WO2013053086A1 - 一种耐热聚酰胺组合物及其应用 - Google Patents

一种耐热聚酰胺组合物及其应用 Download PDF

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WO2013053086A1
WO2013053086A1 PCT/CN2011/002050 CN2011002050W WO2013053086A1 WO 2013053086 A1 WO2013053086 A1 WO 2013053086A1 CN 2011002050 W CN2011002050 W CN 2011002050W WO 2013053086 A1 WO2013053086 A1 WO 2013053086A1
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Prior art keywords
resistant polyamide
heat
polyamide composition
polyamide resin
component unit
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PCT/CN2011/002050
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English (en)
French (fr)
Inventor
易庆峰
姜苏俊
麦杰鸿
蒋智强
龙杰明
严峡
宁凯军
蔡彤旻
Original Assignee
金发科技股份有限公司
上海金发科技发展有限公司
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Application filed by 金发科技股份有限公司, 上海金发科技发展有限公司 filed Critical 金发科技股份有限公司
Priority to EP11873964.8A priority Critical patent/EP2703449B1/en
Priority to KR1020137033418A priority patent/KR20140043901A/ko
Priority to US14/351,127 priority patent/US9051454B2/en
Priority to JP2014515019A priority patent/JP5706583B2/ja
Publication of WO2013053086A1 publication Critical patent/WO2013053086A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/08—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements

Definitions

  • the present invention relates to a heat resistant polyamide composition and its use, and more particularly to a heat resistant polyamide composition suitable for use in a reflective stent for LEDs. Background technique
  • the LED is a light-emitting device formed by mounting an electroluminescence semiconductor module on a substrate (reflective holder) and encapsulating it with epoxy resin, silica gel, or the like, and has various excellent characteristics such as small size and light weight. Therefore, it can be applied to various lighting devices; it has a service life of up to 100,000 hours; its color is vivid and conspicuous, showing excellent visibility and low power consumption.
  • the reflective holder is required not only to be precisely formed, but also to have good heat resistance. In particular, it is required to obtain a stable high reflectance in the performance of reflected light, and in particular, it is required that the LED holder yellow becomes small and the decrease in reflectance due to heating is small after the assembly and reflow process.
  • a resin composition for a reflective stent for example, Chinese Patent No. CN 02826032. 5 discloses a resin composition for a reflecting plate by adding potassium carbonate fiber or wollastonite to a semi-aromatic polyamide resin. And complete with titanium oxide as needed.
  • the heat resistance and dimensional stability of the resin composition are somewhat good, but there is a drawback that the long-term heat aging property is insufficient and the reflectance is remarkably lowered.
  • U.S. Patent No. US 2008 167 404 A1 discloses an aramid composition and an article made thereof comprising more than 5 wt% of at least one crystalline silicate, greater than 2 wt/.
  • At least one white pigment greater than 1% by weight of at least one optionally functionalized olefin copolymer and aramid, the resin composition having the problem of insufficient initial whiteness and reflectance.
  • the Chinese patent CN 200680011812. X discloses a resin composition for a reflecting plate and a reflecting plate comprising 30-80% polyamide, 10-60 wt%/. Inorganic filler material and 5-50% by weight white pigment. This resin composition has high mechanical strength and high reflectance, but has a large mold shrinkage ratio and a linear expansion ratio, and therefore has a problem of poor dimensional stability.
  • WO 03/085029 discloses a polyamide resin for a light-emitting diode reflective stent using 1,9-diaminodecane as a diamine component, but these polyamide resins cannot sufficiently prevent reflectance in assembly and reflow processes of LEDs. The problem of lowering due to heating.
  • an object of the present invention is to provide a heat-resistant polyamide composition having high whiteness, high reflectance, excellent moldability, low form shrinkage, and dimensional stability.
  • a heat resistant polyamide composition comprising, by weight percent, the following components:
  • Heat resistant polyamide resin 40%-90% .
  • Antioxidant 0.1% to 1%.
  • the heat-resistant polyamide resin comprises a dicarboxylic acid component unit a and a diamine component unit b
  • the dicarboxylic acid component unit a contains an aromatic dicarboxylic acid or a partially aromatic dicarboxylic acid substituted with an aliphatic dicarboxylic acid.
  • the content of the dicarboxylic acid component unit in the heat resistant polyamide resin is more than 25 mol%;
  • the diamine component unit b contains a linear aliphatic diamine component unit having 4 to 20 carbon atoms and/or a branched fat. Between 0. 1 ⁇ 0. 8 ⁇ The ratio of the ratio of the ratio of the ratio of the ratio of 0. 1 ⁇ 0.
  • the heat-resistant polyamide resin comprises a dicarboxylic acid component unit a and a diamine component unit b, and the dicarboxylic acid component unit a contains an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, 1, 4- Phenylenedioxy-diacetic acid, 1, 3-phenylenedioxy-diacetic acid, diphenylmethane-4,4'-dicarboxylic acid, may also include aliphatic dicarboxylic acids, such as malonic acid , dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethyl succinic acid, sebacic acid, Azelaic acid and suberic acid.
  • an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, 1, 4- Phenylenedioxy-diacetic acid, 1, 3-phenylenedioxy-di
  • the diamine component unit b contains a linear aliphatic diamine component unit having 4 to 20 carbon atoms and/or a branched aliphatic diamine component unit and/or an alicyclic diamine component unit; a linear aliphatic diamine component unit, such as 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine 1,11-undecyldiamine or 1,12-dodecacarbodiamine; the branched aliphatic diamine component unit, such as 2-methyl-1,5-pentanediamine, 3-methyl Base-1,5-pentanediamine, 2,4-dimethyl- 1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2, 4, 4- Trimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine or 5-methyl-1,9-diamine; the alicyclic diamine
  • the heat-resistant polyamide resin is a polyamide resin having a relative viscosity in the range of 2. 0 to 3. 5 and a melting point of at least 280 °C.
  • the above heat-resistant polyamide resin can be produced by polycondensation in the prior art.
  • the dicarboxylic acid component unit a and the diamine component unit b can be heated under a nitrogen atmosphere to obtain a prepolymer, and the prepolymer is vacuum dried. It is prepared by solid phase thickening under a nitrogen atmosphere.
  • the ratio of the ratio of the terminal amino group to the terminal carboxyl group of the heat-resistant polyamide resin prepared above must be controlled between 0.1 and 0.8, which can be formed during the preparation process by controlling the temperature of the polymerization of the resin and selecting an appropriate one.
  • the proportion and type of the dicarboxylic acid component unit a and the diamine component unit b of the thermal polyamide resin and the blocking agent can be used for the terminal amino group and the terminal carboxyl group of the heat-resistant polyamide resin.
  • the concentration ratio is appropriately adjusted.
  • the above mineral fiber A is a circular cross section glass fiber, a special-shaped cross-section glass fiber, a wollastonite fiber, a boric acid fiber, a potassium titanate fiber, a calcium carbonate whisker or a barium sulfate whisker, and a circular cross-section chopped glass fiber has a diameter of 11 - 13 ym
  • the profiled section glass fiber comprises a rectangular section, an elliptical section and a silkworm cocoon shaped glass fiber
  • the mineral fiber raft of the invention preferably has a profiled section glass fiber having a flat ratio between 2 and 6.
  • the above-mentioned mineral filler B is titanium oxide or nano-zinc oxide, and the particle diameter of the titanium oxide is 0. 2-0. 3 ⁇ ⁇ , and the nano-zinc oxide has a particle diameter of 20-80 nm and a purity of 98%. '
  • the above light stabilizer is a mixture of one or more of a benzophenone compound, a salicylate compound, and a benzotriazole compound.
  • the above flow modifier is a mixture of one or more of a fluorine-containing polymer, PE wax, EBS, sodium montanate or calcium salt, hyperbranched compound.
  • the above antioxidant is a mixture of one or a combination of a hindered phenol antioxidant, a phosphate antioxidant, and a thioester antioxidant.
  • the preparation method of the above heat-resistant polyamide composition is as follows: First, the heat-resistant polyamide resin is uniformly mixed with an antioxidant, a light stabilizer, a flow modifier, and a mineral filler B according to a weight ratio of one hundred The main feed port of the twin-screw extruder is fed into the extruder, and then the mineral fiber A is fed from the side of the extruder, and the processing temperature is set in the range of 300-340 ° C, and finally the pellet is obtained by extrusion.
  • the heat-resistant polyamide composition prepared by the above method can be produced into a molded article suitable for various uses by a known resin molding method such as injection molding, extrusion molding or blow molding.
  • the above heat-resistant polyamide composition can be applied to a reflective holder for preparing a light source such as a backlight of a liquid crystal display such as a cellular phone, a computer, or a television, a headlight of a motor vehicle, an instrument panel, and a lighting fixture.
  • a light source such as a backlight of a liquid crystal display such as a cellular phone, a computer, or a television, a headlight of a motor vehicle, an instrument panel, and a lighting fixture.
  • the invention has the following advantages:
  • the heat-resistant polyamide composition according to the present invention adjusts the ratio of the terminal amino group and the carboxyl group concentration of the heat-resistant polyamide resin to a specific range, and effectively prevents the heat-resistant polyamide resin combination after the assembly and reflow process.
  • the color of the object turns yellow and reflects Problems such as lower rate, higher initial whiteness, reflectivity, and excellent heat resistance;
  • the heat-resistant polyamide composition of the present invention can remarkably improve the processability by using a specific glass fiber and a flow modifier, and has excellent moldability, low mold shrinkage, and good dimensional stability.
  • the temperature was rapidly raised to 330 ° C for 5 min, then lowered to 50 ° C at a rate of 10 ° C / min, and then increased at a rate of 10 ° C / min.
  • the endothermic peak temperature based on melting is taken as the melting point.
  • the heat-resistant polyamide composition granules to be evaluated were dried at 120 ° C for 4 hours, and then subjected to an injection molding machine equipped with a mold for forming a spiral sample at a cylinder temperature of 320 Torr and a mold temperature of 120 ° C.
  • the pellet was molded to obtain a spiral sample having a width of 5 mm and a thickness of 2.5 mm, and the sample length was read to observe the fluidity of the heat-resistant polyamide composition.
  • the sample is shown in Fig. 1.
  • the mechanical properties were based on ISO test standards.
  • the tensile and bending tests were tested with an Instron electronic universal testing machine and the impact tests were tested with a Zwick cantilever beam impact testing machine.
  • the optical performance test is tested by Color-Eye 7000A spectrophotometer. Through this test, the reflectivity and L, a, b values can be obtained, and the Hunter whiteness value W can be obtained by calculation.
  • the 64mm X 64mm X lmm test piece molded according to the test dimensional stability method has passed 3 times of infrared wave soldering.
  • SMT SMT peak temperature is 265'C.
  • the test piece after SMT is tested by Color-Eye 7000A spectrophotometer, and the reflectivity and Hunter whiteness value W after SMT can be obtained by this test.
  • the ratio of the terminal amino group to the terminal carboxyl group of the heat-resistant polyamide resin is controlled to be 0. Within the range of 1-0.
  • the * polyamide resin is mixed with the antioxidant, light stabilizer, flow modifier and mineral filler B, and then added to the main feed port of the twin-screw extruder.
  • the mineral fiber A is then fed from the side of the extruder, and the processing temperature is set in the range of 3O0-340. C, finally extruding the pellet to obtain a granular resin composition.
  • various physical properties of the obtained resin composition were evaluated, and the results are shown in Table 1.
  • Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Heat-resistant polyamide resin w « 60 60 60 70 60 60 60 60
  • the polyamide composition obtained by the present invention is heat-resistant after assembly and reflow process
  • the amide resin composition has a yellowish color and a low degree of reflectance, and has high initial whiteness and reflectance, excellent heat resistance, and remarkable improvement in processability and dimensional stability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种耐热聚酰胺组合物及其应用，该组合物按重量百分比计，包括如下组分：耐热聚酰胺树脂40%-90%，矿物纤维A 5%-35%，矿物填料B 0-35%，光稳定剂0.1%-1%，流动改性剂0.1%-1%，抗氧剂0.1%-1%。本发明选择端氨基与端羧基浓度比例在0.1~0.8之间的耐热聚酰胺树脂，配合扁平比在2-6之间的异形玻璃纤维、矿物填料B及流动改性剂得到的聚酰胺组合物，不仅具有高的初始白度、反射率和优异的耐热性，而且成型性优良、尺寸稳定性好，可应用于制备便携式电话、计算机、电视等液晶显示的背光、机动车前灯、仪表面板、照明器具等光源的反射支架。

Description

一种耐热聚酰胺组合物及其应用
技术领域
本发明涉及一种耐热聚酰胺组合物及其应用， 特别涉及一种适用于 LED用反射支架的耐 热聚酰胺组合物。 背景技术
LED是一种通过在基板 （反射支架）上搭载一块电致发光的半导体模块并用环氧树脂或 硅胶等进行封装而形成的发光装置， 其具有各种非常优异的特性， 如其体积小质量轻， 因此 可以应用在各种照明设备上； 具有长达 10万个小时的使用寿命； 其色彩鲜明、 显眼， 显示出 优异的目视性， 而且耗电量小。 要获得上述优势， 对反射支架不仅要求能够精密成型， 而且 要求耐热性良好。 尤其是在反射光性能上要求能得到稳定的高反射率， 特别是要求在装配和 回流焊工序后， LED支架黄变小、 因加热引起的反射率的降低小。
现有技术中， 反射支架用树脂组合物， 例如中国发明专利 CN 02826032. 5公开了一种反 射板用树脂组合物， 其通过在半芳香族聚酰胺树脂中加入碳酸钾纤维或硅灰石， 以及根据需 要配合氧化钛完成。 该树脂组合物的耐热性和尺寸稳定性在一定程度上较好， 但是存在抗;长 期热老化性能不足、 反射率降低明显的缺陷。 美国发明专利 US 2008167404A1公开了一 芳 族聚酰胺组合物和其制造的制品， 包含大于 5wt%的至少一种晶体的硅酸盐，大于 2wt/。的至少 一种白色颜料， 大于 lwt%的至少一种任选官能化的烯烃共聚物和芳族聚酰胺， 该树脂组合物 存在初始白度和反射率不足的问题。 中国专利 CN 200680011812. X公开了一种反射板用树脂 组合物及反射板， 包含 30-80^%聚酰胺， 10- 60wt°/。无机填充材料和 5- 50wt%白色颜料。 该树 脂组合物机械强度高、 反射率高， 但是成型收缩率和线膨胀率大， 因此存在尺寸稳定性差的 问题。 世界专利 W0 03/085029公开了采用 1 , 9-二氨基壬烷作为二胺成分的发光二极管反射 支架用聚酰胺树脂， 但是这些聚酰胺树脂不能充分防止在 LED的装配和回流焊工序中反射率 因加热而降低的问题。
发明内容
针对上述现有问题， 本发明的目的在于提供一种高白度、 高反射率、 优良成型性及低成 型收缩率、 尺寸稳定性好的耐热聚酰胺组合物。
为实现上述目的， 本发明采用如下技术方案： 一种耐热聚酰胺组合物， 按重量百分比计， 包括如下组分：
耐热聚酰胺树脂 40%-90% . .
矿物纤维 A 5%-35% 一
矿物填料 B . 0-35%
光稳定剂 0. 1%-1%
流动改性剂 0. 1%-1%
抗氧剂 0. 1%-1%。
其中， 耐热聚酰胺树脂包含二羧酸成分单元 a和二胺成分单元 b，所述二羧酸成分单元 a 包含芳香族二羧酸或者部分芳香族二羧酸被脂肪族二羧酸取代， 二羧酸成分单元在耐热聚酰 胺树脂中的含量大于 25mol%; 所述二胺成分单元 b包含碳原子数为 4〜20的直链脂肪族二胺 成分单元和 /或具有支链的脂肪族二胺成分单元和 /或脂环族二元胺成分单元； 所述耐热聚酰 胺树脂的端氨基与端羧基的浓度比值控制在 0. 1〜0. 8之间。
在上述耐热聚酰胺组合物中， 优选如下组分重量百分比范围：
耐热聚酰胺树脂 60%- 80%
矿物纤维 A 10%- 30%
矿物填料 B 5%- 20%
光稳定剂 0. 1%-0. 5%
流动改性剂 0. 1%-0. 5%
抗氧剂 0. 1%-0. 5%。 上述耐热聚酰胺树脂包含二羧酸成分单元 a和二胺成分单元 b， 所述二羧酸成分单元 a 包含芳香族二羧酸， 例如对苯二甲酸、 间苯二甲酸、 1, 4-亚苯基二氧-二乙酸、 1, 3-亚苯基二 氧-二乙酸、 二苯基甲烷 -4, 4' -二羧酸， 也可以包括脂肪族二元羧酸， 例如丙二酸、 二甲基 丙二酸、 丁二酸、 戊二酸、 己二酸、 庚二酸， 2， 2-二甲基戊二酸、 3, 3-二乙基丁二酸、 壬二 酸、 癸二酸和辛二酸。
所述二胺成分单元 b包含碳原子数为 4〜20的直链脂肪族二胺成分单元和 /或具有支链的 脂肪族二胺成分单元和 /或脂环族二元胺成分单元； 所述直链脂肪族二胺成分单元， 例如 1，4 一丁二胺、 1，6—己二胺、 1, 8—辛二胺、 1, 9—壬二胺、 1, 10—癸二胺、 1，11一十一碳二胺或 1, 12—十二碳二胺； 所述支链脂肪族二元胺成分单元， 例如 2—甲基一 1, 5—戊二胺、 3—甲 基— 1, 5—戊二胺、 2, 4—二甲基一1， 6—己二胺、 2, 2，4一三甲基一 1 , 6—己二胺、 2, 4, 4—三 甲基— 1, 6—己二胺、 2—甲基一 1, 8—辛二胺或 5—甲基一 1, 9一壬二胺； 所述脂环族二元胺 成分单元， 例如环己烷二胺、 甲基环己垸二胺或 4, 4 ' 一二氨基二环己基甲垸。 . 上述耐热聚酰胺树脂为相对粘度范围在 2. 0-3. 5之间、 熔点至少为 280°C的聚酰胺树脂。 上述耐热聚酰胺树脂， 可采用现有技术缩聚制成， 例如可在氮气氛围下， 将二羧酸成分 单元 a和二胺成分单元 b加热得到预聚物， 将预聚物真空干燥后在氮气气氛下固相增粘制备 得到。
上述制备得到的耐热聚酰胺树脂的端氨基与端羧基的浓度比值必需控制在 0. 1〜0. 8之 间， 这可以在制备过程中， 通过控制树脂聚合的温度、 适宜的选择构成耐热聚酰胺树脂的二 羧酸成分单元 a和二胺成分单元 b以及封端剂（如苯甲醛及其衍生物）的构成比例、 种类等， 可对耐热聚酰胺树脂的端氨基与端羧基的浓度比值进行适宜的调整。
上述矿物纤维 A为圆形截面玻璃纤维、 异形截面玻璃纤维、 硅灰石纤维、硼酸纤维、钛酸 钾纤维、 碳酸钙晶须或硫酸钡晶须， 圆形截面短切玻璃纤维的直径为 11- 13 y m， 异形截面玻 璃纤维包括矩形截面、 椭圆形截面以及蚕茧形截面玻璃纤维， 本发明矿物纤维 Α优选扁平比 在 2- 6之间的异形截面玻璃纤维。
上述矿物填料 B为氧化钛或纳米氧化锌， 氧化钛的粒径在 0. 2-0. 3 μ ιη， 纳米氧化锌的粒 径在 20- 80nm， 纯度 98%。 '
上述光稳定剂为二苯甲酮化合物、 水杨酸酯化合物、 苯丙三唑化合物中的一种或几种的^ 混合物。
上述流动改性剂为含氟聚合物、 PE蜡、 EBS、 褐煤酸钠盐或钙盐、 超支化寧合物中的.一 种或几种的混合物。
上述抗氧剂为受阻酚类抗氧剂、 磷酸酯类抗氧剂、 硫代酯类抗氧剂中的一种或几种的混 合物。
上述耐热聚酰胺组合物的制备方法如下所述： 首先将所述的耐热聚酰胺树脂与抗氧剂、 光稳定剂、 流动改性剂及矿物填料 B按重量百分配比混合均匀后从双螺杆挤出机主喂料口加 入到挤出机中， 然后将矿物纤维 A从上述挤出机侧面进料， 加工温度设定范围为 300- 340°C， 最后挤出切粒即得。
通过上述方法制备出的耐热聚酰胺组合物，可通过模塑方法如注塑成型、挤出成型或吹塑 成型等公知的树脂成型法生产出适合各种用途的成型品。
上述的耐热聚酰胺组合物可应用于制备便携式电话、计算机、 电视等液晶显示的背光、机 动车前灯、 仪表面板、 照明器具等光源的反射支架。
本发明与现有技术相比， 具有如下优点：
1 )本发明所述的耐热聚酰胺组合物中将耐热聚酰胺树脂末端氨基和羧基浓度的比例调整 在特定范围内， 有效的防止了在装配和回流焊工序后耐热聚酰胺树脂组合物颜色变黄、 反射 率降低等问题， 具有较高的初始白度、 反射率和优异的耐热性；
2 )本发明所述的耐热聚酰胺组合物通过使用特定的玻璃纤维及流动改性剂， 能显著改善 其加工性能， 成型性优良、 成型收缩率低、 尺寸稳定性好。
具体实施方式
下面通过具体实施方式来说明本发明， 但并不限于此。 实施例和比较例中， 各种物性数 值的测定和评价按以下方法进行。
[末端氨基数量]
取 0.5g聚合物， 加苯酚 45ml及无水甲醇 3ml， 加热回流。 用百里酚蓝作指示剂， 将得到 的样品溶液用 0.01N的盐酸水溶液滴定来测定端氨基数量。
[末端羧基数量]
取 0.5g聚合物， 加邻甲酚 50ml， 回流溶解， 冷却后迅速加入 400 μ ΐ甲醛溶液； 将得到 的样品溶液用 0.1N的氢氧化钾的甲醇溶液滴定来测定端羧基数量。
[相对粘度 η «ι对]
在 50ml 96.5%浓硫酸溶液中溶解聚酰胺树脂 0.5g, 用乌氏粘度计在 25°C ±0.05°C条件下 测定试样溶液的流下时间 t1 ; 同时用乌氏粘度计测定 96.5%浓硫酸溶液的流下时间 t2， 由下式 计算得到相对粘度 η ¾对。
相对 /¾
[熔点 Tm]
使用 PE公司制造的 DSC7, 先快速升温至 330°C恒温 5min， 然后以 10°C/min的速率降 温至 50°C， 再以 10'C/min的速率升温。 将基于熔解的吸热峰值温度作为熔点。
[流动性评价]
将所要评价的耐热聚酰胺组合物造粒料在 120°C干燥 4h后， 用装有成型螺旋状试样的模 具的注射成型机以 320Ό的料筒温度和 120°C的模具温度将料粒成型，得到宽 5mm，厚 2.5mm 的螺旋状样品， 读取样品长度来观察耐热聚酰胺组合物的流动性， 试样如附图 1所示。
[力学性能测试]
力学性能依据 ISO测试标准进行， 拉伸与弯曲测试用 Instron电子万能试验机测试， 冲击 测试用 Zwick悬臂梁冲击试验机测试。
Γ尺寸稳 将所要评价的耐热聚酰胺组合物造粒料在 120'C干燥 4h后， 用装有成型长 64mm、 宽 64mm, 1mm测试片的模具的注射成型机在料筒温度为 320'C和 I20'C模具温度将料粒成型， 得到 64 >< 64乂 1111111的试片。使试片完全干透后测量试片长度【L0]。将该测试片在 23Ό的水中 浸泡 24h测定此时试片长度 [Ll]。
尺寸稳定性 <%) =[(L1-L0)/L0] 100
[光学性能测试： I
光学性能测试采用 Color-Eye 7000A分光光度仪测试， 通过此测试可得到反射率及 L, a, b值， 通过计算可得到亨特白度值 W。
W=100-[(100-L)2+a 2+b2]iy2
[耐热变色实验]
将按照测试尺寸稳定性方法成型得到的 64mm X 64mm X lmm 试片过 3 次红外波峰焊
( SMT)， SMT峰值温度为 265'C。 将过完 SMT后的试片采用 Color-Eye 7000A分光光度仪 测试， 通过此测试可得到过 SMT后的反射率及亨特白度值 W。
[耐热聚酰胺树脂的制备 ] : 在氮气下， 向配有磁力偶合搅拌、 冷凝管、 气相口、 加料口、 压力防爆口的 20L压力釜中加入 3323g (20mol )对苯二甲酸、 3446g (20mol)癸二胺、 73.27g
(0.6mol)苯甲酸、 6.77g (基于原材料的总重量计为 0.1wt%)次磷酸钠、 2.2L去离子水， 氮 气吹扫后升温； 在搅拌下升温至 170°C开始脱水， 脱水完毕再升温至 220Ό , 将反应混合物在
220'C搅拌 lh， 然后边搅拌边升温至 230°C ; 保持 230°C、 2.5MPa的条件下继续反应 2h, 反 应完毕后出料， 得到相对粘度为 1.08预聚物； 将预聚物于 80'C下真空干燥 24h, 然后在 260
'C氮气气氛下固相增粘 10h， 得到耐热聚酰胺树脂， 熔点 320'C， 相对粘度为 2.6， 端氨基含 量为 75mmol/kg, 端羧基含量为 94mmol kg, 此时 [氨基 ]/ [羧基]为 0.8。
通过控制树脂聚合的温度、 调整二羧酸成分单元 a和二胺成分单元 b以及封端剂的构成 比例、 种类等， 对耐热聚酰胺树脂的端氨基与端羧基的浓度比值控制在 0. 1-0. 8范围内。
按照下表 1所示的各组分配比， 将耐 *聚酰胺树脂与抗氧剂、 光稳定剂、 流动改性剂及 矿物填料 B混合均匀后从双螺杆挤出机主喂料口加入到挤出机中， 然后将矿物纤维 A从上述 挤出机侧面进料， 加工温度设定范围为 3O0-340。C， 最后挤出切粒得到粒状树脂组合物。最终 评价所得树脂组合物的各种物性， 其结果见表 1。
表 1 各实施冽及对比例测试结果
实施例 1 实施例 2 实施例 3 实施例 4 对比例 1 对比例 2 对比例 3 耐热聚酰胺树脂 w« 60 60 60 70 60 60 60
【NH2】 mmol/kg 75 65 60 25 75 93 58
[COOH] mmol/kg 94 92 151 200 94 75 45 [NH2J/[COOH】 0.80 0.71 0.40 0.13 0.80 1.24 1.29 熔点 Tm (。C ) 320 325 316 305 320 315 318 相对粘度 η 相对 2.6 2.8 2.2 2.0 2.6 2.5 - 2.7 矿物纤维 A wt% 20 20 20 15 20 20 20 矿物填料 B wt% 19.2 19.2 19.2 14.2 19.2 19.2 19.2 光稳定剂 wt% 0.1 0.1 0.1 0.1 0.1 0.1 0.1 流动改性剂 wt% 0.5 0.5 0.5 0.5 0.5 0.5 0.5 抗氧剂 wt% 0.2 0.2 0.2 0.2 0.2 0.2 0.2 拉伸强度 Mpa 115 1 13 116 108 117 112 114 弯曲强度 Mpa 159 150 161 145 165 155 160 弯曲模量 Mpa 9000 8600 8700 8500 9100 8600 8300 缺口冲击强度 KJ/m2 5.5 6.1 5.2 6.5 5.4 6.6 5.8 螺旋长度 2. 5mm ( 320°C mm) 520 500 540 540 440 520 540 尺寸稳定性 (%) 0.05 0.03 0.06 0 08 0.18 0.09 0.07 初始亨特白度 W 97.1 97.5 96.9 97.2 96.5 95.6 95.8 初始反射率 （460nm %) 96.3 96.8 96.5 95.9 96.1 95.1 94.8
3次 SMT后亨特白度 W 95.9 96.1 95.7 96 95.4 90.1 89.5
3次 SMT后反射率 ( 460nm %) 92.1 92.8 93.1 92.6 91 .9 85.2 84.6 从上述实施例及对比例的测试结果来看， 本发明获得的聚酰胺组合物在装配和回流焊工 序后耐热聚酰胺树脂组合物颜色变黄、 反射率降低的程度较轻， 不仅具有高的初始白度及反 射率， 耐热性能优异， 而且能显著改善其加工性能及尺寸稳定性。

Claims

权利要求书
1、 一种耐热聚酰胺组合物， 其特征在于， 按重量百分比计， 包括如下组分：
耐热聚酰胺树脂 40%- 90%
矿物纤维 A 5%- 35%
矿物填料 B 0-35%
光稳定剂 0. 1%-1%
流动改性剂 0. 1%-1%
抗氧剂 0. 1%-1%
其中， 耐热聚酰胺树脂包含二羧酸成分单元 a和二胺成分单元 b，所述二羧酸成分单元 a 包含芳香族二羧酸或者部分芳香族二羧酸被脂肪族二羧酸取代， 二羧酸成分单元在耐热聚酰 胺树脂中的含量大于 25mol%; 所述二胺成分单元 b包含碳原子数为 4 20的直链脂肪族二胺 成分单元和 /或具有支链的脂肪族二胺成分单元和 /或脂环族二元胺成分单元； 所述耐热聚酰 胺树脂的端氨基与端羧基的浓度比值控制在 0. 1 0. 8之间。
2、根据权利要求 1所述的耐热聚酰胺组合物，其特征在于，按重量百分比计，包括如下组分:
耐热聚酰胺树脂 60%-80%
矿物纤维 A 10%-30%
矿物填料 B 5%- 20%
光稳定剂 0. 1%-0. 5%
流动改性剂 0. 1%-0. 5%
抗氧剂 0. 1%- 0. 5%
3、根据权利要求 1或 2所述的耐热聚酰胺组合物， 其特征在于： 所述耐热聚酰胺树脂为相对 粘度范围在 2. 0-3. 5之间、 熔点至少为 280°C的聚酰胺树脂。
4、根据权利要求 1或 2所述的耐热聚酰胺组合物， 其特征在于： 所述矿物纤维 A为圆形截面 玻璃纤维、 异形截面玻璃纤维、 硅灰石纤维、 硼酸纤维、 钛酸钾纤维、 碳酸钙晶须或硫酸钡 晶须。
5、根据权利要求 4所述的耐热聚酰胺组合物， 其特征在于： 所述矿物纤维 A为异形截面玻璃 纤维， 扁平比在 2-6之间。
6、 根据权利要求 1或 2所述的耐热聚酰胺组合物， 其特征在于： 所述矿物填料 B为氧化钛或 纳米氧化锌， 氧化钛的粒径在 0. 2-0. 3 w m， 纳米氧化锌的粒径在 20-80 纯度 98%
7、根据权利要求 1或 2所述的耐热聚酰胺组合物， 其特征在于： 所述光稳定剂为二苯甲酮化 合物、 水杨酸酯化合物、 苯丙三唑化合物中的一种或几种的混合物。
8、 根据权利要求 1或 2所述的耐热聚酰胺组合物， 其特征在于： 所述流动改性剂为含氟聚合 物、 PE蜡、 EBS、 褐煤酸钠盐或钙盐、 超支化聚合物中的一种或几种的混合物。
9、 根据权利要求 1或 2所述的耐热聚酰胺组合物， 其特征在于： 所述抗氧剂为受阻酚类抗氧 剂、 磷酸酯类抗氧剂、 硫代酯类抗氧剂中的一种或几种的混合物。
10、 根据权利要求 1或 2所述的耐热聚酰胺组合物用于制备 LED用反射支架。
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EP2703449A1 (en) 2014-03-05
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