WO2013140947A1 - 難燃性ポリエステルの製造方法および難燃性マスターバッチ - Google Patents
難燃性ポリエステルの製造方法および難燃性マスターバッチ Download PDFInfo
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- WO2013140947A1 WO2013140947A1 PCT/JP2013/054686 JP2013054686W WO2013140947A1 WO 2013140947 A1 WO2013140947 A1 WO 2013140947A1 JP 2013054686 W JP2013054686 W JP 2013054686W WO 2013140947 A1 WO2013140947 A1 WO 2013140947A1
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- component
- flame
- ester
- acid
- retardant polyester
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- KZJBHSXMURQXRM-UHFFFAOYSA-N CP1(Oc(cccc2)c2-c2ccccc12)=O Chemical compound CP1(Oc(cccc2)c2-c2ccccc12)=O KZJBHSXMURQXRM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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 method for producing a flame retardant polyester containing a high concentration of phosphorus.
- the flame retardant polyester obtained by the method of the present invention is useful as a flame retardant masterbatch.
- Patent Document 1 As a method for producing a polyester copolymerized with a phosphorus compound, in addition to a method using a phosphorus compound synthesized in advance (see Patent Document 1), a method using a specific phosphorus compound that is non-ester forming ( Patent Document 2 and Patent Document 3) are known.
- Patent Document 2 discloses a method for producing a flame-retardant polyester in which a specific amount of a specific phosphorus compound and a specific unsaturated aliphatic compound are added before an esterification reaction or an esterification reaction.
- Patent Document 3 discloses flame resistance in which a specific phosphorus compound, a specific unsaturated carboxylic acid or an ester-forming derivative thereof, and a specific amine compound coexist in a reaction system of an esterification reaction or a transesterification reaction.
- a method for producing polyester is disclosed. According to these methods, since it is not necessary to separately produce an ester-forming phosphorus compound copolymerizable with polyester, it is considered that the production cost of the flame-retardant polyester can be considerably reduced.
- the present invention is a method for producing a flame-retardant polyester having a high degree of polymerization and a low copolymerization ratio of the diethylene glycol component and being less colored while containing a high concentration of phosphorus by copolymerization.
- the purpose is to provide.
- the present inventors have found that a specific phosphorus compound, an unsaturated carboxylic acid, or a polyvalent carboxylic acid or an ester-forming derivative thereof and a saturated aliphatic diol or an ester-forming derivative thereof.
- the ester-forming derivative and metal acetate are mixed in the heat and mixed to contain high-concentration phosphorus by copolymerization, while having a high degree of polymerization and a low copolymerization ratio of diethylene glycol components and low coloration and flame retardancy
- polyester can be produced at low cost and have completed the present invention. That is, the present invention is as follows.
- (B) component unsaturated dicarboxylic acid or its ester-forming derivative
- (C) component saturated aliphatic polyhydric alcohol and / or ester-forming derivative mainly composed of ethylene glycol
- (E) component metal acetate metal salt
- (B) component unsaturated dicarboxylic acid or its ester-forming derivative
- (C) component saturated aliphatic polyhydric alcohol and / or ester-forming derivative mainly composed of ethylene glycol
- (E) component metal acetate metal salt
- a method for producing a flame-retardant polyester having:
- a flame retardant masterbatch comprising a flame retardant polyester and a metal acetate,
- the flame retardant polyester is 20 to 60 mol% of the following general formula (2) with respect to a total of 200 mol% of all polyvalent acid components and all polyhydric alcohol components constituting the flame retardant polyester.
- the Co-b value is -5 to 20, and the Co-L value is 50 or more. Flame retardant masterbatch.
- a flame-retardant polyester having a high degree of polymerization and a low copolymerization ratio of the diethylene glycol component and low coloration can be produced at low cost while containing a high concentration of phosphorus by copolymerization.
- the flame retardant polyester obtained by the production method of the present invention as a flame retardant masterbatch, the flame retardant thermoplastic resin composition having high transparency and less coloring without impairing the mechanical properties of the base resin. Can be obtained.
- the present invention includes (A) component: phosphorus compound of general formula (1), (B) component: unsaturated dicarboxylic acid or ester-forming derivative thereof, (C) component: saturated aliphatic diol or ester-forming derivative thereof, Flame retardant polyester having a step (P) of heating and mixing a composition containing (D) component: polyvalent carboxylic acid other than (B) component or ester-forming derivative thereof, and (E) component: acetic acid metal salt. It is related with the manufacturing method. Moreover, it is related with the manufacturing method of the flame-retardant polyester which has the process (Q) which adds (F) component: polymerization catalyst to the composition obtained at process (P), and then heats and pressure-reduces.
- the flame retardant polyester of the present invention is a copolymer of the (B) component adduct of the (A) component, the (C) component, and the (D) component.
- a polymerization catalyst as the component (F) after the esterification reaction and the transesterification reaction.
- the phosphorus compound as the component (A) can stably produce a polyester having a higher degree of polymerization without deactivating the polymerization catalyst as the component (F). Tend to be able to.
- the phosphorus compound of the general formula (1) which is the component (A) used in the present invention is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOP).
- DOP has an effect of imparting flame resistance to polyester, but DOP itself has no ester-forming ability, so it is inactive against ester-forming reaction, and cannot be directly used as a copolymer component of polyester. .
- unsaturated carboxylic acid or ester-forming derivative thereof as component (B) used in the present invention unsaturated monocarboxylic acid such as acrylic acid, crotonic acid, methacrylic acid, maleic acid, fumaric acid, mesaconic acid
- unsaturated dicarboxylic acids such as citraconic acid and itaconic acid
- alkyl esters such as methyl ester and ethyl ester of the unsaturated carboxylic acid
- acid anhydrides such as maleic anhydride, citraconic anhydride and itaconic anhydride.
- unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid or ester-forming derivatives thereof are preferred. These compounds may be used alone or in combination of two or more.
- the phosphorus compound of the general formula (1) as the component (A) and the unsaturated carboxylic acid or the ester-forming derivative thereof as the component (B) are substantially Although it is preferable to use it in an equimolar amount, either one may be in excess or deficiency within a range of 20 mol% with respect to an equimolar amount.
- the component (A) is more than 20 mol% with respect to the component (B)
- the polymerization catalyst is deactivated, and it takes a long time for the polymerization or the color tone of the polyester due to the deactivated catalyst. It tends to cause deterioration and turbidity.
- the amount of each of the component (A) and the component (B) is preferably in a range in which either one is 80 to 120 mol% of the other, particularly preferably 85 to 115 mol%. It is a range.
- the flame-retardant polyester of the present invention it is preferable that 20 to 60 mol% of a dicarboxylic acid component having an organic group represented by the general formula (2) as the component (A) is copolymerized.
- the copolymerization ratio of the dicarboxylic acid component having an organic group represented by the general formula (2) is less than 20 mol%, the flame retardant master batch is added to the base resin in a high proportion in order to sufficiently exert the flame retardant effect. Therefore, the mechanical properties of the blend may be greatly inferior to those of the base resin, which is not preferable.
- the copolymerization ratio of the dicarboxylic acid component having an organic group represented by the general formula (2) is more than 60 mol%, it tends to be difficult to obtain a flame-retardant polyester having a high degree of polymerization. Therefore, the mechanical properties of the blend may be greatly inferior to the mechanical properties of the base resin, which is not preferable.
- the component (D) of the present invention is a polyvalent carboxylic acid other than the component (B) or a derivative thereof.
- the component (D) is preferably mainly composed of an aromatic dicarboxylic acid component or an ester-forming derivative thereof.
- aromatic dicarboxylic acid components include terephthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid.
- Orthophthalic acid isophthalic acid, 5- (alkali metal) sulfoisophthalic acid, diphenic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-dicarboxydiphenyl sulfone, 4,4′-dicarboxydiphenyl ether, 1, Examples thereof include aromatic dicarboxylic acids such as 2-bis (phenoxy) ethane-p, p′-dicarboxylic acid and anthracene dicarboxylic acid, and ester-forming derivatives thereof. Among these aromatic dicarboxylic acids, terephthalic acid, 2 , 6-Naphthalenedicarboxylic acid is preferred.
- the component (C) of the present invention is a saturated aliphatic polyhydric alcohol and / or ester-forming derivative mainly composed of ethylene glycol.
- the component (C) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3- Butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1 , 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-d
- ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol and the like have 2 to 5 carbon atoms. Is preferable in terms of increasing the glass transition point (Tg) of the flame-retardant polyester, and it is preferable that ethylene glycol is mainly 50 mol% or more.
- the flame retardant polyester of the present invention includes trivalent or higher carboxylic acids such as trimellitic acid, trimellitic anhydride and pyromellitic acid, and trivalent or higher alcohols such as glycerin, trimethylolpropane and pentaerythritol. It is preferable to copolymerize a trifunctional or higher polyfunctional component from the viewpoint of increasing the viscosity of the flame retardant polyester, and in particular, a total of 200 mol% of the total polyhydric acid component and the total polyhydric alcohol component constituting the flame retardant polyester.
- the total amount of the polyvalent carboxylic acid and / or the polyvalent polyol is less than 0.05 mol%, it is difficult to increase the polymerization degree to the target viscosity, and if it is 3 mol% or more, the hyperbranching of the polyester becomes excessive, May cause gelation.
- the total amount of the polyvalent carboxylic acid and / or the polyvalent polyol is preferably 0.05 to 3 mol%, more preferably 0.1 to 2 mol%.
- the metal acetate of the component (E) of the present invention is preferably an alkali metal salt, alkaline earth metal salt, transition metal salt or the like of acetic acid.
- sodium acetate, lithium acetate, cobalt acetate, etc. suppress the color tone of the polyester. This is preferable.
- sodium acetate it is preferable to blend sodium acetate that is 5 to 50 ppm as a sodium atom with respect to the flame-retardant polyester, and more preferably 10 to 30 ppm. If it is 5 ppm or less, the effect of suppressing the copolymerization ratio of the diethylene glycol component tends to be low. Further, if it is 50 ppm or more, resin coloring tends to be strong.
- 5 to 50 ppm of cobalt acetate is preferably added as a cobalt atom, and more preferably 10 to 30 ppm. Below 5 ppm, the effect of lowering Co-b is small. Moreover, the resin bluish becomes strong at 50 ppm or more.
- the polymerization catalyst which is the component (F) of the present invention is not particularly limited, but if a catalyst such as a germanium compound or an aluminum compound is used, the effect of suppressing darkening of the flame-retardant polyester is obtained, and a polyester having a high Co-L value. This is preferable.
- germanium compounds are preferred because of their high polymerization activity.
- the metal acetate added to the reaction system before the esterification reaction or transesterification reaction remains in the polycondensation step. Due to the remaining acetic acid metal salt, the reaction system becomes weakly alkaline and the by-product of diethylene glycol is suppressed. By such an action, an effect that the copolymerization ratio of diethylene glycol to the flame-retardant polyester can be kept low is exhibited.
- the diethylene glycol component in the aliphatic polyol component constituting the flame-retardant polyester of the present invention is preferably 30 mol% or less.
- the Tg of the flame-retardant polyester tends to be reduced, and when it is 30 mol% or more, there is a risk of causing deterioration in mechanical properties or blocking during drying.
- the flame-retardant masterbatch of the present invention must contain the flame-retardant polyester of the present invention and a metal acetate metal salt, and may contain other resins, compatibilizers and / or various additives.
- a coloring or antioxidant function can be added to the flame retardant masterbatch by blending a pigment or an antioxidant as an additive.
- effects such as simplification of the melt-kneading process and homogenization of the flame-retardant resin composition can be expected by blending other resins and compatibilizers that are highly compatible with the base resin.
- the flame retardant masterbatch of the present invention preferably has a moisture content of 0.1% by weight or less, further 0.05% by weight or less, and further 0.03% by weight or less. If the moisture content is 0.1% by weight or less, it is sufficiently dried, and blocking and decomposition tend to be suppressed.
- a flame-retardant thermoplastic resin composition containing a predetermined amount of phosphorus can be produced by mixing the flame-retardant masterbatch of the present invention and a thermoplastic resin (base resin).
- the flame retardant masterbatch of the present invention preferably has an L value (whiteness) measured by a Hunter color difference meter of 50 or more, and more preferably 55 or more.
- the b value measured with a Hunter color difference meter is preferably ⁇ 5 or more and 20 or less, more preferably 15 or less and 10 or less.
- the blending ratio of the flame retardant masterbatch with respect to the base resin can be appropriately adjusted depending on the phosphorus content desired by the flame retardant thermoplastic resin composition after blending. 5 to 90% by weight is preferable. Further, it is preferably 1 to 50% by weight, more preferably 10 to 30% by weight.
- the phosphorus content in the flame-retardant thermoplastic resin composition is not particularly limited, but it is effective in terms of flame retardancy when it is 1000 ppm or more, further 2000 ppm or more, and further 4000 ppm or more.
- thermoplastic resin can be used as the base resin in which the flame-retardant masterbatch of the present invention is blended.
- optional thermoplastic resins include polyolefin resin, polystyrene resin, acrylonitrile / butadiene / styrene copolymer resin, acrylonitrile / styrene copolymer resin, (meth) acrylic acid / styrene copolymer resin, (meth) acrylic resin, butadiene ⁇ Styrene copolymer resin, polycarbonate resin, polyamide resin, polyarylate resin, polysulfone resin, polyallylsulfone resin, polyethersulfone resin, polyetherimide resin, polyimide resin, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, poly Examples thereof include polyester resins such as lactic acid, polyester carbonate resins, polyester ether resins, polyurethane resins and alloy resins thereof. When applied
- the non-contact side of the ferro plate of the plate-like sample was analyzed by fluorescent X-ray using a fluorescent X-ray analyzer system 3270 manufactured by Rigaku Corporation to determine the phosphorus concentration.
- (2) Intrinsic viscosity The intrinsic viscosity of the sample was measured at 30 ° C. in a phenol / 1,1,2,2-tetrachloroethane mixed solution (weight ratio (3/2)).
- (3) Color value The color value of the sample was measured with a Hunter color difference meter. The larger the Co-L value, the stronger the whiteness, and the larger the Co-b value, the stronger the yellowness.
- Glass transition temperature (Tg) annealed from room temperature to 200 ° C.
- the upper limit was measured as 240 minutes.
- (6) Pelletizing method After completion of the polycondensation process, the molten polyester is discharged from the base under nitrogen pressure, extruded into a strand shape, submerged in the cooling water in the water tank containing the cooling water, and then a strand cutter. Pelletized. A substantially cylindrical pellet having a diameter of about 3 mm and a length of about 3 mm was obtained.
- Example 1 The polyhydric acid component and phosphorus compound shown in Table 1 are charged in the proportions shown in Table 1, and the polyhydric alcohol component shown in Table 1 is charged so as to be 2 molar equivalents with respect to the total polyhydric acid component, and under pressure.
- the temperature was raised to 240 ° C. to carry out an esterification reaction.
- 200 ppm of germanium dioxide in terms of germanium atoms is added to the resin, transferred to a polycondensation reaction can, and gradually raised in parallel while increasing the temperature to 265 ° C. over 60 minutes.
- Example 2 and 3 Polyesters were produced in the same manner as in Example 1 using the compounds shown in Table 1 at the ratios shown in Table 1.
- Example 4 A polyester was produced in the same manner as in Example 1 except that the sodium acetate compound was changed to cobalt acetate.
- Comparative Example 1 A polyester was produced in the same manner as in Example 1, except that sodium acetate was not added.
- Example 2 A polyester was produced in the same manner as in Example 1 except that sodium acetate was changed to tributylamine. However, polycondensation did not proceed to the target intrinsic viscosity, and the resulting resin was also poorly colored.
- the copolymerization ratio of diethylene glycol is relatively low at 11 to 20 mol% while having a sufficient phosphorus atom content that provides excellent flame retardancy. It was possible to produce a flame-retardant polyester that was suppressed to a level, had a high degree of polymerization, a high glass transition temperature, and had coloring suppressed.
- Comparative Example 1 is a case where no acetate is used, but the copolymerization ratio of diethylene glycol in the obtained flame-retardant polyester is as high as 34 mol%. For this reason, the glass transition temperature of the obtained polyester was lowered, and blocking occurred in the drying process.
- Comparative Example 2 is a case where tributylamine was added without using an acetate salt, but although the copolymerization ratio of diethylene glycol was suppressed to a relatively low level of 15 mol%, tributylamine lost the polymerization catalyst. Even if the activity was partially raised and the polymerization time was extended, a flame-retardant polyester having a high degree of polymerization could not be produced. In addition, the obtained flame-retardant polyester was colored by tributylamine.
- the flame retardant polyester of the present invention is useful as a flame retardant component to be blended in a flame retardant masterbatch, and is colored by blending the flame retardant masterbatch of the present invention into an arbitrary thermoplastic resin (base resin) and melt-kneading.
- a flame-retardant thermoplastic resin composition can be obtained while suppressing deterioration of mechanical properties.
- the obtained flame retardant thermoplastic resin composition can be used for clothing fibers, industrial material fibers, films, engineering plastics, adhesives, and the like by extrusion molding, injection molding, and the like.
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Abstract
Description
即ち、本発明は以下の通りである。
下記(A)~(E)成分、
(A)成分:下記一般式(1)のリン化合物
(C)成分:エチレングリコールから主としてなる飽和脂肪族多価アルコールおよび/またはエステル形成性誘導体、
(D)成分:(B)成分以外の多価カルボン酸又はそのエステル形成性誘導体、
(E)成分:酢酸金属塩、
を含有する組成物を加熱混合する工程を有する難燃性ポリエステルの製造方法。
下記(A)~(E)成分、
(A)成分:下記一般式(1)のリン化合物、
(C)成分:エチレングリコールから主としてなる飽和脂肪族多価アルコールおよび/またはエステル形成性誘導体、
(D)成分:(B)成分以外の多価カルボン酸又はそのエステル形成性誘導体、
(E)成分:酢酸金属塩、
を含有する組成物を加熱混合する工程(P)、
工程(P)で得られた組成物に(F)成分:重合触媒を添加し次いで加熱し減圧する工程(Q)、
を有する難燃性ポリエステルの製造方法。
(B)成分がマレイン酸、フマル酸および/またはイタコン酸である<1>または<2>に記載の難燃性ポリエステルの製造方法。
難燃性ポリエステルと酢酸金属塩とを含有する難燃マスターバッチであって、
前記難燃性ポリエステルが、該難燃性ポリエステルを構成する全多価酸成分と全多価アルコール成分の合計200モル%に対し、20~60モル%の下記一般式(2)
Co-b値が-5~20、Co-L値が50以上である、
難燃マスターバッチ。
前記難燃性ポリエステル樹脂を構成するジエチレングリコール成分の共重合比率が30モル%以下である<4>に記載の難燃マスターバッチ。
(1)リン濃度:小型電子天秤にて試料樹脂7gを秤量した。フェロ板使用面(鏡面)にアルミリングを並べ、その中に秤量した試料を入れた。試料を載せたフェロ板を270℃の熱風乾燥機に入れ、20分間熱処理した。冷却後、フェロ板よりアルミリングごと、溶融した試料を剥離し、厚さ5mm程度の板状試料を得た。板状試料のフェロ板非接触側をリガク社製蛍光X線分析装置システム3270を用いて蛍光X線分析し、リン濃度を決定した。
(2)極限粘度:試料の極限粘度は、フェノール/1,1,2,2-テトラクロロエタン混合溶液(重量比(3/2))、30℃で測定した。
(3)カラー値:試料のカラー値は、ハンター色差計にて測定した。Co-L値は大きくなるほど白色味の強いこと、Co-b値は大きくなるほど黄色味の強いことを示す。
(4)ガラス転移点温度(Tg):示差走査熱量計(DSC)を用いて、室温から200℃まで20℃/分の昇温速度でアニーリングさせ、液体窒素で急冷後、0℃から200℃まで20℃/分の昇温速度で昇温し、ベースラインと変曲点での接線の交点を測定した。サンプルは試料5mgをアルミニウム押え蓋型容器に入れ、クリンプした。
(5)重合時間
重縮合工程で反応缶の内圧が10hPaに低下した時からポリエステルの極限粘度(IV)が0.67(目標値)±0.03dl/gまで上がるのにかかった時間を重合時間とした。但し、上限を240分として計測した。
(6)ペレタイズ加工方法
重縮合工程終了後に、窒素加圧下で溶融状態のポリエステルを口金から吐出し、ストランド状に押出し、冷却水が入った水槽内の冷却水中を潜らせた後、ストランドカッターでペレタイズした。直径3mm程度、長さ3mm程度の略円柱状のペレットを得た。
〔実施例1〕
表1に示す多価酸成分、リン化合物を、表1に記載の割合で仕込み、表1に示す多価アルコール成分が全多価酸成分に対して2モル当量になるように仕込み、加圧下で温度240℃まで昇温し、エステル化反応を行った。このエステル化反応物に二酸化ゲルマニウムを樹脂に対しゲルマニウム原子換算で200ppm添加し、それを重縮合反応缶に移送し、温度を60分間かけて265℃まで昇温しながら同時並行して圧力を徐々に減じて60分後に1.3hPa以下とした。この条件で攪拌しながらポリエステルが目標の極限粘度(0.67±0.03dl/g)になるまで重縮合反応を行って、リン原子を含有するポリエステルを得た。
〔実施例2、3〕
表1に示す化合物を、表1に示す割合で、実施例1と同様にしてポリエステルを製造した。
〔実施例4〕
酢酸ナトリウム化合物を酢酸コバルトに変更した以外は、実施例1と同様にしてポリエステルを製造した。
〔比較例1〕
酢酸ナトリウムを添加せずに仕込んだ以外は、実施例1と同様にしてポリエステルを製造した。しかし、得られたポリエステルのTgが低く、乾燥温度60℃では、ペレットのブロッキングが確認された。
〔比較例2〕
酢酸ナトリウムをトリブチルアミンに変更した以外は、実施例1と同様にしてポリエステルを製造した。しかし、目標の極限粘度まで重縮合が進まず、得られた樹脂も着色が悪化した。
Claims (5)
- (B)成分がマレイン酸、フマル酸および/またはイタコン酸である請求項1または2に記載の難燃性ポリエステルの製造方法。
- 前記難燃性ポリエステル樹脂を構成するジエチレングリコール成分の共重合比率が30モル%以下である請求項4に記載の難燃マスターバッチ。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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CN201380016178.9A CN104245789A (zh) | 2012-03-23 | 2013-02-25 | 阻燃性聚酯的制造方法及阻燃母炼胶 |
KR1020147015718A KR20140147804A (ko) | 2012-03-23 | 2013-02-25 | 난연성 폴리에스테르의 제조 방법 및 난연성 마스터 배치 |
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JP2012-066755 | 2012-03-23 | ||
JP2012066755 | 2012-03-23 |
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WO2013140947A1 true WO2013140947A1 (ja) | 2013-09-26 |
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JP (1) | JPWO2013140947A1 (ja) |
KR (1) | KR20140147804A (ja) |
CN (1) | CN104245789A (ja) |
TW (1) | TWI598376B (ja) |
WO (1) | WO2013140947A1 (ja) |
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KR102360899B1 (ko) * | 2015-09-30 | 2022-02-08 | 코오롱인더스트리 주식회사 | 난연성 폴리에스테르 필름 |
CN115785632B (zh) * | 2022-11-30 | 2024-01-16 | 美瑞新材料股份有限公司 | 高流动性高韧性pla/pbs共混合金材料及其制备方法 |
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JPH05178975A (ja) * | 1991-12-28 | 1993-07-20 | Toyobo Co Ltd | 耐炎性ポリエステルの製造方法 |
JP2000212266A (ja) * | 1999-01-26 | 2000-08-02 | Nippon Ester Co Ltd | 難燃性ポリエステルの製造方法 |
JP2004043535A (ja) * | 2002-05-14 | 2004-02-12 | Toyobo Co Ltd | 耐炎性ポリエステルの製造方法 |
JP2005194499A (ja) * | 2003-12-09 | 2005-07-21 | Toyobo Co Ltd | マスターバッチ用熱可塑性樹脂組成物およびその成形材料の製造方法およびそれらを用いた熱可塑性樹脂組成物およびその製造方法 |
JP2007145727A (ja) * | 2005-11-24 | 2007-06-14 | Sanko Kk | 新規な有機リン化合物及びその製造方法、並びにポリトリメチレンテレフタレート |
JP2011231178A (ja) * | 2010-04-26 | 2011-11-17 | Nippon Ester Co Ltd | ポリエステルエラストマー樹脂組成物 |
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JP2551663B2 (ja) * | 1989-09-11 | 1996-11-06 | 積水化学工業株式会社 | 脂肪族ポリエステルの製造方法 |
JP2004002515A (ja) * | 2002-05-31 | 2004-01-08 | Mitsubishi Chemicals Corp | ポリエステル樹脂、二軸延伸フィルム及びこれよりなるコンデンサー用絶縁フィルム |
CN101397371A (zh) * | 2003-12-09 | 2009-04-01 | 东洋纺织株式会社 | 母料用热塑性树脂组合物及其成形材料的制造方法 |
JP2006169358A (ja) * | 2004-12-15 | 2006-06-29 | Nippon Ester Co Ltd | 繊維用難燃性ポリエステル及びその製造方法 |
JP2008179714A (ja) * | 2007-01-25 | 2008-08-07 | Teijin Fibers Ltd | 難燃性ポリエステル共重合体組成物及び難燃性ポリエステル繊維 |
JP2010241974A (ja) * | 2009-04-07 | 2010-10-28 | Teijin Fibers Ltd | ポリエステルの製造方法 |
JP2011099004A (ja) * | 2009-11-04 | 2011-05-19 | Teijin Dupont Films Japan Ltd | タッチパネル用ポリエステルフィルム |
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2013
- 2013-02-25 JP JP2013548668A patent/JPWO2013140947A1/ja active Pending
- 2013-02-25 KR KR1020147015718A patent/KR20140147804A/ko not_active Application Discontinuation
- 2013-02-25 WO PCT/JP2013/054686 patent/WO2013140947A1/ja active Application Filing
- 2013-02-25 CN CN201380016178.9A patent/CN104245789A/zh active Pending
- 2013-03-19 TW TW102109683A patent/TWI598376B/zh active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH05178975A (ja) * | 1991-12-28 | 1993-07-20 | Toyobo Co Ltd | 耐炎性ポリエステルの製造方法 |
JP2000212266A (ja) * | 1999-01-26 | 2000-08-02 | Nippon Ester Co Ltd | 難燃性ポリエステルの製造方法 |
JP2004043535A (ja) * | 2002-05-14 | 2004-02-12 | Toyobo Co Ltd | 耐炎性ポリエステルの製造方法 |
JP2005194499A (ja) * | 2003-12-09 | 2005-07-21 | Toyobo Co Ltd | マスターバッチ用熱可塑性樹脂組成物およびその成形材料の製造方法およびそれらを用いた熱可塑性樹脂組成物およびその製造方法 |
JP2007145727A (ja) * | 2005-11-24 | 2007-06-14 | Sanko Kk | 新規な有機リン化合物及びその製造方法、並びにポリトリメチレンテレフタレート |
JP2011231178A (ja) * | 2010-04-26 | 2011-11-17 | Nippon Ester Co Ltd | ポリエステルエラストマー樹脂組成物 |
JP2012111812A (ja) * | 2010-11-22 | 2012-06-14 | Toyobo Co Ltd | ポリエステルエラストマー |
JP2013018942A (ja) * | 2011-07-14 | 2013-01-31 | Unitika Ltd | 難燃性ポリエステル樹脂 |
Also Published As
Publication number | Publication date |
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TWI598376B (zh) | 2017-09-11 |
JPWO2013140947A1 (ja) | 2015-08-03 |
KR20140147804A (ko) | 2014-12-30 |
CN104245789A (zh) | 2014-12-24 |
TW201343712A (zh) | 2013-11-01 |
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