WO2014033946A1 - Condensed phosphate compound-based flame retardant, method for manufacturing same and flame-retardant resin composition - Google Patents
Condensed phosphate compound-based flame retardant, method for manufacturing same and flame-retardant resin composition Download PDFInfo
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- WO2014033946A1 WO2014033946A1 PCT/JP2012/072313 JP2012072313W WO2014033946A1 WO 2014033946 A1 WO2014033946 A1 WO 2014033946A1 JP 2012072313 W JP2012072313 W JP 2012072313W WO 2014033946 A1 WO2014033946 A1 WO 2014033946A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
Definitions
- the present invention relates to a condensed phosphate compound-based flame retardant containing a condensed phosphate compound, a method for producing the same, and a flame retardant resin composition obtained by blending such a flame retardant and a resin.
- the present invention relates to a condensed phosphate compound-based flame retardant having improved high thermal stability and flame retardancy, a method for producing the same, and a flame retardant resin composition containing such a flame retardant and a resin.
- Resin compositions with reduced resin flammability by blending a flame retardant with resin are applied in various fields such as paints, adhesives, electrical and electronic parts, automobiles, and interiors of buildings.
- a flame retardant blended in such a resin composition a red phosphorus flame retardant containing red phosphorus, a phosphorous acid flame retardant containing phosphite, and the like are known.
- Patent Document 1 proposes a useful method for producing aluminum phosphite as a typical phosphite used as a phosphite-based flame retardant.
- condensed melamine phosphate is expected to be a useful flame retardant if it has higher heat resistance than other substances and can further improve the flame retardant effect. For this reason, a technique for further improving the flame retardancy of condensed melamine phosphate has been proposed by forming a condensed phosphate compound containing a predetermined amount of aluminum or zinc in condensed melamine phosphate (for example, Patent Document 5).
- An object of the present invention is to provide a condensed phosphate compound-based flame retardant that can be used, a method for producing such a flame retardant, and a flame retardant resin composition comprising such a flame retardant and a resin.
- the condensed phosphate compound-based flame retardant of the present invention capable of achieving the above object is melamine ( ⁇ (MH) 2 O ⁇ equivalent) and zinc with respect to 1 mol of phosphorus oxide (P 2 O 5 equivalent).
- the molar ratio in terms of ZnO
- ZnO zinc with respect to 1 mol of phosphorus oxide
- M represents a melamine and a and b satisfy
- the condensed phosphate compound-based flame retardant of the present invention comprises melamine [ ⁇ (M ⁇ H) 2 O ⁇ equivalent] and aluminum (Al 2 O 3 equivalent) per 1 mol of phosphorus oxide (P 2 O 5 equivalent).
- x and y respectively, it is represented by the following molecular formula (2).
- M represents melamine and x and y satisfy the following relationship. 0.06 ⁇ x ⁇ 1.5, 0.1 ⁇ y ⁇ 0.33
- the condensed phosphate compound-based flame retardant of the present invention exhibits thermally meltability and / or foamability as its physical properties.
- raw materials are blended so as to satisfy the relationship described in the molecular formula (1) or (2), and this is performed at a temperature of 5 to 200 ° C.
- the reaction product may be synthesized by mixing and then calcined at a temperature of 200 to 350 ° C. for 0.1 to 48 hours.
- a predetermined amount of zinc or aluminum is contained in the condensed melamine phosphate, and the manufacturing conditions are strictly defined, thereby exhibiting high heat resistance and flame retardance that cannot be obtained conventionally, A flame retardant exhibiting physical properties not found in conventional flame retardants can be realized.
- the flame-retardant resin composition formed by blending such a condensed phosphate compound-based flame retardant can be used in various fields.
- a flame retardant suitable for the above-mentioned purpose can be realized with a condensed phosphate compound produced by making the amount of zinc or aluminum to be contained in the condensed melamine phosphate strict and making the production conditions appropriate. Completed the invention.
- a and b shown in the molecular formula (1) above represent a molar ratio of melamine [ ⁇ (M ⁇ H) 2 O ⁇ equivalent] and zinc (ZnO equivalent) to 1 mol of phosphorous oxide (P 2 O 5 equivalent). ing. In the condensed phosphate compound-based flame retardant of the present invention, they need to satisfy a predetermined relationship for the following reason.
- a represents the molar ratio of melamine [ ⁇ (M ⁇ H) 2 O ⁇ conversion] to 1 mol of phosphorus oxide (P 2 O 5 conversion), but the value of a is 0.03 or less or 0.60 When it becomes the above, the flame retardance of a condensed phosphate compound will fall. In addition, as a physical property of the condensed phosphate compound, it does not thermally exhibit meltability or foamability.
- the value of a is preferably 0.05 or more (more preferably 0.1 or more) and 0.55 or less (more preferably 0.50 or less).
- the above b represents the molar ratio of zinc (in terms of ZnO) to 1 mol of phosphorus oxide (in terms of P 2 O 5 ).
- the value of b is 0.8 or less or greater than 1.26, condensed phosphorus The flame retardancy of the acid salt compound is reduced.
- the value of b is appropriate, the physical properties are thermally meltable and foamable, but such physical properties are lowered. Furthermore, loss due to sublimation of melamine during synthesis is large, which is economically disadvantageous.
- the value of b is preferably 0.9 or more (more preferably 1.0 or more) and 1.2 or less (more preferably 1.1 or less).
- X and y represented by the molecular formula (2) are the moles of melamine [ ⁇ (MH) 2 O ⁇ equivalent] and aluminum (Al 2 O 3 equivalent) with respect to 1 mol of phosphorus oxide (P 2 O 5 equivalent). Represents the ratio. In the condensed phosphate compound-based flame retardant of the present invention, these must satisfy a predetermined relationship.
- x represents the molar ratio of melamine [ ⁇ (M ⁇ H) 2 O ⁇ conversion] to 1 mol of phosphorus oxide (P 2 O 5 conversion), and the value of x is 0.06 or less or 1.5
- the flame retardance of a condensed phosphate compound will fall.
- meltability and foamability are thermally reduced.
- loss due to sublimation of melamine during synthesis is large, which is economically disadvantageous.
- the value of x is preferably 0.1 or more (more preferably 0.15 or more) and 1.3 or less (more preferably 1.0 or less).
- the above y represents the molar ratio of aluminum (in terms of Al 2 O 3 ) to 1 mol of phosphorus oxide (in terms of P 2 O 5 ).
- y represents the molar ratio of aluminum (in terms of Al 2 O 3 ) to 1 mol of phosphorus oxide (in terms of P 2 O 5 ).
- the flame retardancy of the condensed phosphate compound is reduced.
- the physical properties are thermally meltable and foamable, but such physical properties are not exhibited.
- the value of y is preferably 0.15 or more (more preferably 0.2 or more) and 0.30 or less (more preferably 0.27 or less).
- the raw materials are blended so as to satisfy the relationship described in the above formula (1) or (2), and the mixture is prepared at a temperature of 5 (room temperature) to 200 ° C.
- the reaction product may be synthesized by mixing at a temperature of 200 to 350 ° C. and then fired for 0.1 to 48 hours.
- the temperature at which the reaction product is synthesized is too high, it becomes difficult to produce fine particles when used as a flame retardant in the form of a partial melt, so it is necessary to set the temperature to 200 ° C. or lower. .
- This temperature is preferably 180 ° C. or lower (more preferably 160 ° C. or lower).
- the temperature at this time is normal temperature (20 ⁇ 15 ° C.) or more from the viewpoint of industrial production, and it can be synthesized without heating from the outside.
- the temperature at which the reaction product is calcined is from the viewpoint of establishing the above-described physical properties (melting property and / or foaming property) and a method for industrially producing fine particles necessary as a flame retardant at low cost. Then, it is necessary to set the temperature to 200 ° C. or higher. However, if this temperature becomes too high, it becomes impossible to obtain a target compound by partially melting and expressing the above-described physical properties. It is necessary to.
- the minimum with a preferable firing temperature is 220 degreeC or more (more preferably 250 degreeC or more), and a preferable upper limit is 330 degrees C or less (more preferably 310 degrees C or less).
- the firing time needs to be at least 0.1 hour or more in order to obtain the desired condensed phosphate compound in the above temperature range, but if it becomes too long, a part of the melt will be melted for 48 hours. Must be within.
- the preferable minimum of baking time is 0.3 hours or more (more preferably 1 hour or more), and a preferable upper limit is 24 hours or less (more preferably 20 hours or less).
- the condensed phosphate compound obtained as described above exhibits physical properties different from those of conventional condensed phosphate compounds. That is, the condensed phosphate compound of the present invention shows that it is in a molten state when it is heated to a high temperature where the flame retardancy of the resin is required, and these physical properties are stable at high temperatures. (High heat resistance). Moreover, when heated at a high temperature, it exhibits a foaming property and exhibits a physical property of forming a foam. Such properties are advantageous for further enhancing the flame retardant effect when used as a flame retardant. These physical properties are different from those of conventional condensed phosphate compounds only by showing at least one of them, but it is preferable that both physical properties are shown.
- the phosphoric acid in the compound is mainly polyphosphoric acid, probably by strictly defining the blending ratio of each component and the production conditions. It is assumed that it exists in the form of salt or metaphosphoric acid.
- ammonium polyphosphate causes ammonia to be eliminated due to heating and shows a partially molten state, but a resin having a higher thermal decomposition temperature than ammonium polyphosphate has a flame-retardant effect. Cannot be expressed.
- melamine polyphosphate has a low flame retardant effect because it does not exhibit meltability or foamability in a temperature range where a flame retardant effect is required.
- few condensed phosphates exhibit meltability, and few exhibit meltability and foamability in a temperature range where a flame retardant effect is required.
- the condensed phosphate compound obtained as described above as a flame retardant and blending a resin, it can be used in various fields such as paints, adhesives, electrical and electronic parts, automobiles, building interiors, etc.
- a flame retardant resin composition is obtained.
- the resin used at this time include acrylic resin, ABS resin, olefin resin, styrene resin, vinyl resin, and PET resin.
- the blending ratio of the flame retardant in the flame retardant resin composition is slightly different depending on the type of flame retardant and resin to be blended, but is about 0.1 to 50% by mass in the entire flame retardant resin composition. It is.
- Example 1 [Preparation of flame retardant] Orthophosphoric acid (85% by mass of H 3 PO 4 ) was gradually added dropwise while mixing melamine and zinc oxide so as to have the ratio shown in Table 1 below. This was heated at 200 ° C. for 8 hours, and further heated at 275 ° C. for 8 hours to prepare various condensed phosphate compounds (flame retardants) (Experiment Nos. 1 to 6). In Table 1, the molar ratio of melamine and zinc to one phosphorus atom is also shown for reference.
- a flame retardant resin composition was prepared by blending the various condensed phosphate compounds obtained above with a resin, and the flame retardancy was evaluated (flame retardancy tests 1 and 2 below).
- the material was put into a mold and placed on a hot press where the hot plate temperature was set to 250 ° C. After confirming that the temperature of the mold side surface exceeded 180 ° C., pressurization was started.
- the molded product was taken out of the mold while being pressurized at about 300 MPa, and a test piece having a length: 150 mm ⁇ width: 10 mm ⁇ thickness: 4 mm was produced.
- Example 2 [Preparation of flame retardant] Mixing melamine, aluminum hydroxide [Al (OH) 3 ] and ammonium dihydrogen phosphate so that the ratio is shown in Table 3 below, while stirring, orthophosphoric acid (85 mass% H 3 PO 4 ) was added. Slowly dropped. This was heated at 200 ° C. for 8 hours, and further heated at 275 ° C. for 8 hours to prepare various condensed phosphate compounds (flame retardants) (Experiment Nos. 8 to 114). In Table 3, the molar ratio of melamine and aluminum to one phosphorus atom is also shown for reference.
- Example 1 The various flame retardants obtained above (Experiment Nos. 8 to 14) were evaluated in the same manner as in Example 1 for meltability and foam formation. Also, a flame retardant resin composition was prepared by blending the various condensed phosphate compounds obtained above with a resin, and the flame retardancy was evaluated in the same manner as in Example 1 (flame retardant resin). The preparation procedure of the composition and the flame retardancy test method are the same as in Example 1). The results are shown in Table 4 below.
- the condensed phosphate compound when blending zinc or aluminum with the condensed phosphate compound, by strictly defining the molar ratio thereof, it exhibits excellent heat resistance and excellent flame retardancy, so that it can be widely used in various fields.
- a simple condensed phosphate compound-based flame retardant can be realized.
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Abstract
A condensed phosphate compound-based flame retardant which is represented by formula (1) or formula (2), wherein a and b are molar ratios of melamine [calculated as {(M-H)2O}] and zinc (calculated as ZnO) with respect to 1 mol of a phosphorus oxide (calculated as P2O5), respectively and x and y are molar ratios of melamine [calculated as {(M-H)2O}] and aluminum (calculated as Al2O3) with respect to 1 mol of a phosphorus oxide (calculated as P2O5), respectively.
a{(M-H)2O}]•b(ZnO)•(P2O5)……(1)
x{(M-H)2O}]•y(Al2O3)•(P2O5)……(2)
Provided that M represents melamine and a, b, x and y satisfy the following relationships.
0.03<a<0.60, 0.8<b≤1.26
0.06<x<1.5, 0.1<y<0.33
Description
本発明は、縮合リン酸塩化合物を含む縮合リン酸塩化合物系難燃剤、およびその製造方法、並びにこのような難燃剤と樹脂を配合してなる難燃性樹脂組成物に関するものであり、特に高い熱安定性と難燃性を改善した縮合リン酸塩化合物系難燃剤、およびその製造方法、並びにこのような難燃剤と樹脂とを配合した難燃性樹脂組成物に関するものである。
The present invention relates to a condensed phosphate compound-based flame retardant containing a condensed phosphate compound, a method for producing the same, and a flame retardant resin composition obtained by blending such a flame retardant and a resin. The present invention relates to a condensed phosphate compound-based flame retardant having improved high thermal stability and flame retardancy, a method for producing the same, and a flame retardant resin composition containing such a flame retardant and a resin.
樹脂に難燃剤を配合することによって、樹脂の燃焼性を低減した樹脂組成物が、塗料、接着剤、電気電子部品、自動車、建築物内装品等、様々な分野において適用されている。このような樹脂組成物に配合される難燃剤としては、赤リンを含む赤リン系難燃剤や亜リン酸塩を含む亜リン酸系難燃剤、等が知られている。例えば、特許文献１には、亜リン酸系難燃剤として用いられる亜リン酸塩の代表的なものとしての亜リン酸アルミニウムを製造するための有用な方法が提案されている。
Resin compositions with reduced resin flammability by blending a flame retardant with resin are applied in various fields such as paints, adhesives, electrical and electronic parts, automobiles, and interiors of buildings. As a flame retardant blended in such a resin composition, a red phosphorus flame retardant containing red phosphorus, a phosphorous acid flame retardant containing phosphite, and the like are known. For example, Patent Document 1 proposes a useful method for producing aluminum phosphite as a typical phosphite used as a phosphite-based flame retardant.
また、非ハロゲン系難燃剤の分野におけるリン酸系難燃剤として、ポリリン酸系アンモニウムやリン酸エステル、リン酸エステル、縮合リン酸エステル等、様々なものが提案されている（例えば、特許文献２～４）。しかしながら、これらの技術で提案されている難燃剤では、２５０℃以上の作業温度まで耐えられないものが多く、また耐熱性が高くても、難燃効果があまり期待できないものが多い。更に、リン酸エステルなどでは、湿度に対する安定性が低いという欠点もある。
Various phosphoric acid flame retardants in the field of non-halogen flame retardants have been proposed, such as polyphosphoric ammonium, phosphoric acid ester, phosphoric acid ester, condensed phosphoric acid ester (for example, Patent Document 2). ~ 4). However, many of the flame retardants proposed in these technologies cannot withstand a working temperature of 250 ° C. or higher, and many flame retardant effects cannot be expected even with high heat resistance. Furthermore, phosphoric acid esters and the like have a drawback of low stability against humidity.
上記した各物質のうち、縮合リン酸メラミンは、耐熱性が他の物質と比べて高く、難燃効果をより向上させることができれば、有用な難燃剤となり得ることが期待される。こうしたことから、縮合リン酸メラミンに所定量のアルミニウムや亜鉛を含有させた縮合リン酸塩化合物を形成することによって、縮合リン酸メラミンの難燃性を更に向上させた技術も提案されている（例えば、特許文献５）。
Among the above substances, condensed melamine phosphate is expected to be a useful flame retardant if it has higher heat resistance than other substances and can further improve the flame retardant effect. For this reason, a technique for further improving the flame retardancy of condensed melamine phosphate has been proposed by forming a condensed phosphate compound containing a predetermined amount of aluminum or zinc in condensed melamine phosphate ( For example, Patent Document 5).
しかしながら、こうした縮合リン酸塩化合物においても、難燃性が改善されているとは言えず、更なる特性改善が望まれているのが実情である。
However, even in such condensed phosphate compounds, it cannot be said that the flame retardancy has been improved, and the actual situation is that further improvement in properties is desired.
本発明は上記の様な事情に着目してなされたものであって、その目的は、２５０℃程度の高温であっても耐熱性に優れると共に、優れた難燃性を示し、各種分野で幅広く使用できるような縮合リン酸塩化合物系難燃剤、およびこのような難燃剤を製造する方法、並びにこうした難燃剤と樹脂とを配合してなる難燃性樹脂組成物を提供することにある。
The present invention has been made paying attention to the above-mentioned circumstances, and its purpose is excellent in heat resistance even at a high temperature of about 250 ° C., and exhibits excellent flame retardancy, and is widely used in various fields. An object of the present invention is to provide a condensed phosphate compound-based flame retardant that can be used, a method for producing such a flame retardant, and a flame retardant resin composition comprising such a flame retardant and a resin.
上記目的を達成することのできた本発明の縮合リン酸塩化合物系難燃剤とは、リン酸化物（Ｐ2Ｏ5換算）１モルに対するメラミン〔｛（Ｍ－Ｈ）2Ｏ｝換算〕および亜鉛（ＺｎＯ換算）のモル比を、夫々ａおよびｂとしたとき、下記分子式（１）で表されることを特徴とする。
ａ｛（Ｍ－Ｈ）2Ｏ｝・ｂ（ＺｎＯ）・（Ｐ2Ｏ5）…（１）
但し、Ｍはメラミンを表し、ａおよびｂが下記の関係を満足する。
０．０３＜ａ＜０．６０、０．８＜ｂ≦１．２６ The condensed phosphate compound-based flame retardant of the present invention capable of achieving the above object is melamine ({(MH) 2 O} equivalent) and zinc with respect to 1 mol of phosphorus oxide (P 2 O 5 equivalent). When the molar ratio (in terms of ZnO) is a and b, respectively, it is represented by the following molecular formula (1).
a {(M−H) 2 O} .b (ZnO). (P 2 O 5 ) (1)
However, M represents a melamine and a and b satisfy | fill the following relationship.
0.03 <a <0.60, 0.8 <b ≦ 1.26
ａ｛（Ｍ－Ｈ）2Ｏ｝・ｂ（ＺｎＯ）・（Ｐ2Ｏ5）…（１）
但し、Ｍはメラミンを表し、ａおよびｂが下記の関係を満足する。
０．０３＜ａ＜０．６０、０．８＜ｂ≦１．２６ The condensed phosphate compound-based flame retardant of the present invention capable of achieving the above object is melamine ({(MH) 2 O} equivalent) and zinc with respect to 1 mol of phosphorus oxide (P 2 O 5 equivalent). When the molar ratio (in terms of ZnO) is a and b, respectively, it is represented by the following molecular formula (1).
a {(M−H) 2 O} .b (ZnO). (P 2 O 5 ) (1)
However, M represents a melamine and a and b satisfy | fill the following relationship.
0.03 <a <0.60, 0.8 <b ≦ 1.26
本発明の縮合リン酸塩化合物系難燃剤は、リン酸化物（Ｐ2Ｏ5換算）１モルに対するメラミン〔｛（Ｍ－Ｈ）2Ｏ｝換算〕およびアルミニウム（Ａｌ2Ｏ3換算）のモル比を、夫々ｘおよびｙとしたとき、下記分子式（２）で表されることを特徴とする。
ｘ｛（Ｍ－Ｈ）2Ｏ｝・ｙ（Ａｌ2Ｏ3）・（Ｐ2Ｏ5）…（２）
但し、Ｍはメラミンを表し、ｘおよびｙが下記の関係を満足する。
０．０６＜ｘ＜１．５、０．１＜ｙ＜０．３３ The condensed phosphate compound-based flame retardant of the present invention comprises melamine [{(M−H) 2 O} equivalent] and aluminum (Al 2 O 3 equivalent) per 1 mol of phosphorus oxide (P 2 O 5 equivalent). When the ratio is x and y, respectively, it is represented by the following molecular formula (2).
x {(M−H) 2 O} · y (Al 2 O 3 ) · (P 2 O 5 ) (2)
However, M represents melamine and x and y satisfy the following relationship.
0.06 <x <1.5, 0.1 <y <0.33
ｘ｛（Ｍ－Ｈ）2Ｏ｝・ｙ（Ａｌ2Ｏ3）・（Ｐ2Ｏ5）…（２）
但し、Ｍはメラミンを表し、ｘおよびｙが下記の関係を満足する。
０．０６＜ｘ＜１．５、０．１＜ｙ＜０．３３ The condensed phosphate compound-based flame retardant of the present invention comprises melamine [{(M−H) 2 O} equivalent] and aluminum (Al 2 O 3 equivalent) per 1 mol of phosphorus oxide (P 2 O 5 equivalent). When the ratio is x and y, respectively, it is represented by the following molecular formula (2).
x {(M−H) 2 O} · y (Al 2 O 3 ) · (P 2 O 5 ) (2)
However, M represents melamine and x and y satisfy the following relationship.
0.06 <x <1.5, 0.1 <y <0.33
本発明の縮合リン酸塩化合物系難燃剤は、その物性として熱的に熔融性および／または発泡性を示すものとなる。
The condensed phosphate compound-based flame retardant of the present invention exhibits thermally meltability and / or foamability as its physical properties.
上記のような縮合リン酸塩化合物系難燃剤を製造するに当たり、前記分子式（１）または（２）式に記載の関係を満足するように原料を配合し、これを５～２００℃の温度で混合することによって、反応生成物を合成し、その後更に２００～３５０℃の温度で０．１～４８時間かけて焼成すればよい。
In producing the condensed phosphate compound-based flame retardant as described above, raw materials are blended so as to satisfy the relationship described in the molecular formula (1) or (2), and this is performed at a temperature of 5 to 200 ° C. The reaction product may be synthesized by mixing and then calcined at a temperature of 200 to 350 ° C. for 0.1 to 48 hours.
上記のような縮合リン酸塩化合物系難燃剤と、オレフィン樹脂またはポリエチレンテレフタレート樹脂を配合することによって、塗料、接着剤、電気電子部品、自動車、建築物内装品等、様々な分野で使用できる有用な難燃性樹脂組成物が得られる。
Useful in various fields such as paints, adhesives, electrical and electronic parts, automobiles, building interiors, etc. by blending the above-mentioned condensed phosphate compound flame retardant with olefin resin or polyethylene terephthalate resin Flame retardant resin composition is obtained.
本発明では、縮合リン酸メラミンに所定量の亜鉛やアルミニウムを含有させると共に、その製造条件を厳密に規定することによって、従来では得られないほどの高い耐熱性と難燃性を発揮し、しかもこれまでの難燃剤にはない物性を示す難燃剤が実現できる。こうした縮合リン酸塩化合物系難燃剤を配合してなる難燃性樹脂組成物は様々な分野で使用できるものとなる。
In the present invention, a predetermined amount of zinc or aluminum is contained in the condensed melamine phosphate, and the manufacturing conditions are strictly defined, thereby exhibiting high heat resistance and flame retardance that cannot be obtained conventionally, A flame retardant exhibiting physical properties not found in conventional flame retardants can be realized. The flame-retardant resin composition formed by blending such a condensed phosphate compound-based flame retardant can be used in various fields.
本発明者らは、前記課題を解決するために様々な角度から検討を重ねた。その結果、縮合リン酸メラミンに含有させる亜鉛またはアルミニウムの量を厳密にすると共に、その製造条件を適切にして製造した縮合リン酸塩化合物では、上記目的に適う難燃剤が実現できることを見出し、本発明を完成した。
The present inventors have studied from various angles in order to solve the above problems. As a result, it was found that a flame retardant suitable for the above-mentioned purpose can be realized with a condensed phosphate compound produced by making the amount of zinc or aluminum to be contained in the condensed melamine phosphate strict and making the production conditions appropriate. Completed the invention.
上記分子式（１）で示されるａおよびｂは、リン酸化物（Ｐ2Ｏ5換算）１モルに対するメラミン〔｛（Ｍ－Ｈ）2Ｏ｝換算〕および亜鉛（ＺｎＯ換算）のモル比を表している。本発明の縮合リン酸塩化合物系難燃剤では、これらが所定の関係を満足する必要があるが、その理由は下記の通りである。
A and b shown in the molecular formula (1) above represent a molar ratio of melamine [{(M−H) 2 O} equivalent] and zinc (ZnO equivalent) to 1 mol of phosphorous oxide (P 2 O 5 equivalent). ing. In the condensed phosphate compound-based flame retardant of the present invention, they need to satisfy a predetermined relationship for the following reason.
ａは、リン酸化物（Ｐ2Ｏ5換算）１モルに対するメラミン〔｛（Ｍ－Ｈ）2Ｏ｝換算〕のモル比を表しているが、ａの値が０．０３以下若しくは０．６０以上となると、縮合リン酸塩化合物の難燃性が低下する。また縮合リン酸塩化合物の物性として、熱的に熔融性や発泡性を示さないものとなる。ａの値は、好ましくは０．０５以上（より好ましくは０．１以上）、０．５５以下（より好ましくは０．５０以下）である。
a represents the molar ratio of melamine [{(M−H) 2 O} conversion] to 1 mol of phosphorus oxide (P 2 O 5 conversion), but the value of a is 0.03 or less or 0.60 When it becomes the above, the flame retardance of a condensed phosphate compound will fall. In addition, as a physical property of the condensed phosphate compound, it does not thermally exhibit meltability or foamability. The value of a is preferably 0.05 or more (more preferably 0.1 or more) and 0.55 or less (more preferably 0.50 or less).
上記ｂは、リン酸化物（Ｐ2Ｏ5換算）１モルに対する亜鉛（ＺｎＯ換算）のモル比を表しているが、ｂの値が０．８以下若しくは１．２６よりも大きくなると、縮合リン酸塩化合物の難燃性が低下する。またｂの値が適正なものでは、その物性として熱的に熔融性や発泡性を示すものとなるが、こうした物性が低下する。更に、合成時にメラミンの昇華によるロスが大きく経済的に不利である。ｂの値は、好ましくは０．９以上（より好ましくは１．０以上）、１．２以下（より好ましくは１．１以下）である。
The above b represents the molar ratio of zinc (in terms of ZnO) to 1 mol of phosphorus oxide (in terms of P 2 O 5 ). When the value of b is 0.8 or less or greater than 1.26, condensed phosphorus The flame retardancy of the acid salt compound is reduced. In addition, when the value of b is appropriate, the physical properties are thermally meltable and foamable, but such physical properties are lowered. Furthermore, loss due to sublimation of melamine during synthesis is large, which is economically disadvantageous. The value of b is preferably 0.9 or more (more preferably 1.0 or more) and 1.2 or less (more preferably 1.1 or less).
上記分子式（２）で示されるｘおよびｙは、リン酸化物（Ｐ2Ｏ5換算）１モルに対するメラミン〔｛（Ｍ－Ｈ）2Ｏ｝換算〕およびアルミニウム（Ａｌ2Ｏ3換算）のモル比を表している。本発明の縮合リン酸塩化合物系難燃剤では、これらが所定の関係を満足する必要がある。
X and y represented by the molecular formula (2) are the moles of melamine [{(MH) 2 O} equivalent] and aluminum (Al 2 O 3 equivalent) with respect to 1 mol of phosphorus oxide (P 2 O 5 equivalent). Represents the ratio. In the condensed phosphate compound-based flame retardant of the present invention, these must satisfy a predetermined relationship.
ｘは、リン酸化物（Ｐ2Ｏ5換算）１モルに対するメラミン〔｛（Ｍ－Ｈ）2Ｏ｝換算〕のモル比を表しているが、ｘの値が０．０６以下若しくは１．５以上となると、縮合リン酸塩化合物の難燃性が低下する。また縮合リン酸塩化合物の物性として、熱的に熔融性や発泡性が低下する。更に、合成時にメラミンの昇華によるロスが大きく経済的に不利である。ｘの値は、好ましくは０．１以上（より好ましくは０．１５以上）、１．３以下（より好ましくは１．０以下）である。
x represents the molar ratio of melamine [{(M−H) 2 O} conversion] to 1 mol of phosphorus oxide (P 2 O 5 conversion), and the value of x is 0.06 or less or 1.5 When it becomes the above, the flame retardance of a condensed phosphate compound will fall. Moreover, as a physical property of the condensed phosphate compound, meltability and foamability are thermally reduced. Furthermore, loss due to sublimation of melamine during synthesis is large, which is economically disadvantageous. The value of x is preferably 0.1 or more (more preferably 0.15 or more) and 1.3 or less (more preferably 1.0 or less).
上記ｙは、リン酸化物（Ｐ2Ｏ5換算）１モルに対するアルミニウム（Ａｌ2Ｏ3換算）のモル比を表しているが、ｙの値が０．１以下若しくは０．３３以上となると、縮合リン酸塩化合物の難燃性が低下する。またｙの値が適正なものでは、その物性として熱的に熔融性や発泡性を示すものとなるが、こうした物性も示さないものとなる。ｙの値は、好ましくは０．１５以上（より好ましくは０．２以上）、０．３０以下（より好ましくは０．２７以下）である。
The above y represents the molar ratio of aluminum (in terms of Al 2 O 3 ) to 1 mol of phosphorus oxide (in terms of P 2 O 5 ). When the value of y is 0.1 or less or 0.33 or more, The flame retardancy of the condensed phosphate compound is reduced. Moreover, when the value of y is appropriate, the physical properties are thermally meltable and foamable, but such physical properties are not exhibited. The value of y is preferably 0.15 or more (more preferably 0.2 or more) and 0.30 or less (more preferably 0.27 or less).
本発明の縮合リン酸塩化合物系難燃剤を製造するに当たり、前記（１）または（２）式に記載の関係を満足するように原料を配合し、これを５（常温）～２００℃の温度で混合することによって、反応生成物を合成し、その後更に２００～３５０℃の温度で０．１～４８時間かけて焼成すればよい。
In producing the condensed phosphate compound-based flame retardant of the present invention, the raw materials are blended so as to satisfy the relationship described in the above formula (1) or (2), and the mixture is prepared at a temperature of 5 (room temperature) to 200 ° C. The reaction product may be synthesized by mixing at a temperature of 200 to 350 ° C. and then fired for 0.1 to 48 hours.
反応生成物を合成するときの温度があまり高くなりすぎると、一部熔融物となって難燃剤として使用する場合に細かい粒子を作製することが困難となるので、２００℃以下とする必要がある。尚、この温度は好ましくは１８０℃以下（より好ましくは１６０℃以下）である。このときの温度は、工業的製造という観点から常温（２０±１５℃）以上であり、特に外部からの加熱をしなくても合成することができる。
If the temperature at which the reaction product is synthesized is too high, it becomes difficult to produce fine particles when used as a flame retardant in the form of a partial melt, so it is necessary to set the temperature to 200 ° C. or lower. . This temperature is preferably 180 ° C. or lower (more preferably 160 ° C. or lower). The temperature at this time is normal temperature (20 ± 15 ° C.) or more from the viewpoint of industrial production, and it can be synthesized without heating from the outside.
反応生成物を焼成するときの温度は、上記のような物性（熔融性および／または発泡性）と、難燃剤として必要な微細な粒子を工業的に安価に製造する方法を確立するという観点からして、２００℃以上とする必要があるが、この温度があまり高くなり過ぎると、一部熔融し上記のような物性を発現して目的とする化合物を得ることができなくなるため、３５０℃以下とする必要がある。尚、焼成温度の好ましい下限は２２０℃以上（より好ましくは２５０℃以上）であり、好ましい上限は３３０℃以下（より好ましくは３１０℃以下）である。
The temperature at which the reaction product is calcined is from the viewpoint of establishing the above-described physical properties (melting property and / or foaming property) and a method for industrially producing fine particles necessary as a flame retardant at low cost. Then, it is necessary to set the temperature to 200 ° C. or higher. However, if this temperature becomes too high, it becomes impossible to obtain a target compound by partially melting and expressing the above-described physical properties. It is necessary to. In addition, the minimum with a preferable firing temperature is 220 degreeC or more (more preferably 250 degreeC or more), and a preferable upper limit is 330 degrees C or less (more preferably 310 degrees C or less).
また、焼成時間については、上記温度範囲で希望する縮合リン酸塩化合物を得るためには少なくとも０．１時間以上とする必要があるが、あまり長くなり過ぎると一部熔融物となるので４８時間以内とする必要がある。尚、焼成時間の好ましい下限は０．３時間以上（より好ましくは１時間以上）であり、好ましい上限は２４時間以下（より好ましくは２０時間以下）である。
Further, the firing time needs to be at least 0.1 hour or more in order to obtain the desired condensed phosphate compound in the above temperature range, but if it becomes too long, a part of the melt will be melted for 48 hours. Must be within. In addition, the preferable minimum of baking time is 0.3 hours or more (more preferably 1 hour or more), and a preferable upper limit is 24 hours or less (more preferably 20 hours or less).
上記のようにして得られる縮合リン酸塩化合物は、従来の縮合リン酸塩化合物とは異なる物性を示すものとなる。即ち、本発明の縮合リン酸塩化合物では、樹脂の難燃化が求められる高温まで加熱されたときに熔融した状態となることを示しており、こうした物性は高温での安定性が良好であること（耐熱性が高い）を示すものである。また、高温で加熱したときに発泡性を示し、発泡体を形成するという物性を示すものである。こうした性質は、難燃剤として使用するときに、難燃効果を更に高める上で有利である。これらの物性は、少なくともどちらか一方を示すだけでも従来の縮合リン酸塩化合物とは異なるものとなるが、両方の物性を示すものであることが好ましい。
The condensed phosphate compound obtained as described above exhibits physical properties different from those of conventional condensed phosphate compounds. That is, the condensed phosphate compound of the present invention shows that it is in a molten state when it is heated to a high temperature where the flame retardancy of the resin is required, and these physical properties are stable at high temperatures. (High heat resistance). Moreover, when heated at a high temperature, it exhibits a foaming property and exhibits a physical property of forming a foam. Such properties are advantageous for further enhancing the flame retardant effect when used as a flame retardant. These physical properties are different from those of conventional condensed phosphate compounds only by showing at least one of them, but it is preferable that both physical properties are shown.
上記のような物性を示す理由については、その全てを解明し得た訳ではないが、おそらく各成分の配合割合および製造条件を厳密に規定することによって、化合物中のリン酸が主にポリリン酸塩やメタリン酸の形態で存在していることによると推察される。これに対し、従来の縮合リン酸塩化合物では、例えばポリリン酸アンモニウムでは、加熱によるアンモニアの脱離が起こり一部熔融状態を示すが、加熱分解温度がポリリン酸アンモニウムより高い樹脂などでは難燃効果を発現させることができない。また、ポリリン酸メラミンでは難燃効果が求められる温度域では、熔融性や発泡性を示さないため、難燃効果が低い。そのほか、縮合リン酸塩では、熔融性を示すものが少なく、難燃効果が求められる温度域では、熔融性と発泡性を示すものがほとんどない。
Although not all of the reasons for the above physical properties have been clarified, the phosphoric acid in the compound is mainly polyphosphoric acid, probably by strictly defining the blending ratio of each component and the production conditions. It is assumed that it exists in the form of salt or metaphosphoric acid. In contrast, with conventional condensed phosphate compounds, for example, ammonium polyphosphate causes ammonia to be eliminated due to heating and shows a partially molten state, but a resin having a higher thermal decomposition temperature than ammonium polyphosphate has a flame-retardant effect. Cannot be expressed. In addition, melamine polyphosphate has a low flame retardant effect because it does not exhibit meltability or foamability in a temperature range where a flame retardant effect is required. In addition, few condensed phosphates exhibit meltability, and few exhibit meltability and foamability in a temperature range where a flame retardant effect is required.
上記のようにして得られた縮合リン酸塩化合物を難燃剤として、樹脂を配合することによって、塗料、接着剤、電気電子部品、自動車、建築物内装品等、様々な分野で使用できる有用な難燃性樹脂組成物が得られるのである。このとき用いる樹脂としては、アクリル樹脂、ＡＢＳ樹脂、オレフィン樹脂、スチレン樹脂、ビニル樹脂、ＰＥＴ樹脂等が挙げられる。
By using the condensed phosphate compound obtained as described above as a flame retardant and blending a resin, it can be used in various fields such as paints, adhesives, electrical and electronic parts, automobiles, building interiors, etc. A flame retardant resin composition is obtained. Examples of the resin used at this time include acrylic resin, ABS resin, olefin resin, styrene resin, vinyl resin, and PET resin.
尚、難燃性樹脂組成物における難燃剤の配合割合は、配合される難燃剤と樹脂の種類によっても多少異なるが、難燃性樹脂組成物全体に占める割合で０．１～５０質量％程度である。
The blending ratio of the flame retardant in the flame retardant resin composition is slightly different depending on the type of flame retardant and resin to be blended, but is about 0.1 to 50% by mass in the entire flame retardant resin composition. It is.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
［実施例１］
[難燃剤の調製]
下記表１に示す割合となるように、メラミンと酸化亜鉛を混合しながら、オルトリン酸（８５質量％のＨ3ＰＯ4）を徐々に滴下した。これを、２００℃で８時間加熱し、更に２７５℃で８時間加熱することによって、各種縮合リン酸塩化合物（難燃剤）を調製した（実験Ｎｏ．１～６）。尚、下記表１には、参考のためにリン１原子に対するメラミンおよび亜鉛のモル比も併記した。 [Example 1]
[Preparation of flame retardant]
Orthophosphoric acid (85% by mass of H 3 PO 4 ) was gradually added dropwise while mixing melamine and zinc oxide so as to have the ratio shown in Table 1 below. This was heated at 200 ° C. for 8 hours, and further heated at 275 ° C. for 8 hours to prepare various condensed phosphate compounds (flame retardants) (Experiment Nos. 1 to 6). In Table 1, the molar ratio of melamine and zinc to one phosphorus atom is also shown for reference.
[難燃剤の調製]
下記表１に示す割合となるように、メラミンと酸化亜鉛を混合しながら、オルトリン酸（８５質量％のＨ3ＰＯ4）を徐々に滴下した。これを、２００℃で８時間加熱し、更に２７５℃で８時間加熱することによって、各種縮合リン酸塩化合物（難燃剤）を調製した（実験Ｎｏ．１～６）。尚、下記表１には、参考のためにリン１原子に対するメラミンおよび亜鉛のモル比も併記した。 [Example 1]
[Preparation of flame retardant]
Orthophosphoric acid (85% by mass of H 3 PO 4 ) was gradually added dropwise while mixing melamine and zinc oxide so as to have the ratio shown in Table 1 below. This was heated at 200 ° C. for 8 hours, and further heated at 275 ° C. for 8 hours to prepare various condensed phosphate compounds (flame retardants) (Experiment Nos. 1 to 6). In Table 1, the molar ratio of melamine and zinc to one phosphorus atom is also shown for reference.
上記で得られた各種縮合リン酸塩化合物について、下記の方法によって熔融性および発泡体形成の評価を行った。
The various condensed phosphate compounds obtained above were evaluated for meltability and foam formation by the following methods.
［熔融性および発泡体形成の評価］
スパチュラに化合物の約０．２ｇを取り分け、ガスバーナによってスパチュラ下部から加熱して、加熱による熔融状態を目視によって観察した。また、加熱後に常温まで冷却してから、発泡体の形成状態を目視によって確認した。そして、下記の基準で評価した。その結果を、下記表２に示す。 [Evaluation of meltability and foam formation]
About 0.2 g of the compound was placed in a spatula, heated from the lower part of the spatula with a gas burner, and the molten state by heating was visually observed. Moreover, after cooling to room temperature after heating, the formation state of the foam was visually confirmed. And it evaluated on the following reference | standard. The results are shown in Table 2 below.
スパチュラに化合物の約０．２ｇを取り分け、ガスバーナによってスパチュラ下部から加熱して、加熱による熔融状態を目視によって観察した。また、加熱後に常温まで冷却してから、発泡体の形成状態を目視によって確認した。そして、下記の基準で評価した。その結果を、下記表２に示す。 [Evaluation of meltability and foam formation]
About 0.2 g of the compound was placed in a spatula, heated from the lower part of the spatula with a gas burner, and the molten state by heating was visually observed. Moreover, after cooling to room temperature after heating, the formation state of the foam was visually confirmed. And it evaluated on the following reference | standard. The results are shown in Table 2 below.
［熔融性の評価基準］
○：熔融した。
△：一部熔融した。
×：熔融しない。 [Evaluation criteria for meltability]
○: Melted.
Δ: Partially melted.
X: Not melted.
○：熔融した。
△：一部熔融した。
×：熔融しない。 [Evaluation criteria for meltability]
○: Melted.
Δ: Partially melted.
X: Not melted.
［発泡体形成の評価基準］
○：発泡体を形成した。
△：発泡体を形成したが、崩れた。
×：発泡体を形成しなかった。 [Evaluation criteria for foam formation]
○: A foam was formed.
Δ: Foam was formed but collapsed.
X: A foam was not formed.
○：発泡体を形成した。
△：発泡体を形成したが、崩れた。
×：発泡体を形成しなかった。 [Evaluation criteria for foam formation]
○: A foam was formed.
Δ: Foam was formed but collapsed.
X: A foam was not formed.
上記で得られた各種縮合リン酸塩化合物を樹脂に配合することによって難燃性樹脂組成物を調製し、その難燃性について評価した（下記難燃性試験１、２）。
A flame retardant resin composition was prepared by blending the various condensed phosphate compounds obtained above with a resin, and the flame retardancy was evaluated (flame retardancy tests 1 and 2 below).
[難燃性試験１]
上記表１に示した各種難燃剤（実験Ｎｏ.１～６）について、ポリエチレンテレフタレート樹脂(「Ｊ１２０」（商品名） 三井石油化学工業（株）製)７５質量部に対して、難燃剤２５質量部となるように混合し、ラボプラストミル［（株）東洋精機製作所製］にて混練した。このとき、ローラミキサ内の温度を２５０℃とし、スクリュで溶融・押し出した。得られたペレットを、７０℃で３時間乾燥した後、射出成形して、長さ：１２５ｍｍ×幅：１３ｍｍ×厚さ：１．５ｍｍの試験片を作製した。 [Flame retardancy test 1]
For various flame retardants (Experiment Nos. 1 to 6) shown in Table 1 above, 25 parts by mass of flame retardant with respect to 75 parts by mass of polyethylene terephthalate resin (“J120” (trade name) manufactured by Mitsui Petrochemical Co., Ltd.) And kneaded in a lab plast mill [manufactured by Toyo Seiki Seisakusho]. At this time, the temperature in the roller mixer was set to 250 ° C. and melted and extruded with a screw. The obtained pellets were dried at 70 ° C. for 3 hours and then injection-molded to produce test pieces of length: 125 mm × width: 13 mm × thickness: 1.5 mm.
上記表１に示した各種難燃剤（実験Ｎｏ.１～６）について、ポリエチレンテレフタレート樹脂(「Ｊ１２０」（商品名） 三井石油化学工業（株）製)７５質量部に対して、難燃剤２５質量部となるように混合し、ラボプラストミル［（株）東洋精機製作所製］にて混練した。このとき、ローラミキサ内の温度を２５０℃とし、スクリュで溶融・押し出した。得られたペレットを、７０℃で３時間乾燥した後、射出成形して、長さ：１２５ｍｍ×幅：１３ｍｍ×厚さ：１．５ｍｍの試験片を作製した。 [Flame retardancy test 1]
For various flame retardants (Experiment Nos. 1 to 6) shown in Table 1 above, 25 parts by mass of flame retardant with respect to 75 parts by mass of polyethylene terephthalate resin (“J120” (trade name) manufactured by Mitsui Petrochemical Co., Ltd.) And kneaded in a lab plast mill [manufactured by Toyo Seiki Seisakusho]. At this time, the temperature in the roller mixer was set to 250 ° C. and melted and extruded with a screw. The obtained pellets were dried at 70 ° C. for 3 hours and then injection-molded to produce test pieces of length: 125 mm × width: 13 mm × thickness: 1.5 mm.
上記で得られた試験片を用いて、米国ＵＬ－９４に規定されている垂直燃焼試験に準じて難燃性の評価を行なった。このＵＬ－９４による燃焼性試験は、規定された寸法の試験片にバーナの炎を当てて試験片の燃焼の程度を調査するものであり、難燃性の等級として、５ＶＡ、５ＶＢ、Ｖ－０、Ｖ－１、Ｖ－２、ＨＢ(難燃性の高いものから順に)に区別されている。
Using the test pieces obtained above, flame retardancy was evaluated according to the vertical combustion test specified in US UL-94. This flammability test according to UL-94 investigates the degree of combustion of a test piece by applying a flame of a burner to a test piece of a prescribed size. As a flame retardant rating, 5VA, 5VB, V- They are classified into 0, V-1, V-2, and HB (in order of increasing flame retardancy).
本発明においては、上記等級でＶ－２以上を合格とした。その結果を、用いた難燃剤の種類と共に、下記表２に示す。尚、下記表２には、実験Ｎｏ．７として、難燃剤を配合していない樹脂（ブランク）の難燃性を評価したものも示した（難燃性試験２においても同じ）。
In the present invention, V-2 or higher in the above grade was accepted. The results are shown in Table 2 below together with the type of flame retardant used. In Table 2 below, Experiment No. 7, the evaluation of the flame retardancy of a resin (blank) containing no flame retardant was also shown (the same applies to the flame retardancy test 2).
［難燃性試験２］
上記表１に示した各種難燃剤（実験Ｎｏ.１～６）について、ポリプロピレン樹脂(「ＰＢ２２２Ａ」（商品名） サンアロマー（株）製：適正溶融温度１８０℃のもの)に木粉（粉砕されたスギ）を分散させたウッドプラスチックと、相溶化剤として（「ユーメックス１０１０」（商品名） 三洋化成工業（株）製)を用い、配合割合が、木粉：３９質量％、樹脂：３９質量％、難燃剤：２０質量％、相溶化剤：２質量％となるように混合し、ラボプラストミル［（株）東洋精機製作所製］にて混練した。このとき、ローラミキサ内の温度を１８０℃とし、回転速度１００ｒｐｍで混練した。またミキサー内への材料投入量を調整することによって、トルクを２段階に調整した。 [Flame retardancy test 2]
Various flame retardants (Experiment Nos. 1 to 6) shown in Table 1 above were pulverized into polypropylene resin ("PB222A" (trade name) manufactured by Sun Allomer Co., Ltd .: with an appropriate melting temperature of 180 ° C). Wood plastic in which cedar is dispersed and (Yumex 1010 (trade name) manufactured by Sanyo Chemical Industries Co., Ltd.) as a compatibilizing agent are used. The mixture was mixed so that the flame retardant was 20% by mass and the compatibilizer was 2% by mass, and kneaded with a Laboplast mill [manufactured by Toyo Seiki Seisakusho]. At this time, the temperature in the roller mixer was 180 ° C. and kneading was performed at a rotation speed of 100 rpm. Further, the torque was adjusted in two stages by adjusting the amount of material charged into the mixer.
上記表１に示した各種難燃剤（実験Ｎｏ.１～６）について、ポリプロピレン樹脂(「ＰＢ２２２Ａ」（商品名） サンアロマー（株）製：適正溶融温度１８０℃のもの)に木粉（粉砕されたスギ）を分散させたウッドプラスチックと、相溶化剤として（「ユーメックス１０１０」（商品名） 三洋化成工業（株）製)を用い、配合割合が、木粉：３９質量％、樹脂：３９質量％、難燃剤：２０質量％、相溶化剤：２質量％となるように混合し、ラボプラストミル［（株）東洋精機製作所製］にて混練した。このとき、ローラミキサ内の温度を１８０℃とし、回転速度１００ｒｐｍで混練した。またミキサー内への材料投入量を調整することによって、トルクを２段階に調整した。 [Flame retardancy test 2]
Various flame retardants (Experiment Nos. 1 to 6) shown in Table 1 above were pulverized into polypropylene resin ("PB222A" (trade name) manufactured by Sun Allomer Co., Ltd .: with an appropriate melting temperature of 180 ° C). Wood plastic in which cedar is dispersed and (Yumex 1010 (trade name) manufactured by Sanyo Chemical Industries Co., Ltd.) as a compatibilizing agent are used. The mixture was mixed so that the flame retardant was 20% by mass and the compatibilizer was 2% by mass, and kneaded with a Laboplast mill [manufactured by Toyo Seiki Seisakusho]. At this time, the temperature in the roller mixer was 180 ° C. and kneading was performed at a rotation speed of 100 rpm. Further, the torque was adjusted in two stages by adjusting the amount of material charged into the mixer.
その後、材料を金型に入れ、熱板温度を２５０℃に設定したホットプレス上に設置した。金型側面の温度が１８０℃を超えたことを確認した後、加圧を開始した。約３００ＭＰａで加圧しながら冷却し、成形物を金型から取り出して、長さ：１５０ｍｍ×幅：１０ｍｍ×厚さ：４ｍｍの試験片を作製した。
Then, the material was put into a mold and placed on a hot press where the hot plate temperature was set to 250 ° C. After confirming that the temperature of the mold side surface exceeded 180 ° C., pressurization was started. The molded product was taken out of the mold while being pressurized at about 300 MPa, and a test piece having a length: 150 mm × width: 10 mm × thickness: 4 mm was produced.
上記で得られた試験片を用いて、ＡＳＴＭ Ｄ ２８６３に規定されている酸素指数に準じて難燃性の評価を行なった。この酸素指数による燃焼性試験は、材料の燃焼持続に必要な最低酸素濃度（容量％）を示すものである。
Using the test piece obtained above, flame retardancy was evaluated according to the oxygen index defined in ASTM D 2863. This flammability test based on the oxygen index indicates the minimum oxygen concentration (volume%) necessary for sustaining combustion of the material.
本発明においては、酸素指数が２６容量％以上を合格とした。その結果を、下記表２に示す。
In the present invention, an oxygen index of 26% by volume or more was accepted. The results are shown in Table 2 below.
この結果から、次のように考察できる。まず実験Ｎｏ．３～５のものでは、縮合リン酸塩化合物におけるモル比ａ，ｂが適切な範囲にあるので、いずれの評価においても良好な難燃性を示していることが分かる。
From this result, it can be considered as follows. First, experiment no. In the cases of 3 to 5, since the molar ratios a and b in the condensed phosphate compound are in an appropriate range, it can be seen that good flame retardancy is exhibited in any evaluation.
これに対し、実験Ｎｏ．１、２、６のものでは、縮合リン酸塩化合物におけるモル比ａ，ｂが適切な範囲から外れており、所望の物性を示さず、良好な難燃性が発揮されていないことが分かる。
In contrast, Experiment No. In the cases of 1, 2, and 6, the molar ratios a and b in the condensed phosphate compound are out of an appropriate range, and the desired physical properties are not exhibited, and good flame retardancy is not exhibited.
［実施例２］
[難燃剤の調製]
下記表３に示す割合となるように、メラミン、水酸化アルミニウム[Ａｌ（ＯＨ）3]およびリン酸２水素アンモニウムを混合し、撹拌しながら、オルトリン酸（８５質量％のＨ3ＰＯ4）を徐々に滴下した。これを、２００℃で８時間加熱し、更に２７５℃で８時間加熱することによって、各種縮合リン酸塩化合物（難燃剤）を調製した（実験Ｎｏ．８～１１４）。尚、下記表３には、参考のために、リン１原子に対するメラミンおよびアルミニウムのモル比も併記した。 [Example 2]
[Preparation of flame retardant]
Mixing melamine, aluminum hydroxide [Al (OH) 3 ] and ammonium dihydrogen phosphate so that the ratio is shown in Table 3 below, while stirring, orthophosphoric acid (85 mass% H 3 PO 4 ) was added. Slowly dropped. This was heated at 200 ° C. for 8 hours, and further heated at 275 ° C. for 8 hours to prepare various condensed phosphate compounds (flame retardants) (Experiment Nos. 8 to 114). In Table 3, the molar ratio of melamine and aluminum to one phosphorus atom is also shown for reference.
[難燃剤の調製]
下記表３に示す割合となるように、メラミン、水酸化アルミニウム[Ａｌ（ＯＨ）3]およびリン酸２水素アンモニウムを混合し、撹拌しながら、オルトリン酸（８５質量％のＨ3ＰＯ4）を徐々に滴下した。これを、２００℃で８時間加熱し、更に２７５℃で８時間加熱することによって、各種縮合リン酸塩化合物（難燃剤）を調製した（実験Ｎｏ．８～１１４）。尚、下記表３には、参考のために、リン１原子に対するメラミンおよびアルミニウムのモル比も併記した。 [Example 2]
[Preparation of flame retardant]
Mixing melamine, aluminum hydroxide [Al (OH) 3 ] and ammonium dihydrogen phosphate so that the ratio is shown in Table 3 below, while stirring, orthophosphoric acid (85 mass% H 3 PO 4 ) was added. Slowly dropped. This was heated at 200 ° C. for 8 hours, and further heated at 275 ° C. for 8 hours to prepare various condensed phosphate compounds (flame retardants) (Experiment Nos. 8 to 114). In Table 3, the molar ratio of melamine and aluminum to one phosphorus atom is also shown for reference.
上記で得られた各種難燃剤（実験Ｎｏ.８～１４）について、実施例１と同様にして、熔融性および発泡体形成の評価を行った。また、上記で得られた各種縮合リン酸塩化合物を樹脂に配合することによって難燃性樹脂組成物を調製し、その難燃性について、実施例１と同様にして評価した（難燃性樹脂組成物の調製手順および難燃性試験方法は実施例１と同じ）。その結果を、下記表４に示す。
The various flame retardants obtained above (Experiment Nos. 8 to 14) were evaluated in the same manner as in Example 1 for meltability and foam formation. Also, a flame retardant resin composition was prepared by blending the various condensed phosphate compounds obtained above with a resin, and the flame retardancy was evaluated in the same manner as in Example 1 (flame retardant resin). The preparation procedure of the composition and the flame retardancy test method are the same as in Example 1). The results are shown in Table 4 below.
この結果から、次のように考察できる。まず実験Ｎｏ．１０～１２のものでは、縮合リン酸塩化合物におけるモル比ｘ，ｙが適切な範囲にあるので、いずれの評価においても良好な難燃性を示していることが分かる。
From this result, it can be considered as follows. First, experiment no. In the case of 10 to 12, since the molar ratio x, y in the condensed phosphate compound is in an appropriate range, it can be seen that in any evaluation, good flame retardancy is exhibited.
これに対し、実験Ｎｏ．８、９、１３、１４のものでは、縮合リン酸塩化合物におけるモル比ｘ，ｙが適切な範囲から外れており、所望の物性を示さず、良好な難燃性が発揮されていないことが分かる。
In contrast, Experiment No. In the case of 8, 9, 13, and 14, the molar ratio x, y in the condensed phosphate compound is out of the appropriate range, the desired physical properties are not exhibited, and good flame retardancy is not exhibited. I understand.
本発明では、縮合リン酸塩化合物に亜鉛やアルミニウムを配合するに際して、それらのモル比を厳密に規定することによって、耐熱性に優れると共に優れた難燃性を示し、各種分野で幅広く使用できるような縮合リン酸塩化合物系難燃剤が実現できる。
In the present invention, when blending zinc or aluminum with the condensed phosphate compound, by strictly defining the molar ratio thereof, it exhibits excellent heat resistance and excellent flame retardancy, so that it can be widely used in various fields. A simple condensed phosphate compound-based flame retardant can be realized.
Claims (5)
- リン酸化物（Ｐ2Ｏ5換算）１モルに対するメラミン〔｛（Ｍ－Ｈ）2Ｏ｝換算〕および亜鉛（ＺｎＯ換算）のモル比を、夫々ａおよびｂとしたとき、下記分子式（１）で表されることを特徴とする縮合リン酸塩化合物系難燃剤。
ａ｛（Ｍ－Ｈ）2Ｏ｝・ｂ（ＺｎＯ）・（Ｐ2Ｏ5）…（１）
但し、Ｍはメラミンを表し、ａおよびｂが下記の関係を満足する。
０．０３＜ａ＜０．６０、０．８＜ｂ≦１．２６ When the molar ratio of melamine [{(MH) 2 O} conversion] and zinc (ZnO conversion) to 1 mol of phosphorus oxide (P 2 O 5 conversion) is a and b, respectively, the following molecular formula (1) A condensed phosphate compound-based flame retardant represented by the formula:
a {(M−H) 2 O} .b (ZnO). (P 2 O 5 ) (1)
However, M represents a melamine and a and b satisfy | fill the following relationship.
0.03 <a <0.60, 0.8 <b ≦ 1.26 - リン酸化物（Ｐ2Ｏ5換算）１モルに対するメラミン〔｛（Ｍ－Ｈ）2Ｏ｝換算〕およびアルミニウム（Ａｌ2Ｏ3換算）のモル比を、夫々ｘおよびｙとしたとき、下記分子式（２）で表されることを特徴とする縮合リン酸塩化合物系難燃剤。
ｘ｛（Ｍ－Ｈ）2Ｏ｝・ｙ（Ａｌ2Ｏ3）・（Ｐ2Ｏ5）…（２）
但し、Ｍはメラミンを表し、ｘおよびｙが下記の関係を満足する。
０．０６＜ｘ＜１．５、０．１＜ｙ＜０．３３ When the molar ratios of melamine [{(MH) 2 O} conversion] and aluminum (Al 2 O 3 conversion) to 1 mol of phosphorus oxide (P 2 O 5 conversion) are x and y, respectively, the following molecular formula A condensed phosphate compound-based flame retardant represented by (2).
x {(M−H) 2 O} · y (Al 2 O 3 ) · (P 2 O 5 ) (2)
However, M represents melamine and x and y satisfy the following relationship.
0.06 <x <1.5, 0.1 <y <0.33 - 熱的に熔融性および／または発泡性を示すものである請求項１または２に記載の縮合リン酸塩化合物系難燃剤。 The condensed phosphate compound-based flame retardant according to claim 1 or 2, which thermally exhibits meltability and / or foamability.
- 請求項１～３に記載の縮合リン酸塩化合物系難燃剤を製造するに当たり、前記（１）または（２）式に記載の関係を満足するように原料を配合し、これを５～２００℃の温度で混合することによって、反応生成物を合成し、その後更に２００～３５０℃の温度で０．１～４８時間かけて焼成することを特徴とする縮合リン酸塩化合物系難燃剤の製造方法。 In producing the condensed phosphate compound-based flame retardant according to claims 1 to 3, raw materials are blended so as to satisfy the relationship described in the above formula (1) or (2), A reaction product is synthesized by mixing at a temperature of, and then calcined at a temperature of 200 to 350 ° C. for 0.1 to 48 hours, and a method for producing a condensed phosphate compound-based flame retardant .
- 請求項１～３に記載の縮合リン酸塩化合物系難燃剤と、オレフィン樹脂またはポリエチレンテレフタレート樹脂を配合したものであることを特徴とする難燃性樹脂組成物。 A flame retardant resin composition comprising the condensed phosphate compound-based flame retardant according to claims 1 to 3 and an olefin resin or a polyethylene terephthalate resin.
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| DE102015009598A1 (en) * | 2015-07-24 | 2017-01-26 | Trupti Dave-Wehner | Process for the preparation of a halogen-free flame retardant |
| JP2017137476A (en) * | 2016-02-02 | 2017-08-10 | 積水化学工業株式会社 | Fire-resistant resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001098161A (en) * | 1999-09-30 | 2001-04-10 | Nippon Chem Ind Co Ltd | Flame retardant resin composition |
| JP2004510863A (en) * | 2000-10-05 | 2004-04-08 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Halogen-free flame retardant composition and flame retardant polyamide composition |
| JP2010534692A (en) * | 2007-08-01 | 2010-11-11 | カテナ アディティヴス ゲーエムベーハー アンド コー． カーゲー | Phosphorus-containing triazine compounds as flame retardants |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001098161A (en) * | 1999-09-30 | 2001-04-10 | Nippon Chem Ind Co Ltd | Flame retardant resin composition |
| JP2004510863A (en) * | 2000-10-05 | 2004-04-08 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Halogen-free flame retardant composition and flame retardant polyamide composition |
| JP2010534692A (en) * | 2007-08-01 | 2010-11-11 | カテナ アディティヴス ゲーエムベーハー アンド コー． カーゲー | Phosphorus-containing triazine compounds as flame retardants |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102015009598A1 (en) * | 2015-07-24 | 2017-01-26 | Trupti Dave-Wehner | Process for the preparation of a halogen-free flame retardant |
| JP2017137476A (en) * | 2016-02-02 | 2017-08-10 | 積水化学工業株式会社 | Fire-resistant resin composition |
| JP2017141463A (en) * | 2016-02-02 | 2017-08-17 | 積水化学工業株式会社 | Fire-resistant resin composition |
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