JP2003192921A - Polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame retardant which is lowly toxic and not causing resource exhaustion and global warming and to provide a polymer composition containing the same. <P>SOLUTION: The polymer composition is one containing a polymer and a flame retardant, wherein the flame retardant comprises at least one nucleic- acid-related substance selected from the group consisting of a nucleic acid base, a nucleoside, a nucleotide, and a polynucleotide and/or at least one nucleic- acid-related substance derivative selected from the group consisting of (a) a sulfate, nitrate or borate of a nucleic-acid-related substance and an isocyanurate, (b) a metal salt of a nucleotide, and (c) and a compound formed by replacing the hydrogen atoms bonded to the nitrogen atoms of a nucleic acid base, a nucleoside, or a nucleotide by 1-4C alkyl groups, 6-10C aryl groups, alkoxyl groups, or mercapto groups. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame retardant which has low toxicity and does not impair the original properties of the polymer, and a polymer composition using the same.

[0002]

2. Description of the Related Art Polymers are classified into those that burn like wood. For this reason, it cannot be used as it is for purposes where burning is not convenient, and various flame retardants have been applied.

In this specification, a polymer (sometimes referred to as "resin" or "plastic") is
It is intended to include thermosetting polymers as well as thermoplastic polymers, and the polymeric composition comprises a mixture of polymers and other materials (eg, inorganic fillers).

Generally, flame retardation of a polymer is carried out by blending various flame retardants or by introducing a substituent into the skeleton of the polymer. Further, flame retardants are roughly classified into halogen flame retardants and non-halogen flame retardants.

It has been pointed out that halogen-based flame retardants are toxic by acid gases such as hydrogen bromide and hydrogen chloride generated during combustion, and recently, it has been considered that dioxins may be generated. There is. For this reason, non-halogen flame retardants have recently attracted attention.

Examples of non-halogen flame retardants include metal hydroxides and phosphorus flame retardants. For example, a metal hydroxide such as magnesium hydroxide has a low toxicity of gas generated at the time of combustion as compared with a halogen-based flame retardant, but has a drawback of inferior flame retardancy. Therefore, in order to make the polymer flame-retardant using the metal hydroxide, a large amount of the metal oxide must be blended in the polymer, which causes a problem of impairing the properties of the polymer.

Further, Patent Document 1 discloses a flame-retardant polymer composition obtained by blending a thermoplastic polymer with a sulfate of a triazine compound as a non-halogen flame retardant. But,
Although this composition exhibits a considerable effect of suppressing combustion, it does not have sufficient flame retardancy, and development of a flame retardant and a flame retardant polymer composition having good flame retardancy is desired.

From the viewpoint of global environmental problems,
With the exhaustion of resources such as petroleum and the global warming caused by the incineration of polymers that cannot be material recycled or chemically recycled at the time of waste treatment, biodegradable polymers are being developed. In particular, biodegradable polymers made from biomass without using fossil resources such as petroleum are being actively developed. Among them, when plant-derived biomass in which atmospheric carbon dioxide is immobilized in a relatively short cycle (for example, one year) such as corn and potato is used, even if carbon dioxide is generated by incineration, the immobilized cycle is short. Therefore, it is attracting attention because it has the advantage of not contributing to global warming in the long term.

[0009]

[Patent Document 1] Japanese Unexamined Patent Publication No. 8-48812

[0010]

As described above, a flame retardant and a flame-retardant polymer which do not generate toxic gases such as dioxins, do not impair the properties of the polymer, and have sufficient flame retardancy are provided. Development is desired. Furthermore, no technology has been developed so far from the viewpoint of producing a flame retardant from biomass as a raw material or imparting biodegradability to the flame retardant itself.

The present invention has been made in view of the above points, and a main object of the present invention is to provide a flame retardant which is less toxic and friendly to the global environment, and a polymer composition using the same. .

[0012]

The polymer composition of the present invention is a polymer composition containing a polymer and a flame retardant, wherein the flame retardant is a nucleobase, a nucleoside, a nucleotide,
And at least one nucleic acid-related substance selected from the group consisting of polynucleotides, and / or (a) sulfate, nitrate, borate, hydrochloride and isocyanurate of nucleobase, (b) metal salt of nucleotide ,and,
(C) A group consisting of a nucleobase, a nucleoside, and a compound in which a hydrogen atom bonded to a nitrogen atom of a nucleotide is substituted with an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group, or a mercapto group. It is characterized by containing at least one nucleic acid-related substance derivative selected, whereby the above-mentioned object is achieved.

The thermal decomposition temperature of the at least one nucleic acid-related substance and / or the at least one nucleic acid-related substance derivative is preferably higher than 100 ° C. and lower than the thermal decomposition temperature of the polymer. In one embodiment, the thermal decomposition temperature of the at least one nucleic acid-related substance and / or the at least one nucleic acid-related substance derivative is in the range of higher than 300 ° C and lower than 550 ° C.

It is preferable that the at least one nucleic acid-related substance and / or the at least one nucleic acid-related substance derivative is contained in a ratio of 5 parts by weight or more and 150 parts by weight or less based on 100 parts by weight of the polymer. It is more preferably 10 parts by weight or more and 100 parts by weight or less.

In a preferred embodiment, the at least one nucleic acid-related substance contains at least one compound selected from the group consisting of adenine, guanine, cytosine, uracil, and thymine.

In a preferred embodiment, the at least one nucleic acid-related substance is at least one monomer selected from the group consisting of nucleobases, nucleosides, and nucleotides, and the at least one monomer The body is polymerized with other polymerizable components.

In one preferred embodiment, the other polymerizable component is a monomer and the at least one monomer is copolymerized with the other polymerization component. As the other polymerizable component, at least one monomer selected from the group consisting of dibasic acid, dibasic acid anhydride and diisocyanate can be preferably used.

The polymer preferably contains a biodegradable polymer, and more preferably the polymer is a polymer produced from a raw material of plant origin. A polylactic acid-based polymer can be preferably used as the polymer.

The polymeric composition of one preferred embodiment comprises:
It is thermoplastic and can be injection molded.

Various molded articles can be produced using the polymer composition according to the present invention and are suitably used as a material for a casing for electric equipment.

According to the present invention, at least one nucleic acid-related substance selected from the group consisting of nucleobases, nucleosides, nucleotides and polynucleotides, and / or (a) nucleobase sulfates, nitrates, borates. ,
Hydrochlorides and isocyanurates, (b) metal salts of nucleotides, and (c) nucleobases, nucleosides, hydrogen atoms bonded to nitrogen atoms of nucleotides having 1 to 4 carbon atoms.
Of at least one nucleic acid-related substance derivative selected from the group consisting of compounds substituted with an alkyl group, an aryl group having 6 to 10 carbon atoms, an alkoxy group, or a mercapto group as a flame retardant for a polymer composition. Will be provided.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The composition and characteristics of the polymer composition according to the embodiments of the present invention will be described below.

The polymer composition according to the embodiment of the present invention is
The polymer includes a polymer and a flame retardant, and the flame retardant includes at least one nucleic acid-related substance selected from the group consisting of nucleobases, nucleosides, nucleotides, and polynucleotides. Further, instead of the nucleic acid-related substance or together with the nucleic acid-related substance, (a) a nucleobase sulfate, nitrate,
Borate, hydrochloride and isocyanuric acid salt, (b) metal salt of nucleotide, and (c) nucleobase, nucleoside, alkyl group having 1 to 4 carbon atoms in which hydrogen atom bonded to nitrogen atom of nucleotide, and 6 carbon atoms An aryl group of -10,
At least one nucleic acid-related substance derivative selected from the group consisting of compounds substituted with an alkoxy group or a mercapto group is included.

As will be illustrated later in specific examples, since the nucleic acid-related substance and the nucleic acid-related substance derivative contain a nitrogen atom, nitrogen-containing compounds conventionally used as flame retardants, for example, fats Group amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyan compounds,
Similar to aliphatic amides, aromatic amides, urea and thiourea, they exhibit flame retardant action.

In particular, since the nucleic acid-related substance and the nucleic acid-related substance derivative have a nitrogen-containing heterocyclic ring, they undergo endothermic decomposition when exposed to high temperatures, like conventional nitrogen-containing heterocyclic compound-based flame retardants. By suppressing the thermal decomposition of the polymer by cutting off the fuel supply for combustion, and by forming an inert atmosphere (nitrogen gas atmosphere) around the polymer, it reduces the chance of contact with oxygen and makes it flame-retardant. It is thought that the action is high.

The above-mentioned nucleic acid-related substance and nucleic acid-related substance derivative are both substances of biological origin and have biodegradability. Therefore, unlike compounds synthesized from fossil fuels such as petroleum, it is a material that is manufactured from biomass as a raw material and that has biodegradability and is environmentally friendly.

The flame retardant contained in the polymer composition of the present invention may contain a conventional flame retardant in addition to the nucleic acid-related substance and / or the derivative of the nucleic acid-related substance. In order to obtain the above, it is preferable to use only the above-mentioned nucleic acid-related substance and / or derivative of the above-mentioned nucleic acid-related substance having biodegradability as a flame retardant.

In order for the above-mentioned nucleic acid-related substance and nucleic acid-related substance derivative to suitably act as a flame retardant for a polymer composition, their thermal decomposition temperature is higher than the processing temperature (molding temperature, etc.) of the polymer, It is preferably lower than the thermal decomposition temperature of the polymer.

The high-content composition according to the present invention can be processed into various forms of molded articles such as sheets, films and casings depending on the characteristics of the polymer to be blended.
The material is not limited to a molding material, and can be used as a material such as an adhesive, a paint, or putty. The processing temperature of a general polymer is about 100 ° C. to about 300 ° C., and the temperature of a general polymer material is about 400 ° C. to about 550 ° C. when it burns (corresponding to the thermal decomposition temperature). To reach. Therefore, the flame retardant according to the present invention can be obtained by using a flame retardant having a desired thermal decomposition temperature (that is, the nucleic acid-related substance and the nucleic acid-related substance derivative) according to the type of polymer to be blended and / or the processing temperature. Good. That is, a flame retardant having a thermal decomposition temperature higher than 100 ° C. and lower than 550 ° C. can be appropriately used depending on the application.

The polymer composition of the present invention exhibits its advantages in applications such as electric equipment (including electronic equipment and electronic parts) where flame retardancy is particularly required. Also,
The flame retardant according to the present invention can impart flame retardancy without significantly deteriorating the mechanical properties of the polymer.
It is preferably used as a material for a bulk molded product such as a housing.

As the polymer constituting the polymer composition for these uses, a polymer having a processing temperature (molding temperature) of about 250 ° C. or higher and about 300 ° C. or lower (typically a conventional so-called general-purpose engineering plastic) is used. (“Plastic” here is a plastic in a narrow sense and refers to a thermoplastic resin.) Is used, and the thermal decomposition temperature of the flame retardant is set so that thermal decomposition does not occur during processing of these polymers. It is preferably higher than about 300 ° C. Therefore, by using a flame retardant having a thermal decomposition temperature higher than about 300 ° C. and lower than 550 ° C., the advantages of the present invention are particularly exerted.

The thermal decomposition temperature in this specification is 10 ° C. in a nitrogen atmosphere using a thermogravimetric meter (TG).
The weight change is measured under the temperature rising condition of / min, and the temperature at which the weight loss reaches 10% is defined as the thermal decomposition temperature.

The blend composition of the polymer and the flame retardant in the polymer composition of the present invention depends on the types of the polymer and the flame retardant and the properties required for the final product (for example, flame retardancy and mechanical properties). Depending on the polymer, it is generally preferable to include the flame retardant (that is, the nucleic acid-related substance and the nucleic acid-related substance derivative) in a ratio of 5 parts by weight or more and 150 parts by weight or less with respect to 100 parts by weight of the polymer. Since the flame retardant according to the present invention is typically in the form of powder, since it has a small bulk density and a large volume effect (or surface area effect) compared to the weight ratio, it can exhibit a flame retarding effect from a relatively small amount, In order to surely obtain the flame retardant effect, it is preferable to add 5 parts by weight or more, and more preferably 10 parts by weight or more.
On the other hand, when the blending amount of the flame retardant exceeds 150 parts by weight, the polymer properties (for example, mechanical properties) may deteriorate excessively. In particular, in order to suppress the deterioration of the physical properties of the polymer in applications such as bulk moldings, the blending amount of the flame retardant is preferably 100 parts by weight or less, more preferably 50 parts by weight or less.

Specific examples of the nucleic acid-related substance and nucleic acid-related substance derivative which are preferably used as the flame retardant of the polymer composition of the present invention are shown below.

A nucleobase is a substance that constitutes a nucleic acid together with pentose and phosphate, as is well known. Adenine, guanine, cytosine, uracil, thymine and hypoxanthine can be preferably used. Further, sulfates, nitrates, borates, hydrochlorides and isocyanurates of these nucleic acid bases are also preferably used. For example, adenine sulfate, guanine hydrochloride, guanine sulfate, etc. can be illustrated.

Examples of nucleosides include adenosine, guanosine, cytidine, uridine, thymidine and inosine.

As the nucleotide, for example, adenylic acid, guanylic acid, cytidylic acid, uridylic acid, thymidylic acid or inosinic acid can be preferably used. Further, as the metal salt of nucleotide, 5'-adenylic acid sodium salt, adenosine triphosphate sodium salt, 5'-guanylic acid sodium salt, 5'-uridylic acid sodium salt,
5'-inosinic acid sodium salt can be illustrated.

The hydrogen atom bonded to the nitrogen atom of the above nucleobase, nucleoside and nucleotide has 1 to 4 carbon atoms.
The compound substituted with the alkyl group, aryl group having 6 to 10 carbon atoms, alkoxy group or mercapto group also has flame retardancy. As such a compound, 2-methyladenine,
Examples are 6-diethyl adenine and 6-allyl adenine.

Here, the alkyl group having 1 to 4 carbon atoms means
For example, a methyl group, an ethyl group, a propyl group, a butyl group and the like can be mentioned, and as the aryl group having 6 to 10 carbon atoms,
For example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. can be mentioned. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group and the like. If the carbon number is too large, flame retardancy may decrease.

As described above, the flame retardant used in the polymer composition especially for the bulk molded article is more than 300 ° C. and 550 ° C.
It preferably has a thermal decomposition temperature of less than, and examples of such a compound include adenine, guanine, cytosine, uracil, and thymine. Table 1 shows the thermal decomposition temperatures of the main nucleic acid-related substances that are preferably used as the flame retardant of the present invention. The thermal decomposition temperature was a temperature at which the weight loss reached 10% under a nitrogen atmosphere and a temperature increase condition of 10 ° C./min using a thermal analyzer TAS100 (TG / DTA · DSC) manufactured by Rigaku. .

[0041]

[Table 1]

An atomic group selected from the group consisting of a nucleotide, or a hydrogen atom bonded to a nitrogen atom of a nucleotide, of an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group, and a mercapto group. (Group)
The compound substituted with has phosphoric acid as a constitutional unit, and these compounds form a polyphosphoric acid compound when exposed to high temperature to form a heat resistant film, and / or It is considered that the flame retardant effect is exhibited due to the carbonization promoting mechanism by the solid acid. Therefore, since these compounds have a flame retardant action due to phosphoric acid and a flame retardant action due to a nitrogen-containing heterocycle, a greater effect can be expected. Polynucleotides have excellent flame retardancy as well as nucleotides, but if the molecular weight is too large, the dispersibility in the polymer will decrease, so it is preferable to use those having a molecular weight of tens of thousands or less.

The polymer used in the polymer composition of the present invention includes thermoplastic resins such as polystyrene, ABS resin, polyamide resin, polypropylene, polyurethane, PPS resin, epoxy resin, phenol resin, polyester resin and the like. Although a general-purpose polymer such as a thermosetting resin can be used, it is preferable to use a biodegradable polymer. Since the biodegradable polymer composition can be obtained by using the flame retardant according to the present invention and the biodegradable polymer, it is possible to dispose of it by utilizing decomposition by enzymes and / or microorganisms. Moreover, even if it is buried underground, it can be decomposed and incorporated into the natural material cycle.

Examples of the biodegradable polymer include polymers obtained by ring-opening polymerization of lactones such as polycaprolactone and polypropiolactone, polymers of hydroxy acids such as polylactic acid and polyglycolic acid, polyethylene adipate and poly. Copolymers of glycols and aliphatic dicarboxylic acids such as butylene adipate, polytetramethylene adipate, polyethylene succinate, and polybutylene succinate, and polymers having terminal functional groups such as polycaprolactone diol and polycaprolactone triol. Polyester obtained by fermentation of microorganisms such as 3-hydroxypropionate, 3-hydroxybutyrate, 3-hydroxyvalerate, and 3-hydroxyoctanoate can be preferably used.

Among the biodegradable polymers, polymers produced using biomass of plant origin in which atmospheric carbon dioxide is immobilized in a relatively short cycle (for example, one year) are particularly preferable. These polymers do not require fossil resources and have a short fixing cycle even when carbon dioxide gas is generated by incineration, so that they have an advantage that they do not contribute to global warming in the long term. As such a polymer, for example, corn, starch which is the main component of sweet potatoes, cellulose which is the main component of vegetation or rice straw, or a polymer which is a sugar as its constituent unit such as glucose is a polymer. Examples thereof include polylactic acid and cellulose acetate.

The flame retardant according to the present invention is typically in the form of powder as described above and is dispersed and mixed in the polymer.
It can also be introduced into the polymer chain. For example, when at least one nucleic acid-related substance selected from the group consisting of nucleic acid bases, nucleosides and nucleotides is used as the flame retardant of the present invention, this is used as one monomer (polymerizable component) for other polymerization. It may be polymerized with the sexual component. The amino groups and / or hydroxyl groups of nucleobases, nucleosides and nucleotides serve as functional groups for the polymerization reaction. The polymer obtained by the polymerization may be a linear polymer or 3
You may form a dimensional crosslinked structure.

At least one monomer selected from the group consisting of nucleobases, nucleosides and nucleotides includes adenine, adenosine, adenylic acid, guanine, guanosine, guanylic acid, cytosine, cytidine, cytidylic acid, uracil, uridine, Examples thereof include uridylic acid, thymine, thymidine, thymidylic acid, hypoxanthine, inosine and inosinic acid.

One or more kinds of monomers selected from the group of the above monomers, dibasic acids such as phthalic acid, fumaric acid, maleic acid and succinic acid, phthalic anhydride, fumaric anhydride,
Dibasic acid anhydrides such as maleic anhydride and succinic anhydride,
Linear flame-retardant by copolymerizing with other polymerizable components such as diisocyanate such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane-4,4′-diisocyanate and hexamethylene diisocyanate. A polymer can be obtained.

As described above, a polymer containing a flame retardant as a polymerization component also has a function of a nitrogen-containing heterocycle in the polymer skeleton,
When exposed to high temperatures, it exhibits a flame retardant effect because it undergoes endothermic decomposition to absorb heat and form an inert atmosphere. When the flame retardant is introduced into the polymer chain and used, the preferable blending amount is also 5 parts by weight or more and 150 parts by weight or less, and preferably 10 parts by weight or more and 100 parts by weight or less, as described above. More preferable. Further, a flame retardant may be dispersed and mixed in a polymer containing the flame retardant as a polymerization component. Also in this case, it is preferable that the total amount of the flame retardant is approximately within the above range.

Further, the polymer composition of the present invention, in addition to the polymer as a base material and the flame retardant (the above-mentioned nucleic acid-related substance and the above-mentioned nucleic acid-related substance derivative), does not impair the effects of the present invention, If necessary, conventionally known additive components may be contained.

Examples thereof include antioxidants (phenolic, phosphite, thioether, etc.), weathering agents (benzophenone, salicylate, benzotriazole, hindered amine, etc.), metal deactivators,
Halogen scavenger, lubricant (olefin, fatty acid and its derivative), crystallization nucleating agent (metal salt, talc, sorbitol, etc.), filler (talc, calcium carbonate, barium sulfate, glass fiber, mica, etc.), blooming prevention Agents, anti-blocking agents, anti-fog agents, adhesives, colorants, matting agents, antistatic agents, oxygen and carbon dioxide absorbents,
Examples include gas adsorbents, freshness-retaining agents, enzymes, deodorants, and fragrances.

The polymer composition of the present invention is obtained by blending the raw material components, and then mixing and melt-kneading.
The order of mixing the respective components, the kneading method and the like are not particularly limited.
For example, a kneader, a mixing roll, a tumbler type blender, a V type blender, a Henschel mixer, a ribbon mixer and the like may be used in a conventional manner. The method of melt kneading is also not particularly limited, and for example, it is preferable to use a screw extruder, a heating kneader, a Banbury mixer, a heating mixing roll or the like at a temperature not lower than the melting point of the thermoplastic resin. This melt-kneading can also be performed under an inert gas stream such as nitrogen gas.

The polymer composition of the present invention is suitable for use in various bulk molded articles which require flame retardancy. Examples of such molded articles include various electric appliances (washing machine, refrigerator, tableware dryer, rice cooker, fan, ventilation fan, TV,
Parts and covers for personal computers, stereos, telephones, microwave ovens, heating toilets, irons, etc .; Photothermal equipment (air conditioners, stoves, stoves, fan heaters, water heaters, etc.)
Parts and covers; interior and exterior materials for buildings; parts or interior materials for automobiles, ships, aircraft, and the like.

[0054]

EXAMPLES First, samples of Examples 1 to 5 of polymer compositions in which a flame retardant according to the present invention is dispersed in a polymer and Comparative Examples 1 to 7 of polymer compositions in which a conventional flame retardant is dispersed are prepared. did. Each sample was prepared by blending a polymer and a flame retardant according to the blending ratios shown in Tables 2 and 3, and was heated above the melting temperature of the polymer and melt-mixed.

The obtained polymer composition is compression molded (pressure:
4.9 MPa), 12.7 mm x 3 mm x 127
A strip-shaped test piece of mm was prepared and used as a test piece for a combustion test.

The flame retardancy test was carried out by using the above test piece and UL9
4 Safety standard "Combustion test of plastic materials for parts of equipment" was performed. As a combustion test, a horizontal combustion test 9
4HB (reference standard ASTM-D635) and 20 mm vertical combustion test 94V (reference standard ASTM-D3801) were performed.

In the 94HB test, when the burning velocity in the section of 75 mm does not exceed 40 mm per minute, or when the burning stops before reaching 75 mm, 94H
It was classified into B (indicated as "HB" in the table).

In the 94V test, for all five test pieces, the afterflame time was 10 seconds or less, the sum of the afterflame times of all the test pieces was 50 seconds or less, or each test piece When the sum of the afterflame time after burning and the afterburn time was 30 seconds or less, it was classified as 94V0 (indicated as "V-0" in the table).

[0059]

[Table 2]

[0060]

[Table 3]

As can be seen from Table 2, polystyrene 10
V-0 can be satisfied only by adding 10 parts by weight of adenine to 0 part by weight. On the other hand, Table 3
In the comparative example shown in, the comparative example 6 using the halogen-based flame retardant tetrabromobisphenol A was V-0,
The other compositions were HB grade.

Thus, it can be seen that the nucleic acid-related substance has excellent flame retardancy. Further, the flame retardant of the present invention is a compound of biological origin and does not contribute to exhaustion of petroleum resources, which is one of the environmental problems.

Further, the mechanical properties of the polymer compositions of Examples 1 to 5 were evaluated. Test pieces were prepared by injection-molding pellets of each polymer composition.
Molding standard conditions are mold temperature 60 ℃, injection pressure 80MP
a, injection time 10 seconds (cooling time 40 seconds), injection speed 40
mm / sec, and adjusted appropriately according to the material. Dumbbell and flat test pieces were prepared by injection molding, and tensile test (ASTM-D638) and bending test (ASTM-D) were performed.
790) and Izod impact test (ASTM-D25
6) was performed. The tensile test and the bending test were carried out using Autograph AG-50KEN manufactured by Shimadzu Corporation. The Izod impact test (notched) was performed using an Izod impact tester manufactured by Toyo Seiki Seisakusho.

Table 4 shows the evaluation results of the test pieces of Examples 1 to 5. For comparison, a similar test was conducted on polystyrene containing 20 parts by weight of a conventional halogen-based flame retardant (Comparative Example 8) and high-impact polystyrene containing 20 parts by weight of a halogen-based flame retardant (Comparative Example 9). The results are shown together in Table 4.

[0065]

[Table 4]

As can be seen from the results in Table 4, the mechanical properties of the sample of Example 4 containing 100 parts by weight of adenine are slightly lower than those of Comparative Example 8 containing 20 parts by weight of the conventional flame retardant. However, there is no problem in practical use. As described above, the flame retardant according to the present invention does not significantly deteriorate the mechanical properties of the polymer, and thus can be suitably used for the polymer composition for bulk molded articles.

Further, with respect to Examples 6 to 11 shown in Table 5, test pieces were prepared in the same manner as above, and the results of evaluation of flammability will be described. However, a sample using a thermosetting resin (epoxy resin, phenol resin, unsaturated polyester resin) was mixed with a flame retardant in a prepreg state and then cured by heating to prepare a test piece.

[0068]

[Table 5]

As can be seen from the results shown in Table 6, the samples of all Examples have excellent flame retardancy (V-0).

In particular, since the polymers of Examples 9 to 11 are of plant origin and are biodegradable, the entire polymer composition is composed of all biogenic materials. It is an environmentally friendly material that does not contribute to long-term global warming even when incinerated.

As can be seen from the above examples, the nucleic acid-related substance and the nucleic acid-related substance derivative exhibit excellent flame retardancy due to the action of the nitrogen-containing heterocycle contained in the molecule, and the mechanical properties of the polymer Since the degree of reduction is low, it is suitable for use in bulk molded articles. This effect is not limited to the nucleic acid-related substances and the like of which specific examples are shown in Examples, but can be obtained with other nucleic acid-related substances such as thymine, adenylic acid and hypoxanthine.

Next, the polymer compositions (copolymers) of Examples 12 to 18 in which the flame retardant according to the present invention is introduced into the polymer chain will be described.

[0073]

[Table 6]

The polymer compositions (copolymers) of Examples 12 to 18 were obtained by reacting the copolymerization components shown in Table 6 in equimolar amounts. Each specific copolymerization condition will be described below.

Example 12: 5.35 g of adenine and 3.2 g of sodium hydroxide were added to 100 ml of water to give a solution 1
To get Further, 6.27 g of succinic acid chloride is dissolved in 100 ml of chloroform to obtain a solution 2. Solution 1
While stirring vigorously, add Solution 2 at once through a dropping funnel. Immediately thereafter, fine powdery polymer was deposited. This was filtered, washed well with water, then well washed with methanol, and dried under reduced pressure at 60 ° C. to obtain Example 1.
Two samples were obtained.

Infrared absorption of this was confirmed by the KBr tablet method, and absorption by an amide bond could be confirmed. Moreover, when TG-DSC of this sample was measured, the weight loss at 500 ° C. was 25% or less.
It was found that this polymer is a polymer composition having excellent heat resistance and flame retardancy.

Example 13: 26.7 g of adenosine and 25.0 g of diphenylmethane diisocyanate (MDI) were heated to 60 ° C. and continuously stirred, and the polymer of Example 13 was produced.

Example 14: 205.7 g of adenosine and 53.1 g of succinic acid were placed in a three-necked flask equipped with a rectification column, the reaction mixture was well agitated, and the produced water was distilled by keeping the temperature at 200 ° C. remove. This state is maintained (about 1 hour) until most of the water is removed and the reaction is almost completed (that is, the reaction mixture becomes clear). Thus, the polymer composition of Example 14 was obtained.

Example 15: A bisphenol type epoxy and guanine were mixed in a powder state, and then charged into a mold and compressed to a temperature above the softening temperature of Epokin (for example, 2).
By heating to (00 ° C) and holding for 30 minutes,
A thermosetting polymer composition of Example 15 was obtained.

Example 16: 26.7 g of adenosine and 16.8 g of hexamethylene diisocyanate (HDI) were heated to 60 ° C. and continued to be stirred to produce a polymer composition of Example 16.

Example 17: 85.47 g of cytosine and 53.1 g of succinic acid were placed in a three-necked flask equipped with a rectification column, the reaction mixture was well stirred, and the water produced was distilled by keeping the temperature at 200 ° C. remove. This state is maintained (about 1 hour) until most of the water is removed and the reaction is almost completed (that is, the reaction mixture becomes clear). Thus, the polymer composition of Example 17 was obtained.

Example 18: 5.67 g of adipic acid chloride and 8.34 g of inosine were placed in a polymerization reaction tube equipped with a capillary for introducing nitrogen while flowing nitrogen. 10
After minutes, the reaction mixture is heated to 190 ° C. When this state was maintained for about 1 hour, the polymer composition of Example 18 was obtained.

As a result of conducting a combustion test on the polymer compositions (copolymers) of Examples 12 to 18 by the same method as described above, as shown in Table 6, it has a flame retardancy of HB or higher. I found out that The polymer compositions of Examples 12 to 18 are all biodegradable polymer compositions, and are materials friendly to the global environment. In particular, since succinic acid can be synthesized from glucose by bioprocess, Example 1
The polymer compositions of 2, 14 and 17 are all composed of materials of biological origin, and are further materials friendly to the global environment.

[0084]

EFFECTS OF THE INVENTION According to the present invention, there are provided a flame retardant having low toxicity and not contributing to resource depletion and global warming, and a polymer composition using the same.

The polymer composition of the present invention can be molded by transfer molding, compression molding, injection molding or the like.

Further, since the polymer composition of the present invention has excellent mechanical properties, it can be used for household articles such as furniture and sundries, construction materials, civil engineering materials, bodies and parts of transportation equipment, housing equipment, electric equipment, and decorative boards. , Can be used in various fields such as ornaments.

Continued front page    F term (reference) 4J002 BB121 BC031 BN151 CC001                       CC021 CD001 CF001 CF031                       CF181 CF191 CK021 CL001                       CN011 CQ012 FD070 FD132                       GL00 GN00 GQ00

Claims (15)

[Claims] 1. A polymer composition containing a polymer and a flame retardant, wherein the flame retardant is at least one nucleic acid-related substance selected from the group consisting of nucleobases, nucleosides, nucleotides, and polynucleotides. And / or (a) nucleobase sulfates, nitrates, borates, hydrochlorides and isocyanurates, (b) metal salts of nucleotides, and (c) nucleobases, nucleosides, bound to nitrogen atoms of nucleotides. A compound containing at least one nucleic acid-related substance derivative selected from the group consisting of compounds in which the hydrogen atom is substituted with an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group, or a mercapto group. Molecular composition. 2. The thermal decomposition temperature of the at least one nucleic acid-related substance and / or the at least one nucleic acid-related substance derivative is higher than 100 ° C. and lower than the thermal decomposition temperature of the polymer. 1. The polymer composition according to 1. 3. The high temperature according to claim 1, wherein the thermal decomposition temperature of the at least one nucleic acid-related substance and / or the at least one nucleic acid-related substance derivative is in the range of more than 300 ° C. and less than 550 ° C. Molecular composition. 4. 5 parts by weight or more and 150 parts by weight or more of the at least one nucleic acid-related substance and / or the at least one nucleic acid-related substance derivative, relative to 100 parts by weight of the polymer.
The polymer composition according to any one of claims 1 to 3, which is contained in a ratio of not more than parts by weight. 5. The at least one nucleic acid-related substance,
The polymer composition according to any one of claims 1 to 4, comprising at least one compound selected from the group consisting of adenine, guanine, cytosine, uracil, and thymine. 6. The at least one nucleic acid-related substance,
6. At least one monomer selected from the group consisting of nucleobases, nucleosides, and nucleotides, said at least one monomer being polymerized with another polymerizable component. The polymer composition according to any one of 1. 7. The polymer composition according to claim 6, wherein the other polymerizable component is a monomer, and the at least one monomer is copolymerized with the other polymerization component. 8. The polymer composition according to claim 7, wherein the other polymerizable component is at least one monomer selected from the group consisting of dibasic acids, dibasic acid anhydrides and diisocyanates. object. 9. The polymer composition according to claim 1, wherein the polymer comprises a biodegradable polymer. 10. The polymer composition according to claim 1, wherein the polymer is a polymer produced from a raw material of plant origin. 11. The polymer composition according to claim 8, wherein the polymer is a polylactic acid-based polymer. 12. The polymer composition according to claim 1, which has thermoplasticity and can be injection-molded. 13. A molded article made of the polymer composition according to claim 1. 14. A housing for an electric device, comprising the polymer composition according to claim 1. 15. At least one nucleic acid-related substance selected from the group consisting of nucleobases, nucleosides, nucleotides, and polynucleotides, and / or
(A) Sulfate, nitrate, borate, hydrochloride and isocyanurate of nucleobase, (b) metal salt of nucleotide, and (c) nucleobase, nucleoside, hydrogen atom bonded to nitrogen atom of nucleotide to carbon atom. A flame retardant for a polymer composition containing at least one derivative of a nucleic acid-related substance selected from the group consisting of compounds substituted with an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group, or a mercapto group. As a method to use.