JP2014196448A - Electric-field-shielded crystalline thermoplastic resin molding, method of producing the same and housing for electronic apparatus for transport having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fire-retardant electric-field-shielded crystalline thermoplastic resin molding which has chemical and heat resistances.SOLUTION: An electric-field-shielded crystalline thermoplastic resin molding is a molding of a crystalline thermoplastic resin composition containing a fire-retardant crystalline thermoplastic resin having a fire retardancy of V-1 or higher, based on the UL94 inflammability test with a test specimen of a thickness of 1.6 mm, and a carbide layer is formed on its surface by irradiation of electromagnetic waves. The carbide layer has a diffraction peak at a specified Bragg angle (2θ) in the X-ray diffraction spectrum based on the wide-angle diffraction method. The molding has excellent shielding properties in a relatively low frequency zone and is light and thus suitable as an electric wave shielding material in transports, including automobiles, trains and aircrafts.

Description

  The present invention relates to an electric field shield crystalline thermoplastic resin molded article, a method for producing the same, and a casing of an electronic device for transport aircraft having the electric field shield crystalline thermoplastic resin molded article.

  In recent years, in addition to personal computers, OA equipment, AV equipment, mobile phones, telephones, facsimiles, home appliances, toy products, flat panel displays, etc., errors in electronic equipment such as automobiles, railway vehicles, and aircraft electronic equipment for transportation In order to prevent operation, a radio wave shielding material having a high electric field shielding property is being used as a casing. Among other things, radio noise caused by electronic equipment used in transport aircraft is a cause of audio disturbance of AM / FM radio (0.3-30 MHz), which is a relatively low frequency band, and viewing disturbance of digital TV broadcasting (440-710 MHz). Therefore, it is desired to improve the electric field shielding property. In addition, from the viewpoint of improving fuel consumption, light-weight shielding materials for transport aircraft are also required to be reduced in weight.

  In this respect, there is an increasing need for a radio wave shielding material made of a resin material. As an example, a carbide layer is formed by laser irradiation on a housing component made of a thermoplastic resin composition or a thermosetting resin composition, and a part or all of the carbide layer is connected to the ground to express a shielding characteristic. It has been proposed (see Patent Document 1).

JP 2003-238712 A

  However, since the resin material used in Patent Document 1 is modified poniphenylene ether (modified PPE), it may have sufficient flame resistance, but chemical resistance (gasoline, light oil, oil, grease, etc.), heat resistance Have important issues. Furthermore, an alloy mainly composed of an amorphous polymer such as modified PPE has poor fluidity and has a problem in moldability.

  The present invention has been made to solve the above-described problems, and its purpose is to provide a flame-retardant electric field shielded crystalline thermoplastic resin molded product having chemical resistance and heat resistance. is there.

  The inventors of the present invention have made extensive studies in order to solve the above problems. As a result, a Bragg angle (2θ) 25 in an X-ray diffraction spectrum based on a wide-angle X-ray diffraction method is obtained by irradiating the surface of a molded article of a thermoplastic resin composition containing a flame-retardant crystalline thermoplastic resin with an electromagnetic wave. It has been found that a carbide having a diffraction peak at ˜27 ° is formed, and as a result, a flame-retardant electric field shielded crystalline thermoplastic resin molded article having chemical resistance and heat resistance can be provided. Specifically, the present invention provides the following.

  (1) The present invention relates to a crystallinity containing a flame-retardant crystalline thermoplastic resin having a flame retardancy of V-1 or higher in accordance with the UL94 flammability test when the thickness of the test piece is 1.6 mm. A molded article of a thermoplastic resin composition, a carbide layer having a diffraction peak at a Bragg angle (2θ) of 25 to 27 ° in an X-ray diffraction spectrum based on a wide-angle X diffraction method is formed on the surface by electromagnetic wave irradiation, and the frequency An electric field shielding crystalline thermoplastic resin molded article having an electric field shielding property of 3 dB or more by an Advantest test method or KEC method for electromagnetic waves having a frequency of 1 GHz or less, or a coaxial tube method for electromagnetic waves having a frequency of 1 GHz or more and 18 GHz or less.

  (2) Moreover, this invention is an electric field shield crystalline thermoplastic resin molded article as described in (1) whose said flame-retardant crystalline thermoplastic resin is a flame-retardant crystalline aromatic polymer.

  (3) Moreover, this invention is an electric field shield crystalline thermoplastic resin molded article as described in (2) in which the said flame-retardant crystalline aromatic polymer has a sulfur atom and / or an oxygen atom in a molecule | numerator. .

  (4) Further, the present invention provides the electric field shielded crystalline thermoplastic resin molding according to (2) or (3), wherein the flame-retardant crystalline aromatic polymer is polyarylene sulfide and / or polyalkylene arylate. It is a product.

  (5) In the present invention, when the flame-retardant crystalline aromatic polymer is polyarylene sulfide, the polyarylene sulfide is polyphenylene sulfide, and the crystalline aromatic polymer is polyalkylene arylate. The polyalkylene arylate is an electric field shielded crystalline thermoplastic resin molded article according to (4), which is polybutylene terephthalate.

  (6) The electric field shield according to (4) or (5), wherein the flame-retardant crystalline aromatic polymer is a polymer alloy based on the polyarylene sulfide or the polyalkylene arylate. It is a crystalline thermoplastic resin molded article.

  (7) In the present invention, the crystalline thermoplastic resin composition further contains an electromagnetic wave absorber, and the electromagnetic wave absorber is at least one selected from carbon black, carbon fiber, or graphite. ) To (6), the electric field shielded crystalline thermoplastic resin molded article.

  (8) Further, in the present invention, the crystalline thermoplastic resin composition further contains a flame retardant and / or a flame retardant aid, The electric field shielded crystalline heat according to any one of (1) to (7) It is a plastic resin molded product.

  (9) Further, in the present invention, when the crystalline thermoplastic resin composition further contains the flame retardant, the flame retardant is a phosphorus flame retardant and / or a halogen flame retardant. The electric field shield crystalline thermoplastic resin molded article.

  (10) Further, in the present invention, when the flame retardant is a phosphorus flame retardant, the phosphorus flame retardant is a dialkylphosphinic acid metal salt, and when the flame retardant is a halogen flame retardant, the halogen flame retardant The field-shielding crystalline thermoplastic resin molding according to (9), wherein the flame retardant is at least one selected from halogenated aromatic bisimide, halogenated benzyl acrylate, halogenated polystyrene, halogenated polycarbonate, or halogenated aromatic epoxy. It is a product.

  (11) Further, in the present invention, when the crystalline thermoplastic resin composition further contains the flame retardant aid, the flame retardant aid is selected from a metal oxide, a nitrogen-containing compound, or an aromatic resin. The electric field shield crystalline thermoplastic resin molded article according to (8), which is at least one kind.

  (12) Further, in the present invention, when the flame retardant aid is a metal oxide, the metal oxide is at least one selected from an antimony compound, a boric acid compound, or a tin compound, and the flame retardant When the auxiliary agent is a nitrogen-containing compound, the nitrogen-containing compound is at least one selected from melamine, melam, melem, melon, melamine cyanurate, melamine phosphate, melamine polyphosphate, melamine melam melem polyphosphate double salt When the flame retardant aid is an aromatic resin, the aromatic resin is at least one selected from a novolac resin, a phenol aralkyl resin, a polyphenylene ether resin, a polycarbonate resin, and a polyetherimide resin. (11) It is an electric field shield crystalline thermoplastic resin molded article as described in (11).

  (13) Moreover, this invention is an electric field shield crystalline thermoplastic resin molded article in any one of (1) to (12) whose said electromagnetic waves are laser beams.

  (14) Moreover, this invention is an electric field shield crystalline thermoplastic resin molded product in any one of (1) to (13) which is an injection molded product or an extrusion molded product.

  (15) Moreover, this invention is a housing | casing of the electronic device for transport aircraft which has the electric field shield crystalline thermoplastic resin molded product in any one of (1) to (14).

  (16) Moreover, this invention contains the flame-retardant crystalline thermoplastic resin whose flame retardance based on UL94 flammability test when the thickness of a test piece is 1.6 mm is V-1 or more. Irradiation of electromagnetic waves to the surface of a molded article of a crystalline thermoplastic resin composition to form a carbide having a diffraction peak at a Bragg angle (2θ) of 25 to 27 ° in an X-ray diffraction spectrum based on a wide angle X diffraction method It is a manufacturing method of an electric field shield crystalline thermoplastic resin molding including a process.

  (17) Further, in the electromagnetic wave irradiation step, the present invention irradiates the surface of the molded article with a laser beam having a center frequency of 1 kHz or more once or more, and then applies a continuous wave laser beam having a center frequency of 0 kHz. The method for producing an electric field shielding resin molded product according to (16), wherein the surface of the molded product is irradiated a plurality of times.

  (18) Further, in the present invention, after the electromagnetic wave irradiation step, the entire surface of the molded article of the crystalline thermoplastic resin composition is gradually baked or melted with a laser beam of weak energy (16) or (17 The method for producing an electric field shielding resin molded product according to (1).

  According to the present invention, a flame-retardant electric field shield crystalline thermoplastic resin molded article having chemical resistance and heat resistance can be provided.

It is a figure which shows the relationship between the frequency by the Advantest method, and electric field shielding property of the electric field shielding resin molded product which concerns on Examples 1-3 and Comparative Examples 1-3. It is a figure which shows the relationship between the frequency and electric field shielding property by the Advantest method of the electric field shielding resin molding which concerns on Examples 4-6 and Comparative Examples 4-6. It is a figure which shows the relationship between the frequency by the KEC method, and electric field shielding property of the electric field shielding resin molded product which concerns on Example 1,3 and Comparative Example 1,3. It is a figure which shows the relationship between the frequency by the KEC method, and electric field shielding property of the electric field shielding resin molding which concerns on Example 5 and Comparative Example 5. FIG. It is a figure which shows the relationship between the frequency by the coaxial tube method, and electric field shielding property of the electric field shielding resin molded product which concerns on Examples 1, 3 and Comparative Examples 1, 3. FIG. It is a figure which shows the relationship between the frequency by the coaxial tube method of the electric field shielding resin molded product which concerns on Example 5, and Comparative Example 5, and electric field shielding property. It is the plane photograph and enlarged photograph of the electric field shielding resin molding which concern on Example 2. FIG. 10 is an enlarged photograph of an electric field shielding resin molded product according to Comparative Example 7. The SEM photograph of the electric field shielding resin molding before and after the post-process by a laser beam is shown. 3 is an X-ray diffraction spectrum based on a wide angle X diffraction method according to Examples 21 and 22. FIG.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. .

<Electric field shielded crystalline thermoplastic resin molded product>
The electric field shielded crystalline thermoplastic resin molded article of the present invention is a molded article of a thermoplastic crystalline thermoplastic resin composition containing a flame retardant crystalline thermoplastic resin, and has a wide-angle X by irradiation of electromagnetic waves on the surface. A carbide layer having a specific X-ray diffraction peak based on the diffraction method is formed.

[Crystalline thermoplastic resin composition]
[Flame-retardant crystalline thermoplastic resin]
In this specification, flame retardance means that the flame retardance based on UL94 flammability test when the thickness of a test piece is 1.6 mm is V-1 or more. If the flame retardancy of the resin is less than V-1, the reliability may decrease, which is not preferable. In addition, when the resin has a slow flammability conforming to the UL94 flammability test, even if the surface of the resin molded product is irradiated with electromagnetic waves, the surface of the resin molded product cannot be sufficiently carbonized, resulting in a sufficient electric field. Since it may not have a shielding property, it is not preferable.

  Further, the resin has thermoplasticity. When the resin is a thermosetting resin, productivity and recyclability are lowered, which is not preferable.

  The resin has crystallinity. When the resin is amorphous, the chemical resistance, heat resistance, and moldability are inferior, which is not preferable.

  Although resin will not be specifically limited if it has a flame retardance, thermoplasticity, and crystallinity, It is preferable that it is an aromatic polymer which has a benzene ring in a molecule | numerator. By using the aromatic polymer, a carbide layer can be efficiently formed on the surface of the resin molded product. In this specification, even a polymer having an aromatic compound in which a portion that does not contribute to the polymerization on the benzene ring is substituted in the molecule falls under “aromatic polymer having a benzene ring in the molecule”. And Further, even a polymer having a polycyclic structure such as a naphthalene ring or an anthracene ring in the molecule falls under the “aromatic polymer having a benzene ring in the molecule”.

  From the viewpoint of heat resistance, the aromatic polymer is preferably a crystalline aromatic polymer having a sulfur atom and / or an oxygen atom in the molecule.

  From the viewpoint of moldability, the aromatic polymer is preferably polyarylene sulfide or polyalkylene arylate. When the aromatic polymer is polyarylene sulfide, the polyarylene sulfide is preferably polyphenylene sulfide. When the aromatic polymer is polyalkylene arylate, the polyalkylene arylate is preferably polybutylene terephthalate.

  From the viewpoint of flame retardancy, the aromatic polymer is preferably a polymer alloy based on polyarylene sulfide or polyalkylene arylate.

  The blending amount of the flame retardant crystalline thermoplastic resin thermoplastic resin is preferably 10 parts by weight or more with respect to 100 parts by weight of the crystalline thermoplastic resin composition. If it is less than 10 parts by weight, flame retardancy of V-1 or higher may not be achieved, which is not preferable.

[Electromagnetic wave absorber]
Although not essential, the crystalline thermoplastic resin composition may further contain an electromagnetic wave absorber. In the case of further containing an electromagnetic wave absorber, when a surface of the molded article of the crystalline thermoplastic resin composition is irradiated with electromagnetic waves, a better carbide layer can be formed, and as a result, sufficient electric field barrier properties can be obtained. Is preferable.

  Specific examples of the electromagnetic wave absorber include carbon black, carbon fiber, or graphite. Since these carbides have electrical conductivity, as a result, when the surface of the molded article of the crystalline thermoplastic resin composition is irradiated with electromagnetic waves, the electromagnetic wave absorber suitably promotes carbonization of the crystalline resin, and a good carbide layer As a result, a sufficient electric field barrier property is obtained.

  When the electromagnetic wave absorber is carbon black, the type of carbon black is not particularly limited. Any carbon black such as SAF, ISAF, HAF, FEF, GPF, SRF, FT, and acetylene black may be used. That is, any production method such as furnace black, channel black, thermal black, etc. may be used, and any raw material such as gas black, oil black, acetylene black, etc. may be used.

  When an electromagnetic wave absorber is added, in order to obtain a significant effect by adding the electromagnetic wave absorber, the blending amount of the electromagnetic wave absorber is 0.1 parts by weight or more and 10 parts by weight with respect to 100 parts by weight of the crystalline thermoplastic resin composition. The amount is preferably 0.3 parts by weight or less, and more preferably 0.3 parts by weight or more and 3 parts by weight or less. If it is less than 0.1 part by weight, there is a possibility that a significant electric field barrier property due to the addition of the electromagnetic wave absorber cannot be obtained. If the amount exceeds 10 parts by weight, the amount of the flame-retardant crystalline thermoplastic resin thermoplastic resin is too small, and the physical properties may be deteriorated.

[Flame retardant and / or flame retardant aid]
Moreover, in order to form a carbide layer suitably, it is preferable that a crystalline thermoplastic resin composition further contains a flame retardant and / or a flame retardant aid.

((Flame retardants))
When the electric field shield crystalline thermoplastic resin molded article contains a flame retardant, the flame retardant is preferably a phosphorus flame retardant and / or a halogen flame retardant from the viewpoint of flame retardant imparting performance.

(Phosphorus flame retardant)
When the flame retardant is a phosphorus flame retardant, examples of the phosphorus flame retardant include organic phosphinic acid or a salt thereof (hereinafter also referred to as “organic phosphinic acid compound”).

  As an organic phosphinic acid compound, phosphinic acid or bisphosphinic acid condensed with phosphinic acid is substituted with an organic group (such as an optionally substituted hydrocarbon group), an organic group-substituted phosphinic acid, a polyvalent phosphinic acid ( A polyvalent phosphinic acid in which a plurality of phosphinic acids are linked by a polyvalent organic group), or a salt thereof [a salt with at least one salt-forming component selected from a metal, boron, ammonium and a basic nitrogen-containing compound (metal) Salts, boron salts (boryl compounds, etc.), ammonium salts, salts with amino group-containing nitrogen-containing compounds, etc.].

From the viewpoint of heat resistance, the organic phosphinic acid is preferably an organic phosphinic acid (such as bisphosphinic acid) represented by the following general formula (1).

In the general formula (1), examples of the hydrocarbon group represented by R ¹ and R ² include an aliphatic hydrocarbon group [an alkyl group (straight or branched chain such as methyl, ethyl, t-butyl group, etc.] C _1-20 alkyl group, etc.), alkenyl group (linear or branched C _2-20 alkenyl group such as vinyl, allyl, isopropenyl group, etc.)], alicyclic hydrocarbon group [cycloalkyl group ( C _5-10 cycloalkyl group such as cyclohexyl group)], aromatic hydrocarbon group [aryl group (C _6-10 aryl group such as phenyl group)], aralkyl group (C _6-10 aryl such as benzyl group) _-C1-4 alkyl group, etc.)] and the like.

The ring formed by combining R ¹ and R ² together with the adjacent phosphorus atom is a heterocycle (phosphorus atom-containing heterocycle) having the phosphorus atom as a heteroatom constituting the ring, and is usually a 4- to 20-membered heterocycle. A ring, preferably a 5- to 16-membered heterocycle is mentioned. The phosphorus atom-containing heterocycle may be a bicyclo ring. The phosphorus atom-containing heterocycle may have an unsaturated group (alkenylene group, alkynylene group, etc.) and / or a substituent in the ring.

Examples of the substituent of the hydrocarbon group and the phosphorus atom-containing heterocycle include a halogen atom (fluorine, chlorine, bromine, iodine atom, etc.) and an alkyl group (methyl, ethyl, t-butyl group, etc.) -Like C _1-6 alkyl group, etc.), alkenyl group (linear or branched C _2-6 alkenyl group such as vinyl group, etc.), cycloalkyl group exemplified above, aryl group exemplified above, aralkyl exemplified above. Group, hydroxyl group, alkoxy group (linear or branched C _1-4 alkoxy group such as methoxy and ethoxy group), carboxyl group, acyl group (C _2-6 acyl group such as acetyl group), alkoxy carbonyl group (C _1-4 alkoxy such as methoxy carbonyl group - carbonyl group), an amino group, N- substituted amino group (methylamino group, alkylamine such as dimethylamino group Amino group etc.), a nitro group, a cyano group, an oxo group (= O) and the like. The hydrocarbon and phosphorus atom-containing heterocycle may have one of the above-described substituents and may have a plurality of the same or different substituents.

Examples of the organic phosphinic acid (1) include compounds such as the following formulas (1a) and (1b).

In the formula, rings Z ¹ and Z ² may be the same or different, and represent a 4- to 10-membered ring containing a phosphorus atom as a constituent atom of the ring, and may have the substituent. R ¹ and R ² are the same as described above. Incidentally, the bicyclo ring formed by ring Z ^1, and the ring Z ¹ and the ring Z ^2, in the formula (1), the ring (phosphorus atom-containing hetero forming together with the phosphorus atom to which R ¹ and R ² are adjacent Corresponding to the ring).

The number of members of rings Z ¹ and Z ² may be preferably 4 to 8 members, more preferably about 5 to 6 members. In the heterocycles Z ¹ and Z ² , the heterocycle may have 1 to 2 carbon-carbon unsaturated bonds.

In the formula (1a), R ¹ and R ² are preferably an alkyl group (C _1-16 alkyl group etc.) optionally having a substituent (hydroxyl group, carboxyl group, alkoxy group etc.). .

  Examples of metals that form organic phosphinates include periodic table group 1 metals (alkali metals) (potassium, sodium, etc.), periodic table group 2 metals (alkaline earth metals) (magnesium, calcium, barium, etc.), periodicity. Group 4 metals (titanium, zirconium, etc.), transition metals (periodic table group 7 metals such as manganese; periodic table group 8 metals such as iron; periodic table group 9 metals such as cobalt; periodic table such as nickel Group 10 metal; Periodic table Group 11 metal such as copper), Periodic table Group 12 metal such as zinc, Group 13 metal of periodic table such as aluminum, and the like. These metals can be used alone or in combination of two or more. Among these metals, at least one selected from Group 1 metal, Group 2 metal, Group 4 metal, Group 8 metal, Group 12 metal and Group 13 metal of the periodic table, in particular, Periodic Table 2 Group metals and / or Group 13 metals of the periodic table are preferred. The metal salt may be a hydrate salt such as a hydrate magnesium salt, a hydrate calcium salt, a hydrate aluminum salt, a hydrate zinc salt, and the like. The metal salt also includes a salt in which a metal is partially oxidized (for example, titanyl salt, zirconyl salt, etc.).

  Examples of basic nitrogen-containing compounds that form salts include nitrogen-containing compounds having amino groups [aminotriazine compounds (melamine, guanamine, benzoguanamine and / or condensates thereof (melamine condensates such as melam, melem, melon, etc.) Etc.), guanidine compounds (guanidine etc.), etc.], urea compounds (urea etc.) and the like. The basic nitrogen-containing compounds can be used alone or in combination of two or more. Of these nitrogen-containing compounds, aminotriazine compounds (melamine, melamine condensate, etc.) are particularly preferable.

  These salt-forming components can be used alone or in combination of two or more. The organic phosphinic acid salt includes a double salt of an organic phosphinic acid and a plurality of salt forming components, for example, a melamine, melam, melem, double salt, melamine, melam, melem, melon, and the like.

Specific examples of the organic phosphinic acid compound include the organic phosphinic acid represented by the formula (1a) or a salt thereof, for example, an alkylphosphinic acid [dialkylphosphinic acid (diC _1-10 ) which may have a substituent. Alkylphosphinic acid, etc.), for example, dimethylphosphinic acid, methylethylphosphinic acid, diethylphosphinic acid, ethyl (n-, iso- or t-) butylphosphinic acid, di-n-propylphosphinic acid, diisopropylphosphinic acid, di-n- Dialkylphosphinic acids such as butylphosphinic acid, diisobutylphosphinic acid, di-t-butylphosphinic acid, dipentylphosphinic acid, dioctylphosphinic acid; (hydroxymethyl) methylphosphinic acid, (hydroxyethyl) methylphosphinic acid, bis (hydroxymethyl) phosphine Acid, bi Hydroxyl group-containing dialkylphosphinic acids such as (hydroxyethyl) phosphinic acid; Carboxyl group-containing dialkylphosphinic acids such as (2-carboxyethyl) methylphosphinic acid; Alkoxy group-containing dialkylphosphinic acids such as (methoxymethyl) methylphosphinic acid, etc. ], _{C 6-10} aryl phosphinic acids and aryl phosphinic acid [phenyl phosphinic acid; and di _{C 6-10} aryl phosphinic acid such as diphenyl phosphinic acid], C1-4 alkyl and alkyl aryl phosphinic acid (methylphenyl phosphinic acid -C _6-10 aryl - and phosphinic acid), and salts of these organic phosphinic acid (dimethyl phosphinic acid Ca salt, methyl ethyl phosphinic acid Ca salt, diethyl phosphinic acid Ca salt, di (n- or iso -) Puropiruhosu Phosphate Ca salt, di (n-, iso- or t-) butylphosphinic acid Ca salt, ethyl (n- or iso-) propylphosphinic acid Ca salt, ethyl (n-, iso- or t-) butylphosphine Acid Ca salt, di (n-, iso- or t-) butylphosphinic acid Ca salt, dipentylphosphinic acid Ca salt, dioctylphosphinic acid Ca salt, (2-carboxyethyl) methylphosphinic acid Ca salt and calcium salts thereof Corresponding alkaline earth metal salts such as Mg salt; dimethylphosphinic acid Al salt, methylethylphosphinic acid Al salt, diethylphosphinic acid Al salt, di (n- or iso-) propylphosphinic acid Al salt, di (n-, Iso- or t-) butyl phosphinic acid Al salt, ethyl (n- or iso-) propyl phosphinic acid Al salt, ethyl (n-, iso- or t) ) Aluminum salts such as butylphosphinic acid Al salt, dipentylphosphinic acid Al salt, dioctylphosphinic acid Al salt, (2-carboxyethyl) methylphosphinic acid Al salt; dimethylphosphinic acid Ti salt, methylethylphosphinic acid Ti salt, diethylphosphine Acid Ti salt, di (n- or iso-) propylphosphinic acid Ti salt, di (n-, iso- or t-) butylphosphinic acid Ti salt, ethyl (n- or iso-) propylphosphinic acid Ti salt, ethyl (N-, iso- or t-) butylphosphinic acid Ti salt, dipentylphosphinic acid Ti salt, dioctylphosphinic acid Ti salt, (2-carboxyethyl) methylphosphinic acid Ti salt and titanyl salts corresponding to these salts, etc. Titanium salt: Zn dimethylphosphinate, Zn diethylphosphinate, Zn salt of tilethylphosphinic acid, Zn salt of di (n- or iso-) propylphosphinic acid, Zn salt of di (n-, iso- or t-) butylphosphinic acid, Zn of ethyl (n- or iso-) propylphosphinic acid Salts, zinc salts such as ethyl (n-, iso- or t-) butylphosphinic acid Zn salt, dipentylphosphinic acid Zn salt, dioctylphosphinic acid Zn salt, (2-carboxyethyl) methylphosphinic acid Zn salt; dimethylphosphinic acid Melamine salt, melamine methylethylphosphinate, melamine diethylphosphinate, melamine di (n- or iso-) propylphosphinate, melamine di (n-, iso- or t-) butylphosphinate, ethyl (n -Or iso-) propylphosphinic acid melamine salt, ethyl (n-, iso- or t-) butylphosphite Acid melamine salt, dipentylphosphinic acid melamine salt, dioctylphosphinic acid melamine salt, (2-carboxyethyl) methylphosphinic acid melamine salt, salts with aminotriazine compounds such as melamine, melam, melem double salt corresponding to these melamine salts Etc.).

Specific examples of the organic phosphinic acid compound include organic phosphinic acid represented by the above formula (1b) or a salt thereof, such as 1-hydroxy-1H-phosphorane-1-oxide, 2-carboxy-1-hydroxy- Alkylene phosphinic acid (C _3-8 alkylene phosphinic acid etc.) _optionally having a substituent such as 1H-phosphorane-1-oxide; Alkenylene phosphinic acid (C _3-8 alkenylene phosphinic acid etc.); 1,3-cyclobutylene phosphinic acid, 1,3-cyclopentylene phosphinic acid, 1,4-cyclooctylene phosphinic acid, 1,5-cyclo octylene cycloalkylene phosphinic acids such as Ren phosphinic acid (C _4-10 cycloalkylene phosphinic acid); or These salts (metal salts such as 1-hydroxy-1H-phosphorane-1-oxide alkaline earth metal salts (Ca salt, Mg salt, etc.), Al salt, Ti salt, titanyl salt, Zn salt; melamine salt, Aminotriazine salts such as melamine, melam, and melem double salts).

Among the preferred organic phosphinic acid compounds, specific examples of the polyvalent phosphinic acid include polyvalent phosphinic acids in which a plurality of phosphinic acids (or organic phosphinic acids) are linked by a polyvalent organic group, such as alkanebisphosphines. acid [such as ethane-1,2-bis (phosphinate) _{C 1-10} Arukanbisu (phosphinic acid), such as], _{C 1} such Arukanbisu (alkyl phosphinic acid) [ethane-1,2-bis (methyl phosphinic acid) _-10 alkanebis (C _1-6 alkylphosphinic acid) etc.], or a salt thereof. Examples of the salt include metals such as Ca salt of ethane-1,2-bisphosphinic acid, Ca salt of ethane-1,2-bis (methylphosphinic acid), Mg salt, Al salt, Zn salt, Ti salt, or titanyl salt. Salt; ethane-1,2-bisphosphinic acid melamine salt, ethane-1,2-bis (methylphosphinic acid) melamine salt, melam salt, melem salt, salt with nitrogen-containing compound such as melamine melam memel double salt Etc.

  Specific examples of the organic phosphinic acid salt include, for example, JP-A-55-5979, JP-A-8-73720, JP-A-9-278784, JP-A-11-236392, JP-A-2001-2686. Gazette, JP-A-2004-238378, JP-A-2004-269526, JP-A-2004-269984, JP-A-2004-346325, JP-T-2001-513784, JP-A-2001-525327, JP 2001-525328 A, JP 2001-525329 A, JP 2001-540224 A, US Pat. No. 4,180,495, US Pat. No. 4,083,321, US Pat. No. 4,083,322, US Pat. No. 6,229,044, US Pat. No. 6,303,674 Compounds that are mounting the like.

  Among these, from the viewpoint of excellent flame retardancy imparting ability, thermal stability, blooming resistance, and comparative tracking index (CTI), the phosphorus flame retardant is preferably a dialkylphosphinic acid metal salt.

(Halogen flame retardant)
When the flame retardant is a halogen flame retardant, the type thereof is not particularly limited, and examples thereof include organic halides. The organic halide usually contains at least one halogen atom selected from chlorine, bromine and iodine atoms.

Examples of halogen flame retardants include halogen-containing acrylic resins [halogenated polybenzyl (meth) acrylate resins such as polybrominated polybenzyl (meth) acrylates such as poly (pentabromobenzyl (meth) acrylate), poly (penta) Halogenated benzyl (meth) acrylates such as chlorobenzyl (meth) acrylate) or halogenated styrene resins [halogenated polystyrene (brominated polystyrene, chlorinated polystyrene, etc., halogenated styrene resins)] Treated halides, halogenated styrene monomers alone or copolymers, etc.)], halogen-containing polycarbonate resins (brominated polycarbonates, halogenated polycarbonates such as chlorinated polycarbonate, etc.), halogen-containing epoxy compounds ( Halogenated epoxy resins such as hydrogenated epoxy resins and chlorinated epoxy resins; halogenated phenoxy resins such as brominated phenoxy resins), halogen-containing phosphate esters [eg tris (bromoethyl) phosphate, tris (mono or dibromopropyl)] Bromine-containing phosphate esters such as phosphate, tris (mono or dibromobutyl) phosphate, tris (mono to tribromoneopentyl) phosphate, bis (tribromoneopentyl) phenyl phosphate, tris (mono to tribromophenyl) phosphate, etc.] Halogen-containing triazine compounds (for example, bromine-containing triazine compounds such as tris (tribromophenoxy) triazine), halogen-containing isocyanuric acid compounds [for example, tris (2,3-dibromopropyl) isocyanate Nurate, tris (2,3,4-tribromobutyl) isocyanurate, bromine-containing isocyanuric acid compounds such as tris (pentabromobenzyl) isocyanurate], halogenated polyarylether compounds [for example, octa to decabromodiphenyl ether, Bis (halogenated aryl) ethers such as octa to decachlorodiphenyl ether (for example, bis (halogenated phenyl) ethers); Halogen-containing polyphenylene oxide resins such as brominated polyphenylene ethers], halogenated aromatic imide compounds [for example , brominated aromatic imide compounds such as ethylene bis-brominated phthalimides (e.g., bisimide compounds), etc.], halogenated bis-aryl compound [e.g., bis such brominated diphenyl (halogenated C _6-10 aryl ; Bis brominated diphenylmethane (halogenated C _6-10 aryl) C _1-4 alkane; brominated halogenated bisphenols or their derivatives of bisphenol A such as (brominated polyesters obtained by polymerizing an ethylene oxide adduct of halogenated bisphenols Etc.], halogenated alicyclic hydrocarbons (bridged saturated or unsaturated halogenated alicyclic hydrocarbons, for example, halogenated polycycloalkadienes such as dodecachloropentacyclooctadeca-7,15-diene Etc.). Halogen flame retardants can be used alone or in combination of two or more.

  Among these, from the viewpoint of heat resistance, the halogen flame retardant is preferably at least one selected from halogenated aromatic bisimide, halogenated benzyl acrylate, halogenated polystyrene, halogenated polycarbonate, or halogenated aromatic epoxy.

  Among them, from the viewpoint of imparting flame retardancy, the halogen flame retardant is preferably a compound containing a chlorine atom and / or a bromine atom, particularly an organic bromide containing a bromine atom [bromine-containing acrylic resin, bromine-containing Styrene resins, bromine-containing polycarbonate resins, bromine-containing epoxy compounds (bromine-containing epoxy resins such as brominated epoxy resins, bromine-containing phenoxy resins such as brominated phenoxy resins), bromine-containing phosphate esters, bromine-containing triazine compounds, Bromine atom-containing flame retardants such as bromine-containing isocyanuric acid compounds, brominated polyaryl ether compounds (such as bis (brominated aryl) ether compounds such as octabromodiphenyl ether), brominated aromatic imide compounds, brominated bisaryl compounds, etc.] Is preferred.

((Flame retardant aid))
Flame retardant aids include aromatic resins [phenolic resins, aniline resins, polyphenylene oxide resins, aromatic epoxy resins (bisphenol A type epoxy resins, novolac type epoxy resins, etc.), phenoxy resins (bisphenol A type phenoxy resins). Etc.), polyphenylene sulfide resin, polycarbonate resin, polyarylate resin, aromatic polyamide resin, aromatic polyester resin that may be liquid crystalline, aromatic polyester amide resin that may be liquid crystalline, etc.], containing antimony Compounds, molybdenum-containing compounds (such as molybdenum oxide), tungsten-containing compounds (such as tungsten oxide), bismuth-containing compounds (such as bismuth oxide), tin-containing compounds (such as tin oxide), iron-containing compounds (such as iron oxide), copper-containing compounds (Copper oxide, etc.), phosphorus content Products [phosphorus-containing compounds other than (condensed) phosphate aminotriazine salts, such as phosphate esters, condensed phosphate esters, phosphate ester amides (phosphoramides, etc.), condensed phosphate ester amides, phosphonitrile compounds [eg (cross-linking Non-crosslinked or crosslinked aryloxyphosphazenes such as phenoxyphosphazene, (crosslinked) tolyloxyphosphazene, (crosslinked) xylyloxyphosphazene, (crosslinked) tolyloxyphenoxyphosphazene, (crosslinked) xylyloxyphenoxyphosphazene], organic phosphonic acid A compound or an organic phosphonous acid compound (for example, organic (phosphorous) phosphonic acid ester, organic (phosphorous) phosphonic acid aminotriazine salt, organic (phosphorous) phosphonic acid metal salt, etc.); red phosphorus, boron phosphate, (Nitrous) metal phosphate, hypophosphorous acid Inorganic compounds such as metal salts], silicon-containing compounds [(poly) organosiloxane, layered silicates, etc.], sulfur-containing compounds (organic sulfonic acid compounds, metal salts of perfluoroalkanesulfonic acids, sulfamic acid compounds or salts thereof) Etc.), fluorine-containing resins and the like. These flame retardant aids can be used alone or in combination of two or more. In addition, as the flame retardant aid, components different from the base resin are usually used. In particular, when the flame retardant aid is a resinous flame retardant aid (aromatic resin such as aromatic polyester resin, aromatic polyamide resin, polycarbonate resin, polyphenylene oxide resin, polyphenylene sulfide resin, etc.) A resin different from the resin is used.

  From the viewpoint of imparting flame retardancy, the flame retardant aid is preferably at least one selected from metal oxides, nitrogen-containing compounds, or aromatic resins. When the flame retardant aid is a metal oxide, the metal oxide is preferably at least one selected from an antimony compound, a boric acid compound or a tin compound, and the flame retardant aid is a nitrogen-containing compound. The nitrogen-containing compound is preferably at least one selected from melamine, melam, melem, melon, melamine cyanurate, melamine phosphate, melamine polyphosphate, melamine melam melem polyphosphate double salt. When the flame retardant aid is an aromatic resin, the aromatic resin is preferably at least one selected from a novolak resin, a phenol aralkyl resin, a polyphenylene ether resin, a polycarbonate resin, and a polyetherimide resin.

Examples of the antimony-containing compound include antimony oxide [antimony trioxide (Sb ₂ O ₃ etc.), antimony pentoxide (xNa ₂ O · Sb ₂ O ₅ · yH ₂ O (x = 0 to 1, y = 0 to 4). Etc.)], antimonates [metal antimonates (for example, alkali metal salts such as sodium antimonate, alkaline earth metal salts such as magnesium antimonate, etc.), ammonium antimonate, etc.]. These antimony-containing compounds can be used alone or in combination of two or more. Of the antimony-containing compounds, antimony oxide and alkali metal salts of antimonic acid are preferred.

  Further, the antimony-containing compound may be used after surface treatment with a surface treatment agent such as an epoxy compound, a silane compound, an isocyanate compound and / or a titanate compound, if necessary.

In addition, the average particle diameter of an antimony containing compound may be 0.02-5 micrometers, for example, Preferably about 0.1-3 micrometers may be sufficient.

  The blending amount of the flame retardant and / or flame retardant aid is preferably 3 parts by weight or more and 50 parts by weight or less, and preferably 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin composition. Is more preferable. If it is less than 3 parts by weight, the flame retardancy-imparting performance may be lowered, which is not preferable. If it exceeds 50 parts by weight, the physical properties may be lowered, which is not preferable.

[Other ingredients]
Further, the crystalline thermoplastic resin composition may be added with commonly used additives, fillers, colorants and the like within the range not impairing the effects of the present invention. That is, conventionally known additives and the like can be used as long as they do not significantly exhibit electrical conductivity without significantly irradiating electromagnetic waves, or significantly reduce physical properties, moldability, and the like.

  Examples of the additive include an antioxidant, a flame retardant, a mold release agent, a colorant, a lubricant, a heat resistance stabilizer, a weather resistance stabilizer, a rust inhibitor, and an antibacterial agent.

  Examples of fillers include glass fiber, metal fiber, aramid fiber, potassium titanate, asbestos, silicon carbide, ceramic, silicon nitride, barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, bentonite, sericite, zeolite, Mica, mica, nepheline cinnite, talc, atalpagite, wollastonite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, Examples thereof include glass beads, glass balloons, glass flakes, quartz, quartz glass, and apatite. These may be hollow. These can be used in combination of two or more. If necessary, it can be pre-treated with a silane-based coupling agent.

[Carbide layer]
The carbide layer is modified with a good solvent (in this specification, hexafluoroisopropanol, α-chloronaphthalene) in which the crystalline thermoplastic resin composition is modified by laser irradiation and can properly dissolve the resin molded product. It is a layer that has become insoluble. Therefore, the expression “a layer composed of an insoluble component in a good solvent” is appropriate, but it is a layer that has become insoluble due to an exothermic reaction, and the color is black. It is called “carbide layer”.

  In this specification, whether the carbide layer by the irradiation of electromagnetic waves is formed on the surface shall be confirmed by the following method. First, electric field shield crystallized thermoplastic resin molded product with carbonized surface and uncarbonized sample

  Subsequently, these samples are measured based on a wide-angle X-ray diffraction method. If the appearance and increase of a peak is confirmed at a Bragg angle (2θ) of 25 to 27 ° in the X-ray diffraction spectrum, it is assumed that a carbide layer is formed by irradiation with electromagnetic waves.

[Electric field shielding]
The electric field shielding resin molded product of the present invention has an electric field shielding property of 3 dB or more by the Advantest test method or KEC method for electromagnetic waves having a frequency of 1 GHz or less, or by the coaxial tube method for electromagnetic waves having a frequency of 1 GHz or more and 18 GHz or less. In this specification, the electric field shielding property by the Advantest method indicates the electric field shielding property when measured using an electromagnetic wave shielding effect measuring device U3741 SPECTRUM ANALYZER (manufactured by Advantest). Moreover, in this specification, the electric field shielding property by KEC method and a coaxial tube method shall show electric field shielding property when it measures using the electromagnetic wave shielding effect measuring apparatus which Chiba industry support technology research laboratory owns.

<Method for producing electric field shielding resin molded product>
The electric field shielding resin molded product of the present invention is obtained by subjecting the thermoplastic resin composition to injection molding or extrusion molding, and then irradiating the surface of the subsequent injection molded product or extrusion molding with electromagnetic waves, and X based on the wide angle X diffraction method. It is obtained by forming a carbide having a diffraction peak at a Bragg angle (2θ) of 25 to 27 ° in a line diffraction spectrum.

  As a method of forming a carbide layer on the surface, in addition to a method of irradiating an electromagnetic wave to the surface of an injection molded product or an extrusion molded product, a method of baking near the surface, a method of bringing a flame close to the surface, a hot object or plasma is brought close to or brought into contact with the surface And a method of generating heat by rubbing the surface with another object. However, other than the method of irradiating the surface with electromagnetic waves, it is not preferable because conductivity sufficient to say that it has suitable electric field shielding properties cannot be expressed.

[Electromagnetic waves]
The type of electromagnetic wave is not particularly limited, but it is preferable that the electromagnetic wave is laser light because electromagnetic wave irradiation devices are widely available on the market and are versatile.

The laser beam is not particularly limited as long as it can be absorbed by the target thermoplastic resin composition and has sufficient energy to form a carbide layer on the surface. For example, an Nd: YVO ₄ laser with a wavelength of 1064 nm, an Nd: YAG laser, an Nd: YAG laser using SHG and THG, a second harmonic (532 nm) and a third harmonic (355 nm) visible light laser, an wavelength of 824 nm Examples thereof include a semiconductor laser such as an AlGaAs laser, various excimer lasers such as a XeCl excimer laser having a wavelength of 308 nm, a dye laser having an arbitrarily changed wavelength, and a carbon dioxide gas laser which is an infrared laser.

  Among them, Nd: YAG lasers with a wavelength of 1064 nm are widely available on the market, and the total irradiation energy per unit area can be freely changed by changing the Q switch, lamp current, dot interval or line interval of the irradiated image, and scanning speed. Therefore, it is preferable. In the case of the Nd: YAG laser, the rated output is also preferable in the range of 1 to 10 W in the continuous mode.

  Note that the method of irradiating the resin molded product, which is an object to be irradiated, with a laser beam may be a scan type through a polygon mirror or a mask type that irradiates all at once using a mask. The method of forming a conductive part by irradiating a scanning Nd: YAG laser via a polygon mirror is a very simple method, and is advantageous in that the design of the conductive part can be changed relatively freely. Moreover, it is also suitable from the point that a laser marking apparatus using an Nd: YAG laser that is already commercially available can be diverted. However, when the number of production is large, it may be advantageous in terms of production efficiency to use a mask type or to use a plurality of diode lasers.

  Further, the form of the conductive portion that is the irradiation portion may be a one-stroke continuous image or a dot image.

The energy density of the laser beam is not particularly limited, is preferably 1 kW / cm ² over a million kW / cm ² or less, 10,000 kW / cm ² or more 80,000 kW / cm ² or less Is more preferable. A laser irradiation method using a Q-switch method that instantaneously generates a high energy density is preferable in that a more suitable energy density can be obtained. The giant pulse width of laser light by the Q switch method is preferably 3 ns to 100 ns, and more preferably 6 ns to 50 ns.

  The interval at which the electromagnetic wave is irradiated is preferably equal to or shorter than the wavelength of the electromagnetic wave to be shielded. However, if the carbonized area is small, there is a possibility that sufficient electric field shielding property cannot be obtained.

  The power of the electromagnetic wave, the number of times of irradiation, or the scanning speed may be set under any conditions such that a carbide having a diffraction peak at a Bragg angle (2θ) of 25 to 27 ° in an X-ray diffraction spectrum based on the wide-angle X diffraction method is formed at the irradiated portion. Although it can be selected and is not particularly limited, it is preferable to irradiate under the condition that the irradiation time is shortened in consideration of manufacturing efficiency.

  Although not an indispensable aspect, it is preferable to irradiate electromagnetic waves radially with respect to the surface of the resin molded product at an irradiation angle of 0 degree to 45 degrees.

  In addition, when irradiating electromagnetic waves, first, as a pretreatment, a laser beam having a center frequency of 1 kHz or more is irradiated to the surface of the resin molded product at least once, and then, as a main treatment, a continuous wave laser having a center frequency of 0 kHz. It is preferable to irradiate the surface of the resin molded product a plurality of times. By doing in this way, even when a resin molded product is hard to carbonize, the surface can be carbonized uniformly. This is presumably because irregular reflection of the laser beam occurs in the recessed portion in this treatment because the surface of the resin molded product is slightly damaged by the pretreatment.

  Moreover, after irradiating a laser beam as this process, it is preferable to irradiate the whole surface of a resin molded product several times with the laser beam of weak energy as a post-process. Since the carbonized powder is generated on the surface of the resin molded product after the main treatment, the carbonized powder can be removed by gradually baking or melting the entire surface of the resin molded product with a laser beam with low energy as a post-treatment. In the present specification, weak energy laser light means that when the surface of a resin molded product that has not been carbonized is irradiated, a carbonized powder is produced in which the resin at the irradiated location does not melt or does not carbonize even when melted. When the surface of the resin molded product is irradiated, it means laser light having an energy lower than that of the laser light in the main treatment, in which the resin at the irradiated portion melts and the carbonized powder or the carbonized powder and the molded product are welded to each other. Weak energy laser light can be obtained by adjusting laser power, spot size, scanning speed, and the like.

<Case>
The housing of the present invention has the electric field shielded crystalline thermoplastic resin molded product. The casing component referred to in the present invention is a component called a housing. In general, it is a box-shaped part that forms an exterior, but it may not necessarily be a box-shaped due to restrictions such as a product shape and an assembly method, but these are also included in the scope of the present invention. And this housing | casing component may be comprised by the some molded | formed product even if it was an integrated molded product. There is a device inside the housing. Specifically, digital integrated circuits such as IC, LSI and VLSI, analog integrated circuits, MOS integrated circuits, thin film integrated circuits, hybrid integrated circuits, memory cells such as IIL, multi-emitter transistors such as TTL, liquid crystal devices, etc. . These are generally easily affected by electric fields, electromagnetic waves, static electricity, and the like, which may cause malfunction, deterioration, and destruction.

  Conversely, electric fields, electromagnetic waves, static electricity, etc. are generated from the devices in the housing, which may adversely affect products outside the housing. In order to prevent these, the casing parts are generally required to have a characteristic to prevent them, that is, a shielding characteristic, and the present invention responds to this. Conversely, the electric / electronic circuit in the casing may cause an electric field, electromagnetic wave, or static electricity that adversely affects surrounding electric / electronic devices. Even in such a case, the present invention is effective.

  In particular, the casing of the present invention is useful as a radio wave shielding material in a transport device such as an automobile, a train, and an aircraft because it is excellent in shielding properties in a relatively low frequency band and is lightweight.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.

<Examples 1-5 and Comparative Examples 1-11> Screening of a crystalline thermoplastic resin

In Table 1, various materials are as follows.
(1) Crystalline thermoplastic resin PPS: Polyphenylene sulfide (manufactured by Kureha Co., Ltd., Fortron KPS W214A)
PBT: Polybutylene terephthalate (manufactured by Wintech Polymer Co., Ltd., DURANEX (intrinsic viscosity 0.68 dL / g))
(2) Filler GF: Chopped glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS03T747), average fiber diameter: 13 μm

(3) Flame retardant Aluminum diethylphosphinate (Product name: EXOLIT OP1240, manufactured by Clariant Japan)
Polybenzyl acrylate (Product name: FR-1025, manufactured by ICL-IP JAPAN)
Melamine cyanurate (Product name: MELAPUR MC50, manufactured by BASF Japan)
Antimony trioxide (Product name: PATOX-M manufactured by Nippon Seiko Co., Ltd.)

  The materials shown in Table 1 were mixed in the proportions (parts by weight) shown in Table 1, and kneaded and extruded with an extruder to prepare pellet-shaped resin compositions A to H. Then, each of the resin compositions A to H was used to perform injection molding into a flat plate shape of 80 mm × 80 mm or more × 1 mm or more, and two types of crystalline thermoplastic resin molded products were produced.

Subsequently, Nd: YVO ₄ laser light was irradiated in a lattice pattern on one of the two crystalline thermoplastic resin molded articles produced. The irradiation device was a laser irradiation device 3-Axis YVO ₄ LASER MARKER (manufactured by Keyence Corporation), and the irradiation conditions were as shown in Table 2. The other of the two crystalline thermoplastic resin molded articles produced was not irradiated with laser light. Through the above steps, crystalline thermoplastic resin molded articles according to Examples 1 to 5 and Comparative Examples 1 to 7 were produced.

<Evaluation>
About the electric field shield crystalline thermoplastic resin molded article which concerns on Examples 1-5 and Comparative Examples 1-7, the electric field shielding property with respect to the electromagnetic waves which are 1 GHz or less was measured by the Advantest method. As an example, the measurement result about Examples 1-3 and Comparative Examples 1-3 is shown in FIG. 1, and the measurement result about Examples 4, 5 and Comparative Examples 4-7 is shown in FIG.
Moreover, the electric field shielding property with respect to the electromagnetic waves which are 1 GHz or less was measured by KEC method. As an example, the measurement results for Examples 1 and 3 and Comparative Examples 1 and 3 are shown in FIG. 3, and the measurement results for Example 5 and Comparative Example 5 are shown in FIG.
Moreover, the electric field shielding property with respect to the electromagnetic waves which are 1 GHz or more and 18 GHz or less was measured by the coaxial tube method. As an example, the measurement results for Examples 1 and 3 and Comparative Examples 1 and 3 are shown in FIG. 5, and the measurement results for Example 5 and Comparative Example 5 are shown in FIG.

  The molded article of the crystalline thermoplastic resin composition having a carbide layer formed by irradiation of electromagnetic waves on the surface has an electric field shielding property of 3 dB or more by the Advantest test method, the KEC method and the coaxial tube method for electromagnetic waves having a frequency of 18 GHz or less. It was confirmed (Example). FIG. 3 to FIG. 6 show the measurement results for Examples 1, 3 and 5 as an example, but it was confirmed that the electric field shielding property is 3 dB or more in other examples as well ( Example). (A) of FIG. 7 is a plane photograph of the electric field shield crystalline thermoplastic resin molded article according to Example 2, and (B) of FIG. 7 is an enlarged photograph of a part of the plane photograph. From FIG. 7, it is considered that a carbide layer is appropriately formed on the surface of the electric field shielded crystalline thermoplastic resin molded article according to the example, and as a result, sufficient electric field shielding was obtained.

  On the other hand, from FIGS. 1 to 6, it was confirmed that when the surface was not irradiated with electromagnetic waves, almost no electric field shielding was obtained (Comparative Examples 1 to 6).

  In addition, even when the surface was irradiated with electromagnetic waves, it was confirmed that when the crystalline thermoplastic resin composition was not flame retardant but retarded, sufficient electric field shielding could not be obtained (comparison) Examples 6, 7). FIG. 8 is an enlarged photograph of a part of the resin molded product according to Comparative Example 7. From FIG. 8, when the crystalline thermoplastic resin composition is not flame retardant but slow flame retardant, the surface of the crystalline thermoplastic resin molded article cannot be sufficiently carbonized even when the surface is irradiated with electromagnetic waves. Therefore, as a result, it is considered that sufficient electric field shielding property was not obtained.

<Example 11> Removal of powder generated in carbonized layer by electromagnetic wave irradiation

  The resin composition B was injection molded into a flat plate shape of 80 mm × 80 mm or more × 1 mm or more to produce a resin molded product.

Subsequently, the resin molded product was irradiated with a Nd: YVO ₄ laser beam in a lattice shape under the same conditions as in Example 1 except that the irradiation conditions of the laser beam were as shown in Table 7. Through the above steps, an electric field shield crystalline thermoplastic resin molded article according to Example 11 was produced.

<Evaluation>
The surface of the electric field shielded crystalline thermoplastic resin molded article according to Example 11 was enlarged and observed with an electron microscope (SEM) for two times at the end of the main treatment and the end of the post treatment. The magnification was 100 times. The results are shown in FIG.

  When electromagnetic waves are applied to the surface of the resin molded product, powder is generated on the surface of the resin molded product ((A) in FIG. 9). The carbonized powder can be removed by gradually baking or melting the entire surface of the resin molded product with a weak energy laser beam as a post-treatment (FIG. 9B).

<Example 21 and Comparative Example 21> Confirmation of carbonized layer

  The resin composition C was injection molded into a flat plate shape of 80 mm × 80 mm or more × 1 mm or more to produce two resin molded products.

These two resin molded products were cut into a 30 mm × 30 mm flat plate, and Nd: YVO ₄ laser light was formed in a lattice pattern under the same conditions as in Example 1 except that the irradiation conditions of laser light were as shown in Table 8. Irradiated. Through the above steps, electric field shielded crystalline thermoplastic resin molded articles according to Example 21 and Comparative Example 21 were produced.

<Evaluation>
The X-ray diffraction spectrum based on the wide-angle X-ray diffraction method on the surface of the electric field shielded crystalline thermoplastic resin molded article according to Example 21 and Comparative Example 21 is shown in FIG.

  By irradiating the surface of the resin molded product with electromagnetic waves, it was confirmed that a substance having a diffraction peak at a Bragg angle (2θ) of 25 to 27 ° in the X-ray diffraction spectrum was generated on the surface of the resin molded product ( Example 21, Comparative Example 21, FIG. 10). Since this is a peak derived from graphite, it is considered that a carbide layer is formed on the surface of the resin molded product by irradiation with electromagnetic waves.

Claims (18)

Molding of a crystalline thermoplastic resin composition containing a flame retardant crystalline thermoplastic resin having a flame retardance of V-1 or higher based on the UL94 flammability test when the thickness of the test piece is 1.6 mm Product,
By irradiating the surface with electromagnetic waves, a carbide layer having a diffraction peak at a Bragg angle (2θ) of 25 to 27 ° in an X-ray diffraction spectrum based on the wide-angle X diffraction method is formed,
An electric field shielding crystalline thermoplastic resin molded article having an electric field shielding property of 3 dB or more by an Advantest test method or KEC method for electromagnetic waves having a frequency of 1 GHz or less, or a coaxial tube method for electromagnetic waves having a frequency of 1 GHz or more and 18 GHz or less.   The electric field shielded crystalline thermoplastic resin molded article according to claim 1, wherein the flame-retardant crystalline thermoplastic resin is a flame-retardant crystalline aromatic polymer.   The electric field shielded crystalline thermoplastic resin molded article according to claim 2, wherein the flame-retardant crystalline aromatic polymer has a sulfur atom and / or an oxygen atom in a molecule.   The electric field shielded crystalline thermoplastic resin molded article according to claim 2 or 3, wherein the flame-retardant crystalline aromatic polymer is polyarylene sulfide and / or polyalkylene arylate.   When the flame retardant crystalline aromatic polymer is polyarylene sulfide, the polyarylene sulfide is polyphenylene sulfide, and when the crystalline aromatic polymer is polyalkylene arylate, the polyalkylene arylate is polybutylene terephthalate. The electric field shielded crystalline thermoplastic resin molded article according to claim 4, wherein   The electric field shielded crystalline thermoplastic resin molded article according to claim 4 or 5, wherein the flame-retardant crystalline aromatic polymer is a polymer alloy based on the polyarylene sulfide or the polyalkylene arylate. The crystalline thermoplastic resin composition further contains an electromagnetic wave absorber,
The electric field shield crystalline thermoplastic resin molded article according to any one of claims 1 to 6, wherein the electromagnetic wave absorber is at least one selected from carbon black, carbon fiber, and graphite.   The electric field shielded crystalline thermoplastic resin molded article according to any one of claims 1 to 7, wherein the crystalline thermoplastic resin composition further contains a flame retardant and / or a flame retardant aid.   The electric field shield crystalline thermoplastic resin molding according to claim 8, wherein when the crystalline thermoplastic resin composition further contains the flame retardant, the flame retardant is a phosphorus flame retardant and / or a halogen flame retardant. Goods. When the flame retardant is a phosphorus flame retardant, the phosphorus flame retardant is a dialkylphosphinic acid metal salt,
When the flame retardant is a halogen flame retardant, the halogen flame retardant is at least one selected from halogenated aromatic bisimide, halogenated benzyl acrylate, halogenated polystyrene, halogenated polycarbonate, or halogenated aromatic epoxy. The electric field shield crystalline thermoplastic resin molded article according to claim 9.   When the crystalline thermoplastic resin composition further contains the flame retardant aid, the flame retardant aid is at least one selected from a metal oxide, a nitrogen-containing compound, or an aromatic resin. The electric field shield crystalline thermoplastic resin molded article described in 1. When the flame retardant aid is a metal oxide, the metal oxide is at least one selected from an antimony compound, a boric acid compound, or a tin compound,
When the flame retardant aid is a nitrogen-containing compound, the nitrogen-containing compound is selected from melamine, melam, melem, melon, melamine cyanurate, melamine phosphate, melamine polyphosphate, melamine melam melem polyphosphate double salt At least one kind,
When the flame retardant aid is an aromatic resin, the aromatic resin is at least one selected from a novolak resin, a phenol aralkyl resin, a polyphenylene ether resin, a polycarbonate resin, and a polyetherimide resin. The electric field shield crystalline thermoplastic resin molded article described in 1.   The electric field shield crystalline thermoplastic resin molded article according to any one of claims 1 to 12, wherein the electromagnetic wave is laser light.   The electric field shielded crystalline thermoplastic resin molded article according to any one of claims 1 to 13, which is an injection molded article or an extrusion molded article.   The housing | casing of the electronic device for transport machines which has the electric field shield crystalline thermoplastic resin molded product in any one of Claim 1 to 14.   Molding of a crystalline thermoplastic resin composition containing a flame retardant crystalline thermoplastic resin having a flame retardance of V-1 or higher based on the UL94 flammability test when the thickness of the test piece is 1.6 mm Field shielding crystallizing heat comprising an electromagnetic wave irradiation step of irradiating the surface of the product with electromagnetic waves to form a carbide having a diffraction peak at a Bragg angle (2θ) of 25 to 27 ° in an X-ray diffraction spectrum based on a wide angle X diffraction method A method for producing a plastic resin molded article.   In the electromagnetic wave irradiation step, the surface of the molded product is irradiated with a laser beam having a center frequency of 1 kHz or more at least once, and then a continuous wave laser beam having a center frequency of 0 kHz is irradiated a plurality of times on the surface of the molded product. The manufacturing method of the electric field shielding resin molded product of Claim 16.   The electric field shielding resin molded article according to claim 16 or 17, wherein after the electromagnetic wave irradiation step, the entire surface of the molded article of the crystalline thermoplastic resin composition is gradually baked or melted with a laser beam of weak energy. Production method.