JP4486841B2 - Glass fiber reinforced resin linear material and method for producing the same - Google Patents

Description

  The present invention relates to a glass fiber reinforced resin linear product, and more particularly to a glass fiber reinforced resin linear product used as a tension member such as an optical fiber cable, that is, a tension member.

  An optical fiber cable is a cable in which a plurality of optical fibers are assembled, and is rapidly spreading in offices, condominiums, and the like in Japan. In the optical fiber cable, a tension member is used in order to prevent the optical fiber from extending more than specified. Optical fiber cables are described in Patent Documents 1 to 6, for example.

  As the tension member, an aramid fiber reinforced resin as described in Patent Document 6 or a glass fiber reinforced resin as described in Patent Document 7 is used.

JP 2003-15000 A JP 2000-241681 A JP 2003-107307 A Japanese Patent Laid-Open No. 11-23925 Utility Model Registration No. 2503790 JP 2000-199840 A Japanese Patent Laid-Open No. 10-10382

  In recent years, optical fiber cables have become lighter and more compact, and the optical fiber itself has a very small allowable elongation, and the bending performance (hereinafter referred to as flexibility) of optical fiber cables has been dramatically improved. Accordingly, the tension member itself is required to have higher flexibility.

  However, the tension member of aramid fiber reinforced resin has the disadvantage that the minimum bending diameter (the diameter of the tension member that breaks when it is bent into an arc shape) is larger than the tension member of glass fiber reinforced resin. After being wound around the bobbin, it is unwound for use and exhibits a curved shape corresponding to the winding diameter of the bobbin. In Patent Document 6, a vinyl ester resin containing a peroxide catalyst is used as the matrix resin.

  On the other hand, even in the case of a tension member made of glass fiber reinforced resin, it did not have such a high flexibility that its minimum bending diameter D was less than 20 times the diameter d of the linear object. In Patent Document 7, a tension member having an outer shape d of 0.252 mm is described as a comparative example, but its minimum bending diameter D is 6 to 7 mm, and D / d is 20 or more. In the examples of Patent Document 7, a methacrylic acid ester-based monomer-containing novolak-type vinyl ester resin is used as a matrix resin.

  Usually, the production speed of an ultrafine tension member having a diameter of 0.6 mm or less is 1 m / min or more, but the curing time cannot be 10 minutes or more due to the size of the mold and the production equipment. For this reason, the curing reaction of the matrix resin is usually carried out at an atmospheric temperature of 200 ° C. or less within 10 minutes, preferably within 5 minutes, more preferably within 3 minutes.

  On the other hand, the viscosity of the uncured resin composition is desired to be small. This is because when the viscosity of the resin composition is high, it is difficult for the resin composition to enter the gaps between the glass fibers. Moreover, the thinner the glass fiber, the more difficult it is for the resin composition to enter the yarn made of a plurality of glass fibers.

  From these facts, a thermosetting resin having a fast curing time, high strength and high elasticity, and low viscosity has not been found.

  In the case of a tension member using an unsaturated polyester resin or vinyl ester resin as a matrix resin, there may be a problem when post-processing as an optical fiber cable. That is, when manufacturing an optical fiber cable, there is a process of coating a thermoplastic resin, but styrene gas or the like is generated from the tension member during the heat treatment, and the optical fiber cable may swell.

  Accordingly, the present invention has been completed through intensive studies aimed at improving bending performance and flexibility in a tension member made of glass fiber reinforced resin.

  According to a first aspect of the present invention, there is provided a glass fiber reinforced resin linear material containing a glass fiber having a breaking elongation of 5% or more and a matrix resin, and the matrix resin has a viscosity of 15000 mPa · s at 25 ° C. Provided is a glass fiber reinforced resin linear material obtained by curing the following liquid epoxy resin with a thermal cationic polymerization catalyst or an acid anhydride.

  In the present invention, D / d, which is the ratio of the minimum bending diameter D of the glass fiber reinforced resin linear material to the diameter d of the glass fiber reinforced resin linear material, is 20 or less, and d is 0.6 mm or less. It is preferable.

  The matrix resin is preferably obtained by curing the liquid epoxy resin together with a bisphenol A type epoxy resin having an average molecular weight of 900 or more.

  Furthermore, it is preferable that the matrix resin is obtained by curing the liquid epoxy resin together with a flexibility imparting agent.

  Moreover, it is preferable that the said matrix resin hardens | cures the liquid epoxy resin whose viscosity is 3500 mPa * s or less at 25 degreeC with the said thermal cationic polymerization catalyst.

  Furthermore, the acid anhydride is preferably liquid at 25 ° C.

  Furthermore, it is preferable that the liquid epoxy resin contains an epoxycyclohexane ring or a 2,3-epoxypropyloxy group.

It is preferable that the glass fiber contains 55-79.9 wt% SiO ₂ , 12.6-32 wt% Al ₂ O ₃ , 4-20 wt% MgO.

  According to a second aspect of the present invention, there is provided a method for producing a glass fiber reinforced resin linear material comprising a glass fiber having a breaking elongation of 5% or more and a matrix resin, and having a viscosity of 15000 mPa · s or less at 25 ° C. There is provided a method for producing a glass fiber reinforced resin linear product comprising a step of curing a liquid epoxy resin with a thermal cationic polymerization catalyst or an acid anhydride.

  In this invention, it is preferable to harden within 10 minutes at the atmospheric temperature of 80-200 degreeC.

  Moreover, it is preferable that the viscosity of the uncured resin composition containing the liquid epoxy resin and the thermal cationic polymerization catalyst or the acid anhydride is 10,000 mPa · s or less at 25 ° C.

  In a third aspect of the present invention, there is provided a tension member which is a glass fiber reinforced resin linear material as described above for an optical fiber cable including an optical fiber and a tension member.

  The glass fiber reinforced resin linear material of the present invention is a glass fiber reinforced resin linear material containing a glass fiber having a breaking elongation of 5% or more and a matrix resin, and the matrix resin has a viscosity at 25 ° C. Since the liquid epoxy resin of 15000 mPa · s or less is cured with a thermal cationic polymerization catalyst or acid anhydride, the glass fiber reinforced resin linear material of the present invention has high flexibility and reduces the minimum bending diameter. Can be made. Specifically, D / d which is the ratio of the minimum bending diameter D of the glass fiber reinforced resin linear material and the diameter d of the glass fiber reinforced resin linear material is 20 or less. Even in this case, the diameter d can be maintained at 0.6 mm or less, preferably 0.55 mm or less.

  Moreover, since the matrix resin is an epoxy resin, the glass fiber reinforced resin linear material of the present invention generates styrene gas or the like that adversely affects the heat treatment in the thermoplastic resin coating process when post-processing as an optical fiber cable. It is possible to process a very good optical fiber cable.

  The method for producing a glass fiber reinforced resin linear product according to the present invention is a method for producing a glass fiber reinforced resin linear product comprising a glass fiber having a breaking elongation of 5% or more and a matrix resin, and having a viscosity at 25 ° C. Includes a step of curing a liquid epoxy resin having a viscosity of 15000 mPa · s or less with a thermal cationic polymerization catalyst or an acid anhydride, so that a glass fiber reinforced resin linear material having high flexibility and a reduced minimum bending diameter is obtained. Obtainable.

  When it hardens within 10 minutes at 80-200 degreeC atmospheric temperature, a glass fiber reinforced resin linear thing can be continuously operated at the manufacturing speed of 1 m / min or more.

  The optical fiber cable using the tension member of the present invention has high flexibility since the tension member is the glass fiber reinforced resin linear material described above.

  As shown in FIG. 1, the glass fiber reinforced resin linear product 1 of the present invention includes glass fibers 2 and a matrix resin 4. The monofilament of 25 to 800 glass fibers 2 may form the yarn 3, and the monofilament of 100 to 200 glass fibers 2 preferably forms the yarn 3. The cross section of the yarn 3 is preferably substantially circular. The yarn 3 and the yarn 3 may be in contact with each other or may not be in contact with each other. The glass fiber reinforced resin linear product 1 preferably contains 2 to 15 yarns, and more preferably contains 4 to 10 yarns. The diameter of the glass fiber reinforced resin linear material 1 is preferably 1.0 mm or less, and more preferably 0.6 mm or less. In the present invention, sufficient tensile strength can be maintained even with such a thin glass fiber reinforced resin linear material. Further, the diameter of the glass fiber reinforced resin linear product 1 is preferably 0.1 mm or more, and more preferably 0.2 mm or more.

  The outer periphery of the matrix resin 4 may be covered with a thermoplastic resin 6 in some cases. As the thermoplastic resin, for example, polyolefin, polyester, polyamide or the like is used, and polyolefin such as polyethylene is preferable. Note that the thermoplastic resin 6 is not an essential component.

  In the present invention, the breaking elongation of the glass fiber is 5.0% or more. Thereby, a glass fiber resin linear thing has high softness | flexibility, and can reduce a minimum bending diameter. The breaking elongation of the glass fiber is measured according to “Glass Fiber General Test Method (4) Tensile Strength” defined in JIS R 3420. Depending on the literature, the elongation at break may be referred to as the maximum elongation.

  The elastic modulus of the glass fiber is preferably 70 GPa or more, and more preferably 80 GPa or more. This is to impart high flexibility to the glass fiber resin wire and reduce the minimum bending diameter.

As a glass fiber which shows the above physical properties, for example, a glass composition containing 55-79.9 wt% SiO ₂ , 12.6-32 wt% Al ₂ O ₃ , 4-20 wt% MgO. Is mentioned. The glass composition also may contain ZrO ₂ less than 1 wt%. For example, glass fibers described in US Pat. No. 3,402,055 can be used. As the glass fiber, high-strength glass fiber (trade name “T glass”) sold by Nitto Boseki Co., Ltd. can be suitably used.

  It is preferable that the surface of the glass fiber is treated with epoxy silane. This is because the wettability at the interface between the glass fiber and the matrix resin is improved.

  The matrix resin contained in the glass fiber reinforced resin linear material of the present invention is obtained by curing a liquid epoxy resin having a viscosity of 15000 mPa · s or less at 25 ° C. with a thermal cationic polymerization catalyst or an acid anhydride. Even when this matrix resin is not reinforced with glass fiber, its elongation at break and elastic modulus are improved. Further, since the liquid epoxy resin has a viscosity of 15000 mPa · s or less at 25 ° C., it has good wettability with the glass fiber at the stage of the uncured resin composition, and has good adhesiveness with the glass fiber after curing. .

  Moreover, it is preferable that the breaking elongation λ of the matrix resin is 5.0% or more and the elastic modulus of the matrix resin is 2 GPa or more. When this condition is satisfied, the ratio D / d, which is the ratio of the bending diameter D at which the glass fiber reinforced resin linear material does not break and the diameter d of the glass fiber resin linear material, is stably 20 or less. Because. On the other hand, D / d is preferably 10 or more, and more preferably 12 or more. As for the physical properties of the matrix resin, the resin composition is cured in a state in which no glass fiber is contained to form a matrix resin, and its elongation at break and elastic modulus are measured.

  In the glass fiber reinforced resin linear material of the present invention, the glass fiber content is preferably 60% by weight or more, the matrix resin content is preferably 40% by weight or less, and the glass fiber content is 65% by weight. The content of the matrix resin is more preferably 35% by weight or less. This is to improve the rigidity of the glass fiber reinforced resin linear material.

  In the glass fiber reinforced resin linear material of the present invention, the glass fiber content is preferably 80% by weight or less, the matrix resin content is preferably 20% by weight or more, and the glass fiber content is 75% by weight. More preferably, the content of the matrix resin is 25% by weight or more. This is because when the glass fiber content is greater than 75% by weight, the wettability between the glass fiber and the uncured resin composition becomes poor.

  One type of liquid epoxy resin may be used, or a mixture of two or more types may be used. In the case of a mixture of two or more, the viscosity of at least one liquid epoxy resin may be 15000 mPa · s or less at 25 ° C., and the whole of the two or more mixtures is 15000 mPa · s or less at 25 ° C. It is preferable that

  However, the uncured resin composition contains a curing agent (thermal cationic polymerization catalyst or acid anhydride) and other components as desired in addition to the liquid epoxy resin. The viscosity of the uncured resin composition is preferably 10,000 Pa · s or less at 25 ° C. This is because the lower the viscosity of the uncured resin composition, the easier the uncured resin composition enters between the glass fibers.

  In this specification, the “uncured resin composition” refers to a resin composition before being cured by heat, and typically, the resin composition before being cured at an ambient temperature of 80 to 200 ° C. Say things. Even an “uncured resin composition” may be slightly cured at room temperature.

(1) Liquid Epoxy Resin The liquid epoxy resin preferably contains an epoxycyclohexane ring or a 2,3-epoxypropyloxy group (2,3-epoxypropyloxy). When using a thermal cationic polymerization catalyst, a liquid epoxy resin containing an epoxycyclohexane ring is particularly preferred. This is because, despite the low viscosity of the liquid epoxy resin, the cationic polymerizability is high and the physical properties after curing are excellent. In addition, including a 2,3-epoxypropyloxy group means a glycidyl ether type epoxy resin.

  Examples of the liquid epoxy resin containing an epoxycyclohexane ring include 3,4-epoxycyclohexanoic acid 3,4-epoxycyclohexylmethyl (1) (Daicel Chemical, Celoxide 2021P, viscosity at 25 ° C .: 350 mPa · s), 1- (1,2-epoxy-2-propanyl) -3-methyl-3,4-epoxycyclohexane (2) (Daicel Chemistry, Celoxide 3000, viscosity at 25 ° C. is 3500 mPa · s or less), 3,4-epoxycyclohexane Acid ester (3), (Daicel Chemical, Celoxide 2081, viscosity at 25 ° C .: 350 mPa · s). These chemical formulas are shown below.

  In the case of a liquid epoxy resin containing a 2,3-epoxypropyloxy group, the 2,3-epoxypropyloxy group is preferably bonded to a 6-membered carbon ring. Examples of the 6-membered carbocycle include a benzene ring and a cyclohexane ring. This 6-membered carbocycle may be condensed with a 5-membered carbocycle or 6-membered carbocycle.

  Examples of the liquid epoxy resin containing a 2,3-epoxypropyloxy group include bisphenol F diglycidyl ether, bis (4- (2,3-epoxypropyloxy) phenyl) methane (4) (Asahi Denka Kogyo, EP-4901, Viscosity: 3500 mPa · s), hydrogenated bisphenol A diglycidyl ether, 2,2-bis (4- (2,3-epoxypropyloxy) cyclohexyl) propane (5) (Dainippon Ink and Chemicals, Epicron 830), hydrogen Addition bisphenol F diglycidyl ether, bis (4- (2,3-epoxypropyloxy) cyclohexyl) methane (6) (Asahi Denka Kogyo, EP-4080E, viscosity: 2000 mPa · s; Japan Epoxy Resin, YX8000, viscosity: 1800 mPa S).

  Examples of the liquid epoxy resin containing 2,3-epoxypropyloxy group include diglycidyl ether of propylene oxide adduct of bisphenol A, 2,2-bis [4- (2- (2,3-epoxypropoxy) Propyl) phenyl] propane (7) (Asahi Denka Kogyo, EP-4000S, viscosity: 1800 mPa · s).

  Low viscosity epoxy resins generally classified as reactive diluents can also be used as the liquid epoxy resin of the present invention. Such a reactive diluent is preferably used at 30% by weight or less when the total amount of the liquid epoxy resin is 100% by weight. This is because if the amount is more than 30% by weight, the resin matrix strength after curing may be lowered.

  Examples of reactive diluents include 1,4-bis (2,3-epoxypropyloxymethyl) cyclohexane (8) (Asahi Denka Kogyo, EP-4085, viscosity: 45 mPa · s), diglycidyl dicyclopentadiene dimethanol. Ether (9) (Asahi Denka Kogyo, EP-4088, viscosity: 335 mPa · s), para-t-butylphenyl = glycidyl = ether (10) (Nagase Chemtex, Denacol EX146, viscosity: 20 mPa · s), isopropylphenyl = Glycidyl = ether (11) (Dainippon Ink & Chemicals, Epicron 520, viscosity: 15 mPa · s).

  In addition, an epoxy resin having a viscosity of 3500 mPa · s or more alone can be used with a viscosity of 3500 mPa · s or less as required by mixing with a low-viscosity epoxy resin or a reactive diluent. As an epoxy resin having a viscosity of 3500 mPa · s or more alone, for example, bisphenol A type epoxy resin (12) (Asahi Kasei, AER260, viscosity: 14000 mPa · s), long chain hydrogenated bisphenol A type epoxy resin (13) ( Japan Epoxy Resin, YL6834 (viscosity: 80000 mPa · s).

  When the curing agent is a thermal cationic polymerization catalyst, the matrix resin is preferably a resin obtained by curing a liquid epoxy resin having a viscosity of 3500 mPa · s or less at 25 ° C. About the above-mentioned liquid epoxy resin, even when a hardening | curing agent is a thermal cationic polymerization catalyst and it is an acid anhydride, it is used suitably.

  Next, the liquid epoxy resin mainly used when the curing agent is an acid anhydride will be described.

  As the liquid epoxy resin, diglycidyl ester (14) of a dialkylcyclohexene derivative (Japan Epoxy Resin, Epicoat 871, viscosity: 650 mPa · s) can be used.

  In addition, an epoxy resin having a viscosity of 15000 mPa · s or more alone and a solid epoxy resin alone can also be used at 15000 mPa · s or less by mixing with a low-viscosity epoxy resin or a reactive diluent. Examples of the epoxy resin having a viscosity of 15000 mPa · s or more alone include diglycidyl ester (15) of a dialkylcyclohexene derivative (Japan Epoxy Resin, Epicoat 872).

  As a single solid epoxy resin, for example, 3,5,3 ′, 5′-tetramethyl-4,4′-bis (2,3-epoxypropyloxy) biphenyl (16), (Japan Epoxy Resin, YX4000), 1,4-di-t-butyl-2,5-di (2,3-epoxypropyloxy) benzene (17) (Toto Kasei Kogyo, YDC-1312), novolak epoxy resin (18) (Nippon Kayaku Kogyo) , RE-306), novolak type epoxy resin (19) (Nippon Kayaku Kogyo, EOCN-4500), novolak type epoxy resin (20) (Nippon Kayaku Kogyo, EPPN-501H), dicyclopentadiene type epoxy resin (21 ) (Dainippon Ink and Chemicals, HP-7200).

(2) Thermal cationic polymerization catalyst As the thermal cationic polymerization catalyst, a catalyst that is activated by heating to induce ring opening of an epoxy group is used, and various onium salts such as quaternary ammonium salts, phosphonium salts and sulfonium salts, and And organometallic complexes.

  Examples of the sulfonium salt include heterocyclic derivatives represented by the formulas (22) and (23) (Asahi Denka Kogyo, Adeka Opton CP-66, and Adeka Opton CP-77).

A sulfonium salt represented by the formula (24) can also be used (wherein R represents a substituent of the benzene ring. R ′ and R ″ may be the same or different and may be substituted). Sanshin Chemical Industry Co., Ltd., Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L). As the sulfonium salt, for example, trisarylsulfonium antimony hexafluoride is used. Furthermore, as an onium salt, compounds of Nippon Soda Co., Ltd. and CI series (manufactured) can also be used. Examples of organometallic complexes include alkoxysilane-aluminum complexes.

  Moreover, it is preferable to make the mixture ratio of a cationic polymerization initiator into the range of 0.1-5 weight part with respect to 100 weight part of uncured resin compositions, More preferably, it is 0.3-3 weight part. .

(3) Acid anhydride The acid anhydride preferably has a phthalic anhydride skeleton which may be hydrogenated. Examples of the acid anhydride include methyltetrahydrophthalic anhydride (Me-THPA) (Quinhard 200 (Nippon Zeon), HN-2200 (Hitachi Chemical Co., Ltd.), Ricacid MT-500 (New Nippon Rika)), methyl hexahydrophthalic anhydride Acid (Me-HHPA) (Quinhard 500 (Nippon ZEON), HN-5500 (Hitachi Chemical Industries), Ricacid MH-700 (New Nippon Rika)), Methyl nadic anhydride (25) (MHAC-P (Hitachi Chemical Industries)) , Hydrogenated methyl nadic acid (26) (HNA (New Nippon Rika)), alkyl-modified acid anhydride (27) (Epicure YH-306, Epicure YH-307 (Japan Epoxy Resin)) and the like.

  It mix | blends so that an acid anhydride group may be 0.5-2 mol with respect to 1 mol of epoxy groups of an epoxy resin, Preferably it is 0.7-1.3 mol. MH-700 is preferred from the viewpoint of low viscosity and excellent fast curability. Moreover, YH-306 is preferable from the viewpoint that the acid anhydride is less volatile even under the condition of being hard to be affected by ambient moisture and being cured at a high temperature in a short time.

(3) Bisphenol A-type epoxy resin having an average molecular weight of 900 or more In the present invention, the matrix resin is preferably obtained by curing the liquid epoxy resin together with a bisphenol A-type epoxy resin having an average molecular weight of 900 or more. A bisphenol A type epoxy resin having an average molecular weight of 900 or more is generally solid at 25 ° C.

  The general formula of the bisphenol A type epoxy resin (28) is as follows.

(In the formula, n is an integer of 1 or more.)

  For example, Epicoat 1001 (average molecular weight: 900), Epicoat 1002 (average molecular weight: 1200), Epicoat 1003 (average molecular weight: 1300), and Epicoat 1055 (average molecular weight: 1600) of Japan Epoxy Resin can be used. Epicoat 1002 is desirable from the standpoint that the increase in viscosity of the uncured resin composition is suppressed to a relatively low level, and sufficient toughness is easily imparted after curing.

  In the present invention, an epoxy resin in which the repeating unit is a hydrogenated product of bisphenol A may be used instead of the bisphenol A type epoxy resin (28) having an average molecular weight of 900 or more.

(4) Flexibility imparting agent As the flexibility imparting agent, for example, a carboxylic acid-terminated aliphatic polyester epoxy resin adduct (29), for example, SD551 (Ciba Specialty Chemicals) can be used.

In the formula, n, m and l are the same or different and are integers of 1 or more and 10,000 or less. R ₁ is a linear or branched alkylene group having 2 to 16 carbon atoms, R ₂ is a linear or branched alkylene group having 2 to 16 carbon atoms, and the formula — (CH ₂ —CH (CH ₃ ) —O) _i —CH ₂ —CH (CH ₃ ) — or a group represented by the formula — (CH ₂ —CH ₂ —CH ₂ —CH ₂ —O) —CH ₂ —CH ₂ —CH ₂ —CH ₂ is a group represented by-.

  Also, SD665 (Ciba Specialty Chemicals) can be used. In this, the terminal epoxy part of SD551 (Ciba Specialty Chemicals) is substituted by the following formula (30).

  Further, a hydroxyl-terminated polybutadiene (31), for example, PBR-15HT, PBR-45HT (Idemitsu Petrochemical), or an acid anhydride adduct (32) of a hydroxyl-terminated polybutadiene can be used.

  In the formula, n, m, and l are the same or different and are integers of 1 or more.

  Further, carboxylic acid-terminated acrylonitrile-butadiene copolymer (33) (CTBN), for example, HYCAR CTBN 1300 × 13, HYCAR CTBN 1300 × 8, HYCAR CTBN 1300 × 9 (Ube Industries), or their epoxy resin adducts (34) Can be used.

  Of these, SD551 and CTBN epoxy adduct are preferred from the viewpoints of good reactivity, incorporation into a crosslinked structure after curing, and a high effect of imparting toughness to the cured product.

  The total blending amount of the bisphenol A type epoxy resin having an average molecular weight of 900 or more and the flexibility imparting agent is the blending amount of the liquid epoxy resin, the bisphenol A type epoxy resin having an average molecular weight of 900 or more, and the flexibility imparting agent. It is preferable that it is 5 to 50 weight% of the sum total of, and it is still more preferable that it is 10 to 30 weight%. The matrix resin may contain both a bisphenol A type epoxy resin having an average molecular weight of 900 or more and a flexibility-imparting agent, or may contain either or both. It does not have to be.

(5) Curing accelerator When an acid anhydride is used as the curing agent, it is preferable to use a curing accelerator. As the curing accelerator, an imidazole derivative can be used. For example, alkyl imidazoles such as 1-methylimidazole, 2-methylimidazole, 2-undecylimidazole and 2-heptadecylimidazole; dialkylimidazoles such as 1,2-dimethylimidazole and 2-ethyl-4-methylimidazole; Aryl imidazoles such as phenyl imidazole; 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl 2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazolyl) -ethyl-s-triazine, 2,4-diamino-6- (2′-ethyl-4-methylimidazolyl- (1 ′))-ethyl-s-triazine, 2,4- Diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4 , 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl- , 5-di (2-cyano-ethoxy) can be used methylimidazole.

  In addition, 1,8-diaza-bicyclo (5,4,0) undecene 7 (DBU) and salts thereof can also be used. For example, 1,8-diaza-bicyclo (5,4,0) undecene 7, (for example, FC Cure α-1, Shikoku Kasei Kogyo), DBU · 2 ethylhexanoate (for example, FC Cure α-2, Shikoku Chemicals) Industrial), DBU octylate (eg U-CAT SA102, Sun Apro), DBU phthalate (eg U-CAT SA810, Sun Apro), DBU tetraphenylborate (eg U-CAT) 5002, Sun Apro).

  Further, phosphine and phosphonium salts can also be used. Phosphine includes monophosphine and diphosphine. Examples of the monophosphine include triarylphosphine such as triphenylphosphine, tolylphosphine, tris (methoxyphenyl) phosphine, and tris (parachlorophenyl) phosphine; dicycloalkylarylphosphine such as dicyclohexylphenylphosphine; and diphenylcyclohexylphosphine. Diaryldicycloalkylphosphine is used. Examples of the diphosphine include bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, Α, ω-bisdiarylalkanes such as 1,5-bis (diphenylphosphino) pentane are preferably used. Examples of phosphonium salts include tetraalkylphosphonium halides such as tetra-n-butylphosphonium bromide; tetraarylphosphonium halides such as tetraphenylphosphonium bromide, alkyltriarylphosphonium halides; tetraarylphosphonium such as tetraphenylphosphonium tetraphenylborate Tetraaryl borates are mentioned.

  Tertiary amines can also be used. For example, 1,3,5-trisdimethylaminomethylphenol (for example, Adeka Hardener EHC-30, Asahi Denka Kogyo) can be used. A tertiary amine boron trichloride complex (DY9577, Ciba Specialty Chemicals) can also be used.

  These curing accelerators are themselves liquid or solid soluble in an epoxy resin, and are used after being dissolved in an uncured resin composition. The addition amount of the curing accelerator is preferably 0.8 to 20 parts by weight, more preferably 1 to 8 parts by weight, based on 100 parts by weight of the epoxy resin.

  Further, a microcapsule type latent curing accelerator usually used for the purpose of extending the shelf life of the one-component acid anhydride curable epoxy resin composition, such as NOVACURE HX-3088, HX-3741, HX-3922 ( Asahi Kasei Kogyo) can also be used for the purpose of extending the pot life while having fast curability. Since these accelerators in the form of fine particles having a diameter of about 5 μm cannot penetrate into narrow gaps, they can be used together with the above-mentioned resin-dissolving accelerators to form gaps smaller than the particle size of the microcapsule accelerators. The penetrated resin composition can also be cured efficiently.

  Moreover, it is preferable that an uncured resin composition contains a trace amount antifoamer. Silicone can be used as the antifoaming agent.

  According to a second aspect of the present invention, there is provided a method for producing a glass fiber reinforced resin linear material comprising a glass fiber having a breaking elongation of 5% or more and a matrix resin, and having a viscosity of 15000 mPa · s or less at 25 ° C. There is provided a method for producing a glass fiber reinforced resin linear product comprising a step of curing a liquid epoxy resin with a thermal cationic polymerization catalyst or an acid anhydride.

  It is preferable to cure the uncured resin composition containing at least the liquid epoxy resin and the thermal cation polymerization catalyst or acid anhydride at an atmospheric temperature of 80 to 200 ° C. within 10 minutes, and an atmosphere of 90 to 180 ° C. It is more preferable to cure within 5 minutes at a temperature, and still more preferable to cure within 3 minutes at an atmospheric temperature of 90 ° C to 160 ° C. This is because the shorter the curing time, the faster the glass fiber can be pulled, so that the length of the curing mold can be shortened and the production time can be shortened.

  The viscosity of the uncured resin composition is preferably 10,000 mPa · s or less at 25 ° C., and more preferably 9000 mPa · s or less at 25 ° C. This is because the uncured resin composition easily enters between the glass fibers and improves the wettability.

  According to a third aspect of the present invention, there is provided an optical fiber cable including an optical fiber and a tension member, wherein the tension member is the glass fiber reinforced resin wire. The structure of the optical fiber cable is exemplified in Patent Documents 1 to 6, for example.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail by a suitable Example, the scope of the present invention is not limited to a following example.

Examples 1-3
High-strength glass fiber (trade name “T glass”, elongation at break of 5.5%, elastic modulus of 84.3 GPa) sold by Nitto Boseki Co., Ltd. was used. T glass containing SiO ₂ of 65 wt%, 23 wt% of Al ₂ O _3, 11 wt% of MgO, ZrO ₂ less than 1 wt%. Detailed specifications of the high-strength glass fiber are shown in Table 1.

  As the matrix resin, an epoxy resin with a thermal cationic polymerization catalyst was used. The compounding components of Examples 1 to 3 are shown in Table 2.

  Celoxide 2021P and Celoxide 2081 are liquid epoxy resins and were obtained from Daicel Chemical. Epicoat 1002 is a bisphenol A type epoxy resin having an average molecular weight of 1200, and was obtained from Japan Epoxy Resin. SD551 is a carboxylic acid-terminated aliphatic polyester epoxy resin adduct that acts as a flexibility-imparting agent and was obtained from Ciba Specialty Chemicals. SI-100L is a thermal cationic polymerization catalyst, means Sun-Aid SI-100L, and was obtained from Sanshin Chemical Industry Co., Ltd. ST86PA is a dimethylpolysiloxane obtained from Toray Dow Corning Silicone.

  First, components (1), (2), (3) and (6) were mixed at the blending ratio shown in Table 2, and stirred in a kettle at 100 ° C. under reduced pressure for 1 hour to be dissolved uniformly. Thereafter, the amount of component (4) shown in Table 2 was charged and stirred under reduced pressure to dissolve uniformly. And it cooled to room temperature, the predetermined amount of component (5) was prepared, and it stirred under reduced pressure for 30 minutes. It filtered with 110 mesh, discharged | emitted in the light shielding container, and obtained the uncured resin composition.

  This uncured resin composition was filled in an impregnation tank whose temperature was controlled at 30 ° C. in advance and maintained at 30 ° C. At this time, the viscosity of the resin in the impregnation tank was 3000 mPa · s, 5000 mPa · s, and 6000 mPa · s in Examples 1, 2, and 3, respectively.

  In FIG. 2, the yarn was drawn from the plurality of creels 10. The yarn was converged through the guide 11a and the guide 11b, and then immersed in the impregnation tank 12 to impregnate the uncured resin composition. Next, the linear object was drawn into a predetermined shape by the drawing nozzle 13 to remove excess uncured resin composition. And it guide | induced to the heating metal mold | die 14 about 3 m long heated at 150-160 degreeC, and the resin composition was hardened. Since the yarn pulling speed is about 1.5 m / min, the resin composition was cured in about 2 minutes. The glass fiber reinforced resin linear material after curing was passed between a pair of caterpillars 15 and wound around a winding device 16. As a result, a glass fiber reinforced resin composition having an outer diameter of 0.3 mm and a glass fiber content of about 70% by weight was obtained. The glass fiber reinforced resin linear material is not coated with a thermoplastic resin. Moreover, since the caterpillar 15 is for providing tractive force, it can be omitted as appropriate.

  Moreover, only said uncured resin composition was hardened at 150-160 degreeC, and the elasticity modulus and elongation at break of the obtained resin were measured. The results are shown in Table 3.

  The flexibility (minimum bending diameter) of the obtained glass fiber reinforced resin linear material was measured by the following method. This glass fiber reinforced resin composition is cut to a length of about 100 mm, both ends of the sample are gripped by hand, and the central part of the sample is wound around a beautiful steel cylinder having various diameters. Alternatively, the diameter of the steel cylinder when the fracture started from the inner peripheral side was measured. The number of samples n was 10, and the average value was used. The results are shown in Table 4.

  As is apparent from Table 4, the higher the breaking elongation of the epoxy resin that is the matrix resin, the more flexible the glass fiber reinforced resin composition cannot be obtained. Although it depends on the accuracy of the cross-sectional shape of the glass fiber reinforced resin composition, if the modulus of elasticity is low, the cross-sectional shape will be shifted and flat buckling will occur before the glass fiber reinforced resin composition originally breaks. The upper minimum bending diameter D increases. Therefore, the elongation at break of the matrix resin should be high, but what percentage is optimal should be determined by sufficiently considering the elastic modulus of the matrix resin and the adhesiveness at the interface with the fiber. At that time, as is clear from the present invention, a glass fiber reinforced resin composition in which D / d, which is the ratio of the minimum bending diameter D and the diameter d of the linear object, is 20 or less and d ≦ 0.6 mm. In order to obtain a product, it is preferable that the glass fiber and the epoxy resin each have a breakage of 5% or more and the elastic modulus of the epoxy resin is 2 GPa or more.

Examples 4 and 5
Next, the dimension of a metal mold | die was changed with the combination of the matrix resin and glass fiber of Example 3, and the glass fiber reinforced resin composition of outer diameter 0.42mm (Example 4) and 0.51mm (Example 5) was used. Molded. The minimum bending diameter was measured in the same manner as in Examples 1 to 3, and the minimum bending diameters were 7.0 mm and 9.0 mm, respectively, which were 16.7 times and 17.6 times the diameter of the linear object, respectively. .

Examples 6 and 7
As in Examples 1 to 5, a high-strength glass fiber (trade name “T glass”, elongation at break of 5.5%, elastic modulus of 84.3 GPa) sold by Nitto Boseki Co., Ltd. was used. An epoxy resin with an acid anhydride was used as the matrix resin. Table 5 shows the ingredients of Examples 6 and 7.

  Epicoat 871 is a diglycidyl ester (14) of a dialkylcyclohexene derivative, and was obtained from Japan Epoxy Resin. AER260 is a bisphenol A type epoxy resin (12) and was obtained from Asahi Kasei. Celoxide 2021P is a liquid epoxy resin and was obtained from Daicel Chemical. Epicoat 1002 is a bisphenol A type epoxy resin having an average molecular weight of 1200, and was obtained from Japan Epoxy Resin. SD551 is a carboxylic acid-terminated aliphatic polyester epoxy resin adduct that acts as a flexibility-imparting agent and was obtained from Ciba Specialty Chemicals. ST86PA is a dimethylpolysiloxane obtained from Toray Dow Corning Silicone. MHAC-P is methyl nadic anhydride which is an acid anhydride and was obtained from Hitachi Chemical. MH-700 is methylhexahydrophthalic anhydride, which was obtained from Shin Nippon Rika as Rikacid MH-700. EHC30 is 1,3,5-trisdimethylaminomethylphenol which acts as a curing accelerator, and was obtained from Asahi Denka Kogyo as Adeka Hardener EHC-30. U-CAT SA102 is 1,8-diaza-bicyclo (5,4,0) undecene 7 octylate which acts as a curing accelerator and was obtained from Sun Apro.

  Ingredients (1), (2), (3), (4) and (7) are mixed at a predetermined blending ratio and stirred for 1 hour at 100 ° C. under reduced pressure in a vertical mixer to dissolve completely uniformly. did. Then, it cooled to room temperature, the predetermined amount of component (5) and (6) was added, and it stirred under reduced pressure, and melt | dissolved uniformly. It was filtered through 60 mesh to give formulation R. Separately, components (8), (9), (10) and (11) were charged into the kettle at a predetermined blending ratio and stirred under reduced pressure for 1 hour to dissolve uniformly. Then, it filtered with 110 mesh and was set as the formulation H. Then, it mixed so that the mixing | blending R and the mixing | blending H might become a predetermined | prescribed mixing | blending, and obtained the uncured resin composition.

  The uncured resin composition was filled in an impregnation tank whose temperature was controlled at 20 ° C. in advance, and was controlled to be constant at 20 ° C. At this time, the viscosity of the uncured resin composition in the impregnation tank was 2000 mPa · s and 6500 mPa · s in Examples 6 and 7, respectively.

  And the glass fiber reinforced resin linear thing whose content rate of glass fiber is about 70 weight% was obtained with the apparatus shown in FIG. 2 similarly to Examples 1-3. Subsequently, the flexibility (minimum bending diameter) of the obtained glass fiber reinforced resin linear product was measured in the same manner as in Examples 1 to 3. The results are shown in Table 6.

  Moreover, only said uncured resin composition was hardened at 120-130 degreeC, and the elasticity modulus and elongation at break of the obtained resin were measured. The results are shown in Table 7.

  In Example 6, as shown in Table 7, the elastic modulus of the matrix resin is low. And as shown in Table 6, before the fracture | rupture of the obtained glass fiber resin composition, cross-sectional shape collapse | crumbles and flat buckling generate | occur | produces and the minimum bending diameter D becomes large.

Comparative Example As a comparative example, a glass fiber reinforced resin linear product was molded under the same conditions using a glass fiber having a breaking elongation of 5% or less and a thermosetting vinyl ester resin as a matrix resin.

The glass fiber used was E glass (breaking elongation: 4.8%, elastic modulus: 72.5 GPa) sold by Nitto Boseki Co., Ltd. E-glass is 52 to 56 wt% of SiO _2, 12 to 16 wt% of Al ₂ O _3, 15-25 wt% of CaO, Less than six percent by weight of MgO, 8 to 13 weight percent of B ₂ O ₃ as well, including 0-1 wt% Na ₂ O and K ₂ O.

  As the vinyl ester resin, a novolac vinyl ester resin (Polyhope H8100, Japan Composite Co., Ltd.) was used, and 0.5% of 6% cobalt naphthenate was mixed as a curing accelerator, and 1.0% of 55% MEKPO was mixed as a curing agent. . The physical properties of the vinyl ester resin cured by this compounding are tensile strength of 65 MPa, flexural modulus of 3.8 GPa, and elongation at break of 2.5%. After impregnating the resin with glass fiber guided through a guide plate and guide in an impregnation tank filled with these resins, excess resin was squeezed through a die, guided into a heating mold of about 3 m, and cured. Then, it wound up with the winding device.

  A novolac vinyl ester resin was filled in an impregnation tank whose temperature was controlled at 25 ° C. in advance. The resin viscosity in the impregnation tank when controlled at 25 ° C. was 300 mPa · s. As a result of molding the inner diameter of the thermoforming mold with three types of 0.3 mm (Comparative Example 1), 0.4 mm (Comparative Example 2), and 0.5 mm (Comparative Example 3), the glass fiber content is about 70% % Glass fiber reinforced resin composition was obtained.

  This glass fiber reinforced resin composition is cut to a length of approximately 100 mm, both ends of the sample are gripped by hand, and the central part of the sample is wound around a beautiful steel cylinder having various diameters. Alternatively, the diameter of the steel cylinder when the fracture started from the inner peripheral side was measured. The results are shown in Table 8.

It is sectional drawing of one Embodiment of the glass fiber reinforced resin linear material of this invention. It is explanatory drawing of one Embodiment of the manufacturing method of the glass fiber reinforced resin linear material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass fiber reinforced resin linear material 2 Glass fiber 3 Yarn 4 Matrix resin 6 Thermoplastic resin 10 Creel 11a, 11b Guide 12 Impregnation tank 13 Drawing nozzle 14 Mold 15 Caterpillar 16 Winding device

Claims (9)

A glass fiber reinforced resin linear material containing a glass fiber having a breaking elongation of 5% or more and a matrix resin,
The matrix resin, the viscosity of 15000 mPa · s or less liquid epoxy resin at 25 ° C., all SANYO cured by thermal cationic polymerization catalyst or an acid anhydride, elongation at break is not more 5.0% or more,
The diameter d of the glass fiber reinforced resin linear material is 0.6 mm or less, which is cut into a length of about 100 mm, both ends of the sample are held by hand, and the central portion of the sample has various diameters. The minimum bending diameter D and the diameter of the glass fiber reinforced resin filaments obtained by measuring the diameter of the steel cylinder when it is wound around a beautiful steel cylinder and the fracture starts from the outer or inner circumference of the sample. D / d which is a ratio of d is 20 or less . The glass fiber reinforced resin linear product according to claim 1, wherein the matrix resin is obtained by curing the liquid epoxy resin together with a bisphenol A type epoxy resin having an average molecular weight of 900 or more. The glass fiber reinforced resin linear product according to claim 1 or 2 , wherein the matrix resin is obtained by curing the liquid epoxy resin together with a flexibility imparting agent. The glass fiber reinforced resin linear material according to any one of claims 1 to 3 , wherein the matrix resin is obtained by curing a liquid epoxy resin having a viscosity of 3500 mPa · s or less at 25 ° C with the thermal cationic polymerization catalyst. . The glass fiber-reinforced resin linear product according to any one of claims 1 to 4 , wherein the acid anhydride is liquid at 25 ° C. The glass fiber reinforced resin linear product according to any one of claims 1 to 5 , wherein the liquid epoxy resin contains an epoxycyclohexane ring or a 2,3-epoxypropyloxy group. The glass fibers, 55 to 79.9 wt% of SiO _2, from 12.6 to 32 wt% Al ₂ O _3, glass according to any one of claims 1 to 6 including the 4-20 wt% of MgO Fiber reinforced resin linear material. A glass fiber reinforced resin linear material containing a glass fiber having a breaking elongation of 5% or more and a matrix resin ,
The matrix resin is obtained by curing a liquid epoxy resin having a viscosity of 15000 mPa · s or less at 25 ° C. with a thermal cationic polymerization catalyst or an acid anhydride, and having an elongation at break of 5.0% or more,
The diameter d of the glass fiber reinforced resin linear material is 0.6 mm or less, which is cut into a length of about 100 mm, both ends of the sample are held by hand, and the central portion of the sample has various diameters. The minimum bending diameter D and the diameter of the glass fiber reinforced resin filaments obtained by measuring the diameter of the steel cylinder when it is wound around a beautiful steel cylinder and the fracture starts from the outer or inner circumference of the sample. A method for producing a glass fiber reinforced resin linear product , wherein D / d as a ratio of d is 20 or less ,
A glass fiber comprising a step of curing a liquid epoxy resin having a viscosity of 15000 mPa · s or less at 25 ° C. with a thermal cationic polymerization catalyst or acid anhydride at an atmospheric temperature of 80 to 200 ° C. within 10 minutes. A method for producing a reinforced resin linear material. The glass fiber reinforced resin linear product according to claim 8 , wherein the viscosity of the uncured resin composition containing the liquid epoxy resin and the thermal cationic polymerization catalyst or acid anhydride is 10,000 mPa · s or less at 25 ° C. Manufacturing method.