WO2023276721A1 - 熱可塑性樹脂用誘電特性向上剤およびそれを含む熱可塑性樹脂組成物、熱可塑性樹脂の誘電特性の向上方法およびそのための芳香族リン酸エステルの使用 - Google Patents

熱可塑性樹脂用誘電特性向上剤およびそれを含む熱可塑性樹脂組成物、熱可塑性樹脂の誘電特性の向上方法およびそのための芳香族リン酸エステルの使用 Download PDF

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WO2023276721A1
WO2023276721A1 PCT/JP2022/024301 JP2022024301W WO2023276721A1 WO 2023276721 A1 WO2023276721 A1 WO 2023276721A1 JP 2022024301 W JP2022024301 W JP 2022024301W WO 2023276721 A1 WO2023276721 A1 WO 2023276721A1
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aromatic phosphate
thermoplastic resin
resin
integer
group
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French (fr)
Japanese (ja)
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和男 藤本
沙由里 唐池
広樹 佐藤
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Daihachi Chemical Industry Co Ltd
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Daihachi Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids

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  • the present invention relates to a dielectric property improver for thermoplastic resins, a thermoplastic resin composition containing the same, a method for improving the dielectric properties of thermoplastic resins, and the use of an aromatic phosphate ester therefor. More specifically, the present invention not only improves the dielectric properties of thermoplastic resins, but also provides aromatic phosphate esters (aromatic A dielectric property improver for thermoplastic resins containing the diphosphate-based compound), a thermoplastic resin composition containing the same having excellent dielectric properties and moldability, a method for improving the dielectric properties of thermoplastic resins, and an aroma therefor related to the use of group phosphate esters.
  • aromatic phosphate esters aromatic A dielectric property improver for thermoplastic resins containing the diphosphate-based compound
  • thermoplastic resins super engineering plastics (also called “super engineering plastics”) have excellent flame retardancy and high heat resistance, so their molded products are used in various electrical and electronic parts, mechanical parts, and automobile parts. Used for various purposes.
  • liquid crystal polymer (LCP) and polyphenylene sulfide resin (PPS) have been extensively researched and developed.
  • Patent Document 1 Japanese Patent Laid-Open No. 2002-194188 (Patent Document 1), 5 to 200 parts by weight of filler (B) and 0.5 to 200 parts by weight of styrene resin (C) are added to 100 parts by weight of liquid crystal polyester resin (A).
  • a flame-retardant liquid crystal polyester resin composition is disclosed, which is from /99 to 10/90.
  • Patent Document 2 discloses that (A) 100 parts by weight of a polyphenylene sulfide resin and (B) 1 to 30 parts by weight of a phosphoric acid ester are extruded at a temperature of 200 ° C. to 280 ° C.
  • Patent Document 3 discloses (A) 100 parts by weight of polyarylene sulfide resin, (B) a specific fragrance
  • a polyarylene sulfide resin composition obtained by blending 0.1 to 20 parts by weight of a group phosphate and melt-kneading it at 300 ° C. or higher is disclosed.
  • a polyphenylene sulfide resin composition containing 0.01 to 4 parts by weight of a phosphoric acid ester compound per 100 parts by weight is disclosed.
  • Patent Document 5 discloses an aromatic diphosphate-based flame retardant having a bisphenol skeleton with an alicyclic structure in the cross-linking group.
  • Patent Document 5 discloses an aromatic diphosphate-based flame retardant having a bisphenol skeleton with an alicyclic structure in the cross-linking group.
  • Patent Document 6 the applicant of the present application not only imparts flame retardancy to thermoplastic resins, but also thermal fluidity, heat resistance, hydrolysis resistance and bleed resistance.
  • an aromatic diphosphate having both a bisphenol having a specific aliphatic ring in the crosslinked structure and an aromatic ring structure having a substituent at the ortho position, which can improve the properties.
  • improvements in mechanical properties, heat resistance, and flame retardancy of resins of conventional phosphate esters and aromatic diphosphate compounds it does not describe improvements in dielectric properties. It has not been.
  • thermoplastic resins such as super engineering plastics
  • improving the dielectric properties alone is not sufficient, and various functions are required.
  • super engineering plastics have a high melting temperature
  • their additives are required to withstand the temperature at which they are kneaded with super engineering plastics, have heat resistance so that they do not decompose, and have excellent compatibility with super engineering plastics.
  • moldability is also required in order to use the resin composition as a material. Therefore, the present invention provides a thermoplastic resin containing an aromatic phosphate that not only improves the dielectric properties of a thermoplastic resin, but also has high heat resistance, does not decompose when kneaded with the resin, and has excellent compatibility with the resin.
  • thermoplastic resin composition containing the same and having excellent dielectric property and moldability
  • a method for improving the dielectric property of a thermoplastic resin, and use of an aromatic phosphate ester therefor. is the subject.
  • a phosphate ester having an aromatic ring terminally substituted at the 2,6-position (ortho-position) such as 2,6-xylenol was found to be surprisingly effective in improving the dielectric properties of thermoplastic resins, and the phosphate ester also has a bisphenol having a specific aliphatic ring in the crosslinked structure, making it a super engineering plastic.
  • the present inventors have found that they do not decompose even when mixed with a thermoplastic resin having a high melting temperature, and have high heat resistance and excellent compatibility, leading to the completion of the present invention.
  • R 1 to R 4 , R 7 and R 8 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms
  • R 5 , R 6 and R 9 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms
  • n is an integer of 1 to 10
  • n 1 and n 2 are each independently an integer of 0 to 3
  • , m 1 and m 2 are each independently an integer of 0 to 4
  • k is an integer of 1 to 12
  • p is an integer of 0 to 2 ⁇ (1+k), and when p is 2 or more, any may be joined together to form another ring together with the carbon atoms of the ring to which the R 9 is bonded.
  • a dielectric property improver for thermoplastic resins containing an aromatic phosphate ester represented by.
  • thermoplastic resin composition containing the dielectric property improver for thermoplastic resins and a thermoplastic resin and having improved dielectric properties.
  • thermoplastic resin which comprises adding the aromatic phosphate represented by the general formula (I) to the thermoplastic resin.
  • aromatic phosphoric acid ester represented by the above general formula (I) to be added to a thermoplastic resin to improve dielectric properties.
  • thermoplastic containing an aromatic phosphate ester not only improves the dielectric properties of a thermoplastic resin, but also has high heat resistance, does not decompose when kneaded with the resin, and has excellent compatibility with the resin.
  • a thermoplastic resin composition containing the same and having excellent dielectric property and moldability a method for improving the dielectric property of a thermoplastic resin, and use of an aromatic phosphate ester therefor. can be done.
  • the dielectric property-improving agent for thermoplastic resins of the present invention more effectively exhibits the above effects when it satisfies any one of the following conditions (1) to (4) or a combination of two or more thereof.
  • the aromatic phosphate ester is an aromatic phosphate ester represented by general formula (II) described in the embodiment, wherein n in general formula (I) is 1 and k is 4.
  • Aromatic phosphoric acid esters wherein R 1 to R 4 and R 9 in general formula (II) are methyl groups or ethyl groups, n 1 , n 2 , m 1 and m 2 are 0, and q is an integer of 0 to 3, the substitution position when q is 1 is the 3rd or 4th position, and the substitution position when q is 2 is the 3rd, 3rd, 4,4th, 3,4th or 3,5-position, and the substitution position when q is 3 is 3,3,4-position, 3,3,5-position, 3,4,4-position or 3,4,5-position is.
  • Aromatic phosphate esters are aromatic phosphate esters 1 to 3 described in the embodiments.
  • the aromatic phosphate is aromatic phosphate 2 described in the embodiments.
  • thermoplastic resin composition of the present invention more effectively exhibits the above effects when it satisfies any one of the following conditions (5) to (8) or a combination of two or more thereof.
  • the thermoplastic resin is a super engineering plastic.
  • the super engineering plastic is a resin selected from liquid crystal polymer, polyphenylene sulfide resin, aromatic polyamide resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, polyamideimide resin and polyetheretherketone resin. .
  • the super engineering plastic is a resin selected from liquid crystal polymers and polyphenylene sulfide resins.
  • a dielectric property improver for thermoplastic resin is contained in a compounding ratio of 0.5 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
  • the method for improving the dielectric properties of a thermoplastic resin of the present invention and the use of an aromatic phosphate ester therefor are any of the above (1) to (4), (5) to (7) and the following (9) The above effects are more pronounced when one or a combination of two or more of them are satisfied.
  • An aromatic phosphate ester is added in a proportion of 0.5 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
  • FIG. 1 is a 1 H-NMR chart of aromatic phosphate ester 2 of Synthesis Example 1.
  • FIG. 2 is an enlarged view of area A in FIG. 1;
  • FIG. 2 is an enlarged view of area B of FIG. 1;
  • the dielectric property improver for thermoplastic resins of the present invention has the general formula (I):
  • R 1 to R 4 , R 7 and R 8 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms
  • R 5 , R 6 and R 9 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms
  • n is an integer of 1 to 10
  • n 1 and n 2 are each independently an integer of 0 to 3
  • , m 1 and m 2 are each independently an integer of 0 to 4
  • k is an integer of 1 to 12
  • p is an integer of 0 to 2 ⁇ (1+k), and when p is 2 or more, any may be joined together to form another ring together with the carbon atoms of the ring to which the R 9 is bonded.
  • It is characterized by containing an aromatic phosphate ester represented by.
  • thermoplastic resin in the present invention Although the mechanism for improving the dielectric properties of the thermoplastic resin in the present invention is not clear, the present inventors have found from the following findings 1 and 2 that the phosphate ester having an aromatic ring having substituents at the 2,6-positions It is believed that the inhibition of the rotation of the aromatic ring by the substituent (methyl group when the aromatic ring is 2,6-xylenol) contributes to the improvement of the dielectric properties of the thermoplastic resin.
  • Aromatic phosphate 2 described in the embodiments of the present invention, Aromatic phosphate 5 used in Comparative Examples 2 and 5 of the Examples herein and similarly used in Comparative Examples 3 and 6
  • a phosphate ester having an aromatic ring having substituents at the 2 and 6-positions such as the aromatic phosphate ester 6
  • the dielectric properties of the resin composition are improved.
  • Finding 2 On the other hand, cyclophosphazene oligomer (manufactured by Otsuka Chemical Co., Ltd., product name: SPB-100) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., product name :HCA), the dielectric properties of the resin composition are not improved when a phosphate ester having substituents at the 2 and 6-positions and having no aromatic ring is blended with the thermoplastic resin.
  • improvement in dielectric properties means reduction in transmission loss based on the original dielectric properties of the thermoplastic resin. Transmission loss is proportional to the product of the positive square root of the dielectric constant and the dissipation factor. That is, the lower the product of the positive square root of the dielectric constant and the dielectric loss tangent, the better the dielectric properties.
  • Aromatic Phosphate Ester Substituents in general formula (I) will be described.
  • the substituents R 1 to R 4 , R 7 and R 8 are alkyl groups having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms, or alkyl groups having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably One or two alkoxy groups are preferred. If the number of carbon atoms is within the above range, the hydrolysis resistance of the aromatic phosphate ester is improved, synthesis is relatively easy, and excellent physical properties such as improved dielectric properties can be imparted to the thermoplastic resin. group phosphates are obtained.
  • the alkyl group having 1 to 4 carbon atoms may be either linear or branched, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert- A butyl group is mentioned.
  • methyl group, ethyl group, n-propyl group and isopropyl group are preferred, and methyl group and ethyl group are particularly preferred.
  • the alkoxy group having 1 to 4 carbon atoms may be either linear or branched, and examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and tert. -Butoxy group.
  • methoxy, ethoxy, n-propoxy and isopropoxy are preferred, and methoxy and ethoxy are particularly preferred.
  • Substituents R 5 , R 6 and R 9 are C 1-10, preferably 1-6, more preferably 1-4 alkyl groups or C 1-10, preferably 1-6, more preferably 1 ⁇ 4 alkoxy groups. If the number of carbon atoms is within the above range, an aromatic phosphate ester capable of imparting excellent physical properties such as improved dielectric properties to thermoplastic resins can be obtained.
  • the alkyl group having 1 to 10 carbon atoms may be either linear or branched, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert- Butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, 1,2-dimethylpropyl group, neopentyl group (2,2-dimethylpropyl group), tert-pentyl group (1,1- dimethylpropyl group), n-hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1 , 2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-di
  • the alkoxy group having 1 to 10 carbon atoms may be either linear or branched, and examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert -butoxy group, n-pentyloxy group, isopentyloxy group, 2-methylbutoxy group, 1-methylbutoxy group, 1,2-dimethylpropoxy group, neopentyloxy group (2,2-dimethylpropoxy group), tert -pentyloxy group (1,1-dimethylpropoxy group), n-hexyloxy group, isohexyloxy group, 1-methylpentyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 1-ethylbutoxy group, 2-ethylbutoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,2-dimethylbutoxy group, 2,3-dimethyl
  • Two types of groups an alkyl group and an alkoxy group, may coexist in one molecule, or only one type of group, either an alkyl group or an alkoxy group, may be present in one molecule. preferable.
  • n is an integer of 1 to 10, preferably 1 to 5, more preferably 1 to 3, even more preferably 1; n 1 and n 2 are each independently an integer of 0-3, preferably 0-1, more preferably 0; m 1 and m 2 are each independently an integer of 0-4, preferably 0-2, more preferably 0.
  • k is an integer of 1-12, preferably 3-10, more preferably 4 or 10.
  • p is an integer from 0 to 2 ⁇ (1+k), the maximum value of which depends on the index k and ranges from 0 to 26, preferably from 0 to 22, more preferably from 0 to 10, more preferably from 0 to 5 , particularly preferably an integer of 0 to 3.
  • An aromatic phosphate having each index within the above range can impart excellent physical properties such as improved dielectric properties to the thermoplastic resin.
  • the main component of the aromatic phosphate ester of the present invention is preferably one having each index within the above range, and may be a mixture having different indices. In addition, as long as it does not interfere with the effects of the present invention, those outside the range of the above indices may be included.
  • R 1 to R 9 , n 1 , n 2 , m 1 and m 2 have the same definitions as in general formula (I), q is 0 to 10, preferably 0 to 5, more preferably 0 to 3 is an integer of] a compound represented by and
  • R 1 to R 9 , n 1 , n 2 , m 1 and m 2 are the same as defined in general formula (I), r is 0 to 22, preferably 0 to 10, more preferably 0 to 5 , particularly preferably an integer of 0 to 3, most preferably 0] and the aromatic phosphate represented by general formula (II) is particularly preferred.
  • R 1 to R 4 and R 9 in general formula (II) are methyl groups or ethyl groups, preferably methyl groups, and n 1 , n 2 , m 1 and m 2 are 0, q is an integer of 0 to 3, the substitution position when q is 1 is the 3rd or 4th position, the substitution position when q is 2 is the 3rd, 3rd, 4th, 4th, 3,4-position or 3,5-position, and substitution positions when q is 3 are 3,3,4-position, 3,3,5-position, 3,4,4-position or 3,4,5-position; Aromatic phosphates are preferred.
  • aromatic phosphate ester of the present invention include, for example, aromatic phosphate esters 1 to 4 of the following structural formulas, and compounds selected from these can be suitably used in the present invention.
  • aromatic phosphate esters 1 to 3 are preferred, and aromatic phosphate ester 2 is particularly preferred, from the viewpoint of improving dielectric properties and availability.
  • Aromatic phosphate ester 1 Aromatic phosphate ester 1:
  • Aromatic phosphate ester 2
  • Aromatic phosphate ester 3 is an aromatic phosphate ester
  • Aromatic phosphate ester 4 is an aromatic phosphate ester
  • aromatic phosphate ester of the present invention can be obtained by synthesizing corresponding phenols, bisphenols and phosphorus oxychloride as raw materials by a known method.
  • a bisphenol compound represented by is subjected to a dehydrochlorination reaction in the presence of a Lewis acid catalyst or an esterification reaction using a hydrogen chloride scavenger such as pyridine, triethylamine or tributylamine to obtain the desired aromatic phosphate or
  • the bisphenol of general formula (VI) and phosphorus oxychloride are subjected to a dehydrochlorination reaction in the presence of a Lewis acid catalyst or an esterification reaction using a hydrogen chloride scavenger such as pyridine, triethylamine or tributylamine,
  • a hydrogen chloride scavenger such as pyridine, triethylamine or tributylamine
  • R 7 , R 8 , R 9 , m 1 , m 2 , p and k are synonymous with general formula (I)
  • the phosphorus compound and the phenol of the general formula (IV) are subjected to a dehydrochlorination reaction in the presence of a Lewis acid catalyst or using a hydrogen chloride scavenger such as pyridine, triethylamine or tributylamine. and a method of obtaining the desired aromatic phosphate by subjecting it to an esterification reaction.
  • thermoplastic resin is not particularly limited as long as it is a thermoplastic resin known in the art, but a super engineering plastic (super engineering plastic) having a high melting temperature and excellent heat resistance as a resin is used. preferable.
  • super engineering plastics have excellent flame retardancy and do not require the addition of flame retardants unlike general thermoplastic resins (combustible thermoplastic resins) and thermosetting resins.
  • Super engineering plastics include liquid crystal polymer (LCP), polyphenylene sulfide resin (PPS), aromatic polyamide resin (PPA), polysulfone resin (PSU), polyethersulfone resin (PES), polyetherimide resin (PEI), polyamide Resins such as imide resins (PAI) and polyetheretherketones (PEEK) can be mentioned, and resins selected from these are preferred in the present invention.
  • LCP liquid crystal polymer
  • PPS polyphenylene sulfide resin
  • PPA polysulfone resin
  • PEI polyetherimide resin
  • PAI imide resins
  • PEEK polyetheretherketones
  • Liquid crystal polymer is a general term for synthetic resins belonging to thermoplastic resins that exhibit liquid crystal-like properties in which straight chains of molecules are regularly arranged in a molten state. It is a combined aromatic polyester resin, and is also called liquid crystal polyester. Specifically, polycondensates of ethylene terephthalate and parahydroxybenzoic acid (formula (L1) below), polycondensates of biphenol, phthalic acid and parahydroxybenzoic acid (formula (L2) below), 6-hydroxy-2 -Polycondensates of naphthoic acid and parahydroxybenzoic acid (formula (L3) below), etc., and resins selected from these are preferred in the present invention.
  • crystalline ones are preferred, those having an aromatic ring are more preferred, and resins selected from liquid crystal polymers and polyphenylene sulfide resins are preferred because the effects of the present invention can be remarkably obtained.
  • thermoplastic resin composition of the present invention comprises a dielectric property improver for thermoplastic resins containing the aromatic phosphate ester described in (1) above and the thermoplastic resin composition described in (3) above. It is characterized by containing a resin and having improved dielectric properties.
  • R 1 to R 4 and R 9 in general formula (II) are methyl groups or ethyl groups, preferably methyl groups, and n 1 , n 2 , m 1 and m 2 is 0, q is an integer of 0 to 3, the substitution position when q is 1 is the 3rd or 4th position, and the substitution position when q is 2 is the 3rd, 3rd, 4th, and 4th positions , 3,4-position or 3,5-position, and the substitution positions when q is 3 are 3,3,4-position, 3,3,5-position, 3,4,4-position or 3,4,5-position Certain aromatic phosphate esters, liquid crystal polymer (LCP), polyphenylene sulfide resin (PPS), aromatic polyamide resin (PPA), polysulfone resin (PSU), polyethersulfone resin (PES), polyetherimide resin (PEI ), resins (super engineering plastics) selected from polyamideimide resins (PAI) and polyetheretherket
  • aromatic phosphate esters 1 to 3 with resins selected from liquid crystal polymers and polyphenylene sulfide resins are more preferable, and aromatic phosphate ester 2 is selected from liquid crystal polymers and polyphenylene sulfide resins.
  • aromatic phosphate ester 2 is selected from liquid crystal polymers and polyphenylene sulfide resins.
  • the dielectric property improver for thermoplastic resin of the present invention is preferably contained in a mixing ratio of 0.5 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin. If the mixing ratio of the dielectric property improver for thermoplastic resins is within the above range, a thermoplastic resin composition having excellent dielectric properties can be obtained. If the blending ratio of the dielectric property improver for thermoplastic resin is less than 0.5 parts by mass, a sufficient effect of improving the dielectric property may not be obtained, which is not preferable. On the other hand, if the mixing ratio of the dielectric property improver for thermoplastic resin exceeds 20 parts by mass, the physical properties of the resin itself, particularly the mechanical properties, may be deteriorated, which is not preferable.
  • the blending ratio of the dielectric property improver for thermoplastic resins is more preferably 1 to 15 parts by mass, particularly preferably 2 to 12 parts by mass.
  • a more specific blending ratio (parts by mass) of the aromatic phosphate with respect to 100 parts by mass of the thermoplastic resin is 0.5, 0.7, 1, 1.5, 2, 2.5, 3, 3.5. , 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12 , 12.5, 13, 14, 15, 16, 17, 18, 19 and 20.
  • thermoplastic resin composition of the present invention may optionally contain other components that are usually added to resins within a range that does not impair the effects of the present invention.
  • Other ingredients include, for example, anti-drip agents, antioxidants, fillers, lubricants, modifiers, fragrances, antibacterial agents, pigments, dyes, antistatic agents, UV absorbers, stabilizers, reinforcing agents, and antiblocking. agents and the like.
  • thermoplastic resin composition of the present invention is obtained by adding an aromatic phosphate and, if necessary, other components to a thermoplastic resin.
  • the addition method is not particularly limited, but examples thereof include a known method of melt-kneading each component using a general-purpose kneading device such as a single-screw extruder, twin-screw extruder, Banbury mixer, or kneader.
  • the method for improving dielectric properties of the thermoplastic resin of the present invention comprises adding an aromatic phosphate represented by the general formula (I) to the thermoplastic resin.
  • the aromatic phosphate ester and the thermoplastic resin are as described in the preceding paragraphs (1)
  • Thermoplastic resin composition 3 the preferable combination of the aromatic phosphate and the thermoplastic resin contained in the dielectric property improver for thermoplastic resin.
  • the aromatic phosphate ester is preferably added in a proportion of 0.5 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
  • the addition ratio of the aromatic phosphate is within the above range, the dielectric properties of the thermoplastic resin can be improved. If the amount of the aromatic phosphate ester added is less than 0.5 parts by mass, a sufficient effect of improving the dielectric properties may not be obtained, which is not preferable. On the other hand, if the amount of the aromatic phosphate added exceeds 20 parts by mass, the physical properties of the resin itself, particularly the mechanical properties, may be lowered, which is not preferable. A more preferable addition ratio of the aromatic phosphate is 1 to 15 parts by mass, particularly preferably 2 to 12 parts by mass.
  • the use of the aromatic phosphate ester of the present invention is an aromatic phosphorus ester represented by the above general formula (I) for adding to a thermoplastic resin to improve dielectric properties.
  • the aromatic phosphate ester and the thermoplastic resin are as described in the preceding paragraphs (1)
  • Thermoplastic resin composition 3 the preferable combination of the aromatic phosphate and the thermoplastic resin contained in the dielectric property improver for thermoplastic resin.
  • the addition ratio of the aromatic phosphate is as described in the previous item (8) Method for improving dielectric properties of thermoplastic resin.
  • thermoplastic resin composition The physical properties of the thermoplastic resin compositions obtained in Examples and Comparative Examples were evaluated by the following conditions and methods using the following measuring equipment.
  • the dielectric constant Dk and dielectric loss tangent Df of the liquid crystal polymer (LCP) resin composition at 10 GHz were measured using a PNA microwave network analyzer (manufactured by Keysight Technologies, model: N5222B).
  • the dielectric constant Dk and dielectric loss tangent Df of the polyphenylene sulfide (PPS) resin composition at 1 GHz were measured using an RF impedance/material analyzer (manufactured by Agilent Technologies, model: E4991A).
  • Synthesis Examples The following compounds were used as raw materials in Synthesis Examples. ⁇ 2,6-xylenol (manufactured by Tokyo Chemical Industry Co., Ltd.) ⁇ Phosphorus oxychloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • thermoplastic resin composition [Raw materials for thermoplastic resin composition] The following compounds were used as raw materials in the test examples. ⁇ Liquid crystal polymer (LCP, manufactured by Nantong Haidi New Materials Co., Ltd., China, product name: T3400) ⁇ Polyphenylene sulfide resin (PPS, manufactured by Toray Industries, Inc., product name: Torelina A-900)
  • Aromatic phosphate ester 5 (used in Comparative Examples 2 and 5, the following structural formula, aromatic phosphate ester synthesized by the method described in JP-A-5-1079)
  • Aromatic phosphate ester 6 (used in Comparative Examples 3 and 6, the following structural formula, manufactured by Daihachi Chemical Industry Co., Ltd., product name: PX-200)
  • the pressure in the flask was gradually reduced to 20 kPa at the same temperature (160° C.) to remove xylene, unreacted phosphorus oxychloride, 2,6-xylenol, and by-product hydrogen chloride. 1700 g of a reaction mixture based on silylphosphorochloridate were obtained. Also, the chlorine content of the reaction mixture was 10.9% by mass.
  • Synthesis Example 2 Synthesis of aromatic phosphate 2 460 g of the dixylylphosphorochloridate obtained in Synthesis Example 1 was added to a 2-liter four-necked flask equipped with a stirrer, thermometer, dropping funnel and condenser. , 196 g of bisphenol, 540 g of toluene and 140 g of tetrahydrofuran as solvents. Also, the dropping funnel was filled with 151 g of triethylamine as a hydrogen halide scavenger. The mixed solution in the four-necked flask was heated to a temperature of 65° C.
  • Test Example 1 Evaluation of aromatic phosphate in liquid crystal polymer (LCP)
  • LCP and aromatic phosphate ester 2 are used as resins, and the formulations shown in Table 1 are introduced into a twin-screw kneader (manufactured by Japan Steel Works, Ltd., model: TEX25 ⁇ III) and kneaded at a temperature of 320 to 350 ° C. A pellet was obtained. The obtained pellets were put into an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., model: FN-2000) to obtain a test piece for measuring dielectric properties. Using the obtained test piece, the dielectric properties were evaluated by the method described above. The results obtained by the measurement are shown in Table 1 together with the resin and aromatic phosphate 2 and their mixing ratio.
  • Test Example 2 Evaluation of aromatic phosphate in polyphenylene sulfide resin (PPS)
  • PPS and aromatic phosphate ester 2 were used as resins, and the formulations shown in Table 2 were put into a twin-screw kneader (manufactured by Shibaura Kikai Co., Ltd., model: TEM-37BS) and kneaded at a temperature of 280 to 320 ° C. to obtain pellets.
  • the obtained pellets were put into an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., model: FN-2000) to obtain a test piece for measuring dielectric properties. Using the obtained test piece, the dielectric properties were evaluated by the method described above. The results obtained by the measurement are shown in Table 2 together with the resin and aromatic phosphate 2 and their blending ratios.
  • thermoplastic resin compositions of the present invention (Examples 1 to 2 and 3 to 6) have high heat resistance, do not decompose when kneaded with the resin, and have excellent compatibility with the resin. It can be seen that the thermoplastic resin composition contains the aromatic phosphate ester 2 and has excellent dielectric properties.

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PCT/JP2022/024301 2021-06-28 2022-06-17 熱可塑性樹脂用誘電特性向上剤およびそれを含む熱可塑性樹脂組成物、熱可塑性樹脂の誘電特性の向上方法およびそのための芳香族リン酸エステルの使用 Ceased WO2023276721A1 (ja)

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