(19)
(11)EP 2 690 121 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
10.06.2020 Bulletin 2020/24

(21)Application number: 12761336.2

(22)Date of filing:  22.03.2012
(51)International Patent Classification (IPC): 
C08L 63/04(2006.01)
C08G 59/32(2006.01)
C08K 5/21(2006.01)
C08J 5/24(2006.01)
C08L 63/00(2006.01)
(86)International application number:
PCT/JP2012/057300
(87)International publication number:
WO 2012/128308 (27.09.2012 Gazette  2012/39)

(54)

EPOXY RESIN COMPOSITION, PREPREG, FIBER-REINFORCED COMPOSITE MATERIAL, AND HOUSING FOR ELECTRICAL OR ELECTRONIC EQUIPMENT

EPOXIDHARZZUSAMMENSETZUNG, PREPREG, FASERVERSTÄRKTES VERBUNDMATERIAL UND GEHÄUSE FÜR ELEKTRONISCHE UND ELEKTRISCHE KOMPONENTEN

COMPOSITION DE RÉSINE ÉPOXY, PRÉ-IMPRÉGNÉ, MATIÈRE COMPOSITE RENFORCÉE PAR DES FIBRES, ET BOÎTIER POUR UN ÉQUIPEMENT ÉLECTRIQUE OU ÉLECTRONIQUE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 22.03.2011 JP 2011062751

(43)Date of publication of application:
29.01.2014 Bulletin 2014/05

(73)Proprietor: Mitsubishi Chemical Corporation
Tokyo 100-8251 (JP)

(72)Inventors:
  • TOMIOKA Masao
    Toyohashi-shi Aichi 440-8601 (JP)
  • KANEKO Manabu
    Toyohashi-shi Aichi 440-8601 (JP)
  • HAGIWARA Miyuki
    Toyohashi-shi Aichi 440-8601 (JP)

(74)Representative: Hoffmann Eitle 
Patent- und Rechtsanwälte PartmbB Arabellastraße 30
81925 München
81925 München (DE)


(56)References cited: : 
WO-A1-2005/082982
WO-A1-2010/140351
JP-A- 11 166 035
WO-A1-2010/109957
JP-A- 11 124 489
JP-A- 2008 214 547
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    TECHNICAL FIELD



    [0001] The present invention relates to an epoxy resin composition, a prepreg, a fiber-reinforced composite material, and a housing for electronic/electrical devices. The present application is based upon and claims the benefit of priority to Japanese Patent Application No. 2011-062751, filed March 22, 2011.

    BACKGROUND ART



    [0002] Composite materials of resin and reinforcing fiber are used for various purposes because of their excellent properties such as light weight, rigidity and impact resistance. Especially, since carbon-fiber-reinforced composite materials are lightweight with highly strong and rigid features, they are used for a wide range of purposes, for example, sports/leisure applications such as fishing rods and golf shafts, industrial applications such as automobiles and aircraft, and so on. In recent years, since carbon fibers have magnetic wave shielding properties in addition to mechanical characteristics, carbon-fiber-reinforced composite materials are also used as housing for electronic/electrical devices such as laptop computers.

    [0003] Flame retardance is one of the various properties expected when fiber-reinforced composite materials are used. For example, when used as housing for electronic/electrical devices, flame retardance is required in consideration of the potential for fire caused by heat generated in a device.

    [0004] For setting fiber-reinforced composite material to be flame retardant, methods for adding brominated epoxy resin to the matrix resin have been widely employed. However, considering the toll on humans and the environment from toxic substances generated when resin compositions containing halogen are burnt, methods such as adding red phosphorus or phosphate compounds to epoxy resin (for example, patent publication 1), and adding phosphazene compounds to epoxy resin, for example, have been mainly employed recently as a way for obtaining flame retardance without using brominated epoxy resin. However, those methods have problems: 1) mechanical strength decreases when the amount of added substances increases; 2) storage stability is low; 3) red phosphorus, phosphate and phosphazene compounds seep out (bleed out) gradually over a long period; 4) hydrolysis of red phosphorus or phosphate compounds occurs easily; and 5) when the amount of added phosphate compounds or phosphazene compounds is large, the glass transition temperature (Tg) of cured material of the matrix resin is lowered, and the heat resistance of the cured material decreases. Accordingly, using the above methods, flame-retardant properties can be added to fiber-reinforced composite materials only to a certain degree, and their stability is low. Especially, considering the problem described in 4) above, it is difficult to apply such a method of using red phosphorus or phosphate compounds in the field of printed wiring boards or electronic materials where high insulation and water resistance are required.

    [0005] To form a fiber-reinforced composite material, a method of using prepreg, which is an intermediate material formed by impregnating reinforcing fiber with thermosetting resin, is usually employed. A molded article made from fiber-reinforced composite material is obtained, for example, after the prepreg is cut and molded into a desired shape, and then is thermally cured in a die.

    [0006] Epoxy-resin-based prepreg containing epoxy resin as a thermosetting resin is widely used. Since epoxy resin is hard to cure by itself, it is usually formulated with a curing agent or curing accelerator. However, even when formulated with the curing agent or curing accelerator, since the molding time is long (duration until the curing process is completed) for epoxy-resin-based prepreg, it is difficult to apply the prepreg to members requiring mass production such as automobile parts.

    [0007] On the other hand, performing press molding at elevated temperatures and pressures is known as a high-cycle molding method with high productivity and is widely employed in automobile applications. In such a press molding, methods such as raising the molding temperature to reduce the curing time are employed to further enhance productivity. However, if the molding temperature is raised to be at least approximately 20°C higher than the glass transition temperature (Tg) of the material to be cured, such a procedure results in a soft cured article. When the cured article is taken out from the molding die under such conditions, deformation or the like may cause problems. Therefore, it is necessary to cool the molding die before taking out the cured article from the die, which is not preferable considering the high-cycle aspect.

    [0008] As epoxy-resin compositions capable of curing in a shorter period of time at lower temperatures, patent publication 2 discloses an epoxy-resin composition made of epoxy resin, an amine compound containing at least one sulfur atom in the molecule and/or a reacted product of epoxy resin and an amine compound containing at least one sulfur atom in the molecule, a urea compound, and dicyandiamide, along with prepreg produced made of such an epoxy-resin composition. Also disclosed in patent publication 2 is a method for forming fiber-reinforced composite material by press-molding the prepreg. As for urea compounds, 3-(3,4-dichlorophenyl)-1,1-dimethylurea or phenyl dimethyl urea is used.

    [0009] However, more improvements should be made regarding the curability of the epoxy-resin composition above. In addition, the Tg of the obtained cured product is low, and its heat resistance needs to be improved.

    PRIOR ART PUBLICATION


    PATENT PUBLICATION



    [0010] Patent Publication 1: International Patent Publication Pamphlet 2005/082982

    SUMMARY OF THE INVENTION


    PROBLEM(S) TO BE SOLVED BY THE INVENTION



    [0011] The present invention was carried out considering the above problems. Its objective is to provide an epoxy-resin composition and prepreg for producing fiber-reinforced composite material which exhibits excellent curability and has excellent heat resistance and flame retardance, as well as to provide fiber-reinforced composite materials produced using the prepreg and to provide housing for electronic/electrical devices.

    SOLUTION(S) TO THE PROBLEM(S)



    [0012] The present invention is characterized by the following.
    1. [1] An epoxy-resin composition containing component (A), component (B), component (C) and component (D) described below:

      the component (A): a phosphorus compound;

      the component (B): an epoxy resin which has at least three epoxy groups in the molecule, and which does not correspond to component (A) nor includes component (A);

      the component (C): an epoxy resin curing agent which does not have a urea structure in the molecule; and

      the component (D):

      wherein, the ratio of the amount of substance of a urea group derived from component (D) to the amount of phosphorus atoms derived from component (A) (urea equivalent to phosphorus) is in the range of 0.25 or higher to 1.85 or lower, and

      the amount of component (A) to 100 parts by mass of the amount of the rest of the epoxy-resin composition that excludes component (A) is 7parts by mass or greater,

      the component (A): a phosphorus compound,

      the component (B): an epoxy resin which has at least three epoxy groups in the molecule, and which does not correspond to component (A) nor include component (A),

      the component (C): an epoxy resin curing agent which does not have a urea structure in the molecule, and

      the component (D): a dimethylurea compound represented by formula (a) below.

      ("R" is a hydrogen atom or an alkyl group having any number of 1 to 10 carbons);

      wherein the component (A) is a phosphorus modified epoxy resin made of compound (b) represented by formula (b) below.



      wherein "n" is an integral number of zero or greater; "X" is a group shown in formulas (I), (II) or (III) below; in the formula, (n+2) X groups may be the same or different; at least one "X" among (n+2) X groups is a group shown in the below formula (I) or (II); "Y" represents (-H) or (-CH3) bond, and (n+2) Y bonds in the formula may be same or different.

    2. [2] The epoxy-resin composition described in [1], in which component (A) is a phosphorus compound with a phosphorus atom content of at least 1.0 mass% but no more than 8.0 mass%.
    3. [3] The epoxy-resin composition described in [1] or [2], in which the component (D) is 1,1'-(4-methyl-1,3-phenylene)bis(3,3-dimethylurea).
    4. [4] The epoxy-resin composition described in any one of [1] to [3], in which the ratio of the amount of substance of the urea group derived from component (D) to the amount of substance of phosphorus atoms derived from component A (urea equivalent to phosphorus) is at least 0.48 but no more than 0.90.
    5. [5] The epoxy-resin composition described in any one of [1] to [4], in which the ratio of the amount of substance of the urea group derived from component (D) to the amount of substance of the epoxy group in the epoxy resin composition (urea equivalent to epoxy) is at least 0.03 but no more than 0.25.
    6. [6] The epoxy-resin composition described in any one of [1] to [56], in which the phosphorus atom content in the epoxy resin composition is at least 0.4 mass% but no more than 3.5 mass%.
    7. [7] The epoxy-resin composition described in any one of [1] to [6], in which component (B) includes at least one selected from trisphenolmethane-type epoxy resin, aminophenol-type epoxy resin, diaminodiphenylmethane-type epoxy resin, novolac-type epoxy resin and their modified epoxy resins.
    8. [8] The epoxy-resin composition described in any one of [1] to [7], in which the amount of component (B) is at least 18 parts by mass but no more than 100 parts by mass relative to 100 parts by mass of the entire amount of epoxy resin contained in the epoxy resin composition that excludes compound (A).
    9. [9] The epoxy-resin composition described in any one of [1] to [7], in which the amount of component (B) is at least 58 parts by mass but no more than 100 parts by mass relative to 100 parts by mass of the entire amount of epoxy resin contained in the epoxy resin composition.
    10. [10] The epoxy-resin composition described in any one of [1] to [9], in which compound (C) is dicyandiamide.
    11. [11] The epoxy-resin composition described in any one of [1] to [10], further containing thermoplastic resin (E).
    12. [12] The epoxy-resin composition described in [11], in which thermoplastic resin (E) is phenoxy resin.
    13. [13] A prepreg formed by impregnating reinforcing fiber with the epoxy-resin composition described in any one of [1] to [12].
    14. [14] A fiber-reinforced composite material obtained by curing the prepreg described in [13].
    15. [15] A housing for an electrical/electronic device, in which the housing is partly or entirely formed using the fiber-reinforced composite material described in [14].

    EFFECT(S) OF THE INVENTION



    [0013] The embodiments of the present invention provide epoxy-resin compositions and prepreg which exhibit excellent curability and have excellent flame retardance and heat resistance without containing a halogen-based flame-retardant, red phosphorus, phosphate or phosphazene compound, while providing fiber-reinforced composite materials obtained using such prepreg, and providing housing for electronic/electrical devices.

    MODE TO CARRY OUT THE INVENTION



    [0014] In the following, the embodiments of the present invention are described in detail.

    [EPOXY-RESIN COMPOSITION]



    [0015] Epoxy-resin compositions according to an embodiment of the present invention contain components (A) to (D) below as their necessary components.

    <COMPONENT (A)>



    [0016] The phosphorus atom content of component (A) is preferred to be at least 1.0 mass% but no more than 8.0 mass%. The higher the phosphorus atom content, the more enhanced is the flame retardance of a cured material containing the epoxy-resin composition, thus leading to improved flame retardance of the obtained composite material. The lower the phosphorus atom content, the more enhanced is the heat resistance of the cured product containing the epoxy-resin composition, thus leading to improved heat resistance of the obtained composite material.

    [0017] Component (A) is a phosphorus-modified epoxy resin made of compound (b) shown in formula (b) below. The epoxy-resin composition using the phosphorus-modified epoxy resin is more preferred since such a composition provides fiber-reinforced composite material having excellent curability and heat resistance, as well as excellent flame retardance without containing a halogen-based flame retardant, red phosphorus, phosphate or phosphazene compound.

    [In the formula, "n" is an integral number of zero or greater. "X" is a group shown in formulas (I), (II) or (III). In the formula, (n+2) X groups may be the same or different. However, at least one "X" among (n+2) X groups is a group shown in formula (I) or (II). "Y" represents (-H) or (-CH3) bond, and (n+2) Y bonds in the formula may be the same or different.]





    [0018] In formula (b), "n" is an integral number of zero or greater; "n" is preferred to be an integral number of 0 to 10, more preferably 0 to 5. If "n" is 10 or smaller, heat resistance and fluidity are well balanced.

    [0019] Compound (b) in component (A) is one, or two or more. For example, component (A) may be formed only with a compound in which some of (n+2) X groups in formula (b) are those shown in formula (I) or (II), and some are groups as shown in formula (III). Alternatively, component (A) may be formed only with such a compound in which each of (n+2) X groups in formula (b) is a group as shown in formula (I) or (II). Yet alternatively, component (A) may be formed with a mixture of the following: a compound in which some of (n+2) X groups in formula (b) are groups as shown in formula (I) or (II) and some are groups as shown in formula (III); and another compound in which each of (n+2) X groups in formula (b) is a group as shown in formula (I) or (II).

    [0020] It is an option for component (A) to use a commercially available product, or to use a product synthesized by a well-known method.

    [0021] As for commercially available products, FX-289FA made by Nippon Steel Chemical Co., Ltd. is listed, for example.

    [0022] Component (A) is prepared, for example, by the following method:
    epoxy resin, in which each of (n+2) X groups in formula (b) is a group as shown in formula (III) (for example, phenol novolac epoxy resins or cresol novolac epoxy resins), is reacted with a compound shown in formula (c) below (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) under high temperature using a catalyst.



    [0023] In the epoxy-resin composition according to an embodiment of the present invention, the amount of component (A) is preferred to be at least 7 parts by mass but no more than 100 parts by mass, more preferably at least 25 parts by mass but no more than 90 parts by mass, relative to 100 parts by mass of epoxy resin of the epoxy-resin composition that excludes component (A) (namely, component (B) and any other epoxy resin to be mixed in optionally). If the amount is 7 parts by mass or greater, excellent flame retardance is achieved. The amount is preferred to be 100 parts by mass or less. If the amount is set to be 100 parts by mass or less, appropriate heat resistance is provided to the cured material.

    [0024] In addition, in the epoxy-resin composition according to an embodiment of the present invention, the amount of component (A) is preferred to be set so that the content of phosphorus atoms in the epoxy-resin composition is at least 0.4 mass% but no more than 3.5 mass%, more preferably at least 1.2 mass% but no more than 2.9 mass%. If the amount is 0.4 mass% or greater, excellent flame retardance is achieved. If the amount is 3.5 mass% or less, appropriate heat resistance is provided to the cured material.

    <COMPONENT (B)>



    [0025] Component (B) is an epoxy resin which contains at least three epoxy groups in the molecule, and which does not correspond to component (A) nor include component (A).

    [0026] Examples of component (B) are phenol novolac epoxy resins, cresol novolac epoxy resins, DPP (diphenylolpropane) novolac epoxy resins, trisphenolmethane type epoxy resins, binaphthyl methane type epoxy resins, diaminodiphenylmethane type epoxy resins, aminophenol methane type epoxy resins, and modified epoxy resins of the above. Those resins may be used alone, or may be combined.

    [0027] Component (B) is preferred to contain at least one resin selected from the following resins and their modified resins because they have excellent flame retardance and their cured materials have excellent heat resistance: trisphenolmethane type epoxy resin, aminophenol methane type epoxy resin, diaminodiphenylmethane type epoxy resin and novolac epoxy resin. It is more preferred for component (B) to contain at least one selected from trisphenolmethane type epoxy resin, diaminodiphenylmethane type epoxy resin and aminophenol methane type epoxy resin.

    [0028] In the epoxy-resin composition according to an embodiment of the present invention, the amount of component (B) is preferred to be at least 18 parts by mass but no more than 100 parts by mass, more preferably at least 58 parts by mass but no more than 100 parts by mass, relative to 100 parts by mass of the epoxy resin contained in the epoxy-resin composition excluding component (A). By setting the amount of component (B) at 18 parts by mass or greater, sufficient heat resistance is obtained.

    [0029] In the embodiments of the present invention, epoxy resin is defined as such a resin that has at least two epoxy groups in the molecule and its epoxy equivalent weight is 1400 g/eq or greater. When component (A) has at least two epoxy groups in the molecule (for example, "n" in formula (b) is an integral number of at least 1 (the number for X is at least 3), and at least two X groups among (n+2) X groups are those as shown in formula (III)), and the epoxy equivalent weight of entire component (A) is 1400 g/eq or less, component (A) corresponds to epoxy resin. When component (A) does not include a compound that contains two or more epoxy groups in the molecule, or when the epoxy equivalent weight of entire component (A) exceeds 1400 g/eq, component (A) does not correspond to epoxy resin.

    <COMPONENT (C)>



    [0030] Component (C) is an epoxy-resin curing agent that does not contain a urea structure in the molecule.

    [0031] As for component (C), any conventionally known curing agent is used as long as it does not have a urea structure in the molecule and cures epoxy resin. Examples are amines, acid anhydrides, novolac resins, phenolic compounds, mercaptans, Lewis acid-amine complexes, onium salts, imidazole compounds and the like.

    [0032] As for compound (C), amine-based curing agents such as amine or imidazole compounds are preferred. Examples of amine-based curing agents are: aromatic amines such as diaminodiphenylmethane and diaminodiphenyl sulfone; aliphatic amines, imidazole derivatives, dicyandiamide, tetramethylguanidine, thiourea added amines, and their isomers and modified compounds and the like.

    [0033] Among those, dicyandiamide is preferred because it provides an epoxy-resin composition with potential for thermal activation, and offers excellent storage stability for the epoxy-resin composition.

    [0034] Here, potential for thermal activation means the thermal activation of a composition is low at room temperature, but when certain thermal history is added, phase or chemical conversion is caused and the composition will be highly activated.

    [0035] In the epoxy-resin composition according to an embodiment of the present invention, the amount of component (C) is preferred to be set in such a way that the ratio of the active hydrogen equivalent of component (C) is at least 0.4 but no more than 0.9, more preferably at least 0.5 but no more than 0.8, relative to the epoxy equivalent of the epoxy-resin composition excluding component (C). When the ratio is set at 0.4 or higher, excellent curability is provided for the epoxy-resin composition, and when it is set at 0.9 or lower, the rigidity of the obtained cured material is enhanced.

    <COMPONENT (D)>



    [0036] It is necessary for component (D) to be a dimethylurea compound as shown in formula (a) below.

    (R is a hydrogen atom or an alkyl group having any number of 1 to 10 carbon atoms.)

    [0037] As for component (D), for example, 1,1'-(4-methyl-l,3-phenylene)bis(3,3-dimethylurea) or the like is listed.

    [0038] Examples of commercially available component (D) are Omicure 24 (made by PTI Japan Ltd.) and the like.

    [0039] In the epoxy-resin composition according to an embodiment of the present invention, the amount of component (D) is set so that the amount of substance of a urea group derived from component (D) is at least 0.25 times the amount of substance of phosphorus atoms derived from component (A). Namely, the ratio of the amount of substance of the urea group derived from component (D) to the amount of substance of phosphorus atoms derived from component (A) (hereinafter referred to as "urea equivalent to phosphorus") is 0.25 times or higher to 1.85 times or lower. It is more preferable for the ratio to be set at 0.48 times or higher but 0.90 times or lower, since prepreg made of the resin composition is cured and molded at approximately 150°C to form fiber-reinforced compound material, and deformation is less likely to occur even if the molded article is taken out shortly after it is molded.

    [0040] In the epoxy-resin composition according to an embodiment of the present invention, the amount of component (D) is preferred to be set so that the amount of substance of a urea group derived from component (D) is at least 0.03 times but no greater than 0.25 times the amount of substance of the epoxy group in the epoxy-resin composition. If the ratio is set at 0.03 times or higher, excellent curability is obtained. If the ratio is set at 0.25 times or lower, excellent heat resistance is provided for the cured material. Hereinafter, the ratio of the amount of substance of the urea group derived from component (D) to the amount of substance of the epoxy groups contained in the epoxy-resin composition may be referred to as "urea equivalent to epoxy."

    [0041] To control resin flow during the molding process or to provide toughness for the cured materials, epoxy-resin compositions related to the present invention may contain thermoplastic resin (E) within a range not to undermine the effects of the present invention.

    [0042] Examples of thermoplastic resin (E) are polyamide, polyester, polycarbonate, polyethersulfone, polyphenylene ether, polyphenylene sulfide, polyetheretherketone, polyetherketoneketone, polyimide, polytetrafluoroethylene, polyether, polyolefin, liquid crystal polymer, polyarylate, polysulfone, poly acrylonitrile styrene, polystyrene, polyacrylonitrile, polymethyl methacrylate, ABS, AES, ASA, polyvinyl chloride, poly(vinyl formal), phenoxy resins and the like. Those may be each used alone, or two or more may be combined.

    [0043] Among the resins above, phenoxy resins are preferred since they are excellent in resin-flow control, curability, flame retardance of cured material and the like.

    [0044] It is an option for the epoxy-resin composition according to an embodiment of the present invention to contain an epoxy resin different from component (A) and component (B) above (hereinafter referred to as another epoxy resin) within a range that does not undermine the effects of the present invention.

    [0045] Another epoxy resin is a type that does not correspond to component (A) while containing two epoxy groups in the molecule and having an epoxy equivalent weight of 1400 g/eq or less. Specific examples are bisphenol-based epoxy resins, alicyclic epoxy resins, epoxy resins with a biphenyl skeleton, naphthalene-based epoxy resins, isocyanate modified epoxy resins and the like. Those may each be used alone or two or more may be combined. Among them, bisphenol epoxy resins are especially preferred.

    [0046] As for bisphenol-based epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol E epoxy resins, bisphenol S epoxy resins and the like are listed. Any type may be used.

    [0047] The epoxy-resin composition related to the present invention may contain various well-known additives within a range that does not undermine the effects of the present invention. As for such additives, for example, the following are listed: release agents such as silicone oil, natural waxes, synthetic waxes, metal salts of linear-chain fatty acids, acid amides, esters and paraffins; powders such as crystalline silica, fused silica, calcium silicate, alumina, calcium carbonate, talc and barium sulfate; inorganic fillers such as fiberglass and carbon fiber or the like; coloring agents such as carbon black and red-iron oxide; silane coupling agents or the like. Those additives above may be used alone, or two or more may be combined.

    <METHOD FOR PREPARING EPOXY-RESIN COMPOSITION>



    [0048] Epoxy-resin compositions related to the present invention are prepared by mixing each component described above.

    [0049] For mixing each component, blenders such as three-roll mills, planetary mixers, kneaders, universal agitators, homogenizers, homo dispers or the like may be used.

    [PREPREG]



    [0050] The prepreg related to the present invention is made by impregnating reinforcing fiber with the epoxy-resin composition according to an embodiment of the present invention.

    [0051] In the prepreg according to an embodiment of the present invention, the amount of the epoxy-resin composition to the entire weight of the prepreg (hereinafter referred to as resin content) is preferred to be at least 15 mass% but no more than 50 mass%, more preferably at least 20 mass% but no more than 45 mass%, even more preferably at least 25 mass% but no more than 35 mass%. If the resin content is less than 15 mass%, adhesiveness is reduced between the reinforcing fiber and the epoxy-resin composition, and if the resin content exceeds 50 mass%, flame retardance may decrease.

    [0052] Reinforcing fibers are not limited to any specific type, and reinforcing fiber of fiber-reinforced composite material should be selected appropriately from well-known fibers according to usage purposes or the like. For example, various inorganic or organic fibers such as follows may be used: carbon fibers, aramid fibers, nylon fibers, reinforced polyester fibers, fiberglass, boron fibers, alumina fibers, and silicon nitride fibers. Among the above, carbon fibers, aramid fibers, fiberglass, boron fibers, alumina fibers or silicon nitride fibers are preferred when flame retardance is considered. Carbon fibers are especially preferred due to excellent specific strength, specific modulus and electromagnetic wave-shielding performance.

    [0053] Carbon fibers are preferred to have strand tensile strength of at least 1.0 GPa but no more than 9.0 GPa, and strand tensile modulus of elasticity of at least 150 GPa but no more than 1000 GPa, both measured according to JIS R7601 (1986). It is more preferred for carbon fibers to have strand tensile strength of at least 1.5 GPa but no more than 9.0 GPa, and to have strand tensile modulus of elasticity of at least 200 GPa but no more than 1000 GPa.

    [0054] As for the format of reinforcing fibers, fibers arrayed in one direction, woven fabrics or non-crimp fabrics may be selected.

    [0055] The prepreg related to the present invention is formed by a well-known method using reinforcing fibers and the epoxy-resin composition according to an embodiment of the present invention.

    [0056] The prepreg related to the present invention has excellent curability because it is made from the epoxy-resin composition according to an embodiment of the present invention. For example, the prepreg cures at a curing temperature of 140°C within five minutes.

    [0057] In addition, regarding the epoxy-resin composition according to an embodiment of the present invention, its cured material has a relatively high glass transition temperature (Tg), and exhibits excellent heat resistance. Accordingly, when the prepreg related to the present invention is molded by performing high-cycle press-molding under elevated temperature and pressure, the cured material is less likely to be soft so that removing the cured material from the molding die can be conducted in a short period of time without causing problems such as deformation.

    [0058] Therefore, using the prepreg related to the present invention, fiber-reinforced composite material is produced in a relatively short period of time compared with fiber-reinforced composite material made from conventional epoxy-resin compositions. Therefore, the prepreg related to the present invention can be used for manufacturing members requiring high productivity.

    [FIBER-REINFORCED COMPOSITE MATERIAL]



    [0059] The fiber-reinforced composite material related to the present invention is obtained by curing the prepreg above.

    [0060] The fiber-reinforced composite material related to the present invention is preferred to contain carbon fibers as its reinforcing fibers, because carbon fibers are excellent in exhibiting flame retardance and heat resistance, electromagnetic wave-shielding performance, mechanical characteristics and the like.

    [0061] The fiber-reinforced composite material related to the present invention is manufactured using the prepreg related to the present invention by a well known method, for example, by press-molding using a die.

    [0062] For press-molding using a die, generally set conditions are a curing temperature of at least 100°C but no higher than 150°C, molding pressure of at least 1 MPa but no higher than 15 MPa, and curing time of at least 1 minute but no longer than 20 minutes. Since the epoxy-resin composition according to an embodiment of the present invention has excellent curability as described above, it is molded by high-cycle press-molding, for example, at a curing temperature of 140°C in a short period of time such as within 5 minutes.

    [0063] The fiber-reinforced composite material related to the present invention exhibits excellent flame retardance even though it does not contain a halogen-based flame-retardant agent, red phosphorus or phosphate because the matrix resin is the cured material of the epoxy-resin composition according to an embodiment of the present invention. For example, when a 0.6 mm-thick sheet of fiber-reinforced composite material is formed, level V-0 flame retardance measured by UL-94V is achieved.

    [0064] Accordingly, the fiber-reinforced composite material related to the present invention is suitable for applications that require a high level of flame retardance. Housing for electronic/electrical devices and interior materials for aircraft and automobiles are listed for such applications.

    [0065] Also, the fiber-reinforced composite material related to the present invention exhibits excellent heat resistance.

    [0066] Accordingly, the fiber-reinforced composite material related to the present invention is suitable for applications that require a high level of flame retardance and excellent heat resistance, and thus is especially suitable for housing for electronic/electrical devices.

    [HOUSING FOR ELECTRONIC/ELECTRICAL DEVICE]



    [0067] Housing for an electronic/electrical device related to the present invention is formed partially or entirely using the fiber-reinforced composite material according to the embodiment described above.

    [0068] "Electronic/electrical device" is a generic term for electronic devices and electrical devices. As for electronic/electrical devices, for example, personal computers (laptop or desktop), cell phones, electronic notebooks, portable music players, electronic book readers and the like are listed.

    [0069] Housing for an electronic/electrical device related to the present invention may be formed using the fiber-reinforced composite material related to the present invention, or may also be formed using the fiber-reinforced composite material related to the present invention along with other material (such as metal, thermoplastic resin for injection molding or the like).

    EXAMPLES



    [0070] Next, the present invention is further described by referring to examples.

    [0071] The following show materials (such as resin), methods for preparing epoxy-resin compositions, methods for forming carbon-fiber prepreg, methods for forming carbon-fiber composite material sheets, and evaluation methods for physical properties.

    <RAW MATERIAL>


    [COMPONENT (A)]



    [0072] FX-289FA: phosphorus-modified epoxy resin product (a mixture of compounds where "Y" is (-H) and "n" is 0 to 8 in formula (b)), an epoxy equivalent weight of 7740 g/eq and phosphorus atom content of 7.4 mass%, made by Nippon Steel Chemical Co., Ltd.

    [COMPONENT (B)]



    [0073] 

    TX-0911: liquid phenol novolac epoxy resin, epoxy equivalent weight of 172 g/eq, made by Nippon Steel Chemical Co., Ltd.

    jER 152: liquid phenol novolac epoxy resin, epoxy equivalent weight of 177 g/eq, made by Mitsubishi Chemical Corporation.

    jER 1032H60: trisphenolmethane-type epoxy resin, epoxy equivalent weight of 169 g/eq, made by Mitsubishi Chemical Corporation.

    EPICLON N-540: modified trifunctional phenol novolac epoxy resin, epoxy equivalent weight of 170 g/eq, made by DIC Corporation.

    jER 630: p-aminophenol epoxy resin, epoxy equivalent weight of 97 g/eq, made by Mitsubishi Chemical Corporation.

    jER 604: diaminodiphenylmethane epoxy resin, epoxy equivalent weight of 120 g/eq, made by Mitsubishi Chemical Corporation.


    [Other Epoxy Resins]



    [0074] 

    jER 828: liquid bisphenol A epoxy resin, epoxy equivalent weight of 189 g/eq, made by Mitsubishi Chemical Corporation.

    jER 807: liquid bisphenol F epoxy resin, epoxy equivalent weight of 168 g/eq, made by Mitsubishi Chemical Corporation.


    [COMPONENT (C)]



    [0075] DICY 15: dicyandiamide, active hydrogen equivalent weight of 21 g/eq, made by Mitsubishi Chemical Corporation.

    [COMPONENT (D)]



    [0076] Omicure 24: 1,1'-(4-methyl-1,3-phenylene)bis(3,3-dimethylurea), made by PTI Japan

    [OTHER UREA COMPOUNDS]



    [0077] 

    DCMU 99: 3-(3,4-dichlorophenyl)-1,1-dimethylurea, made by Hodogaya Chemical Co., Ltd.

    Omicure 94: 1-phenyl-3,3-dimethylurea, made by PTI Japan Ltd.

    Omicure 52: 4,4'-methylenebis(phenyl dimethyl urea), made by PTI Japan Ltd.


    [THERMOPLASTIC RESIN (E)]



    [0078] 

    YP-70: phenoxy resin, made by Mitsubishi Chemical Corporation.

    E2020P micro: polyethersulfone, made by BASF Japan Ltd.


    [CARBON FIBER]



    [0079] carbon fiber: Pyrofil TR50S15L, made by Mitsubishi Rayon Co., Ltd.

    <METHOD FOR PREPARING EPOXY-RESIN COMPOSITION>



    [0080] Epoxy-resin compositions in examples 1 to 27, reference example 28 and comparative examples 1 to 10 were prepared as follows.

    [0081] According to their respective component amounts specified in Tables 1 to 6, first, component (C) and component (D) or other urea compounds as solid components, and jER 152 as a liquid component were measured in a container so that the mass ratio of the combined solid components to the liquid component is 1:1, and were then blended to be combined. The mixture was further combined thoroughly using a three-roll mill to obtain a masterbatch-type curing agent (instead of jER 152, jER 828 was used for examples 17 to 23, 26 and 27).

    [0082] Next, among the component amounts specified in Tables 1 to 6, the rest of the components except for those used for the masterbatch-type curing agent were measured in a flask, and heated to 160°C using an oil bath so that the mixture was dissolved and combined. Then, the mixture was cooled to approximately 65°C, to which their respective masterbatch-type curing agents were added and blended to be combined. Accordingly, epoxy-resin compositions were each prepared (as for comparative examples 2 and 5, the curing-agent masterbatch and jER 152 were blended to be combined at 65°C to obtain epoxy-resin compositions).

    <METHOD FOR PRODUCING CARBON-FIBER PREPREG>



    [0083] The obtained epoxy-resin composition was formed into a film using Comma Coater M-500, made by Hirano Tecseed Co., Ltd., and resin film with a basis weight of 37 g/m2 was prepared. The resin film was laminated on both surfaces of unidirectional carbon fibers formed by a drum winding method, and impregnated using a hot roller. Accordingly, carbon-fiber prepreg with a basis weight of 170 g/m2 and a resin content of 30 mass% was obtained.

    <METHOD 1 FOR FORMING CARBON-FIBER COMPOSITE MATERIAL SHEET>



    [0084] The obtained carbon-fiber prepreg was cut to a certain size, and a four-ply cross laminate with fiber orientations of [0°/90°]s=0°/90°/90°/0° was formed. Then, the laminate was cured in an autoclave under conditions of 130°C for 90 minutes, with a rate of temperature rise at 2°C/min, and pressure of 0.6 MPa. Accordingly, 0.6 mm-thick carbon-fiber composite material sheet ([0/90]s) was obtained.

    <METHOD 2 FOR FORMING CARBON-FIBER COMPOSITE MATERIAL SHEET>



    [0085] The obtained carbon-fiber prepreg was cut to a certain size, and a 14-ply cross laminate with fiber orientations of [0°]14=0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0° was formed. Then, the laminate was cured using a pressing machine under conditions of 150°C for 5 minutes, and pressure of 8 MPa. Accordingly, 2 mm-thick carbon-fiber composite material sheet ([0]14) was obtained.

    <EVALUATION METHODS>



    [0086] 
    1. (1) UL-94V Flammability Test (on cured resin material):
      An uncured epoxy-resin composition was cured in an oven at an ambient temperature of 130°C for 120 minutes (a rate of temperature rise at 2°C/min) to obtain a 2 mm-thick resin sheet, and then processed to form a 127 mm-long×12.7 mm-wide test piece. The test piece underwent flammability testing according to the UL-94V standard using a flammability test instrument made by Suga Test Instruments Co., Ltd. Namely, a test piece was vertically mounted to a clamp, which was then brought into contact with a 20-mm flame for 10 seconds and the combustion time was measured. Such flammability testing was conducted on five test pieces, and the number of samples in which even the clamp was burnt, the maximum value among the combustion time, and the sum of combustion time of the five test pieces (total combustion time) were recorded. Also, based on the results, the cured resins were evaluated. The test pieces were evaluated to be at level V-0, V-1, V-2 or failure. V-0 is the least flammable, and the rating decreases in the order of V-1, V-2 and fail.
    2. (2) UL-94V Flammability Test (on carbon-fiber composite material sheet)
      The same as the above UL-94V flammability test (on cured resin material) to evaluate the test sheets was conducted, except that test pieces were prepared by using the carbon-fiber composite material sheet ([0/90]s) obtained in method 1 for forming carbon-fiber composite material sheet, which was cut into 127 mm long×12.7 mm wide.
    3. (3) Measuring Exothermic Peaks Using Differential Scanning Calorimeter (DSC) (curability evaluation):
      Using "Q1000" made by TA Instruments as a measuring instrument, 8 to 12 mg each of uncured resin compositions was heated under conditions of nitrogen atmosphere and a rate of temperature rise at 10°C/min, and temperatures were recorded when the exothermic peaks reached maximum.
      The lower the temperature of the maximum exothermic peak, the better the curability.
    4. (4) Measuring DSC-Tg:
      Using "Q1000" made by TA Instruments, 8 to 12 mg each of uncured resin compositions was heated at 130°C×2 hours, 150°C×2 hours or 155°C×1 hour (a rate of temperature rise at 60°C/min each). Then, using "Q1000" made by TA Instruments as well, intermediate glass transition temperatures were measured according to JISK 7121 under conditions of a nitrogen flow rate of 50 mL/min and a rate of temperature rise at 10°C/min. The obtained values were set as DSC-Tg.
      The higher the DSC-Tg value, the better the heat resistance.
    5. (5) Measuring DMA G'-Tg:
      An uncured epoxy-resin composition was cured in an oven at an ambient temperature of 150°C for 15 minutes (a rate of temperature rise at 10°C/min) to obtain a 2 mm-thick resin sheet (the resin surface temperature at that time was measured using a thermocouple, and the duration of the resin temperature retained at 150°C or higher was recorded) Then, the resin sheet was cut into test sheets 55 mm long×12.7 mm wide. Using "ARES-RDS" made by TA instruments and under conditions of measurement frequency of 1 Hz and a rate of temperature rise at 5°C/min, storage modulus values G' were plotted on a logarithm scale relative to temperatures, and the temperature, obtained where an approximation line in a region showing flat log G' values crosses an approximation line in a region showing transitional log G' values, was recorded as DMA G'-Tg.
      The higher the DSC G'-Tg value, the better the heat resistance.
    6. (6) Bending Test of Carbon-Fiber Composite Material Sheet:
      The carbon-fiber composite material sheet ([0]14) obtained in method 2 for forming a carbon-fiber composite sheet was formed into a test sheet 127 mm long×12.7 mm wide with the fiber direction set as a long side. Using "Instron Universal Testing Machine 5565" made by Instron, a three-point bending test was conducted on the test sheets according to ASTM D790 to measure the bending strength and flexural modulus of elasticity.

    (EXAMPLE 1)



    [0087] As specified in Table 1, an epoxy resin composition was prepared using FX-289FA as component (A), TX-0911 and jER 152 as component (B), DICY 15 as component (C) and Omicure 24 as component (D), and the composition's physical properties were evaluated. The results are shown in Table 1.

    (COMPARATIVE EXAMPLE 1)



    [0088] As specified in Table 1, an epoxy resin composition was prepared the same as in example 1, except that Omicure 24 as component (D) was omitted, and the composition's physical properties were evaluated. The results are shown in Table 1.

    (COMPARATIVE EXAMPLE 2)



    [0089] As specified in Table 1, an epoxy resin composition was prepared using jER 152 as component (B), DICY 15 as component (C) and DCMU 99 as the other urea compound, and the composition's physical properties were evaluated. The results are shown in Table 1.

    (COMPARATIVE EXAMPLE 3)



    [0090] As specified in Table 1, an epoxy resin composition was prepared using FX-289FA as component (A), TX-0911 and jER 152 as component (B), DICY15 as component (C) and DCMU 99 as the other urea component, and the composition's physical properties were evaluated. The results are shown in Table 1.

    (COMPARATIVE EXAMPLE 4)



    [0091] As specified in Table 1, an epoxy resin composition was prepared using FX-289FA as component (A), TX-0911 and jER 152 as component (B), DICY 15 as component (C) and Omicure 94 as the other urea compound, and the composition's physical properties were evaluated. The results are shown in Table 1.

    (COMPARATIVE EXAMPLE 10)



    [0092] As specified in Table 1, an epoxy-resin composition was prepared using FX-289FA as component (A), TX-0911 and jER 152 as component (B), DICY 15 as component (C) and Omicure 52 as the other urea compound, and the composition's physical properties were evaluated. The results are shown in Table 1.

    (COMPARATIVE EXAMPLE 5)



    [0093] As specified in Table 2, an epoxy-resin composition was prepared using and jER 152 as component (B), DICY15 as component (C) and Omicure 24 as component (D), and the composition's physical properties were evaluated. The results are shown in Table 2.

    (COMPARATIVE EXAMPLE 6)



    [0094] As specified in Table 2, an epoxy-resin composition was prepared the same as in example 1, except that TX-0911 and jER 152 were used as component (B) and the amount of FX-289FA as component (A) was reduced, and the composition's physical properties were evaluated. The results are shown in Table 2.

    (EXAMPLES 2 to 5)



    [0095] Epoxy-resin compositions were prepared the same as in example 1, except that TX-0911 and jER 152 were used as component (B) and the amounts of FX-289FA as component (A) were increased or reduced respectively as specified in Table 2, and the compositions' physical properties were evaluated. The results are shown in Table 2.

    (COMPARATIVE EXAMPLE 7)



    [0096] As specified in Table 2, an epoxy-resin composition was prepared the same as in example 6, except that the amount of Omicure 24 as component (D) was reduced, and the composition's physical properties were evaluated. The results are shown in Table 2.

    (EXAMPLE 6)



    [0097] As specified in Table 2, an epoxy-resin composition was prepared using FX-289FA as component (A), TX-0911 and jER 152 as component (B), DICY 15 as component (C) and Omicure 24 as component (D), and the composition's physical properties were evaluated. The results are shown in Table 2.

    (COMPARATIVE EXAMPLES 8, 9)



    [0098] Epoxy-resin compositions were prepared the same as in example 1, except that the amounts of Omicure 24 as component (D) were reduced respectively as specified in Table 3, and the compositions' physical properties were evaluated. The results are shown in Table 3.

    (EXAMPLES 7 to 12, REFERENCE EXAMPLE 28)



    [0099] Epoxy-resin compositions were prepared the same as in example 1, except that the amounts of Omicure 24 as component (D) were increased respectively as specified in Table 3, and the compositions' physical properties were evaluated. The results are shown in Table 3.

    (EXAMPLE 13)



    [0100] An epoxy-resin composition was prepared the same as in example 9, except that the amount of DICY 15 as component (C) was reduced as specified in Table 4, and the composition's physical properties were evaluated. The results are shown in Table 4.

    (EXAMPLES 14, 15)



    [0101] Epoxy-resin compositions were prepared the same as in example 13, except that the amounts of Omicure 24 as component (D) were increased respectively as specified in Table 4, and the compositions' physical properties were evaluated. The results are shown in Table 4.

    (EXAMPLE 16)



    [0102] An epoxy-resin composition was prepared the same as in example 9, except that the amount of DICY 15 as component (C) and the amount of Omicure 24 as component (D) were increased as specified in Table 4, and the composition's physical properties were evaluated. The results are shown in Table 4.

    (EXAMPLES 17 to 20)



    [0103] Epoxy-resin compositions were prepared using FX-289FA as component (A), TX-0911, jER 1032H60 and jER 630 as component (B), DICY 15 as component (C), Omicure 24 as component (D), jER 828 as another epoxy resin, and YP-70 as a thermoplastic resin as specified in Table 5, and the compositions' physical properties were evaluated. The results are shown in Table 5.

    (EXAMPLE 21)



    [0104] An epoxy-resin composition was prepared using FX-289FA as component (A), TX-0911, jER 1032H60 and jER 630 as component (B), DICY 15 as component (C), Omicure 24 as component (D), jER 828 as another epoxy resin, and YP-70 as a thermoplastic resin as specified in Table 5, and the composition's physical properties were evaluated. The results are shown in Table 5.

    [0105] In addition, a carbon-fiber composite material sheet was formed and its physical properties were evaluated. The results were shown in Table 6.

    (EXAMPLES 22, 23)



    [0106] Epoxy-resin compositions were prepared using FX-289FA as component (A), TX-0911 and jER 604 as component (B), DICY 15 as component (C), Omicure 24 as component (D), jER 828 as another epoxy resin, and YP-70 as a thermoplastic resin as specified in Table 5, and the compositions' physical properties were evaluated. The results are shown in Table 5.

    (EXAMPLE 24)



    [0107] An epoxy-resin composition was prepared using FX-289FA as component (A), TX-0911, jER 152, N-540 and jER 630 as component (B), DICY 15 as component (C), Omicure 24 as component (D), and E2020P micro as a thermoplastic resin as specified in Table 5, and the composition's physical properties were evaluated. The results are shown in Table 5.

    (EXAMPLE 25)



    [0108] As specified in Table 5, an epoxy-resin composition was prepared the same as in example 24 except that E2020P micro as a thermoplastic resin was replaced with YP-70, and the composition's physical properties were evaluated. The results are shown in Table 5.

    (EXAMPLE 26)



    [0109] An epoxy-resin composition was prepared using FX-289FA as component (A), TX-0911, jER 1032H60 and jER 604 as component (B), DICY 15 as component (C), Omicure 24 as component (D), jER 828 as another epoxy resin, and YP-70 as a thermoplastic resin as specified in Table 5, and the composition's physical properties were evaluated. The results are shown in Table 5.

    (EXAMPLE 27)



    [0110] An epoxy-resin composition was prepared using FX-289FA as component (A), TX-0911, jER 1032H60 and jER 604 as component (B), DICY 15 as component (C), Omicure 24 as component (D), jER 828 and jER 807 as other epoxy resins, and YP-70 as a thermoplastic resin as specified in Table 5, and the composition's physical properties were evaluated. The results are shown in Table 5.

    [0111] In addition, a carbon-fiber composite material sheet was formed and its physical properties were evaluated. The results are shown in Table 6.
    [Table 1]
     comparative example 1comparative example 2comparative example 3comparative example 4example 1comparative example 10
    component (A) FX-289FA 40 - 40 40 40 40
    component (B) TX-0911 40 - 40 40 40 40
    jER 152 60 100 60 60 60 60
    component (C) DICY15 7 7 7 7 7 7
    component (D) Omicure 24 - - - - 5 -
    other urea compound DCMU 99 - 8.8 8.8 - - -
    Omicure 94 - - - 6.2 - -
    Omicure 52 - - - - - 6.4
    (phosphorus atom content) (mass%) 2.0 0 1.9 1.9 1.9 1.9
    (urea equivalent to epoxy) 0 0.07 0.07 0.07 0.07 0.07
    (urea equivalent to phosphorus) 0 0.40 0.40 0.40 0.40
    physical properties flame retardance (cured resin composition) - fail V-0 V-0 V-0 V-0
    DSC 187.2 156.3 161.2 160.2 156.5 160.8
    exothermic peak (°C)
    DSC-Tg (°C) - 138 138 141 146 142
    cured at 130°Cx2h
    DSC-Tg (°C) - - 134 142 153 142
    cured at 150°Cx2h
    [Table 2]
     comparative example 5comparative example 6example 2example 3example 4example 5comparative example 7example 6
    component (A) FX-289FA - 5 10 20 30 60 80 80
    component (B) TX-0911 - 5 10 20 30 60 80 80
    jER 152 100 95 90 80 70 40 20 20
    component (C) DICY 15 7 7 7 7 7 7 7 7
    component (D) Omicure 24 5 5 5 5 5 5 5 10
    (phosphorus atom content) (mass%) 0 0.3 0.6 1.1 1.6 2.6 3.1 3.0
    (urea equivalent to epoxy) 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.13
    (urea equivalent to phosphorus) 3.22 1.61 0.80 0.54 0.27 0.20 0.40
    physical properties flame retardance (cured resin composition) fail fail V-1 V-1 V-0 V-0 V-0 V-0
    DSC 141.2 148.6 150.9 154.9 155.4 159.4 170.8 153
    exothermic peak (°C)
    DSC-Tg (°C) 148 150 151 151 148 143 132 142
    cured at 130°C×2h
    DSC-Tg (°C) 150 155 156 157 155 146 135 143
    cured at 150°C×2h
    [Table 3]
     comparative example 8comparative example 9example 7example 8example 9example 10example 11example 12Reference example 28
    component (A) FX-289FA 40 40 40 40 40 40 40 40 40
      TX-0911 40 40 40 40 40 40 40 40 40
    component (B) jER 152 60 60 60 60 60 60 60 60 60
    component (C) DICY 15 7 7 7 7 7 7 7 7 7
    component (D) Omicure 24 1 3 6 9 12 15 18 23 37.3
    (phosphorus atom content) (mass%) 2.0 2.0 1.9 1.9 1.9 1.8 1.8 1.7 1.6
    (urea equivalent to epoxy) 0.01 0.04 0.08 0.12 0.16 0.20 0.24 0.30 0.49
    (urea equivalent to phosphorus) 0.08 0.24 0.48 0.72 0.97 1.21 1.45 1.85 3.00
    physical properties flame retardance (cured resin composition) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 -
    DSC 179.3 166.5 155.0 151.1 148.3 147.8 148.0 144.6 142.4
    exothermic peak (°C)
    DSC-Tg (°C) not cured 138 150 149 146 146 145 142 121
    cured at 130°Cx2h
    DSC-Tg (°C) 131 147 154 153 144 133 132 128 101
    cured at 150°Cx2h
    [Table 4]
     example 13example 14example 15example 16
    component (A) FX-289FA 40 40 40 40
    component (B) TX-0911 40 40 40 40
    jER 152 60 60 60 60
    component (C) DICY 15 6 6 6 8
    component (D) Omicure 24 12 14 16 13.7
    (phosphorus atom content) (mass%) 1.9 1.9 1.8 1.8
    (urea equivalent to epoxy) 0.16 0.18 0.21 0.18
    (urea equivalent to phosphorus) 0.97 1.13 1.29 1.10
    physical properties flame retardance (cured resin composition) V-0 V-0 V-0 V-0
    DSC 153.0 154.6 153.0 153.0
    exothermic peak (°C)
    DSC-Tg (°C) 150 148 149 150
    cured at 130°Cx2h
    DSC-Tg (°C) 151 146 145 149
    cured at 150°Cx2h
    [Table 5]
     example 17example 18example 19example 20example 21example 22example 23example 24example 25example 26example 27
    component (A) FX-289FA 40 40 40 40 40 40 40 36 36 30 30
    component (B) TX-0911 40 40 40 40 40 40 40 36 36 30 30
    jE3R 152 - - - - - - - 24 24 - -
    jER 1032H60 8 10 12 14 16 - - - - 31 30
    N-540 - - - - - - - 25 25 - -
    jER 630 10 12.5 15 17.5 20 - - 15 15 - -
    jBR 604 - - - - - 36 27 - - 15 8
    component (C) DICY 15 8 7.5 7.7 7.8 8 8 7.7 7 7 8 8
    component (D) Omicure 24 12 11.3 11.5 11.8 13.7 12 11.5 14 14 12 12
    other epoxy resin jER 828 42 37.5 33 28.5 24 24 33 - - 24 24
    jER 807 - - - - - - - - - - 8
    thermoplastic resin (E) YP-70 11.1 11.1 11.1 11.1 11.1 11.1 11.1 - 10 8.3 8.3
    E2020P micro - - - - - - - 10 - - -
    (phosphorus atom content) (mass%) 1.7 1.7 1.7 1.7 17 1.7 1.7 1.6 1.6 1.4 1.4
    (urea equivalent to epoxy) 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.16 0.16 0.15 0.15
    (urea equivalent to phosphorus) 0.97 0.91 0.93 0.95 1.10 0.97 0.93 1.25 1.25 1.29 1.29
    physical properties flame retardance (cured resin composition) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
    DSC 154.4 154.6 153.6 152.5 151.3 154.5 158.0 154.0 146.9 147.2 144.9
    exothermic peak (°C)
    DMA G'-Tg (°C) 134 (4 min) 139 (4 min) 144 (4 min) 147 (3 min) 151 (5 min) 152 (3 min) 147 (4 min) - - 163 (5 min) 154 (3 min)
    cured at 150°Cx15 min (retention time of resin at 150°C or higher)
    [Table 6]
     example 21example 27
    component (A) FX-289FA 40 30
    component (B) TX-0911 40 30
    jER 1032H60 16 30
    jER 630 20 -
    jER 604 - 8
    component (C) DICY 15 8 8
    component (D) Omicure 24 13.7 12
    other epoxy resin jER 828 24 24
    jER 807 - 8
    thermoplastic resin (E) YP-70 11.1 8.3
    (phosphorus atom content) (mass%) 1.7 1.4
    (urea equivalent to epoxy) 0.14 0.15
    (urea equivalent to phosphorus) 1.10 1.29
    physical properties flame retardance (carbon-fiber composite material sheet) V-0 V-0
    bending strength (MPa) of carbon-fiber composite material 2030 2080
    flexural modulus of elasticity (GPa) of carbon-fiber composite material 143 145


    [0112] In Tables 1 to 6, "phosphorus atom content (mass%)," "urea equivalent to epoxy," and "urea equivalent to phosphorus" indicate the phosphorus atom content (mass%) in an epoxy-resin composition, a ratio of the amount of substance of the urea group derived from component (D) to the amount of substance of epoxy groups contained in an epoxy-resin composition, and a ratio of the amount of substance of the urea group derived from component (D) to the amount of substance of phosphorus atoms derived from component (A).

    [0113] As shown in the above results, epoxy-resin compositions in examples 1 to 27 and reference example 28, which contain components (A) to (D), "urea equivalent to phosphorus" at 0.25 or greater, and at least 7 parts by mass of component (A) to 100 parts by mass of epoxy resin other than component (A) (epoxy resin in component (B) and other epoxy resins), each showed an exothermic peak temperature of 160°C or lower and excellent curability. The cured materials also showed excellent flame retardance and heat resistance. In addition, carbon-fiber composite materials, formed by curing prepreg made of the epoxy-resin compositions in examples 21 and 27, also showed excellent flame retardance as the cured materials, and the compositions' mechanical characteristics were also excellent.

    [0114] By contrast, comparative example 1, which does not contain component (D), showed low curability. Comparative example 2, which does not contain component (A) and contains DCMU 99 in place of component (D), showed low flame retardance and heat resistance. Comparative examples 3, 4 and 10, which contain DCMU 99, Omicure 94 or Omicure 52 in place of component (D), showed low curability and low heat resistance. Comparative example 5, which does not contain component (A), and comparative example 6, which contains 5 parts by mass of component (A) relative to 100 parts by mass of epoxy resin other than component (A), each showed low flame retardance. Comparative examples 7 to 9, whose "urea equivalent to phosphorus" is lower than 0.25, showed low curability and low heat resistance, and comparative example 8, whose "urea equivalent to phosphorus" is lower than 0.08, did not cure under the condition of 130°C×2 hours.

    INDUSTRIAL APPLICABILITY



    [0115] The embodiments of the present invention provide epoxy-resin compositions and prepreg which show excellent curability and have excellent flame retardance and heat resistance without containing a halogen-based flame-retardant agent, red phosphorus, phosphate or phosphazene compound, while providing fiber-reinforced composite materials obtained using such prepreg as well as providing housing for electronic/electrical devices.


    Claims

    1. An epoxy-resin composition, comprising:

    component (A);

    component (B);

    component (C); and

    component (D),

    wherein, the ratio of the amount of substance of a urea group derived from component (D) to the amount of phosphorus atoms derived from component (A) (urea equivalent to phosphorus) is in the range of 0.25 or higher to 1.85 or lower, and
    the amount of component (A) to 100 parts by mass of the amount of the rest of the epoxy-resin composition that excludes component (A) is 7 parts by mass or greater,
    the component (A): a phosphorus compound,
    the component (B): an epoxy resin which has at least three epoxy groups in the molecule, and which does not correspond to component (A) nor include component (A),
    the component (C): an epoxy resin curing agent which does not have a urea structure in the molecule, and
    the component (D): a dimethylurea compound represented by formula (a) below.

    ("R" is a hydrogen atom or an alkyl group having any number of 1 to 10 carbons);
    wherein the component (A) is a phosphorus modified epoxy resin made of compound (b) represented by formula (b) below.

    wherein "n" is an integral number of zero or greater; "X" is a group shown in formulas (I), (II) or (III) below; in the formula, (n+2) X groups may be the same or different; at least one "X" among (n+2) X groups is a group shown in the below formula (I) or (II); "Y" represents (-H) or (-CH3) bond, and (n+2) Y bonds in the formula may be same or different.




     
    2. The epoxy-resin composition according to Claim 1, wherein the component (A) is a phosphorus compound with a phosphorus atom content of at least 1.0 mass% but no more than 8.0 mass%.
     
    3. The epoxy-resin composition according to Claim 1 or 2, wherein the component (D) is 1,1'-(4-methyl-1,3-phenylene)bis(3,3-dimethylurea).
     
    4. The epoxy-resin composition according to any one of Claims 1 to 3, wherein the ratio of the amount of substance of the urea group derived from component (D) to the amount of substance of phosphorus atoms derived from component A (urea equivalent to phosphorus) is at least 0.48 but no more than 0.90.
     
    5. The epoxy-resin composition according to any one of Claims 1 to 4, wherein the ratio of the amount of substance of the urea group derived from component (D) to the amount of substance of the epoxy group in the epoxy resin composition (urea equivalent to epoxy) is at least 0.03 but no more than 0.25.
     
    6. The epoxy-resin composition according to any one of Claims 1 to 5, wherein the phosphorus atom content in the epoxy resin composition is at least 0.4 mass% but no more than 3.5 mass%.
     
    7. The epoxy-resin composition according to any one of Claims 1 to 6, wherein component (B) includes at least one selected from trisphenolmethane-type epoxy resin, aminophenol-type epoxy resin, diaminodiphenylmethane-type epoxy resin, novolac-type epoxy resin and their modified epoxy resins.
     
    8. The epoxy-resin composition according to any one of Claims 1 to 7, wherein the amount of component (B) is at least 18 parts by mass but no more than 100 parts by mass relative to 100 parts by mass of the entire amount of epoxy resin contained in the epoxy resin composition that excludes compound (A).
     
    9. The epoxy-resin composition according to any one of Claims 1 to 7, wherein the amount of component (B) is at least 58 parts by mass but no more than 100 parts by mass relative to 100 parts by mass of the entire amount of epoxy resin contained in the epoxy resin composition that excludes compound (A).
     
    10. The epoxy-resin composition according to any one of Claims 1 to 9, wherein compound (C) is dicyandiamide.
     
    11. The epoxy-resin composition according to any one of Claims 1 to 10, further comprising thermoplastic resin (E).
     
    12. The epoxy-resin composition according to Claim 11, wherein thermoplastic resin (E) is phenoxy resin.
     
    13. A prepreg formed by impregnating reinforcing fiber with the epoxy-resin composition according to any one of Claims 1 to 12.
     
    14. A fiber-reinforced composite material obtained by curing the prepreg according to Claim 13.
     
    15. A housing for an electrical/electronic device, wherein the housing is partially or entirely formed using the fiber-reinforced composite material according to Claim 14.
     


    Ansprüche

    1. Epoxidharzzusammensetzung, umfassend:

    Komponente (A);

    Komponente (B);

    Komponente (C); und

    Komponente (D),

    worin das Verhältnis der Stoffmenge einer von Komponente (D) abgeleiteten Harnstoffgruppe zur Menge der von Komponente (A) abgeleiteten Phosphoratome (Harnstoffäquivalent zu Phosphor) im Bereich von 0,25 oder höher bis 1,85 oder niedriger liegt und
    die Menge der Komponente (A) zu 100 Gewichtsteilen der Menge der restlichen Epoxidharzzusammensetzung, die Komponente (A) ausschließt, 7 Gewichtsteile oder mehr beträgt,
    die Komponente (A): eine Phosphorverbindung,
    die Komponente (B): ein Epoxidharz, das mindestens drei Epoxidgruppen im Molekül aufweist und das weder Komponente (A) entspricht noch Komponente (A) enthält,
    die Komponente (C): ein Epoxidharzhärtungsmittel, das keine Harnstoffstruktur im Molekül aufweist und
    die Komponente (D): eine durch die folgende Formel (a) dargestellte Dimethylharnstoffverbindung.

    ("R" für ein Wasserstoffatom oder eine Alkylgruppe mit einer Anzahl von 1 bis 10 Kohlenstoffen steht);
    worin die Komponente (A) ein Phosphor-modifiziertes Epoxidharz ist, das aus einer durch die folgende Formel (b) dargestellten Verbindung (b) hergestellt ist.

    worin "n" für eine ganze Zahl von Null oder größer steht; "X" für eine in den folgenden Formeln (I), (II) oder (III) gezeigte Gruppe steht; wobei, in der Formel, (n+2) X-Gruppen gleich oder voneinander verschieden sein können; mindestens ein "X" unter den (n+2) X-Gruppen für eine in der folgenden Formel (I) oder (II) gezeigte Gruppe steht; "Y" eine (-H)- oder (-CH3)-Bindung darstellt und (n+2) Y-Bindungen in der Formel gleich oder verschieden sein können.


     
    2. Epoxidharzzusammensetzung gemäß Anspruch 1, worin die Komponente (A) eine Phosphorverbindung mit einem Gehalt an Phosphoratomen von mindestens 1,0 Massen-%, aber nicht mehr als 8,0 Massen-% ist.
     
    3. Epoxidharzzusammensetzung gemäß Anspruch 1 oder 2, worin die Komponente (D) 1,1'-(4-Methyl-1,3-phenylen)bis(3,3-dimethylharnstoff) ist.
     
    4. Epoxidharzzusammensetzung gemäß mindestens einem der Ansprüche 1 bis 3, worin das Verhältnis der Stoffmenge der von Komponente (D) abgeleiteten Harnstoffgruppe zur Stoffmenge der von Komponente A abgeleiteten Phosphoratome (Harnstoffäquivalent zu Phosphor) mindestens 0,48, aber nicht mehr als 0,90 beträgt.
     
    5. Epoxidharzzusammensetzung gemäß mindestens einem der Ansprüche 1 bis 4, worin das Verhältnis der Stoffmenge der von Komponente (D) abgeleiteten Harnstoffgruppe zur Stoffmenge der Epoxidgruppe in der Epoxidharzzusammensetzung (Harnstoffäquivalent zu Epoxid) mindestens 0,03, aber nicht mehr als 0,25 beträgt.
     
    6. Epoxidharzzusammensetzung gemäß mindestens einem der Ansprüche 1 bis 5, worin der Gehalt an Phosphoratomen in der Epoxidharzzusammensetzung mindestens 0,4 Massen-%, aber nicht mehr als 3,5 Massen-% beträgt.
     
    7. Epoxidharzzusammensetzung gemäß mindestens einem der Ansprüche 1 bis 6, worin Komponente (B) mindestens eines umfasst, ausgewählt aus Epoxidharz vom Trisphenolmethan-Typ, Epoxidharz vom Aminophenol-Typ, Epoxidharz vom Diaminodiphenylmethan-Typ, Epoxidharz vom Novolak-Typ und deren modifizierten Epoxidharzen.
     
    8. Epoxidharzzusammensetzung gemäß mindestens einem der Ansprüche 1 bis 7, worin die Menge an Komponente (B) in Bezug auf 100 Massenteile der Gesamtmenge an Epoxidharz, die in der Epoxidharzzusammensetzung, die Verbindung (A) ausschließt, enthalten ist, mindestens 18 Massenteile aber nicht mehr als 100 Massenteile beträgt.
     
    9. Epoxidharzzusammensetzung gemäß mindestens einem der Ansprüche 1 bis 7, worin die Menge an Komponente (B) in Bezug auf 100 Massenteile der Gesamtmenge an Epoxidharz, die in der Epoxidharzzusammensetzung, die Verbindung (A) ausschließt, enthalten ist, mindestens 58 Massenteile aber nicht mehr als 100 Massenteile beträgt.
     
    10. Epoxidharzzusammensetzung gemäß mindestens einem der Ansprüche 1 bis 9, worin Verbindung (C) Dicyandiamid ist.
     
    11. Epoxidharzzusammensetzung gemäß mindestens einem der Ansprüche 1 bis 10, ferner umfassend ein thermoplastisches Harz (E).
     
    12. Epoxidharzzusammensetzung gemäß Anspruch 11, worin das thermoplastische Harz (E) ein Phenoxyharz ist.
     
    13. Prepreg, das durch Imprägnieren von Verstärkungsfasern mit der Epoxidharzzusammensetzung gemäß mindestens einem der Ansprüche 1 bis 12 gebildet ist.
     
    14. Faserverstärktes Verbundmaterial, erhalten durch Härten des Prepregs gemäß Anspruch 13.
     
    15. Gehäuse für eine elektronische/elektrische Vorrichtung, worin das Gehäuse teilweise oder ganz unter Verwendung des faserverstärkten Verbundmaterials gemäß Anspruch 14 gebildet ist.
     


    Revendications

    1. Composition de résine époxy, comprenant :

    un composant (A) ;

    un composant (B) ;

    un composant (C) ; et

    un composant (D),

    dans laquelle, le rapport entre la quantité de substance d'un groupe urée dérivé du composant (D) et la quantité d'atomes de phosphore dérivés du composant (A) (urée équivalent au phosphore) est situé dans la plage allant de 0,25 ou plus à 1,85 ou moins, et

    la quantité de composant (A) par rapport à 100 parties en masse de la quantité du reste de la composition de résine époxy qui exclut le composant (A) est de 7 parties en masse ou plus,

    le composant (A) : un composé phosphoré,

    le composant (B) : une résine époxy qui présente au moins trois groupes époxy dans la molécule, et qui ne correspond pas au composant (A) ni n'inclut le composant (A),

    le composant (C) : un agent de durcissement de résine époxy qui ne présente pas une structure d'urée dans la molécule, et

    le composant (D) : un composé de diméthylurée représenté par la formule (a) ci-dessous.

    (« R » est un atome d'hydrogène ou un groupe alkyle présentant un nombre quelconque de carbones allant de 1 à 10) ;

    dans laquelle le composant (A) est une résine époxy modifiée par le phosphore constituée du composé (b) représenté par la formule (b) ci-dessous.

    dans laquelle « n » est un nombre entier égal à zéro ou plus ; « X » est un groupe représenté dans les formules (I), (II) ou (III) ci-dessous; dans la formule, (n + 2) groupes X peuvent être identiques ou différents; au moins un « X » parmi les (n + 2) groupes X est un groupe représenté dans la formule (I) ou (II) ci-dessous ; « Y » représente une liaison (-H) ou (-CH3), et (n + 2) liaisons Y dans la formule peuvent être identiques ou différentes.




     
    2. Composition de résine époxy selon la revendication 1, dans laquelle le composant (A) est un composé phosphoré ayant une teneur en atome de phosphore d'au moins 1,0 % en masse mais pas supérieure à 8,0 % en masse.
     
    3. Composition de résine époxy selon la revendication 1 ou 2, dans laquelle le composant (D) est la 1,1'-(4-méthyl-1,3-phénylène)bis(3,3-diméthylurée).
     
    4. Composition de résine époxy selon l'une quelconque des revendications 1 à 3, dans laquelle le rapport entre la quantité de substance du groupe urée dérivé du composant (D) et la quantité de substance d'atomes de phosphore dérivés du composant A (urée équivalent au phosphore) est au moins de 0,48 mais pas supérieur à 0,90.
     
    5. Composition de résine époxy selon l'une quelconque des revendications 1 à 4, dans laquelle le rapport entre la quantité de substance du groupe urée dérivé du composant (D) et la quantité de substance du groupe époxy dans la composition de résine époxy (urée équivalent à l'époxy) est au moins de 0,03 mais pas supérieur à 0,25.
     
    6. Composition de résine époxy selon l'une quelconque des revendications 1 à 5, dans laquelle la teneur en atome de phosphore dans la composition de résine époxy est au moins de 0,4 % en masse mais pas supérieure à 3,5 % en masse.
     
    7. Composition de résine époxy selon l'une quelconque des revendications 1 à 6, dans laquelle le composant (B) inclut au moins l'une sélectionnée parmi une résine époxy de type trisphénolméthane, une résine époxy de type aminophénol, une résine époxy de type diaminodiphénylméthane, une résine époxy de type novolaque et leurs résines époxy modifiées.
     
    8. Composition de résine époxy selon l'une quelconque des revendications 1 à 7, dans laquelle la quantité de composant (B) est au moins de 18 parties en masse mais pas supérieure à 100 parties en masse par rapport à 100 parties en masse de la quantité totale de résine époxy contenue dans la composition de résine époxy qui exclut le composé (A).
     
    9. Composition de résine époxy selon l'une quelconque des revendications 1 à 7, dans laquelle la quantité de composant (B) est au moins de 58 parties en masse mais pas supérieure à 100 parties en masse par rapport à 100 parties en masse de la quantité totale de résine époxy contenue dans la composition de résine époxy qui exclut le composé (A).
     
    10. Composition de résine époxy selon l'une quelconque des revendications 1 à 9, dans laquelle le composé (C) est le dicyandiamide.
     
    11. Composition de résine époxy selon l'une quelconque des revendications 1 à 10, comprenant en outre une résine thermoplastique (E).
     
    12. Composition de résine époxy selon la revendication 11, dans laquelle la résine thermoplastique (E) est une résine phénoxy.
     
    13. Préimprégné formé par l'imprégnation d'une fibre de renforcement avec la composition de résine époxy selon l'une quelconque des revendications 1 à 12.
     
    14. Matériau composite renforcé par des fibres obtenu par le durcissement du préimprégné selon la revendication 13.
     
    15. Boîtier pour un dispositif électrique/électronique, dans lequel le boîtier est partiellement ou entièrement formé en utilisant le matériau composite renforcé par des fibres selon la revendication 14.
     






    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description