JP6511226B2 - Fiber-reinforced resin material, resin molded article and method for producing fiber-reinforced resin material - Google Patents

Description

  The present invention relates to a fiber reinforced resin material. The present invention also relates to a resin molded product obtained by heat-processing a fiber reinforced resin material. Further, the present invention relates to a method for producing a fiber reinforced resin material.

Thermoplastic resins are excellent in easiness of molding and processing, appearance, economy, mechanical strength, and other physical and chemical properties. Therefore, electric / electronic / OA equipment, precision machinery, automobile parts, building materials, sundries It is used in a wide range of fields such as For example, Patent Document 1 discloses a flame-retardant polyamide resin composition comprising a polyamide resin, a phosphorus-based flame retardant, and a glass fiber having a non-circular cross section.
Here, as the field of use of thermoplastic resins is expanded, improvement in flame retardancy and mechanical strength of resin molded articles is strongly demanded.

JP, 2008-163317, A

Here, in order to improve the mechanical strength, it is conceivable to blend many fibers, and in order to improve the flame retardancy, it is considered to blend many flame retardants. However, in the thermoplastic resin composition, when the compounding amount of the fiber is increased and the compounding amount of the flame retardant is also increased, the amount of the thermoplastic resin relatively decreases. There is also a problem that it becomes difficult to mix other additives. In particular, when thinning a resin molded product, the mechanical strength of the resin molded product tends to be a problem. However, when the resin molded product is thinned, the thin portion is easily burned, and it becomes more difficult to maintain flame retardancy.
An object of the present invention is to solve such problems, and it is an object of the present invention to provide a resin molded article having high mechanical strength and flame retardance even when thinned. Furthermore, it aims at providing a fiber reinforced resin material for providing such a resin-molded article. Another object of the present invention is to provide a method for producing a fiber reinforced resin material.

Based on the above problems, as a result of intensive investigations conducted by the inventor of the present application, the above problems are solved by using a fiber reinforced resin material in which a continuous fiber is impregnated with a thermoplastic resin composition containing a thermoplastic resin and a flame retardant. It has been found that it is possible to complete the present invention.
Specifically, the above problems are solved by the following means <1>, preferably <2> to <12>.
The fiber reinforced resin material which impregnates a <1> thermoplastic resin and the thermoplastic resin composition containing a flame retardant to a continuous fiber.
The fiber reinforced resin material as described in <1> which the <2> continuous fiber is arranging with regularity.
The fiber reinforced resin material as described in <1> or <2> whose <3> thermoplastic resin is a polyamide resin.
The fiber reinforced resin material in any one of <1>-<3> whose <4> continuous fiber is glass fiber.
The fiber reinforced resin material in any one of <1>-<4> in which a <5> flame retardant contains at least 1 sort (s) of a halogen type flame retardant and a phosphorus base flame retardant.
The fiber reinforced resin material in any one of <1>-<5> whose <6> above-mentioned fiber reinforced resin material is a tape, a film, or a sheet form.
The fiber reinforced resin material in any one of <1>-<5> whose <7> fiber reinforced resin material is a 0.05-2 mm-thick tape, a film, or a sheet form.
The fiber-reinforced resin material has a fiber content of 30 to 70% by weight, and 80% by weight or more of the constituent components is composed of a thermoplastic resin and a fiber, and a flame retardant as a thermoplastic resin 100 The fiber reinforced resin material in any one of <1>-<7> which contains 1-50 weight parts with respect to a weight part.
The resin molded product which heat-processes the fiber reinforced resin material in any one of <9><1>-<8>.
The resin molded product as described in <9> which is a <10> portable electronic device component.
The manufacturing method of the fiber reinforced resin material including making a continuous fiber impregnate the thermoplastic resin composition containing a <11> thermoplastic resin and a flame retardant.

  According to the present invention, it has become possible to provide a resin molded article having high mechanical strength and flame retardance even when thinned. Furthermore, it has become possible to provide a method for producing a fiber-reinforced resin material and a fiber-reinforced resin material for providing such a resin molded product.

  Hereinafter, the contents of the present invention will be described in detail. In the specification of the present application, “to” is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value.

<Fiber-reinforced resin material>
The fiber reinforced resin material of the present invention is a fiber reinforced resin material obtained by impregnating a thermoplastic resin and a thermoplastic resin composition containing a flame retardant into continuous fibers. As described above, by blending the thermoplastic resin with the flame retardant and impregnating the continuous fiber, high mechanical strength can be maintained in the compounding process without breakage of the fiber. Conventionally, a large amount of a flame retardant is required to compound a flame retardant with a thermoplastic resin to impart flame retardancy, and as a result, the mechanical strength of a resin molded product is reduced. In the present invention, such a problem can be avoided by using a continuous fiber as a reinforcing material. As a result, it is possible to provide a thin-walled resin molded product having excellent mechanical strength.
The details of these will be described below.

<< Thermoplastic resin composition >>
The thermoplastic resin composition used in the present invention contains a thermoplastic resin and a flame retardant. Details will be described below.

<<< Thermoplastic resin >>>
The thermoplastic resin used in the present invention is preferably selected from polyamide resins, polyester resins, polyolefin resins, polypropylene resins, polyethylene resins, acrylic resins, polyacetal resins and polycarbonate resins. Among these, polyester resins and polyamide resins are preferable. These may be used alone or two or more may be used.

As polyester resin, the description of Paragraph No. 0013-0016 of Unexamined-Japanese-Patent No. 2010-174223 can be considered into consideration.
As polyacetal resin, the description of Paragraph No. 0011 of Unexamined-Japanese-Patent No. 2003-003041 and Paragraph No. 0018-0020 of Unexamined-Japanese-Patent No. 2003-220667 can be referred to.

As a polyamide resin, the description of Paragraph No. 0011-0013 of Unexamined-Japanese-Patent No. 2011-132550 can be considered into consideration. Preferably, the polyamide resin comprises a diamine structural unit (structural unit derived from diamine) and a dicarboxylic acid structural unit (structural unit derived from dicarboxylic acid), and at least 50 mol% of the diamine structural unit is xylylenediamine. It is a polyamide resin derived from. Preferably, 70 mol% or more, more preferably 80 mol% or more of the diamine structural unit is derived from metaxylylenediamine and / or paraxylylenediamine, and preferably, a dicarboxylic acid structural unit (constituent unit derived from dicarboxylic acid) Is 50 mol% or more, more preferably 70 mol% or more, particularly 80 mol% or more, preferably having 4 to 20 carbon atoms, derived from α, ω-linear aliphatic dicarboxylic acid based on xylylene diamine It is a polyamide resin. As 4-20 α, ω-linear aliphatic dibasic acids, adipic acid, sebacic acid, suberic acid, dodecanedioic acid, eicodynic acid and the like can be suitably used. The dicarboxylic acid is preferably adipic acid and sebacic acid, more preferably sebacic acid. The polyamide resin having such characteristics is strong, has low water absorption, and has high dimensional stability.
The polyamide resin is preferably a polyamide resin having a melting point of 260 ° C. or less. With such a configuration, the flame retardant is difficult to be decomposed by heat, and even with a small amount of flame retardant, a high flame retarding effect can be exhibited.
The polyamide resin preferably contains 0.5 to 5% by weight of a component having a molecular weight of 1,000 or less. By containing such a low molecular weight component in such a range, the strength and low warping property of the obtained molded article become better. By setting the content to 5% by weight or less, bleeding of low molecular weight components becomes difficult, and the surface appearance tends to be improved.
The preferred content of the component having a molecular weight of 1,000 or less is 0.6 to 4.5% by weight, more preferably 0.7 to 4% by weight, still more preferably 0.8 to 3.5% %, Particularly preferably 0.9 to 3% by weight, most preferably 1 to 2.5% by weight.

  The content of the low molecular weight component having a molecular weight of 1,000 or less can be adjusted by adjusting the temperature and pressure at the time of polymerization of the polyamide resin, and the melt polymerization conditions such as the dropping rate of the diamine. In particular, the pressure in the reactor can be reduced at a late stage of the melt polymerization to remove low molecular weight components, and the ratio can be adjusted to an arbitrary rate. The polyamide resin produced by melt polymerization may be subjected to hot water extraction to remove low molecular weight components, or after melt polymerization, solid phase polymerization may be carried out under reduced pressure to remove low molecular weight components. In solid phase polymerization, the low molecular weight component can be controlled to an arbitrary content by adjusting the temperature and the degree of vacuum. It can also be controlled by adding a low molecular weight component having a molecular weight of 1,000 or less to the polyamide resin later.

  In addition, the measurement of the component amount of molecular weight 1,000 or less is based on the standard polymethyl methacrylate (PMMA) conversion value by gel permeation chromatography (GPC) measurement using Tosoh Corporation (TOSOH CORPORATION) "HLC-8320GPC". It can be asked. In addition, two “TSKgel SuperHM-H” are used as measurement columns, hexafluoroisopropanol (HFIP) with a sodium trifluoroacetate concentration of 10 mmol / l is used as a solvent, a resin concentration of 0.02% by weight, and a column temperature It can measure with a refractive index detector (RI) at 40 ° C., at a flow rate of 0.3 ml / min. The calibration curve is prepared by dissolving 6 levels of PMMA in HFIP.

  The content of the thermoplastic resin in the fiber reinforced resin material is preferably 30 to 98% by weight, more preferably 51 to 90% by weight, and still more preferably 60 to 85% by weight. Only one type of thermoplastic resin may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount becomes the said range. By setting it as such a range, the effect of the present invention is exhibited more effectively.

<< flame retardant >>
The fiber reinforced resin material contains a flame retardant. As a flame retardant, although an organic type flame retardant or an inorganic type flame retardant may be sufficient, it is preferable to use an organic type flame retardant. By using the organic flame retardant, the impregnation of the thermoplastic resin composition into continuous fibers can be made better.
As the organic flame retardant, for example, a halogen flame retardant, a phosphorus flame retardant, a silicone flame retardant or the like can be used, and it is preferable to use at least one of a halogen flame retardant or a phosphorus flame retardant.
Examples of inorganic flame retardants include zinc sulfide, zinc stannate, metal salts of borate, antimony compounds, oxides (metal oxides such as iron oxide and magnesium oxide, boron oxides), metal hydroxides (magnesium hydroxide, water Aluminum oxide, calcium hydroxide) are illustrated.

<<< Halogen-based flame retardant >>
As a halogen-based flame retardant, brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, glycidyl brominated bisphenol A, pentabromobenzyl polyacrylate, Brominated imide and the like can be mentioned. Among these, brominated polycarbonates, brominated polystyrene resins, glycidyl brominated bisphenol A or pentabromobenzyl polyacrylate are preferable, and brominated polystyrene resins are more preferable, because they tend to suppress reduction in impact resistance.

<<< phosphorus flame retardant >>>
The phosphorus-based flame retardant is a flame retardant containing a phosphorus atom, and examples thereof include reaction products of melamine and phosphoric acid, (di) phosphinates, phosphazene compounds and the like, and phosphazene compounds are preferable.
The reaction product of melamine and phosphoric acid means that which is obtained from the reaction product of substantially equimolar reaction product of melamine or a condensation product of melamine and phosphoric acid, pyrophosphoric acid or polyphosphoric acid; There are no particular restrictions on In general, mention may be made of melamine polyphosphate (chemical formula “(C ₃ H ₆ N ₆ · HPO ₃ ) _n ” (where n represents the degree of condensation)) obtained by heat condensation of melamine phosphate under a nitrogen atmosphere. it can.
Here, specific examples of the phosphoric acid constituting the melamine phosphate include orthophosphoric acid, phosphorous acid, hypophosphorous acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid and the like, and in particular, orthophosphoric acid. Melamine polyphosphate which condensed the adduct with the acid and the melamine using pyrophosphoric acid is highly effective as a flame retardant, and is preferable. Particularly, from the viewpoint of heat resistance, the condensation degree n of such melamine polyphosphate is preferably 5 or more.
Also, melamine polyphosphate may be an equimolar addition salt of polyphosphoric acid and melamine, and is not limited to those in which all of the above polyphosphoric acid and melamine form an addition salt, and even if they are a mixture thereof Good. That is, as polyphosphoric acid which forms the addition salt with melamine, you may use what is called linear phosphoric acid called condensed phosphoric acid, and cyclic polymetaphosphoric acid. The condensation degree n of these polyphosphoric acids is not particularly limited and is usually 3 to 50, but the condensation degree n of the polyphosphoric acid used here is preferably 5 or more from the viewpoint of the heat resistance of the resulting polyphosphate melamine addition salt. The melamine polyphosphate addition salt is prepared, for example, by mixing a mixture of melamine and polyphosphoric acid as a water slurry and mixing well to form the reaction product of the both into fine particles, and then filtering, washing and drying the slurry If necessary, it is a powder obtained by calcining and crushing the solid obtained.
Also, melamine polyphosphate may be an addition salt of phosphoric acid and a melamine condensation product, and is not limited to those in which all the phosphoric acid and melamine condensation products form an addition salt, and a mixture thereof It may be Examples of melamine condensation products that form addition salts with phosphoric acid include melem, melam, melon and the like.

  The (di) phosphinate is a phosphinate represented by the following formula (I) and / or a diphosphinate represented by the following formula (II), for example, phosphinic acid and metal carbonate, metal water Those prepared in an aqueous medium using oxides or metal oxides are mentioned. The (di) phosphinic acid salt is essentially a monomeric compound, but depending on the reaction conditions, it may be a polymeric phosphinic acid salt having a degree of condensation of 1 to 3 depending on the environment.

（一般式（Ｉ）および（ＩＩ）において、Ｒ¹およびＲ²は、それぞれ、線状もしくは分枝状の炭素数１〜６（「Ｃ₁〜Ｃ₆」と記載する。以下同様）のアルキル基および／またはＣ₆〜Ｃ₁₀のアリール基、Ｒ³は線状もしくは分枝状のＣ₁〜Ｃ₁₀のアルキレン基、Ｃ₆〜Ｃ₁₀のアリーレン基、Ｃ₇〜Ｃ₁₀のアルキルアリーレン基またはＣ₇〜Ｃ₁₀のアリールアルキレン基、ＭはＣａ、Ｍｇ、Ａｌおよび／またはＺｎ、ｍはＭの価数を表し、２ｎ＝ｍｘであり、ｎは１または３、ｘは１または２である。）
ここで、ｍまたはｎが２以上の場合、それぞれの、Ｒ¹〜Ｒ³は同一であっても良いし異なっていても良い。

(In the general formulas (I) and (II), R ¹ and R ² each represent linear or branched alkyl having 1 to 6 carbon atoms (described as “C _{1 to} C ₆ ”, hereinafter the same) And / or a C _{6 to} C ₁₀ aryl group, R ³ is a linear or branched C _{1 to} C ₁₀ alkylene group, a C _{6 to} C ₁₀ arylene group, a C _{7 to} C ₁₀ alkylarylene group Or a C ₇ -C ₁₀ aryl alkylene group, M is Ca, Mg, Al and / or Zn, m is a valence of M, 2n = mx, n is 1 or 3, x is 1 or 2 is there.)
Here, when m or n is 2 or more, each of R ^{1 to} R ³ may be the same or different.

  As phosphinic acid, for example, dimethyl phosphinic acid, ethyl methyl phosphinic acid, diethyl phosphinic acid, methyl-n-propyl phosphinic acid, methanedi (methyl phosphinic acid), benzene-1,4-di (methyl phosphinic acid), methyl phenyl Phosphinic acid and diphenylphosphinic acid can be mentioned. The metal component (M) may, for example, be calcium ion, magnesium ion, aluminum ion and / or zinc ion.

Examples of phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethyl methyl phosphinate, aluminum ethyl methyl phosphinate, zinc ethyl methyl phosphinate, Calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, methyl-n -Propyl zinc phosphinate, calcium methyl phenyl phosphinate, magnesium methyl phenyl phosphinate , Aluminum methylphenyl phosphinate, methyl phenyl phosphinate, zinc, calcium diphenyl phosphinate, magnesium diphenyl phosphinate, aluminum diphenyl phosphinate, and zinc diphenyl phosphinate and the like.
As the diphosphinate, calcium methanedi (methylphosphinate), magnesium methanedi (methylphosphinate), aluminum methanedi (methylphosphinate), zinc methanedi (methylphosphinate), benzene-1,4-di (methylphosphinic acid) Examples thereof include calcium, magnesium in benzene-1,4-di (methylphosphinic acid), aluminum in benzene-1,4-di (methylphosphinate), and zinc in benzene-1,4-di (methylphosphinate).
Among these (di) phosphinates, aluminum ethylmethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate are particularly preferable in terms of flame retardancy and electrical properties.

  The phosphazene compound is an organic compound having -P = N- bond in the molecule, preferably, a cyclic phosphazene compound represented by the following general formula (1), a chain phosphazene represented by the following general formula (2) At least one selected from the group consisting of a compound and a crosslinked phosphazene compound in which at least one phosphazene compound selected from the group consisting of the following general formula (1) and the following general formula (2) is crosslinked by a crosslinking group. Is a compound of The phosphazene compound has a high flame retarding effect, and particularly when used in combination with a metal salt of borate described below, it can exhibit excellent flame retardance even with a small content, so the mechanical strength that may occur due to the composition of the flame retardant And it is easy to suppress the generation of gas and the decrease of

式（１）中、ａは３〜２５の整数であり、Ｒ¹及びＲ²は、同一又は異なっていてもよく、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリロキシ基、アミノ基、ヒドロキシ基、アリール基又はアルキルアリール基を示す。 General formula (1)

In formula (1), a is an integer of 3 to 25, R ¹ and R ² may be the same or different, and an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryloxy group, an amino group, Hydroxy, aryl or alkylaryl is shown.

式（２）中、ｂは３〜１００００の整数であり、Ｒ³及びＲ⁴は、同一又は異なっていてもよく、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリロキシ基、アミノ基、ヒドロキシ基、アリール基又はアルキルアリール基を示す。
Ｒ⁵は、−Ｎ＝Ｐ（ＯＲ³）₃基、−Ｎ＝Ｐ（ＯＲ⁴）₃基、−Ｎ＝Ｐ（Ｏ）ＯＲ³基、−Ｎ＝Ｐ（Ｏ）ＯＲ⁴基から選ばれる少なくとも１種を示し、Ｒ⁶は、−Ｐ（ＯＲ³）₄基、−Ｐ（ＯＲ⁴）₄基、−Ｐ（Ｏ）（ＯＲ³）₂基、−Ｐ（Ｏ）（ＯＲ⁴）₂基から選ばれる少なくとも１種を示す。 General formula (2)

In formula (2), b is an integer of ^{3 to} 10000, R ³ and R ⁴ may be the same or different, and an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryloxy group, an amino group, Hydroxy, aryl or alkylaryl is shown.
R ⁵ is selected -N = P (OR ^{₃₎ 3 group, -N = P (OR 4)} 3 group, -N = P (O) OR 3 group, a -N = P (O) OR ⁴ group R ⁶ represents at least one group, and R ⁶ represents a group of -P (OR ³ ) ₄ , -P (OR ⁴ ) ₄ , -P (O) (OR ³ ) ₂ , -P (O) (OR ⁴ ) ₂ It represents at least one selected from groups.

  As the alkyl group in the above formulas (1) and (2), for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group And dodecyl, etc., but usually, alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl and hexyl are preferable, and methyl is preferred. Particularly preferred is an alkyl group having 1 to 4 carbon atoms such as ethyl, propyl and the like.

  As a cycloalkyl group, although a C5-C14 cycloalkyl group, such as a cyclopentyl group and a cyclohexyl group, is mentioned, for example, a C5-C8 cycloalkyl group is preferable.

  As an alkenyl group, For example, C2-C8 alkenyl groups, such as a vinyl group and an allyl group, are mentioned, As a cycloalkenyl group, C5-C12 cycloalkenyl groups, such as a cyclopentyl group and a cyclohexyl group, for example Can be mentioned.

  As an alkynyl group, C2-C8 alkynyl groups, such as an ethynyl group and propynyl group, aryls, such as an ethynyl benzene group, etc. are mentioned, for example.

  Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, such as phenyl group, methylphenyl (ie, tolyl) group, dimethylphenyl (ie. Xylyl) group, trimethylphenyl group, and naphthyl group. Especially, a C6-C10 aryl group is preferable and a phenyl group is especially preferable.

  Examples of the alkylaryl group include aralkyl groups having 6 to 20 carbon atoms such as benzyl, phenethyl and phenylpropyl groups. Among them, aralkyl groups having 7 to 10 carbons are preferable, and benzyl is particularly preferable. .

Among them, those in which R ¹ and R ² in the general formula (1) and R ³ and R ⁴ in the general formula (2) are an aryl group or an arylalkyl group are preferable. By using such aromatic phosphazene, the thermal stability of the resin composition can be effectively enhanced. From such a point of view, R ¹ , R ² , R ³ and R ⁴ are more preferably an aryl group, particularly preferably a phenyl group.

  Examples of the cyclic and / or linear phosphazene compounds represented by the general formulas (1) and (2) include phenoxyphosphazene, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene etc. ) Tolyloxyphosphazene, o, m-xyloxyphosphazene, o, p-xylyloxy phosphazene, (poly) xylyloxy phosphazene such as m, p-xylyloxy phosphazene, o, m, p-trimethylphenyloxy (Poly) phenoxy tolyloxy phosphazenes such as phosphazenes, phenoxy o-tolyloxy phosphazenes, phenoxy m-tolyloxy phosphazenes, phenoxy p-tolyloxy phosphazenes, phenoxy o, m-xylyloxy phosphazenes, phenoxy o, p-xy Roxyphosphazene, phenoxy m, p-xylyloxy phosphazene, etc. (poly) phenoxy tolyloxy xylyloxy phosphazene, phenoxy o, m, p-trimethylphenyl oxyphosphazene etc. can be exemplified, preferably cyclic and / or chain phenoxy It is phosphazene etc.

As a cyclic phosphazene compound represented by General formula (1), cyclic phenoxy phosphazene whose R ¹ and R ² are a phenyl group is particularly preferable. As such cyclic phenoxy phosphazene compounds, for example, hexachlorocyclotriphosphazene, octachloro, and cyclochlorophosphazenes can be obtained from a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decaphenoxycyclopentaphosphazene, etc. obtained by taking out cyclic chlorphosphazenes such as cyclotetraphosphazenes, decachlorocyclopentaphosphazenes and substituting them with a phenoxy group can be mentioned. . The cyclic phenoxy phosphazene compound is preferably a compound in which a in the general formula (1) is an integer of 3 to 8, and may be a mixture of different compounds of a.

  The average of the above a is preferably 3 to 5 and more preferably 3 to 4. Among them, a mixture of compounds in which a = 3 is 50 wt% or more, a = 4 is 10-40 wt%, and a = 5 or more in total is 30 wt% or less is preferable.

As the linear phosphazene compound represented by the general formula (2), a linear phenoxy phosphazene in which R ³ and R ⁴ are a phenyl group is particularly preferable. Such a chain-like phenoxy phosphazene compound is obtained, for example, by ring-loop polymerization of hexachlorocyclotriphosphazene obtained by the above method at a temperature of 220 to 250 ° C., and linear dichlorophosphazene obtained having a degree of polymerization of 3 to 10,000. The compound obtained by substituting by a phenoxy group is mentioned. B in the general formula (2) of the linear phenoxy phosphazene compound is preferably 3 to 1000, more preferably 3 to 100, and still more preferably 3 to 25.

  As the crosslinked phosphazene compound, for example, a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (that is, bisphenol S residue), a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group Compounds having a crosslinked structure of 4,4'-diphenylene group such as compounds having a crosslinked structure of 4,4'-oxydiphenylene group, compounds having a crosslinked structure of 4,4'-thiodiphenylene group, etc. Etc.

Moreover, as a crosslinked phosphazene compound, a crosslinked phenoxy phosphazene compound in which a cyclic phenoxy phosphazene compound in which R ¹ and R ² in the general formula (1) are a phenyl group is crosslinked by the above crosslinking group, or the above general formula (2) A cross-linked phenoxy phosphazene compound in which a chained phenoxy phosphazene compound in which R ³ and R ⁴ are a phenyl group is cross-linked by the above-mentioned cross-linking group is preferable from the viewpoint of flame retardancy. More preferred is a crosslinked phenoxy phosphazene compound.
In addition, the content of phenylene group in the crosslinked phenoxy phosphazene compound is the total phenyl group in the cyclic phosphazene compound represented by the general formula (1) and / or the chained phenoxy phosphazene compound represented by the general formula (2) It is usually 50 to 99.9% by weight, preferably 70 to 90% by weight, based on the number of phenylene groups. The crosslinked phenoxy phosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  The phosphazene compound includes a cyclic phenoxy phosphazene compound represented by the above general formula (1) and a crosslinked phenoxy phosphazene compound formed by crosslinking the cyclic phenoxy phosphazene compound represented by the above general formula (1) by a crosslinking group. At least one selected from the above is preferable in terms of the flame retardancy and mechanical properties of the resin composition.

  Phosphorus flame retardants, in particular phosphazene, may be formulated as a masterbatch. In addition, the flame retardants described in International Publication WO2009 / 141799 pamphlet can also be preferably used, and the contents thereof are incorporated in the present specification.

<< Inorganic flame retardants >>
Examples of inorganic flame retardants include zinc sulfide, zinc stannate, metal salts of borate, antimony compounds, oxides (metal oxides such as iron oxide and magnesium oxide, boron oxides), metal hydroxides (magnesium hydroxide, water Aluminum oxide and calcium hydroxide are exemplified, and metal salts of borate, antimony compounds and metal hydroxides are preferable, and zinc borate, antimony compounds and magnesium hydroxide are more preferable.

As the metal borate, those which are stable under the commonly used processing conditions and have no volatile component are preferable. Examples of the borate metal salt include alkali metal salts (sodium tetraborate, potassium metaborate, etc.) or alkaline earth metal salts (calcium borate, magnesium orthoborate, barium orthoborate, zinc borate etc.), etc. Be Among the above, a hydrated zinc borate salt represented by _{2ZnO · 3B 2 O 3 · xH} 2 O (x = 3.3~3.7), _{preferably, 2ZnO · 3B 2 O 3 ·} 3 .5 H ₂ O, more preferably stable to temperatures of 260 ° C. or higher.
Antimony compounds include antimony trioxide (Sb ₂ O ₃ ), antimony pentoxide (Sb ₂ O ₅ ), sodium antimonate and the like. In particular, when using a halogen-based flame retardant, it is preferable to use antimony trioxide in combination.

The content of the flame retardant is preferably 1 to 60 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.
In particular, the content of the organic flame retardant is more preferably 10 to 55 parts by weight, further preferably 15 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.

The content of the inorganic flame retardant is more preferably 1 to 30 parts by weight, further preferably 1 to 25 parts by weight, and particularly preferably 3 to 15 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.
The flame retardant may be used alone or in combination of two or more.

<< Other ingredients >>
The thermoplastic resin composition used by this invention may contain the other component in the range which does not deviate from the meaning of this invention. Other components include a mold release agent, a light stabilizer, a heat stabilizer, an elastomer, a pigment, an alkali, an ultraviolet light absorber, a fluorescent whitening agent, an antidripping agent, an antistatic agent, an antifogging agent, a lubricant and an antiblocking agent. And flow improvers, plasticizers, dispersants, fungicides and the like. Two or more of these may be used in combination.
These descriptions are described in paragraphs [0027], [0028], [0038]-0054, JP-A-2007-314766, JP-A-2008-127485 and JP-A-2009-51989, JP-A-2012-5128, pamphlet of International Publication WO 2012/128219 pamphlet. The contents of the disclosure of JP-72338 can be referred to, and the contents thereof are incorporated in the present specification.
The thermoplastic resin composition used in the present invention may contain fibers without departing from the scope of the present invention. Fibers include glass fibers and organic fibers. However, in the present invention, an embodiment in which the thermoplastic resin composition used in the present invention does not substantially contain glass fibers is preferable. The term "substantially free" means, for example, 3% by weight or less of the thermoplastic resin composition, and preferably 1% by weight or less.

<< Method of adjusting thermoplastic resin composition >>
The method for producing the thermoplastic resin composition used in the present invention is not particularly limited, and a wide variety of known methods for producing a thermoplastic resin composition can be adopted. Specifically, each component is mixed in advance using various mixers such as tumblers and Henschel mixers, and then melt-kneaded using a Banbury mixer, rolls, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. By doing this, a thermoplastic resin composition can be produced.

For example, without mixing each component beforehand, or mixing only a part of components beforehand, supplying to an extruder using a feeder and melt-kneading the thermoplastic resin composition used in the present invention It can also be manufactured.
Furthermore, for example, a thermoplastic resin composition obtained by mixing some components in advance and supplying them to an extruder for melt-kneading is used as a masterbatch, and this masterbatch is again mixed with the remaining components and melt-kneaded Thus, the thermoplastic resin composition used in the present invention can also be produced.

<< Continuous fiber >>
The continuous fibers used in the present invention include glass fibers, carbon fibers, plant fibers (including kenaf, bamboo fibers, etc.), alumina fibers, boron fibers, ceramic fibers, metal fibers (steel fibers, etc.), aramid fibers, Polyoxymethylene fibers, aromatic polyamide fibers, polyparaphenylene benzobisoxazole fibers, ultrahigh molecular weight polyethylene fibers and the like can be mentioned. Among them, carbon fibers and / or glass fibers are preferable, and glass fibers are more preferable. The cross section of the fibers may be circular or flat. As a manufacturing method of a continuous fiber, for example, there is a method in which a strand in which several thousands of fibers having an average fiber diameter of 5 to 24 μm are collected is aligned to a predetermined number (several to several tens).
It is preferable that the form of the continuous fiber is regularly arranged. For example, continuous fibers are preferably arranged in one direction or in alternating crossings.

The continuous fiber has a functional group having reactivity with the thermoplastic resin on the surface of the continuous fiber in order to improve the wettability with the thermoplastic resin contained in the thermoplastic resin composition used in the present invention and the interfacial adhesion. Is preferred.
As an example of the continuous fiber which has a functional group which has reactivity with a thermoplastic resin, what was surface-treated with a surface treating agent or a focusing agent is mentioned preferably.

Examples of surface treatment agents include those comprising functional compounds such as epoxy compounds, acrylic compounds, isocyanate compounds, silane compounds and titanate compounds, and silane coupling agents and titanate coupling agents. Etc., and silane coupling agents are preferred.
As a silane coupling agent, trialkoxy or triaryloxysilane compounds such as aminopropyltriethoxysilane, phenylaminopropyltrimethoxysilane, glycidylpropyltriethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, ureido And silanes, sulfide silanes, vinyl silanes, imidazole silanes and the like.

  The focusing agent is an epoxy resin such as a bisphenol A epoxy resin, or an epoxy acrylate resin having an acrylic group or a methacryl group in one molecule, and is a bisphenol A vinyl ester resin, a novolac vinyl ester resin Preferred are vinyl ester resins such as brominated vinyl ester resins. Further, it may be a urethane-modified resin of epoxy resin or vinyl ester resin.

2-80 weight% of a fiber reinforced resin material is preferable, as for the quantity of the continuous fiber in a fiber reinforced resin material, 30-70 weight% is more preferable, and 50-70 weight% is more preferable.
Further, in the fiber reinforced resin material, it is preferable that 80% by weight or more of its constituent components consist of a thermoplastic resin and a continuous fiber.
Moreover, in the fiber reinforced resin material of this invention, 20: 80-80: 20 are preferable and, as for the weight ratio of a thermoplastic resin composition and a continuous fiber, 30: 70-70: 30 are more preferable. With such a range, the effects of the present invention can be achieved more effectively.

<Method of manufacturing fiber reinforced resin material>
The method for producing a fiber-reinforced resin material of the present invention includes impregnating a thermoplastic resin and a thermoplastic resin composition containing a flame retardant into continuous fibers. With such a configuration, it is not necessary to compound the thermoplastic resin composition and the continuous fiber, and breakage of the continuous fiber can be effectively suppressed at the time of compounding. As a result, it is possible to provide a resin molded article having excellent mechanical strength.

  The form of continuous fibers is not particularly limited when the thermoplastic resin composition used in the present invention is impregnated, but continuous fibers are regularly arranged, for example, unidirectional or alternating crossings It is preferred that they be arranged as such. Moreover, the prepreg which laminated | stacked these and was impregnated with the binder etc. is used. More preferably, the continuous fibers are aligned such that the winding direction when winding the sheet is the longitudinal direction of the continuous fibers.

The shape of the thermoplastic resin composition when impregnating the continuous resin with the thermoplastic resin composition used in the present invention may be various shapes such as film, fiber, powder, and melt, and may be melt Is preferred.
As one example of a preferred embodiment of the present invention, it is preferable to supply a molten thermoplastic resin composition to a continuous fiber and then to cool it. The melting temperature in this case is appropriately determined in consideration of the melting point or the like of the thermoplastic resin in the thermoplastic resin composition. Specifically, although it varies depending on the type and molecular weight of the thermoplastic resin composition used in the present invention, the temperature of the glass transition point + 5 ° C. or more of the thermoplastic resin composition used in the present invention generally A temperature range is preferred. Moreover, in the case of the thermoplastic resin composition used by this invention which has melting | fusing point, melting | fusing point +5 degreeC or more is preferable, More preferably, it is melting | fusing point +10 degreeC or more. As for the upper limit, the thermal decomposition temperature of the thermoplastic resin composition is preferably in a temperature range of -5 ° C. In addition, when the thermoplastic resin composition used by this invention has 2 or more melting | fusing point, melting | fusing point here is the temperature of the peak top of the endothermic peak by the side of high temperature.
In addition, pressurization may also be performed during the impregnation. The pressure for pressing is preferably 5 MPa or more, more preferably 5 MPa or more, and particularly preferably 7 to 100 MPa.
By heating or pressurizing in such a temperature range, the continuous fiber of the thermoplastic resin composition used in the present invention is better impregnated, and a fiber reinforced resin material and a resin molded product obtained by molding the same. The physical properties of these tend to improve.

<Shape of fiber reinforced resin material>
The shape of the fiber-reinforced resin material used in the present invention is not particularly limited, and may be a shape of a tape, a film, a sheet or the like. These fiber reinforced composite materials are wound around a core or the like and supplied to the market as wound articles. When being wound, it is preferable to be wound in the fiber direction (longitudinal direction) of the continuous fiber. As a preferred embodiment of the fiber-reinforced resin material of the present invention, a tape, a film or a sheet obtained by impregnating a thermoplastic resin composition with continuous fibers regularly arranged in one direction or alternately and crosswise can be mentioned. 0.05-2 mm is preferable and, as for the thickness of a tape etc., 0.1-1 mm is more preferable.

<Resin molded products>
Although the fiber reinforced material of the present invention may be used as it is, it is usually heat-processed to be used as a resin molded article. When it is used as a resin molded product, it is preferable to heat process by laminating a plurality of fiber reinforced resin materials, or in combination with other resin materials and the like. When laminating | stacking two or more fiber reinforced resin material, it is preferable to laminate | stack so that the fiber direction (longitudinal direction) of the continuous fiber of fiber reinforced resin material may be orthogonal. Such a configuration tends to further improve the mechanical strength of the resulting resin molded article. The fiber-reinforced resin material of the present invention is preferably cut into a desired shape and size, and it is also preferable to heat-process a plurality of these in layers. At the time of heat processing, it is also possible to put a fiber reinforced resin material in a mold and to mold it to obtain a resin molded product.
The heating temperature is preferably in the temperature range of the glass transition temperature + 5 ° C. or higher of the thermoplastic resin composition used in the present invention to the thermal decomposition temperature of −5 ° C. Moreover, when using the thermoplastic resin composition which has melting | fusing point, melting | fusing point +5 degreeC or more is preferable, More preferably, it is melting | fusing point +10 degreeC or more. As for the upper limit, the thermal decomposition temperature of the thermoplastic resin composition is preferably in a temperature range of -5 ° C.
Moreover, 5 MPa or more is preferable, 8 MPa or more is more preferable, and, as for the press pressure in the case of pressurization, 10-100 MPa is especially preferable. The press is preferably 80 to 120 t.

  The resin molded article of the present invention is intended to include not only final products but also composite materials and various parts. The resin molded article in the present invention is preferably used as an electronic component including a component of a portable electronic device, a vehicle and a medical device, and other electric circuits, and a composite material for forming them. In particular, the resin molded article of the present invention has both high impact resistance and rigidity, and excellent heat resistance, and can have small anisotropy and small warpage, so that it can be a smartphone, a tablet, a thin notebook computer, etc. It is extremely effective as the internal structure and housing of In particular, the resin molded product is suitable for flat plate-shaped parts whose average thickness excluding ribs is 1.2 mm or less (the lower limit is not particularly defined, for example, 0.1 mm or more). The resin molded article of the present invention is high in value because it can maintain high flame retardancy even when it is thinned.

  In addition, in the range which does not deviate from the meaning of the present invention, JP 2011-219620 A, JP 2011-195820 A, JP 2011-178873 A, JP 2011-168705 A, JP 2011-148267 A. The description of the publication can be referred to.

  Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.

<Polyamide resin>
(Synthesis of polyamide (PAMP6))
After heating and dissolving adipic acid in a reaction can under a nitrogen atmosphere, while stirring the contents, paraxylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and metaxylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) The mixed diamine having a molar ratio of 3: 7 is gradually dropped under pressure (0.35 Mpa) so that the molar ratio of diamine to adipic acid (made by Rhodia) becomes about 1: 1, Was raised to 270.degree. After completion of the dropwise addition, the pressure was reduced to 0.06 MPa, the reaction was continued for 10 minutes, and the amount of components having a molecular weight of 1,000 or less was adjusted. Thereafter, the contents were taken out in the form of a strand and pelletized by a pelletizer to obtain a polyamide. Hereinafter, it is called "PAMP6". Melting point was 257 ° C.

(Synthesis of polyamide (PAMP10))
After heating and dissolving sebacic acid in a reaction can under a nitrogen atmosphere, the contents are stirred and paraxylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and metaxylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) The temperature is raised to 235 ° C while gradually adding a mixed diamine having a molar ratio of 3: 7 under pressure (0.35 Mpa) so that the molar ratio of diamine to sebacic acid is about 1: 1. I did. After completion of the dropwise addition, the reaction was continued for 60 minutes to adjust the amount of components having a molecular weight of 1000 or less. After completion of the reaction, the contents were taken out in the form of a strand and pelletized by a pelletizer to obtain a polyamide. Hereinafter, it is called "PAMP10". Melting point was 215 ° C.

<Flame retardant>
Brominated polystyrene (halogen flame retardant): Albemarle, part number: HP3010
Zinc borate (ZnB): RIO TINTO, part number: Fire Break ZB
Antimony trioxide (Sb ₂ O ₃ ): manufactured by Nippon Concentrate, part number: PATOX
Magnesium hydroxide: Made by Kamijima Chemical Industries, part number: Magshids S

Preparation method of PME 90 FR After dry blending of 34.7% by weight of polyphenylene ether resin, 0.3% by weight of maleic anhydride, 35% by weight of phosphazene and 30% by weight of zinc borate, using “TEX-30α” manufactured by Toshiba Machine Co., Ltd. The mixture was melt-kneaded under conditions of a barrel set temperature of 280 ° C., a screw rotation speed of 200 rpm and a discharge amount of 20 kg / h to obtain pellets of the phosphazene master batch.
<< Raw materials used for production of master batch >>
Polyphenylene ether resin: made by Mitsubishi Engineering Plastics, part number: PX100L
Phosphazene: made by Otsuka Chemical, part number: SPS-100
ZnB: RIO TINTO, part number: Fire Break ZB

<Fiber>
<< glass fiber >>
T-423: Glass roving (made by Nippon Electric Glass), fiber diameter: 17 μm, linear density: 2400 TEX

Example 1
<Creating a tape>
A tape (fiber reinforced resin material) was prepared by the following method using a thermoplastic resin composition having a composition shown in the table described later. Each component of the thermoplastic resin composition is weighed and blended with a tumbler so as to obtain the composition shown in the following table described later, and the thermoplastic resin composition is introduced from the root of a twin-screw extruder (TEM26SS manufactured by Toshiba Machine Co., Ltd.) And melted.
The roving glass fiber (continuous fiber) 22 rolls were equally spaced, passed through a spreader, and spread to a width of 200 mm. When the spread glass fiber is put between the upper and lower two impregnation rolls, the thermoplastic resin composition melted by a twin screw extruder (TEM26SS manufactured by Toshiba Machine Co., Ltd.) is supplied, and the glass fiber is heated in the impregnation roll. The plastic resin composition was impregnated. Thereafter, while cooling with a cooling roll, it was taken up and wound around a cylindrical core material to make a tape. The set temperature of the extruder was 280 ° C., the number of revolutions was 350, and the take-up speed was 2 mm / min. A 50 m-thick tape having a glass content of 60% by weight and a width of 200 mm and a thickness of 0.25 mm was obtained.

<Preparation of a 4.0 mm thick resin molded product>
The above tape is cut into a width of 200 mm and a length of 200 mm, and the glass fibers are rotated by 90 degrees so that they are orthogonal to each other. 18 tapes arranged alternately are placed in a mold heated to 270 ° C. The press molding was performed using a press of After pressing, the mold was flushed with water and cooled to 80 ° C., and then the mold was opened and taken out to obtain a 4.0 mm-thick resin molded article in which 18 sheets of tape were stacked. The temperature of the mold at the time of pressing was 260 ° C., the pressure was 100 kgf / cm ² (9.8 MPa), the pressing time was 10 minutes, and the cooling time was 20 minutes.

<Creation of ISO test pieces>
From the resin molded article having a thickness of 4.0 mm obtained above, it was cut out in a direction in which the fibers were oriented in the longitudinal direction of the test piece with a size of 10 mm width and 80 mm length, to obtain an ISO test piece.

<Creating a test piece for UL test>
From the above-mentioned tape, a UL94 test specimen having a length of 125 mm and a width of 13 mm was cut out so that the long side was in the fiber orientation direction. The thickness remained at 0.25 mm.

Example 2
A tape was produced in the same manner as in Example 1 except that the thermoplastic resin composition used in Example 1 was changed to the composition shown in the table described later. Further, an ISO test piece was obtained in the same manner as in Example 1.

Example 3
A tape was produced in the same manner as in Example 1 except that the thermoplastic resin composition used in Example 1 was changed to the composition shown in the table described later. Further, an ISO test piece was obtained in the same manner as in Example 1.

Example 4
A tape was produced in the same manner as in Example 1 except that the thermoplastic resin composition used in Example 1 was changed to the composition shown in the table described later. Further, an ISO test piece was obtained in the same manner as in Example 1.

Comparative Example 1
A tape was produced in the same manner as in Example 1 except that the thermoplastic resin composition used in Example 1 was changed to the composition shown in the table described later. Further, an ISO test piece was obtained in the same manner as in Example 1.

<Charpy impact strength>
Notched Charpy impact strength was measured at 23 ° C. in accordance with ISO 179-1 or ISO 179-2 using the ISO tensile test specimen (thickness 4.0 mm) obtained by the method described above. The unit was kJ / m ² . The results are shown in Table 1 below.

<Productivity evaluation at the time of tape creation>
After impregnating the glass fiber with the thermoplastic resin composition in the impregnating roll, the state of the tape at the time of taking off while cooling with a cooling roll was visually evaluated.
A: The resin composition uniformly impregnated the glass fiber, and a uniform tape was obtained.
B: The resin composition did not uniformly impregnate the glass fiber, and fraying of the tape occurred intermittently.

<Flame retardancy (UL94)>
The flame retardancy of each resin composition was evaluated by conditioning the UL test specimen obtained by the above-mentioned method in a constant temperature room at a temperature of 23 ° C. and a humidity of 50% for 48 hours, under the US Underwriters Laboratories, Inc. The test was conducted in accordance with the UL 94 test (combustion test of plastic materials for parts of equipment) defined by (UL). In the following table, "average burning time of test piece after first flame exposure / average burning time of test piece after second flame flame" is shown. For example, “3/0” of Composition 1 means that the average burning time (for 5 specimens) of the test piece after the first flame is 3 seconds, and the average burning time of the test piece after the second flame ((0) 5) represents 0 seconds for the test piece.

  As is clear from the above results, it was found that the fiber-reinforced resin material of the present invention can provide a resin molded product having high notched Charpy impact strength and having good flame retardancy. On the other hand, in Comparative Example 1 using the thermoplastic resin composition containing no flame retardant, the Charpy strength is somewhat high, but the afterflame time after the first ignition exceeds 10 seconds, and the UL94 V0 standard It became nonconforming to

Claims (6)

And a thermoplastic resin, flame retardants, the molten thermoplastic resin composition is impregnated into a continuous fiber are arranged in one direction, to cool with tape, film or sheet-like state A fiber-reinforced resin material containing
The continuous fibers are arranged such that the fiber direction of the continuous fibers is the longitudinal direction of the tape, film or sheet ,
The flame retardant comprises an organic flame retardant comprising at least one of a halogen flame retardant and a phosphorus flame retardant,
The fiber-reinforced resin material has a content of continuous fiber of 30 to 70% by weight, and 80% by weight or more of the component consists of a thermoplastic resin and a continuous fiber, and further, 100% by weight of a flame retardant and thermoplastic resin Less than 50 parts by weight per part,
The amount of the organic flame retardant is 10 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition,
The thermoplastic resin is a polyamide resin comprising a diamine structural unit and a dicarboxylic acid structural unit, wherein 50 mol% or more of the diamine structural unit is derived from xylylene diamine, and 50 mol% or more of the dicarboxylic acid structural unit is adipic acid And / or a polyamide resin derived from sebacic acid,
Fiber reinforced resin material. The fiber reinforced resin material according to claim 1, wherein the continuous fiber is glass fiber. The fiber reinforced resin material according to claim 1 or 2 , wherein the fiber reinforced resin material is in the form of a tape, a film or a sheet having a thickness of 0.05 to 2 mm. The resin molded product which heat-processes the fiber reinforced resin material of any one of Claims 1-3 . The resin molded article according to claim 4 , which is a portable electronic device part. The fiber reinforced resin material according to any one of claims 1 to 3 , comprising cooling the continuous fiber after impregnating the molten thermoplastic resin composition containing a thermoplastic resin and a flame retardant into a continuous fiber. Manufacturing method.