JP2023143263A - Resin composition, and molded article - Google Patents

Abstract

To provide a resin composition which contains a polycarbonate resin and shortens an afterflame time, and a molded article formed from the resin composition.SOLUTION: A resin composition contains, with respect to (A) 100 pts.mass of a polycarbonate resin, (B) 6-20 pts.mass of a phosphate-based flame retardant, and (C) 0.01-3 pts.mass of a fluoropolymer having fibril-forming ability, wherein (A) the polycarbonate resin contains a polycarbonate resin (A-1) and a polycarbonate resin (A-2), the ratio of the polycarbonate resin (A-2) in 100 pts.mass of (A) the polycarbonate resin is 10-99 pts.mass, an integrated light-emission amount of the polycarbonate resin (A-1) when temperature-raising measurement is performed by a chemical luminescence method is less than 8.0×105, and a ratio (maximum light-emission amount on low temperature side)/(maximum light-emission amount on high temperature side) of the maximum light-emission amount on the low temperature side and the maximum light-emission amount on the high temperature side of the polycarbonate resin (A-2) when the temperature-raising measurement is performed by the chemical luminescence method is more than 0.16, and an integrated light-emission amount thereof when the temperature-raising measurement is performed by the chemical luminescence method is 8.0×105 cps or more.SELECTED DRAWING: None

Description

The present invention relates to a resin composition and a molded article. In particular, it relates to resin compositions containing polycarbonate resins.

As a general-purpose engineering plastic, polycarbonate resin has excellent transparency, mechanical strength, electrical properties, heat resistance, and dimensional stability, so it is used in electrical and electronic equipment parts, OA equipment, mechanical parts, vehicle parts, and construction materials. It is used in a wide range of fields, including various containers, leisure goods, and miscellaneous goods.
Resin compositions containing polycarbonate resin (hereinafter sometimes referred to as "polycarbonate resin compositions") are often required to have flame retardancy, and various polycarbonate resin compositions with excellent flame retardancy have been studied. (Patent Document 1, Patent Document 2, etc.).

Japanese Patent Application Publication No. 2021-187863 JP 2021-155499 Publication

As mentioned above, various polycarbonate resin compositions with excellent flame retardancy are known, but with the increasing demand for polycarbonate resin compositions, there is a demand for polycarbonate resin compositions with even newer flame retardance. In particular, there is a need for polycarbonate resin compositions with shortened afterflame times.
The present invention aims to solve such problems, and provides a resin composition containing a polycarbonate resin, which has a shorter afterflame time, and a resin composition formed from the resin composition. The purpose is to provide molded products made by

Based on the above-mentioned problems, the present inventor conducted studies and found that in a flame-retardant polycarbonate resin composition containing a polycarbonate resin, a phosphate ester flame retardant, and a fluoropolymer having fibril-forming ability, It has been discovered that the above problems can be solved by blending polycarbonate resins.
Specifically, the above problem was solved by the following means.
<1> Contains (B) 6 to 20 parts by mass of a phosphate ester flame retardant and (C) 0.01 to 3 parts by mass of a fluoropolymer having fibril-forming ability based on 100 parts by mass of (A) polycarbonate resin. , the polycarbonate resin (A) contains a polycarbonate resin (A-1) and a polycarbonate resin (A-2), and the proportion of the polycarbonate resin (A-2) in 100 parts by mass of the polycarbonate resin (A) is 10 ~99 parts by mass, and the cumulative luminescence amount of the polycarbonate resin (A-1) when measured at elevated temperature by chemiluminescence method is less than 8.0 × 10 ⁵ , and the polycarbonate resin (A-2) has The ratio of the maximum light emission amount on the low temperature side and the maximum light emission amount on the high temperature side when measured by increasing temperature using the chemiluminescence method, (maximum light emission amount on the low temperature side)/(maximum light emission amount on the high temperature side) is more than 0.16. A resin composition having an integrated luminescence amount of 8.0×10 ⁵ cps or more when measured at elevated temperature using a chemiluminescence method.
<2> The ratio of the maximum luminescence amount on the low temperature side and the maximum luminescence amount on the high temperature side when the polycarbonate resin (A-1) is measured at elevated temperature using the chemiluminescence method, (maximum luminescence amount on the low temperature side)/ The resin composition according to <1>, wherein the (maximum luminescence amount on the high temperature side) is 0.16 or less.
<3> The resin composition according to <1> or <2>, wherein the polycarbonate resin (A-2) has a weight average molecular weight of 35,000 or more.
<4> The resin composition according to any one of <1> to <3>, wherein the polycarbonate resin (A-2) is derived from a molded article formed from a polycarbonate resin.
<5> A molded article formed from the resin composition according to any one of <1> to <4>.

ADVANTAGE OF THE INVENTION According to the present invention, it has become possible to provide a resin composition containing a polycarbonate resin, which has a shorter afterflame time, and a molded article formed from the resin composition.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail. Note that the present embodiment below is an illustration for explaining the present invention, and the present invention is not limited only to this embodiment.
In addition, in this specification, "~" is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
In this specification, various physical property values and characteristic values are assumed to be at 23° C. unless otherwise stated.
If the measurement methods, etc. explained in the standards shown in this specification differ from year to year, unless otherwise stated, they shall be based on the standards as of January 1, 2022.

The resin composition of the present embodiment includes (A) 100 parts by mass of polycarbonate resin, (B) 6 to 20 parts by mass of a phosphoric acid ester flame retardant, and (C) 0.01 to 0.01 to 200% of fluoropolymer having fibril-forming ability. 3 parts by mass, and the (A) polycarbonate resin includes polycarbonate resin (A-1) and polycarbonate resin (A-2), and the polycarbonate resin (A-2) in 100 parts by mass of the (A) polycarbonate resin ) is 10 to 99 parts by mass, and the cumulative luminescence amount when the polycarbonate resin (A-1) is measured at elevated temperature by the chemiluminescence method is less than 8.0×10 ⁵ , and the polycarbonate resin ( A-2) is the ratio of the maximum luminescence amount on the low temperature side and the maximum luminescence amount on the high temperature side when measured by temperature increase using the chemiluminescence method, (maximum luminescence amount on the low temperature side) / (maximum luminescence amount on the high temperature side) ) is more than 0.16, and the integrated luminescence amount when measured at elevated temperature by chemiluminescence method is 8.0×10 ⁵ cps or more.
As described above, in a flame-retardant polycarbonate resin composition containing a polycarbonate resin, a phosphate ester flame retardant, and a fluoropolymer having fibril-forming ability, in addition to the polycarbonate resin (A-1), the polycarbonate resin ( By blending A-2), flame retardancy can be further improved. In particular, the afterflame time of the molded product obtained can be further shortened.
The reason for this is presumed to be as follows. That is, when a resin molded product containing a phosphoric acid ester flame retardant as a flame retardant burns, char is formed on its surface to suppress combustion. More specifically, the phosphoric acid ester flame retardant is thermally decomposed, and the generated acid component is further polymerized by heating to generate polymetaphosphoric acid. Since polymetaphosphoric acid is a strong acid, it is also a strong dehydrating agent that protonates other molecules. This strong acid then promotes the formation of char. In this embodiment, by blending the polycarbonate resin (A-2) which has undergone oxidative deterioration to a certain extent, the resin molded product can more easily bond with polymetaphosphoric acid, further promote the formation of char, and reduce the afterflame time. It is assumed that it was possible to shorten the .
The details of the present invention will be explained below.

<(A) Polycarbonate resin>
The resin composition of this embodiment includes (A) a polycarbonate resin. In this embodiment, the polycarbonate resin (A) is usually the main component. In the resin composition of this embodiment, the polycarbonate resin (A) includes polycarbonate resin (A-1) and polycarbonate resin (A-2).

<<Polycarbonate resin (A-1)>>
The resin composition of the present embodiment includes a polycarbonate resin (A-1) whose cumulative luminescence amount is less than 8.0×10 ⁵ cps when measured at elevated temperature using a chemiluminescence method.
Furthermore, the lower limit of the cumulative amount of light emitted when the polycarbonate resin (A-1) is measured at elevated temperature by the chemiluminescence method is not particularly determined, but is, for example, 1.0×10 ⁵ cps or more.
The polycarbonate resin (A-1) also has a ratio of the maximum luminescence amount on the low temperature side and the maximum luminescence amount on the high temperature side when measured at elevated temperature by chemiluminescence method, (maximum luminescence amount on the low temperature side)/( The maximum light emission amount on the high temperature side) is preferably 0.16 or less, more preferably 0.14 or less. The lower limit of (maximum light emission amount on the low temperature side)/(maximum light emission amount on the high temperature side) is not particularly determined, but is preferably 0.01 or more.

The intensity at 2000 cm ^-1 when the Raman spectrum of the polycarbonate resin (A-1) was measured using a laser beam with a wavelength of 532 nm, an exposure time of 1.0 seconds, a number of exposures of 4 times, and a laser output of 1.6 mW was It is preferably less than 1,000 cps, more preferably less than 900 cps, even more preferably less than 800 cps, even more preferably 600 cps or less, even more preferably 400 cps or less, and even more preferably 200 cps or less. Even more preferably. When the content is below the upper limit, flame retardancy tends to be further improved. Further, the lower limit of the intensity at 2000 cm ^-1 when measuring the Raman spectrum is not particularly determined, but 10 cps or more is practical.

The cumulative amount of light emitted when measured at elevated temperature using the chemiluminescence method, the ratio of the maximum light emitted amount on the low temperature side and the maximum amount of light emitted at the high temperature side when measured at elevated temperature using the chemiluminescence method, and when measuring the Raman spectrum. The strength at 2000 cm ⁻¹ is measured according to the description in the Examples below.

The cumulative amount of light emitted when measuring the temperature with the chemiluminescence method mentioned above, the ratio of the maximum light emission amount on the low temperature side and the maximum light amount on the high temperature side when measuring the temperature with the chemiluminescence method, 2000 cm when measuring the Raman spectrum ^- An example of a polycarbonate resin that satisfies the strength in ¹ is virgin polycarbonate resin. Commercial products such as the polycarbonate resins shown in Examples A6 and A7 described below are virgin polycarbonate resins.

Specifically, the polycarbonate resin (A-1) has -[O-R-OC(=O)]- units (R is an organic group, preferably a hydrocarbon group) containing a carbonate ester bond in the molecular main chain. It is not particularly limited as long as it contains an aliphatic group, an aromatic group, or a group containing both an aliphatic group and an aromatic group, and a linear or branched structure. In this embodiment, the polycarbonate resin is preferably an aromatic polycarbonate resin, and more preferably a polycarbonate resin having a bisphenol skeleton. By using such a polycarbonate resin, better heat resistance and toughness can be achieved. In this embodiment, the polycarbonate resin having a bisphenol skeleton is preferably such that 90 mol% or more of all structural units are structural units having a bisphenol skeleton, and 90 mol% or more of all structural units are bisphenol A-derived structural units. It is more preferable that

In this embodiment, the weight average molecular weight (Mw) of the polycarbonate resin (A-1) is preferably 35,000 or more, more preferably 40,000 or more, and still more preferably 45,000 or more. . By setting it to the above lower limit or more, the durability of the obtained molded product tends to be further improved. The upper limit of the weight average molecular weight (Mw) of the polycarbonate resin is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 80,000 or less. By setting it below the above-mentioned upper limit value, the molding processability of the molded article tends to be further improved.
The weight average molecular weight of the polycarbonate resin (A-1) is measured according to the description in the examples below.

The method for producing polycarbonate resin is not particularly limited, and those produced by the conventionally known phosgene method (interfacial polymerization method) or melting method (ester exchange method) can be used. Furthermore, when a melting method is used, a polycarbonate resin in which the amount of OH groups in the terminal groups is adjusted can be used.

In addition to the above, for details of the polycarbonate resin, please refer to paragraphs 0013 to 0041 of JP 2021-084942, and paragraphs 0030 to 0035 of JP 2021-119211, the contents of which are incorporated herein. .

<<Polycarbonate resin (A-2)>>
The resin composition of the present embodiment has the ratio of the maximum luminescence amount on the low temperature side and the maximum luminescence amount on the high temperature side when measured by increasing temperature using the chemiluminescence method. The polycarbonate resin (A-2) has a maximum luminescence amount of more than 0.16 and an integrated luminescence amount of 8.0×10 ⁵ cps or more when measured by a chemiluminescence method at elevated temperatures. It is presumed that by including such a polycarbonate resin (A-2), moderate branching of the polycarbonate resin proceeds, carbonization is promoted, and flame retardancy can be improved.

The ratio (maximum light emission amount on the low temperature side)/(maximum light emission amount on the high temperature side) of the polycarbonate resin (A-2) is preferably 0.20 or more, more preferably 0.25 or more, and 0. It is more preferably .30 or more, even more preferably 0.35 or more, even more preferably 0.40 or more, even more preferably 0.50 or more, and even more preferably 0.60 or more. It is particularly preferred that there be. When the content is equal to or more than the lower limit, the flame retardance of the obtained molded product is improved. Further, the ratio (maximum luminescence amount on the low temperature side)/(maximum luminescence amount on the high temperature side) of the polycarbonate resin (A-2) is preferably 10.00 or less, more preferably 5.00 or less. , more preferably 3.00 or less, even more preferably 1.0 or less, even more preferably 0.80 or less. When the content is below the upper limit, flame retardancy tends to be further improved.

The cumulative luminescence amount of the polycarbonate resin (A-2) when measured at elevated temperature by chemiluminescence method is preferably 8.0×10 ⁵ cps or more, and preferably 1.0×10 ⁶ cps or more. More preferably, it is 1.4 x 10 ⁶ cps or more, even more preferably 2.0 x 10 ⁶ cps or more, it may be 3.0 x 10 ⁶ cps or more, and 4.5 ×10 cps ⁶ or more may be sufficient. When the content is equal to or more than the lower limit, flame retardancy tends to be further improved. Further, the cumulative luminescence amount of the polycarbonate resin (A-2) when measured at elevated temperature by chemiluminescence method is preferably 10.0×10 ⁷ cps or less, and preferably 5.0×10 ⁷ cps or less. It is more preferable that it is 1.0×10 ⁷ cps or less, and even more preferably that it is 9.0×10 ⁶ cps or less. When the content is below the upper limit, flame retardancy tends to be further improved.

When the Raman spectrum of the polycarbonate resin (A-2) was measured using a laser beam with a wavelength of 532 nm, an exposure time of 1.0 seconds, a number of exposures of 4 times, and a laser output of 1.6 mW, the intensity at 2000 cm ^-1 was as follows: It is preferably 1,000 cps or more, more preferably 2,000 cps or more, even more preferably 5,000 cps or more, and even more preferably 10,000 cps or more. Further, the intensity at 2000 cm ^-1 when the Raman spectrum of the polycarbonate resin (A-2) is measured is preferably 200,000 cps or less, and may be 30,000 cps or less. When the content is below the upper limit and above the lower limit, the flame retardance of the obtained molded product tends to be further improved.

In the present embodiment, the weight average molecular weight of the polycarbonate resin (A-2) is preferably 35,000 or more, more preferably 40,000 or more, and still more preferably 42,000 or more. By setting it to the above lower limit or more, the durability of the obtained molded product tends to be further improved. The upper limit of the weight average molecular weight (Mw) of the polycarbonate resin is preferably 100,000 or less, more preferably 80,000 or less, and still more preferably 60,000 or less. By setting it below the above-mentioned upper limit value, the molding processability of the molded article tends to be further improved.

The cumulative amount of light emitted when measuring the temperature with the chemiluminescence method mentioned above, the ratio of the maximum light emission amount on the low temperature side and the maximum light amount on the high temperature side when measuring the temperature with the chemiluminescence method, 2000 cm when measuring the Raman spectrum ^- The strength at ^{No. 1} and the weight average molecular weight are measured according to the description in the examples below.

The cumulative amount of light emitted when measured at elevated temperature using the chemiluminescence method, the ratio of the maximum light emitted amount on the low temperature side and the maximum amount of light emitted at the high temperature side when measured at elevated temperature using the chemiluminescence method, and when measuring the Raman spectrum. Examples of polycarbonate resins that satisfy at least one of the strength requirements at 2000 cm ⁻¹ include polycarbonate resins derived from molded products made from polycarbonate resins.
Polycarbonate resin derived from molded products made from polycarbonate resin refers to virgin polycarbonate resin that has been subjected to some molding processing, and includes recycled polycarbonate resin, rejected polycarbonate resin molded products, and polycarbonate resin molded products. The purpose is to include scrap materials from manufacturing. The molded products include injection molded products, extrusion molded products, and molded products molded by other manufacturing methods.
Recycled polycarbonate resins include those obtained through material recycling in which collected used polycarbonate resin molded products are crushed, washed with alkali, and reused as fibers, etc., those obtained through chemical recycling (chemical decomposition method), and those obtained through mechanical recycling. Examples include those obtained through recycling.
Chemical recycling involves chemically decomposing collected used polycarbonate resin molded products, returning them to raw material level, and resynthesizing polycarbonate resin. On the other hand, mechanical recycling is a method that makes it possible to remove dirt from polycarbonate resin molded products more reliably than material recycling, by performing the alkaline cleaning more strictly in the material recycling mentioned above, or vacuum drying at high temperatures. It is.
For example, recycled polycarbonate resin can be obtained by removing foreign matter from a used polycarbonate resin molded product, pulverizing and washing the product, and then pelletizing it using an extruder.
Examples of used polycarbonate resin molded products include disks, sheets (including films), meter covers, headlamp lenses, and water bottles, and preferably meter covers, sheets, or headlamp lenses.

The polycarbonate resin (A-2) also has a -[OR-OC(=O)]- unit (R is an organic group, preferably a hydrocarbon group, more preferably a hydrocarbon group) containing a carbonate ester bond in the molecular main chain. is not particularly limited as long as it contains an aliphatic group, an aromatic group, a group containing both an aliphatic group and an aromatic group, and a group having a linear or branched structure. In this embodiment, the polycarbonate resin is preferably an aromatic polycarbonate resin, and more preferably a polycarbonate resin having a bisphenol skeleton. By using such a polycarbonate resin, better heat resistance and toughness can be achieved. In this embodiment, the polycarbonate resin having a bisphenol skeleton is preferably such that 90 mol% or more of all structural units are structural units having a bisphenol skeleton, and 90 mol% or more of all structural units are bisphenol A-derived structural units. It is more preferable that

<<Blend form of polycarbonate resins (A-1) and (A-2)>>
In this embodiment, the proportion of the polycarbonate resin (A-2) in 100 parts by mass of the polycarbonate resin (A) is 10 parts by mass or more, furthermore, 15 parts by mass or more, 20 parts by mass or more, and 25 parts by mass. The amount may be 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, or 50 parts by mass or more. Further, in the present embodiment, the proportion of the polycarbonate resin (A-2) in 100 parts by mass of the polycarbonate resin (A) is 99 parts by mass or less, preferably 95 parts by mass or less, and more preferably 90 parts by mass or less. It may be less than 85 parts by mass, or less than 80 parts by mass. When the content is below the upper limit, flame retardancy tends to be further improved.
The resin composition of the present embodiment may contain only one type of polycarbonate resin (A-1) and polycarbonate resin (A-2), or may contain two or more types of polycarbonate resin (A-2). When two or more types are included, it is preferable that the total amount falls within the above range.

In this embodiment, it is preferable that the proportion of polycarbonate resin (A-1) and polycarbonate resin (A-2) in (A) polycarbonate resin contained in the resin composition is 90% by mass or more, and 95% by mass. % or more, even more preferably 97% by mass or more, even more preferably 99% by mass or more.
Further, the content of the polycarbonate resin (A) in the resin composition of the present embodiment is preferably 85% by mass or more, and 90% by mass or more in the resin composition when the resin composition does not contain a reinforcing material. The content is more preferably 95% by mass or more, even more preferably 97% by mass or more.
In addition, when the resin composition contains a reinforcing material, the content of the polycarbonate resin (A) in the resin composition of the present embodiment may be 85% by mass or more of the components other than the reinforcing material in the resin composition. It is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 97% by mass or more.

<(B) Phosphate ester flame retardant>
The resin composition of this embodiment includes (B) a phosphate ester flame retardant. By including a phosphate ester flame retardant, a molded article with excellent flame retardancy can be obtained.
As the phosphate ester flame retardant, a condensed phosphate ester flame retardant is preferable, and a condensed phosphate ester flame retardant represented by the following formula (P) is more preferable.
Formula (P)

In formula (P), k may be a mixture of compounds having different numbers, and in the case of a mixture of condensed phosphoric acid esters with different k, k is the average value of the mixture. k is usually an integer from 0 to 5, and in the case of a mixture of compounds having different k numbers, the average k number is preferably 0.5 or more, more preferably 0.6 or more, and even more preferably 0.8. Above, it is particularly preferably 0.95 or more, preferably 2 or less, more preferably 1.5 or less, still more preferably 1.2 or less, particularly preferably 1.15 or less.

Furthermore, X ¹ represents a divalent arylene group, such as resorcinol, hydroquinone, bisphenol A, 2,2'-dihydroxybiphenyl, 2,3'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 3,3 '-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1 , 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, etc. It is the basis of Among these, divalent groups derived from resorcinol, bisphenol A, and 3,3'-dihydroxybiphenyl are particularly preferred.

p, q, r and s in formula (P) each independently represent 0 or 1, and 1 is particularly preferred.

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in formula (P) each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of such aryl groups include phenyl group, cresyl group, xylyl group, isopropylphenyl group, butylphenyl group, tert-butylphenyl group, di-tert-butylphenyl group, p-cumylphenyl group, etc. A cresyl group, a xylyl group, and a xylyl group are more preferable.

Specific examples of condensed phosphate ester flame retardants represented by formula (P) include triphenyl phosphate (TPP), tricresyl phosphate (TCP), tricylenyl phosphate (TXP), and cresyl diphenyl phosphate (CDP). ), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate, bis-(tert-butylphenyl) phenyl phosphate, tris-(tert-butylphenyl) phosphate, isopropylphenyl diphenyl phosphate, bis-(isopropylphenyl) Aromatic phosphate esters such as diphenyl phosphate and tris-(isopropylphenyl) phosphate; resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A bis-diphenyl phosphate (BDP), biphenyl Condensed phosphoric acid esters such as bis-diphenyl phosphate; and the like.

The acid value of the condensed phosphate ester flame retardant represented by formula (P) is preferably 0.2 mgKOH/g or less, more preferably 0.15 mgKOH/g or less, and even more preferably 0.1 mgKOH or less. , particularly preferably 0.05 mgKOH/g or less. The lower limit of this acid value can also be set to substantially zero. Further, the content of the half ester of the condensed phosphate flame retardant represented by formula (P) is preferably 1% by mass or less, more preferably 0.5% by mass or less. By setting the acid value to 0.2 mgKOH/g or less and by setting the half ester content to 1% by mass or less, the thermal stability and hydrolysis resistance of the obtained molded product tend to be further improved. .

Phosphate-based flame retardants include, in addition to those mentioned above, polyester resins, polycarbonate resins, and epoxy resins containing phosphate moieties.
In addition, the descriptions in paragraphs 0030 to 0034 of International Publication No. 2017/038737 can also be referred to, and the contents thereof are incorporated herein.

The content of the phosphate ester flame retardant (B) in the resin composition of the present embodiment is 6 parts by mass or more, preferably 7 parts by mass or more, based on 100 parts by mass of the (A) polycarbonate resin. It is more preferably 8 parts by mass or more, even more preferably 9 parts by mass or more, and even more preferably 10 parts by mass or more. By setting it to the above lower limit or more, the formation of char during combustion of the resin molded product can be promoted, and the flame retardance can be further improved. In addition, the content of the phosphate ester flame retardant (B) is 20 parts by mass or less, preferably 19 parts by mass or less, and 18 parts by mass or less with respect to 100 parts by mass of (A) polycarbonate resin. The amount is more preferably at most 17 parts by mass, even more preferably at most 16 parts by mass, and even more preferably at most 16 parts by mass. When the content is below the upper limit, the flame retardant effect tends to be more effectively exhibited even though the content of the flame retardant is reduced. Furthermore, the heat resistance of the resulting resin composition is improved, and the productivity of pellets also tends to be improved.
The resin composition of this embodiment may contain only one type of phosphate ester flame retardant (B), or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

The resin composition of this embodiment may or may not contain a flame retardant other than the phosphate ester flame retardant (B). (B) Examples of flame retardants other than phosphate ester flame retardants include alkali metal salts and halogen flame retardants.
An example of the resin composition of this embodiment is that it does not substantially contain any flame retardant other than (B) the phosphate ester flame retardant. "Substantially free" means that among the flame retardants contained in the resin composition, the content of flame retardants other than (B) phosphate ester flame retardants is such that the content of flame retardants other than (B) phosphate ester flame retardants is It refers to the content of 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

<(C) Fluoropolymer having fibril-forming ability>
The resin composition of this embodiment contains a fluoropolymer having fibril-forming ability.
A fluoropolymer with fibril-forming ability is an anti-dripping agent that easily disperses in a resin composition and has a tendency to bond polymers together to form a fibrous structure. It is.
The fluoropolymer having fibril-forming ability preferably has an extremely high molecular weight of 1 million to 10 million, and exhibits a tendency to bond fluoropolymers together and become fibrous due to external action such as shearing force. be. As the fluoropolymer, tetrafluoroethylene (TFE) resin, perfluoroalkoxy (PFA) resin, fluorinated ethylene propylene (FEP) resin, etc. are preferable, and polytetrafluoroethylene is particularly preferable.

Examples of the fluoropolymer having fibril-forming ability include Teflon (registered trademark) 6J manufactured by DuPont Mitsui Fluorochemicals and Polyflon manufactured by Daikin Industries.

It is also preferable to use the fluoropolymer in the form of an aqueous dispersion thereof. This dispersion is an aqueous dispersion produced by adding a surfactant to a fluororesin latex usually obtained by emulsion polymerization, and concentrating and stabilizing it. The content of fluoropolymer in the aqueous dispersion is preferably from 20 to 80% by weight, in particular from 30 to 70% by weight.
Examples of aqueous polytetrafluoroethylene dispersions include Teflon (registered trademark) 30J manufactured by DuPont Mitsui Fluorochemicals, Fluon D-1 manufactured by Daikin Industries, Ltd., and polytetrafluoroethylene having a multilayer structure obtained by polymerizing vinyl monomers. Examples include tetrafluoroethylene polymers, such as Metablen A-3800 manufactured by Mitsubishi Rayon Co., Ltd.

Furthermore, the fluoropolymer having fibril-forming ability preferably has a primary particle diameter in the range of 0.05 to 1.0 μm, more preferably 0.1 to 0.5 μm. The fluoropolymer is preferably in the form of fibrils having a thickness of 0.5 microns or less in the resin composition, and the fibrils preferably exist in a network structure and/or a branched structure.

The content of the (C) fluoropolymer having fibril-forming ability in the resin composition of the present embodiment is 0.01 parts by mass or more, and 0.03 parts by mass or more based on 100 parts by mass of the (A) polycarbonate resin. It is preferably at least 0.05 parts by mass, more preferably at least 0.07 parts by mass, even more preferably at least 0.1 parts by mass. By setting it above the lower limit, the dripping prevention effect tends to be effectively exhibited. Further, the content of (C) the fluoropolymer having fibril-forming ability is 3 parts by mass or less, preferably 2.5 parts by mass or less, and 2.0 parts by mass or less, based on 100 parts by mass of the (A) polycarbonate resin. It is more preferably at most parts by mass, even more preferably at most 1.0 parts by mass, even more preferably at most 0.7 parts by mass, and even more preferably at most 0.5 parts by mass. When the content is below the upper limit, the mechanical strength of the resulting molded product tends to improve, and the appearance tends to improve.
The resin composition of this embodiment may contain only one type of (C) fluoropolymer having fibril-forming ability, or may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

<Elastomer>
It is also preferable that the resin composition of this embodiment contains an elastomer.
The elastomer is preferably a copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable with the rubber component. The method for producing such a graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, and the method of copolymerization may be single-stage grafting or multi-stage grafting. Good too.

The above-mentioned rubber component usually has a glass transition temperature of 0°C or lower, preferably -20°C or lower, and more preferably -30°C or lower. Specific examples of rubber components include polybutadiene rubber, polyisoprene rubber, polyalkyl acrylate rubber such as polybutyl acrylate, poly(2-ethylhexyl acrylate), butyl acrylate/2-ethylhexyl acrylate copolymer, and organopolysiloxane rubber. Silicone rubber, butadiene-acrylic composite rubber, IPN type composite rubber consisting of organopolysiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-α olefin such as ethylene-propylene rubber, ethylene-butene rubber, and ethylene-octene rubber. Examples include rubber, ethylene-acrylic rubber, and fluororubber. These may be used alone or in combination of two or more. Among these, polybutadiene rubber, polyalkyl acrylate rubber, IPN type composite rubber made of organopolysiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferred from the viewpoint of mechanical properties and surface appearance.

Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, glycidyl (meth)acrylate, etc. Epoxy group-containing (meth)acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and their anhydrides (eg, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, from the viewpoint of mechanical properties and surface appearance, aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, and (meth)acrylic acid compounds are preferable, and (meth)acrylic acid esters are more preferable. It is a compound. Specific examples of (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, etc. be able to.

The elastomer used in this embodiment is preferably a core/shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, IPN type composite rubber consisting of organopolysiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and (meth)acrylic acid ester is surrounded by the core layer. A core/shell type graft copolymer consisting of a shell layer formed by copolymerizing is preferred, and a core/shell type elastomer having a core of butadiene rubber is particularly preferred. In the above-mentioned core/shell type graft copolymer, one containing a rubber component in an amount of 40% by mass or more is preferable, and one containing a rubber component in an amount of 60% by weight or more is more preferable. Further, it is preferable that the (meth)acrylic acid component is contained in an amount of 10% by mass or more.

Preferred specific examples of these core/shell type graft copolymers include acrylonitrile-butadiene-styrene copolymer (ABS), methyl methacrylate-butadiene-styrene copolymer (MBS), and methyl methacrylate-acrylonitrile-butadiene-styrene copolymer. Copolymer (MABS), Methyl methacrylate-butadiene copolymer (MB), Methyl methacrylate-acrylic rubber copolymer (MA), Methyl methacrylate-acrylic rubber-styrene copolymer (MAS), Methyl methacrylate-acrylic/butadiene Examples include rubber copolymers, methyl methacrylate-acrylic/butadiene rubber-styrene copolymers, and methyl methacrylate (acrylic/silicone IPN rubber) copolymers. Such rubbery polymers may be used alone or in combination of two or more.
In addition to the above, as the elastomer, those described in paragraphs 0068 to 0079 of JP 2019-123809 A can be used, the contents of which are incorporated herein.

When the resin composition of the present embodiment contains an elastomer, the content thereof is preferably 0.5 parts by mass or more, and preferably 1.0 parts by mass or more, based on 100 parts by mass of (A) polycarbonate resin. is more preferable, and even more preferably 1.5 parts by mass or more. When the content is equal to or more than the lower limit, the impact resistance of the resulting molded product tends to improve. Further, the upper limit of the content of the elastomer is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and 20 parts by mass or less based on 100 parts by mass of (A) polycarbonate resin. It is even more preferable that the amount is 10 parts by mass or less, even more preferably 7 parts by mass or less. When the content is below the upper limit, the surface hardness, heat resistance, rigidity, etc. of the resulting molded product tend to improve.
The resin composition of this embodiment may contain only one type of elastomer, or may contain two or more types of elastomer. When two or more types are included, it is preferable that the total amount falls within the above range.

<Epoxy compound>
It is also preferable that the resin composition of this embodiment contains an epoxy compound. By containing an epoxy compound, a molded article with superior mechanical strength can be obtained.
The epoxy compound may have one or more epoxy groups in one molecule, and is usually a glycidyl compound that is a reaction product of alcohol, phenol, or carboxylic acid with epichlorohydrin, or an olefinic compound. A compound in which the double bond is epoxidized may be used.
Examples of the epoxy compound include novolac type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, alicyclic epoxy compounds, glycidyl ethers, glycidyl esters, epoxidized butadiene polymers, resorcin type epoxy compounds, etc. Can be mentioned.

Examples of the novolak-type epoxy compound include phenol novolac-type epoxy compounds, cresol novolac-type epoxy compounds, and the like.
Examples of bisphenol A-type epoxy compounds include bisphenol A-diglycidyl ether and hydrogenated bisphenol A-diglycidyl ether, and examples of bisphenol F-type epoxy compounds include bisphenol F-diglycidyl ether and hydrogenated bisphenol F-diglycidyl ether. Examples include ether.

Examples of alicyclic epoxy compounds include vinylcyclohexene dioxide, dicyclopentadiene oxide, 3,4-epoxycyclohexyl-3,4-cyclohexylcarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene dioxide, Examples include epoxide, 3,4-epoxycyclohexyl glycidyl ether, and the like.

Specific examples of glycidyl ethers include monoglycidyl ethers such as methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, and allyl glycidyl ether; Examples include diglycidyl ethers such as pentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, and bisphenol A diglycidyl ether.

Examples of the glycidyl esters include monoglycidyl esters such as benzoic acid glycidyl ester and sorbic acid glycidyl ester; diglycidyl esters such as adipic acid diglycidyl ester, terephthalic acid diglycidyl ester, and orthophthalic acid diglycidyl ester.

Examples of the epoxidized butadiene polymer include epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, and epoxidized hydrogenated styrene-butadiene copolymer.
Examples of resorcin type epoxy compounds include resorcin diglycidyl ether.

Further, the epoxy compound may be a copolymer containing a glycidyl group-containing compound as one component. Examples include copolymers of glycidyl esters of α,β-unsaturated acids and one or more monomers selected from the group consisting of α-olefins, acrylic acid, acrylic esters, methacrylic acid, and methacrylic esters. It will be done.

The epoxy compound preferably has an epoxy equivalent of 50 to 10,000 g/eq and a weight average molecular weight of 8,000 or less.

The content of the epoxy compound is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, further preferably 0.01 parts by mass or more, and 2 It is preferably at most 1 part by mass, more preferably at most 1 part by mass, further preferably at most 0.5 part by mass, particularly preferably at most 0.1 part by mass.
The resin composition of this embodiment may contain only one type of epoxy compound, or may contain two or more types of epoxy compounds. When two or more types are included, it is preferable that the total amount falls within the above range.

<Stabilizer>
Examples of stabilizers include heat stabilizers and antioxidants.
Examples of the stabilizer include phenol type, amine type, phosphorus type, thioether type and the like. Among these, in this embodiment, phosphorus-based thermal stabilizers and/or phenolic antioxidants are preferred.

Any known phosphorus thermal stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; Phosphates of Group 1 or Group 2B metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; examples include organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds; is particularly preferred.

Examples of organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl/dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis(4,6-di- Examples include tert-butylphenyl) octyl phosphite.
Specific examples of such organic phosphite compounds include, for example, "ADEKA STAB (registered trademark, hereinafter the same) 1178", "ADEKA STAB 2112", "ADEK STAB HP-10" manufactured by ADEKA, and "ADEKA STAB HP-10" manufactured by Johoku Kagaku Kogyo Co., Ltd. Examples include "JP-351", "JP-360", "JP-3CP", and "Irgafoss (registered trademark, hereinafter the same) 168" manufactured by BASF.

As the phenolic antioxidant, a hindered phenolic antioxidant is preferably used.
Specific examples of hindered phenolic antioxidants include pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert -butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethyl) ethyl)-4-hydroxyphenyl]methyl]phosphate, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m- tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4- hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1) , 3,5-triazin-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, etc. Can be mentioned.

Among them, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferable. Specifically, examples of such hindered phenolic antioxidants include "Irganox (registered trademark) 1010" and "Irganox 1076" manufactured by BASF, "ADEK STAB AO-50" manufactured by ADEKA, and " ADEKA STAB AO-60'' and the like.

The content of the stabilizer in the resin composition of the present embodiment is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass, based on 100 parts by mass of the (A) polycarbonate resin. The amount is usually 1 part by weight or less, preferably 0.5 part by weight or less, more preferably 0.3 part by weight or less. By setting the content of the stabilizer within the above range, the effect of adding the stabilizer is more effectively exhibited.
The resin composition of this embodiment may contain only one kind of stabilizer, or may contain two or more kinds of stabilizers. When two or more types are included, it is preferable that the total amount falls within the above range.

<Release agent>
The resin composition of this embodiment may contain a mold release agent.
Examples of mold release agents include aliphatic carboxylic acids, salts of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils. , ketone wax, light amide, etc., aliphatic carboxylic acids, salts of aliphatic carboxylic acids, and esters of aliphatic carboxylic acids and alcohols are preferred, and salts of aliphatic carboxylic acids are more preferred.
For details of the mold release agent, the descriptions in paragraphs 0055 to 0061 of JP 2018-095706A and paragraphs 0106 to 0115 of JP 2015-117298A can be referred to, and the contents thereof are incorporated herein.
When the resin composition of the present embodiment includes a mold release agent, the content thereof is preferably 0.05 to 3% by mass, and preferably 0.1 to 0.8% by mass in the resin composition. is more preferable, and even more preferably 0.1 to 0.6% by mass.
The resin composition of this embodiment may contain only one type of mold release agent, or may contain two or more types of mold release agents. When two or more types are included, it is preferable that the total amount falls within the above range.

<Other ingredients>
The resin composition of the present embodiment may contain other components other than those mentioned above, as necessary, as long as desired physical properties are not significantly impaired. Examples of other components include reinforcing materials, thermoplastic resins other than polycarbonate resins, and various resin additives.
As for the reinforcing material, the descriptions in paragraphs 0107 to 0115 of JP-A-2014-136710 can be referred to, the contents of which are incorporated herein.
Examples of resin additives include colorants (dyes, pigments), antistatic agents, antifogging agents, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like. In addition, one type of resin additive may be contained, or two or more types may be contained in any combination and ratio.
As the resin additive, the descriptions in paragraphs 0117 to 0128 of JP-A-2015-117298 can also be referred to, the contents of which are incorporated herein.

<Physical properties of resin composition>
It is desired that the resin composition of this embodiment has excellent flame retardancy.
Specifically, the resin composition of this embodiment preferably achieves V-0 when molded to a thickness of 0.8 mm and tested in accordance with UL94.
Further, when the resin composition of the present embodiment is molded to a thickness of 0.8 mm and tested in accordance with UL94, the total afterflame time is preferably 50 seconds or less, and preferably 32 seconds or less. More preferably, the time is 28 seconds or less, and even more preferably 25 seconds or less.

<Manufacture of resin composition>
There are no restrictions on the method for producing the resin composition of this embodiment, and any known method for producing a resin composition can be widely adopted. The fluoropolymer and other components blended as necessary are mixed in advance using various mixers such as a tumbler or Henschel mixer, and then mixed in a Banbury mixer, roll, Brabender, single-screw kneading extruder, or double-screw extruder. Examples include a method of melt-kneading using a mixer such as a axial kneading extruder or a kneader. Note that the melt-kneading temperature is not particularly limited, but is usually in the range of 240 to 320°C.

<Molded product>
The molded article of this embodiment is formed from the resin composition of this embodiment. The above-described resin composition (for example, pellets) is molded into a molded article by various molding methods. The shape of the molded product is not particularly limited and can be selected as appropriate depending on the use and purpose of the molded product, such as film, rod, cylindrical, annular, circular, elliptical, and polygonal shapes. , irregularly shaped products, hollow products, frame-shaped, box-shaped, panel-shaped, button-shaped products, etc.

The method for molding the molded product is not particularly limited, and conventionally known molding methods can be employed, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, blow molding, Gas-assisted blow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding), rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding , pressure molding method, etc. In particular, the resin composition of this embodiment is suitable for molded articles obtained by injection molding, injection compression molding, and extrusion molding. However, it goes without saying that the resin composition of this embodiment is not limited to molded articles obtained by these methods.

The molded article of this embodiment is widely used in applications requiring flame retardancy. Specifically, it is preferably used for electrical and electronic equipment/components, OA equipment/components, information terminal equipment/components, mechanical parts, home appliances, vehicle parts, construction materials, various containers, leisure goods/miscellaneous goods, lighting equipment, etc. .

The present invention will be explained in more detail with reference to Examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
If the measuring equipment used in the examples is difficult to obtain due to discontinuation or the like, measurements can be made using other equipment with equivalent performance.

As the polycarbonate resins A1, A2, and A8, recycled polycarbonate resins derived from water bottles were used. For A3, recycled polycarbonate resin derived from sheets was used. For A4 and A5, polycarbonate resin derived from headlamp lenses was used.
As the polycarbonate resins A6 and A7, the following commercially available virgin polycarbonate resins were used.

<Accumulated luminescence amount and (maximum luminescence amount on low temperature side) / (maximum luminescence amount on high temperature side) when measuring temperature increase using chemiluminescence method>
It is the cumulative amount of light emitted when polycarbonate resin is measured at elevated temperature using the chemiluminescence method, and the ratio of the maximum light emitted amount on the low temperature side and the maximum light emitted amount on the high temperature side when measured at elevated temperature using the chemiluminescence method. The maximum luminescence amount)/(maximum luminescence amount on the high temperature side) was measured as follows.

Approximately 200 mg of the sample (polycarbonate resin) was set in a chemiluminescence measuring device, and the temperature was raised from 50°C to 350°C at a rate of 20°C/min in a nitrogen atmosphere with a nitrogen flow rate of 50 mL/min, every 1 second. The amount of luminescence (unit: cps) was measured.
The cumulative amount of light emitted from 0 seconds to 810 seconds (the cumulative amount of light emitted when the temperature was measured by the chemiluminescence method) (unit: cps) was measured.
The maximum light emission amount between 0 and 500 seconds is defined as the "maximum light emission amount on the low temperature side." amount)/(maximum luminescence amount on the high temperature side) was calculated. However, in the case where the maximum light emission amount was at 810 seconds on the high temperature side, the peak closest to 810 seconds before 810 seconds was taken as the maximum light emission amount.
As the chemiluminescence measuring device, CLA-FS4 (main body) and CLS-SH0 (sample chamber) manufactured by Tohoku Denshi Sangyo were used.
The results are shown in Table 2 below.

<2000cm ^-1 Raman spectrum intensity>
The intensity at 2000 cm ^-1 was measured using a laser beam with a wavelength of 532 nm, an exposure time of 1.0 seconds, an exposure time of 4 times, and a laser output of 1.6 mW. During the measurement, the focus was set on the surface of the pellet.
DXR II manufactured by Thermo Fisher Scientific was used to measure the intensity of the Raman spectrum.
The results are shown in Table 2 below.

<Measurement of weight average molecular weight (Mw) of polycarbonate resin>
The weight average molecular weight of the polycarbonate resin was measured under the following conditions and calculated as the weight average molecular weight in terms of polystyrene. The results are shown in Table 2 below.
Equipment: HLC-8320GPC EcoSEC (manufactured by Tosoh Corporation)
<<Analysis conditions>>
Column Shodex KF-G + KF-805L x 3 + KF-800D
Flow rate 1.2mL/min
Detector HLC-8320GPC
Injection volume 200μL
Column temperature 40℃
Eluent Tetrahydrofuran

Other raw materials are shown in Table 3 below.

Examples 1 to 10, Comparative Examples 1 to 3
<Preparation of resin pellets>
Each component listed in Tables 1 to 3 was blended in the proportions shown in Table 5 or Table 6 (each component is in parts by mass) and mixed in a tumbler for 20 minutes. This mixture was supplied to an extruder manufactured by Japan Steel Works (TEX30HSST), kneaded at a screw rotation speed of 220 rpm, a discharge rate of 30 kg/hour, and a barrel temperature of 260 to 270° C., and extruded into a strand. This was cooled with water and made into pellets using a pelletizer.

<Manufacture of combustion test pieces>
After drying the obtained pellets at 120°C for 5 hours, injection molding was performed using an injection molding machine (“SE100DUHP” manufactured by Sumitomo Heavy Industries, Ltd.) at a set temperature of 280°C and a mold temperature of 80°C. A test piece (UL test piece) was obtained as a molded article with a length of 127 mm, a width of 12.7 mm, and a wall thickness of 0.8 mm. The obtained UL test pieces were subjected to a vertical combustion test in accordance with UL94, and the flammability results were ranked V-0, V-1, and V-2 in descending order of best.

<Evaluation of flame retardancy>
The UL test piece prepared above was conditioned for 48 hours in a constant temperature room with a temperature of 23°C and a humidity of 50%, and then tested for flame retardancy in accordance with the UL94 test (flammability test for plastic materials for equipment parts). evaluated. The results are shown in Tables 5-10. This test is a method of evaluating flame retardancy based on the following criteria based on the afterflame time and drip properties after a test piece held vertically is brought into contact with a burner flame for 10 seconds.

Afterflame time is the length of time that a UL specimen continues to burn flamingly after the burner is removed. Cotton ignition by drip is a test to determine whether or not cotton for marking located approximately 300 mm from the bottom end of the UL test piece is ignited by drips from the test piece. If even one of the five samples does not meet the above criteria, it is indicated as NR (not rated) as not meeting V-2.

As is clear from the above results, the ratio of the maximum luminescence amount on the low temperature side and the maximum luminescence amount on the high temperature side when measured by increasing temperature using the chemiluminescence method is (maximum luminescence amount on the low temperature side) / (maximum luminescence amount on the high temperature side). (Comparative ^Example ) 1) The total afterflame time was long and the flame retardancy rating was V-1. Furthermore, in the case of not containing a phosphate ester flame retardant (Comparative Example 2), the total afterflame time was long, the flame retardancy evaluation was NR, and dripping was also observed. When the content of the phosphate ester flame retardant was large (Comparative Example 3), the total afterflame time further became longer. Furthermore, even if a phosphate ester flame retardant was blended, if the amount blended was small, the total afterflame time was long and the flame retardancy was lowered to V-1.

Claims (5)

(A) For 100 parts by mass of polycarbonate resin,
(B) 6 to 20 parts by mass of a phosphate ester flame retardant;
(C) 0.01 to 3 parts by mass of a fluoropolymer having fibril-forming ability;
The polycarbonate resin (A) includes polycarbonate resin (A-1) and polycarbonate resin (A-2),
The proportion of the polycarbonate resin (A-2) in 100 parts by mass of the polycarbonate resin (A) is 10 to 99 parts by mass,
The cumulative luminescence amount of the polycarbonate resin (A-1) when measured at elevated temperature by chemiluminescence method is less than 8.0 × 10 ⁵ ,
The ratio of the maximum luminescence amount on the low temperature side and the maximum luminescence amount on the high temperature side when the polycarbonate resin (A-2) is measured at elevated temperature using the chemiluminescence method, (maximum luminescence amount on the low temperature side)/(high temperature side) (maximum luminescence amount) is more than 0.16, and the cumulative luminescence amount when measured at elevated temperature by chemiluminescence method is 8.0 × 10 ⁵ cps or more,
Resin composition. The ratio of the maximum luminescence amount on the low temperature side and the maximum luminescence amount on the high temperature side when the polycarbonate resin (A-1) is measured at elevated temperature using the chemiluminescence method, (maximum luminescence amount on the low temperature side)/(high temperature side) The resin composition according to claim 1, wherein the resin composition has a maximum luminescence amount of 0.16 or less. The resin composition according to claim 1 or 2, wherein the polycarbonate resin (A-2) has a weight average molecular weight of 35,000 or more. The resin composition according to any one of claims 1 to 3, wherein the polycarbonate resin (A-2) is derived from a molded article formed from a polycarbonate resin. A molded article formed from the resin composition according to any one of claims 1 to 4.