WO2023243516A1 - Agent de durcissement réactif - Google Patents

Agent de durcissement réactif Download PDF

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Publication number
WO2023243516A1
WO2023243516A1 PCT/JP2023/021191 JP2023021191W WO2023243516A1 WO 2023243516 A1 WO2023243516 A1 WO 2023243516A1 JP 2023021191 W JP2023021191 W JP 2023021191W WO 2023243516 A1 WO2023243516 A1 WO 2023243516A1
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WIPO (PCT)
Prior art keywords
copolymer
mass
curing agent
reactive curing
resin composition
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PCT/JP2023/021191
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English (en)
Japanese (ja)
Inventor
達宏 松原
和希 西川
吉生 岡本
正 澤里
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デンカ株式会社
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Publication of WO2023243516A1 publication Critical patent/WO2023243516A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used

Definitions

  • the present invention relates to a reactive curing agent.
  • Copper clad laminates are known as printed circuit boards that electrically connect/insulate electronic components constituting a circuit and mechanically arrange/fix the components.
  • CCL involves impregnating glass fiber with a thermosetting resin composition containing epoxy resin or polyphenylene ether resin and a reactive curing agent to obtain prepreg, which is a semi-cured resin sheet. It is obtained by stacking multiple sheets sandwiched between copper foils and bonding them under heat.
  • styrene-maleic anhydride copolymer SMA is often used because of its low dielectric loss.
  • the present invention aims to provide a reactive curing agent that has improved solubility in methyl ethyl ketone (MEK) and can improve the heat resistance of a thermosetting resin composition.
  • MEK methyl ethyl ketone
  • a reactive curing agent containing a copolymer containing an aromatic vinyl monomer unit, an unsaturated acid anhydride monomer unit, and a maleimide monomer unit The weight average molecular weight of the copolymer is 10,000 or more and less than 90,000, and the copolymer has a weight average molecular weight of 10,000 or more and less than 90,000, and the copolymer has a weight average molecular weight of 100,000 or more and less than 90,000;
  • a reactive curing agent containing 3.0% by mass or more and less than 49.0% by mass of monomer units the solubility in MEK can be improved, and the thermosetting resin composition It has been found that it is possible to improve the heat resistance of.
  • a reactive curing agent containing a copolymer containing an aromatic vinyl monomer unit, an unsaturated acid anhydride monomer unit, and a maleimide monomer unit The weight average molecular weight of the copolymer is 10,000 or more and less than 90,000, The copolymer contains 3.0% by mass or more and less than 49.0% by mass of the maleimide monomer units when the total monomer units contained in the copolymer is 100% by mass. include, Reactive hardener. [2] The copolymer contains 3.0 to 30.0% by mass of the maleimide monomer units when the total of monomer units contained in the copolymer is 100% by mass. , The reactive curing agent according to [1].
  • the copolymer has 100% by mass of the total monomer units contained in the copolymer, 45.0 to 96.9% by mass of the aromatic vinyl monomer unit, Containing 0.1 to 25% by mass of the unsaturated acid anhydride monomer unit and 0.0 to 20.0% by mass of other monomer units,
  • the reactive curing agent according to [2].
  • the number of the unsaturated acid anhydride monomer units contained per molecular chain of the copolymer is 2 to 25.
  • the reactive curing agent according to any one of [1] to [3].
  • the copolymer has a glass transition temperature of 125 to 200°C.
  • the reactive curing agent according to any one of [1] to [4].
  • the copolymer has a weight average molecular weight of 15,000 to 80,000, The reactive curing agent according to any one of [1] to [5].
  • the copolymer has a weight average molecular weight of 20,000 to 70,000, The reactive curing agent according to any one of [1] to [5]. Regarding.
  • thermosetting resin composition By employing the reactive curing agent of the present invention, solubility in MEK is improved. Moreover, the heat resistance of the thermosetting resin composition can be improved. Therefore, it is suitably used in applications that require heat resistance, such as copper-clad laminates.
  • the reactive curing agent includes a copolymer containing an aromatic vinyl monomer unit, an unsaturated acid anhydride monomer unit, and a maleimide monomer unit.
  • the monomer units contained in the copolymer will be explained below.
  • aromatic vinyl monomer unit examples include styrene, o-methylstyrene, m-methylstyrene, p-methyl Examples include styrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, ⁇ -methylstyrene, ⁇ -methyl-p-methylstyrene, and the like. Among these, styrene is preferred from the viewpoint of solubility of the copolymer in MEK.
  • the aromatic vinyl monomer may be used alone, or two or more types may be used in combination.
  • the copolymer according to the present embodiment contains 45.0 to 96.9% by mass of aromatic vinyl monomer units when the total amount of monomer units contained in the copolymer is 100% by mass.
  • the content is preferably 45.0 to 89.9% by mass, still more preferably 55.0 to 85.0% by mass, and particularly preferably 60.0 to 80.0% by mass.
  • the content of aromatic vinyl monomer units is 45.0% by mass or more, the solubility of the copolymer in MEK will improve, and if it is 96.9% by mass or less, it will contribute to improving heat resistance. Since the copolymer can contain a larger amount of maleimide monomer units that can be used, the heat resistance of the thermosetting resin composition containing the copolymer is improved.
  • the content of aromatic vinyl monomer units is a value measured by 13 C-NMR.
  • the content of the aromatic vinyl monomer units means the total amount of the aromatic vinyl monomer units used together.
  • Examples of the unsaturated acid anhydride monomer from which the unsaturated acid anhydride monomer unit contained in the copolymer according to the present embodiment is derived include maleic anhydride, itaconic anhydride, and citraconic anhydride. and aconitic acid anhydride. Among these, maleic anhydride is preferred from the viewpoint of imparting curability to the thermosetting resin composition blended with the copolymer.
  • the unsaturated acid anhydride monomer may be used alone, or two or more types may be used in combination.
  • the copolymer according to the present embodiment contains 0.1 to 25% by mass of unsaturated acid anhydride monomer units when the total amount of monomer units contained in the copolymer is 100% by mass.
  • the content is preferably from 0.1 to 8.0% by mass, even more preferably from 0.1 to 6.0% by mass, particularly preferably from 0.1 to 4.0% by mass.
  • the content of the unsaturated acid anhydride monomer unit is 0.1% by mass or more, the curability of the thermosetting resin composition containing the copolymer will improve, and if the content is 25% by mass or less, The thermal stability of the copolymer and the moisture absorption resistance and thermal stability of the thermosetting resin composition blended with the copolymer are improved.
  • the content of unsaturated acid anhydride monomer units is a value measured by 13 C-NMR.
  • the content of the unsaturated acid anhydride monomer unit means the total amount of the unsaturated acid anhydride monomer unit used together.
  • maleimide monomer from which the maleimide monomer unit contained in the copolymer according to the present embodiment is derived examples include N-alkyl maleimide such as N-methylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide.
  • maleimide and N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, and N-tribromophenylmaleimide.
  • N-arylmaleimide is preferred from the viewpoint of thermal stability of the copolymer, and N-phenylmaleimide is more preferred.
  • the maleimide monomer may be used alone or in combination of two or more types.
  • a maleimide monomer unit for example, a copolymer obtained by copolymerizing a raw material consisting of an unsaturated acid anhydride monomer unit with other monomers is treated with ammonia or primary It can be imidized with an amine.
  • a raw material consisting of a maleimide monomer may be copolymerized with other monomers.
  • the copolymer according to this embodiment contains maleimide monomer units in an amount of 3.0% by mass or more and 49.0% by mass when the total amount of monomer units contained in the copolymer is 100% by mass.
  • the content is preferably 3.0 to 30.0% by weight, more preferably 14.0 to 28.0% by weight, and even more preferably 18.0 to 26.0% by weight.
  • 3.0, 5.0, 8.0, 10.0, 12.5, 15.0, 17.5, 20.0, 22.5, 25.0, 27.5 It is preferably 30.0, 35.0, 40.0, 45.0, 48.0, or 48.9% by mass, even if it is within the range between any two of the numerical values exemplified here. good.
  • the content of the maleimide monomer unit is 3.0% by mass or more, the heat resistance of the thermosetting resin composition containing the copolymer will improve, and if the content is less than 49.0% by mass, the copolymer will improve the heat resistance.
  • the solubility of the polymer in MEK is improved.
  • the content of maleimide monomer units is a value measured by 13 C-NMR.
  • the content of the maleimide monomer unit means the total amount of the maleimide monomer unit used in combination.
  • the copolymer according to this embodiment contains copolymerizable monomers other than aromatic vinyl monomers, unsaturated acid anhydride monomers, and maleimide monomers as other monomers. Copolymerization may be carried out within a range that does not impede the effects of the invention.
  • Other monomers that can be copolymerized with the copolymer according to this embodiment include vinyl cyanide monomers, acrylic acid ester monomers, methacrylic acid ester monomers, vinyl carboxylic acid monomers, and acrylic acid monomers. Examples include acid amide and methacrylic acid amide. Among these, vinyl cyanide monomers and methacrylic acid ester monomers are preferred from the viewpoint of affinity with epoxy resins.
  • Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, and fumaronitrile.
  • Examples of the acrylic ester monomer include methyl acrylic ester, ethyl acrylic ester, butyl acrylic ester, and the like.
  • Examples of the methacrylate monomer include methyl methacrylate and ethyl methacrylate.
  • Examples of vinyl carboxylic acid monomers include acrylic acid and methacrylic acid. Other monomers that can be copolymerized into the copolymer may be used alone, or two or more types may be used in combination.
  • Such other copolymerizable monomers can be copolymerized within a range that does not impede the effects of the present invention, but from the viewpoint of the balance between affinity with the epoxy resin and solubility in MEK, It is preferable to contain 0.0 to 20.0 mass % of other monomer units, more preferably 0.1 to 10.0 mass % when the total of monomer units contained in is 100 mass %. %, more preferably 0.5 to 5.0% by mass. Specifically, for example, it is preferably 0.0, 0.5, 1.0, 2.0, 5.0, 10.0, 15.0, or 20.0% by mass, and the It may be within a range between any two values.
  • the affinity with the epoxy resin is improved, and when it is 20.0% by mass or less, the solubility in MEK is improved.
  • the content of other monomer units is a value measured by 13 C-NMR.
  • it means the total amount of other monomer units used together.
  • the reactive curing agent according to the present embodiment may contain additives as described below within a range that does not impede the effects of the present invention.
  • heat stabilizers such as hindered phenol compounds, lactone compounds, phosphorus compounds, and sulfur compounds, and hindered amine compounds are added to the polymerization solution as necessary.
  • Compounds, light stabilizers such as benzotriazole compounds, lubricants, plasticizers, colorants, antistatic agents, mineral oil, and other additives may be added.
  • the amount added is preferably less than 0.2 parts by mass per 100 parts by mass of total monomer units. These additives may be used alone or in combination of two or more.
  • the polymerization mode of the copolymer contained in the reactive curing agent according to the present embodiment includes, for example, solution polymerization, bulk polymerization, and the like.
  • Solution polymerization is preferable from the viewpoint that a copolymer having a more uniform copolymer composition can be obtained by polymerizing while performing partial addition or the like.
  • the solvent for solution polymerization is non-polymerizable from the viewpoint that by-products are less likely to be produced and there are fewer adverse effects.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone
  • ethers such as tetrahydrofuran and 1,4-dioxane
  • aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, N,N-dimethylformamide, and dimethyl
  • sulfoxide N-methyl-2-pyrrolidone, etc.
  • methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of ease of solvent removal during devolatilization and recovery of the copolymer.
  • the polymerization process may be a continuous polymerization type, a batch type (batch type), or a semi-batch type.
  • the method for producing the copolymer according to the present embodiment is not particularly limited, but it can preferably be obtained by radical polymerization, and the polymerization temperature is preferably in the range of 80 to 150°C.
  • the polymerization initiator is not particularly limited, but includes known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, and azobismethylbutyronitrile, and benzoyl.
  • Peroxide t-butylperoxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethyl
  • organic peroxides such as hexanoate, di-t-butyl peroxide, dicumyl peroxide, and ethyl-3,3-di-(t-butylperoxy)butyrate can be used; You may use a species or a combination of two or more species.
  • the amount of the polymerization initiator used is not particularly limited, but it is preferably used in an amount of 0.1 to 1.5% by mass, more preferably 0.1 to 1.5% by mass based on 100% by mass of all monomer units. It is 1.0% by mass. It is preferable that the amount of the polymerization initiator used is 0.1% by mass or more because a sufficient polymerization rate can be obtained. When the amount of the polymerization initiator used is 1.5% by mass or less, the polymerization rate can be suppressed, so reaction control becomes easy and it becomes easy to obtain the target molecular weight.
  • a chain transfer agent can be used in the production of the copolymer according to this embodiment.
  • the chain transfer agent used is not particularly limited, but includes, for example, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, ⁇ -methylstyrene dimer, ethyl thioglycolate, limonene, terpinolene, etc. be.
  • the amount of chain transfer used is not particularly limited as long as the target molecular weight can be obtained, but it should be 0.01 to 2.0% by mass based on 100% by mass of all monomer units. It is preferably 0.1 to 1.5% by mass, and more preferably 0.1 to 1.5% by mass. If the amount of chain transfer agent used is 0.01% by mass to 1.2% by mass, the target molecular weight can be easily obtained.
  • a method for introducing the maleimide monomer unit into the copolymer As a method for introducing the maleimide monomer unit into the copolymer according to the present embodiment, a method of copolymerizing a maleimide monomer, an aromatic vinyl monomer, and other monomers (direct method) , or by copolymerizing an unsaturated acid anhydride monomer, aromatic vinyl monomer, or other monomer in advance, and then reacting the unsaturated acid anhydride group with ammonia or a primary amine.
  • post-imidization method There is a method of converting an unsaturated acid anhydride group into a maleimide monomer unit (post-imidization method). The post-imidization method is preferable because it reduces the amount of maleimide monomer remaining in the copolymer.
  • the primary amines used in the post-imidization method include, for example, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, and cyclohexyl.
  • Examples include amines, alkylamines such as decylamine, chloro- or bromine-substituted alkylamines, aromatic amines such as aniline, toluidine, and naphthylamine, and among these, aniline and cyclohexylamine are preferred.
  • These primary amines may be used alone or in combination of two or more.
  • the amount of primary amine added is not particularly limited, but is preferably 0.7 to 1.1 molar equivalent, more preferably 0.85 to 1.05 molar equivalent relative to the unsaturated acid anhydride group. It is. It is preferable that the amount is 0.7 molar equivalent or more based on the unsaturated acid anhydride monomer unit in the crude product raw material because the thermal stability of the copolymer will be good. Moreover, if it is 1.1 molar equivalent or less, it is preferable because the amount of primary amine remaining in the copolymer is reduced.
  • a catalyst may be used when introducing the maleimide monomer unit by the post-imidization method.
  • the catalyst can improve the dehydration ring closure reaction in the reaction between ammonia or a primary amine and an unsaturated acid anhydride group, particularly in the reaction of converting an unsaturated acid anhydride group into a maleimide group.
  • the type of catalyst is not particularly limited, for example, a tertiary amine can be used.
  • Tertiary amines are not particularly limited, but include, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, and the like.
  • the amount of the tertiary amine added is not particularly limited, it is preferably 0.01 molar equivalent or more based on the unsaturated acid anhydride group.
  • the temperature of the imidization reaction in the present invention is preferably 100 to 250°C, more preferably 120 to 200°C. If the temperature of the imidization reaction is 100° C. or higher, the reaction rate is sufficiently high and it is preferable from the viewpoint of productivity. It is preferable that the temperature of the imidization reaction is 250° C. or lower because it is possible to suppress deterioration of physical properties due to thermal deterioration of the copolymer.
  • the method for removing volatile components such as the solvent used for solution polymerization and unreacted monomers from the solution after solution polymerization of the copolymer or from the solution after post-imidization is a known method.
  • a vacuum devolatilization tank equipped with a heater or a devolatilization extruder equipped with a vent can be used.
  • the devolatilized copolymer in a molten state is transferred to the granulation process, extruded into strands from a multi-hole die, and can be processed into pellets using a cold cut method, an air hot cut method, or an underwater hot cut method. .
  • the obtained pellets can be processed into a powdered copolymer by passing through a pulverization process.
  • Forming the copolymer into a powder has the advantage of increasing its dissolution rate when blended into a thermosetting resin composition.
  • the extruded copolymer may be recovered and pulverized to form a powder without going through the step of pelletizing.
  • Suitable crushing devices include rotary blade crusher, turbo mill crusher, turbo disk mill crusher, turbo cutter crusher, jet mill crusher, impact crusher, hammer crusher, and vibration crusher. There are type crushers, etc.
  • the weight average molecular weight (Mw) of the copolymer according to this embodiment is 10,000 or more and less than 90,000, preferably 15,000 to 80,000, more preferably 20,000 to 70,000, More preferably, it is 30,000 to 70,000. Specifically, for example, it is preferably 1, 2, 3, 4, 5, 6, 7, 8, or 89,000, and is within the range between any two of the numerical values exemplified here. Good too. If the weight average molecular weight (Mw) of the copolymer is 10,000 or more, the amount of chain transfer agent used in the copolymerization process is reduced, so the amount of VOC contained in the resulting copolymer can be reduced.
  • the solubility of the copolymer in MEK can be improved.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the copolymer is a polystyrene equivalent value measured by gel permeation chromatography (GPC), and can be measured, for example, under the following conditions.
  • Equipment name SYSTEM-21 Shodex (manufactured by Showa Denko K.K.) Column: 3 PL gel MIXED-B in series Temperature: 40°C Detection: Differential refractive index
  • Solvent Tetrahydrofuran Concentration: 2% by mass Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL).
  • the number average molecular weight (Mn) of the copolymer according to this embodiment is preferably 10,000 to 40,000, more preferably 20,000 to 40,000. Specifically, for example, it is preferably 1, 2, 3, or 40,000, and may be within a range between any two of the numerical values exemplified here. If the number average molecular weight (Mn) of the copolymer is 10,000 or more, the amount of chain transfer agent used in the copolymerization process is reduced, so the amount of VOC contained in the resulting copolymer can be reduced.
  • the solubility of the copolymer in MEK and the curability of the thermosetting resin composition blended with the copolymer can be improved.
  • To control the number average molecular weight (Mn) of the copolymer there are methods such as adjusting the polymerization temperature, polymerization time, and amount of polymerization initiator added, as well as adjusting the solvent concentration and the amount of chain transfer agent added.
  • the number average molecular weight (Mn) of the copolymer is a polystyrene equivalent value measured by gel permeation chromatography (GPC), and can be measured under the same conditions as the weight average molecular weight (Mw) described above, for example. .
  • the number of unsaturated acid anhydride monomer units per molecular chain of the copolymer according to this embodiment is preferably 2 to 25, more preferably 3 to 16, and more preferably 4 to 12. It is more preferable that Specifically, the number of unsaturated acid anhydride monomer units per molecular chain of the copolymer is, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 , 15, 20, or 25, and may be within a range between any two of the numerical values exemplified here.
  • the curability of the thermosetting resin composition containing the copolymer will improve; If it exists, the balance between the thermal decomposability of the copolymer and the curability of the thermosetting resin composition containing the copolymer will be improved.
  • the number of unsaturated acid anhydride monomer units per molecular chain of the copolymer for example, the content of unsaturated acid anhydride monomer units in the copolymer and the number of unsaturated acid anhydride monomer units per molecular chain of the copolymer can be controlled. There are methods such as adjusting the number average molecular weight (Mn) of the coalescence.
  • the glass transition temperature (Tg) of the copolymer according to this embodiment is preferably 125°C to 200°C, more preferably 130°C to 190°C, and even more preferably 135°C to 180°C. preferable. Specifically, for example, it is preferably 125, 130, 135, 140, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, or 200°C, and any of the values exemplified here. or within a range between the two.
  • the glass transition temperature (Tg) of the copolymer is 125°C or higher, the heat resistance of the thermosetting resin composition containing the copolymer will improve, and if it is 200°C or lower, the copolymer will become MEK. can improve the solubility of
  • the glass transition temperature (Tg) of the copolymer can be controlled, for example, by adjusting the content of maleimide monomer units contained in the copolymer and the weight average molecular weight of the copolymer.
  • the glass transition temperature is an intermediate glass transition temperature (Tmg) measured by DSC in accordance with JIS K-7121, and is a measured value under the measurement conditions described below.
  • the amount of residual aromatic vinyl monomer in the copolymer according to the present embodiment is preferably 0 to 500 ppm, more preferably 0 to 400 ppm, and even more preferably 0 to 300 ppm. Specifically, for example, it is preferably 1, 50, 100, 150, 200, 250, 300, 350, 400, 450, or 50 ppm or less. If the amount of residual aromatic vinyl monomer in the copolymer is 500 ppm or less, the amount of VOC contained in the copolymer can be reduced.
  • the amount of residual maleimide monomer in the copolymer according to the present embodiment is preferably 0 to 500 ppm, more preferably 0 to 400 ppm, and even more preferably 0 to 300 ppm. Specifically, for example, it is preferably 1, 50, 100, 150, 200, 250, 300, 350, 400, 450, or 500 ppm or less. If the amount of residual maleimide monomer in the copolymer is 500 ppm or less, the amount of VOC contained in the copolymer can be reduced. The amount of maleimide monomer remaining in the copolymer is measured under the following conditions.
  • GC-2010 manufactured by Shimadzu Corporation
  • Temperature-rising analysis is performed at a column temperature of 80°C (initial). (Temperature rising analysis conditions) 80°C: Hold for 12 minutes
  • 80-280°C Increase temperature at 20°C/min for 10 minutes
  • 280°C Hold for 10 minutes
  • FID Procedure Dissolve 0.5 g of sample in 5 ml of 1,2-dichloroethane solution (0.014 g/L) containing undecane (internal standard substance).
  • the amount of residual maleimide monomer in the copolymer can be reduced, for example, by employing a post-imidization method in the production of the copolymer.
  • the copolymer according to this embodiment has excellent thermal stability.
  • the thermal stability of a copolymer is an index evaluated by the 5% mass reduction temperature by thermogravimetric analysis (TGA), and is a value measured at a heating rate of 5°C/min in a nitrogen atmosphere. be. If the copolymer has a high 5% mass reduction temperature by thermogravimetric analysis (TGA) and has excellent thermal stability, the reactive curing agent containing the copolymer also has excellent thermal stability. Become something.
  • the copolymer according to this embodiment has excellent solubility in ethyl methyl ketone (MEK).
  • MEK ethyl methyl ketone
  • the solubility of the copolymer in MEK is defined as the weight percent concentration (wt%) of the MEK solution in which the maximum amount of copolymer that can be dissolved in 10 g of MEK at 23 ° C. It is. Specifically, a predetermined amount of the copolymer is added to MEK in three portions at 23° C., and the copolymer is dissolved by stirring.
  • the second addition of the copolymer is carried out 1 hour after the first addition of the copolymer
  • the third addition of the copolymer is carried out 1 hour after the second addition of the copolymer.
  • confirm that all added copolymer is completely dissolved within 4 hours. Varying the predetermined amount of copolymer to be dissolved, determining the maximum amount of copolymer that can be dissolved, and calculating the weight percent concentration (wt%) of the MEK solution when the maximum amount of copolymer is dissolved. do.
  • the copolymer according to this embodiment has excellent solubility in ethyl methyl ketone (MEK), and therefore, the reactive curing agent obtained by blending the copolymer also has excellent solubility in MEK. Become something. Therefore, when the reactive curing agent according to the present embodiment is used as a reactive curing agent in a thermosetting resin composition impregnated into glass fibers, for example, in the production of prepreg for copper clad laminates (CCL), In addition, the amount of copolymer blended into the thermosetting resin composition can be increased. If the amount of the copolymer added to the thermosetting resin composition increases, the properties of the various monomer units contained in the copolymer can be utilized to improve the properties of the thermosetting resin composition, such as heat resistance.
  • MEK ethyl methyl ketone
  • solubility in MEK when the solubility in MEK is excellent, it can be expected that the solubility in solvents other than MEK used in the production of CCL, such as acetone, toluene, and cyclohexanone, is also excellent.
  • thermosetting resin composition can be obtained by blending the reactive curing agent according to this embodiment with a thermosetting resin.
  • a thermosetting resin for example, a resin that is impregnated into glass fibers in the production of a prepreg for a copper clad laminate (CCL) can be used, and examples thereof include epoxy resin, cyanate resin, bismaleimide resin, and the like.
  • the thermosetting resin composition may contain other resins, additives, etc. as necessary.
  • thermosetting resin composition obtained by blending the reactive curing agent according to the present embodiment includes butadiene rubber, isoprene rubber, acrylate rubber, Graft copolymers containing these and elastomers such as hydrogenated products of the graft copolymers may be blended within a range that does not impair the effects of the present invention.
  • a curing agent such as a styrene-maleic anhydride copolymer according to the present invention is added to the thermosetting resin composition obtained by blending the reactive curing agent according to the present embodiment for the purpose of improving curability. It may be added to the reactive curing agent to the extent that it does not impair the effects of the present invention. Furthermore, for the purpose of accelerating the curing properties of the curing agent, an amine curing accelerator, an imidazole curing accelerator, a phosphorus curing accelerator, etc. may be blended within a range that does not impair the effects of the present invention.
  • phosphate ester flame retardants such as tricresyl phosphate and triphenyl phosphate, red phosphorus, antimony trioxide, aluminum hydroxide, and hydroxide are added.
  • Flame retardants such as inorganic substances such as magnesium may be added to the extent that the effects of the present invention are not impaired.
  • inorganic fillers such as silica, mica, talc, short glass fibers, fine glass powder, and hollow glass may be blended within the range that does not impair the effects of the present invention. It's okay.
  • thermosetting resin composition is obtained by dissolving the reactive curing agent according to the present embodiment, the thermosetting resin, and other resins and additives in an organic solvent, and then mixing the mixture.
  • organic solvents include ketones such as MEK, cyclohexanone, and methyl isobutyl ketone.
  • thermosetting resin composition obtained by blending the reactive curing agent with this embodiment has excellent heat resistance.
  • the heat resistance of the thermosetting resin composition is a property evaluated by the glass transition temperature (Tg) measured by DSC in accordance with JIS C 6481.
  • the glass transition temperature (Tg) is an intermediate glass transition temperature (Tmg), and is a value measured under the measurement conditions described below.
  • thermosetting resin composition obtained by blending the reactive curing agent according to the present embodiment employs a reactive curing agent with improved solubility in MEK.
  • the amount of reactive curing agent that can be blended increases. Since the reactive curing agent according to the present embodiment contains a maleimide monomer unit that can contribute to improving the heat resistance of the thermosetting resin composition, as a result, the heat resistance of the thermosetting resin composition is improved. is excellent.
  • thermosetting resin composition obtained by this process has excellent heat resistance.
  • the thermosetting resin composition obtained by blending the reactive curing agent according to the present embodiment employs a reactive curing agent with improved solubility in MEK. The amount of reactive curing agent that can be blended increases. Therefore, it is possible to reduce the amount of the styrene-maleic anhydride copolymer used in combination with the thermosetting resin composition.
  • thermosetting resin composition Since the styrene-maleic anhydride copolymer has a lower glass transition temperature than the reactive curing agent according to this embodiment, the amount added to the thermosetting resin composition can be reduced, resulting in a thermosetting resin.
  • the composition has excellent heat resistance.
  • thermosetting resin composition obtained by blending the reactive curing agent with the present embodiment can also be made to have excellent curability by adjusting the number average molecular weight of the copolymer.
  • the curability of a thermosetting resin composition is a property evaluated by the degree of resin curing calculated by measuring the glass transition temperature (Tg) by the TMA method under the following measurement conditions in accordance with JIS C 6481. Device name: Q400 manufactured by T.A. Instrument Japan Co., Ltd. Temperature increase rate: 5°C/min
  • the thermosetting resin composition obtained by blending the reactive curing agent according to this embodiment employs a reactive curing agent with improved solubility in MEK.
  • the reactive curing agent according to the present embodiment contains an unsaturated acid anhydride monomer unit that can react with the thermosetting resin in the thermosetting resin composition. can improve the curability of
  • the cured product of the thermosetting resin composition obtained by blending the reactive curing agent according to the present embodiment has moisture absorption resistance by reducing the amount of unsaturated acid anhydride monomer units in the copolymer. It is also possible to use a material with excellent properties.
  • the moisture absorption resistance of a cured product of a thermosetting resin composition is a property evaluated by water absorption rate measured in accordance with JIS C 6481.
  • thermosetting resin composition obtained by blending the reactive curing agent according to this embodiment is MEK Since a reactive curing agent with improved solubility in the thermosetting resin composition is used, the amount of reactive curing agent that can be blended into the thermosetting resin composition increases. Therefore, it is possible to reduce the amount of the styrene-maleic anhydride copolymer used in combination with the thermosetting resin composition.
  • the styrene-maleic anhydride copolymer has higher hygroscopicity than the reactive curing agent according to this embodiment, it is possible to reduce the amount of the styrene-maleic anhydride copolymer to be added to the thermosetting resin composition. Excellent moisture absorption resistance.
  • St styrene
  • AN acrylonitrile
  • NPMI N-phenylmaleimide
  • MAH maleic anhydride
  • MEK methyl ethyl ketone
  • Example 1 Synthesis of copolymer (P-1)> 83 parts by mass of styrene, 1 part by mass of maleic anhydride, 0.6 parts by mass of ⁇ -methylstyrene dimer, and 26 parts by mass of methyl ethyl ketone were placed in an autoclave with a capacity of approximately 120 liters equipped with a stirrer, and the gas phase was heated with nitrogen gas. After the substitution, the temperature was raised to 92° C. over 40 minutes while stirring.
  • the imidization reaction solution was put into a vent type screw extruder, and volatile components were removed to obtain a pellet-shaped copolymer.
  • the obtained pellets were pulverized using a rotary blade type pulverizer to obtain a powdery copolymer (P-1).
  • P-1 powdery copolymer
  • Table 1 shows the analysis results of the obtained copolymer (P-1).
  • composition analysis of the copolymer (P-1) was carried out by 13 C-NMR method under the measurement conditions described below.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the copolymer (P-1) are polystyrene equivalent values measured by gel permeation chromatography (GPC), and were measured under the following conditions.
  • GPC gel permeation chromatography
  • Equipment name SYSTEM-21 Shodex (manufactured by Showa Denko K.K.) Column: 3 PL gel MIXED-B in series Temperature: 40°C Detection: Differential refractive index Solvent: Tetrahydrofuran Concentration: 2% by mass Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL).
  • N Number of unsaturated acid anhydride monomer units per molecular chain of copolymer
  • the number (N) of unsaturated acid anhydride monomer units per molecular chain of the copolymer (P-1) is the total number of monomer units contained in the copolymer (P-1).
  • N (A/100) ⁇ Mn/98 Formula (1)
  • the glass transition temperature of the copolymer (P-1) is the intermediate glass transition temperature (Tmg) measured by DSC in accordance with JIS K-7121, and was measured under the measurement conditions described below.
  • solubility in MEK is determined by the weight percent concentration (wt%) of an MEK solution in which the maximum amount of copolymer (P-1) that can be dissolved in 10 g of MEK at 23°C is ) was evaluated. At 23° C., a predetermined amount of copolymer (P-1) was added to 10 g of MEK in three portions, and the copolymer was dissolved by stirring. At this time, the second addition of the copolymer (P-1) was carried out 1 hour after the first addition of the copolymer (P-1), and the second addition of the copolymer (P-1) was carried out.
  • Thermal stability of copolymer> The 5% mass reduction temperature of the copolymer (P-1) by thermogravimetric analysis (TGA) was measured at a heating rate of 5° C./min under a nitrogen atmosphere.
  • copolymer (P-17) For the copolymer (P-17), styrene, maleic anhydride, N-phenylmaleimide, ⁇ -methylstyrene dimer, and methyl ethyl ketone are first charged into an autoclave. After the polymerization is completed, the imidization reaction is not performed, and the polymerization reaction solution is charged into a vent type screw extruder to remove volatile components to obtain a pellet-shaped copolymer. The obtained pellets are pulverized using a rotary blade type pulverizer to obtain a powdery copolymer (P-17).
  • the imidization reaction solution after the reaction is put into a vent-type screw extruder to remove volatile components, and then the copolymers are recovered without going through the pelletization process. .
  • the recovered copolymer is pulverized using a rotary blade type pulverizer to obtain a powdered copolymer.
  • the composition and properties of copolymers (P-2) to (P-24) are measured by the same method as for copolymer (P-1).
  • the compositions and properties of copolymers (P-2) to (P-24) are shown in Tables 1 and 2.
  • the recovered copolymer is pulverized using a rotary blade type pulverizer to obtain a powdered copolymer.
  • the composition and physical properties of copolymers (PB-1) to (PB-9) are measured in the same manner as for copolymer (P-1).
  • Table 3 shows the composition and physical properties of copolymers (PB-1) to (PB-9).
  • the amounts of the copolymer as a reactive curing agent and the styrene-maleic anhydride copolymer as a curing agent to be used together are adjusted so that the total amount of the two curing agents is 10 g.
  • the copolymer is mixed according to the value of the weight percent concentration
  • the amount Y (unit: g) of the polymer and the amount Z (unit: g) of the styrene-maleic anhydride copolymer are adjusted as follows.
  • the glass transition temperature (Tg) is an intermediate glass transition temperature (Tmg), and is a value measured under the measurement conditions described below.
  • Device name Robot DSC6200 manufactured by Seiko Instruments Co., Ltd. Temperature rising rate: 10°C/min Evaluation criteria A (very good): Over 180°C B (excellent): Over 175°C, below 180°C C (good): Over 170°C, below 175°C D (slightly poor) : 160°C or higher, 170°C or lower E (poor): Below 160°C Table 1 shows the heat resistance of epoxy resin compositions (R-1) to (R-24) and (RB-1) to (RB-9). It is shown in Table 3.
  • ⁇ Curability of epoxy resin composition The curability of the epoxy resin composition is evaluated by the following method.
  • - Sample preparation method The epoxy resin composition is spread on a Kapton film, heated and dried at 160° C. for 10 minutes, and the solid content is taken out by a casting method to obtain a sample before hardening. Next, using this solid content, pressing is performed for 90 minutes at a pressure of 25 kg/cm 2 and a temperature of 185° C. to obtain a cured sample.
  • ⁇ Measurement method of curing property In accordance with JIS C 6481, the degree of resin curing is calculated by measuring the glass transition temperature (Tg) using the TMA method.Device name: Manufactured by TA Instruments Japan Co., Ltd.
  • ⁇ Moisture absorption resistance of cured product of epoxy resin composition The moisture absorption resistance of the cured product of the epoxy resin composition is evaluated by the following method. - Sample preparation method: Spread the epoxy resin composition on Kapton film, heat and dry at 160°C for 10 minutes, and remove the solid content by casting. Next, using this solid content, pressing is performed for 90 minutes at a pressure of 25 kg/cm 2 and a temperature of 185° C. to obtain a resin plate.
  • the reactive curing agent since a copolymer with improved solubility in MEK is used as the reactive curing agent, a larger amount of the copolymer is added to the epoxy resin composition. It can be added to things. Therefore, the heat resistance of the epoxy resin composition is improved due to the maleimide monomer unit contained in the copolymer.
  • the reactive curing agent according to this embodiment can be obtained by blending the reactive curing agent according to the example.
  • the epoxy resin composition has improved heat resistance.
  • the curability of the epoxy resin composition is improved.
  • an epoxy resin composition containing a reactive curing agent in which the composition of the monomer units contained in the copolymer is appropriately adjusted by blending a larger amount of the copolymer into the epoxy resin composition, the amount of the styrene-maleic anhydride copolymer, which is another curing agent used in combination, can be reduced, and the moisture absorption resistance of the cured product of the epoxy resin composition is improved.
  • the reactive curing agent according to the comparative example has poor performance in at least one of solubility in MEK and improvement in heat resistance of the epoxy resin composition when blended into the epoxy resin composition.
  • the present invention provides a reactive curing agent that has improved solubility in methyl ethyl ketone (MEK) and can improve the heat resistance of a thermosetting resin composition.
  • MEK methyl ethyl ketone
  • the copolymer contained in the reactive curing agent of the present invention can be suitably used as a heat resistance imparting agent that imparts heat resistance to ABS and other resins, or as a compatibilizer for polymer alloys. be done.

Abstract

L'invention concerne un agent de durcissement réactif qui présente une solubilité améliorée dans la méthyléthylcétone et qui peut améliorer la résistance à la chaleur de compositions de résine thermodurcissable.　La présente invention concerne un agent de durcissement réactif comprenant un copolymère contenant un motif monomère à base de vinyle aromatique, un motif monomère anhydride d'acide insaturé et un motif monomère à base de maléimide, le copolymère présentant un poids moléculaire moyen en poids de 10 000 ou plus et inférieur à 90 000 et contenant 3,0 % en masse ou plus et moins de 49,0 % en masse du motif monomère à base de maléimide lorsque la quantité totale des motifs monomères constituant le copolymère est prise comme 100 % en masse.
PCT/JP2023/021191 2022-06-14 2023-06-07 Agent de durcissement réactif WO2023243516A1 (fr)

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JP2001019744A (ja) * 1999-06-30 2001-01-23 Ind Technol Res Inst エポキシ樹脂に使用するための硬化剤
WO2003087230A1 (fr) * 2002-04-16 2003-10-23 Hitachi Chemical Co., Ltd. Composition de resine thermodurcissable, preimpregne et feuille stratifiee utilisant cette composition.
JP2005008847A (ja) * 2003-05-28 2005-01-13 Jsr Corp 硬化性樹脂組成物、保護膜および保護膜の形成方法
JP2005281445A (ja) * 2004-03-29 2005-10-13 Jsr Corp 熱硬化性組成物、固体撮像素子のハレーション防止膜およびその形成方法、ならびに固体撮像素子
JP2007056151A (ja) * 2005-08-25 2007-03-08 Showa Highpolymer Co Ltd エチレン性不飽和基含有マレイミド系樹脂およびその製造方法、ならびにエチレン性不飽和基含有マレイミド系樹脂を含む光硬化性組成物および光・熱硬化性組成物
JP2008133353A (ja) * 2006-11-28 2008-06-12 Hitachi Chem Co Ltd 熱硬化性樹脂組成物、この樹脂組成物を用いたプリプレグ及び積層板
WO2010082617A1 (fr) * 2009-01-16 2010-07-22 電気化学工業株式会社 Copolymère de maléimide, procédé de production du copolymère et compositions de résine thermorésistantes contenant ledit copolymère
WO2022234829A1 (fr) * 2021-05-06 2022-11-10 日本化薬株式会社 Résine de maléimide, composition de résine durcissable et produit durci associé

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001019744A (ja) * 1999-06-30 2001-01-23 Ind Technol Res Inst エポキシ樹脂に使用するための硬化剤
WO2003087230A1 (fr) * 2002-04-16 2003-10-23 Hitachi Chemical Co., Ltd. Composition de resine thermodurcissable, preimpregne et feuille stratifiee utilisant cette composition.
JP2005008847A (ja) * 2003-05-28 2005-01-13 Jsr Corp 硬化性樹脂組成物、保護膜および保護膜の形成方法
JP2005281445A (ja) * 2004-03-29 2005-10-13 Jsr Corp 熱硬化性組成物、固体撮像素子のハレーション防止膜およびその形成方法、ならびに固体撮像素子
JP2007056151A (ja) * 2005-08-25 2007-03-08 Showa Highpolymer Co Ltd エチレン性不飽和基含有マレイミド系樹脂およびその製造方法、ならびにエチレン性不飽和基含有マレイミド系樹脂を含む光硬化性組成物および光・熱硬化性組成物
JP2008133353A (ja) * 2006-11-28 2008-06-12 Hitachi Chem Co Ltd 熱硬化性樹脂組成物、この樹脂組成物を用いたプリプレグ及び積層板
WO2010082617A1 (fr) * 2009-01-16 2010-07-22 電気化学工業株式会社 Copolymère de maléimide, procédé de production du copolymère et compositions de résine thermorésistantes contenant ledit copolymère
WO2022234829A1 (fr) * 2021-05-06 2022-11-10 日本化薬株式会社 Résine de maléimide, composition de résine durcissable et produit durci associé

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