Maleimide-modified styrene elastomer and method for producing maleimide-modified styrene elastomer

Abstract

The present invention relates to a maleimide-modified styrene elastomer which is obtained by reacting a modified styrene elastomer having a group represented by formula (1), a diamine compound, and maleic anhydride, and which has a group represented by formula (3) (in the formula, A1 represents a residue of the diamine compound, and * represents a bond. ) and a method for producing a maleimide-modified styrene elastomer. # imgabs0 #

Description

Technical Field

[0001] The invention relates to a maleimide-modified styrene elastomer and a method for preparing the maleimide-modified styrene elastomer. Background Art

[0002] The high speed and large capacity of signals used in mobile communication devices represented by mobile phones, network infrastructure equipment such as base station equipment, servers, routers, and electronic devices such as large computers are developing year by year. Along with this, for the printed circuit boards carried in their electronic devices, it is necessary to cope with high frequencies, requiring substrate materials with low relative dielectric constants and low dielectric loss tangents that can reduce transmission losses. In recent years, as an application for processing such high-frequency signals, in addition to the above-mentioned electronic devices, in the ITS field (related to automobiles and transportation systems) and the indoor short-distance communication field, new systems for processing high-frequency wireless signals are also being put into practical use and practical plans. It is expected that in the future, for the printed circuit boards carried on their devices, low transmission loss substrate materials will also be further required.

[0003] As a resin material for printed wiring boards, a resin composition containing a styrene-based thermoplastic elastomer and a polyphenylene ether derivative having an N-substituted maleimide structure has been proposed in order to improve dielectric properties, heat resistance, and mechanical properties (for example, see Patent Document 1).

[0004] Previous technical literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2019-6879 Summary of the invention

[0007] Technical issues to be solved by the invention

[0008] The object of the present invention is to provide a novel maleimide-modified styrene elastomer and a method for producing the maleimide-modified styrene elastomer.

[0009] Means for solving technical problems

[0010] One embodiment of the present invention relates to the following maleimide-modified styrene-based elastomer and a method for producing the maleimide-modified styrene-based elastomer.

[0011] [1] A method for producing a maleimide-modified styrene-based elastomer, comprising:

[0012] A step of preparing a first modified styrene-based elastomer having a group represented by the following formula (1);

[0013]

[0014] a step of reacting a diamine compound with an acid anhydride group of the first modified styrene-based elastomer to obtain a second modified styrene-based elastomer having a group represented by the following formula (2); and

[0015]

[0016] A step of reacting maleic anhydride with the amino group of the second modified styrene-based elastomer and then performing a dehydration cyclization reaction to obtain a third modified styrene-based elastomer having a group represented by the following formula (3).

[0017]

[0018] (In the formula, A 1 represents the residue of the diamine compound, and * represents the bonding part. )

[0019] [2] The method for producing a maleimide-modified styrene-based elastomer according to [1] above, wherein:

[0020] The diamine compound is at least one selected from the group consisting of polyoxypropylenediamine, metaphenylenediamine, 2,4-toluenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-methylenebis(2-ethyl-6-methylaniline) and 2,2-bis(4-aminophenyl)hexafluoropropane.

[0021] [3] A maleimide-modified styrene-based elastomer obtained by reacting a modified styrene-based elastomer having a group represented by the following formula (1), a diamine compound, and maleic anhydride, and having a group represented by the following formula (3).

[0022]

[0023] (In the formula, A 1 represents the residue of the diamine compound, and * represents the bonding part. )

[0024] [4] The maleimide-modified styrene-based elastomer according to [3] above, wherein

[0025] The diamine compound is at least one selected from the group consisting of polyoxypropylenediamine, metaphenylenediamine, 2,4-toluenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-methylenebis(2-ethyl-6-methylaniline) and 2,2-bis(4-aminophenyl)hexafluoropropane.

[0026] Effects of the Invention

[0027] According to the present invention, a novel maleimide-modified styrene-based elastomer and a method for producing the maleimide-modified styrene-based elastomer can be provided. DETAILED DESCRIPTION

[0028] 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.

[0029] 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).

[0030] [Maleimide-modified styrene elastomer]

[0031] The method for producing a maleimide-modified styrene elastomer according to the present embodiment comprises: a step of preparing a first modified styrene elastomer having a group represented by the following formula (1) (step 1); a step of reacting a diamine compound with an acid anhydride group of the first modified styrene elastomer to obtain a second modified styrene elastomer having a group represented by the following formula (2) (step 2); and a step of reacting maleic anhydride with an amino group of the second modified styrene elastomer and then performing a dehydration cyclization reaction to obtain a third modified styrene elastomer having a group represented by the following formula (3) (step 3).

[0032]

[0033] In the formula, A 1represents a residue of a diamine compound, and * represents a bonding portion. In addition, the residue refers to a structure in which an amino group used for bonding is removed from a diamine compound.

[0034] The group represented by formula (3) can be introduced by reacting one of the amino groups of the diamine compound with the anhydride group of the styrene elastomer modified with maleic anhydride and then reacting the maleic anhydride with the other amino group. The group represented by formula (3) has a structure including a succinimide group and a maleimide group.

[0035] Here, a method of introducing the group represented by the above formula (3) into the side chain of the styrene elastomer by grafting a bismaleimide compound represented by the following formula (4) onto the styrene elastomer is considered. However, in this method, the two maleimide groups of the bismaleimide compound are polymerized, making it difficult to control the polymerization conditions.

[0036]

[0037] In contrast, by using the manufacturing method according to the present embodiment, the group represented by the above formula (3) can be easily introduced into the side chain of the styrene elastomer. That is, the maleimide-modified styrene elastomer according to the present embodiment is obtained by reacting a modified styrene elastomer having a group represented by the above formula (1), a diamine compound, and maleic anhydride, and has a group represented by the above formula (3) in the side chain. The following describes in detail the various steps for preparing the maleimide-modified styrene elastomer according to the present embodiment.

[0038] (Process 1)

[0039] Step 1 is a step of preparing a first modified styrene elastomer having a group represented by the above formula (1). The first modified styrene elastomer may be a commercially available product, or may be prepared by modifying a styrene elastomer with maleic anhydride. The group represented by formula (1) may be a succinic anhydride group derived from 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] The first modified styrene elastomer can be prepared 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 may be 60 to 100° C., 65 to 95° C., 70 to 90° C., or 75 to 85° C. After the reaction, it is preferred to remove unreacted maleic anhydride by extraction from the viewpoint of suppressing side reactions.

[0044] 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.

[0045] 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. The solvent 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.

[0046] (Process 2)

[0047] Step 2 is a step of reacting a diamine compound with an acid anhydride group (succinic anhydride group) of the first modified styrene elastomer to obtain a second modified styrene elastomer having a group represented by the above formula (2). In step 2, it is preferred to react 2 equivalents of the diamine compound with 1 equivalent of the acid anhydride group of the first modified styrene elastomer. The reaction temperature may be 10 to 60° C., 15 to 50° C., 20 to 40° C., or 25 to 35° C. The group represented by formula (2) has a carboxyl group, an amide bond, and an amino group obtained by the reaction of the succinic anhydride group and the diamine compound.

[0048] The diamine compound is not particularly limited as long as it is a compound having two amino groups, and may be an aliphatic diamine or an aromatic diamine.

[0049] Examples of the aliphatic diamine include 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4′-methylenebiscyclohexylamine, polyoxypropylenediamine, and dimer diamine.

[0050] Examples of the aromatic diamine include 2'-methoxy-4,4'-diaminobenzanilide, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, dianilidefluorene, 2,2-bis-[4-(3-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)]biphenyl, bis[4-(3-aminophenoxy)phenyl]sulfone, Biphenyl, bis[1-(4-aminophenoxy)]biphenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[4-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)benzophenone, bis[4-(3-aminophenoxy)benzophenone, bis[4,4'-(4-aminophenoxy)benzanilide, bis[4,4'-(3-aminophenoxy)benzanilide, 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene, 9,9-bis[4-(3-aminophenoxy)phenyl] 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis-[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-methylenebis(2-ethyl-6-methylaniline), 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-2,6-xylidine, 4,4'-methylene-2,6-diethylaniline, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, benzidine, 3,3'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4"-diamino-p-terphenyl, 3,3"-diamino-p-terphenyl, m-phenylenediamine, p-phenylenediamine, 2,6-diaminopyridine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(1-methylethylidene)]dianiline, 4,4'-[1,3-phenylenebis(1-methylethylidene)]dianiline, bis(p-aminocyclohexyl)methane, bis(p-β-amino-tert-butylphenyl)ether, bis(p-β-methyl-δ-aminopentyl)benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis(β-amino-tert-butyl)toluene, 2,4-toluenediamine, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylene diamine, p-xylene diamine, 2,6-diaminopyridine, 2,5-diaminopyridine and 2,5-diamino-1,3,4-oxadiazole.

[0051] The diamine compound is preferably at least one selected from the group consisting of polyoxypropylenediamine, m-phenylenediamine, 2,4-toluenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-methylenebis(2-ethyl-6-methylaniline) and 2,2-bis(4-aminophenyl)hexafluoropropane, from the viewpoint of excellent solubility in an organic solvent and reactivity during synthesis.

[0052] (Process 3)

[0053] Step 3 is a step of reacting maleic anhydride with the amino group of the second modified styrene elastomer and then performing a dehydration cyclization reaction to obtain a third modified styrene elastomer having a group represented by the following formula (3). In step 3, one equivalent of maleic anhydride is reacted with one equivalent of the amino group of the second modified styrene elastomer and then performing a dehydration cyclization reaction to obtain a third modified styrene elastomer. The temperature for reacting maleic anhydride may be 10 to 60°C, 15 to 50°C, 20 to 40°C or 25 to 35°C. The dehydration cyclization reaction is preferably carried out by adding a catalyst and refluxing it in a solvent such as toluene or xylene. Examples of the catalyst include p-toluenesulfonic acid, benzenesulfonic acid and methanesulfonic acid.

[0054] It is believed that the maleimide-modified styrene elastomer involved in this embodiment is difficult to be hydrolyzed by moisture in the air due to the presence of a succinimide group, and therefore has excellent stability. In addition, by containing a polymerizable functional group, namely a maleimide group, it is reactive and can improve the heat resistance, strength and other properties of the cured product of the maleimide-modified styrene elastomer.

[0055] [Resin composition]

[0056] 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.

[0057] (Thermosetting resin)

[0058] 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.

[0059] 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.

[0060] (Curing accelerator)

[0061] 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.

[0062] (filler)

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] (Flame Retardant)

[0068] The flame retardant is not particularly limited, but 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.

[0069] 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.

[0070] 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., a mixing roller, an extruder, a kneader, a roller, an extruder, etc. are used for mixing, and then the obtained mixed material is cooled and crushed. In addition, there is no particular limitation on the mixing form.

[0071] [Resin film]

[0072] 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.

[0073] The method for preparing the resin film is not limited, and for example, the resin film can be obtained by drying a resin layer formed by coating the resin composition on a supporting substrate. Specifically, the resin composition can be coated on a supporting substrate using a kiss coater, a roll coater, a comma coater, etc., and then 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] [Prepreg]

[0078] 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.

[0079] 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.

[0080] [Laminated board]

[0081] 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.

[0082] 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.

[0083] [Multilayer printed circuit board]

[0084] 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.

[0085] 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.

[0086] 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.

[0087] Example

[0088] Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to the following examples.

[0089] (Example 1)

[0090] In a 1L flask equipped with a cooling tube, a nitrogen inlet tube, a thermocouple and a stirrer, 688 g of toluene and 150 g of a modified styrene elastomer having a group represented by formula (1) (manufactured by Asahi Kasei Corporation, product name "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 9.3 g of 2,2-bis(4-aminophenyl)hexafluoropropane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to 9.3 g of toluene, and the mixture was stirred for 1.0 hour. Then, 2.8 g of maleic anhydride (manufactured by FUJIFILM WakoPure Chemical Corporation) was added, and the mixture was further kept warm for 1.0 hour. After adding 0.53 g of p-toluenesulfonic acid, the temperature in the flask was raised to 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 maleimide-modified styrene elastomer (D-1) having a group represented by formula (3).

[0091] 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.

[0092] (Example 2)

[0093] 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.

[0094] 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.

[0095] (Example 3)

[0096] 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, 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 5.5g of 4,4'-diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to 5.5g of toluene, and 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 maleimide-modified styrene elastomer (D-3) having a group represented by formula (3).

[0097] 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.

[0098] (Example 4)

[0099] 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, 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 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. 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 maleimide-modified styrene elastomer (D-4) having a group represented by formula (3).

[0100] 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.

[0101] (Example 5)

[0102] In a 2 L flask equipped with a cooling tube, a nitrogen inlet tube, a thermocouple and a stirrer, 950 g of xylene, 100 g of a hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Corporation, product name "Tuftec H1041") and 8 g of maleic anhydride (manufactured by FUJIFILM Wako Pure Chemical Corporation) were placed, and stirred at 80°C for 0.5 hour, and then heated at 0.5 cm 3 / L flow rate was nitrogen bubbled for 1.0 hour. Then, 3 g of benzoyl peroxide (FUJIFILM Wako Pure Chemical Corporation) was added, nitrogen bubbled and stirred at 80°C for 6.0 hours to react. Unreacted maleic anhydride was extracted three times from the reaction solution with isopropanol, and after concentration, the solid content was vacuum dried at 70°C to obtain a modified styrene elastomer (M-1) having a group represented by formula (1) with a modification rate of 1.6%.

[0103] In a 2L flask, 150g of (M-1), 1200g of xylene and 133g of propylene glycol monomethyl ether (PGME) were added and stirred at 80°C for 1.0 hour. Then, the temperature in the flask was lowered to 30°C, and a solution of 5.8g of JEFFAMINE D230 dissolved in 26g of toluene and 26g of PGME was added dropwise, and stirred for 1.0 hour. After that, a solution of 2.5g of maleic anhydride was added to 22.5g of PGME, and the mixture was further kept warm for 1.0 hour. After adding 0.5g of p-toluenesulfonic acid, the temperature in the flask was raised to the reflux temperature (about 130°C), nitrogen was circulated, and a dehydration cyclization reaction was carried out for 3.0 hours to obtain a solution of a maleimide-modified styrene elastomer (D-5) having a group represented by formula (3).

[0104] The FT-IR spectrum of (D-5) 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-5). 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.

[0105] (Comparative Example 1)

[0106] In a 2 L flask equipped with a cooling tube, a nitrogen inlet tube, a thermocouple and a stirrer, 950 g of xylene, 100 g of a hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Corporation, product name "Tuftec H1041") and 29.2 g of a bismaleimide compound (manufactured by Daiwa Kasei Industrial Co., Ltd., product name "BMI-1000") were placed, and after stirring at 80°C for 0.5 hour, the mixture was heated at 0.5 cm 3 / L, nitrogen bubbling was performed for 1.0 hour. Next, 3 g of benzoyl peroxide (FUJIFILM Wako Pure Chemical Corporation) was added, nitrogen bubbling was performed at 80°C, and the mixture was stirred for 6.0 hours to react. The reaction solution gelled, and the maleimide-modified styrene elastomer could not be synthesized.

Claims

1. A method for producing a maleimide-modified styrene elastomer, comprising: A step of preparing a first modified styrene-based elastomer having a group represented by the following formula (1); a step of reacting a diamine compound with an acid anhydride group of the first modified styrene-based elastomer to obtain a second modified styrene-based elastomer having a group represented by the following formula (2); and a step of reacting maleic anhydride with the amino group of the second modified styrene elastomer and then performing a dehydration cyclization reaction to obtain a third modified styrene elastomer having a group represented by the following formula (3); In the formula, A 1 represents the residue of the diamine compound, and * represents a bonding portion.

2. The method for producing a maleimide-modified styrene-based elastomer according to claim 1, wherein: The diamine compound is at least one selected from the group consisting of polyoxypropylenediamine, metaphenylenediamine, 2,4-toluenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-methylenebis(2-ethyl-6-methylaniline) and 2,2-bis(4-aminophenyl)hexafluoropropane.

3. A maleimide-modified styrene-based elastomer obtained by reacting a modified styrene-based elastomer having a group represented by the following formula (1), a diamine compound and maleic anhydride, and has a group represented by the following formula (3), In the formula, A 1 represents the residue of the diamine compound, and * represents a bonding portion.

4. The maleimide-modified styrene-based elastomer according to claim 3, wherein The diamine compound is at least one selected from the group consisting of polyoxypropylenediamine, metaphenylenediamine, 2,4-toluenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-methylenebis(2-ethyl-6-methylaniline) and 2,2-bis(4-aminophenyl)hexafluoropropane.

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