JP6334935B2 - Resin molded product, thermoplastic resin molded product manufacturing kit, resin molded product manufacturing method, and resin molded product processing method - Google Patents

Description

  The present invention relates to a resin molded product, a thermoplastic resin molded product manufacturing kit, a resin molded product manufacturing method, and a resin molded product processing method.

  Resin molded products are widely used in various applications. Moreover, in order to increase the mechanical strength of a resin molded product, fiber is blended in the resin molded product. On the other hand, in order to improve the flame retardancy of a resin molded product, a flame retardant is blended with the resin molded product. For example, Patent Document 1 contains 100 parts by weight of a thermoplastic resin, 0.1 to 100 parts by weight of a layered silicate, and 5 to 100 parts by weight of a non-halogen flame retardant. A sheet is disclosed. In Patent Document 2, a heat-resistant or flame-resistant incombustible sheet is bonded to a housing surface for an electronic device that houses an electronic device component inside and facing the housing of the electronic device component. There is disclosed a casing for electronic equipment characterized by the above. Patent Document 3 discloses a layer in which a continuous fiber woven or knitted fabric of carbon fibers is impregnated with a matrix resin made of a thermoplastic resin, and a layer in which a fiber structure made of heat-resistant fibers is impregnated with a matrix resin made of a thermoplastic resin. Discloses a fiber-reinforced thermoplastic resin sheet that is integrally laminated. In Patent Document 4, a heat-resistant or flame-resistant incombustible sheet is bonded to a housing surface for an electronic device in which an electronic device component is housed and which faces the electronic device component to be housed. There is disclosed a casing for electronic equipment characterized by the above.

Japanese Patent Laid-Open No. 2003-335902 JP 2005-165930 A Japanese Patent Laid-Open No. 5-117411 JP 2005-165930 A

Here, there are various difficulties in producing a resin molded product by blending both a flame retardant and a fiber into a resin. For example, since a flame retardant is easily decomposed by heat, if a resin having a high melting point is used, it may be decomposed at the time of compounding for pellet molding. Further, considering that the flame retardant decomposes, there is also a problem that when the amount of the flame retardant is increased, the amount of the resin component is relatively decreased. On the other hand, the fibers also have problems such as being broken during the compounding of the pellet molding.
The object of the present invention is to provide a resin molded product having high flame retardancy and high mechanical strength.
Furthermore, in recent years, there has been a demand for thinning of a resin molded product, but an object is to provide a resin molded product that can cope with such a thin molded product. The present invention also relates to a thermoplastic resin molded product manufacturing kit, a resin molded product manufacturing method, and a resin molded product processing method for providing the resin molded product.

  Under such circumstances, the inventors of the present application have conducted intensive studies. As a result, they have found that the above-mentioned problems can be solved by providing a flame retardant reinforced resin composition on both sides of a resin sheet containing fibers. Specifically, the above problem has been solved by the following means <1>, preferably <2> to <17>.

Under such circumstances, as a result of intensive studies by the present inventors, it has been found that the above-mentioned problems can be solved by providing a flame retardant reinforced resin composition on both surfaces of a resin sheet containing fibers. Specifically, the above problem has been solved by the following means <1>, preferably <2> to <17>.
<1> At least one flame retardant selected from a thermoplastic resin of the same system as the thermoplastic resin, a phosphorus flame retardant, and a halogen flame retardant, on both surfaces of a sheet containing a thermoplastic resin and fibers, respectively. A resin molded product obtained by thermoforming with a composition containing the same.
<2> The resin molded product according to <1>, wherein the amount of the flame retardant is 10 to 90 parts by weight with respect to 100 parts by weight of the thermoplastic resin in at least one of the compositions provided on both surfaces of the sheet.
<3> The resin molded product according to <1>, wherein the amount of the flame retardant is 10 to 90 parts by weight with respect to 100 parts by weight of the thermoplastic resin in both of the compositions provided on both surfaces of the sheet.
<4> The resin molded product according to any one of <1> to <3>, wherein the fibers are regularly arranged in the sheet.
<5> The resin molded product according to any one of <1> to <4>, wherein the fiber is impregnated with the thermoplastic resin contained in the sheet.
<6> The resin molded product according to any one of <1> to <5>, wherein the thermoplastic resin contained in the sheet is a polyamide resin.
<7> The resin molded product according to any one of <1> to <6>, wherein the fiber is a glass fiber.
<8> The resin molded product according to any one of <1> to <7>, wherein the resin molded product has a portion having a thickness of 0.5 mm or less of 1 cm ² or more.
<9> A composition comprising a thermoplastic resin of the same type as the thermoplastic resin and at least one flame retardant selected from a phosphorus-based flame retardant and a halogen-based flame retardant is a film, <1> to < The resin molded product according to any one of 8>.
<10> a thermoplastic resin and fiber-containing sheet, at least two thermoplastic resins of the same system as the thermoplastic resin, at least one flame retardant selected from a phosphorus-based flame retardant and a halogen-based flame retardant A kit for producing a thermoplastic resin molded article, comprising a film comprising a composition comprising
<11> The kit for manufacturing a thermoplastic resin molded article according to <10>, wherein the fibers are regularly arranged in the sheet.
<12> The kit for manufacturing a thermoplastic resin molded article according to <10> or <11>, wherein the fiber is impregnated with the thermoplastic resin contained in the sheet.
<13> A thermoplastic resin of the same system as the thermoplastic resin, and at least one flame retardant selected from a phosphorus-based flame retardant and a halogen-based flame retardant, on both surfaces of a sheet containing a thermoplastic resin and fibers, respectively. A method for producing a resin molded article, comprising arranging the composition containing the composition and thermoforming the composition.
<14> The step of arranging and heat-molding the composition includes thermoforming a film made of a composition comprising at least one flame retardant selected from a phosphorus-based flame retardant and a halogen-based flame retardant. The manufacturing method of the resin molded product as described in <13> containing.
<15> The method for producing a resin molded product according to <13> or <14>, wherein the thermoforming is a hot press method.
<16> The method for producing a resin molded product according to <13> or <14>, wherein the thermoforming is insert molding or outsert molding.
<17> A method for processing a resin molded product, comprising further heating the resin molded product according to any one of <1> to <9>.

  According to the present invention, it is possible to provide a resin molded product having high flame retardancy and high mechanical strength. Furthermore, it has become possible to provide resin molded products that can be used for thin molded products. Also, it is possible to provide a thermoplastic resin molded product manufacturing kit, a resin molded product manufacturing method, and a resin molded product processing method for providing the resin molded product.

It is an image figure which shows an example of the resin molded product of this invention. It is a section schematic diagram showing an example of an embodiment of a resin molded product of the present invention. It is a cross-sectional schematic diagram which shows another example of embodiment of the resin molded product of this invention.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

The resin molded product of the present invention comprises a thermoplastic resin and a thermoplastic resin of the same type as the thermoplastic resin on both sides of a sheet containing a thermoplastic resin and fibers (hereinafter sometimes referred to as a “fiber reinforced resin sheet”). A composition containing at least one flame retardant selected from a flame retardant and a halogen flame retardant (hereinafter sometimes referred to as a “flame retardant reinforced resin composition”) and thermoformed. Features.
By arranging the flame retardant reinforced resin composition on both sides of the fiber reinforced resin sheet and thermoforming, respectively, both sides of the fiber reinforced resin sheet are covered with the flame retardant resin composition. A resin molded product having excellent properties and mechanical strength can be obtained.
In particular, the layer containing the fiber and the layer containing the flame retardant tend to be inferior in adhesion, but in the present invention, the adhesion can be improved by using the same type of resin for these layers.
Moreover, in this invention, a flame retardant reinforced resin composition is provided on both surfaces of a fiber reinforced resin sheet. Thus, by providing a flame retardant reinforced resin composition on both sides, when the resin molded product burns, the flame retardant resin composition forms a flame retardant char on both sides of the fiber reinforced resin sheet, and these are combustible. By wrapping the porous fiber reinforced resin sheet, it is possible to prevent the fire of the resin molded product.

<Layer structure of resin molded product>
FIG. 1 is an image diagram showing an example of a resin molded product of the present invention, wherein 1 is a fiber reinforced resin sheet, 2 is a film made of a flame retardant reinforced resin composition (hereinafter referred to as “flame retardant reinforced resin film”). Each). In the present embodiment, the flame retardant reinforced resin composition is in the form of a film, but may be in other forms. Further, in the present invention, since the fiber reinforced resin sheet and the flame retardant reinforced resin composition are thermoformed, in the finally obtained molded product, the fiber reinforced resin sheet and the flame retardant reinforced resin composition are distinguished. It is not always possible.

  Although the fiber reinforced resin sheet 1 of this invention may be only 1 sheet and may laminate | stack 2 or more sheets, 1-5 sheets are preferable and 1 sheet or 2 sheets is more preferable. When two or more sheets are laminated, it is preferable that the fibers are laminated so that the fibers are alternately perpendicular to each other because the mechanical strength is further improved.

The flame retardant reinforced resin film is provided on both sides of the fiber reinforced resin sheet. The flame retardant reinforced resin film may be only one sheet on each side of the fiber reinforced resin sheet, or two or more sheets may be laminated, preferably 1 to 5 sheets, more preferably 1 One or two.
FIG. 2 is an embodiment in which two flame retardant reinforced resin films are provided on both sides of a fiber reinforced resin sheet, where 1 indicates a fiber reinforced resin sheet and 21 indicates a first flame retardant resin sheet. 22 represents a second flame-retardant reinforced resin film. In the present embodiment, two sheets each containing a flame retardant are provided on both sides of the fiber reinforced resin sheet, but three or more sheets may be provided on each side. As an upper limit, 4 sheets or less are preferable and 3 sheets or less are more preferable. Moreover, the structure which laminates | stacks a flame-retardant reinforced resin film at least 1 sheet | seat on one surface of a fiber reinforced resin sheet, and 2 or more on the other surface may be sufficient.
When two or more flame retardant reinforced resin films are laminated on one surface of the fiber reinforced resin sheet, the second flame retardant reinforced resin film 22 disposed on the outside is closer to the fiber reinforced resin sheet. It is preferable that the content of the flame retardant is larger than that of the first flame retardant reinforced resin film 21 disposed on the side. By setting it as such a structure, a flame retardance can be improved more, keeping mechanical strength favorable.

The flame retardant reinforced resin film is usually provided on both surfaces of the fiber reinforced resin sheet, respectively, but between the fiber reinforced resin sheet and the flame retardant reinforced resin film, other ranges can be used without departing from the spirit of the present invention. A film may be included. FIG. 3 shows a film containing a thermoplastic resin of the same system as the fiber reinforced resin sheet between the fiber reinforced resin sheet and the fiber reinforced resin sheet (hereinafter referred to as “other resin film”). Is sometimes referred to as a “layer”. In FIG. 3, 1 is a fiber reinforced resin sheet, 2 is a fiber reinforced resin sheet, and 3 is another resin film. In the present embodiment, the other resin films 3 are arranged on both surfaces of the fiber reinforced resin sheet 1, respectively, but only one surface may be used.
By setting it as such a structure, it exists in the tendency for the adhesiveness of a fiber reinforced resin sheet to improve more.

The resin molded product of the present invention is usually in the form of a sheet, and the thickness is preferably 0.1 to 2 mm, and more preferably 0.2 to 1 mm. In particular, the present invention is highly valuable in that the resin molded product can be a thin-walled resin molded product having a portion having a thickness of 0.5 mm or less of 1 cm ² or more.

<Fiber-reinforced resin sheet>
The fiber reinforced resin sheet used in the present invention includes a thermoplastic resin and fibers, and is preferably a sheet in which the fibers are impregnated with the thermoplastic resin. By using such a fiber reinforced resin sheet, the mechanical strength of the resin molded product can be increased. In particular, the present invention is advantageous in that the fiber reinforced resin sheet can be configured to contain substantially no flame retardant (for example, the blending amount of the flame retardant is 0.1% by weight or less of the sheet). That is, the flame retardant is beneficial for improving the flame retardancy, but if the amount of the flame retardant increases, the mechanical strength may be adversely affected. In this invention, since it can be set as the structure which does not contain a flame retardant in a fiber reinforced resin sheet, favorable mechanical strength can be achieved.

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

As the polyester resin, the description of paragraph numbers 0013 to 0016 in JP2010-174223A can be referred to.
As the polyacetal resin, description of paragraph number 0011 of JP-A-2003-003041 and paragraph numbers 0018 to 0020 of JP-A-2003-220667 can be referred to.

As the polyamide resin, the description in paragraph numbers 0011 to 0013 of JP2011-132550A can be referred to. Preferably, 50 mol% or more of the diamine structural unit (structural unit derived from diamine) is a polyamide resin derived from xylylenediamine. More than 50 mol% of the diamine is derived from xylylenediamine and is a xylylenediamine-based polyamide resin polycondensed with a dicarboxylic acid.
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 (a structural unit derived from dicarboxylic acid). Is a xylylenediamine system derived from an α, ω-linear aliphatic dicarboxylic acid having 50 mol% or more, more preferably 70 mol% or more, particularly 80 mol% or more, preferably having 4 to 20 carbon atoms. Polyamide resin. Adipic acid, sebacic acid, suberic acid, dodecanedioic acid, eicodioic acid and the like can be preferably used as the 4-20 α, ω-linear aliphatic dibasic acid.
In the present invention, a polyamide resin containing an aromatic ring in the molecule and having a ratio of carbon atoms constituting the aromatic ring to the polyamide resin molecule is preferably 30 mol% or more. By adopting such a resin, the water absorption rate is reduced, and as a result, the water absorption dimensional change is more effectively suppressed.
Moreover, it is preferable that a polyamide resin contains 0.5 to 5 weight% of components with a molecular weight of 1,000 or less. By including such a low molecular weight component in such a range, the impregnation property of the polyamide resin is improved, that is, the fluidity between the fibers of the polyamide resin is improved, and the generation of voids during molding processing is suppressed. can do. As a result, the strength and low warpage of the obtained molded product become better. When the content is 5% by weight or less, the low molecular weight component is less likely to bleed 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% by weight. %, 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 melt polymerization conditions such as the temperature and pressure at the time of polyamide resin polymerization and the dropping rate of diamine. In particular, the inside of the reaction apparatus can be depressurized at the latter stage of the melt polymerization to remove low molecular weight components and adjusted to an arbitrary ratio. Further, the polyamide resin produced by melt polymerization may be subjected to hot water extraction to remove low molecular weight components, or after melt polymerization, the low molecular weight components may be removed by solid phase polymerization under reduced pressure. In the 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 adjusted 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 amount of components having a weight average molecular weight of 1,000 or less is converted to standard polymethyl methacrylate (PMMA) by gel permeation chromatography (GPC) measurement using “HLC-8320GPC” manufactured by Tosoh Corporation. It can be obtained from the value. Two “TSKgel SuperHM-H” were used as the measurement columns, hexafluoroisopropanol (HFIP) having a sodium trifluoroacetate concentration of 10 mmol / l was used as the solvent, the resin concentration was 0.02% by weight, and the column temperature was It can be measured with a refractive index detector (RI) at 40 ° C., a flow rate of 0.3 ml / min. A calibration curve is prepared by dissolving 6 levels of PMMA in HFIP.

The number average molecular weight (Mn) of the polyamide resin used in the present invention is preferably 6,000 to 30,000, more preferably 8,000 to 28,000.
The glass transition temperature of the polyamide resin used in the present invention is preferably 50 to 130 ° C, more preferably 60 to 100 ° C. Moreover, 180-320 degreeC is preferable and, as for melting | fusing point of the polyamide resin used by this invention, 200-300 degreeC is more preferable.

  As content of the thermoplastic resin in a fiber reinforced resin sheet, 20 to 98 weight% is preferable, 25 to 80 weight% is more preferable, and 30 to 70 weight% is further more preferable. Only one type of thermoplastic resin may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range. In particular, the ratio of the resin of the same system as the resin contained in the flame retardant reinforced resin composition to be described later is preferably 60% by weight or more among all thermoplastic resins contained in the fiber reinforced resin sheet. % Or more is more preferable. By setting it as such a range, the effect of this invention is exhibited more effectively. In addition, even when outside the above range, if the matrix (sea part of the sea-island structure) is the same in the morphology, the effect is sufficiently exerted.

Moreover, it is also preferable that the fiber reinforced resin sheet used by this invention impregnates the fiber with the thermosetting resin composition which has a thermoplastic resin as a main component.
Components other than the thermoplastic resin that the thermoplastic resin composition may contain include elastomers, talc, mold release agents, antioxidants, stabilizers such as heat stabilizers, hydrolysis resistance improvers, weather resistance stabilizers. Additives such as matting agents, ultraviolet absorbers, nucleating agents, plasticizers, dispersants, antistatic agents, anti-coloring agents, anti-gelling agents, coloring agents, release agents, and the like can be added. For details of these, reference can be made to the description of paragraph numbers 0130 to 0155 of Japanese Patent No. 4894982, the contents of which are incorporated herein. Moreover, about an elastomer, a talc, and a mold release agent, these description in the flame-retardant reinforced resin composition mentioned later can be considered, and a preferable range is also synonymous.
These components are preferably 20% by weight or less of the thermoplastic resin composition.

<< fiber >>
Examples of fibers used in the present invention include glass fibers, carbon fibers, plant fibers (including kenaf and bamboo fibers), alumina fibers, boron fibers, ceramic fibers, metal fibers (such as steel fibers), aramid fibers, and poly fibers. Examples thereof include oxymethylene fibers, aromatic polyamide fibers, polyparaphenylene benzobisoxazole fibers, and ultrahigh molecular weight polyethylene fibers. Among these, carbon fibers and / or glass fibers are preferable, and glass fibers are more preferable.

  These fibers are preferably, for example, monofilaments or multifilaments arranged so as to cross one direction or alternately. Furthermore, a prepreg in which these are laminated and impregnated with a binder or the like is also preferably used.

  The average fiber diameter of the fibers is preferably 1 to 100 μm, more preferably 3 to 50 μm, further preferably 4 to 20 μm, and particularly preferably 5 to 10 μm. When the average fiber diameter is within this range, processing becomes easy. The average fiber diameter can be measured by observation with a scanning electron microscope (SEM) or the like. In the present invention, 50 or more fibers are randomly selected, the length is measured, and the number average average fiber diameter is calculated.

The fiber preferably has a functional group having reactivity with the thermoplastic resin on the surface of the fiber in order to improve wettability and interfacial adhesion with the thermoplastic resin.
As an example having a functional group having reactivity with a thermoplastic resin, a surface treated with a surface treating agent or a sizing agent is preferably mentioned.

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

  As the sizing agent, an epoxy resin such as a bisphenol A type epoxy resin, an epoxy acrylate resin having an acrylic group or a methacryl group in one molecule, a bisphenol A type vinyl ester resin, a novolac type vinyl ester resin, Preferred examples include vinyl ester resins such as brominated vinyl ester resins. Further, it may be a urethane-modified resin of an epoxy resin or a vinyl ester resin.

The amount of fibers in the fiber reinforced resin sheet is preferably 20 to 80% by weight, more preferably 30 to 70% by weight of the fiber reinforced resin sheet.
Moreover, it is preferable that 80 weight% or more of the structural component of a fiber reinforced resin sheet consists of a thermoplastic resin and a fiber.

<< Structure of fiber reinforced resin sheet >>
In the fiber reinforced resin sheet, it is preferable that the fibers are regularly arranged. Here, the regular arrangement means a case where the fibers are arranged in one direction or a case where the fibers are arranged in a cross shape, and the fibers are usually arranged at regular intervals. Here, the equal interval means not only an equal interval in a mathematical sense but also an interval that is achieved by arranging fibers in one direction by a known means.
More specifically, the fibers in the first embodiment of the fiber reinforced sheet of the present invention are arranged in equal intervals in one direction. In the first embodiment, the fibers arranged at equal intervals in one direction are made of a thermoplastic resin or a thermoplastic resin composition mainly composed of a thermoplastic resin (hereinafter referred to as “thermoplastic resin etc.”). Is more preferable. The impregnation is preferably performed by heat processing. The shape of the thermoplastic resin or the like when the fiber is impregnated with the thermoplastic resin or the like is not particularly defined, and a film shape, a fiber shape, a powder shape, a melted shapeless shape, or the like can be adopted. In the present embodiment, it is preferable to extrude and impregnate molten thermoplastic resin or the like into fibers arranged at equal intervals in one direction. The obtained fiber reinforced resin sheet may be used as it is, or may be laminated and hot-pressed so as to satisfy a desired thickness and strength. When laminating, it is preferable to laminate so that the fibers are orthogonal. By setting it as such a structure, it exists in the tendency for the mechanical strength of the molded article obtained to improve more.
2nd embodiment of the fiber reinforced resin sheet | seat of this invention is the state by which the fiber was woven in the cross shape. Examples of the cloth woven include plain weave, twill, satin weave and the like. In the second embodiment, the fibers woven in a cloth shape can be hot-pressed with a resin sheet to form a fiber-reinforced resin sheet. Further, the thermoplastic resin may also be made into a thread shape and woven in a cloth shape together with the fiber to form a fiber reinforced resin sheet. Furthermore, the fiber reinforced sheet obtained in the first embodiment or the like may be slit with an arbitrary width, and a sheet band obtained thereby may be woven into a cloth to form a fiber reinforced resin sheet.
In the third embodiment, a plurality of glass fibers and a thread-like thermoplastic resin are twisted, and the obtained twisted thread is used as a hot press. Further, the obtained twisted yarn may be further knitted into a cross shape and hot-pressed. Here, the Comingle method is exemplified as a method of twisting a plurality of glass fibers and a thread-like thermoplastic resin.
The thickness of the fiber reinforced resin sheet is preferably 0.01 to 5 mm, more preferably 0.05 to 1 mm, still more preferably 0.1 to 0.8 mm, and still more preferably 0.1 to 0.5 mm. 0.1 to 0.4 mm is even more preferable.

<Flame Retardant Reinforced Resin Composition>
The flame retardant reinforced resin composition used in the present invention is at least one flame retardant selected from the same series of thermoplastic resins as the thermoplastic resin contained in the fiber reinforced resin sheet, a phosphorus flame retardant, and a halogen flame retardant. including.

<< Thermoplastic resin >>
The flame retardant reinforced resin composition used in the present invention includes a thermoplastic resin of the same system as the thermoplastic resin contained in the fiber reinforced resin sheet. The same series of thermoplastic resins include, for example, polyamide resins, polyester resins, polyolefin resins, polypropylene resins, polyethylene resins, acrylic resins, polyacetal resins, polycarbonate resins, styrene resins, and polyamide resins. Examples include combinations of polyurethane resins.
In the present invention, as the resin of the same system, the flame retardant reinforced resin composition and the fiber reinforced resin sheet may contain the same resin, or the same system and different resins.
In the present invention, in the resin component contained in the flame-retardant reinforced resin composition, the proportion of the thermoplastic resin of the same system is preferably 80% by weight or more, and more preferably 90% by weight or more. Moreover, the flame retardant reinforced resin composition may contain two or more kinds of thermoplastic resins. In this case, it is preferable that the two or more kinds of resins are the same series of thermoplastic resins.
The total amount of the thermoplastic resin in the flame retardant reinforced resin composition is preferably 30% by weight or more, more preferably 35% by weight or more, and further preferably 50% by weight.

<< Flame Retardant >>
The flame retardant reinforced resin composition used in the present invention contains at least one flame retardant selected from a phosphorus flame retardant and a halogen flame retardant as a flame retardant. By using such an organic flame retardant, it is possible to more effectively suppress brittleness when the flame retardant reinforced resin composition is molded.

  Examples of phosphorus flame retardants include condensed phosphate ester flame retardants and phosphazene flame retardants.

（式中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ炭素数１〜６のアルキル基またはアルキル基で置換されていてもよい炭素数６〜２０のアリール基を示し、ｐ、ｑ、ｒおよびｓは、それぞれ０または１であり、ｋは１から５の整数であり、Ｘ¹はアリーレン基を示す。） Condensed phosphate ester flame retardant As the condensed phosphate ester flame retardant, a phosphate ester compound represented by the following general formula (1) is preferable.

(Wherein R ¹ , R ² , R ³ and R ⁴ each represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, and p, q , R and s are each 0 or 1, k is an integer of 1 to 5, and X ¹ represents an arylene group.)

  The phosphate ester compound represented by the above general formula (1) may be a mixture of compounds having different numbers of k, and in the case of a mixture of phosphate esters having different k, k is a mixture of those compounds. Average value. In the case of a mixture of compounds having different k numbers, the average k number is preferably 1 to 2, more preferably 1 to 1.5, still more preferably 1 to 1.2, particularly preferably 1 to 1.15. It is a range.

X ¹ represents a divalent arylene group such as resorcinol, hydroquinone, bisphenol A, 2,2′-dihydroxybiphenyl, 2,3′-dihydroxybiphenyl, 2,4′-dihydroxybiphenyl, 3,3 ′. -Dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, Divalent derivatives derived from dihydroxy compounds such as 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene It is a group. Of these, divalent groups derived from resorcinol, bisphenol A, and 3,3′-dihydroxybiphenyl are particularly preferable.

Further, p, q, r and s in the general formula (1) each represent 0 or 1, and 1 is particularly preferable.
R ¹ , R ² , R ³ and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of such aryl groups include phenyl group, cresyl group, xylyl group, isopropylphenyl group, butylphenyl group, tert-butylphenyl group, di-tert-butylphenyl group, and p-cumylphenyl group. Group, cresyl group and xylyl group are more preferred.

  Specific examples of the condensed phosphate ester flame retardant represented by the general formula (1) include phenyl resorcin / polyphosphate, cresyl / resorcin / polyphosphate, phenyl / cresyl / resorcin / polyphosphate, xylyl / resorcin / polyphosphate. Phenyl-pt-butylphenyl / resorcin / polyphosphate, phenyl / isopropylphenyl / resorcin / polyphosphate, cresyl / xylyl / resorcin / polyphosphate, phenyl / isopropylphenyl / diisopropylphenyl / resorcin / polyphosphate, etc. .

  The acid value of the condensed phosphate ester compound represented by the general formula (1) is preferably 0.2 mgKOH / g, more preferably 0.15 mgKOH / g or less, still more preferably 0.1 mgKOH or less. Preferably it is 0.05 mgKOH / g or less. The lower limit of the acid value can be substantially zero. On the other hand, the content of the half ester is more preferably 1.1 parts by weight or less, and further preferably 0.9 parts by weight or less. When the acid value exceeds 0.2 mgKOH / g or the half ester content exceeds 1.5 mg, the heat stability and hydrolysis resistance of the flame-retardant reinforced resin composition used in the present invention are likely to be lowered. .

Phosphazene Flame Retardant The phosphazene flame retardant is an organic compound having a -P = N- bond in the molecule, preferably a cyclic phosphazene compound represented by the following general formula (2), and the following general formula (3) A chain phosphazene compound represented by the following formula, and a group consisting of a crosslinked phosphazene compound in which at least one phosphazene compound selected from the group consisting of the following general formula (2) and the following general formula (3) is crosslinked by a crosslinking group At least one compound selected. As the crosslinked phosphazene compound, those crosslinked by a crosslinking group represented by the following general formula (4) are preferable from the viewpoint of flame retardancy.
The phosphazene-based flame retardant (B2) has a high flame-retardant effect, and particularly when used in combination with carbon black (D), which will be described later, can exhibit excellent flame retardancy. The reduction in mechanical strength and the generation of gas can be suppressed.

（式（２）中、ｍは３〜２５の整数であり、Ｒ¹は、同一又は異なっていてもよく、アリール基又はアルキルアリール基を示す。）

(In Formula (2), m is an integer of 3-25, R < ¹ > may be the same or different and shows an aryl group or an alkylaryl group.)

（式（３）中、ｎは３〜１０，０００の整数であり、Ｘは、−Ｎ＝Ｐ（ＯＲ¹）₃基又は−Ｎ＝Ｐ（Ｏ）ＯＲ¹基を示し、Ｙは、−Ｐ（ＯＲ¹）₄基又は−Ｐ（Ｏ）（ＯＲ¹）₂基を示す。Ｒ¹は、同一又は異なっていてもよく、アリール基又はアルキルアリール基を示す。）

(In Formula (3), n is an integer of 3 to 10,000, X represents a —N═P (OR ¹ ) ₃ group or a —N═P (O) OR ¹ group, and Y represents a — P (OR ¹ ) ₄ group or —P (O) (OR ¹ ) ₂ group is shown, R ¹ may be the same or different and represents an aryl group or an alkylaryl group.

（式（４）中、Ａは−Ｃ（ＣＨ₃）₂−、−ＳＯ₂−、−Ｓ−、又は−Ｏ−であり、ｌは０又は１である。）

(In formula (4), A is —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and 1 is 0 or 1.)

Examples of the cyclic and / or chain phosphazene compounds represented by the general formulas (2) and (3) include, for example, phenoxyphosphazene and (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, o, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, o, m, p-tolyloxyphosphazene, etc.), (poly) xylyloxyphosphazene, etc. Cyclic and / or chain C _1-6 alkyl C _6-20 aryloxyphosphazenes, (poly) phenoxytolyloxyphosphazenes (eg, phenoxy o-tolyloxyphosphazenes, phenoxy m-tolyloxyphosphazenes, phenoxy p-tolyloxy) Phosphazene, Fe Xy o, m-tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o, m, p-tolyloxyphosphazene, etc.), (poly) phenoxyxyloxyphosphazene, ( Examples thereof include cyclic and / or chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazene such as poly) phenoxytolyloxyxyloxyphosphazene, preferably cyclic and / or chain phenoxyphosphazene, Cyclic and / or chain C _1-3 alkyl C _6-20 aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 aryloxyphosphazene (for example, cyclic and / or chain tolyloxyphosphazene, Cyclic and / or chain phenoxytolylphenoxyphosphazene etc. ).

As the cyclic phosphazene compound represented by the general formula (2), cyclic phenoxyphosphazene in which R ¹ is a phenyl group is particularly preferable. Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. . The cyclic phenoxyphosphazene compound is preferably a compound in which m in the general formula (2) is 3 to 5, and may be a mixture of compounds having different m. Among them, a mixture of compounds in which m = 3 is 50% by weight or more, m = 4 is 10 to 40% by weight, and m = 5 or more is 30% by weight or less is preferable.

As the chain phosphazene compound represented by the general formula (3), chain phenoxyphosphazene in which R ¹ is a phenyl group is particularly preferable. Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above-described method to reverse polymerization at a temperature of 220 to 250 ° C., and the obtained linear dichloromethane having a polymerization degree of 3 to 10,000. Examples thereof include compounds obtained by substituting phosphazene with a phenoxy group. N in the general formula (3) of the linear phenoxyphosphazene compound is preferably 3 to 1,000, more preferably 3 to 100, and still more preferably 3 to 25.

Examples of the crosslinked phenoxyphosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. Compounds having a crosslinked structure of 4,4′-diphenylene groups, such as compounds, compounds having a crosslinked structure of 4,4′-oxydiphenylene groups, compounds having a crosslinked structure of 4,4′-thiodiphenylene groups, etc. Is mentioned.
As the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ¹ is a phenyl group in the general formula (2) with a crosslinking group represented by the general formula (4), or the above A crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R ¹ is a phenyl group in the general formula (3) with a crosslinking group represented by the above general formula (4) is preferable from the viewpoint of flame retardancy, and cyclic A crosslinked phenoxyphosphazene compound obtained by crosslinking a phenoxyphosphazene compound with a crosslinking group represented by the general formula (4) is more preferable.
The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (2) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (3) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the phosphazene flame retardant (B2) is preferably a cyclic phenoxyphosphazene compound represented by the above general formula (2) from the viewpoint of flame retardancy and mechanical properties.

Halogen-based flame retardant Examples of the halogen-based flame retardant include brominated flame retardants, such as brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A. Glycidyl brominated bisphenol A, pentabromobenzyl polyacrylate and brominated imide are preferred, and glycidyl brominated bisphenol A, pentabromobenzyl polyacrylate and brominated imide are more preferred.

  Moreover, the polyphosphate which consists of a salt of phosphoric acid, polyphosphoric acid, a periodic table group 1-14 group metal, ammonia, an aliphatic amine, and an aromatic amine can also be mentioned. As typical salts of polyphosphates, lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts and the like as metal salts, methylamine salts as aliphatic amine salts, Examples include ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, and examples of aromatic amine salts include pyridine salts and triazines.

  In addition to the above, halogen-containing phosphate esters such as trischloroethyl phosphate, trisdichloropropyl phosphate, tris (β-chloropropyl) phosphate), and structures in which a phosphorus atom and a nitrogen atom are connected by a double bond Phosphazene compounds having phosphoric acid and phosphoric ester amides.

A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more types.
As a compounding quantity of a flame retardant, the quantity of a flame retardant with respect to 100 weight part of thermoplastic resins in a flame retardant reinforced resin composition can be 10-90 weight part, Furthermore, it is 20-80 weight part. You can also. In the present invention, the flame retardant can be blended only in the flame retardant reinforced resin composition, and the fiber reinforced resin sheet can be composed of no flame retardant. Can be reduced. In the present invention, the flame retardant reinforced resin composition is provided on both surfaces of the fiber reinforced sheet. However, the blending amount of the flame retardant in each composition may be the same or different.

<< Flame retardant aid >>
The flame retardant reinforced resin composition used in the present invention may contain a flame retardant aid without departing from the spirit of the present invention. Examples of the flame retardant aid include antimony trioxide, antimony pentoxide, zinc borate, carbon black, graphite, boehmite, pentaerythritol, and the like, and examples include antimony trioxide, antimony pentoxide, and zinc borate. Flame retardant aids may be used alone or in combination of two or more.

  The blending amount of the flame retardant aid is preferably 2 to 40 parts by weight, more preferably 2 to 30 parts by weight, and 3 to 20 parts by weight with respect to 100 parts by weight of the resin component contained in the flame retardant reinforced resin composition. Further preferred.

The flame retardant reinforced resin composition used in the present invention may contain other components as necessary. Ingredients other than thermoplastic resins that may be included include elastomers, talc, mold release agents, antioxidants, stabilizers such as heat stabilizers, hydrolysis resistance improvers, weathering stabilizers, matting agents, Additives such as ultraviolet absorbers, nucleating agents, plasticizers, dispersants, flame retardants, antistatic agents, anti-coloring agents, anti-gelling agents, coloring agents, mold release agents, LDS additives, and the like can be added. For details of these, reference can be made to the description of paragraph numbers 0130 to 0155 of Japanese Patent No. 4894982, the contents of which are incorporated herein.
These components are preferably 20% by weight or less of the thermoplastic resin composition.
In addition, the flame-retardant reinforced resin composition used in the present invention may contain fibers, but the composition does not substantially contain (for example, the blending amount of the fibers is 0.1% by weight of the flame-retardant reinforced resin composition). % Or less).

<< Method for Producing Flame Retardant Reinforced Resin Composition >>
As the flame retardant reinforced resin composition used in the present invention, known methods for producing thermoplastic resin compositions can be widely adopted. Specific examples of the method for producing a flame retardant reinforced resin composition are as follows: each component is weighed at a predetermined ratio, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single or twin screw extruder And a kneading method using a kneader or the like.

  In addition, for example, each component is not mixed in advance, or only a part of the components is mixed in advance, and supplied to an extruder using a feeder and melt-kneaded to produce a flame-retardant reinforced resin composition. You can also.

Furthermore, for example, a resin composition obtained by mixing some components in advance, supplying them to an extruder and melt-kneading is used as a master batch, and this master batch is mixed with the remaining components again and melt-kneaded. The flame-retardant reinforced resin composition can also be produced by This method is particularly effective when a phosphazene flame retardant is used.
On the other hand, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and is kneaded with the solution or dispersion. It can also improve sex.

Examples of a method for melt-kneading after mixing each component in advance by the above method include a method using a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader and the like. The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C. When the molten resin is pelletized in the melt-kneading, the molten resin is extruded in a strand shape, and is usually provided with a cooling water tank through a discharge die, and after being cooled, it is cut by a cutting means such as a pelletizer, The pellet has an average particle size of about 1 to 5 mm.
In the present invention, a resin melt-kneaded by an extruder may be directly used as a sheet or film.

<< Film made of flame retardant reinforced resin composition >>
The flame retardant reinforced resin composition of the present invention is preferably used in the form of a film. By setting it as the film form, it becomes easy to heat-press between a fiber reinforced resin sheet with a flame-retardant reinforced resin film.
The thickness of the flame retardant reinforced resin film is preferably 10 to 400 μm, more preferably 30 to 300 μm, and still more preferably 50 to 200 μm.

<Other resin films>
In the present invention, a composition comprising a sheet containing a thermoplastic resin and fibers, a thermoplastic resin of the same system as the thermoplastic resin, and at least one flame retardant selected from a phosphorus flame retardant and a halogen flame retardant Another resin film may be used between the two. Examples of such other resin films include films that are substantially free of fibers and flame retardant (for example, the blending amounts of flame retardant and fibers are each 0.1% by weight or less of the film).
The thickness of the other resin film is preferably 10 to 400 μm, more preferably 30 to 300 μm, and further preferably 50 to 200 μm.

<Kit>
The kit of the present invention includes at least one sheet selected from a thermoplastic resin and a fiber-containing sheet, at least two thermoplastic resins of the same system as the thermoplastic resin, a phosphorus flame retardant, and a halogen flame retardant. A film comprising a composition containing the above flame retardant is included.
The sheet | seat containing a thermoplastic resin and a fiber is synonymous with the said fiber reinforced resin sheet, and its preferable range is also the same. Only one fiber reinforced resin sheet may be included in one kit, or two or more may be included, but 1 to 5 sheets are preferable, and 1 or 2 sheets are more preferable. A film made of a composition containing a thermoplastic resin of the same type as the thermoplastic resin and at least one flame retardant selected from a phosphorus-based flame retardant and a halogen-based flame retardant is also synonymous with the above-mentioned flame-retardant reinforced tree film. The preferred range is also the same. The flame retardant reinforced resin film may be two or more in one kit, preferably 2 to 10 sheets, more preferably 2 to 4 sheets.
Furthermore, the kit of the present invention may contain other resin films without departing from the spirit of the present invention. The description of the other resin film mentioned above can be referred to for the other resin film.
In the kit of the present invention, for example, at least one flame-retardant reinforced resin film, at least one fiber-reinforced resin sheet, and at least one flame-retardant reinforced resin film are laminated in that order, and then heat processed to form a sheet. It is a kit for making it a resin molded product. About the heat processing conditions, description of the manufacturing method of the resin molded product mentioned later can be referred.
In addition, the kit of the present invention comprises a flame retardant reinforced resin film, a fiber reinforced resin sheet, and a flame retardant reinforced resin film, which are laminated in that order, and processed directly into a final product or a part by insert molding or outsert molding. It is also possible to do.

<Method for producing resin molded product>
The method for producing a resin molded product according to the present invention includes at least one selected from a thermoplastic resin of the same type as the thermoplastic resin, a phosphorus-based flame retardant, and a halogen-based flame retardant on both sides of the fiber-reinforced resin sheet. It is obtained by arranging a composition containing the above flame retardant.
The method for disposing the flame retardant reinforced resin composition on the surface of the fiber reinforced resin sheet is not particularly defined, but the molten flame retardant reinforced resin composition is extruded or powdered onto the surface of the fiber reinforced resin sheet. The flame retardant reinforced resin composition can be applied, or a film made of the flame retardant reinforced resin composition can be stacked. The method of arranging the flame retardant reinforced thermoplastic resin composition may be different on one side and the other side of the fiber reinforced resin sheet. In the present invention, it is preferable that a film made of a flame retardant reinforced resin composition is layered and thermoformed on the surface of the fiber reinforced resin sheet. By setting it as such a structure, the resin molded product excellent in the flame retardance and mechanical strength is obtained. In particular, in the present invention, since the same series of thermoplastic resin is used for the fiber reinforced resin sheet and the flame retardant reinforced resin composition, these films and sheets can be effectively fused by thermal fusion.
The thermoforming conditions of the present invention are appropriately determined depending on the type of resin used, etc., but the thermoforming temperature is the glass transition point of the resin in the case of an amorphous resin, and the melting point of the resin in the case of a crystalline resin. It is preferably in the range of 20 to + 80 ° C, more preferably in the range of the heat distortion temperature 0 to + 50 ° C. The heat distortion temperature can be determined according to the DSC method. For example, when using a mold, the temperature of the mold can be set to the above temperature.
Moreover, in the manufacturing method of this invention, it is preferable that it is the hot press method which applies a pressure in the case of thermoforming. In the case of hot press method, the pressure is preferably ^{1~500kgf / cm 2, 3~200kgf / cm} 2 is more preferable.
In the present invention, the fiber reinforced resin sheet and the flame retardant reinforced resin film are thermoformed, but the ratio of both when thermoforming is preferably 99.5: 0.5 to 50:50, 95: 5-70: 30 is more preferable.

  In the production method of the present invention, the flame retardant reinforced resin composition, the fiber reinforced resin sheet, and the flame retardant reinforced resin composition are laminated in this order, and the final product or part is directly formed by insert molding or outsert molding. It can also be processed into a shape.

  In insert molding, for example, a flame retardant reinforced resin film and a fiber reinforced resin sheet are laminated in this order in a cavity of a mold having a desired shape for injection molding, and a flame retardant reinforced resin composition is formed in the outer space. An example is a method of injection molding (injection filling) of a product to obtain a resin molded product. Furthermore, other layers such as an adhesive layer may be included. By performing the insert molding, it is possible to improve the strength of the resin molded product or to form fine irregularities.

  In outsert molding, for example, a method of outsert molding by laminating a flame retardant reinforced resin film, a fiber reinforced resin sheet, and a flame retardant reinforced resin film in this order is rough. In this case, the fiber reinforced resin film and the flame retardant reinforced resin film are stacked and hot pressed. The hot press temperature can be appropriately determined in consideration of the melting point of the thermoplastic resin. Furthermore, by performing hot pressing in a mold having a desired shape, a resin molded product having a desired shape can be obtained.

<Processing method for resin molded products>
The resin molded product of the present invention can be further heated and processed to be press-molded into a part shape. For example, the resin molded product of the present invention can be processed by preheating a sheet-shaped resin molded product, supplying it to a mold, press-molding it into a mold shape, and then cooling it.

  Examples of application of the resin molded product of the present invention processed in this way are electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods and miscellaneous goods. And parts such as automobile interior equipment. Among these, the molded product of the present invention is used particularly for parts such as electric and electronic equipment, OA equipment, information terminal equipment, home appliances, and automobile interior equipment because of its excellent surface appearance, surface hardness, and impact resistance. It is suitable, and is particularly suitable for use in parts of electrical and electronic equipment and automobile interior equipment.

  Examples of the electric and electronic devices include display devices such as personal computers, game machines, televisions, car navigation systems, and electronic paper, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, Examples include a video camera, a mobile phone, a battery pack, a recording medium drive and reading device, a mouse, a numeric keypad, a CD player, an MD player, and a portable radio / audio player. Especially, it can use suitably for the designable parts of housing | casings, such as a television, a personal computer, a car navigation system, and electronic paper.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Polyamide resin>
(Synthesis of polyamide (PAMP6))
After adipic acid is heated and dissolved in a reactor under a nitrogen atmosphere, the contents are stirred and paraxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) and metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) 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 and adipic acid (manufactured by Rhodia) is about 1: 1, Was raised to 270 ° C. After completion of the dropping, the pressure was reduced to 0.06 MPa and the reaction was continued for 10 minutes to adjust the amount of the component having a weight average molecular weight of 1,000 or less. Thereafter, the contents were taken out in a strand shape and pelletized with a pelletizer to obtain polyamide. The obtained polyamide resin MP6 had a melting point of 254 ° C. and a glass transition point of 85 ° C. The number average molecular weight was 15,000. Hereinafter, it is referred to as “PAMP6”.

(Synthesis of polyamide (PAMP10))
After heating and dissolving sebacic acid in a reactor under a nitrogen atmosphere, while stirring the contents, paraxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) and metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) The temperature was raised to 235 ° C. while gradually dropping 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 was about 1: 1. I let you. After completion of the dropping, the reaction was continued for 60 minutes to adjust the amount of the component having a weight average molecular weight of 1000 or less. After completion of the reaction, the contents were taken out in a strand shape and pelletized with a pelletizer to obtain polyamide. The obtained polyamide resin had a melting point of 213 ° C. and a glass transition point of 63 ° C. The number average molecular weight was 16,000. Hereinafter, it is referred to as “PAMP10”.

<Flame Retardant>
<< Manufacture of flame retardant (phosphazene) masterbatch >>
After dry blending 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, barrel setting using “TEX-30α” manufactured by Toshiba Machine Co., Ltd. Melt kneading was performed under the conditions of a temperature of 280 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 20 kg / h to obtain phosphazene master batch pellets (PME90FR).

<<< Raw Materials Used for Masterbatch Production >>>
Polyphenylene ether resin: Made by Mitsubishi Engineering Plastics, PX100L
Phosphazene: Otsuka Chemical, SPS-100
Zinc borate: RIO TINTO, Fire Break ZB

Brominated polystyrene: HP3010, made by Albemarle

<Flame retardant aid>
Zinc borate: RIO TINTO, Fire Break ZB
Antimony trioxide: NIPPON SEIKO, PATOX-M
Magseeds N, manufactured by magnesium hydroxide Mizushima Chemical

Example 1
<Making fiber reinforced resin tape>
Using the PAMP6 synthesized above, a fiber reinforced resin tape was prepared by the following method.
Roving-like glass fiber 18 rolls were arranged at equal intervals, passed through a spreader, and spread to 200 mm width. When the spread glass fiber was put between two upper and lower impregnation rolls, PAMP6 melted by a single screw extruder (manufactured by Ikekai Co., Ltd., VS40) was supplied, and the glass fibers were impregnated with PAMP6 in the impregnation roll. Then, while cooling with a cooling roll, it was taken up and wound around a cylindrical core material to prepare a tape. The set temperature of the extruder was 280 ° C., the rotation speed was 60 rpm, and the take-up speed was 2 mm / min. A tape 50m having a glass content of 50% by weight and a width of 200 mm and a thickness of 0.25 mm was obtained. In the table described later, this is indicated as “PAMP6-impregnated GF sheet”.
Further, in the “PAMP6 impregnated GF sheet”, PAMP6 was changed to PAMP10 and the others were carried out in the same manner to obtain 50 m of a tape having a glass content of 50% by weight and a width of 200 mm and a thickness of 0.25 mm. In the table described later, this is indicated as “PAMP10-impregnated GF sheet”.
Further, in the above “PAMP6 impregnated GF sheet”, PAMP6 was changed to PP (manufactured by Nippon Polypro, Novatec PP MA3), and the setting temperature of the extruder was changed to 200 ° C. A tape 50m having a width of 200 mm and a thickness of 0.25 mm was obtained. In the table described later, this is indicated as “PP-impregnated GF sheet”.

<Manufacture of resin pellets (flame retardant reinforced resin composition)>
Each component is weighed so as to have the composition shown in the table below, blended with a tumbler, put into a twin-screw extruder (Toshiki Machine Co., Ltd., TEM26SS), melted, and resin pellets (flame retardant reinforced resin) Composition). The temperature setting of the extruder was 280 ° C., and the rotation speed was 350 rpm.

上記表において、配合量は、重量部で示した。

In the said table | surface, the compounding quantity was shown by the weight part.

<Creation of flame retardant reinforced resin film>
Using resin pellets (a flame retardant reinforced resin composition), a film was prepared using a short-axis extruder with a 150-mm wide T-die. As film production conditions, the barrel temperature and the die temperature were 280 ° C. and the roll temperature was 80 ° C., and a film having a thickness of about 100 μm was obtained.

<Creation of sheet-shaped resin molded product>
Using a fiber reinforced resin tape and a flame retardant reinforced resin film, a sheet-like molded product was created by a press. Specifically, the above-mentioned fiber reinforced resin tape was cut into a width of 200 mm and a length of 200 mm, and two tapes and a 100 μm flame-retardant reinforced resin film rotated 90 degrees so that the glass fibers were orthogonal to each other were set at a set temperature. The mold was placed in a mold heated to a temperature of 100 mm and press-molded using a 100-ton press. After pressing, water was poured into the mold, and after cooling to 80 ° C., the mold was opened and a sheet-like molded product was taken out. The mold temperature during pressing was 280 ° C., pressure 100 kgf / cm ² , pressing time 5 minutes, and cooling time 20 minutes. The thickness of the obtained sheet-shaped resin molded product was about 0.3 mm.

<Adhesion>
About the sheet-like resin molded product obtained above, the interface between the two materials was enlarged and observed using a digital microscope.
A: It was confirmed that the interface between the two materials was in close contact.
B: It was confirmed that the adhesion between the interfaces of the two materials was insufficient (partially peeled).

<Impact resistance>
About the sheet-like resin molded product obtained above, impact resistance was evaluated by a ball drop test. A 100 g weight was dropped from a height of 50 cm, and a comparison with before dropping was performed.
A: No change before dropping B: The interface between the two materials was peeled off

<Flame retardance evaluation>
The obtained sheet-like resin molded product was tested according to the vertical burn test method shown in UL94 “Burn test for material classification” (hereinafter, UL94) of Underwriters Laboratories, Inc. Specifically, a 125 mm long and 13 mm wide combustion test piece is cut out from a 0.3 mm thick sheet-shaped resin molded product so that the fiber orientation is the long side, and the test piece is vertically attached to the clamp, and 20 mm. A 10-second indirect flame with flame was performed twice, the burning time after the first / second flame contact (T1 / T2) was measured, and the average burning time with five test pieces was calculated.

The results are shown in the table below.

As is clear from the above results, when the sheet-shaped resin molded product of the present invention is used, it has excellent adhesion between the fiber reinforced resin sheet and the flame retardant reinforced resin film, has high impact resistance, and is flame retardant. High resin molded products were obtained (Examples 1 to 4).
On the other hand, when a flame-retardant reinforced resin film was not used (Comparative Example 1), the flame retardancy was poor. Moreover, when not laminating | stacking a fiber reinforced resin sheet and a flame-retardant reinforced resin film so that it might become the layer structure prescribed | regulated by this invention (comparative examples 2-4), it resulted in inferior flame retardance or impact resistance. .
When the resin film which does not mix | blend a flame retardant was used instead of the flame retardant reinforcement | strengthening resin film (comparative example 5), although it was excellent in adhesiveness and impact resistance, it resulted in inferior flame retardance.
In addition, as a resin component of the fiber reinforced resin sheet and the flame retardant reinforced resin film, when the resin of the same system is not used (Comparative Example 6), the film has peeled off, and the impact resistance and flame resistance are tested. could not.

1 Fiber Reinforced Resin Sheet 2 Flame Retardant Reinforced Resin Film 21 First Flame Retardant Reinforced Resin Film 22 Second Flame Retardant Reinforced Resin Film 3 Other Resin Film

Claims (17)

At least one kind of difficulty selected from a thermoplastic resin of the same type as the thermoplastic resin, a phosphorus flame retardant, and a halogen flame retardant, on both sides of a sheet formed from a thermoplastic resin and roving fibers, respectively. Ri Na thermoformed by disposing a composition comprising a retardant,
The fibers are regularly arranged in the sheet;
A resin molded product in which the flame retardant content in the sheet is 0.1% by weight or less . The resin molded product according to claim 1, wherein the amount of the flame retardant is 10 to 90 parts by weight with respect to 100 parts by weight of the thermoplastic resin in at least one of the compositions provided on both surfaces of the sheet. The resin molded product according to claim 1, wherein the amount of the flame retardant is 10 to 90 parts by weight with respect to 100 parts by weight of the thermoplastic resin in both of the compositions provided on both surfaces of the sheet, respectively. The said sheet | seat is a resin molded product of any one of Claims 1-3 formed by superposing | stacking two or more sheets so that a fiber may orthogonally cross, arrange | positioning the said composition on both surfaces, and thermoforming. The resin molded product according to any one of claims 1 to 4, wherein the fiber is impregnated with a thermoplastic resin contained in the sheet. The resin molded product according to any one of claims 1 to 5, wherein the thermoplastic resin contained in the sheet is a polyamide resin. The resin molded product according to any one of claims 1 to 6, wherein the fiber is a glass fiber. The resin molded product according to any one of claims 1 to 7, wherein the resin molded product has a portion having a thickness of 0.5 mm or less by 1 cm ² or more. 9. The composition according to claim 1, wherein the composition comprising a thermoplastic resin of the same system as the thermoplastic resin and at least one flame retardant selected from a phosphorus-based flame retardant and a halogen-based flame retardant is a film. The resin molded product according to Item 1. At least one sheet selected from a thermoplastic resin and roving-like fibers, at least two thermoplastic resins of the same system as the thermoplastic resin, a phosphorus-based flame retardant, and a halogen-based flame retardant look including a film made from a composition comprising a flame retardant, wherein the fibers are regularly arranged to have, a thermoplastic resin molded article produced kit during the sheet. The kit for manufacturing a thermoplastic resin molded article according to claim 10, wherein the fiber is impregnated with a thermoplastic resin contained in the sheet. At least one kind of difficulty selected from a thermoplastic resin of the same type as the thermoplastic resin, a phosphorus flame retardant, and a halogen flame retardant, on both sides of a sheet formed from a thermoplastic resin and roving fibers, respectively. look including the thermoforming by disposing a composition comprising a retardant, said fibers, a method of manufacturing a resin molded article are regularly arranged in a said seat. The said sheet | seat is a manufacturing method of the resin molded product of Claim 12 which laminates | stacks two or more sheets so that a fiber may orthogonally cross, arrange | positions the said composition on the both surfaces, and thermoforms. The step of thermoforming by arranging the composition includes thermoforming a film made of a composition comprising at least one flame retardant selected from a phosphorus-based flame retardant and a halogen-based flame retardant. Item 14. A method for producing a resin molded article according to Item 12 or 13. The method for producing a resin molded product according to any one of claims 12 to 14, wherein the thermoforming is a hot press method. The method for producing a resin molded product according to any one of claims 12 to 14 , wherein the thermoforming is insert molding or outsert molding. The processing method of a resin molded product including further heating the resin molded product of any one of Claims 1-9.

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