WO2007058111A1

WO2007058111A1 - Flame-retardant resin composition

Info

Publication number: WO2007058111A1
Application number: PCT/JP2006/322353
Authority: WO
Inventors: Susumu Nikkeshi
Original assignee: Tohoku Ricoh Co., Ltd.
Priority date: 2005-11-18
Filing date: 2006-11-09
Publication date: 2007-05-24
Also published as: JP4283329B2; JPWO2007058111A1

Abstract

Disclosed is a flame-retardant resin composition which exhibits excellent frame retardance while containing no halogen element or phosphorus element. Such a flame-retardant resin composition is safe and does not adversely affect the environment or human health. Specifically disclosed is a flame-retardant resin composition containing a thermoplastic resin composed of a polylactic acid or an alloy resin containing a polylactic acid, and at least one substance selected from the group consisting of organic sulfonic acid compounds, organic carboxylic acid compounds and metal salts of them. A mode wherein the thermoplastic resin is a polylactic acid and a mode wherein the content of the at least one substance selected from the group consisting of organic sulfonic acid compounds, organic carboxylic acid compounds and metal salts of them is 0.0002-0.8 part by mass per 100 parts by mass of the thermoplastic resin composed of a polylactic acid or an alloy resin containing a polylactic acid are preferable.

Description

Specification

Flame retardant resin composition

Technical field

[0001] The present invention provides at least an organic sulfonic acid compound, an organic carboxylic acid compound, and a metal salt thereof. / It relates to a flame retardant rosin composition containing any of the above.

Background art

[0002] Resin used in home appliances OA products must satisfy the flame retardancy specified by LJL94 in the UL standard (Underwriters Laboratories Inc., standard) for each part in the United States. is there.

In recent years, the UL standard has been adopted in most countries including Japan, not only in the United States.

[0003] Conventionally, in order to impart flame retardancy to a flammable resin, the following three methods have been generally used depending on the type of resin.

First, 10-20 parts by mass of a halogen compound is added to 100 parts by mass of the resin, and the combustion rate is reduced by acting as a negative reaction for acid flame reaction to the flame in which the halogen compound is combusted. This is a technique for imparting flame retardancy.

The second is the addition of several to several tens of parts by weight of a silicone compound with respect to 100 parts by weight of the resin, or several to several tens of parts by weight of a phosphoric acid compound, By bleeding the silicon compound or causing a dehydrogenation reaction of the phosphoric acid compound in the resin, a chi- ter (carbonized layer) is formed on the surface and a heat insulating film is formed to burn it. It is a technique to stop.

The third is the addition of about 40 to 110 parts by weight of metal hydroxides such as magnesium hydroxide and aluminum hydroxide with respect to 100 parts by weight of the resin. It is a technique that stops the combustion by cooling the entire resin by the endothermic reaction at the time of decomposition and the latent heat of vaporization of the generated water.

[0004] However, in the case of the first method, when a home appliance OA product having flame-retarded coagulum is burned as waste, if a sufficient amount of oxygen and combustion temperature are not given, There is a problem that dioxin is generated by the halogen compound used. In the case of the second method, when the flame retardant used is the silicone compound, it is necessary to add a large amount of the flame retardant to the resin. If the flame retardant is the above-mentioned phosphoric acid compound, burning household appliances OA products with oil as waste will cause water pollution due to phosphoric acid contained in the combustion ash. There is a problem.

In addition, in the case of the third method, it is necessary to add a large amount of metal hydroxide, which is a flame retardant, to the fat, so there is a problem that the fat is hydrolyzed and mechanical properties are lowered. is there.

[0005] In view of this, the present inventor previously proposed that it is extremely effective as a flame retardant having a high thermal stability effect because it captures radicals generated in the tanned compound strength resin. (See Patent Documents 1 to 4).

However, it is also known that combustion of coconut oil generates gas by decomposition of the coconut resin, and this gas continuously reacts with oxygen in the air to continue combustion. At present, it is difficult to impart a sufficiently satisfactory level of flame retardancy only by improving the stability of the resin by adding the compound.

[0006] Patent Document 1: Japanese Patent No. 3046962

Patent Document 2: Japanese Patent No. 3046963

Patent Document 3: Japanese Patent No. 3046964

Patent Document 4: Japanese Patent No. 3607901

Disclosure of the invention

Problems to be solved by the invention

[0007] The present invention has been made in view of the current situation, and it is an object of the present invention to solve the conventional problems and achieve the following objects. That is, an object of the present invention is to provide a flame retardant resin composition that is safe and does not adversely affect the environment and the human body because it does not contain a halogen element or a phosphorus element, and is excellent in flame retardancy.

Means for solving the problem

[0008] As a result of intensive studies by the present inventors in order to solve the above problems, the following knowledge was obtained. . That is, the combustion of thermoplastic resin made of either polylactic acid or an alloy resin containing polylactic acid generates gas by decomposition of the resin, and this gas continuously reacts with oxygen in the air. Combustion continues. At this time, when at least one of an organic sulfonic acid compound, an organic carboxylic acid compound, and a metal salt thereof is present in the resin, these compounds particularly include an alloy containing polylactic acid and polylactic acid. In addition to having a high thermal stability effect on thermoplastic resin made of any of the resins, when the resin is thermally decomposed, a relatively incombustible gas such as benzoic acid and phthalic acid is released into the combustion gas. Therefore, by adding these compounds to the resin, combustible gas generated during the combustion of the resin is reduced and hydrocarbons generated by the thermal decomposition reaction are suppressed. Combustion is effectively suppressed, and high flame retardancy that meets UL94 flame retardant standards is obtained. Moreover, since these compounds have a sufficient effect when added in a small amount, there is no adverse effect on changes in the physical properties of the resin. In addition, organic sulfonic acid compounds, organic carboxylic acid compounds, and metal salts thereof are excellent in safety because they do not contain halogen elements and phosphorus elements, and are particularly effective as flame retardants. is there.

The present invention is based on the above knowledge obtained by the present inventor, and means for solving the above problems are as follows. That is,

<1> A polylactic acid and an alloy resin containing polylactic acid containing a thermoplastic resin composed of a certain amount and an organic sulfonic acid compound, an organic carboxylic acid compound, and at least one of these metal salts. It is a flame retardant resin composition characterized by this.

<2> The flame retardant resin composition according to <1>, wherein the thermoplastic resin is polylactic acid.

<3> Content power of at least one of organic sulfonic acid compounds, organic carboxylic acid compounds and metal salts thereof 100 parts by mass of thermoplastic resin composed of polylactic acid or alloy resin containing polylactic acid The flame-retardant resin composition according to any one of the above items 1> Karaku 2>, which is 0.0002 to 0.8 parts by mass.

<4> Content power of at least one of an organic sulfonic acid compound, an organic carboxylic acid compound, and a metal salt thereof. 100 parts by mass of a thermoplastic resin composed of polylactic acid or an alloy resin containing polylactic acid. 0 to 01 to 0.05 parts by weight It is a flame retardant resin composition.

<5> At least one part of the organic sulfonic acid compound and the organic carboxylic acid compound other than the sulfonic acid group or the carboxylic acid group is an aliphatic compound, an aromatic compound, a heteroaliphatic compound, or a hetero compound. 5. The flame retardant resin composition according to any one of the above 1> Karaku 4> having at least one skeleton selected from aromatic compounds.

<6> At least a portion other than the sulfonic acid group or the carboxylic acid group in at least one of the organic sulfonic acid compound and the organic carboxylic acid compound is selected from an aliphatic compound and an aromatic compound. The flame-retardant resin composition according to <5>, which has one skeleton, the aliphatic compound is olefins or monoterpenes, and the aromatic compound is an alkylbenzene.

<7> An aliphatic carboxylic acid compound or a heteroaliphatic carboxylic acid compound having a divalent polyvalent carboxylic acid compound having a valence of 2 or more, wherein from <5> to <6> It is a flame retardant resin composition.

<8> The compound according to any one of <5> to <7>, wherein the compound is an aromatic carboxylic acid compound or a heteroaromatic carboxylic acid compound having a monovalent or higher carboxylic acid compound. It is a flame retardant rosin composition.

<9> The difficulty according to any one of <1> to <8>, wherein at least one of the metal salt of the organic sulfonic acid compound and the metal salt of the organic carboxylic acid compound is an alkali metal salt. It is a flammable rosin composition.

<10> The metal salt strength of at least one of a metal salt of an organic sulfonic acid compound and a metal salt of an organic carboxylic acid compound, which is at least one of a sodium salt and a potassium salt. It is a thing.

The invention's effect

[0010] According to the present invention, various conventional problems can be solved, and since it contains a halogen element and a phosphorus element, the flame retardant resin composition is safe and does not adversely affect the environment and the human body and has excellent flame retardancy. Can be provided.

Brief Description of Drawings

[0011] [Fig. 1] Fig. 1 shows the amount of camphor sulfonic acid (CPS) added in Example 3 and the combustion test. It is a graph which shows the relationship with the burning time by.

FIG. 2 is a graph showing the relationship between the amount of adipic acid (AZA) added in Example 8 and the combustion time in the combustion test.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] (Flame-retardant resin composition)

The flame retardant resin composition of the present invention comprises a poly (lactic acid) and an alloy resin containing poly (lactic acid), a thermoplastic resin consisting of any of them, an organic sulfonic acid compound, an organic carboxylic acid compound, and a metal salt thereof. It contains at least one of them, and further contains other components as necessary.

[0013] Thermoplastic resin

The thermoplastic resin is composed of polylactic acid and an alloy resin containing polylactic acid. Examples of the polylactic acid (PLA) include poly L lactic acid (PLLA), poly D lactic acid (PDLA), and L lactic acid. D Random copolymers with lactic acid. These may be used alone or in combination of two or more.

As said polylactic acid, what was synthesize | combined suitably may be used and a commercial item can also be used. Examples of the commercially available products include Terramac (registered trademark) TE-2000 (manufactured by Utica Co., Ltd.), Lashia (registered trademark) H-100J (manufactured by Mitsui Engineering Co., Ltd.), and Bayro Ecole (registered trademark) BE-400. (Toyobo Co., Ltd.).

The molecular weight of the polylactic acid can be appropriately selected from known ones that are not particularly limited.

The alloy resin containing the polylactic acid is one or two of the polylactic acid and a thermoplastic resin other than the polylactic acid (for example, polyamide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, acrylic resin). Polymer alloy with more than seeds. Such an alloy resin containing polylactic acid may be appropriately synthesized, or a commercially available product may be used. Examples of the commercially available products include Terramac (registered trademark) TE-1030, Terramac (registered trademark) TE-7300 (both manufactured by UCHIKA CORPORATION), and the like. The content of thermoplastic resin other than polylactic acid is preferably 75% by mass or less, more preferably 65% by mass or less, and particularly preferably 0% by mass. When the content of the thermoplastic resin other than polylactic acid exceeds 75% by mass, the strength depends on the type of thermoplastic resin other than polylactic acid. For example, in the case of acrylic resin, flame retardancy is obtained. It may be difficult to get caught. On the other hand, in the case of polycarbonate, polybutylene terephthalate, polyethylene terephthalate, etc., the flame retardancy can be satisfied even with the addition of about 75% by mass.

Mono-organic sulfonic acid compounds and metal salts thereof

The organic sulfonic acid compound is not particularly limited and can be appropriately selected according to the purpose. For example, the portion other than the sulfonic acid group in the organic sulfonic acid compound can be an aliphatic compound. , Aromatic compounds, heteroaliphatic compounds, heteroaromatic compounds, and the like. Among these, thermoplastic resins made of any of the above-mentioned polylactic acid and alloy resin containing polylactic acid. Those having a skeleton of either an aliphatic compound or an aromatic compound are preferable in that high flame retardancy can be imparted. These compounds may be used alone or in combination of two or more. These compounds may be extracted from natural plants, synthesized, or derivatives from natural compounds.

The aliphatic compound is not particularly limited and can be appropriately selected depending on the purpose. However, the aliphatic resin has high flame retardancy to a thermoplastic resin made of any one of the polylactic acid and an alloy resin containing polylactic acid. The difference between olefins and monoterpenes is preferable in that they can be imparted. Examples of the olefins include otataene, nonaen, decene, undecene, dodecene, and tridecene. As the monoterpenes, the camphane type is preferable. Specific examples of the camphane-type monoterpenes include camphor, borneol, and vol-lene.

The aromatic compound is not particularly limited and can be appropriately selected according to the purpose, but imparts high flame retardancy to a thermoplastic resin made of either the polylactic acid or an alloy resin containing polylactic acid. In view of the ability, alkylbenzenes are preferred. The alkyl group of the alkylbenzenes is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include octyl, nosyl, decacil, undecyl, dodecyl, tridecyl, and the like. Can be mentioned.

The metal salt of the organic sulfonic acid compound is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include powers such as alkali metal salts and alkaline earth metal salts. Among the alkali metal salts preferred by alkali metal salts in terms of being able to impart high flame retardancy to the thermoplastic resin comprising any one of the above polylactic acid and polylactic acid, sodium salts, potassium A salt is more preferred. These metal salts of organic sulfonic acid compounds may be used alone or in combination of two or more. Therefore, the olefins, monoterpenes, or alkylbenzenes-derived sulfonic acid compounds or metal salts thereof include, for example, decyl sulfonate, camphor sulfonic acid, dodecyl benzene sulfonic acid, and sodium salts thereof. And potassium salts. Among these, camphorsulfonic acid, which is a natural sulfonic acid derivative of camphor, is preferred because of its low environmental impact.

The organic sulfonic acid compound and the metal salt of the organic sulfonic acid compound may be used alone or in combination of two or more.

Mono-organic carboxylic acid compounds and metal salts thereof

The organic carboxylic acid compound is not particularly limited and can be appropriately selected according to the purpose. As the part other than the carboxyl group in the organic carboxylic acid compound, the polylactic acid and the polylactic acid can be used. The skeleton of any one of an aliphatic compound, an aromatic compound, a heteroaliphatic compound, and a heteroaromatic compound from the point that high thermoplasticity can be imparted to the thermoplastic resin composed of the alloy resin contained therein Those having the following are preferred. These compounds may be used alone or in combination of two or more. Note that these compounds may be extracted from natural plants, synthesized, or derivatives from natural compounds.

The aliphatic carboxylic acid compound or heteroaliphatic carboxylic acid compound is preferably a divalent or higher carboxylic acid compound. As the divalent carboxylic acid compound, for example, oxalic acid, malonic acid, succinic acid, adipic acid, pimelic acid and the like are preferable. In these compounds, an alkyl group or a hydroxyl group may be introduced. As the trivalent carboxylic acid compound, for example, -trimethyltriacetic acid, aconitic acid, camphoric acid and the like are preferable. Tetravalent cal As the boronic acid compound, for example, ethylenedioxybisethylamine tetraacetic acid is preferable. As the pentavalent carboxylic acid compound, for example, 1, 2, 3, 4, 5-cyclohexanepentacarboxylic acid and the like are preferable. As the hexavalent carboxylic acid compound, for example, 1,2,3,4,5,6-cyclohexanehexacarboxylic acid is preferable.

The aromatic carboxylic acid compound or heteroaromatic carboxylic acid compound is preferably a monovalent or higher carboxylic acid compound. As the monovalent carboxylic acid compound, for example, benzoic acid, salicylic acid, cinnamic acid and the like are preferable. Preferred examples of the divalent carboxylic acid compound include quinoline dicarboxylic acid, carboxycinnamic acid, carboxyphenol acetic acid, naphthalene dicarboxylic acid, and furandicarboxylic acid. Preferred examples of trivalent carboxylic acid compounds include benzene tricarboxylic acid and pyridine tricarboxylic acid!

The metal salt of the organic carboxylic acid compound is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include alkali metal salts and alkaline earth metal salts. Among these, among the alkali metal salts preferred by alkali metal salts, sodium hydroxide is preferable in that it can impart high flame retardancy to the thermoplastic resin comprising either polylactic acid or an alloy resin containing polylactic acid. More preferred are salts and potassium salts. These metal salts of organic carboxylic acid compounds may be used alone or in combination of two or more. Among these, as the organic carboxylic acid compound or a metal salt thereof particularly preferably used for the flame retardant resin composition of the present invention, adipic acid, Salicylic acid and their sodium or potassium salts are preferred.

In addition, the said organic carboxylic acid compound and the metal salt of the said organic carboxylic acid compound may use together 1 type (s) or 2 or more types, respectively.

The organic sulfonic acid compound, organic carboxylic acid compound, and metal salts thereof have good compatibility with thermoplastic resins made of either polylactic acid or alloy resin containing polylactic acid. For example, when it is added to polylactic acid, a molded product having sufficient transparency can be obtained if the degree of crystallinity of the organic carboxylic acid compound and its metal salt is small after molding of the polylactic acid resin composition. If the degree of crystallization is high due to conditions and product shape, a milky white molded product can be obtained.

The organic sulfonic acid compound, organic carboxylic acid compound and metal salts thereof are 1 type may be used alone, or 2 or more types may be used in combination, but the combined use of the organic sulfonated compound and the organic carboxylic acid compound is more than using each of them alone. It is preferable because it can impart extremely high V and flame retardancy to thermoplastic resin made of alloy resin containing polylactic acid and polylactic acid!

[0017] The organic sulfonic acid compound, the organic carboxylic acid compound, and the metal salts thereof are at least! / Less than the amount of heat that also becomes the force of the above-mentioned polylactic acid and the alloy resin containing polylactic acid. It is 0.0002-0. 8 parts by mass with respect to 100 parts by mass of the plastic resin, preferably 0.0005 to 0.5 mass repulsive force S, more preferably 0.005 to 0.1 mass repulsive force S, 01 to 0.05 parts by mass is particularly preferred. When the content is less than 0.0002 parts by mass, it may be difficult to sufficiently impart flame retardancy to a thermoplastic resin made of either polylactic acid or an alloy resin containing polylactic acid, When the amount exceeds 8 parts by mass, the organic sulfonic acid compound, the organic carboxylic acid compound, and the like between the molecules of the poly (lactic acid) and the thermoplastic resin comprising the polylactic acid-containing poly (lactic acid) A large amount of these metal salts may reduce the thermal characteristics and mechanical strength of the thermoplastic resin made of either polylactic acid or an alloy resin containing polylactic acid.

[0018] As a method of adding the organosulfonic acid compound, the organic carboxylic acid compound, and an alloy resin containing these metal salts to a thermoplastic resin comprising a certain amount of polylactic acid and polylactic acid, In particular, the organic sulfonic acid compound, organic carboxylic acid compound, and metal salts thereof can be directly selected from alloy resins containing polylactic acid and polylactic acid. A mixture (master batch) in which the organic sulfonic acid compound, the organic carboxylic acid compound, and their metal salts are mixed in a high concentration in advance is prepared. The polylactic acid and the alloy resin containing polylactic acid may be added to a thermoplastic resin consisting of a certain amount.

[0019] Other ingredients

The other components can be appropriately selected according to the purpose from known additives used in the resin composition without particular limitation, such as inorganic fibers, organic fibers, inorganic particles, etc. Is mentioned. Examples of the inorganic fiber include glass fiber and carbon fiber. Fiber or whisker. Examples of the organic fiber include Kepler fiber. Examples of the inorganic particles include minerals such as silica, talc, my strength, wollastonite, clay, calcium carbonate, and the like.

In addition, the flame retardant resin composition of the present invention may further include, as necessary, existing flame retardants, flame retardant aids other than the organic sulfonic acid compounds, organic carboxylic acid compounds, and metal salts thereof. Various deterioration agents, antibacterial agents, and the like can also be contained.

[0020] Method of molding

The method for molding the flame retardant resin composition can be appropriately selected from known methods depending on the purpose for which there is no particular limitation. For example, film molding, extrusion molding, injection molding, blow molding , Compression molding, transfer molding, calendar molding, thermoforming, fluid molding, laminate molding, and the like.

[0021] Applications

The flame retardant resin composition of the present invention is excellent in flame retardancy and moldability, and can be formed into molded bodies of various shapes, structures, and sizes. For example, a notebook computer, a printer, a television, a stereo, a copy It can be widely used as a part of various home appliance OA products such as single machine, air conditioner, refrigerator, washing machine, stereo.

Example

[0022] The following is a description of the embodiments of the present invention. The present invention is not limited to these embodiments.

[0023] (Example 1)

Preparation of a flame retardant resin composition

Polylactic acid (PLA) (manufactured by Unitica Co., Ltd., Terramac (registered trademark) TE-2000) is dried with a dehumidifying dryer (Matsui Seisakusho Co., Ltd., PO-200 type) at 100 ° C for 5 hours, then organic As the sulfonic acid compound, camphorsulfonic acid (reagent grade 1, manufactured by Kanto Chemical Co., Ltd .; hereinafter abbreviated as “CPS”), an aliphatic sulfonic acid compound, was added to 100 parts by mass of polylactic acid. On the other hand, the flame retardant resin composition of lot numbers 1 to 3 was prepared by adding at a ratio shown in Table 1.

For the flame retardant resin composition of the obtained lot numbers 1 to 3, the following method is used. The combustion test was conducted. The results are shown in Table 1.

[0024] Combustion test

The flame-retardant resin composition was stirred and mixed for 4 minutes at a stirring blade rotation speed of 300 rpm using a tumbler (Nissui Processing Co., Ltd., Tumble Mixer TM-50 type, 8 blades). Using this, an injection molding machine (F-85, made by Crocna Company, clamping pressure of 85 tons) can be used to collect combustion test pieces of each thickness shown in UL 94 (lZl6in: l. 47-: L 59mm). A test piece was produced by molding using a mold designed as described above.

The obtained specimens were subjected to a combustion test based on the UL94V vertical combustion test method. The burning time is the sum of two ignitions and is the average of five test pieces. The obtained results were evaluated as V-0, V-1, or V-2 according to the following criteria. In addition, those that did not satisfy these gaps were considered “failed”.

Evaluation criteria

V—0: The average burning time after removing the ignition flame is 10 seconds or less, and all samples do not drop the flame that ignites the absorbent cotton!

V-1: Remove the ignition flame! /, The average burning time after 30 seconds or less, and all samples should not drop fine flame that ignites absorbent cotton!

V-2: The average burning time after removing the ignition flame is 30 seconds or less, and the particulate flame that ignites absorbent cotton is dropped.

[Example 2]

Preparation of a flame retardant resin composition

In Example 1, instead of CPS, an aromatic sulfonic acid compound, dodecyl benzene sulfonic acid (manufactured by Kao Corporation, Neobelex (registered trademark) GS; hereinafter abbreviated as “DB-Ac”) is used. Except for the addition, a flame-retardant resin composition of lot numbers 4 to 6 was prepared in the same manner as in Example 1.

About the obtained rosin composition, the combustion test was done like Example 1. FIG. The results are shown in Table 1.

[Comparative Example 1]

-Preparation of rosin composition In Example 1, a rosin composition of Lot No. 7 was prepared in the same manner as in Example 1 except that CPS was not added.

[table 1]

As a result of Table 1, the resin composition of Examples 1 and 2 to which an aliphatic or aromatic sulfonated compound was added as an organic sulfonic acid compound was the same as that of Comparative Example 1 with no addition. Compared to products, it is recognized that the total burning time is reduced to about 1/15, and it is recognized that it has high flame retardancy that meets UL94 flame retardant standards.

[0028] (Example 3)

Preparation of a flame retardant resin composition

In Example 1, each resin composition was prepared in the same manner as in Example 1 except that CPS was added at a ratio selected in the range of 0 to 10 parts by mass with respect to 100 parts by mass of polylactic acid. Made.

About each obtained resin composition, the combustion test was done like Example 1. FIG. The results are shown in Figure 1.

From the results in Fig. 1, the flame retardance time was clearly shortened by adding CPS, and the effect of addition was noticeable.

[0029] (Example 4)

Preparation of a flame retardant resin composition

In Example 1, in place of CPS, the flame-retardant resin composition of lot numbers 8 to 12 was prepared in the same manner as in Example 1 except that 0.05 part by mass of the organic sulfonic acid compound shown in Table 2 was added. The Prepared.

About the obtained rosin composition, the combustion test was done like Example 1. FIG. The results are shown in Table 2.

[0030] [Table 2]

From the results in Table 2, even when the organic sulfonic acid compound is replaced with the aromatic sulfonic acid compound shown in Table 2 from CPS, combustion of the resin composition can be effectively suppressed. It is recognized that it meets the flame resistance standard of UL94.

[0031] (Example 5)

Preparation of a flame retardant resin composition

In Example 1, in place of CPS, sodium dodecylbenzenesulfonate (made by Kao Corporation), which is a metal salt of an aromatic or aliphatic sulfonate compound, as a metal salt of an organic sulfonate compound. Neobelex (registered trademark) G-25; hereinafter abbreviated as "DB-Na"), sodium olefin sulfonate (manufactured by Lion Corporation, Liporan (registered trademark) PB-800; hereinafter referred to as "OS — Abbreviated as “Na”), or potassium toluenesulfonate (manufactured by Kanto Chemical Co., Ltd., reagent grade 1; hereinafter abbreviated as “STS”). Similarly, the flame-retardant resin composition of lot numbers 13 to 15 was prepared. About the obtained rosin composition, the combustion test was done like Example 1. FIG. The results are shown in Table 3.

[0032] [Table 3] Specimen thickness Total of two burning times UL standard Lot number Organic sulfonate

i.mm) (average of 5 pieces, sec) 94V class

13 1.59 7.3 V-2 Example 5 14 OS- Na 1.59 6.4 V- 2

15 STS 1.59 6 V-2 Based on the results in Table 3, even when a metal salt of an organic sulfonic acid compound is added in place of the organic sulfonic acid compound, combustion of the resin composition is effectively suppressed. UL94 flame retardant

Q

GQ is recognized to meet the standards.

I

[0033] (Example 6) US

Preparation of a flame retardant resin composition

After drying polylactic acid (PLA) (manufactured by Unitica Co., Ltd., Terramac (registered trademark) TE-2000) with a dehumidifying dryer (Matsui Seisakusho Co., Ltd., PO-200 type) at 110 ° C for 10 hours, organic As the carboxylic acid compound, adipic acid (reagent grade 1, manufactured by Kanto Chemical Co., Ltd .; hereinafter abbreviated as “AZA”), an aliphatic carboxylic acid compound, is added to 100 parts by mass of polylactic acid. The flame retardant resin composition of lot numbers 16 to 18 was prepared by adding at a ratio shown in Table 4. About the flame retardant resin composition of the obtained lot numbers 16-18, the combustion test was done like Example 1. The results are shown in Table 4.

[Example 7]

Preparation of a flame retardant resin composition

In Example 6, instead of AZA, salicylic acid that is an aromatic carboxylic acid compound (Kanto Chemical Co., Ltd., reagent grade 1; hereinafter abbreviated as “SAA”) was added. In the same manner as in 6, flame retardant rosin compositions having lot numbers 19 to 21 were prepared.

About the obtained flame-retardant resin composition, the combustion test was done like Example 1. FIG. The results are shown in Table 4.

[0035] (Comparative Example 2)

-Preparation of rosin composition

In Example 6, a rosin composition of lot number 22 was prepared in the same manner as in Example 6 except that AZA was not added.

About the obtained rosin composition, the combustion test was done like Example 1. FIG. The result Table 4 shows.

[0036] [Table 4]

From the results shown in Table 4, the resin compositions of Examples 6 to 7 to which an aliphatic or aromatic carboxylic oxide compound was added as an organic carboxylic acid compound were the same as those of Comparative Example 2 with no addition. Compared to products, it is recognized that the total burning time is reduced to about 1/10, and it is recognized that it has high flame retardancy that meets UL94 flame retardant standards.

[0037] (Example 8)

Preparation of a flame retardant resin composition

In Example 6, each flame-retardant resin composition was prepared in the same manner as in Example 6 except that AZA was added at a ratio selected in the range of 0 to 10 parts by mass with respect to 100 parts by mass of polylactic acid. A product was prepared.

About each obtained flame-retardant resin composition, the combustion test was done like Example 1. FIG. The result is shown in figure 2.

From the results in Fig. 2, the flame retarding time was clearly shortened by the addition of AZA, and the effect of addition was noticeable.

[0038] (Example 9)

Preparation of a flame retardant resin composition

In Example 6, instead of AZA, similar to Example 6 except that 0.025 parts by mass of organic carboxylic acid compounds shown in Table 5 (all reagents grade 1, manufactured by Kanto Yigaku Co., Ltd.) were added. Thus, a flame retardant rosin composition having lot numbers 23 to 30 was prepared.

About the obtained flame-retardant resin composition, the combustion test was done like Example 1. FIG. The results are shown in Table 5.

[0039] [Table 5]

From the results of Table 5, the organic carboxylic acid compound can be replaced with the aliphatic carboxylic acid compound, heteroaliphatic carboxylic acid compound, or aromatic carboxylic acid compound shown in Table 5 from AZA. It is recognized that it can effectively suppress the combustion of and meet the flame resistance standard of UL94.

[Example 10]

Preparation of a flame retardant resin composition

In Example 6, in place of AZA, flame retardancy of lot numbers 31 to 33 was obtained in the same manner as in Example 6 except that 0.025 part by mass of a metal salt of an organic carboxylic acid compound shown in Table 6 was added. A fat composition was prepared.

About the obtained flame-retardant resin composition, the combustion test was done like Example 1. FIG. The results are shown in Table 6.

[0041] [Table 6]

From the results shown in Table 6, even when a metal salt of an organic carboxylic acid compound is added in place of the organic carboxylic acid compound, combustion of the resin composition can be effectively suppressed, and UL94 flame retardant is achieved. It is allowed to meet the standards.

[Example 11]

Preparation of combustible rosin composition

In Example 1, the addition amount of CPS was 0.01 parts by mass with respect to 100 parts by mass of polylactic acid, and AZA used in Example 6 was further added with 0.01 parts by mass with respect to 100 parts by mass of polylactic acid. In the same manner as in Example 1, a flame retardant resin composition of lot number 34 was prepared. With respect to the obtained flame-retardant resin composition of Example 11, a combustion test was conducted in the same manner as in Example 1. The results are shown in Table 7.

[0043] [Table 7]

From the results of Table 7, the resin composition of Example 11 to which the organic sulfonic acid compound and the organic carboxylic acid compound were added was compared with Example 1 and Example 6 in which each was added alone. Thus, it is recognized that combustion of the resin composition can be particularly effectively suppressed and has high flame retardancy satisfying the flame resistance standard of UL94.

(Example 12 and Comparative Example 3)

Preparation of a flame retardant resin composition

In Example 1 and Comparative Example 1, polylactic acid (PLA) (manufactured by Utica Co., Ltd., Terramac (registered trademark) TE-2000) and alloy resin containing polylactic acid (manufactured by Utica Co., Ltd., Terramac) (Registered trademark) TE-1030, high rigidity grade, alloy resin containing about 50% by mass of polycarbonate) A resin composition of Example 12 and Comparative Example 3 was prepared in the same manner as in Example 1 and Comparative Example 1 except that it was dried at 80 ° C. for 10 hours.

For the obtained resin compositions of Example 12 and Comparative Example 3, a combustion test was conducted in the same manner as in Example 1. The results are shown in Table 8.

[0045] [Table 8] CPS content Test piece thickness Total of two burning times ULi rating Lot number

(Mass) (mm (average of 5 pieces, sec) 94V class

35 0.01 1.58 5.4 V-2 Example 1 2 36 0.02 1.58 0.3 V-2

37 0.05 1.58 0.0 V- 0 Comparative Example 3 38 No addition 1.58 75.4 Failed Based on the results in Table 8, the rosin composition of Example 12 using an alloy resin containing polylactic acid instead of polylactic acid is a comparative example. It is recognized that it has higher flame retardancy that meets the flame resistance standard of UL94, compared with the resin composition of No. 3.

(Example 13 and Comparative Example 4)

Preparation of flammable resin composition

In Example 6 and Comparative Example 2, polylactic acid (PLA) (manufactured by Utica Co., Ltd., Terramac (registered trademark) TE-2000) and alloy resin containing polylactic acid (manufactured by Utica Co., Ltd., Terramac) (Registered trademark) TE-1030, high rigidity grade, alloy resin containing about 50% by mass of polycarbonate) A resin composition of Example 13 and Comparative Example 4 was prepared in the same manner as in Example 6 and Comparative Example 2, except that it was dried at 80 ° C. for 10 hours.

With respect to the obtained resin compositions of Example 13 and Comparative Example 4, a combustion test was conducted in the same manner as in Example 1. The results are shown in Table 9.

[0047] [Table 9]

From the results shown in Table 9, the resin composition of Example 13 using alloy resin containing polylactic acid instead of polylactic acid satisfies the flame resistance standard of UL94 compared with the resin composition of Comparative Example 4. It is recognized that it has high flame retardancy.

Industrial applicability

The flame retardant resin composition of the present invention does not contain a halogen element or a phosphorus element, and is suitable for the environment and the human body. Because it is safe and has high flame resistance without adverse effects, it is suitable for use in parts of various household appliances such as copiers, printers, televisions, personal computers, air conditioners, refrigerators, washing machines, and stereos. be able to.

Claims

The scope of the claims

[1] A thermoplastic resin comprising at least one of polylactic acid and an alloy resin containing polylactic acid, an organic sulfonic acid compound, an organic carboxylic acid compound, and at least a shearing force of these metal salts. A flame retardant resin composition characterized by comprising:

[2] The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is polylactic acid.

[3] A thermoplastic resin comprising at least one of an organic sulfonic acid compound, an organic carboxylic acid compound, and an alloy resin containing polylactic acid, at least one of these metal salts. The flame-retardant resin composition according to any one of claims 1 to 2, wherein the composition is 0.0002 to 0.8 parts by mass with respect to 100 parts by mass of the resin.

[4] Thermoplastic property in which the content of at least one of the organic sulfonic acid compound, the organic carboxylic acid compound, and the metal salt thereof is polylactic acid or an alloy resin containing polylactic acid. The flame-retardant resin composition according to claim 3, wherein the content is 0.01 to 0.05 parts by mass with respect to 100 parts by mass of the resin.

[5] At least one of the organic sulfonic acid compound and the organic carboxylic acid compound other than the sulfonic acid group or the carboxylic acid group is an aliphatic compound, an aromatic compound, a heteroaliphatic compound, or a heterocycle. The flame-retardant resin composition according to any one of claims 1 to 4, wherein the flame-retardant resin composition has at least one skeleton selected from aromatic compounds.

[6] At least organic sulfonic acid compound and organic carboxylic acid compound! / Any part other than the sulfonic acid group or carboxylic acid group has at least one skeleton selected from aliphatic compounds and aromatic compounds, and the aliphatic compounds are olefins or monoterpenes. The flame retardant resin composition according to claim 5, wherein the aromatic compound is an alkylbenzene.

[7] The aliphatic carboxylic acid compound or the heteroaliphatic carboxylic acid compound strength is a divalent or higher polyvalent carboxylic acid compound compound. Flame retardant rosin composition.

[8] Aromatic carboxylic acid compound or heteroaromatic carboxylic acid compound force Monovalent or higher force Rubonic acid compound compound The flame-retardant resin composition as described. The metal salt of an organic sulfonic acid compound and / or the metal salt of an organic carboxylic acid compound is at least one of a sodium salt and a potassium salt. Flame retardant rosin composition.