WO2019176213A1 - Transparent flame-retardant resin composition and method for producing transparent flame-retardant resin composition - Google Patents

Abstract

The purpose of the present invention is to provide a transparent flame-retardant resin composition that exhibits excellent transparency and excellent flame retardancy. Provided is a transparent flame-retardant resin composition which contains at least two types of polycarbonate resin and at least one type of organic flame retardant. The weight average molecular weight of one polycarbonate resin (A) among the at least two types of polycarbonate resin is 52,000 or less in terms of polystyrene, and the content of the organometallic flame retardant is 0.001-3.0 parts by mass relative to a total of 100 parts by mass of the at least two types of polycarbonate resin.

Description

Transparent flame retardant resin composition and method for producing transparent flame retardant resin composition

This technology relates to a transparent flame retardant resin composition and a method for producing the transparent flame retardant resin composition.

For applications that require transparency, such as optical lenses and optical recording media, polycarbonate resins are widely used by taking advantage of the high light transmittance of polycarbonate resins and the excellent transparency typified by extremely low haze. In recent years, from the viewpoint of reducing environmental impact and design, there has been an increasing demand for transparency of polycarbonate even in fields that did not require transparency so far, such as OA equipment, electrical / electronic equipment field, automobile field, and building field. ing. Among these fields of use, there are fields that require a high degree of flame retardancy, mainly in the fields of OA equipment and electrical / electronic equipment.

For example, a flame retardant polycarbonate composition containing a fluorine compound is proposed (see Patent Document 1), and a flame retardant polycarbonate resin composition containing a carbon material and a silicone material is proposed (see Patent Document 2). ), Branched and aromatic polycarbonate resins, and flame retardant polycarbonate resins using organometallic salts have been proposed (see Patent Document 3).

Further, for example, a flame retardant polycarbonate resin composition using a small amount of an aromatic sulfonic acid metal salt, an organic phosphate ester, a polysiloxane and a polyarylene sulfide is proposed (see Patent Document 4), and a polycarbonate having a dihydroxy component A flame retardant polycarbonate composition using a copolymer and a flame retardant has been proposed (see Patent Document 5).

JP 51-45159 JP 2009-149780 A Japanese Patent Laid-Open No. 7-258532 JP-A-11-323118 Japanese Patent Laid-Open No. 11-80529

However, the techniques proposed in Patent Documents 1 to 5 may not be able to further improve transparency and flame retardancy.

Therefore, the main object of the present technology is to provide a transparent flame retardant resin composition having excellent transparency and excellent flame retardancy, and a method for producing the transparent flame retardant resin composition.

As a result of intensive studies to solve the above-mentioned object, the present inventors have surprisingly succeeded in dramatically improving transparency and flame retardancy, and have completed the present technology. It was.

That is, in the present technology, at least two types of polycarbonate resins and at least one type of organic flame retardant are included, and among these at least two types of polycarbonate resins, the weight average molecular weight of one polycarbonate resin (A) is polystyrene. In conversion, it is 52,000 or less,
Provided is a transparent flame retardant resin composition in which the at least one organic flame retardant is 0.001 to 3.0 parts by mass with respect to a total of 100 parts by mass of the at least two types of polycarbonate resins.

In the transparent flame retardant resin composition according to the present technology, the one polycarbonate resin (A) may include a recovered polycarbonate resin.

In the transparent flame-retardant resin composition according to the present technology, the weight average molecular weight of the other polycarbonate resin (B) among the at least two types of polycarbonate resins may be more than 52,000 and not more than 70,000 in terms of polystyrene. .
In the transparent flame retardant resin composition according to the present technology, the other polycarbonate resin (B) may include a polycarbonate resin having a branched structure of 0.01 to 10.0 mol%.
In the transparent flame retardant resin composition according to the present technology, the other polycarbonate resin (B) may contain an aromatic polycarbonate-polyorganosiloxane copolymer.

In the transparent flame retardant resin composition according to the present technology, the at least one organic flame retardant may be an organic sulfonic acid and / or a metal salt compound of an organic sulfonic acid.
In the transparent flame retardant resin composition according to the present technology, the at least one organic flame retardant may be a polymer type organic sulfonic acid and / or a metal salt compound of a polymer type organic sulfonic acid.
In the transparent flame-retardant resin composition according to the present technology, the polymer-type organic sulfonic acid and / or the metal salt compound of the polymer-type organic sulfonic acid may have a polystyrene equivalent weight average molecular weight of 30,000 or more.
In the transparent flame retardant resin composition according to the present technology, the polymer-type organic sulfonic acid and / or the metal salt compound of the polymer-type organic sulfonic acid may contain an aromatic ring in an amount of 1 mol% to 100 mol%, Furthermore, a sulfonic acid group and / or a sulfonic acid metal base may be introduced into the aromatic ring in an amount of 0.1 to 10 mol%.

The transparent flame retardant resin composition according to the present technology may be a flat plate having a thickness of 3.0 mm having an average roughness (Ra) of 0.03 μm or less. Further, in the transparent flame retardant resin composition, The rate may be 80% or more.

In the transparent flame retardant resin composition according to the present technology, the at least one organic flame retardant may be a polymer type organic sulfonic acid and / or a metal salt compound of a polymer type organic sulfonic acid, and has a total light transmittance. May be 85% or more, and the transparent flame-retardant resin composition according to the present technology may be a flat plate having a thickness of 3.0 mm and an average roughness (Ra) of 0.03 μm or less.

The transparent flame retardant resin composition according to the present technology may be a flat plate having a thickness of 3.0 mm having an average roughness (Ra) of 0.03 μm or less. Further, in the transparent flame retardant resin composition, The total light transmittance may be 65% or more under the environment.

The transparent flame retardant resin composition according to the present technology further includes a silicon-based flame retardant auxiliary, and in the transparent flame retardant resin composition, the silicon-based flame retardant auxiliary is a total of 100 of the at least two types of polycarbonate resins. The amount may be 0.01 to 5.0 parts by mass with respect to parts by mass.

In the transparent flame retardant resin composition according to the present technology, the UL94 flame retardance with a thickness of 1.0 mm may be V-0.

In the transparent flame-retardant resin composition according to the present technology, the one polycarbonate resin (A) may include a recovered resin produced for use as an optical component.
In the transparent flame retardant resin composition according to the present technology, the one polycarbonate resin (A) may include an optical component having a weight average molecular weight of 45,000 or less in terms of polystyrene.
In the transparent flame retardant resin composition according to the present technology, the one polycarbonate resin (A) may include an optical component having a polystyrene equivalent weight average molecular weight of 35,000 or less.

In the present technology, adding at least two types of polycarbonate resins and at least one type of organic flame retardant,
Kneading the at least two polycarbonate resins and the at least one organic flame retardant,
Production of transparent flame retardant resin composition, wherein the addition amount of the at least one organic flame retardant is 0.001 to 3.0 parts by mass with respect to 100 parts by mass in total of the at least two types of polycarbonate resins. Provide a method.

According to the present technology, transparency and flame retardancy can be further improved. Note that the effects described here are not necessarily limited, and may be any of the effects described in the present disclosure.

Hereinafter, preferred embodiments for implementing the present technology will be described. The embodiment described below shows an example of a typical embodiment of the present technology, and the scope of the present technology is not interpreted narrowly.

The description will be given in the following order.
1. Overview of this technology First Embodiment (Example of Transparent Flame Retardant Resin Composition)
2-1. Transparent flame retardant resin composition 2-2. Polycarbonate resin 2-3. Organic flame retardant 2-4. Silicon-based flame retardant aid 2-5. Other components Second Embodiment (Example of Production Method of Transparent Flame Retardant Resin Composition)
3-1. 3. Method for producing transparent flame retardant resin composition Third Embodiment (Example of Transparent Flame Retardant Resin Molded Body)
4-1. Transparent flame-retardant resin molding 4-2. Method for producing transparent flame-retardant resin molding

<1. Overview of this technology>
First, an outline of the present technology will be described.
The present technology relates to a transparent flame retardant polycarbonate resin composition and a method for producing the transparent flame retardant resin composition. Specifically, the present technology relates to a transparent flame retardant polycarbonate resin composition excellent in flame retardancy without impairing the original transparency of the polycarbonate resin, and relates to a method for producing the transparent flame retardant resin composition. is there. Further, the present technology may relate to a molded product formed by molding the transparent flame retardant polycarbonate resin composition.

Polycarbonate resin is excellent in transparency and heat resistance, and has excellent mechanical properties such as impact resistance. The polycarbonate resin is a resin having a high oxygen index among various thermoplastic resins and generally having a self-extinguishing property. However, as described above, in order to satisfy safety requirements in the OA equipment, electric / electronic equipment fields, and other various uses, there is a strong demand for a resin composition with further improved flame retardancy. In addition, there is a demand for thinning the material, and it has become necessary to increase the flame retardancy without impairing transparency.

In order to increase the flame retardancy of polycarbonate resin, it is necessary to suppress dripping during combustion. As a method for suppressing dripping during combustion, there is a method of adding polytetrafluoroethylene. For example, by adding an organic alkali metal salt or alkaline earth metal salt to an aromatic polycarbonate and further adding polytetrafluoroethylene, dripping during combustion can be prevented. When blended with an aromatic polycarbonate resin, the polytetrafluoroethylene and the aromatic polycarbonate resin are incompatible with each other, so that the transparency of the molded product is lowered.

As a method of preventing dripping during combustion without using polytetrafluoroethylene, there is a method of adding a carbon nanotube and a specific silicone resin to a polycarbonate resin. In this case, the transparency of the polycarbonate should be maintained. I can't.

As described above, in order to improve the flame retardancy of the polycarbonate resin, a method of adding a flame retardant has been used, but in order to improve the flame retardancy without impairing the transparency inherent in the polycarbonate, There is a limit to the method, and studies have been made to impart flame retardancy to the polycarbonate resin itself, which is the main resin. For example, by using a branched polycarbonate as the main resin and adding an organic alkali metal salt, it is possible to provide a flame-retardant polycarbonate resin composition having transparency, and a high level of flame retardancy is insufficient. It is.

Further, for example, a resin composition comprising a branched polycarbonate resin, an aromatic sulfonic acid metal salt, a halogenated organophosphate, a phenyl group-containing polysiloxane, and a polyarylene sulfide, and maintains the original transparency of the polycarbonate resin. On the other hand, it is possible to provide a flame-retardant polycarbonate resin composition having high flame retardancy that does not exhibit a dripping phenomenon (hereinafter referred to as “drip”) during combustion even when it is thinned. However, at present, a high degree of flame retardancy with a thin wall may be required. Generally, the thinner the wall, the more easily the entire molded product is softened during combustion, and drip is more likely to occur during combustion. Such a phenomenon occurs extremely sensitively to the thickness of the molded product, and even if the thickness difference is about 0.1 mm, there may be a difference in the presence or absence of drip. Furthermore, with the diversification of uses of polycarbonate and the thinning of products, the flame retardant level of materials has become very important.

That is, if the flame retardancy of the material is improved even slightly, the usage of the material will be greatly expanded and the product design will be widened. For example, regarding the UL94 standard, which is widely used as a flame retardant index of materials in electrical applications, the minimum thickness of a test piece that can achieve the flame retardant rank V-0 by improving the flame retardant properties of the material is thin even at 0.1 mm. If this can be done, very great value will be added to the material.

Further, for example, a polycarbonate copolymer containing a carbonate constituent unit composed of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene as a main resin, an organic sulfonate, an organic sulfate, a phosphoric acid It is possible to provide a flame retardant polycarbonate composition comprising a flame retardant amount of at least one compound selected from the group consisting of esters of phosphonic acid and esters of phosphonic acid. However, an organic metal salt flame retardant containing a fluoroalkyl group is not described, and it is considered that the flame retardancy is not sufficient.

As described above, imparting excellent transparency and excellent flame retardancy to the polycarbonate resin, and further imparting compatibility between excellent transparency and excellent flame retardancy are the transparency and difficulty. Since the relationship with flammability is in a trade-off relationship, it is technically difficult.

Under the circumstances as described above, the present technology has been made as a result of extensive research conducted by the present inventors. Since both transparency and flame retardancy are in a trade-off relationship, both excellent transparency and excellent flame retardancy, and compatibility between excellent transparency and excellent flame retardancy are technical. It is difficult to. The transparent flame-retardant polycarbonate resin composition according to the present technology can improve flame retardancy without lowering transparency. In addition, this technology can use recycled polycarbonate (PC) resin, which is a waste material for optical applications, and can be greatly linked to the expansion of recycled material applications from the availability of transparent flame retardant polycarbonate using recycled materials. Can do.

<2. First Embodiment (Example of Transparent Flame Retardant Resin Composition)>
[2-1. Transparent flame retardant resin composition]
Below, the transparent flame-retardant resin composition of 1st Embodiment which concerns on this technique is demonstrated in detail. The transparent flame retardant resin composition of the first embodiment according to the present technology includes at least two types of polycarbonate resins and at least one type of organic flame retardant, and one of the at least two types of polycarbonate resins. The weight average molecular weight of the polycarbonate resin (A) is 52,000 or less in terms of polystyrene, and at least one organic flame retardant is 0.001 to 100 parts by mass with respect to a total of 100 parts by mass of at least two kinds of polycarbonate resins. It is a resin composition which is 3.0 mass parts.

According to the transparent flame retardant resin composition of the first embodiment according to the present technology, excellent transparency and excellent flame retardant effects are exhibited. In particular, since the transparent flame retardant resin composition of the first embodiment according to the present technology has excellent flame retardancy while having excellent transparency, it achieves both transparency and flame retardancy effects. be able to. Regarding flame retardancy, the transparent flame retardant resin composition of the first embodiment according to the present technology has a V-0 effect in UL94 flame retardance of, for example, a thickness of 1.0 mm. Moreover, since the transparent flame-retardant resin composition of 1st Embodiment which concerns on this technique has polycarbonate resin (A) whose weight average molecular weight is 52,000 or less in polystyrene conversion, it was excellent in fluidity | liquidity (workability). Improvement).

And the transparent flame-retardant resin composition of 1st Embodiment which concerns on this technique is a flat plate with a thickness of 3.0 mm which has an average roughness (Ra) of 0.03 micrometer or less, and the total light transmittance of 80% or more. It is preferable to have a rate. Moreover, the transparent flame-retardant resin composition according to the present technology is a flat plate having a thickness of 3.0 mm having an average roughness (Ra) of 0.03 μm or less, and a total light transmittance of 65% or more in a high-temperature and high-humidity environment. It is preferable to have a rate. Here, the high temperature and high humidity environment means, for example, an environment of 120 ° C., 100%, and 24 hours. The total light transmittance (transmittance) can be measured in accordance with JIS K7136 standard at a wavelength of 380 to 730 nm.

The transparent flame retardant resin composition of the first embodiment according to the present technology includes a polymer type organic sulfonic acid and / or a metal salt compound of a polymer type organic sulfonic acid described later as at least one organic flame retardant. , A flat plate having a thickness of 3.0 mm having an average roughness (Ra) of 0.03 μm or less, and preferably having a total light transmittance of 85% or more.

[2-2. Polycarbonate resin]
Of the at least two types of polycarbonate resins included in the transparent flame retardant resin composition of the first embodiment according to the present technology, one may be a polycarbonate resin (A) and the other may be a polycarbonate resin (B). In addition, at least 2 types of polycarbonate resin contains 1 type or more of other types of polycarbonate resins other than polycarbonate resin (A) and polycarbonate resin (B) other than polycarbonate resin (A) and polycarbonate resin (B). It may be configured.

(Polycarbonate resin (A))
As described above, the transparent flame retardant resin composition of the first embodiment according to the present technology includes a polycarbonate resin (A). As described above, the weight average molecular weight of the polycarbonate resin (A) is 52,000 or less in terms of polystyrene.

The polycarbonate resin (A) having a weight average molecular weight (polystyrene conversion) of 52,000 or less is used as a raw material for producing a molded part of the transparent flame-retardant polycarbonate resin according to the first embodiment of the present technology, Used for applications such as optical discs and housing materials for home appliances. For example, an aromatic polycarbonate resin produced by a reaction between a dihydric phenol and a carbonate precursor can be used. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. About these dihydric phenol and carbonate precursor, there is no restriction | limiting in particular and various things can be used.

As described above, the polycarbonate resin (A) is a polycarbonate resin having a weight average molecular weight (polystyrene conversion) of 52,000 or less, and is used for optical applications such as disks, lenses, optical sheets, and headlight lamps used as optical applications. Waste material recovery resin (recovered polycarbonate resin) can be used. The polycarbonate resin (A) preferably contains an optical component (for example, a disk, a lens, or the like) having a polystyrene equivalent weight average molecular weight of 45,000 or less, and further has a polystyrene equivalent weight average molecular weight of 35,000 or less. It is preferable that the optical component (for example, an optical sheet etc.) is included. By these preferable aspects, the transparent flame-retardant resin composition of the first embodiment according to the present technology has further excellent fluidity (further improvement in processability). Also, use an optical component (for example, a disk, a lens, etc.) having a weight average molecular weight of 45,000 or less in terms of polystyrene and / or an optical component (for example, an optical sheet, etc.) having a weight average molecular weight of 35,000 or less in terms of polystyrene. Thereby, the fluidity | liquidity of the transparent flame-retardant resin composition of 1st Embodiment which concerns on this technique can be adjusted efficiently.

The polycarbonate resin (A) having a weight average molecular weight (polystyrene equivalent) of 52,000 or less is used as the polycarbonate resin (B) as shown below if the polystyrene equivalent weight average molecular weight is 52,000 or less. A polycarbonate resin, polyorganosiloxane copolymer, recovered polycarbonate resin and the like may be used.

(Polycarbonate resin (B))
As described above, the transparent flame retardant resin composition of the first embodiment according to the present technology may include a polycarbonate resin (B). Although the weight average molecular weight of polycarbonate resin (B) is not specifically limited, It is preferable that it is more than 52,000 and 70,000 or less in polystyrene conversion. The polycarbonate resin (B) may be a branched type, polyorganosiloxane copolymer, recovered recycled material, or the like shown below.

<Polycarbonate resin (B) having a branched structure>
The polycarbonate resin (B) that may be included in the transparent flame-retardant resin composition of the first embodiment according to the present technology includes a polycarbonate resin having a branched structure (sometimes referred to as a branched polycarbonate resin). It is preferable. Further, the polycarbonate resin having a branched structure may have a branched structure at an arbitrary mol%, but preferably has a branched structure at 0.01 to 10.0 mol%. If the amount of the branched structure is less than 0.01 mol%, it does not change significantly from the normal linear structure, and the drip prevention effect may be small. This increases the anti-drip effect, but there is a possibility that the fluidity may be greatly reduced, which may be undesirable.

The branched polycarbonate (PC) resin is not particularly limited as long as it is a branched polycarbonate resin. The branched polycarbonate (PC) resin has, for example, a branched nucleus structure derived from a branching agent represented by the following general formula (I), and the amount of the branching agent used is based on the dihydric phenol compound. Examples include branched aromatic polycarbonates that may be in the range of 0.01 to 3 mol% or in the range of 0.1 to 2.0 mol%.

R is hydrogen or an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or an n-pentyl group. R1 to R6 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, etc.) or a halogen atom (for example, chlorine Atoms, bromine atoms, fluorine atoms, etc.).

The branching agent represented by the general formula (I) is more specifically 1,1,1-tris (4-hydroxyphenyl) -methane; 1,1,1-tris (4-hydroxyphenyl) -ethane 1,1,1-tris (4-hydroxyphenyl) -propane; 1,1,1-tris (2-methyl-4-hydroxyphenyl) -methane; 1,1,1-tris (2-methyl-4); -Hydroxyphenyl) -ethane; 1,1,1-tris (3-methyl-4-hydroxyphenyl) -methane; 1,1,1-tris (3-methyl-4-hydroxyphenyl) -ethane; , 1-tris (3,5-dimethyl-4-hydroxyphenyl) -methane; 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) -ethane; 1,1,1-tris (3 -Chloro-4-hydride 1,1,1-tris (3-chloro-4-hydroxyphenyl) ethane; 1,1,1-tris (3,5-dichloro-4-hydroxyphenyl) -methane; 1-tris (3,5-dichloro-4-hydroxyphenyl) -ethane; 1,1,1-tris (3-bromo-4-hydroxyphenyl) -methane; 1,1,1-tris (3-bromo- 4-hydroxyphenyl) -ethane; 1,1,1-tris (3,5-dibromo-4-hydroxyphenyl) -methane; 1,1,1-tris (3,5-dibromo-4-hydroxyphenyl)- Ethane, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene A compound having three or more functional groups such as phloroglysin, trimellitic acid, and isatin bis (o-cresol). Of the above, 1,1,1-tris (4-hydroxyphenyl) ethane is preferably used from the viewpoints of availability, reactivity, and economy.

These branching agents may be used alone or in combination of two or more. When 1,1,1-tris (4-hydroxyphenyl) ethane is used as the branching agent, the amount used is 0.2 to 2.0 mol% with respect to the dihydric phenol compound. Preferably, it is 0.3 to 2.0 mol%, more preferably 0.4 to 1.9 mol%. If it is 0.2 mol% or more, the degree of freedom of blending will be widened, and if it is 2.0 mol% or less, it will be difficult to gel during polymerization and the production of polycarbonate will be easy.

The branched polycarbonate resin has a branched nucleus structure derived from the branching agent represented by the above general formula (I), and is specifically represented by the following formula.

Here, in the above formula, a, b and c are integers, and PC represents a polycarbonate portion.

PC represents a repeating unit represented by the following formula, for example, when bisphenol A is used as a raw material component.

The amount (ratio) of the branched polycarbonate resin (for example, branched aromatic polycarbonate resin) in 100 parts by mass of the polycarbonate resin (B) is preferably 10 to 100 parts by mass, and 50 to 100 parts by mass. More preferably. If the amount of the branched polycarbonate resin (for example, the branched aromatic polycarbonate resin) is not 10 parts by mass or more, the thin flame retardant effect may not be obtained.

<Aromatic polycarbonate-polyorganosiloxane copolymer>
The polycarbonate resin (B) that may be included in the transmission resin composition of the first embodiment according to the present technology preferably includes an aromatic polycarbonate-polyorganosiloxane copolymer. When an aromatic polycarbonate-polyorganosiloxane copolymer is used in the transmission resin composition of the first embodiment according to the present technology, the flame retardant structure having a high siloxane structure of the aromatic polycarbonate-polyorganosiloxane copolymer Therefore, flame retardancy can be further improved while maintaining transparency and fluidity.

The aromatic polycarbonate-polyorganosiloxane copolymer comprises an aromatic polycarbonate part and a polyorganosiloxane part, and includes an aromatic polycarbonate structural unit represented by the following general formula (V) and a polyorgano represented by the general formula (VI). It contains a siloxane structural unit.

In the above formula (V), R ⁵ and R ⁶ each represent a halogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) or an optionally substituted phenyl group, and R ^When there are a plurality of ⁵ and R ⁶ , they may be the same or different. Y is a single bond, an alkylene group or alkylidene group having 1 to 20 carbon atoms (preferably 2 to 10 carbon atoms), a cycloalkylene group or cycloalkylidene group having 5 to 20 carbon atoms (preferably 5 to 12 carbon atoms),- O—, —S—, —SO—, —SO 2 — or —CO— is shown, and an isopropylidene group is preferred. p and q are each an integer of 0 to 4 (preferably 0), and when there are a plurality of p and q, they may be the same or different. m represents an integer of 1 to 100 (preferably an integer of 5 to 90). When m is from 1 to 100, an appropriate viscosity average molecular weight can be obtained in the aromatic polycarbonate-polyorganosiloxane copolymer.

In the above formula (VI), R ⁷ to R ¹⁰ each represents an alkyl group having 1 to 6 carbon atoms or a phenyl group which may have a substituent, and they may be the same or different. Specific examples of R ⁷ to R ¹⁰ include methyl groups, ethyl groups, propyl groups, n-butyl groups, isobutyl groups, amyl groups, isoamyl groups, hexyl groups and other alkyl groups, phenyl groups, tolyl groups, xylyl groups, and the like. Mention may be made of phenyl aryls such as naphthyl groups. R ¹¹ represents an aliphatic or aromatic organic residue, and is preferably a divalent organic compound residue such as an o-allylphenol residue, a p-hydroxystyrene residue, and an eugenol residue.

The method for producing the aromatic polycarbonate-polyorganosiloxane copolymer includes, for example, using an aromatic polycarbonate oligomer and a polyorganosiloxane having a reactive group at the end constituting the polyorganosiloxane part in a solvent such as methylene chloride. It can be produced by dissolving and adding a dihydric phenol such as bisphenol A using a catalyst such as triethylamine and interfacial polycondensation reaction.

The degree of polymerization of the aromatic polycarbonate structural unit of the aromatic polycarbonate-polyorganosiloxane copolymer is preferably 3 to 100, and the degree of polymerization of the polyorganosiloxane structural unit is preferably about 2 to 500, more preferably about 2 to 300. More preferably, about 2 to 140 is used. The polyorganosiloxane content of the aromatic polycarbonate-polyorganosiloxane copolymer is usually about 0.1 to 10% by mass, preferably 0.3 to 6% by mass. The viscosity-average molecular weight of the aromatic polycarbonate-polyorganosiloxane copolymer used in the transmission resin composition of the first embodiment according to the present technology is usually about 5,000 to 100,000, preferably 10,000 to 30,000, particularly preferably 12,000 to 30,000. Here, these viscosity average molecular weights (Mv) can be obtained in the same manner as the polycarbonate resin.

(Recovered polycarbonate resin)
The polycarbonate resin (B) shown above may be a newly manufactured virgin material, waste material, scrap material, sprue material, waste, etc., produced in the manufacturing process, or a product (for example, a digital versatile disc (DVD)) It may be a recovered material or a waste material of an optical disc (substrate) such as a compact disc (CD), MO, MD, or Blu-ray disc (BD). The polycarbonate resin (A) may also be a newly manufactured virgin material, waste material, scrap material, sprue material, waste, etc. generated in the manufacturing process, or a product (for example, a digital versatile disc (DVD), compact) It may be a recovered material or a waste material of an optical disc (substrate) such as a disc (CD), MO, MD, or Blu-ray disc (BD).

Therefore, the polycarbonate resin (B) may contain 1 to less than 100% by mass of the recovered polycarbonate resin, or may be composed of the recovered polycarbonate resin (100% by mass). Similarly, the polycarbonate resin (A) may contain the recovered polycarbonate resin in an amount of 1 to less than 100% by mass, or may be composed of the recovered polycarbonate resin (100% by mass).

When using the recovered optical disc, there are various deposits such as a metal reflection layer, a plating layer, a recording material layer, an adhesive layer, a label, etc., but in the present invention, these may be used as provided. Such impurities and sub-materials may be used after being separated and removed by a conventionally known method.

Specifically, a metal reflection layer such as Al, Au, Ag, Si, an organic dye containing a cyanine dye, Te, Se, S, Ge, In, Sb, Fe, Tb, Co, Ag, Ce, Bi, etc. Recording material layers, acrylic acrylates, ether acrylates, vinyl monomers and oligomers, adhesive layers comprising at least one polymer, UV curable monomers, oligomers, at least one polymer and polymerization initiators and pigments, Examples include label ink layers in which an auxiliary agent is mixed, but are not limited thereto, and may include a film forming material and a coating material that are usually used in an optical disk. From the viewpoint of recycling, since it is desirable that the raw material is low-cost, it is preferable to reuse the resin while impurities from various materials are included. For example, the optical disk can be crushed finely, as it is, or kneaded and melted with a predetermined additive, pelletized, and used as a PC resin raw material (component A). Alternatively, depending on the structure of the injection molding machine, the recovery disk may be directly put into a hopper or the like of the injection molding machine together with various additives described later to obtain a molded body made of the resin composition. When using a PC resin (component A) that does not contain the above-mentioned various impurities, deposits such as metal reflective layers, recording material layers, adhesive layers, surface hardened layers, and labels are, for example, It can be removed by a mechanical or chemical method proposed in JP-A-6-223416, JP-A-10-269634, JP-A-10-249315, or the like.

By the way, the weight average molecular weights of the polycarbonate resin (A) and the polycarbonate resin (B) are measured by polystyrene conversion based on a polystyrene molecular weight standard substance (sample) by GPC (Gel Permeation Chromatography) measurement using a chloroform solvent. can do.

The arithmetic average of the respective weight average molecular weights (polystyrene conversion) of the polycarbonate resin (A) and the polycarbonate resin (B) may be any value, for example, 40,000 to 70,000, and 45,000. Preferably it is ˜65,000.

The reason why the arithmetic average of the weight average molecular weights (polystyrene conversion) of the polycarbonate resin (A) and the polycarbonate resin (B) is preferably 45,000 to 65,000 is that the weight average molecular weight of the aromatic polycarbonate resin is When it is larger than 65000, the flowability (workability) at the time of melting of the flame retardant resin composition of the final object may tend to deteriorate. On the other hand, if it is smaller than 45000, the solvent resistance tends to decrease and solvent cracks (cracks due to chemicals) tend to occur, and the impact resistance tends to decrease.

In the transparent flame retardant resin composition of the first embodiment according to the present technology, the mass ratio of the polycarbonate resin (A) and the polycarbonate resin (B) may be arbitrary, but is 20:80 to 75:25. It is preferably 35:75 to 50:50. According to this preferable aspect and a more preferable aspect, the transparent flame-retardant resin composition of the first embodiment according to the present technology has further excellent transparency and further excellent flame-retardant effect, and further excellent transparency. Therefore, the effects of transparency and flame retardancy can be more compatible.

[2-3. Organic flame retardant]
The transparent flame retardant resin composition of the first embodiment according to the present technology preferably includes at least one organic flame retardant, and preferably includes two organic flame retardants. Moreover, the transparent flame-retardant resin composition of the first embodiment according to the present technology may include three or more organic flame retardants.

The content of the at least one organic flame retardant in the transparent flame retardant resin composition is at least two types of polycarbonate resins (for example, two types of polycarbonate resins (A) and polycarbonate resins (B)). Polycarbonate resin) is 0.001 to 3.0 parts by mass with respect to 100 parts by mass in total. When at least one organic flame retardant is composed of, for example, two organic flame retardants, the total content of the two organic flame retardants is at least two polycarbonate resins (for example, The amount is 0.001 to 3.0 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the polycarbonate resin (B).

The organic flame retardant is not particularly limited as long as it is an organic flame retardant composed of an organic compound, for example, but is preferably an organic sulfonic acid and / or a metal salt compound of an organic sulfonic acid. And / or a metal salt compound of a polymer type organic sulfonic acid. The weight average molecular weight of the polymer type organic sulfonic acid and / or the metal salt compound of the polymer type organic sulfonic acid may be any molecular weight, but is preferably 30,000 or more. The polymer type organic sulfonic acid preferably contains an aromatic ring in an amount of 1 mol% to 100 mol%. Further, the aromatic ring contains 0.1 to 10 mol of a sulfonic acid group and / or a sulfonic acid metal base. % Is preferably introduced. Further, the metal salt compound of a polymer type organic sulfonic acid preferably contains an aromatic ring in an amount of 1 mol% to 100 mol%. Further, the aromatic ring has a sulfonic acid group and / or a sulfonic acid metal base. It is preferably introduced at 0.1 to 10 mol%. Below, the example of an organic type flame retardant is demonstrated in detail.

As the organic sulfonic acid or the same salt, examples of low molecular weight compounds include alkali metal salts and alkaline earth metal salts such as perfluoroalkanesulfonic acid, alkylbenzenesulfonic acid, halogenated alkylbenzenesulfonic acid, alkylsulfonic acid, and naphthalenesulfonic acid, Alternatively, examples of the high molecular weight compound include those having a predetermined amount of sulfonic acid and / or a salt thereof in a polymer having an aromatic ring as described in Patent Documents 1 and 2 below. Examples of the polymer having an aromatic ring include polystyrene (PS), high impact polystyrene (HIPS), and styrene / acrylonitrile copolymer resin (AS).

As described above, there are various organic sulfonic acids or salts thereof, from low molecular weight to high molecular weight, but generally high molecular weight is dispersibility when kneaded with polycarbonate (PC) resin. Is preferable, and storage stability under high temperature and high humidity conditions (for example, prevention of bleed out) is excellent. Therefore, for example, when the transparent flame retardant resin composition of the first embodiment according to the present technology uses two types of organic flame retardants, from the viewpoint of further improving transparency and storage stability, It is preferable to use a low molecular weight compound of the same salt in combination with an organic sulfonic acid or a high molecular weight compound of the same salt.

More preferably, it is a core-shell type styrene polymer in which a sulfonic acid group is bonded to the particle surface layer portion, and an alkali metal salt or an alkaline earth metal salt thereof. There is potassium salt. One or more selected from these may be mixed and used at an appropriate ratio, but when using polystyrene sulfonic acid or its potassium salt, a high flame retardant effect can be obtained with a very small amount of addition, preferable. Furthermore, it is more preferable that the weight average molecular weight (polystyrene conversion) is 40,000 or more and 300,000 or less because the balance between solvent resistance and compatibility is further maintained.

As content of the above-mentioned organic sulfonic acid and / or the same salt, a total of 100 masses of at least two types of polycarbonate resins (for example, two types of polycarbonate resins composed of polycarbonate resin (A) and polycarbonate resin (B)). The amount is 0.001 to 3.0 parts by mass with respect to parts. When it is less than 0.001, it is difficult to obtain a flame retardant effect, and when it exceeds 3.0 parts by mass, the compatibility with the polycarbonate resin is reduced or a negative flame retardant effect is exhibited. That is, the flame retardant level may be lower than when the organic sulfonic acid and / or salt is not contained.

The content of the organic sulfonic acid and / or the salt is preferably 0.05 to 1.5 parts by mass, and when it is 0.05 to 1.5 parts by mass, the flame retardant effect is further enhanced. The content of the organic sulfonic acid and / or the salt is more preferably from 0.1 to 1 part by mass, and when it is from 0.1 to 1 part by mass, an even higher flame retardant effect is achieved.

As the organic sulfonic acid and / or the salt thereof, an organic metal salt flame retardant containing a fluoroalkyl group may be used. Organometallic salt-based flame retardants containing fluoroalkyl groups are alkali metal perfluoroalkyl sulfonate (earth) metal salt, alkali metal perfluoroalkyl carboxylic acid (earth) metal salt, alkali perfluoroalkyl phenyl sulfonate (earth) Examples include metal salts and alkali (earth) metal salts of perfluoroalkylphenylcarboxylic acid, and among these, alkali (earth) metal salts of perfluoroalkylsulfonic acid are most preferable. Perfluoroalkyl sulfonate alkali (earth) metal salts include perfluoromethane sulfonate, perfluoroethane sulfonate, perfluoropropane sulfonate, perfluorobutane sulfonate, perfluoromethylbutane sulfonate. Perfluorohexanesulfonate, perfluoroheptanesulfonate, perfluorooctanesulfonate, and the like, and those having 1 to 8 carbon atoms are particularly preferable. These can be used alone or in combination of two or more. Specific examples thereof include potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium perfluorobutane sulfonate, sodium perfluorooctane sulfonate, lithium perfluorobutane sulfonate, lithium perfluorobutane sulfonate, Examples include lithium fluoroheptane sulfonate, cesium perfluorobutane sulfonate, cesium perfluorooctane sulfonate, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and rubidium perfluorohexane sulfonate. Sodium butanesulfonate, potassium perfluorobutanesulfonate, and cesium perfluorobutanesulfonate are more preferred.

As the alkali (earth) metal in the alkali (earth) metal salt of perfluoroalkyl sulfonate, rubidium and cesium are preferred when the flame retardancy requirement is higher, but these are not universal and Since it is difficult to purify, it may be disadvantageous in terms of cost. On the other hand, although it is advantageous in terms of cost, lithium and sodium may be disadvantageous in terms of flame retardancy. Taking these into consideration, the alkali (earth) metal in the alkali (earth) metal salt of perfluoroalkylsulfonic acid can be properly used, but potassium having an excellent balance of properties is most suitable in any respect. From these points, potassium perfluorobutanesulfonate is preferable.

As the organic sulfonic acid or its salt, there are various kinds of organic sulfonic acids or salts having a high molecular weight to a low molecular weight as described above, but they may be used in combination. Combined use of high molecular weight and low molecular weight organic sulfonic acids and / or salts thereof results in better dispersibility when kneaded with polycarbonate (PC) resin and storage stability under high temperature and high humidity conditions It is preferable because the properties are more excellent and the total light transmittance and durability are further improved.

[2-4. Silicon-based flame retardant aid]
The transparent flame retardant resin composition of the first embodiment according to the present technology preferably further includes a silicon-based flame retardant aid.

The silicon-based flame retardant aid is used for imparting further flame retardancy to the transparent flame retardant resin composition of the first embodiment. The addition amount of the silicon-based flame retardant aid in the transparent flame retardant resin composition is not particularly limited and may be any amount, but at least two types of polycarbonate resins (for example, polycarbonate resin (A) and polycarbonate resin ( B)) is preferably 0.01 to 5.0 parts by mass with respect to 100 parts by mass in total. When the addition amount of the silicon flame retardant aid is less than 0.01 parts by mass, the effect of imparting further flame retardancy to the transparent flame retardant resin composition may not be sufficient. On the other hand, if the addition amount of the silicon-based flame retardant auxiliary is more than 5.0%, the economic efficiency may be deteriorated due to a decrease in flame retardant efficiency, and the effect of imparting further flame retardancy is saturated. In some cases, the flame retardant efficiency is lowered.

Examples of the silicon flame retardant aid include polyorganosiloxane (silicone and organic silicate, etc.) and silica. Any one of these can be used alone or in combination. For example, polymethylphenylsiloxane, poly (dimethyl-diphenyl-methylhydrogen) siloxane, polydimethyldiphenylsiloxane, polymethylethylsiloxane, polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, polydiethylsiloxane, polyethylphenylsiloxane, Resins such as these mixtures and oils can be mentioned.

Examples of the alkyl group portion of these polyorganosiloxanes include alkyl group, alkoxy group, hydroxy group, amino group, carboxy group, silanol group, mercapto group, epoxy group, vinyl group, aryloxy group, polyoxyalkylene group, hydrogen A functional group such as a group or a halogen group may be contained, and in particular, an alkyl group, an alkoxy group, a hydroxy group, a vinyl group, or the like is preferably contained. Of these, methylphenylsiloxane resin is most preferred. A methyl group, a phenyl group, a hydrogen group, and a methoxy group are preferable, and a methyl group and a phenyl group, a dimethyl group, a diphenyl group, a methyl group and a hydrogen group, a methyl group and a methoxy group, a phenyl group and a methoxy group, and a methoxy group A combination of hydrogen group and the like is preferable.

When the silicon-based flame retardant aid is a polyorganosiloxane resin, the average molecular weight is 100 or more, preferably in the range of 500 to 5000000. Examples of the form include oil, varnish, gum, and powder. , And any of pellets. Moreover, about silica, what was surface-treated with the silane coupling agent of a hydrocarbon type compound is suitable, but the above-mentioned polyorganosiloxane resin is more preferable.

[2-5. Other ingredients]
The transparent flame retardant resin composition of the first embodiment according to the present technology may be blended with other resins and fillers as long as transparency and flame retardancy, in particular, transparency is not impaired. Although many other resins and fillers interfere with transparency, the selection of the type and amount should take that into consideration.

As described above, the transparency and flame retardancy, in particular, unless the transparency is impaired, the transparent flame retardant resin composition of the first embodiment according to the present technology includes the mechanical properties of the molded product, In order to improve chemical properties or electrical properties, other thermoplastic resins than the polycarbonate resin can be blended. The blending amount of the other thermoplastic resin varies depending on the kind and purpose thereof, and is not particularly limited. Usually, a total of 100 masses of at least two kinds of polycarbonate resins (for example, polycarbonate resin (A) and polycarbonate resin (B)). The amount is preferably 1 to 30 parts by mass and more preferably 2 to 20 parts by mass with respect to parts. Other thermoplastic resins include, for example, general-purpose plastics represented by polyethylene resin, polypropylene resin, polyalkyl methacrylate resin, polyphenylene ether resin, polyacetal resin, polyamide resin, cyclic polyolefin resin, polyarylate resin (non-crystalline) And so-called super engineering plastics such as engineering plastics typified by polyarylate and liquid crystalline polyarylate), polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, and polyphenylene sulfide. . Furthermore, thermoplastic elastomers such as olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers can also be used.

In the transparent flame-retardant resin composition of the first embodiment according to the present technology, additives can be blended in a small proportion for imparting various functions to the molded product and improving characteristics. This additive can be blended in a usual blending amount as long as transparency and flame retardancy are not impaired. Such additives include heat stabilizers, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, sliding agents (PTFE particles, etc.), colorants (pigments such as carbon black and titanium oxide, dyes), light diffusion. Agents (acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterials Agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), impact modifiers typified by graft rubber, infrared absorbers or photochromic agents.

In addition to the above, the transparent flame retardant resin composition of the first embodiment according to the present technology includes, for example, an antioxidant (hindered phenol-based, phosphorus-based, sulfur-based) as another additive. , Antistatic agent, ultraviolet absorber (benzophenone, benzotriazole, hydroxyphenyltriazine, cyclic imino ester, cyanoacrylate), light stabilizer, plasticizer, compatibilizer, colorant (pigment, dye) Contains light diffusing agents, light stabilizers, crystal nucleating agents, antibacterial agents, flow modifiers, infrared absorbers, phosphors, hydrolysis inhibitors, mold release agents, silicone flame retardants or surface treatment agents, etc. It may be. Thereby, injection moldability, impact resistance, appearance, heat resistance, weather resistance, color or rigidity are improved.

<3. Second Embodiment (Example of Production Method of Transparent Flame Retardant Resin Composition)>
[3-1. Method for Producing Transparent Flame Retardant Resin Composition] The method for producing a transparent flame retardant resin composition according to the second embodiment (an example of a method for producing a transparent flame retardant resin composition) according to the present technology is at least two kinds. Adding at least one organic flame retardant, and kneading the at least two polycarbonate resins and the at least one organic flame retardant, the at least one In the production method, the amount of the organic flame retardant added is 0.001 to 3.0 parts by mass with respect to 100 parts by mass in total of the at least two types of polycarbonate resins. Examples of the at least two types of polycarbonate resins include polycarbonate resin (A) and polycarbonate resin (B) as described above. Since the polycarbonate resin (A), the polycarbonate resin (B), and the organic flame retardant are as described above, detailed description thereof is omitted here. Further, since the transparent flame retardant resin composition produced by the production method of the transparent flame retardant resin composition of the second embodiment according to the present technology is also as described above, the detailed explanation is here. Omitted.

The method for producing a transparent flame retardant resin composition of the second embodiment according to the present technology includes adding at least two types of polycarbonate resins and at least one type of organic flame retardant, and then adding at least two types of polycarbonate resins. And mixing at least one organic flame retardant. Moreover, the manufacturing method of the transparent flame-retardant resin composition of 2nd Embodiment which concerns on this technique is substantially uniform with a Henschel mixer and a tumbler, at least 2 types of polycarbonate resin, and at least 1 type of organic flame retardant May be dispersed.

In the method for producing a transparent flame retardant resin composition according to the second embodiment of the present technology, kneading at least two types of polycarbonate resin and at least one type of organic flame retardant is, for example, after the dispersion described above. Melting and kneading can be mentioned with a single screw or twin screw extruder, and a strand obtained by melt kneading may be cut with a pelletizer to produce pellets. In addition, the transparent flame retardant resin composition manufactured by the method for manufacturing the transparent flame retardant resin composition of the second embodiment according to the present technology is not limited to those processed into pellets, and each component is mixed. What processed into the form (sheet shape etc.) different from a state (powder state or fluid state) and a pellet may also be included.

Further, the method for producing the transparent flame retardant resin composition of the second embodiment according to the present technology may include adding a silicon-based flame retardant aid. The addition amount of the silicon-based flame retardant aid may be any addition amount, but is preferably based on a total of 100 parts by mass of at least two types of polycarbonate resins (for example, polycarbonate resin (A) and polycarbonate resin (B)). 0.01 to 5.0 parts by mass. Moreover, in the manufacturing method of the transparent flame-retardant resin composition of 2nd Embodiment which concerns on this technique, you may include adding the other component described above, for example.

<3. Third Embodiment (Example of Transparent Flame Retardant Resin Molded Body)>
[3-1. Transparent flame retardant resin molding]
The transparent flame retardant resin molded product of the third embodiment according to the present technology is a resin molded product obtained by molding the transparent flame retardant resin composition of the first embodiment according to the present technology. The transparent flame-retardant resin molded product of the third embodiment according to the present technology has excellent transparency and excellent flame retardancy, and in particular, can achieve both excellent transparency and excellent flame retardancy. Since the transparent flame retardant resin composition of the first embodiment according to the present technology is included, the transparent flame retardant resin molded body of the third embodiment according to the present technology is also excellent in transparency and excellent It has excellent flame retardancy, and in particular, it can be compatible with both excellent transparency and excellent flame retardancy.

Moreover, the transparent flame-retardant resin molded product of the third embodiment according to the present technology is a transparent flame-retardant resin manufactured by the method for manufacturing the transparent flame-retardant resin composition of the second embodiment according to the present technology. It is a resin molded body obtained by molding the composition. The transparent flame-retardant resin molded product of the third embodiment according to the present technology has excellent transparency and excellent flame retardancy, and in particular, can achieve both excellent transparency and excellent flame retardancy. The transparent flame retardant resin composition produced by the production method of the transparent flame retardant resin composition of the second embodiment according to the present technology is included, so that the transparency of the third embodiment according to the present technology can be achieved. The flame-retardant resin molded article also has excellent transparency and excellent flame retardancy, and in particular, can achieve both excellent transparency and excellent flame retardancy.

[3-2. Method for producing transparent flame-retardant resin molding]
The transparent flame-retardant resin molded product of the third embodiment according to the present technology can be manufactured, for example, as follows. The above-described pellets and the like are formed into a predetermined shape (for example, home appliances, automobiles, information devices, etc.) by a molding method such as injection molding, injection compression molding, extrusion molding, blow molding, vacuum molding, press molding, foam molding, or supercritical molding. It is possible to obtain a transparent flame-retardant resin molded body by molding into office equipment, telephones, stationery, furniture, or housings or parts of various products such as fibers.

Hereinafter, the effects of the present technology will be described in detail with examples. Note that the scope of the present technology is not limited to the examples.

Transparent flame retardant resin compositions according to Examples 1 to 16 and resin compositions according to Comparative Examples 1 to 7 were prepared, and the transparent flame retardant resin compositions of each Example and the resin compositions of each Comparative Example were prepared. Evaluation was performed.

Composition of transparent flame retardant resin compositions according to Examples 1 to 16 (composition ratio is expressed in parts by mass), fluidity (g / 10 min), transmittance (%), transmittance after durability test ( %) And evaluation results of flame retardancy are shown in Table 1 and Table 2 below.

Composition of resin compositions according to Comparative Examples 1 to 7 (composition ratio is expressed in parts by weight), fluidity (g / 10 min), transmittance (%), transmittance after durability test (%), and difficulty Table 3 below shows the evaluation results of flammability.

[Configurations of Transparent Flame Retardant Resin Compositions According to Examples 1 to 16 and Resin Compositions According to Comparative Examples 1 to 7]
The components contained in the transmissive resin compositions according to Examples 1 to 16 and the resin compositions according to Comparative Examples 1 to 7 will be described. In addition, each component (A component, B component, C component, and D component) is the polycarbonate resin (A), polycarbonate resin (B), organic flame retardant, and silicon-based flame retardant described in the first embodiment. Corresponds to each of the fuel aids.

(Component A: polycarbonate resin (A))
The following components A-1 to A-3 were used as the polycarbonate resin (A) as the component A.

A-1: Commercially available low molecular weight polycarbonate (PC) resin (AD-5503: Teijin Chemicals, Mw in terms of polystyrene (PS): 33000).
A-2: Used CD is pulverized (2 to 20 mm) and treated with an alkaline hot water solution to form a coating film (recording material layer, label, adhesive layer, hardened layer, metal reflective layer, etc.) After the removal, polycarbonate (PC) resin polystyrene (Mw in terms of polystyrene (PS): 32000) pelletized after melting and kneading with a twin screw extruder.
A-3: A polycarbonate (PC) resin (Mw: 51000 in terms of polystyrene (PS)) obtained by roughly pulverizing a used vehicle headlight lamp, melting and kneading with a twin screw extruder, and then pelletizing.

(B component: polycarbonate resin (B))
The following components B-1 to B-3 were used as the polycarbonate resin (B) as the B component.

B-1: Commercially available high molecular weight polycarbonate (PC) resin (K-1300Y: Teijin Chemicals, polystyrene (PS) equivalent Mw: 65000).
B-2: Polycarbonate (PC) resin (Mw in terms of polystyrene (PS): 58500) obtained by roughly crushing a used water bottle for drinking water, melting and kneading with a twin screw extruder, and then pelletizing.
・ B-3:

(C component: organic flame retardant)
The following components C-1 to C-2 were used as the organic flame retardant as the component C.
C-1: Polymer type organic sulfonic acid metal salt, in which potassium sulfonate is introduced into the surface layer of polystyrene (manufactured by Sony Corporation: PSS-K).
C-2: perfluorobutanesulfonic acid potassium salt (manufactured by Mitsubishi Materials Corporation: F-top KFBS).

(D component: silicon flame retardant aid)
The following component D-1 was used as a silicon-based flame retardant aid as component D.
D-1: Dimethyl-diphenyl-methyl hydrogen silicone oil (trade name KR-2710; manufactured by Shin-Etsu Chemical Co., Ltd.)

[Preparation and Molding of Transparent Flame Retardant Resin Compositions According to Examples 1 to 16 and Resin Compositions According to Comparative Examples 1 to 7]
The various components shown above (components A-1 to A-3, components B-1 to B-3, components C-1 to C-2, and component D-1) are shown in Table 1 (Examples). 1 to Example 14) and Table 2 (Comparative Examples 1 to 12) are blended at respective blending ratios, blended with a tumbler, and then twin-screw co-rotating mixed extruder (Toyo Seiki) Manufactured by Seisakusho: Lab Plast Mill, using a biaxial extrusion unit) was melt kneaded to obtain pellets (transparent flame-retardant resin composition and resin composition). The extrusion conditions were a discharge rate of 4 kg / h and a screw rotation speed of 48 rpm, and the extrusion temperature was 270 ° C. from the first supply port to the die part. The obtained pellets were dried with a hot air circulation dryer at 120 ° C. for 8 hours, and then using an injection molding machine at a cylinder temperature of 290 ° C. and a mold temperature of 70 ° C., a test piece for optical measurement and flame retardancy Each test specimen for measurement was molded.

Next, according to the following test method, using the test piece for optical measurement and the test piece for flame retardancy measurement prepared above, fluidity (g / 10 min), total light transmittance (%) (simply, The transmittance (also referred to as%), the total light transmittance after the durability test (also simply referred to as the transmittance (%) after the durability test), and the flame retardancy were evaluated.

[Flowability (MFR: Melt Flow Rate)]
In accordance with JIS K7210, under the conditions of a resin temperature of 280 ° C. and a load of 2.16 Kg, the flowability measurement of the transparent flame retardant resin compositions according to Examples 1 to 14 and the resin compositions according to Comparative Examples 1 to 12 at the time of melting was performed. went.

[Total light transmittance]
Using haze meter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), a plate test piece having a thickness of 3.0 mm (molded product obtained above (test piece for optical measurement)) according to JIS K 7136. The total light transmittance was measured.

[Transmittance after durability test]
The value of the total light transmittance when the molded article (test piece for optical measurement) obtained above is allowed to stand for 24 hours under high-temperature and high-humidity conditions of 120 ° C. and 100% RH, thereby promoting deterioration. Was evaluated. In addition, the measuring method of a total light transmittance is as above-mentioned.

[Flame retardancy test method]
Using the molded product (flame retardancy measurement test piece) obtained above, a vertical combustion test of UL standard 94 was conducted at a thickness of 1.5 mm and a thickness of 1.0 mm, respectively, and the grade was evaluated. . V-0 or higher was judged as very good. The UL94V standard and judgment criteria are shown in Table 4 below. In addition, evaluation (failure) of V unachieved was judged as VNG (V nonconformity).

Tables 1 and 2 below show the results of Examples 1 to 16, and Table 3 below shows the results of Comparative Examples 1 to 7.

As is clear from Tables 1 to 3, the transparent flame retardant resin compositions of Examples 1 to 16 can cope with thin-wall molding compared to the resin compositions of Comparative Examples 1 to 7. Thin molded articles can be produced using 1 to 16 transparent flame retardant resin compositions.

As is clear from Tables 1 to 3, the transparent flame retardant resin compositions of Examples 1 to 14 are more transparent than the conventional polycarbonate resin compositions and the resin compositions of Comparative Examples 1 to 7. And excellent flame retardancy, and furthermore, it is possible to achieve both excellent transparency and excellent flame retardancy.

Hereinafter, the results of Comparative Examples 1 to 7 will be described in detail.
In Comparative Examples 1 to 7, the amount of one type of polycarbonate (PC) resin or organic flame retardant (component C) is a predetermined amount (that is, polycarbonate resin (A) (component A) and polycarbonate resin (B) (B The resin composition is not 0.001 to 3.0 parts by mass with respect to 100 parts by mass in total with the component), and thus is not excellent in transparency and flame retardancy. It was difficult to achieve both sexiness.

The present technology is not limited to the above embodiments and examples, and can be changed without departing from the gist of the present technology.

It should be noted that the effects described in the present disclosure are merely examples and are not limited. Accordingly, the present technology may exhibit effects not described in the present disclosure as well as effects described in the present disclosure.

In addition, the present technology may have the following configurations.
[1]
Comprising at least two polycarbonate resins and at least one organic flame retardant;
Of the at least two kinds of polycarbonate resins, the weight average molecular weight of one polycarbonate resin (A) is 52,000 or less in terms of polystyrene,
A transparent flame retardant resin composition, wherein the at least one organic flame retardant is 0.001 to 3.0 parts by mass with respect to a total of 100 parts by mass of the at least two types of polycarbonate resins.
[2]
The transparent flame retardant resin composition according to [1], wherein the one polycarbonate resin (A) includes a recovered polycarbonate resin.
[3]
Of the at least two kinds of polycarbonate resins, the other polycarbonate resin (B) has a weight average molecular weight of more than 52,000 and not more than 70,000 in terms of polystyrene, as described in [1] or [2]. A flammable resin composition.
[4]
The transparent flame retardant resin composition according to any one of [1] to [3], wherein the other polycarbonate resin (B) includes a polycarbonate resin having a branched structure of 0.01 to 10.0 mol%. object.
[5]
The transparent flame retardant resin composition according to any one of [1] to [4], wherein the other polycarbonate resin (B) contains an aromatic polycarbonate-polyorganosiloxane copolymer.
[6]
The transparent flame retardant resin composition according to any one of [1] to [5], wherein the at least one organic flame retardant is an organic sulfonic acid and / or a metal salt compound of an organic sulfonic acid.
[7]
The transparent flame retardancy according to any one of [1] to [5], wherein the at least one organic flame retardant is a polymer type organic sulfonic acid and / or a metal salt compound of a polymer type organic sulfonic acid. Resin composition.
[8]
The transparent flame-retardant resin composition according to [7], wherein the polymer-type organic sulfonic acid and / or the metal salt compound of the polymer-type organic sulfonic acid has a weight average molecular weight in terms of polystyrene of 30,000 or more.
[9]
The polymer type organic sulfonic acid and / or the metal salt compound of the polymer type organic sulfonic acid contains an aromatic ring in an amount of 1 mol% to 100 mol%, and the aromatic ring has a sulfonic acid group and / or a metal sulfonic acid. The transparent flame retardant resin composition according to [7] or [8], wherein a base is introduced at 0.1 to 10 mol%.
[10]
The transparency difficulty according to any one of [1] to [9], which is a flat plate having a thickness of 3.0 mm having an average roughness (Ra) of 0.03 μm or less and having a total light transmittance of 80% or more. A flammable resin composition.
[11]
The at least one organic flame retardant is a polymer type organic sulfonic acid and / or a metal salt compound of a polymer type organic sulfonic acid,
The transparency difficulty according to any one of [1] to [10], which is a flat plate having a thickness of 3.0 mm having an average roughness (Ra) of 0.03 μm or less and having a total light transmittance of 85% or more. A flammable resin composition.
[12]
Any one of [1] to [11], which is a flat plate having a thickness of 3.0 mm having an average roughness (Ra) of 0.03 μm or less and having a total light transmittance of 65% or more in a high temperature and high humidity environment. The transparent flame-retardant resin composition described in 1.
[13]
Further comprising a silicon-based flame retardant aid,
[1] to [12], wherein the silicon-based flame retardant auxiliary is 0.01 to 5.0 parts by mass with respect to 100 parts by mass in total of the at least two types of polycarbonate resins. Transparent flame retardant resin composition.
[14]
The transparent flame-retardant resin composition according to any one of [1] to [13], wherein the UL94 flame-retardant property having a thickness of 1.0 mm is V-0.
[15]
The transparent flame retardant resin composition according to any one of [1] to [14], wherein the one polycarbonate resin (A) includes a recovered resin produced for use as an optical component.
[16]
The transparent flame retardant resin composition according to any one of [1] to [15], wherein the one polycarbonate resin (A) includes an optical component having a polystyrene equivalent weight average molecular weight of 45,000 or less.
[17]
The transparent flame retardant resin composition according to any one of [1] to [15], wherein the one polycarbonate resin (A) includes an optical component having a polystyrene equivalent weight average molecular weight of 35,000 or less.
[18]
Adding at least two polycarbonate resins and at least one organic flame retardant;
Kneading the at least two polycarbonate resins and the at least one organic flame retardant,
Production of transparent flame retardant resin composition, wherein the addition amount of the at least one organic flame retardant is 0.001 to 3.0 parts by mass with respect to 100 parts by mass in total of the at least two types of polycarbonate resins. Method.
[19]
The method for producing a transparent flame retardant resin composition according to [18], wherein the weight average molecular weight of the one polycarbonate resin (A) is 52,000 or less in terms of polystyrene.
[20]
The method for producing a transparent flame retardant resin composition according to [18] or [19], wherein the one polycarbonate resin (A) includes a recovered polycarbonate resin.
[21]
Of the at least two types of polycarbonate resins, the other polycarbonate resin (B) has a weight average molecular weight of more than 52,000 and not more than 70,000 in terms of polystyrene, and any one of [18] to [20] The manufacturing method of the transparent flame-retardant resin composition as described in any one of.
[22]
The transparent flame retardant resin composition according to any one of [18] to [21], wherein the other polycarbonate resin (B) includes a polycarbonate resin having a branched structure of 0.01 to 10.0 mol%. Manufacturing method.
[23]
The method for producing a transparent flame retardant resin composition according to any one of [18] to [22], wherein the other polycarbonate resin (B) comprises an aromatic polycarbonate-polyorganosiloxane copolymer.
[24]
The transparent flame retardant resin composition according to any one of [18] to [23], wherein the at least one organic flame retardant is an organic sulfonic acid and / or a metal salt compound of an organic sulfonic acid. Production method.
[25]
The transparent flame retardancy according to any one of [18] to [23], wherein the at least one organic flame retardant is a polymer type organic sulfonic acid and / or a metal salt compound of a polymer type organic sulfonic acid. A method for producing a resin composition.
[26]
Manufacture of the transparent flame-retardant resin composition as described in [25] whose polystyrene average weight average molecular weights of the said polymer type organic sulfonic acid and / or the metal salt compound of the said polymer type organic sulfonic acid are 30,000 or more. Method.
[27]
The polymer type organic sulfonic acid and / or the metal salt compound of the polymer type organic sulfonic acid contains an aromatic ring in an amount of 1 mol% to 100 mol%, and the aromatic ring has a sulfonic acid group and / or a metal sulfonic acid. The method for producing a transparent flame retardant resin composition according to [25] or [26], wherein the base is introduced at 0.1 to 10 mol%.
[28]
The transparency difficulty according to any one of [18] to [27], which is a flat plate having a thickness of 3.0 mm having an average roughness (Ra) of 0.03 μm or less and having a total light transmittance of 80% or more. A method for producing a flammable resin composition.
[29]
The at least one organic flame retardant is a polymer type organic sulfonic acid and / or a metal salt compound of a polymer type organic sulfonic acid,
The difficulty in transparency according to any one of [18] to [28], which is a flat plate having a thickness of 3.0 mm having an average roughness (Ra) of 0.03 μm or less and having a total light transmittance of 85% or more. A method for producing a flammable resin composition.
[30]
Any one of [18] to [29], which is a flat plate having a thickness of 3.0 mm having an average roughness (Ra) of 0.03 μm or less and having a total light transmittance of 65% or more in a high temperature and high humidity environment. The manufacturing method of the transparent flame-retardant resin composition as described in one.
[31]
Further comprising a silicon-based flame retardant aid,
[18] to [30], wherein the silicon-based flame retardant aid is 0.01 to 5.0 parts by mass with respect to a total of 100 parts by mass of the at least two types of polycarbonate resins. Method for producing a transparent flame-retardant resin composition.
[32]
The method for producing a transparent flame retardant resin composition according to any one of [18] to [31], wherein the UL94 flame retardant having a thickness of 1.0 mm is V-0.
[33]
The method for producing a transparent flame retardant resin composition according to any one of [18] to [32], wherein the one polycarbonate resin (A) includes a recovered resin produced for use as an optical component.
[34]
The transparent flame retardant resin composition according to any one of [18] to [33], wherein the one polycarbonate resin (A) includes an optical component having a polystyrene equivalent weight average molecular weight of 45,000 or less. Production method.
[35]
The transparent flame retardant resin composition according to any one of [18] to [33], wherein the one polycarbonate resin (A) includes an optical component having a polystyrene equivalent weight average molecular weight of 35,000 or less. Production method.

Claims (18)

Comprising at least two polycarbonate resins and at least one organic flame retardant;
Of the at least two kinds of polycarbonate resins, the weight average molecular weight of one polycarbonate resin (A) is 52,000 or less in terms of polystyrene,
A transparent flame retardant resin composition, wherein the at least one organic flame retardant is 0.001 to 3.0 parts by mass with respect to a total of 100 parts by mass of the at least two types of polycarbonate resins. The transparent flame retardant resin composition according to claim 1, wherein the one polycarbonate resin (A) contains a recovered polycarbonate resin. The transparent flame-retardant resin composition according to claim 1, wherein, among the at least two kinds of polycarbonate resins, the other polycarbonate resin (B) has a weight average molecular weight of more than 52,000 and not more than 70,000 in terms of polystyrene. object. The transparent flame retardant resin composition according to claim 1, wherein the other polycarbonate resin (B) contains a polycarbonate resin having a branched structure of 0.01 to 10.0 mol%. The transparent flame retardant resin composition according to claim 1, wherein the other polycarbonate resin (B) contains an aromatic polycarbonate-polyorganosiloxane copolymer. The transparent flame retardant resin composition according to claim 1, wherein the at least one organic flame retardant is an organic sulfonic acid and / or a metal salt compound of an organic sulfonic acid. The transparent flame retardant resin composition according to claim 1, wherein the at least one organic flame retardant is a polymer type organic sulfonic acid and / or a metal salt compound of a polymer type organic sulfonic acid. The transparent flame retardant resin composition according to claim 7, wherein the polymer-type organic sulfonic acid and / or the metal salt compound of the polymer-type organic sulfonic acid has a polystyrene-equivalent weight average molecular weight of 30,000 or more. The polymer type organic sulfonic acid and / or the metal salt compound of the polymer type organic sulfonic acid contains an aromatic ring in an amount of 1 mol% to 100 mol%, and the aromatic ring has a sulfonic acid group and / or a metal sulfonic acid. The transparent flame retardant resin composition according to claim 7, wherein the base is introduced at 0.1 to 10 mol%. The transparent flame retardant resin composition according to claim 1, which is a flat plate having a thickness of 3.0 mm having an average roughness (Ra) of 0.03 μm or less and a total light transmittance of 80% or more. The at least one organic flame retardant is a polymer type organic sulfonic acid and / or a metal salt compound of a polymer type organic sulfonic acid,
The transparent flame-retardant resin composition according to claim 1, which is a flat plate having a thickness of 3.0 mm having an average roughness (Ra) of 0.03 μm or less and a total light transmittance of 85% or more. The transparent flame retardant resin according to claim 1, which is a flat plate having a thickness of 3.0 mm having an average roughness (Ra) of 0.03 µm or less and having a total light transmittance of 65% or more in a high temperature and high humidity environment. Composition. Further comprising a silicon-based flame retardant aid,
The transparent flame retardant resin composition according to claim 1, wherein the silicon-based flame retardant aid is 0.01 to 5.0 parts by mass with respect to 100 parts by mass in total of the at least two types of polycarbonate resins. The transparent flame-retardant resin composition according to claim 1, wherein the UL94 flame-retardant property having a thickness of 1.0 mm is V-0. The transparent flame retardant resin composition according to claim 1, wherein the one polycarbonate resin (A) includes a recovered resin produced for use as an optical component. The transparent flame retardant resin composition according to claim 1, wherein the one polycarbonate resin (A) includes an optical component having a weight average molecular weight of 45,000 or less in terms of polystyrene. The transparent flame retardant resin composition according to claim 1, wherein the one polycarbonate resin (A) includes an optical component having a polystyrene-equivalent weight average molecular weight of 35,000 or less. Adding at least two polycarbonate resins and at least one organic flame retardant;
Kneading the at least two polycarbonate resins and the at least one organic flame retardant,
Production of transparent flame retardant resin composition, wherein the addition amount of the at least one organic flame retardant is 0.001 to 3.0 parts by mass with respect to 100 parts by mass in total of the at least two types of polycarbonate resins. Method.