containing a blocked isocyanate group in a side chain (hereinafter referred to as "succinimide-modified styrene elastomer containing a blocked isocyanate group"), the isocyanate group of the succinimide-modified styrene elastomer containing the isocyanate group is protected by a blocking agent.

[0064] As the blocking agent, a compound generally known as a blocking agent for an isocyanate group can be used. Examples of the blocking agent include methanol, methyl ethyl ketoxime, and dimethylpyrazole.

[0065] The N-substituted succinimide group including a maleimide group may be a group having a structure represented by the following formula (5).

[0066]

[0067] In formula (5), R 6 represents a residue of a diamine compound.

[0068] The modified styrene elastomer having an N-substituted succinimide group containing a maleimide group in a side chain (hereinafter referred to as "maleimide group-containing succinimide-modified styrene elastomer") may be a reaction product of a maleic anhydride-modified styrene elastomer, a diamine compound, and maleic anhydride.

[0069] Examples of the diamine compound include aliphatic diamines such as polyoxypropylenediamine, and aromatic diamines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, and 9,9-bis(4-aminophenyl)fluorene.

[0070] The N-substituted succinimide group including a benzoxazinyl group may be a group having a structure represented by the following formula (6).

[0071]

[0072] In formula (6), R 7 represents an alkylene group, R 8 represents an alkyl group, a phenyl group or an allyl group, and * represents a bonding part. 8 It may be a residue of a monoamine compound.

[0073] The modified styrene elastomer having an N-substituted succinimide group containing a benzoxazine group in a side chain (hereinafter referred to as "benzoxazine group-containing succinimide-modified styrene elastomer") may be a reaction product of the above-mentioned phenolic hydroxyl group-containing succinimide-modified styrene elastomer, paraformaldehyde and a monoamine compound.

[0074] Examples of the monoamine compound include aromatic amines such as aniline and aliphatic amines such as allylamine.

[0075] [Resin composition]

[0076] The modified styrene elastomer of the present embodiment can be mixed with other components (e.g., thermosetting resin, curing accelerator, filler, flame retardant, etc.) to prepare a resin composition. The modified styrene elastomer of the present embodiment has reactivity to thermosetting resin, and the cured product of the resin composition has excellent heat resistance, strength, etc.

[0077] (Thermosetting resin)

[0078] Examples of the thermosetting resin include epoxy resins, cyanate resins, acrylic resins, silicone resins, phenolic resins, maleimide resins, thermosetting polyimide resins, polyurethane resins, melamine resins, and urea resins. These can be used alone or in combination of two or more.

[0079] As epoxy resins, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, alicyclic epoxy resins, aliphatic chain epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, phenol aralkyl type epoxy resins, naphthol novolac type epoxy resins, naphthol aralkyl type epoxy resins and other naphthalene skeleton-containing epoxy resins, bifunctional biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, dicyclopentadiene type epoxy resins and dihydroanthracene type epoxy resins.

[0080] (Curing accelerator)

[0081] As the curing accelerator, for example, various imidazole compounds of latent heat curing agents, BF3 amine complexes, phosphorus-based curing accelerators, etc. can be cited. When a curing accelerator is formulated, imidazole compounds and phosphorus-based curing accelerators are preferred from the viewpoints of storage stability of the resin composition, handling properties of the semi-cured resin composition, and solder heat resistance of the cured product.

[0082] (filler)

[0083] Examples of fillers include silicon dioxide, aluminum oxide, titanium oxide, mica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, talc, aluminum borate, and silicon carbide. These may be used alone or in combination of two or more.

[0084] There is no particular restriction on the shape and particle size of the filler. The particle size of the filler can be, for example, 0.01 to 20 μm, or 0.1 to 10 μm. Here, the particle size refers to the average particle size, which is the particle size at the point corresponding to 50% of the volume when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles as 100%. The average particle size can be measured by a particle size distribution measuring device using a laser diffraction scattering method, etc.

[0085] In order to improve the dispersibility of the filler, the adhesion with the organic component, etc., a coupling agent can be used as needed. As a coupling agent, there is no particular limitation, for example, various silane coupling agents, titanate coupling agents, etc. can be used. They can be used alone or in combination of two or more. In addition, the amount of the coupling agent used is also not particularly limited, for example, it can be set to 0.1 to 5 parts by mass, or 0.5 to 3 parts by mass relative to 100 parts by mass of the filler used. If it is within this range, the reduction of various characteristics is small, and it becomes easy to effectively play the advantages based on the use of fillers.

[0086] When a coupling agent is used, the coupling agent may be added after the filler is mixed in the resin composition, which is a so-called overall mixing treatment method. Preferably, a method is used in which the coupling agent is surface-treated in the filler in advance by dry or wet methods. By using this method, the advantages of the above-mentioned filler can be more effectively demonstrated.

[0087] (Flame Retardant)

[0088] The flame retardant is not particularly limited, and preferably a bromine flame retardant, a phosphorus flame retardant, a metal hydroxide, etc. are used. Examples of the bromine flame retardant include brominated epoxy resins, brominated addition flame retardants, brominated reaction flame retardants containing unsaturated double bond groups, etc. Examples of the phosphorus flame retardant include aromatic phosphates, phosphonates, phosphinates, phosphazene compounds, etc. Examples of the metal hydroxide flame retardant include magnesium hydroxide, aluminum hydroxide, etc.

[0089] The resin composition can be diluted with a solvent as needed. The solvent is not particularly limited, and volatility during film formation can be determined from the boiling point. As the solvent, for example, solvents with lower boiling points such as methanol, ethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene, and xylene can be cited. The solvent can be used alone or in combination of two or more.

[0090] The resin composition of the present embodiment can be obtained by uniformly dispersing and mixing the above-mentioned components, and its preparation means, conditions, etc. are not particularly limited. For example, it can be cited that after the various components of the prescribed allocation amount are fully and uniformly stirred and mixed by a mixer, etc., mixing is carried out using a mixing roller, an extruder, a kneader, a roller, an extruder, etc., and then the obtained mixed material is cooled and crushed. In addition, there is no particular limitation on the mixing form.

[0091] [Resin film]

[0092] The resin composition according to the present embodiment can be used to produce a resin film. The resin film refers to an uncured or semi-cured film-like resin composition.

[0093] The method for preparing the resin film is not limited, and for example, it can be obtained by drying a resin layer formed by coating a resin composition on a supporting substrate. Specifically, after the resin composition is coated on a supporting substrate using a kiss coater, a roll coater, a notch wheel coater, etc., it is dried in a heating drying furnace, for example, at a temperature of 70 to 250° C., preferably 70 to 200° C., for 1 to 30 minutes, preferably 3 to 15 minutes. Thus, a resin film in which the resin composition is in a semi-cured state can be obtained.

[0094] The resin film can be thermally cured by further heating the semi-cured resin film in a heating furnace at a temperature of, for example, 170 to 250° C., preferably 185 to 230° C., for 60 to 150 minutes.

[0095] The thickness of the resin film of the present embodiment is not particularly limited, but is preferably 1 to 200 μm, more preferably 2 to 180 μm, and further preferably 3 to 150 μm. By setting the thickness of the resin film within the above range, it is easy to achieve both thinning and good high-frequency characteristics of the printed wiring board obtained by using the resin film of the present embodiment.

[0096] The supporting substrate is not particularly limited, and is preferably at least one selected from the group consisting of glass, metal foil and PET film. Since the resin film has a supporting substrate, it has a tendency to improve the storage and handling properties when used to manufacture a printed wiring board. That is, the resin film involved in the present embodiment can be in the form of a support body with a resin layer and a supporting substrate including the resin composition involved in the present embodiment, and can also be peeled off from the supporting substrate when used.

[0097] [Prepreg]

[0098] The resin composition involved in the present embodiment can be used to make a prepreg. The resin composition involved in the present embodiment can be applied to a fiber substrate as a reinforcing substrate, and the applied resin composition can be dried to obtain a prepreg. In addition, the prepreg can be obtained by impregnating the fiber substrate with the resin composition involved in the present embodiment and then drying the impregnated resin composition. Specifically, the fiber substrate attached with the resin composition is heated and dried in a drying furnace usually at a temperature of 80 to 200° C. for 1 to 30 minutes to obtain a prepreg in which the resin composition is semi-cured. From the viewpoint of good formability, the amount of the resin composition attached to the fiber substrate is preferably applied or impregnated in such a manner that the resin content in the dried prepreg becomes 30 to 90% by mass.

[0099] The reinforcing substrate of the prepreg is not limited, but is preferably a sheet-like fiber substrate. Examples of the sheet-like fiber substrate include inorganic fibers such as E glass, NE glass, S glass, and Q glass; and organic fibers such as polyimide, polyester, and tetrafluoroethylene. The sheet-like fiber substrate may be a substrate in the shape of a woven fabric, a nonwoven fabric, or a chopped strand mat.

[0100] [Laminated board]

[0101] According to the present embodiment, a laminate having a resin layer including a cured product of the resin composition and a conductor layer can be provided. For example, a metal-clad laminate can be produced using the resin film or the prepreg.

[0102] The manufacturing method of the metal-clad laminate is not limited. For example, one or more layers of the resin film or prepreg involved in the present embodiment can be overlapped, and a metal foil as a conductor layer can be configured on at least one surface. For example, heating and pressurizing are performed for 60 to 150 minutes at a temperature of 170 to 250° C., preferably 185 to 230° C. and a pressure of 0.5 to 5.0 MPa, thereby obtaining a metal-clad laminate having a metal foil on at least one surface of the resin layer or prepreg that becomes an insulating layer. Heating and pressurizing can be performed, for example, under the condition that the vacuum degree is less than 10 kPa, preferably less than 5 kPa, and is preferably performed in a vacuum from the viewpoint of improving efficiency. Heating and pressurizing are preferably performed from 30 minutes from the start to the end of the forming.

[0103] [Multilayer printed circuit board]

[0104] According to the present embodiment, a multilayer printed wiring board having a resin layer and a circuit layer comprising a cured product of the resin composition can be provided. The upper limit of the number of circuit layers is not particularly limited, and can be 3 to 20 layers. The multilayer printed wiring board can also be manufactured using, for example, the resin film, prepreg or metal-clad laminate.

[0105] There is no particular limitation on the method for manufacturing a multilayer printed circuit board. For example, a multilayer printed circuit board can be manufactured in the following manner: first, a resin film is arranged on one or both sides of a core substrate that has been subjected to circuit forming processing, or a resin film is arranged between multiple core substrates, and each layer is bonded by pressurized and heated lamination or pressurized and heated extrusion, and then a circuit forming process using laser hole opening processing, drilling hole opening processing, metal plating processing, metal etching, etc. is performed. In the case where the resin film has a supporting substrate, the supporting substrate can be peeled off in advance before the resin film is arranged on the core substrate or between the core substrates, or can be peeled off after the resin layer is attached to the core substrate.

[0106] The preferred embodiments of the present invention have been described above, but these are examples for explaining the present invention and do not limit the scope of the present invention to the gist of these embodiments. The present invention can be implemented in various ways different from the above embodiments without departing from the gist of the present invention.

[0107] Example

[0108] Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to the following examples.

[0109] (Example A-1)

[0110] 150 g of maleic anhydride-modified hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Corporation, product name "Tuftec M1913") and 656 g of toluene were placed in a 1 L flask, stirred and heated to 80°C in about 0.5 hours, then kept warm for 1 hour to dissolve "Tuftec M1913". Next, the temperature was lowered to 40°C, and a solution of 4.5 g of tyramine (manufactured by FUJIFILM Wako Pure Chemical Corporation) dissolved in 85.5 g of propylene glycol monomethyl ether (PGME) was added dropwise. Then, the temperature was stirred and heated to 60°C in about 0.5 hours, then kept warm for 1 hour. Furthermore, the temperature was raised to 110°C in about 1 hour, nitrogen was circulated and kept warm for 2 hours, and a toluene solution of a succinimide-modified styrene elastomer (A-1) containing a phenolic hydroxyl group was obtained.

[0111] The FT-IR spectrum of (A-1) was measured using an FT-IR spectrum (manufactured by Shimadzu Corporation, product name: "IRSpirit"), and it was confirmed that -1 The peaks derived from the anhydride groups disappeared and the peak at 1700 cm -1 There is a peak derived from an imide group in the vicinity.

[0112] (Example A-2)

[0113] 150 g of "Tuftec M1913" and 636 g of toluene were placed in a 1 L flask, stirred and heated to 80°C for about 0.5 hours, then kept warm for 1 hour to dissolve "Tuftec M1913". Next, the temperature was lowered to 40°C, and a solution containing 5.0 g of dopamine (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added dropwise to 95.0 g of PGME. Then, stirred and heated to 60°C for about 0.5 hours, then kept warm for 1 hour. Furthermore, the temperature was raised to 110°C for about 1 hour, nitrogen was circulated and kept warm for 2 hours to obtain a toluene solution of a succinimide-modified styrene elastomer (A-2) containing a catechol group.

[0114] The FT-IR spectrum of (A-2) was measured and it was confirmed that -1 The peaks derived from the anhydride groups disappeared, and the peak at 1700 cm -1 There is a peak derived from an imide group in the vicinity.

[0115] (Example B-1)

[0116] 150 g of "Tuftec M1913" and 656 g of xylene were placed in a 1 L flask, stirred and heated to 80°C in about 0.5 hours, then kept warm for 1 hour to dissolve "Tuftec M1913". Next, the temperature was lowered to 40°C, and a solution containing 3.6 g of diphenylmethane diisocyanate (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added dropwise to 68.4 g of xylene. Then, stirred and heated to 60°C in about 0.5 hours, then kept warm for 1 hour. Furthermore, the temperature was raised to 135°C in about 1 hour, nitrogen was circulated and kept warm for 2 hours, to obtain a toluene solution of a succinimide-modified styrene elastomer (B-1) containing an isocyanate group.

[0117] The FT-IR spectrum of (B-1) was measured and it was confirmed that -1 The peaks derived from the anhydride groups disappeared and the peak at 1700 cm -1 There are peaks derived from imide groups near 2260 cm -1 There is a peak derived from an isocyanate group in the vicinity.

[0118] (Example B-2)

[0119] 150 g of "Tuftec M1913" and 607 g of xylene were placed in a 1 L flask, stirred and the temperature was raised to 80°C in about 0.5 hours, and then kept warm for 1 hour to dissolve "Tuftec M1913". Next, the temperature was lowered to 40°C, and a solution of 7.0 g of hexamethylene diisocyanate (manufactured by Asahi Kasei Corporation, product name "DURANATE D101") having a urethane bond was added dropwise to 133 g of xylene. Then, the temperature was raised to 60°C in about 0.5 hours while stirring, and then kept warm for 1 hour. Furthermore, the temperature was raised to 135°C in about 1 hour, nitrogen was circulated and kept warm for 2 hours, and a toluene solution of a succinimide-modified styrene elastomer (B-2) containing an isocyanate group was obtained.

[0120] The FT-IR spectrum of (B-2) was measured and it was confirmed that -1 The peaks derived from the anhydride groups disappeared and the peak at 1700 cm -1 There are peaks derived from imide groups near 2260 cm -1 There is a peak derived from an isocyanate group in the vicinity.

[0121] (Example B-3)

[0122] 150 g of "Tuftec M1913" and 679 g of toluene were placed in a 1 L flask, stirred, and heated to 80°C for about 0.5 hours, then kept warm for 1 hour to dissolve "Tuftec M1913". Next, the temperature was lowered to 40°C, and a solution containing 2.0 g of ethanolamine was added dropwise to 38 g of PGME. Then, the temperature was raised to 60°C for about 0.5 hours while stirring, and kept warm for 1 hour. Furthermore, the temperature was raised to 110°C for about 1 hour, and nitrogen was circulated and kept warm for 2 hours to obtain a toluene solution of a succinimide-modified styrene elastomer containing an ethanolic hydroxyl group.

[0123] 6.0 g of diphenylmethane diisocyanate was added to the toluene solution of the succinimide-modified styrene elastomer containing an ethanolic hydroxyl group, and the mixture was reacted at 90° C. for 2 hours to obtain a toluene solution of a succinimide-modified styrene elastomer (B-3) having an isocyanate group and a urethane bond.

[0124] The FT-IR spectrum of (B-3) was measured and it was confirmed that -1 The peaks derived from the anhydride groups disappeared and the peak at 1700 cm -1 There is a peak derived from the imide group near 1730 cm -1 There are peaks derived from carbamate bonds near 2260 cm -1There is a peak derived from an isocyanate group in the vicinity.

[0125] (Example B-4)

[0126] 10.3 g of "DURANATE D101" was added to the toluene solution of the succinimide-modified styrene elastomer having an ethanolic hydroxyl group, and the mixture was reacted at 90° C. for 2 hours to obtain a toluene solution of a succinimide-modified styrene elastomer (B-4) having an isocyanate group and a urethane bond.

[0127] The FT-IR spectrum of (B-4) was measured and it was confirmed that -1 The peaks derived from the anhydride groups disappeared and the peak at 1700 cm -1 There is a peak derived from the imide group near 1730 cm -1 There are peaks derived from carbamate bonds near 2260 cm -1 There is a peak derived from an isocyanate group in the vicinity.

[0128] (Example C-1)

[0129] 0.1 g of methanol (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added to the toluene solution of (B-1), and the mixture was reacted at 90°C for 2 hours to obtain a toluene solution of a succinimide-modified styrene-based elastomer (C-1) having a blocked isocyanate group.

[0130] The FT-IR spectrum of (C-1) was measured and it was confirmed that -1 The nearby peak derived from the isocyanate group disappeared.

[0131] (Example C-2)

[0132] A toluene solution of a succinimide-modified styrene-based elastomer (C-2) containing a blocked isocyanate group was obtained in the same manner as in (C-1) except that 0.1 g of methanol was replaced with 0.2 g of methyl ethyl ketoxime (manufactured by FUJIFILM Wako Pure Chemical Corporation).

[0133] The FT-IR spectrum of (C-2) was measured and it was confirmed that -1 The nearby peak derived from the isocyanate group disappeared.

[0134] (Example C-3)

[0135] A toluene solution of a succinimide-modified styrene-based elastomer (C-3) containing a blocked isocyanate group was obtained in the same manner as in (C-1) except that 0.1 g of methanol was replaced with 0.2 g of dimethylpyrazole (manufactured by FUJIFILM Wako Pure Chemical Corporation).

[0136] The FT-IR spectrum of (C-3) was measured and it was confirmed that -1 The nearby peak derived from the isocyanate group disappeared.

[0137] (Example D-1)

[0138] In a 1L flask equipped with a cooling tube, a nitrogen inlet tube, a thermocouple and a stirrer, 688g of toluene and 150g of "Tuftec M1913" were added, the temperature was raised to 80°C, stirred and dissolved for 1.0 hour. Next, the temperature in the flask was lowered to 30°C, and a solution of 9.3g of 2,2-bis(4-aminophenyl)hexafluoropropane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise in 9.3g of toluene, and stirred for 1.0 hour. Then, 2.8g of maleic anhydride (manufactured by FUJIFILM WakoPure Chemical Corporation) was added and the mixture was further kept warm for 1.0 hour. After adding 0.53g of p-toluenesulfonic acid, the temperature in the flask was raised to the reflux temperature (about 110°C), nitrogen was circulated and a dehydration cyclization reaction was carried out for 3.0 hours to obtain a toluene solution of a succinimide-modified styrene elastomer (D-1) containing a maleimide group.

[0139] The FT-IR spectrum of (D-1) was measured and it was confirmed that -1 The peaks derived from the anhydride groups disappeared and the peak at 1700 cm -1 There is a peak derived from the imide group near (D-1). 13 C-NMR spectrum (manufactured by Bruker) was used for measurement, and it was confirmed that two or three peaks derived from the carbonyl carbon of the succinimide group and the carbonyl carbon of the maleimide group appeared in the region of 170 to 180 ppm.

[0140] (Example D-2)

[0141] In a 1L flask equipped with a cooling tube, a nitrogen inlet tube, a thermocouple and a stirrer, 722g of toluene and 150g of "Tuftec M1913" were added, the temperature was raised to 80°C, and the mixture was stirred and dissolved for 1.0 hour. Next, the temperature in the flask was lowered to 30°C, and a solution of 6.6g of polyoxypropylene diamine (manufactured by Huntsman International LLC., product name "Jeffermine D230") dissolved in 6.6g of toluene was added dropwise, and the mixture was stirred for 1.0 hour. Thereafter, 2.8g of maleic anhydride was added, and the mixture was further kept warm for 1.0 hour. After adding 0.53g of p-toluenesulfonic acid, the temperature in the flask was raised to the reflux temperature (about 110°C), nitrogen was circulated, and a dehydration cyclization reaction was carried out for 3.0 hours to obtain a toluene solution of a succinimide-modified styrene elastomer (D-2) containing a maleimide group.

[0142] The FT-IR spectrum of (D-2) was measured and it was confirmed that -1 The peaks derived from the anhydride groups disappeared and the peak at 1700 cm -1 There is a peak derived from the imide group near (D-2). 13 C-NMR spectrum measurement confirmed that 2 to 3 peaks derived from the carbonyl carbon of the succinimide group and the carbonyl carbon of the maleimide group appeared in the region of 170 to 180 ppm.

[0143] (Example D-3)

[0144] In a 1L flask equipped with a cooling tube, a nitrogen inlet tube, a thermocouple and a stirrer, 692g of toluene and 150g of "Tuftec M1913" were added, the temperature was raised to 80°C, stirred and dissolved for 1.0 hour. Next, the temperature in the flask was lowered to 30°C, and a solution of 5.5g of 4,4-methylenedianiline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to 5.5g of toluene, and stirred for 1.0 hour. After that, 2.8g of maleic anhydride was added and the mixture was further kept warm for 1.0 hour. After adding 0.53g of p-toluenesulfonic acid, the temperature in the flask was raised to the reflux temperature (about 110°C), nitrogen was circulated and a dehydration cyclization reaction was carried out for 3.0 hours to obtain a toluene solution of a succinimide-modified styrene elastomer (D-3) containing a maleimide group.

[0145] The FT-IR spectrum of (D-3) was measured and it was confirmed that -1 The peaks derived from the anhydride groups disappeared and the peak at 1700 cm -1 There is a peak derived from the imide group near (D-3). 13C-NMR spectrum measurement confirmed that 2 to 3 peaks derived from the carbonyl carbon of the succinimide group and the carbonyl carbon of the maleimide group appeared in the region of 170 to 180 ppm.

[0146] (Example D-4)

[0147] In a 1L flask equipped with a cooling tube, a nitrogen inlet tube, a thermocouple and a stirrer, 692g of toluene and 150g of "Tuftec M1913" were added, the temperature was raised to 80°C, stirred and dissolved for 1.0 hour. Next, the temperature in the flask was lowered to 30°C, and a solution of 5.6g of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to 5.6g of toluene, and stirred for 1.0 hour. After that, 2.8g of maleic anhydride was added and the mixture was further kept warm for 1.0 hour. After adding 0.53g of p-toluenesulfonic acid, the temperature in the flask was raised to the reflux temperature (about 110°C), nitrogen was circulated and a dehydration cyclization reaction was carried out for 3.0 hours to obtain a toluene solution of a succinimide-modified styrene elastomer (D-4) containing a maleimide group.

[0148] The FT-IR spectrum of (D-4) was measured and it was confirmed that -1 The peaks derived from the anhydride groups disappeared and the peak at 1700 cm -1 There is a peak derived from the imide group near (D-4). 13 C-NMR spectrum measurement confirmed that 2 to 3 peaks derived from the carbonyl carbon of the succinimide group and the carbonyl carbon of the maleimide group appeared in the region of 170 to 180 ppm.

[0149] (Example E-1)

[0150] In a 1L glass container equipped with a cooling tube, a nitrogen inlet tube, a thermocouple, and a stirrer, 672g of toluene and 150g of "Tuftec M1913" were added, the temperature was raised to 80°C, and the mixture was stirred and dissolved for 1.0 hour. After that, the temperature in the flask system was lowered to 40°C, and a solution obtained by dissolving 3.8g of tyramine in 72.2g of PGME was added dropwise. Then, the mixture was stirred and heated to 60°C for about 0.5 hours, and then kept warm for 1 hour. Furthermore, the mixture was heated to 110°C for about 1 hour, and nitrogen was circulated and kept warm for 2 hours to obtain a toluene solution of a succinimide-modified styrene elastomer containing a phenolic hydroxyl group. Then, 2.6 g of aniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.6 g of polyformaldehyde were added, and the temperature in the flask system was raised to the reflux temperature (about 110° C.), and then nitrogen was circulated and a dehydration cyclization reaction was carried out for 3.0 hours to obtain a toluene solution of a benzoxazine-containing succinimide-modified styrene elastomer (E-1).

[0151] The FT-IR spectrum of (E-1) was measured and it was confirmed that -1 The peaks derived from the anhydride groups disappeared and the peak at 1700 cm -1 There is a peak derived from the imide group at 1029 cm -1 and 1232cm -1 There is a peak derived from a benzoxazinyl group nearby.

[0152] (Example E-2)

[0153] A toluene solution of a benzoxazine group-containing succinimide-modified styrene-based elastomer (E-2) was obtained in the same manner as in (E-1) except that 2.6 g of aniline was replaced with 1.6 g of allylamine (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0154] The FT-IR spectrum of (E-2) was measured and it was confirmed that -1 The peaks derived from the anhydride groups disappeared and the peak at 1700 cm -1 There is a peak derived from the imide group at 1029 cm -1 and 1232cm -1 There is a peak derived from a benzoxazinyl group nearby.

Claims

1. A modified styrene-based elastomer having an N-substituted succinimide group containing a phenolic hydroxyl group, an isocyanate group, a blocked isocyanate group, a maleimide group or a benzoxazine group in a side chain.

2. The modified styrene elastomer according to claim 1, wherein The N-substituted succinimide group has a structure represented by the following formula (1): In formula (1), X represents a monovalent organic group having a phenolic hydroxyl group, an isocyanate group, a blocked isocyanate group, a maleimide group or a benzoxazine group, and * represents a bonding portion.

3. The modified styrene-based elastomer according to claim 1 or 2, wherein The N-substituted succinimide group containing a phenolic hydroxyl group has a structure represented by the following formula (2): In formula (2), R 1 represents an alkylene group or a single bond, R 2 represents an alkyl group, m is 0 or 1, n is 1 or 2, and * represents a bonding part.

4. The modified styrene-based elastomer according to claim 1 or 2, wherein The N-substituted succinimide group containing an isocyanate group has a structure represented by the following formula (3), In formula (3), R 3 represents an aliphatic hydrocarbon group, a hydrocarbon group having an aromatic ring, or an organic group having a urethane bond, and * represents a bonding portion.

5. The modified styrene-based elastomer according to claim 1 or 2, wherein The N-substituted succinimide group containing a blocked isocyanate group has a structure represented by the following formula (4): In formula (4), R 4 represents the residue of a diisocyanate compound, R 5 represents the residue of the blocking agent, and * represents the bonding part.

6. The modified styrene-based elastomer according to claim 1 or 2, wherein The N-substituted succinimide group containing a maleimide group has a structure represented by the following formula (5), In formula (5), R 6 It represents the residue of a diamine compound.

7. The modified styrene-based elastomer according to claim 1 or 2, wherein The N-substituted succinimide group containing a benzoxazine group has a structure represented by the following formula (6), In formula (6), R 7 represents an alkylene group, R 8 represents an alkyl group, a phenyl group or an allyl group, and * represents a bonding part.

Images