JP2002155210A - Flame-retardant resin composition and flame-retardant laminate obtained by applying or laminating the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-halogen type flame retardant, excellent smoke suppression effect, good adhesion to a substrate, good water resistance, and excellent non-halogen flame retardant dispersibility. The present invention provides a flame-retardant resin composition and a flame-retardant laminate obtained by applying or laminating the same, and furthermore, a flame-retardant resin composition which is suitable mainly for molding material labels and lamination to molded articles. And a flame-retardant laminate obtained by applying or laminating the same. SOLUTION: The flame-retardant resin composition contains a halogen-free flame retardant (X) having a cyclic structural unit containing a nitrogen atom and an organic resin (Y).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition used as a flame-retardant paint, adhesive, coating agent or binder, and more particularly to a flame-retardant film for labels, decorative films and retroreflective films. The present invention relates to a flame-retardant resin composition used as a coating agent. Further, the present invention relates to a laminate in which the flame-retardant resin composition is laminated.

[0002]

2. Description of the Related Art Flame retardants for flame-retardant laminates have conventionally been halogen-based flame retardants (eg, decabromodiphenyl ether, hexabromodiphenyl ether, etc.) and inorganic flame retardants such as silica, clay, antimony compounds and the like. Fillers and the like were added. However, the flame-retardant adhesive film containing the halogen-based flame retardant has a problem that a large amount of smoke is generated during combustion. Smoke generation increases personal injury in the event of a fire, and material safety has become an important technology along with flame retardant technology.

[0003] In consideration of recent environmental protection, non-halogen flame retardants have been used as flame retardants instead of halogen flame retardants. For example, a method using a phosphoric acid ester or melamine cyanurate has been proposed as a method of flame retardation using a non-halogen flame retardant. (JP-A-3-281652, JP-A-5-70671, JP-A-6-157880, JP-A-7-304959).
These methods still have insufficient flame retardancy. Also,
Inorganic flame retardants represented by magnesium hydroxide are materials excellent in low smoke generating effect, but they are not always satisfactory in terms of flame retardant effect.

[0004] JP-A-9-208812, JP-A-20
JP-A-00-109969, JP-A-2000-05383
Ammonium polyphosphate and the like described in Japanese Patent Publication No. 6 and the like are materials which are thermally decomposable, generate little smoke, and have good flame retardancy, but have poor water resistance and dispersibility and are not satisfactory.

[0005] Further, ammonium polyphosphate and the like described in Japanese Patent Application Laid-Open No. 2000-053836 are materials which are thermally decomposable, generate little smoke, and have good flame retardancy. Monomer 5 with polar group
It is improved by dispersing in a resin containing an ethylene-based copolymer containing up to 30% by weight as a main component, but the adhesion to the substrate film is not satisfactory.

[0006]

DISCLOSURE OF THE INVENTION The present invention is excellent in non-halogen type flame retardancy, excellent smoke suppressing effect, good adhesion to base material, good water resistance, and excellent dispersibility of non-halogen flame retardant. The present invention provides a flame-retardant resin composition and a flame-retardant laminate obtained by applying or laminating the same, and further,
An object of the present invention is to provide a flame-retardant resin composition and a flame-retardant laminate obtained by applying or laminating the same, which is suitable mainly for laminating on a molding material label or a molded article.

[0007]

Means for Solving the Problems The present inventors have intensively studied to solve the above-mentioned problems, and have excellent flame retardancy and smoke suppressing effect, good adhesion to a substrate, and a non-halogen type. Various experiments and studies were conducted to provide a flame-retardant resin composition having excellent dispersibility of a flame retardant, and as a result, the present invention was completed.

That is, the present invention provides a non-halogen flame retardant (X) having a cyclic structural unit containing a nitrogen atom and an organic resin (Y).
It is a flame-retardant resin composition characterized by containing.
Furthermore, the non-halogen flame retardant (X) having a cyclic structural unit containing a nitrogen atom contains at least one structural unit represented by the following formula (1) or (2). It is a flame retardant tree.

[0009]

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[0010] The non-halogen flame retardant (X) having a cyclic structural unit containing a nitrogen atom in the molecule may further contain a phosphorus atom.

A non-halogen flame retardant having a structural unit represented by the formula 1 in the molecule is nitrilotris (alkylene)
Phosphonate (formula 3 below) and / or 1-hydroxyalkylidene-1,1′-diphosphonate (formula 4 below)
At least one of them. The nitrilotris (alkylene) phosphonate used in the resin composition of the present invention is a compound represented by the following formula 3, wherein R1 is an alkylene group having 5 or less carbon atoms, and further an alkylene group having 3 or less carbon atoms. Preferably, the alkylene group may have a substituent. M represents at least one of melamine, melam and melem, and is preferably melamine.

[0012]

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The melamine 1-hydroxyalkylidene-1,1'-diphosphonate used in the resin composition of the present invention is a compound represented by the following formula 4, wherein R2 has 3 or less carbon atoms, An alkyl group or a hydroxy group of the number 1 or less is preferable, and the alkyl group may have a substituent. M represents at least one of melamine, melam and melem, and is preferably melamine.

[0014]

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[0015] Further, there is provided a flame-retardant laminate obtained by laminating any of the above-mentioned flame-retardant resin compositions on a substrate.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The nitrogen-containing cyclic structural unit of the non-halogen flame retardant (X) having a nitrogen-containing cyclic structural unit used in the present invention includes a melamine ring, a melem ring, a guanamine ring and a benzoguanamine ring. Guanine ring, triazole ring, tetrazole ring and the like. Among these, the non-halogen flame retardant (X) having a cyclic structural unit containing a nitrogen atom is preferably a structural unit represented by Formula 1 or Formula 2. Examples of the non-halogen flame retardant containing at least one structural unit represented by Formula 1 or 2 in the molecule include melamine derivatives such as melamine cyanurate and melamine, and melamine such as melamine phosphate (formula 5) Salts, melamine double salts such as melamine polyphosphate double salt (formula 6), melam salts such as melam polyphosphate double salt (formula 7), and melem polyphosphate double salt (formula 8)
And the like, a nitrile tris (methylene) phosphonic acid melamine salt (formula 9 below), a 1-hydroxyethylidene-1,1′-diphosphonic acid melamine salt (formula 1 below)
Melamine salts of phosphonic acid such as 0) are mentioned as preferred examples.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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Of these, non-halogen flame retardants containing phosphorus are preferred from the viewpoint of flame retardancy.
Those having a polyphosphate or phosphonate structure are preferred. Specifically, melamine nitrilotris (methylene) phosphonate (the following formula 3), 1-hydroxyethylidene-1,1′-diphosphonic melamine salt (the following formula 4)
And melamine phosphate (formula 5), melamine polyphosphate double salt (formula 6), melam polyphosphate double salt (formula 7), and melem polyphosphate double salt (formula 8) are also preferable.

By using these, a flame-retardant resin composition excellent in flame retardancy, smoke-suppressing effect, adhesion to a substrate film and the like, which has been difficult to obtain in the past, and difficulties in coating or laminating the same. A flammable laminate is obtained.

The halogen-free flame retardant (X) is dispersed in 20 to 300 parts by weight, preferably 20 to 200 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the organic resin (Y). By applying or laminating this, it is excellent in flame retardancy, smoke suppression effect, water resistance,
Furthermore, excellent adhesion to the substrate film can be obtained.
If the amount of the halogen-free flame retardant (X) used is 20 parts or less, the flame retardancy tends to decrease. When the amount of the non-halogen flame retardant (X) used is 300 parts or more, the adhesion to the base film tends to decrease.

The flame-retardant resin composition of the present invention and the flame-retardant laminate obtained by applying or laminating the same may further contain a general non-halogen flame retardant. For example, as a non-halogen flame retardant containing phosphorus, tricresyl phosphate, triphenyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol bisdiphenyl phosphate, 2-ethylhexyl diphenyl phosphate, diphenyloctyl phosphate Phosphate compounds such as phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triallyl phosphate, dimethylethyl phosphate, methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid Phosphate, stearyl acid phos Acid compounds such as phosphates, 2-ethylhexyl acid phosphate and isodecyl acid phosphate; condensed phosphate compounds such as phenylene bisphenylglycidyl phosphate; polyphosphate compounds; phosphorus alone such as red phosphorus; and nitrogen compounds. And guanidine derivatives such as guanidine, guanidine phosphate, guanidine sulfamate, guanyl urea phosphate, and guanyl urea sulfate; boric acid; and ammonium borate.

The flame-retardant resin composition and the flame-retardant laminate obtained by coating or laminating the resin composition include general flame-retardant auxiliaries such as manganese borate, zinc borate, lead borate, aluminum hydroxide, and water. Magnesium oxide or the like can be added.

The base material to which the resin composition of the present invention is applied includes metals such as aluminum, stainless steel, galvanized steel, tinplate, steel plate, inorganic materials such as concrete, mortar, slate, glass, paper, wood, woven fabric, and the like. Non-woven fabric, molded resin, resin sheet, resin film, etc., but are not particularly limited, resin film, resin sheet, resin injection,
It is preferably formed by extrusion or the like. It is preferable that the flame-retardant resin composition of the present invention is laminated on these substrates to give flame retardancy.

Examples of the base film include polyester films such as polyethylene terephthalate film and polyethylene naphthalate film, polycarbonate films, polyimide films, polyphenylene sulfide films, polypropylene films, polyolefin films such as polyethylene films and polypropylene films, and polyamide films. And the like, preferably a polyethylene terephthalate film, a polyethylene naphthalate film, a polyimide film, a polyphenylene sulfide film, a propylene oxide film, and a polyamide film improve the adhesion between the base film and the flame-retardant adhesive layer. There is a tendency. Further, the flame retardant resin composition of the present invention can provide very excellent flame retardancy even when used for an inexpensive polyester film, although the base film itself has poor flame retardancy.

The thickness of these films can be appropriately selected according to the purpose of use.
Can be several hundred μm

Examples of the material of the base material include polyester such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and polyethylene terephthalate, ABS resin, nylon, polyacetal, methacrylic resin, polycarbonate, phenolic resin, amino Resins. Among them, polycarbonate is preferred from the viewpoint of flame retardancy, but ABS resin, polystyrene and polyester, which are low-cost but low-cost general-purpose resins, are preferred from the viewpoint of cost and hygiene such as environmental hormones. The flame-retardant resin composition of the present invention can provide very good flame retardancy even when applied to these resins having low flame retardancy.

As the organic resin (Y), various thermoplastic resins such as polyester resin, polyurethane resin, epoxy resin, polyamide resin and acrylic resin can be used. Among these, preferably, a polyester resin and / or a modified polyester resin (A) can be used. The reason why the polyester-based resin and / or the modified polyester resin (A) is preferable is that the adhesiveness to the base film and the flexibility tend to be good.

As the polyester resin and / or modified polyester resin (A), acid components include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid and 2,6-naphthalenedicarboxylic acid, succinic acid and glutaric acid. Aliphatic dicarboxylic acids such as aliphatic dicarboxylic acids such as acids, adipic acid, sebacic acid, dodecanedicarboxylic acid and azelaic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Acids. These can be used alone or in combination of two or more. Also,
As long as the content of the invention is not impaired, trimellitic anhydride,
A polyvalent carboxylic acid such as pyromellitic anhydride may be used in combination.

In the acid component of the polyester resin and / or the modified polyester resin (A), the total amount of the aromatic dicarboxylic acid and the alicyclic dicarboxylic acid is preferably at least 60 mol%, more preferably at least 70 mol%. Above, especially 8
It is preferably at least 0 mol%. When the total amount of the aromatic dicarboxylic acid and the alicyclic dicarboxylic acid is 60 mol% or more, high water resistance can be obtained. Further, in the acid component of the polyester resin and / or the modified polyester resin (A), the content of the aromatic dicarboxylic acid is preferably at least 40 mol%, more preferably at least 50 mol%, further preferably at least 60 mol%, particularly preferably at least 60 mol%. It is preferably at least 70 mol%, most preferably at least 80 mol%. When the content is in the above range, the carbon content in the resin can be increased, and higher flame retardancy can be obtained.

The polyester resin used in the present invention and / or
Or a glycol copolymerized with the modified polyester resin (A)
Specifically, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-
Butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-
Examples include pentanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,9-nonanediol, and 1,10-decanediol. Examples of the alicyclic glycol include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 3,8-bisvidroxymethyltricyclodisican, hydrogenated bisphenol A, and hydrogenated bisphenol. F, TCD (tricyclodecane) glycol and the like, and these can be used alone or in combination of two or more.

The glycol component of the polyester resin and / or the modified polyester resin (A) contains 4 carbon atoms.
The above glycol is preferably at least 40 mol%, more preferably at least 50 mol%, further preferably at least 60 mol%, particularly preferably at least 70 mol%, most preferably at least 80 mol%. When the content is in the above range, the ester bonding group concentration can be reduced, and high water resistance can be obtained. In addition, polyester resin and / or
Or in the glycol component of the modified polyester resin (A),
Ethylene glycol, diethylene glycol, 1,4-
The total amount of butanediol is preferably at most 60 mol%, more preferably at most 50 mol%, further preferably at most 40 mol%, particularly preferably at most 30 mol%. When the content is in the above range, the oxygen content in the resin can be reduced, and high flame retardancy can be obtained.

It is also preferable to introduce an ionic group into the organic resin (Y) used in the present invention. By introducing an ionic group, not only can the dispersibility of the halogen-free flame retardant (X) be improved and the storage stability of the dispersion can be improved, but also the viscosity of the dispersion can be reduced, so handling during application This makes it possible to improve the properties and the appearance of the laminate to make the surface smooth. Furthermore, since the halogen-free flame retardant is finely dispersed, the flame retardancy is further improved, and in addition, the water resistance and the adhesive strength of the flame retardant resin composition layer can be improved.

Examples of the ionic group include a sulfonic group, a sulfonic group, a sulfate group, a sulfate group, a phosphonate group, a phosphonate group, a carboxylate group and a carboxylate group. Preferred ionic groups are preferred.

These ionic groups can be introduced into an organic resin by a known method, and are not particularly limited. For example, when an ionic group is introduced into a polyester resin or a modified polyester resin, a method of copolymerizing a dicarboxylic acid or glycol containing an ionic group such as a sulfonic acid group into a polyester resin, a glycol containing a sulfonic acid group is used. Known methods such as a method of synthesizing a urethane-modified resin using a chain extender and a method of introducing a carboxyl group-containing glycol into a urethane-modified resin using a chain extender and then neutralizing with an alkali are used. As the ionic group, a metal sulfonate and a phosphonium sulfonate are preferred.

Examples of the dicarboxylic acid or glycol containing a sulfonic acid group include 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5 [4-sulfophenoxy] isophthalic acid. Metal salt or 2-sulfo-1,4-butanediol;
Metal salts such as 2,5-dimethyl-3-sulfo-2,5-hexanediol are exemplified.

As the phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid or a sulfonic acid group-containing glycol, those represented by the following general formula may be mentioned.

[0042]

Embedded image (Where A is an aromatic group, X1 and X2 are ester-forming functional groups, R1, R2, R3 and R4 are alkyl groups, at least one of which is an alkyl group having 6 to 20 carbon atoms)

Specifically, tri-n-sulfoisophthalic acid
-Butyldecylphosphonium salt, tri-n-butyloctadecylphosphonium sulfoisophthalate, tri-n-butylhexadecylphosphonium sulfoisophthalate, tri-n-butyltetradecylphosphonium sulfoisophthalate, tri-n sulfoisophthalate -Butyl dodecyl phosphonium salt, tri-n-sulfoterephthalate
-Butyldecylphosphonium salt, tri-n-butyloctadecylphosphonium sulfoterephthalate, tri-n-butylhexadecylphosphonium sulfoterephthalate, tri-n-butyltetradecylphosphonium sulfoterephthalate, tri-n sulfoterephthalate -Butyl dodecyl phosphonium salt, 4-sulfonaphthalene-2,
7-dicarboxylic acid tri-n-butyldecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyloctadecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butylhexa Decylphosphonium salt, 4-sulfonaphthalene-
And 2,7-dicarboxylic acid tri-n-butyltetradecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyldodecylphosphonium salt, and the like.

As a method for introducing a carboxyl group, after the above polyester resin is polymerized, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, 1,8-naphthalic anhydride, 2-cyclohexanedicarboxylic acid or the like is added later to give an acid value, and as the modified polyester, dimethylolpropionic acid,
A method of extending the chain with dimethylolbutanoic acid or the like may be used. By imparting an acid value, the adhesion to the substrate film and the dispersibility of the non-halogen flame retardant (X) can be improved.

Further, a polyhydric polyol such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and the like may be used in combination as long as the content of the invention is not impaired.

The polyester resin and / or modified polyester resin (A) preferably used in the present invention has a number average molecular weight of 2,000 or more, preferably 3,000 or more, more preferably 7,000 or more, and most preferably 10,000 or more. 00
0 or more. If the number average molecular weight is less than 2,000, the adhesion to a good base film tends to decrease. The upper limit of the number average molecular weight is preferably 100,000, more preferably 7
10,000, more preferably 50,000. Those having a molecular weight of more than 100,000 have a high viscosity, which may make lamination difficult or dispersion difficult.

The modified polyester resin can be prepared by modifying a polyester resin having the composition described above. Examples of the modification method include urethane modification, epoxy modification, acrylic modification, and silicon modification.

The flame-retardant resin composition of the present invention may contain a curing agent capable of reacting with the organic resin (Y). By adding a curing agent, water resistance is imparted, and various coating film properties can be improved. Examples of the curing agent include an alkyl etherified amino formaldehyde resin, an epoxy compound and an isocyanate compound. Among them, alkyl etherified aminoformaldehyde resin and / or isocyanate compound are preferable from the viewpoint of processability and weather resistance.

The alkyletherified aminoformaldehyde resin is, for example, formaldehyde or paraformaldehyde alkyletherified with an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol and urea. Condensation products with N, N-ethylene urea, dicyandiamide, aminotriazine, etc. Butoxylated methylol melamine, mixed methoxylated / butoxylated methylol melamine, butoxylated methylol benzoguanamine, and the like. It preferred from the viewpoint of workability, methoxylated methylolmelamine, butoxy methylol melamine or methoxylated / butoxylated mixed melamine, may be used alone, or in combination.

As the isocyanate compound, there are aromatic and aliphatic diisocyanates, and polyisocyanates having a valency of 3 or more. Either a low molecular compound or a high molecular compound may be used. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimers of these isocyanate compounds, and excess of these isocyanate compounds Amount and, for example, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, low-molecular-weight active hydrogen compounds such as triethanolamine or various polyester polyols,
Examples of the compound include a terminal isocyanate group-containing compound obtained by reacting a polyether polyol, a polyamide with a polymer active hydrogen compound, or the like.

The isocyanate compound may be a blocked isocyanate. As the isocyanate blocking agent, for example, phenol, thiophenol,
Phenols such as methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, acetoxime, methylethylketoxime, cyclohexanone oxime and its oximes, alcohols such as methanol, ethanol, propanol and butanol, ethylene chlorohydroxide Phosphorus, halogen-substituted alcohols such as 1,3-dichloro-2-propanol, t-butanol, t-
Tertiary alcohols such as pentanol, ε-caprolactam, δ-valerolactam, γ-butyrolactam,
lactams such as β-propyrolactam; and other active methylene compounds such as aromatic amines, imides, acetylacetone, acetoacetate, and malonic acid ethyl ester; mercaptans, imines, ureas, and diaryls. Compounds such as sodium bisulfite are also included. The blocked isocyanate can be obtained by subjecting the above isocyanate compound to an isocyanate blocking agent to undergo an addition reaction by a conventionally known appropriate method.

As the epoxy compound, bisphenol A
Diglycidyl ethers and oligomers thereof, diglycidyl ethers of hydrogenated bisphenol A and oligomers thereof, diglycidyl orthophthalate, diglycidyl isophthalate, diglycidyl terephthalate, diglycidyl p-oxybenzoate, tetrahydrophthalate Acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol di Glycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trime Triglycidyl citrate, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether And glycerol alkylene oxide adduct triglycidyl ether.

These curing agents may be used in combination with known curing accelerators selected according to their types.

The flame-retardant resin composition of the present invention is usually dissolved in an organic solvent, and is dissolved in a known manner, for example, reverse roll coating, roll coating, gravure coating, kiss coating, plate coating, smooth coating, screen printing, comma coating, etc. Is used by applying and drying, but can also be melt-extrusion coated or dispersed in water for use. As the organic solvent to be used, for example, toluene, xylene, cellosolve acetate, ethyl acetate, butyl acetate, carbitol acetate, cyclohexanone, methyl ethyl ketone, isophorone, Solvesso 100, Solvesso 150
(Exxon Chemical Co., Ltd.) and other general-purpose solvents such as aromatic hydrocarbons. Appropriate ones are selected according to the coating method. The amount of the flame-retardant resin composition of the present invention applied to a substrate film or the like varies depending on the thickness and the material of the substrate film, sheet, or molded product, but is generally about 5 μm or more.
300 μm is preferred.

The flame-retardant resin composition of the present invention contains a pigment,
It can be dispersed and colored. There is no limitation on the type of pigment to be compounded. For example, various titanium oxide pigments, iron oxide (bengala), graphite, molybdate orange, cadmium pigment, inorganic color pigments such as carbon black, copper phthalocyanine green or blue Organic pigments such as pigments, cyclic high-grade pigments, soluble azo pigments and dyed pigments; inorganic pigments such as barium sulfate, zinc white, talc, clay, calcium carbonate and silica; (meth) acrylic beads, acrylonitrile beads, A crystalline polyester resin powder which is difficult to be used as a solvent for the coating material is exemplified.

The flame-retardant resin composition of the present invention contains 1
More than one additive may be mixed. The additives used are not particularly limited, and include, for example, various commonly used leveling agents, pigment dispersants, ultraviolet absorbers, antioxidants, viscosity modifiers, light stabilizers, metal deactivators, Oxide decomposers, fillers, reinforcing agents, plasticizers, lubricants, anticorrosives,
Examples include rust preventives, emulsifiers, mold decolorizers, fluorescent brighteners, organic flame retardants, inorganic flame retardants, dripping inhibitors, melt flow modifiers, antistatic agents, and the like. Suitable additives mentioned above are
Illustrated in Canadian Patent 1,190,038.

The flame-retardant resin composition of the present invention can be used, for example, as a flame-retardant label applied to a film. This label is not only adhered to the molding material, but also made of inorganic material such as aluminum, stainless steel, tin, tinplate, steel plate, concrete, mortar, slate, glass, etc. Can be adhered to.

It is also preferable that the flame-retardant resin composition of the present invention is a flame-retardant laminate in which at least a flame-retardant intermediate layer is provided on a substrate, and an adhesive layer is further provided thereon.

As the adhesive that can be used for the adhesive layer on the flame-retardant intermediate layer, known adhesives can be used. For example, SBR
Any pressure-sensitive adhesive, such as a system-based, natural rubber-based, solvent-based acrylic resin, emulsion-based acrylic resin, butyl rubber-based, isobutyl rubber-based thermoplastic elastomer-based (hot melt), silicone-based, or polyester-based, can be used. Preferably, a solvent-based acrylic resin, butyl rubber-based, silicone-based is preferred, as a preferred reason,
This is because the adhesion to the base film tends to be good.
These resins are diluted if necessary to a viscosity suitable for coating, and then coated by a known coating method, for example, reverse roll coating, roll coating, gravure coating, kiss coating, plate coating,
Coating by smooth coating.
The thickness of the adhesive layer is generally from 10 to 200 μm, preferably from 15 to 150 μm.

The adhesive may contain the halogen-free flame retardant of the present invention. The compounding amount is 30 parts by weight of the halogen-free flame retardant of the present invention with respect to 100 parts by weight of the adhesive.
Less than 0 parts by weight, preferably less than 200 parts by weight, and more preferably less than 100 parts by weight, and when the amount of the non-halogen flame retardant used is 300 parts or more, the adhesion to the flame-retardant intermediate layer and the molding material tends to decrease. It is in.

Further, the adhesive can be colored by blending and dispersing a pigment. There is no limitation on the type of pigment to be compounded. For example, various titanium oxide pigments, iron oxide (bengala), graphite, molybdate orange, cadmium pigment, inorganic color pigments such as carbon black, copper phthalocyanine green or blue Organic pigments such as pigments, cyclic high-grade pigments, soluble azo pigments, dyed pigments, barium sulfate, zinc white,
Examples include inorganic extender pigments such as talc, clay, calcium carbonate, and silica, (meth) acrylic beads, acrylonitrile-based beads, and crystalline polyester resin powder that is difficult to use in a solvent used for paint.

Such a laminate is preferably used as a label, and this label can be produced according to a known method. For example, an adhesive base resin and an organic solvent (for example, toluene ), Mixed with a predetermined non-halogen flame retardant, dispersed with a mixer such as a roll mill, ball mill, bead mill, blender, roller coating, reverse roll coating,
It can be manufactured by applying and drying a base film by roll coating, gravure coating, kiss coating, plate coating, smooth coating, screen printing, comma coating, spray coating, electrostatic coating, or the like.

When the label is adhered, if the adhesive strength of the label is not sufficient at room temperature due to the presence of the flame retardant, a method of using a press heated to 40 to 200 ° C. when laminating is used. It is preferable to employ

Further, the flame-retardant resin composition of the present invention can be formed into a laminate by applying it to a molded product molded by injection molding, extrusion molding, blow molding or the like. Moreover,
After being formed into a sheet, the flame-retardant resin composition of the present invention can be applied or laminated to the sheet, and then formed in a mold.

Further, the resin composition of the present invention may be used as a flame-retardant paint, adhesive, coating agent, binder, etc.
It can be used for applications requiring flame retardancy in various fields.

[0066]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments. In the examples, “parts” means “parts by weight”. Each measurement item followed the following method.

1. Number average molecular weight (Preparation of sample) Using tetrahydrofuran as a solvent, 0.05 g of a resin for a sample was dissolved in 1 g of tetrahydrofuran to prepare a sample. (Apparatus) High-speed GPC device 150 manufactured by Waters Corporation
C was used. (Standard polystyrene) TSK standard polystyrene manufactured by Tosoh Corporation was used. (Measurement conditions) Measurement was performed at a measurement temperature of 30 ° C. and a flow rate of 1 ml / min.

2. Flame retardancy The flame retardancy is evaluated by a flame retardancy test: Underwriter.
s Laboratories Inc. VTM /
UL94, measured by combustion test. The test piece used had a flame-retardant resin composition applied to a predetermined thickness on a polyethylene terephthalate film (E-5000 manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm. Flame retardant levels are VTM-0, VTM-1, VTM-2, NOT-VT
M and VTM-0 is the best. The test results were expressed as the level of flame retardancy that passed these tests.

3. Combustion Gas Analysis Combustion gas analysis was conducted in accordance with JIS K7217. Combustion gas analysis was shown as も の when no generation of hydrogen halide was detected, and as X when detection was detected.

4. Adhesion The adhesion was measured based on the grid tape method of JIS K 5400. The cutter knife is L type (11S) manufactured by Olfa Corporation.
P) was used. The cellophane adhesive tape used was Nichiban Cellotape (TM) CT-24F. (1) Adhesion with base film A cut was made so as to reach the base film layer from the flame-retardant layer surface of the flame-retardant film. The cuts are 11mm 2mm each
The cuts are perpendicular to each other, and the length of each side is 2 mm in a grid.
Made 100 squares. Others are JIS K5
400. The number of squares remaining without peeling was counted. Any peeling was counted as the number of peels. (2) Adhesion to Molded Material (= Adhesion Before Water Resistance Test) A flame-retardant film was attached to a molded article, and a cut was made from the flame-retardant film surface to reach the molded article. The cuts were eleven vertical and horizontal cuts perpendicular to each other at 2 mm intervals, and 100 squares each having a side length of 2 mm were formed in a lattice shape. Others were performed according to JISK5400. The number of squares remaining without peeling was counted. Any peeling was counted as the number of peels. (3) Adhesion after water resistance test A test sample with cuts similar to the above (2) was immersed in boiling water for 1 hour in the same manner as in the evaluation of water resistance, taken out, immediately wiped off water, and then dried at 25 ° C. A cellophane adhesive tape was attached to a test sample left for 1 hour in an HR 50% room for testing.

5. Dispersibility A predetermined amount of a non-halo flame retardant (X) was mixed with a resin solution obtained by dissolving an organic resin in a predetermined solvent, followed by stirring to prepare a dispersion resin solution. The obtained dispersion resin solution was stored at 25 ° C. for 2 hours. The dispersibility was evaluated by the aggregation, sedimentation and viscosity change of the particles of the dispersion resin solution. The evaluation criteria are shown below. ：: No aggregation, sedimentation or increase in viscosity of the particles was observed. Δ: Some aggregation or sedimentation of the particles is observed or the viscosity increases. ×: Aggregation and sedimentation of the particles are remarkably observed or the viscosity is significantly increased. 6. Water resistance The test piece was immersed in boiling water for 1 hour, and the appearance was visually checked. No change in appearance: ○ Poor appearance: ×

Synthesis Example of Polyester Resin (A) 131 parts of cyclohexanedicarboxylic acid and isophthalic acid were placed in a reaction vessel equipped with a stirrer, a condenser and a thermometer.
26 parts, 5-sulfo sodium isophthalic acid 9 parts, 1,
174 parts of 6-hexanediol, 78 parts of neopentyl glycol, and 0.068 part of tetrabutyl titanate were charged, and an esterification reaction was performed from 160 ° C. to 240 ° C. for 4 hours. Then, the pressure inside the system was gradually reduced, and then reduced to 5 mmHg over 50 minutes.
The polycondensation reaction was performed at 250 ° C. for 60 minutes under a vacuum of mmHg or less. The obtained polyester resin (A) is NMR
As a result of the composition analysis, the acid component is cyclohexanedicarboxylic acid / isosophthalic acid / 5-sulfosodium isophthalic acid = 80/16/4 in molar ratio, and the glycol component is 1,6-hexanediol / neopentyl in molar ratio. Glycol was 50/50. Moreover, the number average molecular weight was 3,000 when measured. Table 1 shows the results.

The following Table 1 was obtained by the method according to the above synthesis example.
Polyester resins (B) to (C) having the following compositions were synthesized. Table 1 shows the results.

Synthesis Example of Polyester Resin (D) 83 parts of terephthalic acid, 80 parts of isophthalic acid, 3.8 parts of trimellitic acid, 174 of 1,6-hexanediol were placed in a reaction vessel equipped with a stirrer, a condenser and a thermometer.
Parts, 78 parts of neopentyl glycol and 0.068 parts of tetrabutyl titanate.
The esterification reaction was performed over 4 hours up to ° C. Then, the pressure inside the system was gradually reduced, and the pressure was reduced to 5 mmHg over 50 minutes.
After a 60 minute polycondensation reaction in nitrogen atmosphere.
The temperature was lowered to 30 ° C., 3.8 parts of trimellitic acid was added, and the mixture was stirred at 230 ° C. for 30 minutes to perform an addition reaction after trimellitic acid. Table 1 shows the results.

[0075]

[Table 1]

Synthesis Example of Urethane-Modified Polyester Resin (E) 100 parts of the polyester (A) obtained in Synthesis Example (A),
After charging and dissolving 100 parts of toluene, 20 parts of toluene was distilled and the reaction system was dehydrated by azeotropic distillation of toluene / water. 60
After cooling to ℃, 80 parts of methyl ethyl ketone, 5 g of neopentyl glycol and 18 parts of isophorone diisocyanate were added. Further, after adding 0.03 part of dibutyltin dilaurate as a reaction catalyst, heating at 80 ° C. for 6 hours, adding 65 parts of toluene and 147 parts of cyclohexanone, and adding a urethane-modified polyester resin solution (E) having a solid concentration of 30% (E).
I got Table 2 shows the composition and characteristic values of the obtained urethane-modified polyester resin solution (E).

Hereinafter, Table 2 was prepared by the method according to the above synthesis example.
The urethane-modified polyester resin (F) having the composition shown in the following was synthesized.

[0078]

[Table 2]

Synthesis Example of Acrylic-Modified Polyester Resin (G) 131 parts of cyclohexanedicarboxylic acid, 20 parts of isophthalic acid, and 9 parts of 5-sulfosodium isophthalic acid were placed in a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser. 94 parts of neopentyl glycol, 71 parts of 1,4-cyclohexanedimethanol,
And 0.068 part of tetra-n-butyl titanate were charged, and a transesterification reaction was performed at 160 to 220 ° C. for 4 hours. Then, the mixture was cooled to 200 ° C., 4.6 parts of fumaric acid was added, and the temperature was raised from 200 ° C. to 220 ° C. over 1 hour to carry out an esterification reaction. Then, the temperature was raised to 255 ° C., and the pressure of the reaction system was gradually reduced.
The reaction was carried out for 1 hour and 30 minutes under reduced pressure to obtain an acrylic-modified base polyester resin (A-1). The obtained polyester resin (A-1) is light yellow and transparent and has a number average molecular weight of 12
000. Table 3 shows the results of composition analysis measured by NMR and the like.

[0080]

[Table 3]

In a reactor equipped with a stirrer, a thermometer, a refluxing device and a metered-drip device, 75 parts of polyester resin (A-1), 56 parts of methyl ethyl ketone and isopropyl alcohol 1
9 parts were added and heated and stirred at 65 ° C. to dissolve the resin. After the resin was completely dissolved, a mixture of 25 parts of ethyl acrylate and a solution of 1.2 parts of azobisdimethylvaleronitrile dissolved in 25 parts of methyl ethyl ketone were dropped into the polyester solution at 0.2 ml / min. Stirring was continued for 2 hours. The resulting acrylic-modified polyester (G) was pale yellow and transparent, and had a number average molecular weight of 14,000. Table 4 shows the results of composition analysis measured by NMR and the like.

Hereinafter, Table 4 was prepared by a method according to the above synthesis example.
An acrylic-modified polyester resin (H) having the composition shown in the following was synthesized.

[0083]

[Table 4]

Example 1 A glass bead-type high-speed shaker was prepared by dissolving 65 solid parts of a resin solution obtained by dissolving a polyester resin (A) in a 50/50 weight ratio of methyl ethyl ketone / toluene and 35 solid parts of melamine phosphate (Taihei Chemical Co., Ltd.). The mixture was dispersed for 5 hours by a machine to obtain a dispersion solution. The resulting dispersion exhibited good dispersibility. The test results are shown in Table 5. The dispersed resin solution has a dry film thickness of 50 μm.
Was coated on a 100 μm-thick polyethylene terephthalate film (E-5000 manufactured by Toyobo Co., Ltd.) with a bar coater and dried to prepare a flame-retardant laminate having a flame-retardant adhesive layer.

The obtained flame-retardant adhesive film had good flame retardancy and excellent smoke-suppressing effect, and also had excellent adhesion to the base film and excellent water resistance. Table 5 shows the test results. Further, the flame-retardant laminated film is 70 mm long x 1 mm wide.
A flame-retardant laminated film was pressure-bonded to a 50 mm × 3 mm thick ABS (acrylonitrile-butadiene-styrene) resin molded product with a hand press at a force of 0.5 kg / cm ² . The sticking temperature was appropriately adjusted at 110 to 150 ° C. The obtained sample had excellent adhesion to the molded product.

Comparative Example 1 A resin solution prepared by dissolving a polyester resin (A) at a weight ratio of methyl ethyl ketone / toluene = 50/50 was used in the form of a glass bead having 65 solid parts, 20 solid parts of perchloropentacyclodecane, and 15 solid parts of antimony trioxide. 5 with a high-speed shaker
Time-dispersed to obtain a dispersion solution. The dispersibility of the resulting dispersion was shown. The test results are shown in Table 7. A 100 μm thick polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., E) was used so that the dispersed resin solution had a dry film thickness of 50 μm.
-5000) and dried with a bar coater to produce a flame-retardant laminate having a flame-retardant adhesive layer. Table 7 shows the test results.

The flame-retardant adhesive films of Examples 2 to 11 and Comparative Examples 1 to 3 were prepared in the same manner using the compositions shown in Tables 6 to 8. Tables 5 to 7 show the test results of the obtained flame-retardant adhesive film. However, the compounding ratio is shown in terms of solid content.

[0088]

[Table 5]

[0089]

[Table 6]

[0090]

[Table 7]

In Tables 5 to 7, the trade names are as follows. 1) Melamine phosphate: (Taihei Chemical Co., Ltd.) 2) PMP-100: Melamine polyphosphate (Nissan Chemical Co., Ltd.) 3) PMP-200: Melam polyphosphate (Nissan Chemical Co., Ltd.) 4) PMP-300: Melem polyphosphate (manufactured by Nissan Chemical Co., Ltd.) 5) Epicoat # 1004: Bisphenol A type epoxy (manufactured by Yuka Shell Co., Ltd.) 6) Aminoformaldehyde resin (manufactured by Mitsui Cytec Co., Ltd.) 7) Colonate HX: Hexamethylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd.) 8) Tien S: ammonium polyphosphate (manufactured by Taihei Chemical Co., Ltd.)

Synthetic Examples of Polyester Resins (I) to (K) Table 8 shows the same as the synthetic example of the polyester resin (A). Polyester resins (I) to (K) were synthesized. The results are shown in Table 8.

[0093]

[Table 8]

Urethane-modified polyester resin (L),
Synthesis Example of (M) Urethane-modified polyester resins (L) and (M) were obtained in the same manner as in the synthesis example of the urethane-modified polyester resin (E). The results are shown in Table 9.

[0095]

[Table 9]

Acrylic modified polyester resin (N),
Synthesis Example of (O) In the same manner as in the synthesis example of the acrylic-modified polyester resin (G), polyester resins (C-1) and (D-1) were synthesized (Table 10), and then acrylic-modified and acrylic-modified polyester resin (N) and (O) were obtained. Table 11 shows the results.

[0097]

[Table 10]

[0098]

[Table 11]

Examples 13 to 22, Comparative Examples 4 to 6 In the same manner as in Example 1, Examples 13 to 22, Comparative Examples 4 to
6 was performed. The results are shown in Tables 12-14.

[0100]

[Table 12]

[0101]

[Table 13]

[0102]

[Table 14]

The trade names of Tables 12 to 14 are as shown in Tables 5 to 7. 9) Paraloid b-44: a methyl methacrylic resin (manufactured by Rohm and Haas Japan KK).

Example 23 70 parts by weight of a resin solution obtained by dissolving a polyester resin (A) at a weight ratio of methyl ethyl ketone / toluene = 50/50 and JPCN-300M (melamine nitrilotris (methylene) phosphonate: manufactured by Johoku Chemical Co., Ltd.) ) 30 solid parts were dispersed with a glass bead-type high-speed shaker for 5 hours to obtain a dispersion solution. The resulting dispersion exhibited good dispersibility. The test results are shown in Table 15. Disperse resin solution with dry film thickness of 5
A 100 μm-thick polyethylene terephthalate film (E-5000 manufactured by Toyobo Co., Ltd.) was applied by a bar coater and dried so as to have a thickness of 0 μm to prepare a flame-retardant laminate having a flame-retardant adhesive layer.

The obtained flame-retardant adhesive film had good flame retardancy and excellent smoke suppressing effect, and also had excellent adhesion to the base film and water resistance. Table 1 shows the test results.
It is shown in FIG.

The flame-retardant adhesive films of Examples 24 to 33 and Comparative Examples 7 to 9 were prepared in the same manner using the compositions shown in Tables 5 to 17. Tables 15 to 17 show the test results of the obtained flame-retardant adhesive film. However, the compounding ratio is shown in terms of solid content.

[0107]

[Table 15] 1) Thaien S: ammonium polyphosphate (manufactured by Taihei Chemical Co., Ltd.) 2) Sumisafe PM: ammonium polyphosphate (manufactured by Sumitomo Chemical Co., Ltd.) 3) Exolit AP750: ammonium polyphosphate (manufactured by Client Japan Co., Ltd.) 4) Epicoat # 1004: bisphenol A type epoxy (manufactured by Yuka Shell) 5) aminoformaldehyde resin (manufactured by Mitsui Cytec Co., Ltd.) 6) colonate HX: hexamethylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd.)

[0108]

[Table 16] 1) Thaien S: ammonium polyphosphate (manufactured by Taihei Chemical Co., Ltd.) 2) Sumisafe PM: ammonium polyphosphate (manufactured by Sumitomo Chemical Co., Ltd.) 3) Exolit AP750: ammonium polyphosphate (manufactured by Client Japan Co., Ltd.) 4) Epicoat # 1004: bisphenol A type epoxy (manufactured by Yuka Shell) 5) aminoformaldehyde resin (manufactured by Mitsui Cytec Co., Ltd.) 6) colonate HX: hexamethylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd.)

[0109]

[Table 17] 1) Thaien S: ammonium polyphosphate (manufactured by Taihei Chemical Co., Ltd.) 5) Amino formaldehyde resin (manufactured by Mitsui Cytec Co., Ltd.) 6) Colonate HX: hexamethylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd.)

Example 33 A glass bead type high-speed vibrator was prepared by mixing 70 solid parts of a resin solution obtained by dissolving a polyester resin (A) in methyl ethyl ketone / toluene at a weight ratio of 50/50 and 30 solid parts of melamine polyphosphate (manufactured by Taihei Chemical Co., Ltd.). The mixture was dispersed for 5 hours with a shaking machine to obtain a flame-retardant dispersion solution. The resulting flame-retardant dispersion exhibited good dispersibility. The test results are shown in Table 18.

The dispersion resin solution was applied on a 100 μm-thick polyethylene terephthalate film (E-5000 manufactured by Toyobo Co., Ltd.) with a bar coater and dried so as to have a dry film thickness of 50 μm. A flame-retardant laminate was produced. The resulting flame-retardant laminate had good substrate film adhesion. The test results are shown in Table 18.

Further, a silicone modified polymer (PM210, manufactured by Cemedine Co., Ltd.) was applied by a bar coater and dried to prepare a flame-retardant laminated film having an adhesive layer having a thickness of 100 μm. The resulting flame-retardant laminated film had good flame retardancy and smoke-suppressing effects. The test results are shown in Table 18.

Further, the flame-retardant laminated film is 70 mm long.
A flame-retardant laminated film was pressure-bonded to an ABS (acrylonitrile-butadiene-styrene) resin molded product having a width of 150 mm and a thickness of 3 mm using a hand press with a force of 0.5 kg / cm ² . The obtained sample had excellent adhesion to the molded product. The test results are shown in Table 18.

Hereinafter, the flame-retardant adhesive films of Examples 34 to 54 and Comparative Examples 13 to 15 were prepared in the same manner with the compositions shown in Tables 18 to 23. The test results of the obtained flame-retardant adhesive film are shown in Tables 18 to 23. However, the compounding ratio is shown in terms of solid content.

[0115]

[Table 18]

[0116]

[Table 19]

[0117]

[Table 20]

[0118]

[Table 21]

[0119]

[Table 22]

[0120]

[Table 23]

In Tables 18 to 23, the trade names and the like are the same as those in the above tables.

[0122]

According to the present invention, there is provided a composition in which a halogen-free flame retardant (X) having a specific structure is dispersed in an organic resin (Y). The flame retardant is prepared by coating or laminating the flame retardant dispersion. It is possible to provide a flame-retardant resin composition having excellent heat resistance and smoke-suppressing effect, and having good adhesion to a substrate molded article or substrate film. Further, it has excellent water resistance, and hardly causes peeling or the like even after long-term use. Further, by introducing an ionic group into the organic resin, excellent dispersibility can be imparted, and various properties such as flame retardancy, adhesion, and water resistance can be further improved. By coating or laminating the flame-retardant resin composition of the present invention, an inexpensive and excellent flame-retardant laminate is provided, which can meet the high required quality in the field of home electric appliances and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AA04B AA04H AA04K AH03B AH03H AH03K AK01B AK42A AK42B AL06B AT00A BA02 CA08B GB48 JB07 JJ07 JK06 JL16 4J002 AA001 BG001 CD001 CF001 CK021 GF 186 EUFD 186 EU186

Claims (5)

[Claims] 1. A flame-retardant resin composition comprising a halogen-free flame retardant (X) having a cyclic structural unit containing a nitrogen atom and an organic resin (Y). 2. The non-halogen flame retardant (X) having a cyclic structural unit containing a nitrogen atom comprises at least one structural unit represented by the following formula (1) or (2). 3. The flame-retardant resin composition according to item 1. Embedded image 3. The flame-retardant resin composition according to claim 1, wherein the non-halogen flame-retardant (X) agent having a cyclic structural unit containing a nitrogen atom further contains a phosphorus atom in the molecule. object. 4. A non-halogen flame retardant containing at least one structural unit represented by the formula 1 or 2 in the molecule:
Nitrilotris (alkylene) phosphonate (formula 3 below) and / or 1-hydroxyalkylidene-1,
The flame-retardant resin composition according to claim 2, wherein the composition is at least one of 1′-diphosphonate (formula 4 below). 5. Embedded image Embedded image 5. A flame-retardant laminate obtained by laminating the flame-retardant resin composition according to claim 1 on a substrate.