JP2006160789A - Phosphorus-containing hyper-branched polymer and flame retardant resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphorus-containing copolymer having an excellent flame retardance and also improved with hydrolysis resistance. <P>SOLUTION: This hyper-branched polymer is provided by having terminal groups ≥5% of which is a functional group expressed by general formula (1) or (2) [wherein, R<SP>1</SP>to R<SP>3</SP>are each a monovalent or divalent organic residue without containing a halogen, and the R<SP>2</SP>and R<SP>3</SP>may be each an independent functional group or bond each other], and 1,000-50,000 number-average molecular weight. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hyperbranched polymer excellent in flame retardancy, and a flame retardant resin composition combined with a flame retardant, and more specifically, an additive imparting flame retardancy and a coating agent imparting flame retardancy. Or it relates to a flame retardant adhesive.

As a highly branched polymer, a polymer that grows while repeating branching during polymerization is known. This polymer is called a hyperbranched polymer. It is known that a hyperbranched polymer can be synthesized by polymerization of AB _x (x is an integer of 2 or more) type molecules (Non-patent Documents 1 and 2). Here, A and B are organic groups having different functional groups a and b, and the functional groups a and b are capable of chemically condensing and adding to each other. It is also known to copolymerize AB type molecules (compounds each having one organic group of A and B in one molecule) during the polymerization of AB _x .

It is also known that a hyperbranched polymer can be obtained from an equimolar reaction of A ₂ (a compound having two organic groups of A in one molecule) and B ₃ (a compound having _three organic groups of B in one molecule). It has been. In this case, a hyperbranch structure is formed when the initial reaction between A ₂ and B ₃ is earlier than the subsequent reaction, but it has also been reported that gelation easily occurs depending on the reaction conditions (Non-patent Document 3). ).

A ₂ and B′B ₂ (a compound having one organic group of B ′ and two organic groups of B in one molecule, B ′ does not react with B, but reacts with A. It is also known that a hyperbranched polymer can be obtained from the reaction of B ′ and B (reactivity is different) (Non-patent Document 4).

  As the hyperbranched polymer, in Patent Document 1 and Patent Document 2, polyesters are terminated with a hydroxyl group obtained from one having two hydroxyl groups and one carboxylic acid group in one molecule such as dimethylolpropionic acid. Polyester is described. Moreover, hyperbranched polyester is also known as aromatic polyester (Patent Document 3).

  As a method for imparting flame retardancy to a thermoplastic resin, it is common to use a halogen compound as a flame retardant and an antimony compound as a flame retardant aid. However, it has been pointed out that halogen compounds emit halogen-based gases during combustion, and antimony compounds have problems from environmental conservation. Accordingly, various halogen-free flame retardant formulations related to environmental problems have been studied. Known additive flame retardants include hydrated metal compound flame retardants, phosphorus compound flame retardants, silicone compound flame retardants, nitrogen-containing compound flame retardants, and the like. On the other hand, various compounds are known as reactive flame retardants, and polyester resins containing phosphorus are also known (Patent Documents 4 and 5).

P. J. et al. Flori (Co-authored by Oka Koten and Kanamaru Ko), “Polymer Chemistry”, Chapter 9, Maruzen Co., Ltd. (1956) Koji Ishizu, “Nanotechnology of Branched Polymers”, Chapter 6, IPC Corporation (2000) M. Jikei, S. H. Chon, M. Kakimoto, S. Kawauchi, T. Imase and J. Watanabe, Macromolecules, 1999, 32, 2061. D. Yan and C. Gao, Macromolecules, 2000, 33, 7693. U.S. Pat. No. 3,669,939 Japanese Patent No. 2574201 Japanese Patent Laid-Open No. 5-214083 JP 52-98089 A JP-A-51-82391

  The demand for flame retardant materials is becoming increasingly sophisticated. In addition to high flame retardancy, environmental safety, physical properties, moldability, recyclability, etc. are also required. Flame retardancy is insufficient by the method of blending conventional phosphorous flame retardants such as phosphate ester compounds, phosphate amide compounds, aromatic phosphate compounds, and phosphates with plastics and coating agents. Have the problem of bleed-out, where the phosphorus compound oozes out on the surface of the molded product.

  In the prescription which makes it flame-retardant by copolymerization of a phosphorus compound, when sufficient flame retardance is ensured, there are a problem that physical properties of the copolymer are lowered, and a problem that heat stability and hydrolysis characteristics are deteriorated. An object of the present invention is to obtain a phosphorus-containing copolymer having excellent flame retardancy and improved hydrolysis resistance.

  As a result of intensive studies on the modification of hyperbranched polymers, the present inventors have reached the present invention. That is, the present invention relates to the following hyperbranched polymer and flame retardant resin composition.

（Ｒ¹、Ｒ²、Ｒ³はハロゲンを含有しない１価または２価の有機残基を表し、Ｒ²とＲ³は独立した官能基でも互いに結合していても良い。） 1st invention is a hyperbranched polymer whose number average molecular weight is 1000-50000 characterized by 5% or more of terminal groups being a functional group represented by following General formula (1) or (2).

(R ¹ , R ² and R ³ represent a monovalent or divalent organic residue containing no halogen, and R ² and R ³ may be independent functional groups or bonded to each other.)

  2nd invention is the hyperbranched polymer as described in 1st invention whose hyperbranch frame | skeleton is polyester.

  A third invention is a flame retardant resin composition comprising a hyperbranched polymer according to the first or second invention and a flame retardant containing no halogen.

  The polymer of the present invention can contain phosphorus at a high concentration and has a highly branched structure resulting from the hyperbranched structure, and therefore has excellent compatibility with other resins, reactivity with curing agents, and the like. Furthermore, the flame retardance is superior to that of the linear structure due to the hyperbranch structure. It is extremely useful for flame retardant resins, flame retardant coating agents, and flame retardant adhesives.

The hyperbranched polymer used in the present invention is preferably a polymer synthesized by polycondensation of AB _x (x is an integer of 2 or more) type molecules in the presence or absence of a core substance. Here, A and B are organic groups having different functional groups a and b, and the functional groups a and b are capable of chemically condensing and adding to each other.

  When the hyperbranched polymer is polyester, it is desirable that the functional group of A is a carboxylic acid group and B is a hydroxyl group. However, when A and B are reversed, A is a methyl ester group or ethyl ester group of carboxylic acid. In other words, B may be a hydroxyl group, B may be a carboxylic acid methyl ester group, and A may be a hydroxyl group. As in these cases, in addition to the reaction of releasing water and lower alcohol during ester formation, A is a hydroxyl acetate group, B is a carboxylic acid, B is a hydroxyl acetate group, and A is a carboxylic acid Thus, the hyperbranched polyester may be polymerized by a reaction that releases acetic acid during ester formation. When the terminal group of the obtained polyester is a carboxylic acid or ester group, an operation for converting the terminal group to a hydroxyl group may be required for the purpose of the present invention. The hydroxyl group may be a phenolic hydroxyl group in addition to the alcoholic hydroxyl group.

When the hyperbranched polymer is polyester, specific examples of the raw material AB _x (x is an integer of 2 or more) type molecules include dimethylolpropionic acid, dimethylolbutanoic acid, and 3,5-bis (2-hydroxyethoxy) benzoic acid. Acid, 5- (2-hydroxyethoxy) isophthalic acid, 5-hydroxyisophthalic acid, 5-acetoxyisophthalic acid, 3,5-diacetoxyisophthalic acid, diphenolic acid, bis (4-hydroxyphenyl) acetic acid, 2,2 -Methyl ester of bis (4-hydroxyphenyl) propionic acid, 2,2-bis (4-hydroxyphenyl) propionic acid, and the like, among which dimethylolpropionic acid and dimethylolbutanoic acid are desirable.

  The hyperbranched polymer used in the present invention is an AB-type molecule (A and B are organic groups having different functional groups a and b for functional group concentration adjustment and physical property optimization, and the functional groups a and b). May be chemically copolymerized with each other). When the hyperbranched polymer is polyester, specific examples of AB type molecules include glycolic acid, lactic acid, 4-hydroxyphenylacetic acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, or AB type molecules. Lactone compounds and lactide compounds which are self-condensates of the above. The AB type molecule is preferably 70% or less, more preferably 50% or less in terms of weight ratio in the polyester.

（Ｒ¹、Ｒ²、Ｒ³はハロゲンを含有しない１価または２価の有機残基を表し、Ｒ²とＲ³は独立した官能基でも互いに結合していても良い。） The present invention is a hyperbranched polymer in which 5% or more of the end groups are functional groups represented by the following general formula (1) or (2).

(R ¹ , R ² and R ³ represent a monovalent or divalent organic residue containing no halogen, and R ² and R ³ may be independent functional groups or bonded to each other.)

The functional group represented by the general formula (1) is present at the terminal. Therefore, R ¹ represents an organic residue connected to the hyperbranched polymer. Moreover, as represented by the general formula (2), a structure in which a phosphorus atom is directly connected to a hyperbranch structure may be used. R ² and R ³ are preferably an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a cycloalkyl group, a cycloalkoxyl group, an aralkyl group, an aralkyloxy group, an aryl group, or an aryloxy group.

  As a method for introducing the phosphorus-containing functional group into the end group of the hyperbranched polymer, an ordinary organic synthesis reaction can be used depending on each example.

（Ｒ⁴、Ｒ⁵はハロゲンを含有しない１価または２価の有機残基を表し、それぞれ独立した官能基であっても互いに結合していても良い。） When the hyperbranched polymer is a polyester, the method of introducing the functional group of the general formula (1) into the terminal group of the hyperbranched polyester includes esterification of a hydroxyl-terminated hyperbranched polyester and a carboxylic acid or a carboxylic acid ester-containing phosphorus compound. A transesterification reaction, an esterification reaction between a carboxylic acid-terminated hyperbranched polyester and a hydroxyl group-containing phosphorus compound, or an amidation reaction between a carboxylic acid-terminated hyperbranch polyester and an amino group-containing phosphorus compound can be used. Moreover, when the phosphorus compound to be used is a compound represented by the general formula (3), a reaction between the terminal hydroxyl group of the hydroxyl group-terminated hyperbranched polyester and the functional group of the general formula (3) is provided in advance at the end of the hyperbranched polyester. An addition reaction between the double bond and the functional group of the general formula (3), a substitution reaction with the functional group of the general formula (3) on an aromatic ring provided in advance at the end of the hyperbranched polyester, and the like can also be used.

(R ⁴ and R ⁵ represent a monovalent or divalent organic residue containing no halogen, and may be independent functional groups or bonded to each other.)

R ⁴ and R ⁵ of the functional group represented by the general formula (3) are alkyl groups having 1 to 12 carbon atoms, alkoxy groups, cycloalkyl groups, cycloalkoxyl groups, aralkyl groups, aralkyloxy groups, aryl groups, aryloxy Represents a group.

  5% or more of the end groups of the hyperbranched polymer used in the present invention is a functional group represented by the general formula (1) or (2). When the functional group represented by the general formula (1) or (2) is less than 5%, the phosphorus concentration is low and the flame retarding effect may not be obtained. The terminal group can be determined by titration in the case of a carboxyl group or a hydroxyl group, and by determination of the integration ratio by NMR analysis in the case of other functional groups.

  As for the molecular weight of the hyperbranched polymer of this invention, it is desirable to use the thing of 1000-50000 in a number average molecular weight. If the number average molecular weight is 1000 or less, the resin is fragile and has many practical problems. When the number average molecular weight exceeds 50,000, compatibility with other resins and solvent solubility may be reduced.

  As the flame retardant containing no halogen used in the present invention, phosphate ester, condensed phosphate ester, red phosphorus compound, phosphate compound, polyphosphate compound, nitrogen-containing compound, hindered amine compound, silicone compound, A hydrated metal compound is mentioned. In particular, melamine phosphate, melamine polyphosphate, melamine, melamine cyanurate, phosphoric acid amide, polyphosphoric acid amide, aluminum hydroxide, and magnesium hydroxide are excellent, and these are difficult because of the synergistic effect with the hyperbranched polyester containing phosphorus at the terminal. Increases flammability and provides a drip suppression effect during combustion. The blending ratio of the flame retardant containing no halogen and the phosphorus-containing hyperbranched polymer is preferably 0 to 300 parts by weight of the flame retardant containing no halogen with respect to 100 parts by weight of the phosphorus-containing hyperbranched polymer. If it exceeds 300 parts by weight, it will be difficult to maintain mechanical properties. Preferably it is 0-100 weight part.

  The phosphorus-containing hyperbranched polymer of the present invention can impart flame retardancy to a thermoplastic resin by blending with the thermoplastic resin. Examples of the thermoplastic resin include polyester resin, polyamide resin, polycarbonate resin, polyurethane resin, phenol resin, polypropylene resin, polyethylene resin, and acrylic resin. In addition, flame retardancy can be imparted to these molded products by using them as a coating or adhesive on films, sheets or molded products. When used as a coating agent or an adhesive, it may be dissolved in an organic solvent such as ethyl acetate, methyl ethyl ketone, toluene, propylene glycol propyl ether, or the like. Alternatively, an ion group such as a carboxylate salt or a sulfonate salt or a polyoxymethylene group may be introduced into a phosphorus-containing hyperbranched polymer and used as an aqueous dispersion by a conventional method.

  When the phosphorus-containing hyperbranched polymer of the present invention is used as a coating agent or an adhesive, it can be used as it is, but it contains one or more compounds selected from the group of amino resins, epoxy resins and isocyanate compounds as crosslinking agents. May be.

  Examples of amino resins include formaldehyde adducts such as urea, melamine, and benzoguanamine, and alkylated products having 1 to 6 carbon atoms.

  Epoxy resins include bisphenol A diglycidyl ether and oligomers thereof, hydrogenated bisphenol A diglycidyl ether and oligomers thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid Diglycidyl ester ether, tetrahydrophthalic acid diglycidyl ester, adipic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimellitic acid triglycidyl ester, triglycidyl isocyanate Nurate, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythri Lumpur polyglycidyl ether, and polyglycidyl ethers of glycerol alkylene oxide adducts.

  Examples of the isocyanate compound include aromatic and aliphatic diisocyanates and trivalent or higher polyisocyanates, and any of low molecular compounds and high molecular compounds may be used. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimers of these isocyanate compounds, and excess of these isocyanate compounds Amount of low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine or various polyester polyols, polyether polyols, polyamides Against high molecular active hydrogen compounds It includes terminal isocyanate group-containing compounds obtained by.

  The isocyanate compound may be a blocked isocyanate. Examples of isocyanate blocking agents include phenols such as phenol, thiophenol, methylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, oximes such as acetoxime, methylethyl ketoxime, cyclohexanone oxime, methanol, ethanol, propanol , Alcohols such as butanol, halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol, tertiary alcohols such as t-butanol and t-pentanol, ε-caprolactam, δ-valerolactam , Γ-butyrolactam, lactams such as β-propyllactam, and other aromatic amines, imides, acetylacetone, acetoacetate, Active methylene compounds such as Ron acid ethyl ester, mercaptans, imines, ureas, and also such as diaryl compounds sodium bisulfite. The blocked isocyanate is obtained by subjecting an isocyanate compound and an isocyanate blocking agent to an addition reaction by a conventionally known appropriate method.

  The phosphorus-containing hyperbranched polymer of the present invention is used in the fields of flame retardant imparting additives, paints, inks, coating agents, and treating agents such as textile products and paper.

  Hereinafter, in order to describe the present invention in more detail, examples will be described. In the examples, “parts” means “parts by weight”. In addition, the measurement in an Example was performed with the following method.

(1) Number average molecular weight Polystyrene was calculated from the results of GPC measurement using a gel permeation chromatography (GPC) 150c manufactured by Waters with tetrahydrofuran as an eluent at a column temperature of 35 ° C. and a flow rate of 1 ml / min. A converted measured value was obtained. However, Showa Denko Co., Ltd. shodex KF-802, 804, 806 was used for the column.

(2) Acid value 0.2 g of the resin was dissolved in 20 cm ³ of chloroform, and titrated with a 0.1 N potassium hydroxide ethanol solution to obtain an equivalent (equivalent / ton) per 10 ⁶ g of the resin. Phenolphthalein was used as the indicator.

(3) Hydroxyl value 0.2 g of resin was dissolved in a mixed solvent of 50 g of toluene and 50 g of 2-butanone, 4 g of diphenylmethane-4,4′-diisocyanate was added, and the mixture was reacted at 80 ° C. for 2 hours. Subsequently, the residual isocyanate group concentration in the reaction solution was quantified by titration to determine the hydroxyl value. For the value of the hydroxyl value, the equivalent (equivalent / ton) per 10 ⁶ g of the resin was determined. In the case of a phenolic hydroxyl group, since reactivity with an isocyanate group is poor, 0.001 g of dibutyltin dilaurate was used as a catalyst.

(4) Quantitative determination of phosphorus By wet decomposition molybdenum blue colorimetric method. The sample was placed in an Erlenmeyer flask in accordance with the phosphorus concentration in the sample, 3 ml of sulfuric acid, 0.5 ml of perchloric acid and 3.5 ml of nitric acid were added, and the mixture was gradually hydrolyzed with an electric heater over a half day. When the solution becomes clear, it is further heated to produce white sulfuric acid smoke, allowed to cool to room temperature, this decomposition solution is transferred to a 50 ml volumetric flask, 5 ml of 2% ammonium molybdate solution and 2 ml of 0.2% hydrazine sulfate solution. Was added, and the contents were mixed well with pure water. The flask was placed in boiling water for 10 minutes to cause color development by heating, then cooled to room temperature and degassed with ultrasonic waves. The solution was taken in a 10 mm absorption cell, and the absorbance was measured with a spectrophotometer (wavelength 830 nm) using the blank test solution as a control. The phosphorus content was calculated from a calibration curve prepared in advance, and the phosphorus concentration in the data was calculated.

(5) Carboxylic acid methyl ester group and phosphorus-containing functional group end group concentrations
¹ H, ¹³ C-NMR analysis was performed and determined from the integration ratio.

[Example 1]
As a phosphorus-containing compound, HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) manufactured by Sanko Co., Ltd. was used. At room temperature in a reaction vessel, 22 parts of HCA was dissolved in 150 parts of methanol, and 7.2 parts of acrylic acid was gradually added dropwise to this solution over 60 minutes. After completion of the dropwise addition, the mixture was heated to reflux for 5 hours to add HCA to the double bond of acrylic acid. After removing volatile components by drying under reduced pressure, 45 parts of Perstop Bolton H40 (polycondensate of dimethylolpropane having trimethylolpropane as a core) as hyperbranched polyester and 0.01 part of tetrabutoxytitanium as an esterification catalyst The mixture was charged and heated at 170 ° C. for about 3 hours under a nitrogen atmosphere to remove generated water. The composition of the obtained resin was determined by deuterated chloroform by ¹ H-NMR. Further, the number average molecular weight, acid value, and hydroxyl value were measured. For the evaluation of flame retardancy, the oxygen index was measured by Suga Test Instruments Co., Ltd. “Oxygen Index Method Flammability Test Device” in accordance with JIS K7201. The higher the oxygen index, the better the flame retardancy. The results are shown in Table 1.

[Examples 2 to 6]
In Examples 2 and 3, phosphorus-containing hyperbranched polyester was obtained in the same manner as in Example 1 using HCA, acrylic acid, and Bolton H40 used in Example 1. However, although equimolar amounts of HCA and acrylic acid were used, the phosphorus content was changed from that in Example 1.
In Example 4, trimethyl phosphonoacetate ((CH ₃ O) ₂ P (═O) CH ₂ CO ₂ CH ₃ , 16 parts) was added to the hydroxyl group of Bolton H40 (100 parts) used in Example 1 with no solvent, nitrogen It was introduced into the hyperbranched polyester by transesterification at 160 ° C. for 2 hours under an atmosphere.
In Example 5, diphenylphosphinic chloride ((C ₆ H ₅ ) ₂ P (O) Cl ₂ , 20 parts) was reacted with the hydroxyl group of Bolton H40 (100 parts) used in Example 1 at 10 ° C. in chloroform. The generated hydrogen chloride was neutralized with triethylamine. After reprecipitation with diethyl ether, filtration and drying were performed.
In Example 6, the hydroxyl group of Bolton H40 (100 parts) used in Example 1 was added with parahydroxybenzoic acid (17.8 parts) in the absence of solvent, and 0.1 part of tetrabutoxytitanium as a catalyst in a nitrogen atmosphere at 160 ° C. Then, it was introduced into the hyperbranched polyester by an esterification reaction over 3 hours. After cooling the system to 80 ° C., 1.5 times moles of HCA (41.8 parts) of parahydroxybenzoic acid used was added over 30 minutes, and the reaction was further continued for 5 hours. It was confirmed by ¹ H-NMR that HCA was introduced at the ortho position of the phenolic hydroxyl group of the parahydroxybenzoic acid residue. The obtained resin was evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1.

[Comparative Examples 1-3]
In Comparative Example 1, Bolton H40 used in Example 1 was evaluated as it was. The analysis results and the oxygen index measurement results are shown in Table 1.
In Comparative Example 2, as in Example 1, phosphorus-containing hyperbranched polyester was obtained in the same manner as in Example 1 using HCA, acrylic acid, and Bolton H40. However, the content rate of a terminal group is outside the scope of the present invention.
Comparative Example 3 shows a comparison between linear polyester obtained by copolymerizing HCA and itaconic acid adduct. The composition of the linear polyester resin of Comparative Example 3 was such that the acid component was terephthalic acid / isophthalic acid / HCA.itaconic acid 1: 1 adduct (40/40/20 mol%), and the glycol component was ethylene glycol / neopentyl glycol (50 / 50 mol%).

[Example 7]
A reaction vessel was charged with 50 parts of diphenolic acid methyl ester and 0.5 part of zinc acetate as a transesterification catalyst, and heated at 170 ° C. for 30 minutes in a nitrogen atmosphere. Furthermore, the pressure inside the system was gradually reduced, and the reaction was performed at a temperature of 230 ° C. and a pressure of 5 mmHg for 3 hours. The obtained resin was a hyperbranched polyester having a phenolic hydroxyl group as a terminal group, which had been polymerized by a transesterification reaction between the phenolic hydroxyl group and the methyl ester moiety. 20 parts of the obtained polyester was dissolved by heating in 50 parts of toluene, cooled to 50 ° C., and then 5 parts of HCA used in Example 1 was added over 30 minutes. After completion of the addition, the mixture was heated and reacted at 80 ° C. for 5 hours. After evaporating the solvent from the obtained resin solution, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 8]
In the same manner as in Example 6, 20 parts of the hyperbranched polyester having a terminal phenolic hydroxyl group obtained in Example 7 and 9 parts of HCA were reacted. The evaluation results of the obtained resin are shown in Table 1.

[Comparative Example 4]
The hyperbranched polyester having a phenolic hydroxyl group as a terminal group used in Example 7 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 9]
100 parts of the phosphorus-containing hyperbranched polyester obtained in Example 1 was dissolved in 200 parts of methyl ethyl ketone / toluene (1/1 weight ratio), cooled to room temperature, and then 30 parts of a polyisocyanate compound (Coronate HX manufactured by Nippon Polyurethane) was added. added. This solution was applied to a biaxially stretched polyester film having a thickness of 50 μm so that the thickness after drying was 5 μm. After aging at 40 ° C. for 2 days, a flammability test was conducted according to JIS L 1091 fiber product flammability test method A-4 (vertical method). Further, after the aging coat film was boiled for 10 hours, a combustion test was conducted. The results are shown in Table 2.

[Examples 10 to 13] [Comparative Examples 5 and 6]
In Examples 10 to 13, the flame retardant listed in Table 2 was added to the coating liquid in Example 9, and the same coated product as in Example 9 was obtained. A combustion test was conducted in the same manner as in Example 9. In Comparative Example 5, Bolton H40 before introducing phosphorus was used instead of the phosphorus-containing hyperbranched polyester used in Example 9. In Comparative Example 6, the linear phosphorus-containing polyester used in Comparative Example 3 was used. The results are shown in Table 2.
In addition, the phosphorus-free linear polyester used in Examples 12 and 13 has a composition produced by a conventional method having terephthalic acid / isophthalic acid // ethylene glycol / neopentyl glycol (50/50 // 50/50 molar ratio, number An average molecular weight 15000) resin is shown.

[Example 14]
150 parts of the phosphorus-containing hyperbranched polyester obtained in Example 1 was heated to 170 ° C. in a nitrogen atmosphere. 9 parts of phthalic anhydride was added and the reaction was continued for another 30 minutes. 100 parts of the obtained resin was dissolved in 100 parts of methyl ethyl ketone, cooled to room temperature at 50 ° C., and then an aqueous solution in which 3 parts of N-methyldiethanolamine was dissolved in 200 parts of water was added. The obtained self-emulsified liquid was heated to distill off methyl ethyl ketone. 40 parts of water dispersion type polyisocyanate “Aquanate 210” manufactured by Nippon Polyurethane Co., Ltd. and 10 parts of powdered melamine as a flame retardant were added to the obtained water dispersion. This blended solution was coated on a polyester film in the same manner as in Example 9 and evaluated. The evaluation results are shown in Table 2.

[Examples 15 and 16]
In a reaction apparatus equipped with a stirrer, a dropping device, and a cooling tube, 2.7 parts of trimethylolpropane was dissolved in toluene / methyl ethyl ketone / cyclohexanone (40/40/20 weight ratio). To this solution, 133 parts of diisopropanolamine / 50 parts of cyclohexanone and 222 parts of isophorone diisocyanate were simultaneously added dropwise over 30 minutes. After completion of dropping, 0.1 part of dibutyltin dilaurate was added, the temperature was raised to 80 ° C., and the reaction was further continued for 10 hours. From the ¹ H-NMR analysis, the obtained polymer was found to be a hyperbranched polyurethane urea having a hydroxyl group as a terminal group. In Examples 15 and 16, diphenylphosphinic chloride ((C ₆ H ₅ ) ₂ P (O) Cl) used in Example 5 was added to the end group of this hyperbranched polyurethane urea in the same manner as in Example 5 to reduce the modification rate. Changed and reacted. The oxygen index was measured in the same manner as in Example 1. The results are shown in Table 3.

[Comparative Examples 7 to 9]
In Comparative Example 7, the hyperbranched polyurethane urea used in Example 15 was evaluated in the same manner as in Example 1. In Comparative Examples 8 and 9, a hydroxyl-terminated prepolymer was synthesized from isopropanolamine and isophorone diisocyanate in N, N-dimethylacetamide, and this was chain extended with phenylphosphonic dichloride to obtain a linear phosphorus-containing polyurethaneurea. The generated hydrogen chloride was neutralized with triethylamine. After reprecipitation with diethyl ether, filtration, and drying, the same evaluation as in Example 1 was performed. The resin compositions of Comparative Example 8 and Comparative Example 9 are as follows.
Comparative Example 8 Composition: isopropanolamine / isophorone diisocyanate / -OP (= O) (C 6 H 5) -O- (83/222 / 12wt ratio)
Comparative Example 9 Composition: isopropanolamine / isophorone diisocyanate / -OP (= O) (C 6 H 5) -O- (90/222 / 22wt ratio)
The results are shown in Table 3.

  The phosphorus-containing functional group in the table shows the following structure.

含リン官能基II；

含リン官能基III；

含リン官能基IV；

含リン官能基Ｖ；

Phosphorus-containing functional group I;

Phosphorus-containing functional group II;

Phosphorus-containing functional group III;

Phosphorus-containing functional group IV;

Phosphorus-containing functional group V;

  As described above, the phosphorus-containing hyperbranched polyester of the present invention is excellent in flame retardancy, and in particular, a compound containing a curing agent is not only excellent in flame retardancy but also excellent in flame retardancy. It is useful.

Claims (3)

A hyperbranched polymer having a number average molecular weight of 1000 to 50000, wherein 5% or more of the end groups are functional groups represented by the following general formula (1) or (2).

(R ¹ , R ² and R ³ represent a monovalent or divalent organic residue containing no halogen, and R ² and R ³ may be independent functional groups or bonded to each other.)   The hyperbranched polymer according to claim 1, wherein the hyperbranched skeleton is polyester.   A flame retardant resin composition comprising the hyperbranched polymer according to claim 1 or 2 and a flame retardant containing no halogen.