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WO2019065514A1 - Élastomère composite à fibres très solides - Google Patents

Élastomère composite à fibres très solides Download PDF

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Publication number
WO2019065514A1
WO2019065514A1 PCT/JP2018/035109 JP2018035109W WO2019065514A1 WO 2019065514 A1 WO2019065514 A1 WO 2019065514A1 JP 2018035109 W JP2018035109 W JP 2018035109W WO 2019065514 A1 WO2019065514 A1 WO 2019065514A1
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WO
WIPO (PCT)
Prior art keywords
group
composite
ibxa
substituted
unsubstituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2018/035109
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English (en)
Japanese (ja)
Inventor
剣萍 グン
孝幸 黒川
桃林 孫
亮 陳
為 崔
猿渡　欣幸
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Hokkaido University NUC
Osaka Organic Chemical Industry Co Ltd
Original Assignee
Hokkaido University NUC
Osaka Organic Chemical Industry Co Ltd
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Priority claimed from PCT/JP2018/015583 external-priority patent/WO2019064659A1/fr
Application filed by Hokkaido University NUC, Osaka Organic Chemical Industry Co Ltd filed Critical Hokkaido University NUC
Priority to JP2019545066A priority Critical patent/JP7232474B2/ja
Publication of WO2019065514A1 publication Critical patent/WO2019065514A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material

Definitions

  • the present invention relates to tough and flexible composites comprising fibers and polymers.
  • Non-Patent Document 1 Conventional fiber reinforced materials have hard and high strength fibers as their skeleton, and hard plastic has been used as a matrix (For hard plastic, Plastics and Functional Polymers Encyclopedia, Journal of the Industrial Research Council, 2004, See Chapter 5 (Non-Patent Document 1).
  • the present invention provides a composite that uses a soft, high toughness material as a matrix (such as a high toughness elastomer) and its application technology. Thereby, the following advantages can be obtained. (1) It is possible to avoid the separation of the interface. (2) The matrix phase can dissipate energy. (3) A large process zone can be gained by combining soft and hard materials. In the present invention, the physical properties of either or both of the hard material represented by the fiber and the soft material represented by the matrix or their correlation may be important.
  • the present invention provides the following items.
  • a composite material comprising a fiber and a glass transitionable polymer,
  • the glass transferable polymer is a homopolymer or copolymer formed by polymerizing monomer components comprising one or more monomers.
  • the monomer component comprises a monomer (A) and optionally a vinyl monomer (B),
  • Item 2 The composite material according to any one of the above items, wherein the glass transition temperature of the monomer (A) is ⁇ 70 ° C. or higher and lower than 10 ° C.
  • the monomer (A) is represented by the general formula (1) (Wherein, R 1 is hydrogen, R 2 is an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group, X 1 is oxygen, X 2 is oxygen or sulfur, and n is 0 to 3, provided that when R 2 is unsubstituted C 1-4 alkyl or hydroxy substituted C 1-4 alkyl, n is 1 to 3), and the vinyl monomer (B ) But the general formula (2) (Wherein, R 3 is hydrogen, R 4 is —C (-O) —O—R 6 , and R 6 is an unsubstituted or substituted tertiary carbon-containing C 4-6 alkyl group, or unsubstituted or substituted C 3 ⁇ 12 cycloalkyl group.) represented by the composite material according to any one of the above items.
  • R 2 is an unsubstituted or substituted C 1-18 alkyl group or unsubstituted or substituted C 6 ⁇ 18 aryl group, a composite material according to any one of the above items.
  • Section 7A R 2 is an unsubstituted or substituted C 6 ⁇ 18 C 1-18 alkyl group substituted with an aryl group or an unsubstituted or substituted C 6 ⁇ 18 aryl group, any one of the above items Composite material as described in.
  • the monomer (B) is a glass having a temperature of about 30 ° C. to 120 ° C. when the homopolymer comprising only the monomer (B) is produced under the conditions for producing the composite material.
  • R 6 may be substituted with one or more substituents selected from C 1 ⁇ 4 alkyl group, t- butyl group, isobornyl group, adamantyl group, C 5 ⁇ 7 cycloalkyl
  • (Section 12) The composite according to any one of the above sections, wherein the monomer (B) contains at least one selected from the group consisting of t-butyl acrylate, isobornyl acrylate, and cyclohexyl acrylate.
  • the fiber comprises glass fiber, carbon fiber, aramid (Kevlar (registered trademark)) fiber, plant fiber, wood fiber, animal fiber, mineral fiber, metal fiber, synthetic polymer fiber, and a combination thereof
  • a composite according to any one of the preceding items which is one or more fibers selected from the group.
  • the present invention also provides the following items.
  • (Item A1) A composite containing fibers and a glass transitionable polymer.
  • (Item A2) The composite material according to any one of the above items, wherein the glass transition temperature of the glass transitionable polymer is about ⁇ 70 to 30 ° C. or about ⁇ 50 to 20 ° C.
  • (Item A3) The composite according to any one of the above items, wherein the polymer is a homopolymer or a copolymer formed by polymerizing a monomer component containing one or more monomers.
  • (Item A4) The composite material according to any one of the above items, wherein the viscosity of the monomer component is about 0.1 to 50 mPa ⁇ s or about 0.5 to 30 mPa ⁇ s.
  • the glass transitionable polymer comprises (meth) acrylic polymer, ethylene polymer, urethane polymer, ether polymer, amide polymer, carbonate polymer and silicone polymer, and any combination thereof A composite according to any one of the preceding clauses selected from the group.
  • the monomer component is represented by the general formula (1) (R 1 is hydrogen or a C 1-4 alkyl group, R 2 is an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted cycloalkenyl group, It is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted heteroaryl group, and X 1 and X 2 are each independently O, S, NR x , and CR x 1 R x 2 is selected from the group consisting of, R x is hydrogen, C 1 ⁇ 6 alkyl group, C 1 ⁇ 6 alkoxy group, C 1 ⁇ 6 haloalkyl group or a C 2 ⁇ 6 haloalkenyl group, R x1 and R x2
  • R 2 is halogen, hydroxyl group, cyano group, C 1 ⁇ 10 alkyl group, C 1 ⁇ 6 alkoxy group, C 1 ⁇ 6 alkyloxycarbonyl group, C 1 ⁇ 6 haloalkyl group, C 2 ⁇ 6 alkenyl group, C 2 ⁇ 6 haloalkenyl group, C 3 ⁇ 6 cycloalkyl group, C 3 ⁇ 6 halocycloalkyl group, selected from the group consisting of 3-8 membered heterocyclic group and a C 6 ⁇ 18 arylthio group it may be substituted with one or more groups, C 1 ⁇ 6 alkyl group, C 2 ⁇ 6 alkenyl group, C 3 ⁇ 6 cycloalkyl group, C 6 ⁇ 18 aryl, 5 to 18-membered heteroaryl group there is, however, if X 1 is bonded directly with R 2, R 2 is not a 5 to 18 membered heteroaryl group at C 6
  • R 2 is hydroxyl group, may be substituted with one or more groups selected from the group consisting of C 1 ⁇ 6 alkyl group and C 6 ⁇ 18 arylthio group, C 1 ⁇ 18 alkyl group, a C 6 ⁇ 18 aryl or 5-18 membered heteroaryl group, the composite material according to any one of the above items.
  • (Item A13) The composite material according to any one of the above items, wherein R 2 is a C 1-6 alkyl group, a phenyl group, a benzyl group or a phenylthioethyl group.
  • the monomer (A) is 2-methoxyethyl acrylate, ethyl carbitol acrylate, triethylene glycol methyl ether acrylate, benzyl acrylate, phenoxyethyl acrylate, phenylthioethyl acrylate, lauryl acrylate, isostearyl acrylate, phenoxy diethylene glycol
  • the composite material according to any one of the above items, which comprises at least one selected from the group consisting of acrylate and cyclohexyl acrylate.
  • the monomer (B) is a glass having a temperature of about 30 ° C. to 120 ° C.
  • L is a bond or -CH 2 - is
  • R 6 is unsubstituted or substituted tertiary carbon-containing C 4 ⁇ 8 alkyl group, an unsubstituted or substituted C 3 ⁇ 12 cycloalkyl group, unsubstituted or substituted C 3 ⁇ 12 cycloalkenyl group, an unsubstituted or substituted 5-12 membered heterocyclic group, unsubstituted or substituted C 6 ⁇ 18 aryl group or an unsubstituted or substituted 5 to 18 membered heteroaryl group, said The composite material according to any one of the above items.
  • R 6 may be substituted with one or more substituents selected from C 1 ⁇ 4 alkyl group, t- butyl group, isobornyl group, adamantyl group, C 5 ⁇ 7 cycloalkyl A composite according to any one of the preceding clauses which is a group or a 5-6 membered heterocyclic group.
  • the monomer (B) contains at least one selected from the group consisting of t-butyl acrylate, isobornyl acrylate, adamantyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, cyclic trimethylol propane formal acrylate
  • the homopolymer component or the copolymer has a tensile modulus of about 0.05 MPa or more when the monomer component is a homopolymer or a copolymer composed only of the monomer component under the conditions for producing the composite material.
  • the tensile modulus is about 0.05 to 100 MPa or more when it is measured alone by a tensile test at a tensile speed of 50 mm / min, according to any one of the above items Composite material.
  • the impregnation step includes the step of fixing the fiber in the interior of the mold, injecting the monomer component into the interior of the mold, and immersing the fiber in the monomer component. Composite material described.
  • the glass transitionable polymer has a general formula (1) (R 1 is hydrogen or a C 1-4 alkyl group, R 2 is an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted cycloalkenyl group, It is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted heteroaryl group, and X 1 and X 2 are each independently O, S, NR x , and CR x 1 R x 2 is selected from the group consisting of, R x is hydrogen, C 1 ⁇ 6 alkyl group, C 1 ⁇ 6 alkoxy group, C 1 ⁇ 6 haloalky
  • the monomer component is polymerized according to a polymerization method selected from the group consisting of bulk polymerization method, solution polymerization method, emulsion polymerization method, and suspension polymerization method. Method.
  • Vehicle parts such as automobiles, aircraft, ships, trains, motorcycles, bicycles, helmets, masks, goggles, protective gear, pads, golf clubs, tennis rackets, skis, sports goods such as stock, bulletproof walls, bulletproof vests , Protective equipment such as bulletproof car, artificial leg equipment such as artificial hand and artificial leg, bag case such as suitcase and carry case, household appliance such as vacuum cleaner and electric tool, portable chemical products such as umbrella and cane, bed, mat, cushion Such as in furniture products, dishes, toys, play equipment, building materials, clothing materials, electronic materials, medical materials, healthcare materials, life science materials, and robot materials, and any of the composites according to any one of the above items use.
  • the present invention further provides the following items.
  • (Item B1) A composite material containing a first material and a second material, and (i) a tensile test method according to JIS R 7606 for the first material and JIS K 7161 for the second material.
  • the ratio of the breaking stress between the first material and the second material is about 50 or more, and (ii) the tensile test method
  • the modulus of elasticity (tensile modulus) is measured at a speed of 50 mm / min at about 20 ° C.
  • the ratio of the modulus of elasticity (tensile modulus) between the first material and the second material is about 100 or more Composites that meet at least one of the conditions.
  • (Item B2) A composite material containing a first material and a second material, and (i) a tensile test method according to JIS R 7606 for the first material and JIS K 7161 for the second material.
  • the first material When the breaking stress is measured at a rate of 50 mm / min at 20 ° C., the first material has a breaking stress of about 50 MPa or more, and (ii) 50 mm / min at about 20 ° C. according to the tensile test method.
  • a composite, wherein the second material meets at least one of about 200% or greater strain at break when the strain at break is measured at a rate of minutes. (Item B3) A composite material comprising a first material and a second material, wherein (i) the breaking stress is measured at a speed of 50 mm / min at about 20 ° C.
  • (Item B6) The composite according to any one of the preceding items, wherein the second material has a strain at break of about 300% or more or about 400% or more.
  • (Item B7) A composite material comprising a first material and a second material, wherein (i) the composite material wherein the ratio of the fracture stress of the first material to the second material is 50 or more .
  • (Item B8) A composite material comprising a first material and a second material, and (ii) a composite material having a ratio of tensile modulus of 100 or more between the first material and the second material. .
  • (Item B9) The composite material according to any one of the above items, wherein the ratio of the breaking stress is about 100 or more or about 150 or more.
  • the first material has a fibrous form, and the fiber unit of the first material is about 1 TEX to about 1000 TEX, about 10 TEX to about 950 TEX, about 30 TEX to about 900 TEX, about 45 TEX to about A composite according to any one of the preceding claims which is 850 TEX or about 60 TEX to about 800 TEX thick.
  • the cross-sectional area of the fiber unit of the first material is at least about 0.05 mm 2, at least about 0.075 mm 2, or at least about 0.1 mm 2 .
  • Composite material (Item B14) The composite material according to any one of the above items, wherein the first material is a fiber unit and the second material is a glass transitionable polymer. (Item B15) Any one of the above items, wherein the glass transition temperature of the glass transitionable polymer is about ⁇ 150 to 150 ° C., about ⁇ 100 to 100 ° C., about ⁇ 70 to 30 ° C. or about ⁇ 50 to 20 ° C. The composite material according to item 1.
  • the glass-transferable polymer comprises (meth) acrylic polymer, ethylene polymer, urethane polymer, ether polymer, amide polymer, carbonate polymer and silicone polymer, and any combination thereof A composite according to any one of the preceding clauses selected from the group.
  • the monomer component is represented by the general formula (1) (R 1 is hydrogen or a C 1-4 alkyl group, R 2 is an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted cycloalkenyl group, It is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted heteroaryl group, and X 1 and X 2 are each independently O, S, NR x , and CR x 1 R x 2 is selected from the group consisting of, R x is hydrogen, C 1 ⁇ 6 alkyl group, C 1 ⁇ 6 alkoxy group, C 1 ⁇ 6 haloalkyl group or a C 2 ⁇ 6 haloalkenyl group, R x1 and R
  • R 2 is halogen, hydroxyl group, cyano group, C 1 ⁇ 10 alkyl group, C 1 ⁇ 6 alkoxy group, C 1 ⁇ 6 alkyloxycarbonyl group, C 1 ⁇ 6 haloalkyl group, C 2 ⁇ 6 alkenyl group, C 2 ⁇ 6 haloalkenyl group, C 3 ⁇ 6 cycloalkyl group, C 3 ⁇ 6 halocycloalkyl group, selected from the group consisting of 3-8 membered heterocyclic group and a C 6 ⁇ 18 arylthio group it may be substituted with one or more groups, C 1 ⁇ 6 alkyl group, C 2 ⁇ 6 alkenyl group, C 3 ⁇ 6 cycloalkyl group, C 6 ⁇ 18 aryl, 5 to 18-membered heteroaryl group there is, however, if X 1 is bonded directly with R 2, R 2 is not a 5 to 18 membered heteroaryl group at C 6
  • R 2 is hydroxyl group, may be substituted with one or more groups selected from the group consisting of C 1 ⁇ 6 alkyl group and C 6 ⁇ 18 arylthio group, C 1 ⁇ 18 alkyl group, a C 6 ⁇ 18 aryl or 5-18 membered heteroaryl group, the composite material according to any one of the above items.
  • (Item B24) The composite material according to any one of the above items, wherein R 2 is a C 1-6 alkyl group, a phenyl group, a benzyl group or a phenylthioethyl group.
  • the monomer (A) is 2-methoxyethyl acrylate, ethyl carbitol acrylate, triethylene glycol methyl ether acrylate, benzyl acrylate, phenoxyethyl acrylate, phenylthioethyl acrylate, lauryl acrylate, isostearyl acrylate, phenoxy diethylene glycol
  • the composite material according to any one of the above items, which comprises at least one selected from the group consisting of acrylate and cyclohexyl acrylate.
  • the monomer (B) is a glass having a temperature of about 30 ° C. to 120 ° C.
  • L is a bond or -CH 2 - is
  • R 6 is unsubstituted or substituted tertiary carbon-containing C 4 ⁇ 8 alkyl group, an unsubstituted or substituted C 3 ⁇ 12 cycloalkyl group, unsubstituted or substituted C 3 ⁇ 12 cycloalkenyl group, an unsubstituted or substituted 5-12 membered heterocyclic group, unsubstituted or substituted C 6 ⁇ 18 aryl group or an unsubstituted or substituted 5 to 18 membered heteroaryl group, said The composite material according to any one of the above items.
  • R 6 may be substituted with one or more substituents selected from C 1 ⁇ 4 alkyl group, t- butyl group, isobornyl group, adamantyl group, C 5 ⁇ 7 cycloalkyl A composite according to any one of the preceding clauses which is a group or a 5-6 membered heterocyclic group.
  • the monomer (B) contains at least one selected from the group consisting of t-butyl acrylate, isobornyl acrylate, adamantyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, cyclic trimethylol propane formal acrylate
  • the polymer is thermally or photopolymerized or thermally polymerized.
  • the first material is a fiber, and the fiber is glass fiber, carbon fiber, aramid fiber, plant fiber, wood fiber, animal fiber, mineral fiber, metal fiber, synthetic polymer fiber, and combinations thereof
  • a composite according to any one of the preceding clauses selected from the group consisting of (Item B38) The material according to any one of the preceding items, wherein said first material is a fiber, said fiber being selected from the group consisting of glass fibers, carbon fibers and aramid (Kevlar®) fibers.
  • Composite material (Item B39) The composite material according to any one of the above items, wherein the first material is a fiber formed as a woven fabric, a knitted fabric or a non-woven fabric.
  • the homopolymer component or the copolymer has a tensile coefficient of about 0.05 MPa or more when the monomer component is a homopolymer or a copolymer composed only of the monomer component under the conditions for producing the composite material.
  • the impregnation step fixes the fabric composed of the fiber unit constituting the first material in the interior of the mold, injects the monomer component into the interior of the mold, and the fiber unit is the monomer component A composite according to any one of the preceding claims, comprising the steps of (Item B49) A method of producing a composite containing fibers and a glass transitionable polymer.
  • the glass transitionable polymer has a general formula (1) (R 1 is hydrogen or a C 1-4 alkyl group, R 2 is an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted cycloalkenyl group, It is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted heteroaryl group, and X 1 and X 2 are each independently O, S, NR x , and CR x 1 R x 2 is selected from the group consisting of, R x is hydrogen, C 1 ⁇ 6 alkyl group, C 1 ⁇ 6 alkoxy group, C 1 ⁇ 6 haloalkyl group or a C 2 ⁇ 6 haloalkenyl group, R x1 and R
  • the monomer component is polymerized according to a polymerization method selected from the group consisting of a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method. Method.
  • (Section B 54) Vehicle parts such as automobiles, aircraft, ships, trains, motorcycles, bicycles, helmets, masks, goggles, protective gear, pads, golf clubs, tennis rackets, skis, stock such as sporting goods, bulletproof walls, bulletproof vests, bulletproof vehicles, etc.
  • Composites according to any one of the preceding clauses, or for use as dishes, toys, play equipment items, building materials, clothing materials, electronic materials, medical materials, healthcare materials, life science materials and robot materials A composite manufactured by the method according to any one of the above items, or a composition containing the composite, or Vehicle products, sports products, protective products, prosthetic products, bag products, household appliances, portable chemical products, furniture products, dishes, toys, play equipment, buildings, clothes, electronic products, medical products, medical products, including the composite materials Products such as health care products, life science products and robot products.
  • the composite material of the present invention can be used in all fields where high toughness and flexibility are required, for example, in the field of material science of traditional materials such as metal materials, polymer materials and inorganic materials, as well as interface science , Process engineering, production engineering, mechanical engineering, aerospace engineering, ship engineering, architectural civil engineering, etc., and so on, and so on, and more specifically, motorcycles (bicycles, motorcycles etc.), automobiles, planes, trains, ships, rockets , Spacecraft, transportation, leisure furniture, bedding, clothes, protective clothing, sporting goods, bathtubs, kitchens, dishes, cooking utensils, containers and packaging materials, buildings (buildings, roads, building parts, etc.), agricultural films, industrial films , Water and sewage, paint, cosmetics, electrical industry and electronics industry (electrical appliances, computer parts, printed circuit boards, insulators, conductors, wire coating materials, Electric elements, speakers, microphones, noise cancelers, transducers, etc., optical communication cables, medical materials and devices (catheters, guide wires, artificial blood vessels, artificial
  • FIG. 1 is a stress-strain curve of a tensile test of a PHDEA-IBXA copolymer (PHDEA-co-IBXA) with different mole fractions of phenoxydiethylene glycol acrylate (PHDEA) and isobornyl acrylate (IBXA).
  • FIG. 2 is a force-displacement curve of the tear test of PHDEA-co-IBXA cuts with different mole fractions of PHDEA and IBXA.
  • FIG. 3 is a force-displacement curve of the tear test of a carbon fiber composite cut with PHDEA-co-IBXA with different mole fractions of PHDEA and IBXA.
  • PHDEA: IBXA 0.4: 0.6, 0.45: 0.55, and 0.7: 0.3
  • the size of the test sample is 50 mm long ⁇ 30 mm wide ⁇ about 1.3 mm thick and the incision is 10 mm.
  • PHDEA: IBXA 0.5: 0.5, 0.6: 0.4
  • the size of the test sample is 60 mm long ⁇ 30 mm wide ⁇ about 1.3 mm thick, and the incision is 20 mm.
  • FIG. 4 is a graph of tear energy versus PHDEA mole fraction for the copolymer (dotted line) and the composite (solid line) for each PHDEA-co-IBXA with different PHDEA and IBXA mole fractions.
  • the size of the copolymer tear test sample is 40 mm long ⁇ 30 mm wide ⁇ about 1 mm thick, and the incision is 20 mm.
  • the gray solid line shows a tensile speed of 1000 mm / min
  • the black solid line shows 500 mm / min
  • the gray broken line shows 100 mm / min
  • the black dashed dotted line also looks like a thick broken line) shows 50 mm / min.
  • the black solid line represents a tensile speed of 1000 mm / min
  • the black dotted line represents 500 mm / min
  • the gray dotted line represents 100 mm / min
  • the gray solid line represents 50 mm / min
  • the black dashed line represents 10 mm / min. Is 2 mm / min.
  • the black double line has a tear speed of 1000 mm / min, the black dotted line is 500 mm / min, the gray solid line is 100 mm / min, the black solid line is 50 mm / min, the gray dotted line is 10 mm / min, The black dashed line is 2 mm / min.
  • the black double line has a tear speed of 1000 mm / min, the black dotted line is 500 mm / min, the black dashed line is 100 mm / min, the gray solid line is 50 mm / min, the gray dotted line is 10 mm / min, The black solid line is 2 mm / min.
  • FIG. 13 is a correlation graph of the tearing energy (T m ) of the matrix and the tearing energy (T c ) of the matrix and the carbon fiber composite material.
  • the softest polymers are represented by squares and the hardest polymers are represented by circles.
  • FIG. 14 is a stress-strain curve of a tensile test of a PHEA-IBXA copolymer (PHEA-co-IBXA) with different mole fractions of phenoxyethyl acrylate (PHEA) and IBXA.
  • FIG. 15 is a force-displacement curve of the tear test for PHEA and IBXA copolymers (PHEA-co-IBXA) with different mole fractions of PHEA and IBXA.
  • FIG. 16 is a graph showing the tensile modulus and stress of copolymers with different mole fractions of PHEA and IBXA.
  • the bar graph on the left represents the tensile modulus and the right represents the stress.
  • FIG. 17 is a graph showing strain energy density and tear energy of copolymers having different PHEA and IBXA mole fractions.
  • the bar on the left represents strain energy density
  • the right represents tear energy.
  • the gray double-dashed line represents the results for a sample width of 5 mm
  • the black solid line is 7.5 mm
  • the black double-dashed line is 10 mm
  • the thin gray solid line is 15 mm
  • the black dotted line is 20 mm
  • the double gray solid line is 30 mm
  • a thick black solid line represents a result of 35 mm
  • a gray dotted line represents 45 mm
  • a thick gray solid line represents 60 mm
  • a black broken line represents 70 mm
  • a double black solid line represents a result of 80 mm.
  • the gray double-dashed line represents the results for a sample width of 5 mm
  • the double-black dashed line is 10 mm
  • the thin gray solid line is 15 mm
  • the black dotted line is 20 mm
  • the double gray solid line is 25 mm
  • the thick black solid line is 30 mm
  • the gray dotted line represents a result of 40 mm
  • the thick gray solid line represents a 50 mm
  • the black broken line represents a 65 mm
  • the double solid black solid line represents a result of 80 mm.
  • the gray double-dashed line represents the results for a sample width of 5 mm
  • the double-black dashed line is 10 mm
  • the thin gray solid line is 15 mm
  • the black dotted line is 20 mm
  • the double gray solid line is 30 mm
  • the thick black solid line is 40 mm
  • the gray dotted line represents the result of 55 mm
  • the thick gray solid line represents the result of 65 mm
  • the black broken line represents the result of 75 mm
  • the double solid black solid line represents the result of 85 mm.
  • FIG. 24 is a schematic view showing the relationship between the sample width and the process zone in the correlation diagram of FIG.
  • the sample width is smaller than W c , the fibers are only drawn, and when the sample width is larger than W c , the fiber drawing and the fiber breakage coexist, and when the sample width is much larger than W c , Mainly fiber breakage occurs.
  • the gray double-dashed line represents the results for a sample width of 5 mm
  • the double-dashed black dashed line is 10 mm
  • the gray dashed line is 15 mm
  • the black dotted line is 20 mm
  • the double-doted gray solid line is 30 mm
  • the thick black solid line is 35 mm
  • the gray dotted line represents the result of 40 mm
  • the thick gray solid line represents the 50 mm
  • the black broken line represents the 65 mm
  • the double solid black solid line represents the result of 110 mm.
  • the gray double-dashed line represents the results for a sample width of 5 mm
  • the double-dashed black dashed line is 10 mm
  • the black dotted line is 15 mm
  • the double-doted gray solid line is 20 mm
  • the thick black solid line is 30 mm
  • the gray dotted line is 40 mm
  • the thick gray solid line represents the result of 50 mm
  • the black broken line represents the 70 mm
  • the double solid black solid line represents the result of 120 mm.
  • FIG. 29 shows tear energy (T c , kJ / m 2 ) vs.
  • FIG. 32 shows tear energy (T c , kJ / m 2 ) vs. prefactor (D) ⁇ energy density of matrix (W m ) ⁇ width in carbon fiber composites with different PHFR and IBXA mole fractions It is a correlation diagram with (kJ / m 2 ).
  • the black square is
  • Black dashed lines represent approximate straight lines for all points.
  • FIG. 33 shows tear energy (T c , kJ / m 2 ) vs.
  • the black triangles represent the results of 0.8: 0.2
  • the black triangles represent the results of 0.8: 0.2
  • Black dashed lines represent approximate straight lines for all points.
  • FIG. 36 is a graph depicting the tensile and flexural modulus of PHEA-co-IBXA / carbon fiber composites where the matrix components have different mole fractions.
  • M PHEA : M IBXA 0.7: 0.3 to 0.9: 0.1.
  • the bar graph on the left represents the tensile modulus, and the right side represents the flexural modulus.
  • the black solid line is the case where polymerization is initiated by UV
  • the gray broken line is the case where polymerization is initiated by heat.
  • FIG. 40 is a force-displacement curve for the tear test of a 40 mm wide PDMS (polydimethylsiloxane) polymer / carbon fiber composite and PHEA-co-IBXA / carbon fiber composite.
  • the black dotted line is a carbon fiber composite material (PDMS / CFC) with polydimethylsiloxane
  • 41 is a correlation diagram of the tear energy of a 40 mm wide PDMS (polydimethylsiloxane) polymer / carbon fiber composite and a PHEA-co-IBXA / carbon fiber composite versus the tear energy of the matrix.
  • PDMS polydimethylsiloxane
  • the white diamonds are shown as 0.2, the white diamonds as 0.9: 0.1, and the gray diamonds as 1: 0.
  • the black solid line is the case where the polymerization is initiated by heat, and the gray broken line is the case where the polymerization is initiated by UV.
  • the black solid line is the case where the polymerization is initiated by heat, and the gray broken line is the case where the polymerization is initiated by UV.
  • the black solid line is the case where the polymerization is initiated by heat, and the gray broken line is the case where the polymerization is initiated by UV.
  • the black solid line is the case where the polymerization is initiated by heat, and the gray broken line is the case where the polymerization is initiated by UV
  • the black solid line is the case where the polymerization is initiated by heat, and the gray broken line is the case where the polymerization is initiated by UV.
  • the black solid line is the case where the polymerization is initiated by heat
  • the gray broken line is the case where the polymerization is initiated by UV.
  • a composite material derived from thermally initiated polymerization (using AIBN) on the left side is shown, and a composite material derived from UV initiated polymerization (using benzophenone) is shown on the right side.
  • the black solid line is the case where the polymerization is initiated by heat, and the gray broken line is the case where the polymerization is initiated by UV.
  • the black solid line is the case where the polymerization is initiated by heat, and the gray broken line is the case where the polymerization is initiated by UV.
  • the black solid line is the case where the polymerization is initiated by heat
  • the gray broken line is the case where the polymerization is initiated by UV.
  • the black solid line is the case where the polymerization is initiated by heat
  • the gray broken line is the case where the polymerization is initiated by UV.
  • the black solid line is the case where the polymerization is initiated by heat, and the gray broken line is the case where the polymerization is initiated by UV.
  • the bar graph on the left represents the result of heat onset, and the right side represents the result of UV onset.
  • the bar graph on the left represents the result of heat onset, and the right side represents the result of UV onset.
  • FIG. 55 is a plot of PI / CFC tear energy (T c ) versus strain energy density (S m ) ⁇ critical width (W c ) with different mole fractions of PHEA and IBXA.
  • FIG. 56 is a stress-strain curve of a PHEA-IBXA copolymer (PHEA-co-IBXA) with different PHEA and IBXA mole fractions by tensile testing at different rates.
  • the unit mm / min is millimeter per minute.
  • FIG. 57 is a force-displacement curve of PHEA and IBXA copolymer (PHEA-co-IBXA) with different mole fractions of PHEA and IBXA by tear test at different rates.
  • FIG. 58 is a graph showing the tensile modulus and stress of copolymers with different mole fractions of PHEA and IBXA by testing at speeds of 500 mm / min or 5 mm / min.
  • the bar graph on the left represents the tensile modulus and the right represents the stress.
  • FIG. 59 is a graph showing strain energy density and tear energy of a composite of carbon fiber and copolymer with different mole fractions of PHEA and IBXA by testing at a speed of 500 mm / min or 5 mm / min.
  • the bar on the left represents strain energy density
  • the right represents tear energy.
  • a thin black solid line represents the result of a sample width of 5 mm, a thick gray solid line is 10 mm, a black broken line is 15 mm, a gray dotted line is 20 mm, a thin gray solid line is 25 mm, a thin black dashed line is 30 mm, a thick black solid line is 35 mm, a gray dashed dotted line Represents the result of 40 mm, respectively.
  • the tearing speed is 500 mm / min.
  • the thin gray dotted line represents the results for a sample width of 5 mm, and the thin gray solid line is 10 mm, the thick black dashed line is 15 mm, the thick gray dashed line is 20 mm, the thin black solid line is 25 mm, the thick gray solid line is 30 mm, and the thin gray dashed line is 35 mm
  • the thick black solid line shows the result of 40 mm, the thin gray dotted line shows the result of 50 mm, and the thin black broken line shows the result of 65 mm.
  • the thin gray dotted line represents the results for a sample width of 5 mm; thin black dashed line 10 mm, thick black dotted line 15 mm, gray solid line 20 mm, gray dashed line 25 mm, thick black solid line 30 mm, thin black solid line 35 mm, gray dashed dotted line Represents the result of 40 mm, respectively.
  • the tearing speed is 500 mm / min.
  • the thick black one-dotted line represents the results for a sample width of 5 mm; gray dashed line 10 mm, thick black solid line 15 mm, thin gray solid line 20 mm, black dotted line 25 mm, thick gray solid line 30 mm, black dashed line 35 mm, thin black solid line Represents a result of 45 mm, a thin gray dashed line represents 50 mm, and a gray dotted line represents a result of 65 mm.
  • the tearing speed is 5 mm / min.
  • the black dashed line represents the results for a sample width of 5 mm; gray dotted line is 10 mm, thick black dashed dotted line is 15 mm, thick black solid line is 20 mm, thick gray solid line is 25 mm, thin black solid line is 30 mm, thin black dashed dotted line is 35 mm, black dot
  • the line represents a result of 40 mm and the thin gray solid line represents a result of 50 mm.
  • the tearing speed is 500 mm / min.
  • the black dotted line represents the result of the sample width 5 mm
  • thin gray dashed line is 10 mm
  • black dashed dotted line is 15 mm
  • gray dotted line is 20 mm
  • thick gray solid line is 25 mm
  • black dotted line is 30 mm
  • thin gray solid line is 35 mm
  • thick black solid line Represents a result of 40 mm
  • a thin black solid line represents 45 mm
  • a gray broken line represents 50 mm.
  • the tearing speed is 500 mm / min.
  • the thin black double-dotted line represents the results for a sample width of 5 mm, the gray broken line is 10 mm, the thick black double-dotted line is 15 mm, the thick gray solid line is 20 mm, the thin black solid line is 25 mm, the thin gray dotted line is 30 mm, the thick black solid line
  • the thin gray solid line represents the result of 35 mm, and the thin black broken line represents the result of 45 mm.
  • the tearing speed is 500 mm / min.
  • FIG. 68 shows a graph of tear energy (T c ) -sample width in a tear test at 500 mm / min.
  • the tensile speed is 50 mm / min.
  • the tearing speed is 50 mm / min.
  • the thin black dot-dotted line represents the results for a sample width of 5 mm
  • the gray dotted line is 7.5 mm
  • the thick black dashed line is 10 mm
  • the thick black solid line is 15 mm
  • the thick gray solid line is 20 mm
  • the black dotted line is 30 mm
  • the thin gray solid line is 35 mm
  • the thin black broken line represents the result of 45 mm
  • the thin black solid line represents the result of 55 mm
  • the gray broken line represents the result of 70 mm.
  • the tearing speed is 50 mm / min.
  • the thick black dashed line represents the results for a sample width of 3 mm, the gray dotted line is 5 mm, the thin black dashed line is 8 mm, the thick gray solid line is 10 mm, the thin gray solid line is 15 mm, the thick black solid line is 20 mm, the thick black dashed line is 30 mm, thin
  • the black solid line represents the result of 40 mm, the black dotted line represents the 50 mm, and the thin gray dashed dotted line represents the result of 60 mm.
  • FIG. 75 shows a graph of tear energy (T c ) -sample width in a tear test at 50 mm / min.
  • FIG. 76 shows a graph of tear energy (T c ) -sample width in a tear test at 50 mm / min.
  • T c tear energy
  • S m strain energy density
  • W c critical width
  • FIG. 78 shows a graph of tear energy (T c ) -prefactor (D) ⁇ strain energy density (S m ) ⁇ critical width (W c ) for five composites.
  • the stars M PHEA : M IBXA 0.75 at a tearing speed of 50 mm / min: Each is based on the results in the case of glass fiber composites with 0.25 copolymer.
  • FIG. 79 shows the force-displacement curve of the tear test of the fiber bundle.
  • the carbon fiber bundle (CF) is measured at a speed of 5 mm / min (black broken line), 50 mm / min (grey solid line) or 500 mm / min (black solid line), and for glass fiber bundle (GF), 50 mm / min It measured by (gray dashed dotted line).
  • FIG. 80 shows stress-strain curves for tension tests of two fiber bundles.
  • FIG. 81 shows a graph of tear energy (T c ) -prefactor (D) ⁇ (strain energy density of matrix (S m ) + strain energy density of fiber bundle (S f )) ⁇ critical width (W c ) .
  • Black squares, black circles, and black triangles are based on the tear test results of the carbon fiber composite with PHEA-co-IBXA at tearing speeds of 5 mm / min, 50 mm / min and 500 mm / min, respectively; white circles are 5 mm Carbon fiber composites with BZA-co-IBXA at a tear rate of / min, stars, respectively, based on the results in the case of glass fiber composites with PHEA-co-IBXA at a tear rate of 50 mm / min.
  • Fig. 82 shows a graph of tear energy ( Tc )-(prefactor (D) x matrix strain energy density ( Sm ) + fiber bundle strain energy density ( Sf )) x critical width ( Wc ) .
  • Gray squares, black circles, and black triangles are based on the tear test results of the carbon fiber composite with PHEA-co-IBXA at tearing speeds of 5 mm / min, 50 mm / min and 500 mm / min, respectively; Carbon fiber composites with BZA-co-IBXA at a tear rate of / min, stars, respectively based on the results in the case of glass fiber composites with PHEA-co-IBXA at a tear rate of 50 mm / min FIG.
  • T c tear energy calculated by the thickness of the fiber ((fiber shear modulus (G f ) / matrix shear modulus (G f )) ⁇ matrix strain energy density (S m ) + The graph of distortion energy density (S f )) ⁇ critical width (W c ) of fiber bundle is shown.
  • Black squares, gray circles and black triangles are based on the tear test results of carbon fiber composites with PHEA-co-IBXA at tearing speeds of 5 mm / min, 50 mm / min and 500 mm / min, respectively; Carbon fiber composites with BZA-co-IBXA at a tearing speed of 50 mm / min, the stars are respectively based on the results in the case of glass fiber composites with PHEA-co-IBXA at a tearing speed of 50 mm / min.
  • Figure 84 is a tear energy is calculated from the thickness of the composite material (T c) - ((shear modulus of the fiber (G f) / matrix shear modulus of (G f)) ⁇ matrix strain energy density (S m)
  • the graph of + distortion energy density (S f ) of fiber bundle ⁇ critical width (W c ) is shown.
  • Black squares, gray circles, and black triangles are the results of tear test of carbon fiber composite (PI / CFC) with PHEA-co-IBXA at tearing speeds of 5 mm / min, 50 mm / min and 500 mm / min, respectively.
  • FIG. 85 shows a graph of critical width (W c ) -tensile modulus.
  • Gray squares, black circles, and black triangles are based on the results of tear tests of carbon fiber composites with PHEA-co-IBXA at tearing speeds of 5 mm / min, 50 mm / min and 500 mm / min, respectively; Based on the results in the case of a carbon fiber composite (BI / CFC) with BZA-co-IBXA at a tear rate of / min.
  • FIG. 86 shows a graph of critical width (W c ) -breaking stress. Black squares, black circles, and black triangles are based on the results of tear test of carbon fiber composite with PHEA-co-IBXA at tearing speeds of 5 mm / min, 50 mm / min and 500 mm / min, respectively.
  • the tearing speed is 50 mm / min.
  • the upper left sample is after the tear test at 24 ° C., the upper right is at 50 ° C., the lower left is at 100 ° C., and the lower right is at 150 ° C.
  • the tearing speed is 50 mm / min.
  • the upper left sample is after the tear test at 24 ° C., the upper right is at 50 ° C., the lower left is at 100 ° C., and the lower right is at 150 ° C.
  • the black solid line is after the tear test at 24 ° C.
  • the gray dashed line is at 50 ° C.
  • the black broken line is at 100 ° C.
  • the gray solid line is at 150 ° C.
  • the tensile modulus E is 0.56 MPa
  • the strain energy density is 8.29 MJ / m ⁇ 3
  • the fracture stress ⁇ is 1.86 MPa.
  • FIG. 91 shows the force-displacement curve for the tear test of a single aramid fiber.
  • the cross-sectional area of the aramid fiber tested is 0.396 mm 2 .
  • FIG. 92 shows stress-strain curves for tensile tests of single aramid fibers.
  • the strain energy density of the aramid fibers tested is 0.396 MJ / m -3 .
  • a thin black solid line represents the result of a sample width of 5 mm
  • a thin gray solid line is 10 mm
  • a thin black dotted line is 15 mm
  • a gray dotted line is 20 mm
  • a thick black dot dashed line is 25 mm
  • a gray dot dashed line is 30 mm
  • a thin black dot dashed line is 35 mm
  • thick The black solid line represents the result of 40 mm
  • the thin black broken line represents 50 mm
  • the thick black dotted line represents 65 mm
  • the thick black broken line represents 85 mm
  • the thick gray solid line represents 110 mm.
  • the length of the incision made before the test is 20 mm.
  • the tearing speed is 50 mm / min.
  • the length of the incision made before the test is 20 mm.
  • the tearing speed is 50 mm / min.
  • the photograph on the right is the appearance of the sample after the tear test.
  • the photograph on the right is the appearance of the sample after the tear test.
  • the length of the incision made before the test is 20 mm, and the tearing speed is 50 mm / min.
  • FIG. 99 shows the correlation between tear energy and the ratio of fiber tensile modulus to matrix tensile modulus.
  • the star represents the value when measuring the composite material (PI / CFC) of PHEA-co-IBXA and carbon fiber at 5 mm / min
  • the black circle represents the composite material of PHEA-co-IBXA and carbon fiber 50 mm / In min
  • the square represents the composite of PHEA-co-IBXA and carbon fiber at 500 mm / min
  • the white circle represents the composite of PHEA-co-IBXA and carbon fiber at 50 mm / min
  • the triangle represents CBA-co-IBXA
  • FIG. 100 shows the correlation between the critical width and the ratio of fiber tensile modulus to matrix tensile modulus.
  • the star represents the value when PI / CFC is measured at 5 mm / min
  • the black circle is PI / CFC at 50 mm / min
  • the square is PI / CFC at 500 mm / min
  • the white circle is PHEA-co-IBXA and glass It shows the value when the composite material with fiber (PI / GFC) is measured at 50 mm / min.
  • FIG. 101 shows the correlation between tear energy and the ratio of the fracture stress of the fiber to the fracture stress of the matrix.
  • the star represents the value when PI / CFC was measured at 5 mm / min
  • the black circle represents PI / CFC at 50 mm / min
  • the gray square represents PI / CFC at 500 mm / min
  • the white circle represents PI / GFC 50 mm / In min
  • triangles represent values when CI / CFC was measured at 50 mm / min.
  • FIG. 102 shows the correlation between the critical width and the ratio of fiber fracture stress to matrix fracture stress.
  • the star represents the value when PI / CFC is measured at 5 mm / min
  • the black circle is PI / CFC at 50 mm / min
  • the square is PI / CFC at 500 mm / min
  • the white circle is PI / GFC 50 mm / min It shows the value when measured by.
  • FIG. 103 shows a correlation diagram between matrix tear energy and strain energy density.
  • White triangles, black squares and circles represent values obtained when PI is measured at 5 mm / min, 50 mm / min and 500 mm / min, respectively.
  • FIG. 104 shows a geometric shape of a model for explaining the relationship between the amount of work and the process zone.
  • FIG. 105 shows the stress / strain behavior of the bond ⁇ c and ⁇ c represent the breaking strain and breaking stress of the matrix at shear.
  • ⁇ c and ⁇ c represent breaking strain and breaking stress of the matrix at shear.
  • FIG. 106 shows stress-strain curves for tensile testing, assumed to be obtained from rigid fibers and a soft matrix.
  • FIG. 107 shows a graph of F c ⁇ 2 ⁇ RL ⁇ c.
  • T tear energy
  • ⁇ c fracture stress
  • ⁇ c fracture strain
  • the dotted straight line in the figure is an approximate straight line, and the slope is 0.16.
  • 2-MTA 2-methoxyethyl acrylate
  • IBXA IBXA
  • glass transitionable refers to the ability to cause a glass transition
  • a glass transitionable substance can be determined by confirming that the substance undergoes a glass transition, For example, it can be carried out with the naked eye, or it can be judged by confirming that it has a glass transition point when measured by a differential scanning calorimeter (DSC) or the like.
  • DSC differential scanning calorimeter
  • a glass transitionable polymer is referred to as a "glass transitionable polymer”.
  • the glass-transferable polymer used or contained in the present invention is, for example, (meth) acrylic polymer (poly (meth) acrylic, acrylic resin, methacrylic resin), ethylene polymer (polyethylene), urethane polymer (polyurethane) , Amide polymers (polyamides), ester polymers (polyesters), ether polymers (polyethers), imide polymers (polyimides), amide-imide polymers (poly (amide-imide)), carbonate polymers (polycarbonates) G) acetal polymers (polyacetal, polyoxymethylene), sulfone polymers (polysulfone, polyether sulfone), phenylene sulfide polymers (polyphenylene sulfide), ether ether ketone polymers (Polyether ether ketone), silicone polymers (silicone, polysiloxane), and copolymers thereof, and AES resin (acrylonitrile ethylene-propy
  • a “fiber” is comprised of a thin thread (ie, elongated solid) material such as a single fiber, filament or yarn, or multiple fibers, filaments or yarn, or combinations thereof. Means material or material.
  • the term “fiber” includes material in the form of untwisted or twisted fibers, filaments or yarns.
  • the term “fiber” includes strands, tows or yarns.
  • fibers examples include plant fibers, animal fibers, mineral fibers, natural fibers such as dietary fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, glass fibers, carbon fibers, aramid fibers, artificial mineral fibers (rock wool, glass wool, Chemical fiber such as ceramic fiber) and metal fiber such as stainless fiber, aluminum fiber, iron fiber, nickel fiber, copper fiber, tungsten fiber, tungsten fiber, molybdenum fiber, beryllium fiber, gold fiber, silver fiber, titanium fiber, brass fiber etc. It can be mentioned.
  • the fibers of the present invention are, for example, those having a diameter of about 3 ⁇ m or more and a longitudinal length greater than the diameter.
  • fibrous form refers to a specific state (a state of an elongated solid defined as a fiber) of the shape of a material, and may be a form having a single fiber structure, 2 It may be in the form of a fiber bundle in which the fiber structure of the present invention or more is integrated.
  • the material in fibrous form has a single fiber structure.
  • the material in fibrous form is a bundle of fiber bundles comprised of two or more fiber structures.
  • a "fiber unit” is a collection of fiber structures that combine behavior. Specific examples of the fiber unit include the structure of a fiber bundle constituting carbon fiber, glass fiber, and / or aramid fiber, and a single fiber structure constituting metal fiber.
  • fabric refers to a woven fabric, a knitted fabric, a non-woven fabric or a fabric composed of fibers. In one embodiment, the term “fabric” is a textile.
  • breaking stress refers to the stress required to break a material by compression, tension, or shearing (in English, “breaking stress” and “breaking stress” are both It corresponds to "fracture stress”.
  • “Breaking stress” as used herein is the maximum stress between the start of the test and the breaking of the test specimen in a tensile test, typically the stress at break.
  • the fracture stress of the polymer and composite of the present invention is in accordance with JIS K7161 and the fiber is in accordance with JIS R7606 using a tensile tester (for example, Tensilon RTC-1310A, Orientec Co., Ltd. and Instron 5965, Instron). Tensile tests are carried out at approximately 20 ° C. in air to determine the fracture stress of each sample.
  • dumbbell-shaped sample For samples of polymers and composites, use a dumbbell-shaped sample with a size of 12 mm (length) x 2 mm (width) x 1 mm (thickness) according to JIS-K6251 (dumbbell shape No. 7) which is the standard. .
  • a single fiber with a diameter of 12 mm was used (12 mm long ⁇ 2 mm wide ⁇ 1 mm thick dumbbell-shaped No. 7 single fiber).
  • a tensile test one end and the opposite end of the test sample are clamped separately. The upper clamp is pulled upward at a constant speed of 50 mm / min while the lower clamp is fixed. The stress-strain curve of the sample is recorded from the start of the test, usually to the break of the sample.
  • the "elastic modulus (tensile modulus)" of the polymer and the composite material is the tensile stress within the tensile proportional limit and the tensile stress when the tensile test is performed using a dumbbell-shaped test piece according to JIS K7161. Means the ratio of strain corresponding to In the present specification, the tensile test conditions when measuring the elastic modulus (tensile modulus) of the polymer and composite of the present invention are the same as the tensile test conditions of the fracture stress unless otherwise specified.
  • the "elastic modulus (tensile modulus)" of a fiber means the elastic modulus (tensile modulus) of a single fiber measured by performing a tensile test according to JIS R7606.
  • the tensile test conditions for measuring the elastic modulus (tensile modulus) of the fiber of the present invention are the same as the tensile test conditions for the fracture stress unless otherwise specified.
  • breaking strain refers to an increase in the length of a test specimen at break relative to the initial length of a test specimen of the polymer and composite material of the present invention when a tensile test according to JIS K7161 is performed. Means quantity, expressed as a percentage. For example, if the initial length of the test part is 1 and the length at break is 2.5, the strain at break is 150%.
  • the tensile test conditions for measuring the breaking strain of the polymer and the composite of the present invention are the same as the tensile test conditions of the breaking stress unless otherwise specified.
  • tear energy means the energy required to tear a test specimen completely to tear it.
  • tear energy of the polymer, composite material and fabric of the present invention in accordance with JIS K7128-1, using a tensile tester (for example, Tensilon RTC-1310A, Orientec Co., Ltd. and Instron 5965, Instron) in the air The tear test is performed at about 20 ° C. to measure the tear energy of each sample. A rectangular sample having a width of 40 mm, a length of 60 mm and a thickness of 1 mm is used as a test sample of polymer only.
  • a rectangular sample having a width of 40 mm, a length of 60 mm and a thickness of about 1 mm is used as a fabric-only test sample.
  • a rectangular sample having a width of 5 to 110 mm, a length of 30 to 100 mm and a thickness of 1.3 mm is used as a test sample of the composite material.
  • the first incision is made, using a razor blade, from the middle point of the end of the side parallel to the width direction of the sample to the center direction parallel to the length direction by a third of the length The The two separated ends of the test piece were clamped with separate clamps. The upper clamp was pulled upward at a constant speed of 50 mm / min while the lower clamp was fixed.
  • L represents the displacement during the test
  • L bulk represents the length of the torn path in the tear test
  • F represents the force required to tear the test sample
  • t represents It represents the thickness of the test sample.
  • bending elastic modulus means a bending elastic modulus (bending elastic modulus) when a bending test is performed in accordance with JIS K 7074.
  • viscosity refers to the viscosity measured according to JIS Z 8803 unless otherwise specified, and is measured using a B-type viscometer or an E-type viscometer (for example, manufactured by Toki Sangyo Co., Ltd.).
  • surface tension refers to a value measured according to the Wilhelmy method, unless otherwise specified.
  • the viscosity in the present specification is typically a value measured at 25 ° C. by a plate method using a surface tension meter (eg, CBVP-A3, manufactured by Kyowa Interface Science Co., Ltd., Wilhelmy method).
  • self-rebuilding or “self-rebuilding function” when referring to a polymer, dissolves the polymer in any solvent (typically chloroform) and then dissolves the solvent (typically Most of them) (typically, volatilization, evaporation, compression, air-drying) and drying the residue (typically, heat-drying in an oven) to the original normal state or By returning to a state close to that, it means that the function of the polymer can be reappeared to the same degree or more, or the property or function.
  • solvent typically chloroform
  • solvent typically, volatilization, evaporation, compression, air-drying
  • drying the residue typically, heat-drying in an oven
  • tensile testing is meant a polymer in which the tensile modulus or breaking stress of the polymer recovers to at least about 80% of the original polymer prior to dissolution. The details of this term are described in "[8] Measurement of self-reconstruction function" described later.
  • polymer refers to a compound formed by polymerizing a plurality of monomers.
  • the monomer is the "starting material (material)” and the polymer is the product (final product).
  • a “homopolymer” is a compound made by polymerizing only one monomer
  • a “copolymer” is a compound made by polymerizing two or more monomers. It is.
  • (meth) acrylate means acrylate or methacrylate, and acrylate and methacrylate may be used alone or in combination.
  • (Meth) acryloyloxy means acryloyloxy or methacryloyloxy, and acryloyloxy and methacryloyloxy may be used alone or in combination.
  • (Meth) acrylic acid means acrylic acid or methacrylic acid, and acrylic acid and methacrylic acid may be used alone or in combination.
  • (meth) acrylic polymer and “(meth) acrylic polymer” refer to homopolymers or copolymers such as acrylic acid or acrylate or a salt or derivative thereof.
  • monomer refers to a compound that polymerizes two or more to form a polymer.
  • examples of the monomer of the present invention include (meth) acrylic monomers, ethylene monomers, urethane monomers, amide monomers, ester monomers, ether monomers, imide monomers, amide-imide monomers, carbonate monomers, Examples include an acetal monomer, a sulfone monomer, a phenylene sulfide monomer, an ether ether ketone monomer, a silicone monomer, and a monomer formed by polymerization of an AES resin, a diallyl phthalate resin, an ABS resin, or a silicone resin.
  • the monomer (A) is represented by the general formula (1) (R 1 is hydrogen or a C 1-4 alkyl group, R 2 is an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted cycloalkenyl group, It is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted heteroaryl group, and X 1 and X 2 are each independently O, S, NR x , and CR x 1 R x 2 is selected from the group consisting of, R x is hydrogen, C 1 ⁇ 6 alkyl group, C 1 ⁇ 6 alkoxy group, C 1 ⁇ 6 haloalkyl group or a C 2 ⁇ 6 haloalkenyl group, R x1 and R
  • the vinyl-based monomer (B) has a general formula (2) (R 3 is hydrogen or a C 1-4 alkyl group, and R 4 is an organic group).
  • the monomer (B) is a kind of vinyl monomer.
  • the “monomer component” may be composed only of the monomer (A), or may be a mixture of the monomer (A) and one or more other monomers.
  • the halogen atom, halo and halogen include, for example, fluorine atom, chlorine atom, bromine atom and iodine atom.
  • the number of halogen atoms contained in the alkyl group varies depending on the carbon number of the alkyl group and the like, and can not be determined indiscriminately. Therefore, it is preferable to appropriately adjust the number within the scope of the object of the present invention.
  • alkyl group refers to a monovalent group formed by the loss of one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane or propane, and is generally C n H 2n + 1- . (Where n is a positive integer).
  • alkyl group may be linear or branched.
  • alkyl (C 1-4 alkyl) group having 1 to 4 carbon atoms for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group Although a group etc.
  • alkyl (C 1-6 alkyl) group having 1 to 6 carbon atoms examples include C 1-4 alkyl group, n-pentyl group, isoamyl group, n-hexyl group, isohexyl group and the like. Is not limited to such an example.
  • alkyl (C 1-10 alkyl) group having 1 to 10 carbon atoms for example, a C 1 to 6 alkyl group, n-octyl group, n-nonyl group, isononyl group, branched nonyl group, n-decanyl group Although an isodecyl group etc.
  • alkyl (C 1-18 alkyl) group having 1 to 18 carbon atoms e.g., C 1 ⁇ 10 alkyl group, undecyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl group And isostearyl groups, but the present invention is not limited to such examples.
  • tertiary carbon-containing alkyl group refers to an alkyl group having 4 or more carbons and containing one or more tertiary carbons. Examples of tertiary carbon-containing C 4 ⁇ 5 alkyl group, t- butyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group.
  • Examples of tertiary carbon-containing C 4 ⁇ 7 alkyl group, a tertiary carbon-containing C 4 ⁇ 6 alkyl group, 1,1,2,2-methylpropyl group, 1,1,3,3 Examples include methylpropyl group and 1,1,2-trimethylbutyl group, but the present invention is not limited to such examples.
  • alkenyl group refers to a monovalent group formed by the loss of one hydrogen atom from an aliphatic hydrocarbon (alkene) containing at least one double bond such as ethene, propene and butene. good, generally represented by C m H 2m-1 (where, m is an integer of 2 or more). Alkenyl groups may be straight or branched. Examples of the alkenyl group having 2 to 6 carbon atoms include ethenyl group, 1-propenyl group, 2-propenyl group, butenyl group, pentenyl group, hexenyl group and the like, but the present invention is limited to only such examples It is not a thing.
  • alkenyl group having 2 to 10 carbon atoms examples include, for example, alkenyl group having 2 to 6 carbon atoms, heptenyl group, octenyl group, nonenyl group, decenyl group and the like, but the present invention is limited to only such an illustration. It is not a thing.
  • alkoxy group refers to a monovalent group formed by loss of a hydrogen atom of a hydroxyl group of alcohols, and is generally represented by C n H 2n + 1 O- (where n is 1 or more) Is an integer of As the alkoxy group having 1 to 6 carbon atoms, for example, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, sec-butyloxy group, n- Examples include pentyloxy group, isoamyloxy group, n-hexyloxy group, isohexyloxy group and the like, but the present invention is not limited to such examples.
  • haloalkyl group refers to an alkyl group in which one or more hydrogen atoms on the above alkyl group are substituted by a halogen atom.
  • perhaloalkyl refers to an alkyl group in which all hydrogen atoms on the above alkyl group are substituted with halogen atoms.
  • haloalkyl group having 1 to 6 carbon atoms
  • examples of the haloalkyl group having 1 to 6 carbon atoms include trifluoromethyl group, trifluoroethyl group (such as 2,2,2-trifluoroethyl group), perfluoroethyl group, trifluoro n-propyl group, tetrafluoropropyl group (such as 2,2,3,3-tetrafluoropropyl group), perfluoro n-propyl group, trifluoroisopropyl group, perfluoroisopropyl group, trifluoro n-butyl group, perfluoro n-butyl group Butyl group, trifluoroisobutyl group, perfluoroisobutyl group, trifluoro tert-butyl group, perfluoro tert-butyl group, trifluoro n-pentyl group, octafluoropentyl group (2,2,
  • C 1-8 haloalkyl group (C 1-8 haloalkyl group), a C 1-6 haloalkyl group, an undecafluoro n-heptyl group, a perfluoro n-heptyl group, a tridecafluorooctyl group (3,3, Examples include 4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group), perfluoro n-octyl group, etc., but the present invention is not limited to such examples. It is not limited.
  • cycloalkyl group means a monocyclic or polycyclic saturated hydrocarbon group, and also includes those having a bridged structure.
  • C 3-12 cycloalkyl group means a cyclic alkyl group having 3 to 12 carbon atoms.
  • Specific examples of the C 6-12 cycloalkyl group include a cyclohexyl group, cycloheptyl group, cyclooctyl group, adamantyl group, isobornyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, etc.
  • the present invention is not limited to such examples.
  • C 5-12 cycloalkyl group examples include a cyclopentyl group, a C 6-12 cycloalkyl group and the like, but the present invention is not limited to such examples.
  • Specific examples of the C 3-12 cycloalkyl group include cyclopropyl group, cyclobutyl group, C 5-12 cycloalkyl group and the like.
  • a "C 6-12 cycloalkyl group" is mentioned, but the present invention is not limited to such an illustration only.
  • cycloalkenyl group means a monocyclic or polycyclic unsaturated hydrocarbon group containing a double bond, and also includes those having a crosslinked structure. What one or more of the carbon-carbon bonds of the above-mentioned "cycloalkyl group” became a double bond is mentioned.
  • C 3-12 cycloalkenyl group means a cyclic alkenyl group having 3 to 12 carbon atoms.
  • C 6-12 cycloalkenyl group 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclononenyl group etc. are mentioned.
  • C 3-12 cycloalkyl group cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, C 6-12 cycloalkenyl group and the like can be mentioned.
  • a "C 6-12 cycloalkenyl group” is mentioned, but the present invention is not limited to such an illustration only.
  • heterocyclic group means a cyclic group having 1 to 3 atoms of the same or different type selected from nitrogen atom, oxygen atom and sulfur atom in the ring, and the group is , May contain one or more unsaturated bonds but does not contain aromatic groups.
  • a 3- to 8-membered heterocyclic group means a heterocyclic group having 3 to 8 ring atoms.
  • heterocyclic group examples include oxetanyl group, pyranyl group, pyrrolidinyl group, imidazolidinyl group, piperidinyl group, morpholinyl group, thiomorpholinyl group, hexamethylene iminyl group, thiazolidinyl group, tetrahydrofuranyl group, tetrahydropyridinyl Group, oxetanyl group, tetrahydropyranyl group, 1,3-dioxolanyl group, 1,3-dioxanyl group, 1,4-dioxanyl group, etc., but the present invention is not limited to such examples. .
  • the heterocyclic group which has a crosslinked structure is also contained in this group.
  • aryl group refers to a group formed by splitting off one hydrogen atom bonded to the aromatic hydrocarbon ring.
  • a phenyl group from the benzene C 6 H 5 -
  • tolyl from toluene
  • xylyl from xylene
  • naphthalene naphthyl group C 10 H 8 -
  • C 6-14 aryl group means an aromatic hydrocarbon group having a carbon number of 6 to 14.
  • C 6 ⁇ 14 aryl group for example, phenyl, 1-naphthyl, 2-naphthyl group, azulenyl group, acenaphthenyl group, acenaphthyl group, an anthryl group, fluorenyl group, phenalenyl group, phenanthryl group and the like Can be mentioned.
  • C 6 ⁇ 18 aryl group for example, C 6 ⁇ 14 aryl group, a benzo [a] anthryl group, benzo [a] fluorenyl group, benzo [c] phenanthryl group, a chrysenyl group, fluoranthenyl Groups, pyrenyl groups, tetracenyl groups, triphenylenyl groups and the like.
  • An arylthio group refers to an aryl-S- group.
  • a phenyl-S- group (phenylthio group) and the like can be mentioned, but the present invention is not limited to such exemplification.
  • heteroaryl group means a monocyclic or polycyclic hetero atom-containing aromatic group, which is a homogeneous or hetero hetero atom selected from nitrogen atom, sulfur atom and oxygen atom.
  • One or more (for example, 1 to 4) atoms are included.
  • “5 to 18-membered heteroaryl group” means a heteroaryl group having 5 to 18 ring atoms.
  • “Haloheteroaryl group” refers to one in which one or more hydrogens on a ring member atom are substituted with halogen.
  • heteroaryl group examples include, for example, pyrrolyl group, thienyl group, benzothienyl group, benzofuranyl group, benzoxazolyl group, benzothiazolyl group, furyl group, oxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, Benzoisoxazolyl group, benzisothiazolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, pyridazyl group, quinolyl group, isoquinolyl group, triazolyl group, triazinyl group, tetrazolyl group, indolyl group, imidazo [1,2-a] pyridyl group, pyrazolo [1,5-a] pyridyl group, [1,2,4] triazolo [1,5-a
  • alkylene refers to methane, ethane, a divalent group in which a hydrogen atom from an aliphatic hydrocarbon (alkane) such as propane occurs lost two generally - (C m H 2m )-(Where m is a positive integer).
  • alkane an aliphatic hydrocarbon
  • propane propane occurs lost two generally - (C m H 2m )-(Where m is a positive integer).
  • alkylene group may be linear or branched.
  • alkylene group having 1 to 10 carbon atoms examples include a methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, tert-butylene group, n -A pentene group, an n-hexylene group, an isohexylene group and the like can be mentioned, but the present invention is not limited to such examples.
  • An alkylene group having 1 to 6 carbon atoms (C 1 to 6 alkylene group) is preferable, an alkylene group having 1 to 4 carbon atoms (C 1 to 4 alkylene group) is more preferable, a methylene group and an ethylene group are more preferable, and a methylene group Is even more preferred.
  • an "alkenylene group” is a divalent group such as ethenylene, propenylene, butenylene, etc., which is formed by losing two hydrogen atoms from an aliphatic hydrocarbon (alkene) containing at least one double bond. It refers to, generally - (C m H 2m-2 ) - represented by (wherein, m is an integer of 2 or more).
  • the alkenylene group may be linear or branched.
  • the alkenylene group having 2 to 10 carbon atoms includes, for example, ethenylene group, n-propenylene group, isopropenylene group, n-butenylene group, isobutenylene group, n-pentenylene group, n-hexenylene Although a group, an isohexenylene group, etc. are mentioned, this invention is not limited only to this illustration.
  • An alkenylene group having 2 to 6 carbon atoms (C 2 to 6 alkenylene group) is preferable, an alkenylene group having 2 to 4 carbon atoms (C 2 to 4 alkenylene group) is more preferable, and an ethenylene group and an n-propenylene group are more preferable. Even more preferred is an ethenylene group.
  • substituted refers to the replacement of one or more hydrogen radicals in a given structure by the radical of a particular substituent.
  • optionally substituted is used interchangeably with the phrase “unsubstituted or substituted”.
  • C 1 ⁇ 10 alkyl optionally substituted C 6 ⁇ also be 18 aryl group group
  • unsubstituted C 6 ⁇ 18 aryl group or a C 1 ⁇ 10 C 6 ⁇ substituted with an alkyl group It is synonymous with " 18 aryl group”.
  • the number of substituents in the group defined by using “substituted (substituted)” or “optionally substituted” is not particularly limited as long as it can be substituted, and one or more may be used. is there.
  • the description of each group also applies where the group is part of or is a substituent of another group.
  • the number of carbon atoms in the definition of “substituent” may be indicated as, for example, “C 1-6 ” or the like.
  • the notation “C 1-6 alkyl” has the same meaning as an alkyl group having 1 to 6 carbon atoms.
  • a substituent that does not specifically indicate the term “substituted (substituted)” or “optionally substituted” means a “unsubstituted” substituent.
  • Preferred examples of the substituents include halogen, C 1 ⁇ 10 alkyl group, C 1 ⁇ 6 alkoxy group, C 2 ⁇ 6 alkenyl group, C 1 ⁇ 6 haloalkyl group, C 2 ⁇ 6 haloalkenyl group, C 6 ⁇ 18 aryl group, -S-C 6 ⁇ 18 aryl group include C 1 ⁇ 6 alkyl group substituted with a C 6 ⁇ 18 aryl group.
  • organic group means a monovalent functional group containing any of carbon, oxygen, nitrogen, or sulfur.
  • organic group for example, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an arylalkyl group, an alkylaryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an arylalkyloxycarbonyl group, a complex
  • a cyclic group, an amino group, a cyano group, a sulfo group etc. are mentioned, this invention is not limited only to this illustration.
  • hard segment means a monomeric compound that imparts elasticity to the polymer resulting from its polymerization.
  • the monomer (B) of the general formula (2) is a hard segment.
  • Hard segments are sometimes referred to as "glassy parts”.
  • soft segment means a monomeric compound that serves to dissipate the energy received by the resulting polymer upon polymerization.
  • the monomer (A) of the general formula (1) is a soft segment.
  • elastomer is a generic name for materials having rubbery elasticity at around normal temperature, and refers to, for example, an elastic polymer that responds to external pressure rapidly by having elastic properties. .
  • the nature of rubber elasticity is the recovery force that causes the state in which the entropy is reduced by elongation to return to the state in which the entropy is large (entropy elasticity).
  • entropy elasticity is usually composed of polymers. It is characterized by having a small elastic modulus (tensile modulus), high elongation, and high recovery.
  • “Elastomer” also includes “viscoelastic elastomer”.
  • viscoelastic elastomer refers to a visco-elastic elastomer.
  • the viscoelasticity of an elastomer can be evaluated by measuring a dynamic viscoelasticity spectrum with a rheometer.
  • the dynamic viscoelasticity spectrum can be measured in the angular frequency range of 10 -10 rad / s to 10 7 rad / s based on the temperature-time conversion law.
  • Viscoelastic elastomers exhibit some degree of interaction between macromolecules, and in many cases the interaction is due to dynamic physical bonding between molecules.
  • the present invention utilizes a viscoelastic elastomer.
  • this dynamic physical interaction produces viscosity, which together with the entropy elasticity of the polymer exhibits visco-elasticity.
  • Such visco-elastic elastomers dissipate energy during deformation and exhibit high toughness.
  • a high toughness visco-elastic elastomer is effective as a matrix to be combined with fibers.
  • the matrix refers to a portion other than fibers contained in the composite material of the present invention.
  • the matrix is a polymer.
  • the matrix is a homopolymer, in another embodiment a copolymer.
  • f may be the mole fraction of soft segments (herein 1) in the polymerization of the hard segment (ie, monomer (B)) and the soft segment (ie, monomer (A)), In that case, a homopolymer of monomer (A) is formed.
  • the combination of isobornyl acrylate and phenoxyethyl acrylate refers to the mole fraction of phenoxyethyl acrylate.
  • M refers to the mole fraction of a monomer relative to the total number of moles of monomer contained in the polymer.
  • the term “monomer abbreviation” in the term means that the abbreviation of monomer such as PHDEA is displayed, and in the case of PHDEA, it is displayed as “M PHDEA”.
  • M PHDEA represents the mole fraction of phenoxydiethylene glycol acrylate (PHDEA)
  • M PHDEA : M IBXA represents the ratio of the mole fraction of phenoxy diethylene glycol acrylate to isobornyl acrylate (IBXA).
  • M PHEA : M IBXA refers to the ratio of the mole fraction of phenoxyethyl acrylate (PHEA) to isobornyl acrylate.
  • M PHDEA M IBXA
  • PHDEA IBXA
  • This notation may be the mole fraction of certain monomers in the copolymer alone, or the mole fraction of monomers used in the matrix of the composite.
  • the tensile modulus is a proportionality constant of strain and stress in the coaxial direction in an elastic range in which Hook's law holds. It is also called longitudinal modulus.
  • the low tensile modulus indicates that the slope of the stress-strain curve in the elastic range is small.
  • the rubber examples include natural rubber (eg, gum arabic, tragacanth gum, guar gum, etc .; usually diene polymer), synthetic rubber produced by bulk polymerization, synthetic latex rubber produced by emulsion polymerization, etc.
  • natural rubber eg, gum arabic, tragacanth gum, guar gum, etc .
  • synthetic rubber produced by bulk polymerization e.g., synthetic latex rubber produced by emulsion polymerization, etc.
  • the present invention is not limited to such examples.
  • the present invention provides a composite material comprising a first material and a second material, the composite material having the following conditions (i) and (ii): (I) When the breaking stress is measured at a speed of 50 mm / min at about 20 ° C. by a tensile test method according to JIS R 7606 for the first material and according to JIS K 7161 for the second material, the first The ratio of the fracture stress of the material to the second material is about 50 or more (ii) when the elastic modulus (tensile modulus) is measured at a speed of 50 mm / min at about 20 ° C. by the above-mentioned tensile test method, A condition of at least one of the ratio of the elastic modulus (tensile modulus) of the first material to the second material being about 100 or more is satisfied.
  • the invention provides a composite comprising a first material and a second material, the composite having the following conditions (i) and (ii): (I) When the breaking stress is measured at a speed of 50 mm / min at about 20 ° C. by a tensile test method according to JIS R 7606 for the first material and according to JIS K 7161 for the second material, the first The material has a breaking stress of about 50 MPa or more (ii) when the breaking strain is measured at a speed of 50 mm / min at about 20 ° C. according to the above tensile test method, the second material is about 200% or more At least one condition of having a strain at break is satisfied.
  • the first material is a fiber and the second material is a glass transitionable polymer.
  • the first material may be a fabric, and the second material may be expressed as a glass transitionable polymer.
  • the breaking stress when the breaking stress is measured at a speed of 50 mm / min at about 20 ° C. by a tensile test method according to JIS R 7606 for the first material and JIS K 7161 for the second material,
  • the ratio of the fracture stress of one material to the second material is in the range above a certain lower limit, and examples of the lower limit are about 5, about 10, about 15, about 20, about 25, about 30 About 35, about 40, about 50, about 60, about 70, about 80, about 90, about 100, about 110, about 120, about 130, about 140, about 150, about 160, about 170, about 170, about 180, about 190 and about 200 can be mentioned.
  • a composite comprising a first material and a second material has a ratio of fracture stress between the first material and the second material of about 50 or more.
  • the ratio of the fracture stress of the first material to the second material is about 100 or more, more preferably about 150 or more.
  • “the ratio of the fracture stress of the first material to the second material” refers to the value (in MPa) of the fracture stress of the first material obtained by the above-mentioned tensile test method of the second material. It is a value obtained by dividing by the value of fracture stress (MPa unit).
  • the elastic modulus tensile modulus
  • the ratio of tensile modulus between the first material and the second material is in the range above a certain lower limit, and examples of the lower limit are about 10, about 50, about 100, about 500, about 1000, about 1500, about 2000, about 2500, about 3000, about 3500, about 4000, about 4500, about 5000, about 5500, about 6000, about 6500, about 7000, about 7500, about 8000, about 8500, about 9000, about 9000 There are about 9500 and about 10000.
  • a composite comprising a first material and a second material has a tensile modulus ratio of about 100 or greater for the first material and the second material.
  • the ratio of tensile modulus of the first material to the second material is about 2500 or more, more preferably about 5000 or more.
  • “the ratio of the tensile modulus of the first material to the second material” is the value of the tensile modulus (in MPa) of the first material obtained by the above-mentioned tensile test method to that of the second material. It is a value obtained by dividing by the value of tensile modulus (MPa unit).
  • the breaking stress of the first material is measured at a speed of 50 mm / min at about 20 ° C. by the tensile test method according to JIS R 7606, the breaking stress of the first material is a lower limit
  • the lower limit is, for example, about 50 MPa, about 100 MPa, about 150 MPa, about 200 MPa, about 250 MPa, about 300 MPa, about 350 MPa, about 400 MPa, about 450 MPa, about 500 MPa, about 500 MPa, about 650 MPa, about 700 MPa, about 750 MPa, about 800 MPa, about 850 MPa, about 900 MPa, about 950 MPa, and about 1000 MPa can be mentioned.
  • the first material has a breaking stress of about 100 MPa or more when the breaking stress is measured at a speed of 50 mm / min at about 20 ° C. by the tensile test method. In a preferred embodiment, the first material has a breaking stress of about 250 MPa or more, more preferably about 500 MPa or more, when the breaking stress is measured at a speed of 50 mm / min at about 20 ° C. by the tensile test method. Have. In one embodiment, when the breaking stress of the second material is measured at a speed of 50 mm / min at about 20 ° C.
  • the breaking stress of the second material is a lower limit value It is the above-mentioned range, as an example of a lower limit, about 1.5MPa, about 1.6MPa, about 1.7MPa, about 1.8MPa, about 1.9MPa, about 2.0MPa, about 2.1MPa, about 2.2MPa, about 2.2MPa, about 2.3MPa, about 2.4 MPa, about 2.5 MPa, about 3 MPa, about 4 MPa, about 5 MPa, about 6 MPa, about 7 MPa, about 8 MPa, about 9 MPa, and about 10 MPa.
  • the second material has a breaking stress of at least about 1.5 MPa when the breaking stress is measured at a rate of 50 mm / min at about 20 ° C. by the tensile testing method. In a preferred embodiment, when the breaking stress is measured at a speed of 50 mm / min at about 20 ° C. by the tensile test method, the second material has a breaking strength of about 2.0 MPa or more, more preferably about 2.5 MPa or more. Have stress.
  • the breaking strain is measured at a rate of 50 mm / min at about 20 ° C. by a tensile test method according to JIS R 7606 for the first material and according to JIS K 7161 for the second material
  • the strain at break of the second material is in the range above a certain lower limit, and as an example of the lower limit, about 10%, about 50%, about 100%, about 150%, about 200%, about 250%, about 300 %, Approximately 350%, approximately 400%, approximately 450%, approximately 500%, approximately 650%, approximately 700%, approximately 750%, approximately 800%, approximately 850%, approximately 900%, approximately 950%, approximately 1000%, About 1100%, about 1200%, about 1300%, and about 1400% can be mentioned.
  • the second material has a strain at break greater than or equal to about 200% when the strain at break is measured at a rate of 50 mm / minute at about 20 ° C. by the tensile testing method. In a preferred embodiment, when the breaking strain is measured at a speed of 50 mm / min at about 20 ° C. by the tensile test method, the second material has a breaking of about 300% or more, more preferably about 400% or more. It has a strain.
  • the maximum value of force is 6, 7, 8, when measured at a tear rate of 50 mm / min at about 20 ° C. by a tear test method according to JIS K7128-1. It is 9 or 10 MPa or more.
  • the displacement of the second material is 150 mm or 160 mm or more when measured at a tear rate of 50 mm / min at about 20 ° C. by a tear test method according to JIS K7128-1.
  • the interface between the first material and the second material is attached and / or physically interlocked. In one embodiment, the first material and the second material are bonded at the interface. In one embodiment, the first material and the second material are physically interlocked.
  • the thickness of the fiber unit of the material in fibrous form is in the range between a lower limit and an upper limit, and as an example of the lower limit, about 1 TEX, about 5 TEX, about 10TEX, about 20TEX, about 25TEX, about 30TEX, about 35TEX, about 40TEX, about 45TEX, about 50TEX, about 55TEX, about 60TEX, about 65TEX, about 70TEX, about 75TEX, about 80TEX, about 85TEX, about 90TEX, about 90TEX, About 95 TEX, and about 100 TEX, and examples of the upper limit value are about 100 TEX, about 150 TEX, about 200 TEX, about 250 TEX, about 300 TEX, about 350 TEX, about 400 TEX, about 450 TEX, about 500 TEX, about 550 TEX, about 600 TEX, About 650 TEX, about 700 TEX, about 750 TEX, about 800 TEX, about 850
  • the first material has a fibrous form
  • the fiber unit of the one material has a thickness of about 1 TEX to about 1000 TEX.
  • the fiber unit of the material in fibrous form is about 10 TEX to about 950 TEX, more preferably about 30 TEX to about 900 TEX, more preferably about 45 TEX to about 850 TEX, still more preferably about 60 TEX to about 800 TEX. It is the thickness of
  • the diameter of the fiber unit (the major diameter in the case of an elliptical cross section of the fiber, the diameter of the circumscribed circle in the case of a polygon) of the material in the fibrous form has a lower limit and an upper limit
  • the lower limit is, for example, about 0.001 mm, about 0.005 mm, about 0.01 mm, about 0.05 mm, about 0.10 mm, about 0.15 mm, about 0.20 mm, about 0.25 mm, about 0.30 mm.
  • the first material has a fibrous form, and the diameter of the fiber unit of the one material is about 0.001 mm to about 2.0 mm.
  • the diameter of the fiber unit of the material in fibrous form is about 0.01 mm to about 1.0 mm, more preferably about 0.05 mm to about 0.90 mm, more preferably about 0.1 mm to about 0.8 mm, more preferably More preferably, it is about 0.20 mm to about 0.8 mm.
  • the cross-sectional area of the fiber unit of the fibrous form of the material is in the range above a certain lower limit, and as an example of the lower limit, about 0.001 mm 2 , about 0.0025 mm 2 , about 0.005 mm 2 , About 0.0075 mm 2 , about 0.01 mm 2 , about 0.025 mm 2 , about 0.05 mm 2 , about 0.075 mm 2 , about 0.1 mm 2 , about 0.25 mm 2 , about 0.5 mm 2 , about 0.75 mm 2 , and about 1.0 mm 2 is mentioned.
  • the cross-sectional area of a fiber unit of said fibrous form of material is about 0.05 mm 2 or more.
  • the cross-sectional area of the fiber unit of the material in fibrous form is about 0.075 mm 2 or more, more preferably about 0.1 mm 2 or more.
  • the fibers comprise glass fibers, carbon fibers, aramid (Kevlar®) fibers, vegetable fibers, wood fibers, animal fibers, mineral fibers, metal fibers and synthetic polymer fibers and combinations thereof.
  • the fiber is glass fiber, carbon fiber, aramid fiber or metal fiber, more preferably glass fiber, carbon fiber or aramid fiber, most preferably carbon fiber.
  • the fibers form a woven fabric, a knitted fabric or a non-woven fabric.
  • Glass fibers, carbon fibers, aramid fibers, and metal fibers may be commercially available from the manufacturers exemplified in the examples, and may be prepared according to methods known to those skilled in the art.
  • Glass spinning methods include Direct Melt, which directly spins glass melted from raw materials, and Marble Melt, which melts and fibrillates the molten glass in the spinning process, once it is molded into a sphere or rod.
  • Glass fiber such as roving, roving cloth, chopped strand, milled fiber, chopped strand mat, continuous strand mud, yarn, glass cloth, glass tape and the like.
  • Raw materials of carbon fiber mainly include carbonized polyacrylonitrile type (PAN-based carbon fiber) and carbonized pitch precursor (pitch-based carbon fiber), and the shape is filament, tow, staple yarn, cross Types such as blades, chopped yarn, milled, felt mats, and paper.
  • PAN-based carbon fiber carbonized polyacrylonitrile type
  • Pitch-based carbon fiber carbonized pitch precursor
  • raw materials of metal fibers include stainless steel, aluminum, iron, nickel, copper and the like.
  • a metal fiber a stainless steel mesh made of SUS316, etc. may be mentioned.
  • the invention provides a composite comprising fibers and a glass transitionable polymer.
  • the glass-transferable polymer is a homopolymer or a copolymer formed by polymerizing a monomer component containing one or more monomers, preferably, the monomer component is a monomer (A) And optionally a vinyl-based monomer (B), and more preferably, the glass transition temperature of the monomer (A) is -100 ° C. or higher and lower than 10 ° C.
  • the glass transferable polymer is (meth) acrylic polymer, urethane polymer, amide polymer, ether polymer, silicone polymer, carbonate polymer, It is selected from the group consisting of any combination. Examples of any combination include any copolymer such as ABS which is a copolymer of an acrylic polymer and an ethylene polymer, a graft copolymer, a block copolymer, a random copolymer, an alternating copolymer And terpolymers, mixtures of two or more polymers, and the like, but not limited thereto.
  • the glass transitionable polymer is a (meth) acrylic polymer.
  • the glass transition temperature of the glass transitionable polymer is in a range between a lower limit and an upper limit, and examples of the lower limit include about -100 ° C, about -90 ° C, about -80 ° C., about -70 ° C., about -60 ° C., about -50 ° C., about -40 ° C., about -30 ° C., about -20 ° C., about -10 ° C., and about 0 ° C.
  • the glass transition temperature of the glass transitionable polymer is about -90 to 40 ° C, preferably about -70 to 30 ° C, more preferably about -50 to 20 ° C, Still more preferably, it is about -20 to 20 ° C.
  • the glass transition temperature of the glass transitionable polymer is about -70 to 70 ° C, preferably about -60 to 50 ° C, more preferably about -50 to 40 ° C, Still more preferably, it is about -40 to 40 ° C.
  • the polymer is a homopolymer or copolymer formed by polymerizing monomer components comprising one or more monomers.
  • the viscosity of the monomer component is in a range between a lower limit and an upper limit, and examples of the lower limit are about 0.1, about 0.5, about 1.0, about 1.5, about 2.0, About 2.5, about 3.0, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7.0, about 7.5, about 8.0, about 8.5, about 9.0, about 9.5 and about 10 mPa ⁇ s
  • the upper limit value include about 10, about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55 and about 60 mPa ⁇ s.
  • the viscosity of the monomer component is about 0.1 to 50 mPa ⁇ s, preferably about 0.5 to 30 mPa ⁇ s.
  • the surface tension of the monomer component is in the range between a lower limit and an upper limit, and examples of the lower limit are about 5, about 6, about 7, about 8, about 9 About 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, about 18, about 19 and about 20 mN / m, and examples of the upper limit value are about 40, about 41, about 42, about 43, about 44, about 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 55, about 56, about 57, About 58, about 59 and about 60 mN / m can be mentioned.
  • the surface tension of the monomer component is about 15 to 55 mN / m, preferably about 20 to 40 mN / m.
  • the monomer component comprises a monomer (A) and optionally a vinyl-based monomer (B).
  • the monomer component is General formula (1) (R 1 is hydrogen or a C 1-4 alkyl group, R 2 is an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted cycloalkenyl group, It is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted heteroaryl group, and X 1 and X 2 are each independently O, S, NR x , and CR x 1 R x 2 is selected from the group consisting of, R x is hydrogen, C 1 ⁇ 6 alkyl group, C 1 ⁇ 6 alkoxy group, C 1 ⁇ 6 haloalkyl group or a C 2 ⁇ 6 haloalkenyl group, R x1 and R x2 Each independently represents
  • the glass transition temperature of the monomer (A) is in the range between a lower limit and an upper limit, and as an example of the lower limit, about -100 ° C, about -90 ° C, about -80 ° C., about -70 ° C., about -60 ° C., about -50 ° C., about -40 ° C., about -30 ° C., about -20 ° C., about -10 ° C., and about 0 ° C.
  • the glass transition temperature of the monomer (A) is -100 ° C. or more and less than 10 ° C., preferably -70 ° C. or more and less than 10 ° C.
  • R 1 is hydrogen or a methyl group. In a preferred embodiment, R 1 is a methyl group. In another preferred embodiment, R 1 is hydrogen.
  • R 2 is halogen, hydroxyl group, cyano group, C 1 ⁇ 10 alkyl group, C 1 ⁇ 6 alkoxy group, C 1 ⁇ 6 alkyloxycarbonyl group, C 1 ⁇ 6 haloalkyl group, C 2 ⁇ 6 alkenyl group, C 2 ⁇ 6 haloalkenyl group, C 3 ⁇ 6 cycloalkyl group, C 3 ⁇ 6 halocycloalkyl group, 3- to 8-membered heterocyclic group and a C 6 ⁇ 18 arylthio group
  • a C 1-6 alkyl group optionally substituted by one or more (for example, one, two, three, four, five or more) groups selected from the group consisting of If C 2 ⁇ 6 alkenyl group, C 3 ⁇ 6 cycloalkyl group, C 6 ⁇ 18 aryl, is a 5 to 18 membered heteroaryl group, provided that the X 1 is bonded directly with R 2, R 2 is in C
  • R 2 is hydroxyl group, one or more of which may be substituted with a group
  • C 1 ⁇ 6 alkyl group is selected from the group consisting of C 1 ⁇ 10 alkyl and C 6 ⁇ 18 arylthio group a C 6 ⁇ 18 aryl or 5-18 membered heteroaryl group.
  • R 2 is a C 1-6 alkyl group, a phenyl group, a benzyl group or a phenylthioethyl group.
  • R 2 is a C 1-4 alkyl group, a phenyl group, a benzyl group or a phenylthioethyl group.
  • R 2 is an unsubstituted or substituted C 1-18 alkyl group or an unsubstituted or substituted C 6 ⁇ 18 aryl group. In one embodiment, R 2 is an unsubstituted or substituted C 1 ⁇ 18 alkyl group, more preferably an unsubstituted or substituted C 1 ⁇ 10 alkyl group, even more preferably, an unsubstituted or substituted C 1 To 6 alkyl groups.
  • R 2 is an unsubstituted C 1-18 alkyl group, 5 or C 1 ⁇ 6 alkyl substituted with 6-membered heterocyclic group or C 6 ⁇ 18 aryl or hydroxyl group,, C 1 ⁇ 6 alkyl groups, and C 1 ⁇ 6 is a one or more optionally C 6 ⁇ 18 aryl which is substituted with a group selected from the group consisting of an alkoxy group, provided that a direct bond X 1 is and R 2 If you, R 2 is not C 6 ⁇ 18 aryl group.
  • R 2 is unsubstituted C 1 ⁇ 18 alkyl group, with 5 or C 1 ⁇ 3 alkyl substituted with 6-membered heterocyclic group or C 6 aryl, or unsubstituted C 6 ⁇ 10 aryl, is there.
  • R 2 is a methyl group, an ethyl group, a lauryl group, an isostearyl group, a tetrahydrofurfuryl group, a phenyl group or a benzyl group.
  • R x is hydrogen, C 1 ⁇ 6 alkyl group, C 1 ⁇ 6 alkoxy group, C 1 ⁇ 6 haloalkyl group or a C 2 ⁇ 6 haloalkenyl group,.
  • R x is hydrogen, methyl, ethyl, trifluoromethyl or pentafluoroethyl.
  • R x is hydrogen, methyl or trifluoromethyl.
  • R x is hydrogen.
  • R x is methyl.
  • R x1 and R x2 are each independently hydrogen, unsubstituted or substituted alkyl group, unsubstituted or substituted alkenyl group, unsubstituted or substituted cycloalkyl group, unsubstituted or substituted A cycloalkenyl group, an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, or together with the carbon atom to which they are attached, Or form a substituted cycloalkyl group, an unsubstituted or substituted cycloalkenyl group, an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted heteroaryl group.
  • R x1 and R x2 are each independently hydrogen, a C 1-6 alkyl group, a C 1-6 alkoxy group, a C 1-6 haloalkyl group, or a C 1-6 haloalkoxy group, Preferably, it is hydrogen, a C 1-4 alkyl group, a C 1-4 alkoxy group, a C 1-4 haloalkyl group or a C 1-4 haloalkoxy group, and more preferably a hydrogen, a methyl group, an ethyl group, a methoxy It is a group, an ethoxy group, a trifluoromethyl group or a pentafluoroethyl group, and more preferably a hydrogen, a methyl group or a trifluoromethyl group.
  • R x1 and R x2 are each independently hydrogen or a C 1-6 alkyl group, preferably hydrogen or a C 1-4 alkyl group, more preferably hydrogen, a methyl group or It is an ethyl group, more preferably hydrogen or a methyl group.
  • X 1 and X 2 are each independently O, S or CH 2 , more preferably X 1 is O and X 2 is O, S or CH And more preferably X 1 is O and X 2 is O or CH 2 .
  • X 1 and X 2 are each independently O or S.
  • X 1 is O and X 2 is O or S.
  • X 1 is O and X 2 is S.
  • X 1 and X 2 are CH 2 .
  • X 1 and X 2 are O.
  • X 1 is O and X 2 is CH 2 .
  • n is 0 to 20, 0 to 19, 0 to 18, 0 to 17, 0 to 16, 0 to 15, 0 to 14, 0 to 13, 0 to 12, 0 to 11, 0 to 10, 0 to 9, 0 to 8, 0 to 7, 0 to 6, 0 to 5, 0 to 4, 0 to 3, 0 to 2, 0 to 1, or 0, 1, 2 , 3, 4 or 5.
  • n is 0-4.
  • n is 0-3.
  • n is 0 or 1.
  • n is one.
  • n is 0-3, with the proviso that n is 1 to 3 when R 2 is unsubstituted C 1-4 alkyl or hydroxy substituted C 1-4 alkyl.
  • R 2 is an unsubstituted or substituted C 1-18 alkyl group or an unsubstituted or substituted C 6 ⁇ 18 aryl group, preferably, R 2 is unsubstituted or substituted with substituted C 6 ⁇ 18 aryl group a C 1-18 alkyl group, or an unsubstituted or substituted C 6 ⁇ 18 aryl group.
  • R 2 C 1-18 alkyl group substituted by an unsubstituted or substituted C 6 ⁇ 18 aryl group or an unsubstituted or substituted C 6 ⁇
  • the monomer (A) is 2-methoxyethyl acrylate, ethyl carbitol acrylate (or 2- (2-ethoxyethoxy) ethyl acrylate), triethylene glycol methyl ether acrylate, phenyl At least one selected from thioethyl acrylate, lauryl acrylate, isostearyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenoxyethyl acrylate and phenoxy diethylene glycol acrylate.
  • the monomer (A) is 2-methoxyethyl acrylate, ethyl carbitol acrylate (or 2- (2-ethoxyethoxy) ethyl acrylate), triethylene glycol methyl ether acrylate, phenylthioethyl acrylate, It is one monomer selected from the group consisting of lauryl acrylate, isostearyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenoxyethyl acrylate and phenoxy diethylene glycol acrylate.
  • the monomer (A) is 2-methoxyethyl acrylate, ethyl carbitol acrylate, triethylene glycol methyl ether acrylate, benzyl acrylate, phenoxyethyl acrylate, phenylthioethyl acrylate, lauryl acrylate And at least one selected from the group consisting of isostearyl acrylate, phenoxydiethylene glycol acrylate and tetrahydrofurfuryl acrylate.
  • the monomer (A) is 2-methoxyethyl acrylate, triethylene glycol methyl ether acrylate, benzyl acrylate, phenoxyethyl acrylate, phenylthioethyl acrylate, lauryl acrylate, isostearyl acrylate, It includes those selected from the group consisting of phenoxydiethylene glycol acrylate and tetrahydrofurfuryl acrylate.
  • the monomer (A) is triethylene glycol methyl ether acrylate, benzyl acrylate, phenoxyethyl acrylate, phenylthioethyl acrylate, lauryl acrylate, isostearyl acrylate, phenoxy diethylene glycol acrylate and tetrahydrofulfuro At least one selected from the group consisting of furyl acrylate is included.
  • the monomer (A) contains at least one selected from the group consisting of benzyl acrylate, phenoxyethyl acrylate, phenylthioethyl acrylate, and phenoxy diethylene glycol acrylate.
  • R 1 is hydrogen
  • R 2 is a methyl group
  • X is O
  • n is 1.
  • the monomer (A) is 2-methoxyethyl acrylate.
  • R 1 is hydrogen
  • R 2 is a phenyl group
  • X is O
  • n is 1.
  • the monomer (A) is phenoxyethyl acrylate.
  • R 1 is hydrogen
  • R 2 is a phenyl group
  • X is O
  • n is 2.
  • the monomer (A) is phenoxydiethylene glycol acrylate.
  • the glass transition temperature of the vinyl-based monomer (B) is in the range between a lower limit and an upper limit, and examples of the lower limit are about -100 ° C, about -90 ° C. About -80 ° C., about -70 ° C., about -60 ° C., about -50 ° C., about -40 ° C., about -30 ° C., about -20 ° C., about -10 ° C., and about 0 ° C.
  • the glass transition temperature of the vinyl monomer (B) is 10 ° C. or more and 120 ° C. or less, preferably 10 ° C. or more and 100 ° C. or less.
  • the monomer component has the general formula (2) It further includes a vinyl-based monomer (B) represented by (R 3 is hydrogen or a C 1-4 alkyl group, and R 4 is an organic group).
  • the homopolymer when the monomer (B) is a homopolymer composed only of the monomer (B) under the conditions for producing the composite material, the homopolymer has a temperature of about 30 ° C. to 120 ° C. It is chosen to have a glass transition temperature.
  • vinyl-based monomer (B) of the present invention include the following monofunctional monomers and polyfunctional monomers.
  • monofunctional monomers include (meth) acrylic acid; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, Tert-butyl acrylate, tert-butyl methacrylate, neopentyl acrylate, neopentyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, cetyl acrylate, methacrylic acid (Meth) acrylic acid alkyl ester having 1 to 18 carbon atoms in an alkyl group such as cetyl; cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl
  • the polyfunctional monomer includes, for example, two or more, preferably two (meth) acryloyl groups such as alkylenebis (meth) acrylamide having 1 to 4 carbon atoms in the alkylene group such as methylenebisacrylamide and methylenebismethacrylamide.
  • Aromatic compounds having two or more, preferably two or three carbon-carbon double bonds such as divinylbenzene and diallylbenzene; ethylene diacrylate, ethylene dimethacrylate, ethylene glycol diacrylate Ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate Triethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonane Diol diacrylate, 1,9-nonanediol dimethacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, 2-n-butyl-2-ethyl
  • Biscoat # 700 HV bisphenol A diglycidyl ether acrylic acid adduct
  • Biscoat # 540 trimethylolpropane ethylene oxide (3.5) adduct triacrylate
  • Biscoat # 360 tripentaerythritol acrylate
  • Metal acrylate compounds having two or more, preferably two or three (meth) acryloyl groups such as commercially available from Osaka Organic Chemical Industry Ltd. under the trade name of Biscoat # 802); diallylamine, triallylamine, etc.
  • polyfunctional monomers may be used alone or in combination of two or more. These polyfunctional monomers may also be used as crosslinkers.
  • R 3 is hydrogen or a methyl group. In a preferred embodiment, R 3 is a methyl group. In another preferred embodiment, R 3 is hydrogen.
  • L is a bond.
  • L is -C 1-4 alkylene-, preferably -C 1-3 alkylene-, more preferably-(CH 2 ) 2- , -CH (CH 3 )-or -CH 2- , more preferably -CH 2- .
  • R 6 is unsubstituted or substituted tertiary carbon-containing C 4 ⁇ 7 alkyl group, an unsubstituted or substituted C 5 ⁇ 12 cycloalkyl group or an unsubstituted or substituted 5-6 membered heterocyclic group,
  • t-butyl, cyclopentyl, cyclohexyl isobornyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, tetrahydrofuranyl, 1,3-dioxane-5- Or 5-ethyl-1,3-dioxane-5-yl group or 1,1,2,2-tetramethylpropyl group.
  • R 6 may be substituted by one or more substituents selected from ,, C 1 ⁇ 4 alkyl group, t- butyl group, isobornyl group, adamantyl group, C 5 ⁇ 7 It is a cycloalkyl group or a 5- to 6-membered heterocyclic group.
  • the vinyl monomer (B) is a C 5 ⁇ 12 cycloalkyl (meth) acrylates, in a more preferred embodiment, isobornyl acrylate or isobornyl methacrylate.
  • monomer (B) comprises at least one selected from the group consisting of t-butyl acrylate, isobornyl acrylate, and cyclohexyl acrylate.
  • the monomer component is polymerized in the absence of a crosslinking agent. In another embodiment, the monomer component is polymerized in the presence of a crosslinker.
  • the polymer is thermally or photopolymerized. In another embodiment, the polymer is thermally polymerized. In another embodiment, the polymer is photopolymerized.
  • Examples of the method of polymerizing the monomer include bulk polymerization method, solution polymerization method, emulsion polymerization method, suspension polymerization method and the like, but the present invention is not limited to such examples. Among these polymerization methods, bulk polymerization and solution polymerization are preferable.
  • the polymerization of the monomer can be carried out by, for example, radical polymerization, living radical polymerization, anion polymerization, cation polymerization, addition polymerization, polycondensation, catalytic polymerization and the like.
  • the monomer when the monomer is polymerized by a solution polymerization method, for example, the monomer can be polymerized by dissolving the monomer in a solvent and adding the polymerization initiator to the solution while stirring the obtained solution, as well as polymerization
  • the monomers can be polymerized by dissolving the initiator in the solvent and adding the monomers to the solution while stirring the resulting solution.
  • the solvent is preferably an organic solvent compatible with the monomer.
  • the above monomer (A) is used in the range of about 70 parts by weight or more and less than 100 parts by weight, and the above vinyl monomer (B) in the range of more than 0 parts by weight and about 30 parts by weight or less
  • copolymerization is carried out.
  • the polymerization is carried out using 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight or 90 parts by weight to 100 parts by weight of the monomer (A).
  • the polymerization is carried out using the monomer (B) in an amount of more than 0 parts by weight and 50 parts by weight, 40 parts by weight, 30 parts by weight, 20 parts by weight or 10 parts by weight or less.
  • chain transfer agents When polymerizing the monomers, chain transfer agents may be used to adjust the molecular weight. Chain transfer agents can usually be used by mixing with the monomers.
  • a chain transfer agent for example, 2- (dodecylthiocarbonothioylthio) -2-methylpropionic acid, 2- (dodecylthiocarbonothioylthio) propionic acid, methyl 2- (dodecylthiocarbonothioylthio)- 2-Methylpropionate, 2- (Dodecylthiocarbonothioylthio) -2-methylpropionic acid 3-azido-1-propanol ester, 2- (dodecylthiocarbonothioylthio) -2-methylpropionic acid pentafluoro ester Mercaptan group-containing compounds such as phenyl ester, lauryl mercaptan, dodecyl mercaptan and thioglycerol, inorgan
  • polymerization initiator When polymerizing the monomers, it is preferable to use a polymerization initiator.
  • the polymerization initiator include thermal polymerization initiators, photopolymerization initiators, redox polymerization initiators, ATRP (atom transfer radical polymerization) initiators, ICAR ATRP initiators, ARGET ATRP initiators, RAFT (reversible addition-cleavage Chain transfer polymerization agents, NMP (polymerization via nitroxide) agents, polymer polymerization initiators and the like. These polymerization initiators may be used alone or in combination of two or more.
  • thermal polymerization initiator for example, azobisisobutyronitrile (AIBN), 2,2′-azobis (methyl isobutyrate), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 Azo polymerization initiators such as' -azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), peroxides such as benzoyl peroxide, potassium persulfate and ammonium persulfate
  • AIBN azobisisobutyronitrile
  • 2,2′-azobis methyl isobutyrate
  • 2,2 Azo polymerization initiators such as' -azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), peroxides such as benzoyl peroxide, potassium persulfate and ammonium persulfate
  • the amount of the thermal polymerization initiator is preferably in the range of about 0.01 to about 20 parts by weight per 100 parts by weight of all monomers.
  • the resulting composite When using a polymerization initiator that generates nitrogen (N 2 ) during the polymerization reaction, such as AIBN, the resulting composite contains air bubbles. Since such air bubbles can be a starting point of breakage, it is predicted that the impact absorption capacity can be improved while the properties such as the extensibility of the composite material may be deteriorated.
  • the bubbles contained in the composite material are not limited to those derived from the polymerization initiator, and the resin or the like contains bubbles, such as those obtained by adding a foaming agent, and those obtained by removing a solvent. It may be a bubble obtained by any known method that can be used.
  • photopolymerization initiator examples include 2-oxoglutaric acid, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl 1 -Propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide And the like, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more.
  • the amount of the photopolymerization initiator is preferably about 0.01 to about 20 parts by weight per 100 parts by weight of all monomers.
  • the homopolymer or copolymer contained in the composite of the present invention uses a peroxide-based initiator (for example, benzoyl peroxide, and azobisisobutyronitrile, and their analogs) as a polymerization initiator.
  • a peroxide-based initiator for example, benzoyl peroxide, and azobisisobutyronitrile, and their analogs
  • the amount of the polymerization initiator is preferably about 0.01 parts by weight to about 20 parts by weight per 100 parts by weight of all monomers.
  • electron beam polymerization is performed by irradiating the monomer with an electron beam.
  • the monomer component can be polymerized by irradiation with only an electron beam.
  • the electron beam is irradiated in the presence of a photopolymerization initiator and in another embodiment in the absence of a photopolymerization initiator. Any embodiment is within the scope of the present invention.
  • the polymerization reaction temperature and atmosphere at the time of polymerizing a monomer there is no limitation in particular about the polymerization reaction temperature and atmosphere at the time of polymerizing a monomer.
  • the polymerization reaction temperature is about 50 ° C to about 120 ° C.
  • the atmosphere at the time of the polymerization reaction is preferably, for example, an inert gas atmosphere such as nitrogen gas.
  • the polymerization reaction time of the monomer can not be determined indiscriminately because it varies depending on the polymerization reaction temperature etc., but it is usually about 3 to 20 hours.
  • the homopolymer obtained by homopolymerization of the monomer (A) used in the present invention may have a glass transition temperature in the range of -100.degree. C. to 50.degree.
  • the lower limit of the glass transition temperature of the homopolymer is about -100 ° C, about -90 ° C, about -80 ° C, about -70 ° C, about -60 ° C, about -50 ° C, about -40. C., about -30.degree. C., about -20.degree. C. and about -10.degree. C. are exemplified, and as upper limit values, about 10.degree. C., about 20.degree. C., about 30.degree. C., about 40.degree.
  • the glass transition temperature is in the range of about -70 ° C to 30 ° C. In another preferred embodiment, the glass transition temperature is in the range of about -60 ° C to 30 ° C. In yet another preferred embodiment, the glass transition temperature is in the range of about -50 ° C to 20 ° C. In still further preferred embodiments, the glass transition temperature is in the range of about -20 ° C to 20 ° C.
  • the homopolymer obtained by homopolymerization of the monomer (A) used in the present invention is about 0.1 to 50 mPa ⁇ s in one embodiment, about 0.5 to 30 mPa ⁇ s or about 0.3 to 40 mPa ⁇ s or about in a preferred embodiment. It may have a viscosity of 0.4 to 35 mPa ⁇ s.
  • the monomer (A) used in the present invention has a surface tension of about 15 to 55 mN / m in one embodiment, about 20 to 40 mN / m or about 20 to 45 mN / m or about 20 to 50 mN / m in a preferred embodiment. It can have
  • the weight average molecular weight of the polymer of the present invention is 1,000,000 to 10,000,000, preferably 1,000,000 to 5,000,000, and more preferably 1,000,000 to 3,000,000, as measured by gel filtration chromatography (GPC). It is.
  • the present invention provides compounds of general formula (1) (R 1 is hydrogen or a C 1-4 alkyl group, R 2 is an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted cycloalkenyl group, It is an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted heteroaryl group, and X 1 and X 2 are each independently O, S, NR x , and CR x 1 R x 2 is selected from the group consisting of, R x is hydrogen, C 1 ⁇ 6 alkyl group, C 1 ⁇ 6 alkoxy group, C 1 ⁇ 6 haloalkyl group or a C 2 ⁇ 6 haloalkenyl group, R x1 and R x2 Each independently
  • the monomer component has a general formula (2) It further includes a vinyl-based monomer (B) represented by (R 3 is hydrogen or a C 1-4 alkyl group, and R 4 is an organic group).
  • the monomer component is polymerized in the presence of a crosslinking agent. In one embodiment, the monomer component is polymerized in the absence of a crosslinker.
  • the crosslinking agent is 10 mol% or less, 9 mol% or less, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5 mol% or less, 4 mol% or less, 3 mol% or less, 2 mol%, based on the monomer Or less, 1 mol% or less, 0.9 mol% or less, 0.8 mol% or less, 0.7 mol% or less, 0.6 mol% or less, 0.5 mol% or less, 0.4 mol% or less, 0.3 mol% or less, 0.2 mol% or less, or 0.1 mol% The following amounts may be added.
  • the crosslinking agent when the solvent is added to the monomer component to prepare a concentrated solution (> 1 to 2 molar concentration), the crosslinking agent is 10 mol% or less, 9 mol% or less, 8 mol% with respect to the monomer 7 mol% or less, 6 mol% or less, 5 mol% or less, 4 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less, 0.9 mol% or less, 0.8 mol% or less, 0.7 mol% or less, 0.6 mol% or less It may be added in an amount of 0.5 mol% or less, 0.4 mol% or less, 0.3 mol% or less, 0.2 mol% or less, or 0.1 mol% or less.
  • the polymerization is carried out in the presence of an initiator.
  • the initiator is benzophenone or an analogue thereof, more preferably benzophenone.
  • the initiator is azobisisobutyronitrile or an analogue thereof, more preferably azobisisobutyronitrile.
  • the homopolymers or copolymers of the present invention are those polymerized by using benzophenone or an analogue thereof, or azobisisobutyronitrile or an analogue thereof as a polymerization initiator.
  • the polymerization of the monomer component is performed according to a polymerization method selected from the group consisting of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization.
  • a polymerization method selected from the group consisting of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization.
  • the monomers of the present invention may be polymerized by chain polymerization, sequential polymerization, or living polymerization.
  • the monomer (A) and the vinyl-based monomer (B) used in the present invention may be those commercially available from the manufacturers etc. exemplified in the Examples, and those skilled in the art It may be prepared according to methods known to
  • the composite material of the present invention is in the presence of a polymerization initiator in a state in which a monomer component (containing one or more monomers) is in contact with fibers. It is obtained in one step by exposure polymerization.
  • the composite material of the present invention contains a homopolymer and a fiber, it can be produced by irradiating ultraviolet light in the presence of a polymerization initiator in the state where the monomer (A) is in contact with the fiber.
  • the composite material of the present invention contains a copolymer and a fiber
  • it may be produced by irradiating ultraviolet light in the presence of a polymerization initiator in the state where the monomer (A) and the monomer (B) are in contact with the fiber.
  • the polymerization initiator is selected from, for example, the polymerization initiators exemplified later, but preferred examples include benzophenone. This step is usually carried out at room temperature for about 10 hours, preferably under an argon atmosphere.
  • the composite of the present invention can also be manufactured by irradiating only an electron beam instead of ultraviolet light. When the electron beam is irradiated, the monomer component can be polymerized in the presence or absence of a photopolymerization initiator.
  • electron beams may be irradiated instead of ultraviolet rays, ultraviolet rays and electron beams may be irradiated simultaneously, and ultraviolet rays and electron beams may be alternately irradiated.
  • the polymerization is carried out without the use of a crosslinking agent. In one embodiment of the process for producing a composite of the invention, the polymerization is carried out without the use of a solvent. In a preferred embodiment of the process for producing a composite according to the invention, unlike the process for producing double network elastomers, it is possible to cure the monomer mixture as it is by means of ultraviolet light (UV) without using a solvent or a crosslinking agent. Operation is simple.
  • UV ultraviolet light
  • an embodiment using a crosslinking agent is also within the scope of the present invention, since it may exhibit physical properties that may be obtained when a small amount of crosslinking agent (generally about 1 mol% or less based on the monomer) is added. Ru. In some cases, it may be preferable to include a small amount of crosslinker. Therefore, in this case, it may show physical properties that may be obtained when a crosslinking agent is added to a concentrated solution (1 to 2 M) containing a solvent.
  • the desired molded product is formed by forming a mold corresponding to the desired shape, charging the starting material monomer into the mold, irradiating the ultraviolet light to form a polymer, and removing the produced polymer from the mold. can get.
  • This method can be used when the starting material monomer is of low viscosity.
  • the desired membrane product may be obtained by applying the starting monomer on a flat surface and irradiating it with ultraviolet light to form a polymer.
  • a film made of a (meth) acrylate polymer can be obtained by casting the monomer on a substrate and polymerizing the monomer by irradiating the formed film of the monomer with ultraviolet light or the like.
  • the composite material of the present invention is in the presence of a polymerization initiator in a state where a monomer component (containing one or more monomers) is in contact with fibers. It is obtained in one step by thermal polymerization.
  • the composite material of the present invention contains a homopolymer and a fiber, it can be produced by heating in the presence of a polymerization initiator while the monomer (A) is in contact with the fiber.
  • the composite material of the present invention contains a copolymer and a fiber, it can be produced by heating in the presence of a polymerization initiator with the monomer (A) and the monomer (B) in contact with the fiber.
  • a polymerization initiator is selected from the polymerization initiator etc. which are illustrated by a postscript, azobisisobutyronitrile is mentioned as a preferable example. This step is usually carried out at 70 ° C. for about 10 hours, preferably under an argon atmosphere.
  • crosslinker examples include those listed as polyfunctional monomers.
  • the crosslinker is ethylene glycol dimethacrylate.
  • the determination of whether or not the composite of the present invention is flexible can be made by measuring the tensile modulus.
  • it can measure according to JIS K7161.
  • the said measuring method is as follows, for example.
  • a reaction cell is prepared by sandwiching the fiber with two 0.5 mm thick spacers (like a sandwich) and further sandwiching it in turn with a hydrophobic film and a glass sheet.
  • a mixture of a monomer and a photopolymerization initiator is placed in the cell, and an illuminance of 4 mW / cm 2 and an irradiation time of 10 hours are accumulated using an ultraviolet irradiator (manufactured by UVP, product number: 95-0042-12) from the side thereof.
  • UVP ultraviolet irradiator
  • a composite material is obtained by placing a mixture of a monomer and a thermal polymerization initiator in the cell and subjecting it to room temperature or heating conditions (for example, 70 ° C.).
  • Dumbbell-shaped test pieces of 12 mm (length) ⁇ 2 mm (width) ⁇ 1 mm (thickness) are prepared according to JIS-K6251 (dumbbell shape No. 7) which is a standard.
  • the tensile speed is 50 mm / min.
  • the tensile strength and tensile modulus of the test piece obtained by the above method are measured with a tensile tester (manufactured by ORIENTEC Co., Ltd., product number: Tensilon RTC-1310A).
  • the tensile modulus of a polymer (matrix) is measured, it is measured in the same manner as described above except that no fiber is used.
  • the tensile modulus of the composite material of the present invention is typically 5 MPa or more, 10 MPa or more, 15 MPa or more, 20 MPa or more. In one embodiment, the tensile modulus of the composite is 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1200, 1400, 1600, 1800, 2000, 2500, 3000 MPa or more. .
  • the tensile modulus of the polymer is typically 0.005 MPa or more, 0.01 MPa or more, 0.02 MPa or more, or 0.03 MPa or more. In one embodiment, the tensile modulus of the composite is 0.05, 0.1, 0.5, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 300, 400, It is 500 MPa or more.
  • the determination as to whether or not the polymer has "toughness" can be made by measuring the tear energy by the tear test (for example, by the test method described in the examples). For example, it can be determined by measuring whether the tearing energy is at least 200 kJ / m 2 .
  • the said measuring method is as follows, for example.
  • a reaction cell is prepared as in the case of measuring the tensile modulus.
  • a mixture of a monomer and a photopolymerization initiator is placed in the cell, and an illuminance of 4 mW / cm 2 and an irradiation time of 10 hours are accumulated using an ultraviolet irradiator (manufactured by UVP, product number: 95-0042-12) from the side thereof.
  • the composite material is obtained on the resin film by irradiating ultraviolet light with a light amount of 144 J / cm 2 .
  • the composite is obtained by placing a mixture of a monomer and a thermal polymerization initiator in the cell and subjecting it to room temperature or heating conditions (for example, 70 ° C.).
  • a sample of a composite material of a rectangular parallelepiped (for example, length 50 mm ⁇ width 30 mm ⁇ thickness about 1.3 mm) is prepared and notched (for example, width from the middle of the side surrounded by the width direction and the thickness direction side, width Make one notch of 10-20 mm perpendicular to the direction and parallel to the thickness direction). Clamp the two ends on the cut side with separate clamps. The upper clamp is pulled upward at a constant speed (e.g. 50 mm / min) while the lower clamp is fixed. The force-displacement curve of the sample is recorded during the deformation.
  • a constant speed e.g. 50 mm / min
  • T c is the toughness (tear energy) of the composite
  • F is the tear force
  • L is the displacement during the test
  • t is the thickness of the composite
  • L bulk is the torn path
  • the tear energy to which reference is made in evaluating the toughness of the inventive composite is, for example, about 100, about 200, about 300, about 400, about 500, about 600, about 700, about 800, It is about 900, or about 1000 kJ / m 2 or higher.
  • the tear energy of the inventive composite is about 200 kJ / m 2 or more.
  • the tear energy of the inventive composite is about 300 kJ / m 2 or more.
  • the tear energy of the inventive composite is about 400 kJ / m 2 or more.
  • the tear energy of the inventive composite is about 500 kJ / m 2 or more.
  • the tear seeks the path that consumes the least energy, resulting in a shift of the process zone.
  • Process Zone (6-1) Saturation of Process Zone
  • the term "process zone” refers to an area of a certain size capable of transmitting a force when the composite is torn in the above-mentioned tear test. Say In this range, the energy applied to tear the test piece is dissipated. The wider the range, the higher the toughness.
  • the fibers will break before the matrix (polymer) is broken.
  • the process zone is nearly saturated with the composite, the fibers break or come out when a force is applied in the tearing direction.
  • part of the process zone is saturated with the composite and a force is applied in the tearing direction, the fibers come out before breaking.
  • the toughness of the composite can be determined by certain physical factors and coefficients, It has been clarified in the present invention that the rules can be generalized. Such factors and coefficients are important for a complete understanding of the composite system, and also apply to various matrices (here, the gel, the second material of the present invention, the glass transition polymer, etc. It can be used to produce the desired composites from the obtained) and fabrics (which may correspond to the first material of the invention, fibers etc.).
  • this amount of work is generally expressed as (1), and the energy density of the matrix and the process zone Equal to the product of volume, ie Where W is the amount of work required to tear the composite, F is the tearing force, L is the displacement during the test, and S m is the energy density of the matrix (herein Where S m may be expressed as W m ) and V is the volume of the process zone. V relates to the shape of the composite. Where W c is the critical width, t is the thickness of the composite, and L bulk is the length of the torn path, thereby establishing the relationship between W and the sample parameters Can.
  • the toughness (tearing energy) of the composite can be calculated from W and the sample shape.
  • T c is the toughness (tearing energy) of the composite material. Therefore, when Equations (1), (2) and (3) are combined, the relationship between T c and S m ⁇ W c can be understood. It should be noted that the conditions described above are based on the premise that the process zone is saturated with the composite. For composites where the process zone is not saturated, the size of the process zone is limited by the width, so equation (4) gives: And corrected.
  • V is related to the shape of the composite material and can be calculated as in the following equation (2).
  • W c is the critical width
  • t is the thickness of the composite
  • L bulk is the length of the torn path, thereby establishing the relationship between W and the sample parameters
  • W is expressed by equation (8).
  • G f is the shear modulus of the fabric
  • G m is the shear modulus of the matrix
  • S m is the strain energy density of the matrix
  • S f is the strain energy density of the fabric.
  • the toughness (tearing energy T c ) of the composite can be calculated from W and the sample shape as in the following formula (3).
  • T c is the tearing energy of the composite. Therefore, when the equations (8), (2) and (3) are combined, the relationship between T c and S (m + f) ⁇ W c can be understood. It should be noted that the conditions described above are based on the premise that the process zone is saturated with the composite. For composites where the process zone is not saturated, the size of the process zone is limited by the width, so equation (9) is It is preferable to correct
  • the “critical width” is determined in the tearing test, and specifically, when the pulling out of the fiber stably occurs from the end of the tearing, the tearing Point at twice the distance to the tip. For example, typically, the following tests are performed to determine the critical width of the composite of the present invention.
  • Composite samples are prepared that have the same length (eg, about 50 mm) and thickness (eg, about 1.3 mm) but different widths (eg, about 5 mm to about 110 mm). Each sample is subjected to a tear test to observe tear behavior. For samples narrower than the critical width inherent in the composite, the fibers are pulled out completely from the onset of tearing. For samples that are about the same or wider than the inherent critical width, fiber breakage occurs, especially immediately after the onset of tearing. From the observation of the tear behavior, the critical width of the sample is determined to be the minimum width at which fiber breakage occurs. It may be advantageous that the composite of the present invention is preferably provided with a width greater than or equal to such critical width.
  • this fiber is embedded in a soft matrix cylinder of thickness d and the outer edge of this soft matrix cylinder is adhesively bonded to a hard wall (which is of course It is for modeling, and it is a very rough approximate model created after excluding the detailed conditions from the actual situation.)
  • a shear-delay model is used to describe the transfer of load along the fiber.
  • the soft matrix only carries shear in an area of length L and shear strain ⁇ is Given by
  • u (x) is the displacement of the fiber in the x direction (uniform across fibers). Note that d is small, and as a result, the distortion of the matrix may be large even if the displacement u is small. The balance of fiber power is less Will be required.
  • ⁇ is the shear stress on the fiber-matrix interface
  • ⁇ (x) is the fiber stress. In general, ⁇ depends on the distortion in the matrix.
  • the fiber stress ⁇ (x) is, for the fiber force F, It will be related to
  • Equation (12) can then be integrated to obtain the fiber stress / force, which is It is.
  • Get If x> L the fiber does not carry any load.
  • the stresses and strains in the fiber are zero in the region of x> L.
  • ⁇ represents the fiber strain
  • E represents the Young's modulus of the fiber, It becomes.
  • Equation (14) represents that the fiber breaks when L reaches L c .
  • a model of toughness is created and the combination of rigid but friable fibers and a soft but highly stretchable matrix gives very high toughness Can be clearly shown.
  • the rigid fibers and soft matrix can be assumed to exhibit a stress-strain curve as shown in FIG.
  • ⁇ represents the ratio of fracture stress of rigid fiber to soft matrix
  • ⁇ represents the rupture strain ratio of soft matrix to rigid fiber.
  • ⁇ c is used for the fracture stress of fibers as a parameter different from the above description.
  • Toughness The energy required to break or break a composite is equal to the toughness of the composite.
  • the work W performed for one composite cell shown in FIG. And if L ⁇ Lc, then Because It is. In the case of L> Lc, Because It is. Therefore, the work per unit cell is equal to the tear energy of our experimental value T, and It becomes.
  • the toughness of the composite is the product of fiber strength and matrix extensibility ((0,0), (0, ⁇ c ), ( ⁇ c , ⁇ c ), ((10) in FIG. 105), It represents that it is proportional to a square area surrounded by four points of ⁇ c , 0).
  • the amount of can be understood as the strain energy density (or work from elongation to break) of the composite.
  • the strain energy density of the composite can be understood to be amplified by the facts of ⁇ (>> 1) and ⁇ (>> 1), respectively, as compared to neat matrix and neat fibers. This explains why the combination of a stiff but high strength fiber and a soft but stretchable matrix results in the high breaking energy as observed in the examples.
  • k has a length scale that can be understood as the characteristic length of the composite. k is equal to the length scale which correlates with the tear energy and strain energy density of the neat material.
  • Equation 43 indicates that the thinner the matrix layer, the higher the interfacial exfoliation stress. Therefore, by adjusting from thin to thick one can see the transition from interface peeling to matrix failure.
  • L c represents the fabric critical width for the transition from “pulling” to “fiber failure”
  • ⁇ c represents the failure stress of the fiber bundle
  • ⁇ c represents the failure stress of the matrix
  • R represents the radius of the fiber bundle
  • the various tearing behavior of the composite was fiber breakage.
  • the plot of FIG. 108 showed linear correlation.
  • T represents the tearing energy of the composite
  • ⁇ c represents the fracture stress of the fiber
  • ⁇ c represents the fracture strain of the matrix
  • L represents the width of the sample.
  • the plot of FIG. 109 showed linear correlation.
  • the correlation diagrams shown in FIGS. 107, 108 and 109 show approximately linear correlation. This means that the above-mentioned simple model represents the essence of the complex strengthening mechanism.
  • peelability refers to the property of the matrix (polymer) in the composite material to be easily peeled from the fibers.
  • the reduction of the releasability of the polymer toughened the composite.
  • the determination as to whether or not the composite material has the “self-reconstruction function” can be made by measuring the self-reconstruction function. For example, when the composite material of the present invention is dissolved in a solvent (for example, chloroform), the solvent is evaporated, the residue is dried (for example, at 65 ° C.), and the composite material obtained is subjected to a tear test. It can be determined by measuring whether the tearing energy is at least 80% relative to the tearing energy of the original composite.
  • a solvent for example, chloroform
  • the tear energy after a single self-reconstruction referred to in assessing the self-reconstruction of the inventive composite is, for example, about 80% relative to the value of the initial composite prior to dissolution, About 90%, about 100%, about 110%, about 120%, about 130%, about 140%, about 150%, about 160%, about 170%, about 180%, about 190% or about 200%, or It is a higher value.
  • the tear energy after one self-reconstruction is about 100% or more relative to the value of the initial composite prior to dissolution.
  • the tear energy after one self-reconstruction is about 150% or more relative to the value of the original composite prior to dissolution.
  • the tear energy after one self-reconstruction is about 200% or higher relative to the value of the initial composite prior to dissolution.
  • the tear energy after two self-reconstructions referred to in evaluating the self-reconstruction of the inventive composite is, for example, about the value of the first polymer before the first dissolution. 80%, about 90%, about 100%, about 110%, about 120%, about 130%, about 140%, about 150%, about 160%, about 170%, about 180%, about 190% or about 200% Or higher.
  • the tear energy after two self-reconstructions is about 100% or more relative to the value of the initial composite prior to the first dissolution.
  • the tear energy after two self-reconstructions is about 120% or more relative to the value of the first composite prior to the first dissolution. In the most preferred embodiment, the tear energy after two self-reconstructions is about 150% or higher relative to the value of the initial composite prior to the first dissolution.
  • the measurements after one self-reconstruction may be the same as or greater than the values of the first composite before dissolution, and the measurements after two self-reconstruction are the first composite before dissolution It may be the same as, greater than, or less than the value of the material.
  • the measurement of tear energy after one self-reconstruction may be the same as, greater than, or less than the value after two self-reconstructions. In one embodiment, the measurement of tear energy after two self-reconstructions is greater than the value after one self-reconstruction. In another embodiment, the measurement of tear energy after two self-reconstructions is less than the value after one self-reconstruction.
  • the measurement of tear energy after one self-reconstruction is greater than the value of the first composite prior to dissolution, and the measurements after two self-reconstruction are after one self-reconstruction Although smaller than the value of, it is larger than the measurement value of the first composite before dissolution. In one embodiment, the measurement of tear energy after one self-reconstruction is equal to or greater than the value of the first composite prior to dissolution, and the measurements after two self-reconstruction are Less than the value of the first composite before dissolution and the value after one self-reconstruction. In one embodiment, the measurement of tear energy after one self-reconstruction is equal to or greater than the value of the first composite prior to dissolution, and the measurements after two self-reconstruction are The same as or greater than the value after one self-reconstruction.
  • the composite of the present invention may be a composite containing fibers and a glass transitionable polymer.
  • the composite material of the present invention includes two-wheeled vehicles (bicycles, motorcycles, etc.), automobiles, planes, trains, ships, rockets, spacecraft, transportation, leisure, furniture (eg, tables, chairs, desks, shelves, etc.), bedding (eg, Bed, hammock, etc., clothes, protective clothes, sporting goods, bathtubs, kitchens, dishes, utensils, containers, containers and packaging materials (food containers, cosmetic containers, cargo containers, waste containers, etc.), architecture (buildings, roads, etc.) , Architectural parts, etc.) agricultural films, industrial films, water and sewage, paints, cosmetics, electric industry and electronic industry (electrical appliances, computer parts, printed circuit boards, insulators, conductors, wiring coatings, power generation elements, Speakers, microphones, noise cancelers, transducers, etc.), optical communication cables, medical materials and devices (catheters, guide wires, Industrial blood vessels, artificial muscles, artificial organs, dialysis membranes, endoscopes, etc.) Small pumps, actuators, robot materials
  • the composite material of the present invention is a vehicle, an aircraft, a ship, a train, a motorcycle, a vehicle such as a bicycle, a helmet, a mask, a goggle, an armor, a pad, a golf club, a tennis racket, a ski, a sporting article such as a stock, a bulletproof Protective products such as walls, bulletproof vests, bulletproof vehicles, artificial limbs such as artificial hands and feet, bag items such as suitcases and carry cases, household appliances such as vacuum cleaners and electric tools, portable chemical products such as umbrellas and canes, beds, It may be used for furniture products such as mats and cushions, dishes, toys, play equipment, building materials, clothing materials, electronic materials, medical materials, healthcare materials, life science materials, robot materials and the like.
  • the composite material of the present invention can be used, for example, as a material for catheters, guide wires, containers for pharmaceuticals, tubes and the like.
  • the composite material of the present invention is an automobile component (body panel, bumper band, rocker panel, side molding, engine component, drive component, drive component, steering component, stabilizer component, suspension / brake component, brake component, shaft component, It can be used for pipes, tanks, wheels, seats, seat belts, etc.).
  • the composite material of the present invention can be used as an automotive anti-vibration material, automotive paint, automotive synthetic resin and the like.
  • Carbon fiber, glass fiber and aramid fiber were purchased from Intercross Co., Ltd.
  • Metal fiber stainless fiber was produced by Okuya Wire Mesh Co., Ltd., and was purchased from Mutual Science and Chemical Glass Co., Ltd.
  • carbon fiber fabric carbon fiber (thick) woven fabric CCP 3200-100 was used unless otherwise specified. All monomers listed in Table 2 are, in addition to Osaka Organic Chemical Industry Co., Ltd. (all monomers), Nippon Catalyst (IBXA and 2-MTA), Eternal Materials CO., LTD. (IBXA), or Kyoeisha What was marketed from Chemical Co., Ltd.
  • Benzoyl peroxide (BPO) and benzophenone (BP) (commercially available from Kanto Chemical Co., Ltd.) were used as ultraviolet light polymerization initiators. Further, azobisisobutyronitrile (AIBN) (commercially available from Kanto Chemical Co., Ltd.) was used as a thermal polymerization initiator.
  • BPO Benzoyl peroxide
  • BP benzophenone
  • AIBN azobisisobutyronitrile
  • a fabric composed of carbon fibers (thick) or (thin), glass fibers, or aramid fibers used in the examples is made of fiber bundles containing many fibers ing. Unlike other fibers, stainless steel fibers have a mesh structure woven one by one. Therefore, the radius and cross-sectional area of the stainless steel fiber bundle can not be measured. a) the diameter of one fiber, b) the spacing of one fiber.
  • Example 1 Preparation of composite of homopolymer and carbon fiber (thick) of phenoxydiethylene glycol acrylate (PHDEA) Carbon fiber fabric CCP 3 200-100 (Yarn: CF3K 200 TEX, density: 12.5 x 12.5 / 25 mm, mass: 200 g / m A reaction cell was prepared by sandwiching a plain weave), purchased from Intercross Co., Ltd.) with two 0.5 mm thick spacers (like a sandwich) and further sandwiching it in turn with a hydrophobic film and a glass sheet.
  • PHDEA phenoxydiethylene glycol acrylate
  • Example 2 Preparation of a Composite of a Copolymer of Phenoxydiethylene Glycol Acrylate (PHDEA) and Isobornyl Acrylate (IBXA) and Carbon Fiber (Thick)
  • PHDEA 40 parts by weight or more and less than 100 parts by weight
  • a copolymer of PHDEA and IBXA poly (PHDEA-IBXA) was prepared in the same manner as in Example 1 except that isobornyl acrylate (more than 0 parts by weight, 60 parts by weight or less) (as a hard segment) was used.
  • carbon fiber composites were obtained.
  • poly (PHDEA-IBXA) containing no carbon fiber was also prepared.
  • Example 3 Preparation of Composite of 2-Methoxyethyl Acrylate (2-MTA) Homopolymer and Carbon Fiber (Thick)
  • 2-methoxyethyl acrylate (as a soft segment) was used instead of PHDEA.
  • a composite of a 2-methoxyethyl acrylate homopolymer (poly (2-MTA)) and a carbon fiber was obtained in the same manner as in Example 1 except for the above.
  • poly (2-MTA-IBXA) containing no carbon fiber was also prepared.
  • Example 4 Preparation of a composite of copolymer of 2-methoxyethyl acrylate (2-MTA) and isobornyl acrylate (IBXA) and carbon fiber (thick)
  • 2-methoxyethyl acrylate instead of PHDEA
  • a composite of a copolymer of 2-methoxyethyl acrylate and IBXA poly (2-MTA-IBXA)
  • a carbon fiber in the same manner as in Example 1 except that and isobornyl acrylate (as a hard segment) I got the material.
  • poly (2-MTA-IBXA) containing no carbon fiber was also prepared.
  • Example 5 Preparation of Composite of Homopolymer and Carbon Fiber (Thick) of Phenoxyethyl Acrylate (PHEA)
  • Example 5 except that phenoxyethyl acrylate (as a soft segment) was used in place of PHDEA.
  • poly (PHEA) containing no carbon fiber was also prepared.
  • Example 6 Preparation of a Composite of a Copolymer of Phenoxyethyl Acrylate (PHEA) and Isobornyl Acrylate (IBXA) and Carbon Fiber (Thick)
  • PHEA Phenoxyethyl Acrylate
  • IBXA Isobornyl Acrylate
  • Thick Carbon Fiber
  • phenoxyethyl acrylate (PHEA) and isobol in place of PHDEA.
  • a composite of a PHEA-IBXA copolymer (poly (PHEA-IBXA)) and a carbon fiber was obtained in the same manner as in Example 1 except that nyl acrylate (as a hard segment) was used.
  • poly (PHEA-IBXA) containing no carbon fiber was also prepared.
  • Example 7 Preparation of Composite of Homopolymer and Carbon Fiber (Thick) of Benzyl Acrylate (BZA)
  • BZA Benzyl Acrylate
  • Example 8 Preparation of Composite of Copolymer of Benzyl Acrylate (BZA) and Isobornyl Acrylate (IBXA) and Carbon Fiber (Thick)
  • BZA Benzyl Acrylate
  • IBXA Isobornyl Acrylate
  • Thick Carbon Fiber
  • Example 9 Preparation of a Composite of a Copolymer of Phenoxydiethylene Glycol Acrylate (PHDEA) and t-Butyl Acrylate (TBA) and Carbon Fiber (Thick)
  • PHDEA Phenoxydiethylene Glycol Acrylate
  • TBA t-Butyl Acrylate
  • Carbon Fiber Thiick
  • Example 10 Preparation of a Composite of a Copolymer of Phenoxydiethylene Glycol Acrylate (PHDEA) and Cyclohexyl Acrylate (CHA) (as Hard Segment) and Carbon Fiber (Thick)
  • PHDEA Phenoxydiethylene Glycol Acrylate
  • CHA Cyclohexyl Acrylate
  • Thick Carbon Fiber
  • Example 11 Preparation of Composite of Homopolymer and Carbon Fiber (Thick) of Methoxytriethylene Glycol Acrylate (MTG)
  • methoxytriethylene glycol acrylate (as a soft segment) was used instead of PHDEA.
  • a composite of a methoxytriethylene glycol acrylate homopolymer (poly (MTG)) and a carbon fiber was obtained.
  • poly (MTG) containing no carbon fiber was also prepared.
  • Example 12 Preparation of a Composite of a Copolymer of Methoxytriethylene Glycol Acrylate (MTG) and Isobornyl Acrylate (IBXA) and Carbon Fiber (Thick)
  • MTG and IBXA copolymer poly (MTG-IBXA)
  • carbon fibers were obtained in the same manner as in Example 1 except that bornyl acrylate was used.
  • poly (MTG-IBXA) containing no carbon fiber was also prepared.
  • Example 13 Preparation of a Composite of Tetrahydrofurfuryl Acrylate (THFA) Homopolymer and Carbon Fiber (Thick)
  • THFA Tetrahydrofurfuryl Acrylate
  • Thiick Carbon Fiber
  • Example 14 Preparation of Composite of Copolymer of Tetrahydrofurfuryl Acrylate (THFA) and Isobornyl Acrylate (IBXA) and Carbon Fiber (Thick)
  • THFA Tetrahydrofurfuryl Acrylate
  • IBXA Isobornyl Acrylate
  • Carbon Fiber Thiick
  • Example 15 Preparation of Composite of Lauryl Acrylate (LA) Homopolymer and Carbon Fiber (Thick)
  • LA Lauryl Acrylate
  • Thick Carbon Fiber
  • Example 16 Preparation of Composite of Copolymer of Lauryl Acrylate (LA) and Isobornyl Acrylate (IBXA) and Carbon Fiber (Thick)
  • LA Lauryl Acrylate
  • IBXA Isobornyl Acrylate
  • Thick Carbon Fiber
  • Example 17 Preparation of a Composite of Isostearyl Acrylate (ISTA) Homopolymer and Carbon Fiber (Thick)
  • Isostearyl Acrylate (ISTA) Homopolymer and Carbon Fiber (Thick)
  • isostearyl acrylate (as a soft segment) was used instead of PHDEA.
  • PHDEA isostearyl acrylate
  • a composite of isostearyl acrylate homopolymer (poly (ISTA)) and carbon fiber was obtained.
  • poly (ISTA) containing no carbon fiber was also prepared.
  • Example 18 Preparation of Composite of Copolymer of Isostearyl Acrylate (ISTA) and Isobornyl Acrylate (IBXA) and Carbon Fiber (Thick)
  • Isostearyl acrylate and isobornyl acrylate are substituted for PHDEA.
  • a composite of a copolymer of ISTA and IBXA (poly (ISTA-IBXA)) and a carbon fiber was obtained in the same manner as in Example 1 except that it was used.
  • poly (ISTA-IBXA) not containing carbon fiber was also prepared.
  • Example 19 Preparation of Composite of Homopolymer and Carbon Fiber (Thick) of Ethyl Carbitol Acrylate (CBA)
  • CBA Ethyl Carbitol Acrylate
  • Example 20 Preparation of a Composite of Ethyl Carbitol Acrylate (CBA) and Isobornyl Acrylate (IBXA) and Composite of Carbon Fiber (Thick)
  • CBA Ethyl Carbitol Acrylate
  • IBXA Isobornyl Acrylate
  • Thiick Composite of Carbon Fiber
  • ethyl carbitol acrylate and isobornyl instead of PHDEA
  • a composite of CBA and IBXA copolymer (poly (CBA-IBXA)) and carbon fiber was obtained in the same manner as in Example 1 except that acrylate was used.
  • poly (CBA-IBXA) containing no carbon fiber was also prepared.
  • Example 21 Preparation of Composite of Homopolymer and Carbon Fiber (Thick) of Phenylthioethyl Acrylate (PHSEA)
  • PHSEA Phenylthioethyl Acrylate
  • Example 22 Preparation of a Composite of a Copolymer of Phenylthioethyl Acrylate (PHSEA) and Isobornyl Acrylate (IBXA) and Carbon Fiber (Thick)
  • PHSEA Phenylthioethyl Acrylate
  • IBXA Isobornyl Acrylate
  • Carbon Fiber Thiick
  • Examples 23 to 44 In the preparation of the composites of Examples 1 to 22 above, carbon fiber fabric CCP 1120-1000 (yarn: CF1K 68TEX, density: 22 ⁇ 22/25 mm, weight: 120 g / m 2) instead of carbon fiber fabric CCP 3200-100 A composite of each polymer and carbon fiber (thin) was prepared in the same manner as in each Example except that plain weave was used.
  • Examples 67 to 88 A composite was prepared in the same manner as in each of the examples except that aramid fibers were used instead of carbon fibers in the preparation of the composites of Examples 1 to 22 above.
  • Examples 89 to 110 A composite material was prepared in the same manner as in each of the examples except that stainless steel fibers were used instead of carbon fibers in the preparation of the composite materials of the above Examples 1-22.
  • Example 111 Testing of Mechanical Properties of Polymer Only In this example, testing of the mechanical properties of the polymers produced in Examples 1-110 was performed. The method is shown below.
  • Method (1-1) Tensile test of polymer and composite material (refer to JIS K7161) Tensile stress-strain measurement of polymers and composites to determine toughness, yield point, tensile modulus, breaking strain, hysteresis ratio etc.
  • Tensile tester Teensilon RTC-1310A, ORIENTEC and Instron 5965, Instron ) At a temperature of 20.degree. C. in air at a tension rate of 50 mm / min.
  • a dumbbell-shaped sample having a size of 12 mm (length) ⁇ 2 mm (width) ⁇ 1 mm (thickness) was used according to JIS-K6251 (dumbbell shape No. 7) which is a standard.
  • the breaking strain of poly (PHEA) was about 1300% (mm / mm).
  • (1-2) Tensile test of single fiber (refer to JIS R7606) In order to determine the tensile modulus and the fracture stress etc., the tensile stress-strain measurement of single fiber is carried out at 50 mm / min in air using a tensile tester (Tensilon RTC-1310A, Orientec Co., Ltd. and Instron 5965, Instron) Carried out at a tensile speed of Glass fiber was about 700 MPa and carbon fiber was about 900 MPa (see FIG. 80).
  • the tear energy T of the samples was measured by a tear test.
  • the experiment was carried out on a Instron tensile tester using a 250 N load cell.
  • the polymer-only test sample was a rectangular solid having a width of 40 mm, a length of 60 mm, and a thickness of 1 mm.
  • the fabric-only test sample was a rectangular solid having a width of 40 mm, a length of 60 mm, and a thickness of about 1 mm.
  • the test sample of the composite was a rectangular solid having a width of 5 to 110 mm, a length of 30 to 100 mm, and a thickness of 1.3 mm.
  • the first incision was made one-third of the length from the midpoint of the end of the side parallel to the width direction of the sample to the center parallel to the length direction using a razor blade.
  • the two separated ends of the test piece were clamped with separate clamps.
  • the upper clamp was pulled upward at a constant speed of 50 mm / min while the lower clamp was fixed.
  • the force-displacement curve of the sample was recorded during the deformation. Tear energy following formula Calculated by Here, L represents the displacement during the test, L bulk represents the length of the torn path in the tear test, F represents the force required to tear the test sample, and t represents It represents the thickness of the test sample.
  • FIG. 3 is a force-displacement curve of composites with different mole fractions. From these curves, it is possible to calculate correlated tear energy. As shown in FIG. 4, when the mole fraction of PHDEA (soft segment) increases, the toughness of the neat polymer monotonously decreases. However, the toughness (tear energy) of the composite decreases after reaching a peak. This indicates that the toughness of the matrix (tear energy) is not the only factor that determines the toughness of the composite.
  • PHDEA soft segment
  • Process zones differ significantly between the composites (not shown). The softer the matrix, the larger the process zone of the resulting composite. Thus, it can be concluded that both the matrix and the process zone affect the toughness of the composite.
  • the tear test results are shown respectively.
  • the process zone of the composite with the hardest matrix shrinks dramatically as the tensile modulus at high speeds increases. Instead, the process zone of the composite with the hardest matrix shrinks dramatically as the tensile modulus at high speeds increases, resulting in a very limited energy dissipation zone during the test (see figure Not shown). Even with the matrix, the higher the test rate, the more energy can be dissipated, and the toughness of the composite (tear energy) is greatly limited by the process zone that allows the matrix to contribute.
  • the soft segment monomer was changed to PHEA.
  • the reason is that the resulting polymer has higher stiffness, resulting in a smaller process zone of the composite that can be more easily identified.
  • the preparation method and the measurement are the same as the above-mentioned example.
  • the only difference in the sample shapes was that the width of the composite varied from 5 mm to 110 mm.
  • the other conditions were the same as in the above example.
  • the critical width was examined by tearing test at different tearing rates for the same samples (Tables 7 and 8, Figures 67 and 68). (See also Figure 110.)
  • T c (kJ / m 2 ) versus W m ⁇ width (kJ / m 2 ) is shown in FIG. 29 for composites of carbon fiber and each polymer having different mole fractions of PHEA-co-IBXA.
  • T c shows a linear relationship with W m ⁇ width in all composites.
  • the slopes of each series are different from one another. This indicates that there is a prefactor that affects the equation.
  • FIG. 30 and 31 the deformation of each matrix is distinguished from one another (FIGS. 30 and 31). The harder the matrix, the higher the energy density, but the deformation during the tear test is less.
  • Equations (4) and (5) can be converted to equations (51) and (52) according to the premise proposed above. Can be corrected. However, it will be appreciated that this equation is obtained by ignoring the energy density of the fabric, so it does not hold in comparison between composites with different fabrics. In order to compare between composites with different fabrics, it is preferable to use equations (9) and (10).
  • aramid fibers eg, Kevlar® fibers
  • FIG. 34 is a graph in which the data of the glass fiber base composite material is added to the graph of FIG. 29, and FIG. 35 is a graph in which the X axis is D ⁇ W m ⁇ width based on the graph of FIG.
  • this linear law can be used to estimate the T c of any fiber based composite under the pullout mechanism.
  • the choice of matrix is very important in order to make tough composites. In order to achieve a large D, it is necessary that the tensile modulus be low, ie soft. Alternatively, the ratio of fiber to matrix fracture stress may be important. In order to achieve a large W m is the energy density is high, i.e., it is necessary to have high toughness. Therefore, in order to produce a tough composite, a soft and tough matrix is required.
  • Example 113 Universality of methodology for producing high toughness composites from various matrices and fibers (1) Experiment Sample preparation Several monomers and fabrics, fiber-based composites, to demonstrate whether the method of making the fiber-based high-toughness and flexible composites proposed above from various matrices and fabrics is universal. Selected to prepare the material. The toughness of the resulting composite was tested, as well as the toughness of the neat polymer and neat fabric as a comparison.
  • carbon fiber (thick) refers to carbon fiber fabric CCP 3200-100 (yarn: CF3K 200 TEX, density: 12.5 ⁇ 12.5 / 25 mm, weight: 200 g / m 2 , plain weave)
  • carbon fiber (thick "Slim) refers to carbon fiber fabric CCP 1120-1000 (yarn: CF1K 68TEX, density: 22 x 22 threads / 25 mm, weight: 120 g / m 2 , plain weave), glass fiber, glass fiber fabric R 590 H 102 D (yarn: GF Roving 600 TEX, density: 12 ⁇ 12/25 mm, weight: about 590 g / m 2 , plain weave),
  • aramid fiber refers to aramid fiber fabric K 300 H 100 (Technola®, density: 1.39 g / cm 3 , single fiber diameter 12 ⁇ (round shape), tensile strength 350 kg / mm 2 ).
  • Metal fiber or “stainless fiber” refers to stainless steel wire mesh (DSM 200, 200 mesh, wire diameter 0.05 mm, plain weave, material: SUS 316). Notes for all samples a. The width of the sample is 40 mm. b. The unit of tearing energy is kJ / m 2 . c. The process zone of composite samples using other than metal fibers is not saturated. The process zone of the composite sample with metal fibers is saturated. d. ND: Not measured. e. Polymerization initiation conditions: UV
  • the toughness of the composite with the polymer having an aromatic ring is higher than that of the composite with a polymer having no aromatic ring.
  • the toughness of the composite increases in proportion to the weight ratio of the aromatic ring (for example, C6) to the molecular weight of the monomer It is also understood.
  • Example 114 High Toughness and Flexible Composites
  • energy dissipative, flexible matrices have been shown to be extremely important in constructing high toughness composites.
  • Figure 90 Our recent findings also show that strong and tough fibers play a large role in forming very tough composites.
  • Example 115 Fiber to matrix tensile modulus ratio Measure the tensile modulus and tear energy for various fibers, copolymers and composites at different test rates to investigate the relationship between the ratio of fiber tensile modulus to matrix tensile modulus and the tear energy (Table 10). There is no close correlation between the tensile modulus ratio and the tear energy (T c ) or the critical width (W c ), but generally, as the ratio increases, the tear energy and critical width also tend to increase It is understood that there are ( Figures 99 and 100).
  • PI PHEA-co-IBXA
  • CI CBA-co-IBXA
  • f molar fraction of PHEA or CBA
  • E cf tensile modulus of carbon fiber
  • E gf tensile modulus of glass fiber
  • E kf Tensile modulus of aramid fiber
  • E m tensile modulus of matrix
  • T c tear energy of composite material
  • Example 116 Fiber to Matrix Fracture Stress Ratio To determine the relationship between fiber fracture stress to matrix fracture stress and tear energy, measure the fracture stress and tear energy for various fibers, copolymers and composites at different test rates (Table 11). For the same fabric composite, the tear energy (T c ) and the critical width (W c ) show a linear correlation with the fiber and matrix fracture stress (FIGS. 101 and 102). These results show that the transfer of force between the fibers and the matrix is highly promoted in composite systems consisting of fibers with relatively high stress and matrices with relatively low stress, which results in high tear toughness.
  • Example 117 Matrix tear energy and strain energy density at different test speeds (Abbreviations) f: PHEA mole fraction of, T m: Matrix tear energy, S m: in energy density above Table 12 strain of the matrix, the stress - strain PHEA-co-IBXA polymer estimated from strain curves The energy density and the tearing energy of the PHEA-co-IBXA polymer at different test rates are roughly linearly correlated.
  • Example 118 Effect of Temperature on Mechanical Performance of Composites
  • 24 ° C, 50 ° C, 100 ° C and 150 ° C for PHEA-co-IBXA / carbon fiber composite The tear test was performed at ( Figures 87 and 88). The higher the test temperature, the lower the force and tear energy required for tearing. It can be clearly understood that the matrix is exfoliated from the fibers at high temperatures (100 ° C. and 150 ° C.) when looking at the state of the composite in FIG. 87 after the tear test. This exfoliation results in poor transmission of force from the fibers to the matrix due to the undesirable interface.
  • the matrix exhibits viscoelastic properties at room temperature, its viscosity may disappear at relatively high temperatures, which may result in the matrix acting as a high modulus polymer. Thus, interfacial bonding is degraded, resulting in delamination and a corresponding reduction in mechanical performance.
  • Example 119 Anisotropic Mechanical Properties of Polymer / Fiber Composites
  • PHEA-co-IBXA copolymer of phenoxy ethylene glycol acrylate and isobornyl acrylate
  • the tensile modulus and flexural modulus of the material were measured. The results are shown in FIG. Adjustment of the mole fraction of the matrix component is considered to have little effect on the coefficient of the composite. All composites exhibit dramatic anisotropic mechanical properties, whose tensile modulus (about 1000 MPa) is two orders of magnitude greater than its flexural modulus (about 10 MPa).
  • Example 120 Effect of Initiation Method on Toughness of Composite
  • PHEA-co-IBXA / carbon fiber composites with various molar ratios of PHEA to IBXA from thermal initiation, instead of benzophenone (BP), to total monomer amount The polymerization was carried out at 70 ° C. for 10 hours in an oven under an argon atmosphere, using 0.1 mol% of azobisisobutyronitrile (AIBN).
  • AIBN azobisisobutyronitrile
  • the resulting composite exhibited high tear energy as compared to the UV initiated composite system.
  • the results of the tear test for the composite by thermal polymerization, together with the results of the composite by UV initiated photopolymerization as a comparison, are shown in FIG.
  • thermally initiated polymerization is an efficient way to prepare tough and flexible composites, as composites obtained by thermal polymerization show very high tear resistance compared to composites obtained by photopolymerization. It is. The force-displacement curve and the tear energy of the corresponding composite L bulk based composites are presented in FIG. All thermally polymerized composites were tougher than the photopolymerized composites in terms of tear resistance.
  • the W m and elastic modulus (tensile modulus) (E) of the above-described polymer are shown in FIGS. 53 and 54, respectively.
  • all polymers derived from thermal polymerization are less tough (relatively lower W m ) than polymers derived from photopolymerization, while relatively softer (relatively lower E) ).
  • E is included Elastic modulus (tensile modulus) of any sample.
  • the lower E the higher D. That is, elastomers derived from thermal polymerization have higher D but lower W m as compared to elastomers derived from photopolymerization.
  • the competition between D and W m is responsible for the different tearing energy between the thermally and UV polymerized composites.
  • Example 121 Preparation of carbon fiber composite material with PDMS
  • PDMS polydimethylsiloxane
  • a type of polydimethylsiloxane (PDMS) solution containing 10% by weight of a crosslinking agent) in an amount appropriate to the type is a type in which a carbon fiber (thick) fabric is sandwiched. It was injected into. It was cured by heating in an oven at 70 ° C. for 2 hours.
  • a flexible composite was also prepared by direct blending of polydimethylsiloxane (PDMS) polymer and carbon fibers to test the universality of our preparation method.
  • the results of the tear test of the resulting composite are shown in FIG. 41 with the PHEA-co-IBXA / carbon fiber composite as a comparison.
  • the PI / CFC system has much higher toughness than the PDMS / CFC system for the same geometry.
  • the tensile modulus of PDMS is about 1.18 MPa, which is lower than that of the PHEA-co-IBXA system. Therefore, the equation proposed by the present inventors for estimating the toughness of the composite material According to, the T c of PDMS should be higher than the T c of some PI / CFC systems with identical geometry. This anomalous result makes it essential to clarify the energy dissipation mechanism of the PDMS / CFC system.
  • the PI / CFC is significantly deformed and broken into two parts, but neither of the parts remains intact, ie the composite is not separated from the fabric from the fabric It was a material.
  • peeling of the matrix from the fabric occurred in PMDS / CFC during the tear test. This is because it was difficult for PDMS to penetrate into the fabric during preparation of PMDS / CFC. This gives a reasonable explanation for the low toughness of the PDMS / CFC system.
  • the PDMS / CFC system is, strictly speaking, not a flexible composite but a flexible compound. This result also reinforces our belief that incorporating the matrix inside the fabric plays a major role in toughening the composite.
  • Example 122 Tear test of the sample with two cuts:
  • the tear test was performed using samples in which two cuts were inserted.
  • the appearance of the sample cut into pieces of 10 mm-20 mm-10 mm shown in FIG. 96 before and after the test is shown in FIG. Similar to the procedure described in (1) Method (1-2) Tear test, in the case of the sample of FIG. 96, the 10 mm wide end is fixed with one clamp and the inner 20 mm wide end is separated.
  • the clamp is fixed by a clamp and pulled upward at a constant speed of 50 mm / min so as to be 180 degrees reverse direction.
  • the path length was the total length of the two paths from the two cuts to the torn.
  • the tear energy of the 10 mm-20 mm-10 mm sample (Fig. 95), 10 mm-10 mm-10 mm sample (Fig. 97) and 10 mm-5 mm-10 mm sample (Fig. 98) is about 487, about 359, about 261 kJ / It was m 2 .
  • Criterion 1 The matrix is flexible and energy dissipating so that the composite obtained therefrom produces a large process zone.
  • Criterion 2 Precursor solutions of monomers can penetrate the edges of the fabric to form the desired interface.
  • Example 123 Evaluation of self-rebuilding property The composite material is placed in chloroform, and while stirring, the matrix part is dissolved (concentration: 2 M). Chloroform in this solution is allowed to evaporate for 6 to 24 hours. It is then dried in an oven at 65 degrees for 3 days.
  • the tear test of the sample before the first dissolution, the sample after one cycle of dissolution, volatilization and drying, and the sample after repeating the cycle twice are performed.
  • Example 124 Evaluation of Rheological Behavior of Copolymers
  • M IBXA 0: 1 to 1: 0 copolymers
  • Dynamic viscoelastic spectra were obtained by measuring the rheological behavior using an ARES rheometer from Rheometric Scientific Inc.
  • ARES rheometer from Rheometric Scientific Inc.
  • the upper and lower surfaces of a disk-shaped sample having a diameter of 15 mm and a thickness of 1.5 mm were attached with an adhesive so as to be positioned at the center of a 25 mm-diameter parallel plate.
  • the temperature was increased stepwise from ⁇ 8 ° C. to 128 ° C., and frequency sweep measurements were performed at an angular frequency range of 0.1 to 100 rad / s at each temperature with a shear strain of 0.5%.
  • FIG. 42 shows a graph of Tan ⁇ -angular frequency for each of the copolymers having different mole fractions.
  • the horizontal axis is the angular frequency, which corresponds to the reciprocal of the observation time.
  • Tan ⁇ exhibits a maximum at a certain angular frequency, and the maximum value is 1 or more. This means that the copolymers of this system exhibit very strong visco-elastic properties. Also, as M PHEA increases, the angular frequency at which Tan ⁇ exhibits a maximum also increases. This means that as the mole fraction of the soft segment increases, the bonds between side chains in the copolymer become weaker and the bond life (relaxation time) becomes shorter. In fact, relaxation time decreases with increasing M PHEA (Table 13). As used herein, relaxation time is the inverse of the angular frequency at which Tan ⁇ exhibits a maximum.
  • the copolymer of this system can be regarded as an excellent viscoelastic elastomer.
  • Example 125 Synthesis of Polymer of Phenoxyethyl Acrylate (PHEA) Polymerized in the Presence of Crosslinking Agent
  • PHEA Phenoxyethyl Acrylate
  • phenoxyethyl acrylate (PHEA) was used instead of phenoxydiethylene glycol acrylate, and ethylene glycol dimethacrylate (total A crosslinked polymer of phenoxyethyl acrylate (poly (PHEA) + crosslinker) was obtained in the same manner as in Example 1 except that 5% based on the weight of the monomer was added.
  • Example 126 Glass Transition Temperature of Monomer, Homopolymer, and Crosslinked Polymer
  • the glass transition temperature of the homopolymer used in the examples and the crosslinked polymer of Example 125 was measured according to JIS K7121. The results are shown in Table 14.
  • a) Differential scanning calorimetry (DSC) was performed from -50 ° C. to 150 ° C. at a heating rate of 5 ° C./min under nitrogen flow. As an exception, CBA was measured from -70 ° C to 150 ° C.
  • ND not measured.
  • the glass transition temperature of the copolymer used in the examples was determined by differential scanning calorimetry. The results are shown in Table 10. From this result, it can be seen that as the ethylene glycol chain becomes longer, the glass transition temperature becomes lower. a) Glass transition temperatures from -50 ° C. to 150 ° C. at a heating rate of 5 ° C./min under nitrogen flow by differential scanning calorimetry (DSC).
  • a composite material comprising a first material such as a fiber of the present invention and a second material such as a glass-transferable polymer and having specific fracture stress characteristics is used as a material for achieving both flexibility and toughness. obtain.

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Abstract

L'invention fournit un matériau composite souple et robuste qui contient des fibres et un polymère permettant une transition vitreuse. Plus précisément, l'invention concerne un matériau composite qui contient des fibres et un polymère permettant une transition vitreuse, lequel polymère permettant une transition vitreuse peut consister en un homopolymère ou en un copolymère, et peut être choisi dans un groupe constitué d'un polymère (méth)acrylique, d'un polymère à base d'éthylène, d'un polymère à base d'uréthane, d'un polymère à base d'éther, d'un polymère à base d'amide, d'un polymère à base de carbonate ainsi que d'un polymère à base de silicone, et d'une combinaison arbitraire de ces polymères.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220162491A1 (en) * 2019-03-14 2022-05-26 Showa Denko Materials Co., Ltd. Curable composition, heat storage material, and article
CN114773942A (zh) * 2022-04-02 2022-07-22 广东希贵光固化材料有限公司 一种led固化涂料

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52100574A (en) * 1976-02-19 1977-08-23 Ciba Geigy Ag Manufacture of preepreg
JP2015113412A (ja) * 2013-12-12 2015-06-22 東レコーテックス株式会社 熱可塑性繊維強化複合材料およびそれを用いた成形体ならびにその複合材料の製造方法

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4338233A (en) * 1981-06-15 1982-07-06 Ppg Industries, Inc. Aqueous sizing composition and sized glass fibers and method
JP2716798B2 (ja) * 1989-05-17 1998-02-18 ダイセル化学工業株式会社 弾力性カラー舗装材組成物
DE4016056A1 (de) * 1990-05-18 1991-11-21 Basf Ag Waessrige kunstharzzubereitungen
EP0489878A1 (fr) * 1990-06-29 1992-06-17 Vinamul Ltd. Polymerisation d'emulsion
DE4306808A1 (de) * 1993-03-04 1994-09-08 Wacker Chemie Gmbh Vernetzbare Dispersionspulver als Bindemittel für Fasern
JP3604187B2 (ja) * 1995-02-22 2004-12-22 ソニー株式会社 昇華型熱転写記録紙用印画紙
JPH1135632A (ja) * 1997-07-25 1999-02-09 Nippon Shokubai Co Ltd 吸液性樹脂および中極性溶剤含有ゲル
JP2002047397A (ja) * 2000-07-31 2002-02-12 Kanegafuchi Chem Ind Co Ltd 金型表面転写性の良好な高剛性熱可塑性ポリエステル樹脂組成物
EP1486518B2 (fr) * 2002-02-27 2015-10-14 Mitsubishi Rayon Co., Ltd. Antichoc, procede de production et composition a base de resine thermoplastique
KR101298892B1 (ko) * 2005-09-30 2013-08-21 가부시키가이샤 구라레 피혁형 시트 및 그 제조 방법
WO2010029096A1 (fr) * 2008-09-12 2010-03-18 Henkel Ag & Co. Kgaa Composition à base d’époxy contenant un copolymère
JP2013079292A (ja) * 2010-02-12 2013-05-02 Mitsui Chemicals Inc フェノール樹脂組成物、その硬化物および摩擦材
WO2013047145A1 (fr) * 2011-09-28 2013-04-04 日本ゼオン株式会社 Composition adhésive sensible à la pression conductrice de la chaleur, corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur, procédé de fabrication d'une composition adhésive sensible à la pression conductrice de la chaleur, procédé de fabrication d'un corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur, et composant électronique
JP2013199613A (ja) * 2012-03-26 2013-10-03 Toray Coatex Co Ltd 繊維強化複合材料及びその製造方法
JP6326801B2 (ja) * 2013-12-12 2018-05-23 大日本印刷株式会社 積層体
FR3046606B1 (fr) * 2016-01-11 2019-09-06 Arkema France Composition (meth)acrylique liquide comprenant un polymere a phases multiples et un monomere (meth)acrylique, son procede de preparation et son utilisation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52100574A (en) * 1976-02-19 1977-08-23 Ciba Geigy Ag Manufacture of preepreg
JP2015113412A (ja) * 2013-12-12 2015-06-22 東レコーテックス株式会社 熱可塑性繊維強化複合材料およびそれを用いた成形体ならびにその複合材料の製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220162491A1 (en) * 2019-03-14 2022-05-26 Showa Denko Materials Co., Ltd. Curable composition, heat storage material, and article
CN114773942A (zh) * 2022-04-02 2022-07-22 广东希贵光固化材料有限公司 一种led固化涂料
CN114773942B (zh) * 2022-04-02 2023-06-23 广东希贵光固化材料有限公司 一种led固化涂料

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