JP2000230121A - Flame-retardant antimicrobial resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having excellent flame retardance and antimicrobial properties with excellent durability free from drip in combustion, useful as a film, or the like, by using a thermoplastic resin containing phosphorus in the molecule. SOLUTION: This composition is obtained by mixing (A) 100 pts.wt. of a thermoplastic resin containing phosphorus in the molecule with (B) 1-100 pts.wt. of a salt composed of a triazine compound and cyanuric acid or isocyanuric acid, (C) 0-1,000 pts.wt. of a thermoplastic resin and (D) 0.05-10 pts.wt., based on 100 pts.wt. of the total of the component A and the component C, of one or more phosphorous acid ester compounds of the formula [R1 is a 4-12C branched alkyl, a cycloalkyl, or the like; R2 is H or a 1-12C alkyl; R3 is H, a 1-12C alkyl, a cycloalkyl, or the like; R4 and R5 are each a 1-8C alkyl, a (substituted) 1-4C alkyl, or the like] and heating and melting the mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant antibacterial resin composition using a non-halogen flame retardant and having antibacterial properties. More specifically, it relates to a flame-retardant antibacterial resin composition having high flame retardancy and high durability antibacterial property.

[0002]

2. Description of the Related Art Thermoplastic resins represented by polyesters, polyamides, polycarbonates, polyphenylene oxides and the like represented by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, etc.
Utilizing its excellent properties, it is used in various fields. However, since these thermoplastic resins and molded articles made of them are inherently flammable, flame retardancy is often required for applications that require flame safety.

As a method for imparting flame retardancy to fibers made of these thermoplastic resins, it is common to add a halogen-based organic compound as a flame retardant and an ammonia compound as a flame retardant auxiliary to the resin. However, this method has problems such as a large amount of smoke generated during combustion.

[0004] In order to overcome the disadvantages of these halogen-based flame retardants, it has become desirable to use a flame retardant containing no halogen.

[0005] Hitherto, as a method for imparting flame retardancy to fibers without using a halogen-based flame retardant, copolymerization of a phosphorus compound or addition of a phosphorus compound is known. For example, JP-A-48-90348 and JP-A-48-91147 disclose flame-retarding techniques by adding aromatic phosphates and aromatic phosphate oligomers. Further, EP-A-491986 discloses a method of adding a resorcinol-type aromatic phosphate oligomer as a method of making a polybutylene terephthalate-based alloy flame-retardant, and JP-A-05-70671 discloses a method of adding resorcinol to polyalkylene terephthalate. Japanese Patent Application Publication No. 6-504563 discloses a method of adding a type aromatic bisphosphate, melamine cyanurate and an inorganic filler to a mixture of polybutylene terephthalate and polycarbonate or a mixture of polybutylene terephthalate and polyetherimide. A method is disclosed for adding a type aromatic bisphosphate.

As the copolymerization of a phosphorus compound, copolymerization of a phosphonic acid unit or a phosphinic acid unit into a polyester (JP-A-51-54691, JP-A-50-54691).
-56488, JP-A-63-168452).

On the other hand, as a method for imparting antibacterial properties, various antibacterial agents have been used, and various treatments for combining antibacterial agents have been used. For example, a method in which metal or metal compound fine particles exhibiting antibacterial properties are brought into contact with an organic polymer material as a dispersion to coat and adhere to the surface of the organic polymer (Japanese Patent Application Laid-Open No. 7-97769). (JP-A-7-310284, JP-A-10-110388, etc.) and a method of kneading an inorganic metal-based material such as a silver zeolite (Japanese Patent Laid-Open No. 5-2).
72008, JP-B-63-54013, etc.), a method of adding fine metal powder such as copper and zinc (Japanese Patent Laid-Open No. 55-130371), and a method of kneading an organic antibacterial agent with quaternary ammonium. Salt-based compounds (JP-A-6
JP-A-2-69883), a crude drug-type antibacterial agent as a natural compound (JP-A-7-216731 and the like), and a method of mixing a halogen-based phenol compound (JP-A-60-2).
No. 52713) has been proposed.

[0008]

Applications requiring flame retardancy generally require not only excellent flame retardancy but also mechanical properties and thermal stability. However, when a thermoplastic resin blended with a resorcinol-type aromatic bisphosphate or a resorcinol-type aromatic phosphate oligomer, which is a conventional technique, is formed into a molded product, the flame retardancy is insufficient, and further, these phosphorus compounds are present on the fiber surface. There was a problem of bleeding out.

Further, the flame-retarding technique by copolymerization of a phosphorus compound cannot impart sufficient flame retardancy because the melt of the resin composition drops (drips) during combustion.
Furthermore, the thermal stability, heat resistance, and mechanical properties of phosphorus copolymers deteriorate, so that a copolymer of these phosphorus compounds could not be directly applied to a molded article.

On the other hand, applications requiring antimicrobial properties generally require durability. However, the conventional method of contacting an organic polymer material with a metal or metal compound fine particles exhibiting antibacterial properties as a dispersion and coating and attaching the organic polymer surface is because the antibacterial metal only adheres to the surface. , And poor durability.

Further, a method of forming a cross-linked structure of an antibacterial agent with a melamine resin to coat the surface is easy, but is not preferable because of poor durability.

A method of kneading an inorganic metal material such as a silver zeolite material and a method of adding a fine metal powder such as copper or zinc include zeolite and metal powder having inorganic silver, copper and zinc ions. The loading amount is limited, and a large amount is not preferable because the physical properties of the composition are deteriorated. Further, if the surface is coated to prevent agglomeration, there is a problem that the antibacterial property is lowered, and this is not preferable. In addition, there is a problem that coloring occurs due to elution of metal ions.

On the other hand, the method of kneading an organic antibacterial agent has a problem that heat stability is poor and versatility is poor. Conventional methods for imparting flame retardancy and antibacterial properties have had many problems, for example, the method of mixing a halogen-based phenol compound cannot use a general-purpose thermoplastic resin because halogenated phenols are contained in paraffin.

Therefore, the present invention uses a thermoplastic resin containing phosphorus in its molecule, has excellent flame retardancy with no drip during burning, and has excellent antibacterial properties with excellent durability. An object is to obtain an antibacterial resin composition.

[0015]

Means for Solving the Problems In view of the above situation, the present inventors have conducted intensive studies and as a result, have found that a thermoplastic resin containing phosphorus in a molecule of a thermoplastic resin, a triazine compound and cyanuric acid or isocyanate. By compounding a salt with nouric acid and further adding a phosphite compound that shows almost no antibacterial property by itself, by heating and melting,
The present inventors have found that a molded product having extremely short burning time, high drip resistance during combustion, high anti-flammability, and excellent durability and antibacterial properties can be obtained, and arrived at the present invention.

That is, the present invention provides: (A) 1 to 100 parts by weight of a salt comprising a triazine-based compound and cyanuric acid or isocyanuric acid, and (C) 0 to 100 parts by weight of a thermoplastic resin containing phosphorus in the molecule. 1000 parts by weight (D) 0.05 to 10 parts by weight when at least one of the phosphite compounds represented by the following general formula (1) is 100 parts by weight as the total amount of (A) and (C) A flame-retardant antibacterial resin composition obtained by heating and melting after containing.

Embedded image (In the above formula, R ¹ represents a branched alkyl group having 4 to 12 carbon atoms, a cycloalkyl group or an arylalkyl group, and R ² represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group or R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an arylalkyl group or —R
⁶ COOR ⁷ represents, R ⁶ represents an alkylene group having 1 to 6 carbon atoms, R ⁷ represents an alkyl group or an aryl group having 1 to 18 carbon atoms, and R ⁴ and R ⁵ each independently represent a carbon atom. An alkyl group having 1 to 8 atoms, an alkyl group having 1 to 4 carbon atoms substituted with a hydroxy group, or a group having the following structure (2) in which R ⁴ and R ⁵ are combined. )

Embedded image (In the above formula, R ¹ , R ² and R ³ are the same as in the general formula (1).) 2. The flame-retardant antibacterial resin composition according to the above 1, wherein the phosphite compound of the general formula (1) is the following compound (α).

Embedded image 3. 2. The flame-retardant antibacterial resin composition according to the above item 1, wherein the phosphite compound of the general formula (1) is the following compound (β).

Embedded image 4. (A) wherein the thermoplastic resin containing phosphorus in the molecule is a thermoplastic resin containing a structural unit represented by the following general formula (3) in a polymer main chain or a polymer side chain.
3. The flame-retardant antibacterial resin composition according to 3.

Embedded image (R ⁸ , R ⁹ and R ¹⁰ are monovalent or divalent containing no halogen)
Represents a valent organic residue. ) 5. 4. The flame-retardant antibacterial resin composition according to any one of the above items 1 to 3, wherein the thermoplastic resin containing phosphorus in the molecule is a polyester containing the structural unit represented by the general formula (3) in a main chain or a side chain.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin containing phosphorus in the molecule of the present invention includes a monomer containing phosphorus and another monomer polymerizable with the monomer containing phosphorus. Copolymers that can be produced by copolymerization of,
The resin obtained by such a method is composed of a unit containing phosphorus and other units, and is not particularly limited as long as it is a copolymer showing fluidity when heated, but the structure represented by the following general formula (3) A thermoplastic resin containing a unit in a polymer main chain or a polymer side chain can be preferably used.

Embedded image (R ⁸ , R ⁹ and R ¹⁰ are monovalent or divalent containing no halogen)
Represents a valent organic residue. )

When the structural unit represented by the general formula (3) is contained in the polymer main chain, R ⁸ and R ⁹ represent a polymer skeleton. R ¹⁰ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aralkyl group, an aralkyloxy group, an aryl group, and an aryloxy group. Specific examples thereof include methyl, methoxy, and ethyl. , Ethoxy, propyl, poloxy, pentyl, pentoxy, phenyl, phenoxy, tolyl, toloxy, xylyl, xylyloxy, cumenyl, cumenyloxy, methysyl, methysiloxy, naphthyl, naphthyloxy, indenyl, indenyloxy, anthonyl, anthonyloxy, and the like. Methyl, methoxy, phenyl, phenoxy, tolyl, toloxy, xylyl,
Xylyloxy, cumenyl, cumenyloxy, naphthyl and naphthyloxy are preferred, and methyl, methoxy, phenyl, phenoxy, tolyl, toloxy, xylyl, xylyloxy and the like are particularly preferred.

The structural unit represented by the above general formula (3)
Is contained in the polymer side chain, ⁸Indicates the structural skeleton
You.

R ⁹ and R ¹⁰ represent a monovalent organic residue containing no halogen, for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aralkyl group, an aralkyloxy group. , Aryl group, aryloxy group, and specific examples thereof include methyl, methoxy, ethyl, ethoxy, propyl,
Propoxy, pentyl, pentoxy, phenyl, phenoxy, tolyl, toloxy, xylyl, xylyloxy,
Cumenyl, cumenyloxy, methysyl, methysyloxy, naphthyl, naphthyloxy, indenyl, indenyloxy,
Anthryl, antoniloxy, etc. are mentioned, but methyl, methoxy, phenyl, phenoxy, tolyl, toloxy, xylyl, xyloxy, cumenyl, cumenyloxy, naphthyl and naphthyloxy are preferred, and in particular, methyl, methoxy, phenyl, phenoxy, tolyl, toloxy , Xylyl and xylyloxy are preferred. R ⁹ ,
R ¹⁰ may bond these groups to form a ring.
Specific examples thereof include biphenyl-2,2′-diyl,
Biphenyl-2-oxy-2'-yl, naphthalene-
1,8-diyl, naphthalen-1-oxy-8-yl,
Naphthalene-2,3-diyl, naphthalene-2,3-diyl, naphthalen-2-oxy-3-yl, anthracene-2,3-diyl, anthracene-2-oxy-3-
Il, anthracene-1,9-diyl, anthracene
1-oxy-9-yl, 9,10-dihydro-9,10
-Ethanoanthracene-12,13-diyl, 9,10
-Dihydro-9,10-ethanoanthracene-12-oxy-13-diyl, phenanthrene-4,5-diyl, phenanthrene-4-oxy-5-yl, phenanthrene-1,2-diyl, phenanthrene-1-oxy- 2-yl, phenanthrene-9,10-diyl, phenanthrene-9-oxy-10-yl, biphenylene-
2,3-diyl, biphenylene-2-oxy-3-diyl, naphthacene-2,3-diyl, naphthacene-2-oxy-3-yl, naphthacene-5,6-diyl, naphthacene-5-oxy-6 Yl, naphthacene-4,5-diyl, naphthacene-4-oxy-5-yl, pyrene-
Examples thereof include 2,3-diyl and pyren-2-oxy-3-yl, and biphenyl-2,2′-diyl, biphenyl-2-oxy-2′-yl, naphthalene-1,8-yl.
Diyl, naphthalen-1-oxy-8-yl, naphthalene-2,3-diyl, naphthalene-2,3-diyl, naphthalen-2-oxy-3-yl, anthracene-2,
3-Diyl, anthracene-2-oxy-3-yl and anthracene-1,9-diyl are preferred, and biphenyl-2,2′-diyl is more preferred.

Further, as the thermoplastic resin containing in the molecule phosphorus containing the structural unit represented by the general formula (3) in the polymer main chain or polymer side chain, polyester can be particularly preferably used.

In the present invention, flame retardancy is improved by further blending a salt composed of a triazine compound and cyanuric acid or isocyanuric acid with 100 parts by weight of the thermoplastic resin containing phosphorus in the molecule. Further, the phenomenon that the melt of the resin composition drops (drips) during combustion can be significantly suppressed. That is, it was found that high flame retardancy can be imparted.

The salt of cyanuric acid or isocyanuric acid used in the present invention is an immiscible product of cyanuric acid or isocyanuric acid and a triazine-based compound, and is usually 1: 1 (molar ratio), and sometimes 1: 1. An adduct having a composition of 2 to 2 (molar ratio). Among the triazine compounds,
Those that do not form cyanuric acid or isocyanuric acid are excluded.

Further, the triazine-based compounds include:
It represents a compound represented by the following general formula (4).

[0025]

Embedded image(However, in the above formula, R¹¹, R¹², R¹³, R¹⁴Is the same
Or different hydrogen, alkyl, aralkyl, cyclo
Alkyl group, or -CONH_TwoIt is. Also, R is above
-NR in the above formula¹¹R¹²Or -NR¹³R¹⁴The same group as
Or independently of these, hydrogen, an aryl group, an alkyl group,
Aralkyl group, cycloalkyl group, -NH _Two, Or-
C0NH_TwoIt is a group selected from ) In the general formula (4), R¹¹, R¹², R¹³, R¹⁴Is the same
One or different hydrogens, alkyl groups, aralkyl groups,
Cycloalkyl group, or -CONH_TwoIt is. here
Aryl groups having 6 to 15 carbon atoms, alkyl groups
Has 1 to 10 carbon atoms, and as an aralkyl group,
7 to 16 cycloalkyl groups, 4 to 15
Are preferred. R is -NR in the above formula.¹¹R
¹²Or -NR¹³R¹⁴The same group as or independent of
Hydrogen, aryl group, alkyl group, aralkyl group,
Loalkyl group, -NH_TwoOr -CONH_TwoChosen from
Wherein the aryl group has 6 to 15 carbon atoms
, An alkyl group having 7 to 16 carbon atoms,
As the chloroalkyl group, those having 4 to 15 are preferable.

Specific examples of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ include hydrogen, phenyl, p-toluyl, α-naphthyl, β-naphthyl, methyl, ethyl and n-propyl. Group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hydroxymethyl group, methoxymethyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-pentyl group, Examples thereof include a 4-methyl-1-cyclohexyl group and an amide group, and among them, hydrogen, a phenyl group, a hydroxymethyl group, a methoxymethyl group, a benzyl group, and an amide group are preferable.

Specific examples of R include an amino group,
Amido group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, mono (hydroxymethyl) amino group, di (hydroxymethyl) amino group, mono (methoxymethyl) amino group, di (methoxymethyl)
Amino group, phenylamino group, diphenylamino group, hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β
-Naphthyl group, methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-
Examples thereof include a pentyl group and a 4-methyl-1-cyclohexyl group, and among them, hydrogen, an amino group, a di (hydroxymethyl) amino group, a di (methoxymethyl) amino group, a phenyl group, and a benzyl group are preferable.

Among the salts of the compound represented by the general formula (4) with cyanuric acid or isocyanuric acid, particularly preferred examples include melamine and mono (hydroxymethyl).
Melamine, di (hydroxymethyl) melamine, trihydroxymethyl) melamine, benzoguanamine, acetoguanamine, 2-amide-4,6-diamino-1,3,5
-Salts of triazines, of which melamine, benzogamine and acetogamine salts are particularly preferred.

The salt of the compound represented by the general formula (4) with cyanuric acid or isocyanuric acid is obtained by converting a mixture of the compound represented by the general formula (4) with cyanuric acid or isocyanuric acid into an aqueous slurry. This is a powder obtained by mixing well to form both salts into fine particles, and then filtering and drying this slurry, which is different from a mere mixture. This salt does not need to be completely pure, and may have a somewhat unreacted compound of the formula (4), cyanuric acid,
Isocyanuric acid may remain. The form of the salt is not particularly limited, but it is preferable to use a powder obtained as fine powder as possible from the viewpoint of mechanical strength and surface properties of a molded product obtained from the composition of the present invention. It is particularly preferable that the average particle size before blending with the resin is 1 μm or less. When the dispersibility of the salt is poor,
A dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination.

The amount of the salt used is 1 to 100 parts by weight, preferably 2 to 80 parts by weight, more preferably 3 to 70 parts by weight, based on the thermoplastic resin (A) containing phosphorus in the molecule. If the amount of the salt is less than 1 weight, the effect of improving flame retardancy and the effect of suppressing drip are not recognized,
Exceeding the weight part is not preferred because the mechanical properties and appearance of the surface of the molded article are impaired.

The thermoplastic resin (C) of the present invention is a synthetic resin which exhibits fluidity when heated and can be molded by utilizing this. Specific examples thereof include, for example, non-liquid crystalline polyester such as semi-aromatic polyester or wholly aromatic polyester, polyesters such as semi-aromatic or wholly aromatic liquid crystalline polyester, polyamide, polyamide such as wholly aromatic polyamide, polycarbonate , Polyimide, polybenzimidazole, polyketone, polyetheretherketone, polyetherketone, polyethersulfone, polyphenylene oxide,
Phenoxy resin, polyphenylene sulfide, phenol resin, phenol formaldehyde resin, olefin polymers such as polypropylene and polyethylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene Olefin-based copolymers such as ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene / propylene-g-maleic anhydride copolymer, polyester One type or a mixture of two or more types selected from elastomers such as polyether elastomers and polyester polyester elastomers may be used. Further, as specific examples of the polyester resin, polyethylene terephthalate, polypropylene terephthalate,
Polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate, and polyethylene-1,2
-Bis (phenoxydi) ethane-4,4'-dicarboxylate, etc., as well as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decane dicarboxylate and polycyclohexane dimethylene terephthalate / isophthalate, etc. And the like. Further, among these, polybutylene terephthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, and the like, which are well-balanced in mechanical properties, workability, and the like, can be particularly preferably used.

The amount of the thermoplastic resin (C) used is 0 to 1000 with respect to the thermoplastic resin (A) containing phosphorus in the molecule.
Parts by weight, preferably 0 to 100 parts by weight, more preferably 0 to 50 parts by weight
Parts by weight are preferred.

The resin composition of the present invention further comprises a phosphorus-based flame retardant (E) in addition to a thermoplastic resin containing phosphorus in its molecule, thereby further improving the flame retardancy without lowering the bleed-out characteristics. Can be improved.

The phosphorus-based flame retardant is not particularly limited as long as it is a compound containing phosphorus.

The amount of the phosphorus-based flame retardant (E) to be used is usually 0.1 to the thermoplastic resin (A) containing phosphorus in the molecule.
It is 1 to 100 parts by weight, preferably 0.1 to 80 parts by weight, more preferably 0.1 to 50 parts by weight.

When the resin composition of the present invention is further added with a fluorine-based resin, fluidity and resin orientation at the time of molding the resin composition are improved, and further, drop (drip) of the melt during combustion.
Can be further suppressed. Examples of such a fluororesin include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethene / hexafluoropropylene) copolymer, and (tetrafluoroethylene / Perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, (polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer, etc. Among them, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, and (tetrafluoroethylene / ethylene) copolymer are preferable. Usually 0.1 to 100 with respect to the thermoplastic resin (A) 100 parts by weight of the phosphorus from the physical properties and moldability of the surface in the molecule
Parts by weight, preferably 0.1 to 80 parts by weight, more preferably 0.1 to 50 parts by weight.

The flame retardant used in the present invention has an extremely small effect of promoting the hydrolysis of a thermoplastic resin having a dehydration-condensation type structure such as an ester bond as compared with other known phosphorus-based flame retardants. It has been found that when a hindered phenol-based stabilizer is used in combination, extremely good hydrolysis resistance is maintained even when exposed to a high temperature for a long time. Examples of such a stabilizer include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol-bis [3- (3.5 -Di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di- t-butyl-4-hydroxybenzylphosphonate diethyl ester 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N ' -Trimethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide)
And the like.

In the present invention, such a hindered phenol-based stabilizer can be added as needed, and the amount of the hindered phenol-based stabilizer added at that time is usually such that phosphorus is contained in the molecule. Thermoplastic resin (A) 1
The amount is 0.1 to 100 parts by weight, preferably 0.1 to 80 parts by weight, more preferably 0.1 to 50 parts by weight, per 100 parts by weight.

In the present invention, the antimicrobial property is imparted by heating and melting with the addition of the phosphite compound represented by the general formula (1).

The phosphite compound represented by the general formula (1) is a known compound and has been conventionally used as an antioxidant. The present inventors have conducted intensive studies,
Surprisingly, it has been found that the compound exhibits excellent antibacterial properties when melted and mixed with a thermoplastic resin. The reason why the compound exhibits antibacterial properties is not well understood, but since the compound exhibits an effect of decomposing peroxides, it is considered that this causes some inhibition in bacterial metabolism and the like.

In the general formula (1) representing the phosphite compound, the branched alkyl group having 4 to 12 carbon atoms represented by R ¹ includes, for example, secondary butyl, tertiary butyl, tertiary amyl , Tertiary octyl, isodecyl, isododecyl and the like.

The number of carbon atoms represented by R ² and R ³ is 1 to 1
Examples of the alkyl group 2 include methyl, ethyl, propyl,
Isopropyl, butyl, sec-butyl, tert-butyl, amyl, sec-amyl, tert-amyl, octyl, decyl, dodecyl and the like.

The arylalkyl groups represented by R ¹ , R ² and R ³ include, for example, benzyl, cumyl and the like. Similarly, examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl and the like.

1 to 8 carbon atoms represented by R ⁴ and R ⁵
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, amyl, sec-amyl, tert-amyl, and octyl. Examples of the alkyl groups (1) to (4) include hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl.

Examples of the alkylene group having 1 to 6 carbon atoms represented by R ⁶ include methylene, ethylene, propylene, trimethylene, tetramethylene, isobutylene, pentamethylene, hexamethylene and the like.

Examples of the alkyl group having 1 to 18 carbon atoms represented by R ⁷ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,
Pentyl, tertiary pentyl, hexyl, heptyl, octyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl,
Tridecyl, tetradecyl, hexadecyl, octadecyl and the like can be mentioned.

The phosphite compound in the present invention is a compound represented by the aforementioned general formula (1).
Phosphite of 2,4,6-tri-tert-butylphenol and 2-hydroxymethyl-2-ethylhexanol, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert. Tributyl-4
-Methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite,
Bis [2,6-di-tert-butyl-4- (2-butyloxycarbonylethyl) phenyl] pentaerythritol phosphite; and the bis (2,6-di-tert. Butyl-4-methylphenyl) pentaerythritol diphosphite is preferred in that it has excellent compatibility with the thermoplastic resin and has excellent thermal stability.

When the phosphite compound in the present invention is contained in a thermoplastic resin, the content is 0.05 to 100 parts by weight of the thermoplastic resin (A) + (C).
10 parts by weight, preferably 0.05 to 5 parts by weight,
More preferably, it is 0.05 to 2 parts by weight. If the content is 0.05 parts by weight, antibacterial properties cannot be sufficiently exhibited,
Not preferred. If the content exceeds 10 parts by weight, the phosphite compound bleeds out, impairs the appearance of a molded article made of a thermoplastic resin, and is not preferable in terms of cost.

Further, the resin composition used as the raw material of the flame-retardant antibacterial fiber of the present invention may contain phosphorus-based or sulfur-based antioxidants, heat stabilizers, and ultraviolet absorbers as long as the object of the present invention is not impaired. And additives such as a lubricant, a release agent, and a coloring agent including a dye or a pigment.

By adding a fibrous and / or granular filler to the flame-retardant antibacterial resin composition of the present invention, the strength, rigidity, heat resistance and the like can be greatly improved. In addition, it is possible to further suppress the solution from falling during combustion.

Specific examples of such a filler include glass fibers, carbon fibers, metal fibers, aramid fibers, polybenzobizoxazole fibers, asbestos, potassium titanate whiskers, wollastenite, glass flakes, glass beads, talc, and the like. Mica, clay, calcium carbonate, barium sulfate, titanium oxide, aluminum oxide and the like can be mentioned, and among them, chopped strand type glass fiber is preferably used. The amount of these additives is 5 to 14 with respect to the thermoplastic resin (A) containing phosphorus in the molecule.
The amount is preferably 0 parts by weight, particularly preferably 5 to 100 parts by weight.

The method for producing the flame-retardant antibacterial resin composition of the present invention is not particularly limited. For example, a thermoplastic resin (A) containing phosphorus in a molecule, a triazine compound and an ianuric acid or isocyanuric acid can be used. There is a method in which the salt (B), the phosphite compound (C), the thermoplastic resin (D) and other necessary additives are melt-mixed with an extruder.

Since the flame-retardant antibacterial resin composition of the present invention can be melt-molded, extrusion molding, injection molding, press molding and the like are possible. For example, films, pipes, rods, fibers and any desired ones can be used. It can be formed into a molded product having a shape and size.

[0054]

EXAMPLES The effects of the present invention will be described below with reference to examples. The evaluation in the examples was performed by the following method.

(1) Evaluation of antibacterial activity This was based on the Manual for Quantitative Antibacterial Testing Method for Textile Products established by the Council for Evaluation of New Functions of Textile Products. That is, 0.4 g of a sample of the following test bacteria (1 ± 0.3 × 10 ⁵ cells / ml) is uniformly inoculated into a sterilized 1/20 concentration nutrient broth and cultured at 37 ° C. for 18 hours. After completion of the culture, the test bacteria were washed out, and a pour plate agar medium was prepared using the solution.
The cells are cultured at 7 ° C for 24-48 hours, and the number of viable cells is measured. In addition,
As for the unprocessed product, the test bacteria are washed out immediately after inoculation, and the solution is used to prepare a pour plate agar medium at 37 ° C. for 24 to 48 hours.
After culturing for a period of time, the number of inoculated viable bacteria is measured. The antibacterial activity is evaluated by a bacteriostatic activity value according to the following formula. The higher the bacteriostatic activity value is, the better the antibacterial property is, but the bacteriostatic activity value ≥ 2.2 means that the substance has antibacterial property. In addition, Staphylococcus (Staphylococcus) was used as a test bacterium.
us Aureus ATCC 6538P) was used. Bacteriostatic activity value = Log (B)-Log (C) However, test establishment conditions: Log (B)-Log (A)>
1.5 must be satisfied. A: Average value of the number of bacteria collected immediately after inoculation of the raw product B: Average value of the number of bacteria collected and cultured for 18 hours of the raw product C: Average value of the number of bacteria collected and cultured for 18 hours of the processed product

(2) LOI Value (Limit Oxygen Concentration Index) A 150 mm × 6 mm × 1 mm strip-shaped test piece was prepared from the pellet, and the LOI value was measured according to ASTM D-2863. The higher the LOI value, the higher the flame retardancy.

(3) Flame Retardancy Strip-shaped test pieces of 127 mm × 12.7 mm × 0.8 mm were prepared from the pellets, and the flame retardancy was evaluated according to the evaluation standard defined in UL94.

The flame retardancy level is V-0>V-1>V-2>
HB

In addition to the flame-retardant level specified in UL94, the total burning time of five flame-retardant evaluations in UL94 measurement was measured and used as an index of flame retardancy. In addition, when the combustion did not stop and continued to burn, the fire was not extinguished.

The non-dripping (non-drip) property of the polymer during combustion was measured by the following index. UL94
The number of samples that did not drip in the five measurements specified in the above was used as a non-drip (non-drip) parameter.
A value close to 5 indicates that dripping during combustion is suppressed (non-drip property is high), that is, it has high flame retardancy.

(4) Evaluation of Bleed-out of Flame Retardant and Antibacterial Agent The surface condition of the sample after injection molding was observed by SEM, and qualitatively evaluated in three steps.

Reference Example 1 Method for producing a thermoplastic resin containing phosphorus in a molecule Dimethyl terephthalate and butanediol or ethylene glycol were used as catalysts with antimony trioxide as a catalyst.
The mixture was heated at 20 ° C. under a nitrogen atmosphere to perform transesterification.
Then, a phosphorus-containing dicarboxylic acid derivative, a phosphorus-containing diol derivative, and a phosphorus-containing hydroxycarboxylic acid derivative are shown in Table 1.
, A predetermined amount was added, and the temperature was gradually raised to 220 ° C to 265 ° C, and the degree of pressure reduction was also gradually increased.
The pressure was reduced to 5 mmHg, and an esterification reaction and a polycondensation reaction were performed to produce a phosphorus-containing polyalkylene terephthalate. The copolymerization amount in the polymer was calculated by conversion from the phosphorus content measured from fluorescent X-rays. The production results of a series of phosphorus-containing polyalkylene terephthalate copolymers are shown.

[0063]

[Table 1]

The abbreviations and structures of the non-halogen flame retardants (D) used in Examples and Comparative Examples are shown below.

[0065]

Embedded image

The average particle size of each of the cyanuric acid salts used in this example was smaller than 1 μm.

Examples 1 to 8, Comparative Examples 1 to 5 The thermoplastic resins containing phosphorus in the molecule prepared in Reference Example 1 (A-1, B-2, B-3, B-4, B-5) )
(A), a salt of cyanuric acid or isocyanuric acid (B), a polybutylene terephthalate as a thermoplastic resin (C), or a mixture of polybutylene terephthalate and a phenoxy resin, or a mixture of polybutylene terephthalate, a phenoxy resin, and polyphenylene sulfide ( D) As the phosphite compound, 30 ° C.
(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (hereinafter abbreviated as BMPP) or bis (2,6-di-tert-butyl) Phenyl) pentaerythritol diphosphite (hereinafter abbreviated as BHPP), a phosphorus-based flame retardant (E) and other additives were mixed, and a resin temperature of 27 was obtained using a 30 mmφ biaxial screw.
Melt extruded at 0 ° C.

After the obtained pellets were dried, a tensile test piece specified in ASTM D-638 was prepared by injection molding. Further, a sample for LOI value measurement and a sample for flame retardancy evaluation based on UL94 were prepared by press molding. Table 2 shows the formulation and results.

[0069]

[Table 2]

Examples 1 and 2 show that the combined use of a phosphorus-containing thermoplastic resin and melamine cyanurate shortens the burning time and specifically increases the number of non-drips during burning. Further, in Examples 5 and 7 in which a phosphorus-based flame retardant was added, the burning time was further shortened and the non-drip property was improved. Further, the bleed out of the phosphorus-based flame retardant can be controlled by the combined use of the phosphorus-containing thermoplastic resin-based compound.

Further, in the antibacterial properties, it can be seen that increasing the amount of the phosphite compound increases the bacteriostatic activity value, that is, the so-called antibacterial property increases.

On the other hand, as in Comparative Example 1, PBT alone
It can be seen that the flame retardancy was not obtained, and that the PBT copolymerized with phosphorus alone had a flame retardancy of V-2, a long burning time of 200 seconds, and further dripped during burning. When a phosphorus-based flame retardant and melamine cyanurate are added to PBT as in Comparative Examples 3 and 5, the flame retardancy is V-0,
Drip occurs during combustion, and the added phosphorus-based flame retardant bleeds out.

In the evaluation of antibacterial properties, when no phosphite compound was added as in Comparative Examples 1 and 3 or when the amount was less than the range of the present invention, the level of antibacterial properties was not reached. Further, when the phosphite is added in an amount exceeding the range of the present invention as in Comparative Example 5, the phosphite bleeds out to the product surface, which is not preferable.

[0074]

According to the present invention, the thermoplastic resin (A) containing the phosphorus of the present invention in the molecule, the salt of a triazine compound and cyanuric acid or isocyanuric acid (B), and (D) The combined use of an acid ester compound has higher flame retardancy than conventionally known phosphorus-based flame retardants, and also exhibits high durability and antibacterial properties.

 ──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Kenji Yoshino 2-1-1 Katata, Otsu-shi, Shiga F-term in Toyobo Co., Ltd. General Research Laboratory 4J002 AA01X BB00X BB03X BB05X BB06X BB07X BB10X BB12X BB15X BB21X CC03X CF00 CF03X CF04X CF05X CF06X CF07X CF08X CF15W CF16X CG00X CH00X CH07X CH08X CH09X CJ00X CL00X CM04X CN01X CN03X CQ01W EU186 EW087 FD136 FD137 FD187 GK00

Claims (5)

[Claims] 1. A salt (B) comprising a triazine compound and cyanuric acid or isocyanuric acid per 100 parts by weight of (A) a thermoplastic resin containing phosphorus in a molecule.
00 parts by weight, (C) 0 to 1000 parts by weight of the thermoplastic resin (D), and one or more of the phosphite compounds represented by the following general formula (1) in a total amount of 100 parts by weight of (A) and (C). A flame-retardant antibacterial resin composition characterized by being obtained by adding 0.05 to 10 parts by weight and then heating and melting the composition. Embedded image (In the above formula, R ¹ represents a branched alkyl group having 4 to 12 carbon atoms, a cycloalkyl group or an arylalkyl group, and R ² represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group or R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an arylalkyl group or —R
⁶ COOR ⁷ represents, R ⁶ represents an alkylene group having 1 to 6 carbon atoms, R ⁷ represents an alkyl group or an aryl group having 1 to 18 carbon atoms, and R ⁴ and R ⁵ each independently represent a carbon atom. An alkyl group having 1 to 8 atoms, an alkyl group having 1 to 4 carbon atoms substituted with a hydroxy group, or a group having the following structure (2) in which R ⁴ and R ⁵ are combined. ) (In the above formula, R ¹ , R ² and R ³ are the same as in the general formula (1).) 2. The flame-retardant antibacterial resin composition according to claim 1, wherein the phosphite compound of the general formula (1) is the following compound (α). Embedded image 3. The antibacterial resin composition according to claim 1, wherein the phosphite compound of the general formula (1) is the following compound (β). Embedded image 4. The thermoplastic resin (A) containing a phosphorus unit in a molecule, wherein the thermoplastic unit contains a structural unit represented by the following general formula (3) in a polymer main chain or a polymer side chain. 4. The flame-retardant antibacterial resin composition according to any one of claims 1 to 3. Embedded image (R ⁸ , R ⁹ and R ¹⁰ are monovalent or divalent containing no halogen)
Represents a valent organic residue. ) 5. The flame retardant according to claim 1, wherein the thermoplastic resin containing phosphorus in the molecule is a polyester containing the structural unit represented by the general formula (3) in a main chain or a side chain. Antibacterial resin composition.