WO2016107184A1 - 在塑料中具有抗翘曲性能的颜料组合物 - Google Patents

在塑料中具有抗翘曲性能的颜料组合物 Download PDF

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WO2016107184A1
WO2016107184A1 PCT/CN2015/086550 CN2015086550W WO2016107184A1 WO 2016107184 A1 WO2016107184 A1 WO 2016107184A1 CN 2015086550 W CN2015086550 W CN 2015086550W WO 2016107184 A1 WO2016107184 A1 WO 2016107184A1
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pigment
warpage
group
formula
dpp
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PCT/CN2015/086550
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French (fr)
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龙夏株
李秀娟
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先尼科化工（上海）有限公司
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Publication of WO2016107184A1 publication Critical patent/WO2016107184A1/zh

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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
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/004—Diketopyrrolopyrrole dyes
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions

Definitions

  • the present invention relates to a warp-free pigmented pigment composition for plastics.
  • Warpage refers to the deformation phenomenon caused by mold release cooling during plastic injection molding. This causes deformation, shrinkage, and crack formation of the injection molded part, making processing of the material difficult.
  • the main reason for this phenomenon is that the added pigment acts as a nucleating agent, resulting in a non-uniform crystallization shrinkage rate and deformation of the plastic when it is cooled and crystallized.
  • US4889562A mentions the coating of alkylcellulose-coated polymers on the surface of pigments to improve the warpage resistance of pigments
  • US6180694B and US5274010A use polymers such as polyvinyl alcohol polyvinylpyrrolidone to improve the warpage resistance of pigments
  • 7,417,154 discloses the use of a copolymer of acrylic acid to coat the surface of the pigment;
  • US 5,721,759 A mentions the use of a sodium, potassium or ammonium salt of a DPP pigment to modify the surface of the pigment to improve warpage resistance; used in CN1068362C Titanium or a complex of a metal such as zirconium to modify the pigment;
  • 5,738,719 to the pigment is added to the pigment to improve the warpage resistance of the DPP pigment substituted with a cyano group; JP2004083673A, US6409956, US7417154, US2008194742, US20060052490 and CN1509319
  • long-chain derivatives of DPP pigment or quinacridone are added to bulk pigments, such as alkyl thioether group, alkyl benzoate, benzoylalkyl group in the para and meta positions of the benzene ring.
  • a long chain quaternary ammonium salt of an amine, sulfonic acid to improve the warpage resistance of the bulk pigment.
  • novel pigment composition of the present invention having anti-warpage properties in plastic consists of the following weight percentage components:
  • R 1 , R 2 , R 4 , R 5 , 1 , 2 , 3 or 4 groups are R 11 , OR 11 , SR 11 , and R 3 , R 6 , R 7 , R 8 , R 9
  • the substituent of R 10 is H, F, Cl, Br, I, tert-butyl, methyl, cyano, phenyl, nitro or other straight or branched alkyl group having 1 to 4 carbon atoms or Alkoxy, and if only one of R 1 , R 2 , R 4 , R 5 is R 11 , OR 11 , SR 11 , then R 2 and R 4 may not be simultaneously R 11 , OR 11 , SR 11 and H;
  • R 11 is an unsubstituted or halogen-substituted linear alkane having 1 to 30 carbon atoms or a branched alkane group;
  • OR 11 is an unsubstituted or halogen-substituted linear alkane having 1 to 30 carbon atoms or a branched alkoxy group.
  • SR 11 is an unsubstituted or halogen-substituted linear alkane having 1 to 30 carbon atoms or a branched alkylthio group.
  • the new pigment composition having anti-warping properties in plastic consists of the following weight percentage components:
  • DPP pigment having the structural formula of formula (1) 0.03% to 0.1%
  • the bulk pigments are quinacridones, benzimidazolones, azos, anthraquinones, quinophthalones, DPPs, isoindolinones or isoporphyrin pigments;
  • the DPP pigment having the structural formula of formula (1) is selected from the group consisting of:
  • the compound of the formula (1) can be produced by the method reported in the literature of CN1871309A;
  • the preparation method of the present invention is a simple physical mixing.
  • the main feature of the invention is that one or two of the two meta positions on one side of the benzene ring of the DPP structure are added to the bulk pigment, or both the meta and the para are long chained.
  • Alkyl, alkoxy or alkylthio substituted derivatives which greatly improve the warpage resistance of bulk pigments in plastics.
  • (1-1a or 1-1b) structure is synthesized by the method of CN1871309A; wherein: n represents a positive long chain alkyl group;
  • Test method 600 g of polyethylene pellets and 0.6 g of the above pigment mixture were uniformly mixed, dispersed in a single-screw extruder at 200 ° C, and then granulated, and then the masterbatch was injection molded into a disc having a diameter of 15 cm and a thickness of 2.5 cm in an injection molding machine. The disc was kept warm in hot water at 90 ° C for 30 minutes, and placed at room temperature for 24 hours, tested 10 times repeatedly, and the warpage height of 10 injection molded parts was measured and averaged.
  • the test results are as follows:
  • the warpage of the polyethylene sheet was tested by dry-mixing the additive of 19.4 g of the pigment yellow 110 and 0.6 g of the structure of (1-2), and then using the mixture for coloring of the polyethylene sheet.
  • the polyethylene sheet colored with the composition of the present invention has a significantly lower warpage than the pure pigment yellow 110 colored polyethylene sheet.
  • the warp of the polyethylene sheet was tested by uniformly mixing 18 g of the pigment red 254 with 2 g of the additive of the formula (1-3), and then applying the mixture to the coloring of the polyethylene sheet.
  • the polyethylene sheet colored with the composition of the present invention has a significantly lower warpage than the pure pigment red 254 colored polyethylene sheet.
  • the warpage of the polyethylene sheet was tested by uniformly mixing 9.3 g of the pigment yellow 139 and 0.7 g of the structure of the formula (1-4), and then using the mixture for coloring the polyethylene sheet.
  • the polyethylene sheet colored with the composition of the present invention has a significantly lower warpage than the pure pigment yellow 139 colored polyethylene sheet.
  • the warp of the polyethylene sheet was tested by uniformly mixing 9 g of the pigment yellow 109 with 1 g of the additive of the formula (1-5), and then applying the mixture to the coloring of the polyethylene sheet.
  • the polyethylene sheet colored with the composition of the present invention has a significantly lower warpage than the pure pigment yellow 109 colored polyethylene sheet.
  • a polyethylene sheet colored with the composition of the present invention has a significantly lower warpage than a pure pigment red 255 colored polyethylene sheet.

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

Abstract

本发明公开了一种在塑料中具有抗翘曲性能的颜料组合物，由具有式(1)结构通式的DPP和本体颜料组成；本发明在本体颜料中加入DPP结构的其中一侧苯环上两个间位的一个或两个，或者两个间位以及对位都被长链的烷基、烷氧基或者烷硫基取代的衍生物，从而大大提高了本体颜料在塑料中的抗翘曲性能。

Description

在塑料中具有抗翘曲性能的颜料组合物 技术领域
本发明涉及一种用于塑料的无翘曲着色的颜料组合物。
背景技术
翘曲(warpage)是指塑料注塑成型时，脱模冷却发生的变形现象。由此会导致注塑件的变形、收缩和裂纹的形成，使材料的加工变得困难。这一现象的主要原因为加入的颜料起到成核剂的作用，导致的塑料冷却结晶时各向结晶收缩速率不均匀，从而变形。
之前已经有许多国内外公司提出了改进和消除此现象的方法。US4889562A中提及在颜料表面包覆烷基纤维素的聚合物来提高颜料的抗翘曲性能；US6180694B和US5274010A中使用聚乙烯醇聚乙烯吡咯烷酮等聚合物来提高颜料的抗翘曲性能；US6409956和US7417154中提及使用丙烯酸的共聚物对颜料表面进行包覆改性；US5271759A中提及使用DPP颜料的钠盐、钾盐或者铵盐来对颜料表面进行改性提高抗翘曲性能；CN1068362C中使用钛或者是锆等金属的配合物来对颜料进行改性；US5738719中在颜料中加入苯环被氰基取代的DPP颜料来改进抗翘曲性能；JP2004083673A、US6409956、US7417154、US2008194742、US20060052490和CN1509319中先后提到了在本体颜料中加入DPP颜料或者喹吖啶酮的长链衍生物，如在苯环的对位和间位分别含烷基硫醚基、苯甲酸烷基酯、苯甲酰烷基胺，磺酸的长链季铵盐来改善本体颜料的抗翘曲性能。
上述专利存在的一个共同的问题是：翘曲度不能满足相关领域的需要，需要进一步的提高。
发明内容
本发明的目的在于发明一种在塑料中具有抗翘曲性能的新颜料组合物，以克服现有技术存在的缺陷。
本发明所述的在塑料中具有抗翘曲性能的新颜料组合物，由如下重量百分比的组分组成：
具有式(1)结构通式的DPP 0.01％～99.99％
本体颜料              0.01％～99.99％
Figure PCTCN2015086550-appb-000001
在R1，R2，R4，R5中，有1、2、3或者4个基团为R11、OR11、SR11，而R3，R6，R7，R8，R9，R10的取代基为H，F，Cl，Br，I，叔丁基，甲基，氰基，苯基，硝基或者其他含1～4个碳原子的直链或者支链烷基或者烷氧基，且如果R1，R2，R4，R5仅一个为R11、OR11、SR11时，则R2和R4不能同时为R11、OR11、SR11和H；
R11为没有取代的或者卤素取代的碳原子数1～30的直链烷烃或者含支链的烷烃基团；
OR11为没有取代的或者卤素取代的碳原子数1～30的直链烷烃或者含支链的烷氧基团
SR11为没有取代的或者卤素取代的碳原子数1～30的直链烷烃或者含支链的烷硫基团。
优选的，所述的在塑料中具有抗翘曲性能的新颜料组合物，由如下重量百分比的组分组成：
具有式(1)结构通式的DPP颜料 0.03％～0.1％
本体颜料                   余量
所述的本体颜料为喹吖啶酮类，苯并咪唑酮类，偶氮类，蒽醌类，喹酞酮累，DPP类，异吲哚啉酮或异吲哚啉类颜料；
优选的，具有式(1)结构通式的DPP颜料选自：
Figure PCTCN2015086550-appb-000002
Figure PCTCN2015086550-appb-000003
式(1)的化合物，可采用CN1871309A文献报道的方法制备；
本发明的制备方法为简单的物理混合。
本发明的有益效果是：本发明的主要特征是在本体颜料中加入DPP结构的其中一侧苯环上两个间位的一个或两个，或者两个间位以及对位都被长链的烷基、烷氧基或者烷硫基取代的衍生物，从而大大提高了本体颜料在塑料中的抗翘曲性能。
具体实施方式
实施例1
将38g颜料红254与2g式(1-1a或者1-1b)结构的添加物干混均匀，在将该混合物用于聚乙烯板的着色，测试聚乙烯板的翘曲度。
Figure PCTCN2015086550-appb-000004
(1-1a或者1-1b)结构的添加物是采用CN1871309A的方法合成；其中：n代表正长链烷基；
测试方法：将600g聚乙烯粒和0.6g上述颜料混合物混合均匀，在单螺杆挤出机中200℃分散后造粒，然后将色母粒在注塑机中注塑成直径15cm厚2.5cm的圆盘，该圆盘继续在90℃的热水中保温30分钟，并放置在室温中24小时，反复测试10次，测量10个注塑件的翘曲高度并取平均值。测试结果如下：
Figure PCTCN2015086550-appb-000005
实施例2
向将19.4g颜料黄110与0.6g(1-2)结构的添加物干混均匀，再将该混合物用于聚乙烯板的着色，测试聚乙烯板的翘曲度。
Figure PCTCN2015086550-appb-000006
(1-2)结构的添加物是采用CN1871309A的方法合成；其中：n代表正十二烷基，采用与实施例1相同的方法测试，结果如下：
实施例 翘曲度/mm
不含添加物 42.0
含添加物 6.8
用本发明的组合物着色的聚乙烯板比纯颜料黄110着色的聚乙烯板具有明显的更低的翘曲度。
实施例3
向将18g颜料红254与2g式(1-3)结构的添加物干混均匀，再将该混合物用于聚乙烯板的着色，测试聚乙烯板的翘曲度。
Figure PCTCN2015086550-appb-000007
(1-3)结构的添加物是采用CN1871309A的方法合成；其中：n为代表正十二烷基，结果如下：
实施例 翘曲度/mm
不含添加物 39.6
含添加物 7.5
用本发明的组合物着色的聚乙烯板比纯颜料红254着色的聚乙烯板具有明显的更低的翘曲度。
实施例4
向将9.3g颜料黄139与0.7g式(1-4)结构的添加物干混均匀，再将该混合物用于聚乙烯板的着色，测试聚乙烯板的翘曲度。
Figure PCTCN2015086550-appb-000008
(1-4)结构的添加物是采用CN1871309A的方法合成；其中： n为代表正十二烷基，结果如下：
实施例 翘曲度/mm
不含添加物 44.1
含添加物 9.5
用本发明的组合物着色的聚乙烯板比纯颜料黄139着色的聚乙烯板具有明显的更低的翘曲度。
实施例5
向将9g颜料黄109与1g式(1-5)结构的添加物干混均匀，再将该混合物用于聚乙烯板的着色，测试聚乙烯板的翘曲度。
Figure PCTCN2015086550-appb-000009
(1-5)结构的添加物是采用CN1871309A的方法合成；其中：n为代表正十二烷基，结果如下：
实施例 翘曲度/mm
不含添加物 40.9
含添加物 8.0
用本发明的组合物着色的聚乙烯板比纯颜料黄109着色的聚乙烯板具有明显的更低的翘曲度。
实施例6
将19g颜料红255与1g式(1-6)结构的添加物干混均匀，再将该混合物用于聚乙烯板的着色，测试聚乙烯板的翘曲度。
Figure PCTCN2015086550-appb-000010
Figure PCTCN2015086550-appb-000011
(1-6)结构的添加物是采用CN1871309A的方法合成；其中：n代表正十二烷基，结果如下：
实施例 翘曲度/mm
不含添加物 40.6
含添加物 6.2
用本发明的组合物着色的聚乙烯板比纯颜料红255着色的聚乙烯板具有明显的更低的翘曲度。

Claims (5)

  1. 在塑料中具有抗翘曲性能的颜料组合物，其特征在于，由具有式(1)结构通式的DPP和本体颜料组成；
    Figure PCTCN2015086550-appb-100001
    在R1，R2，R4，R5中，有1、2、3或者4个基团为R11、OR11、SR11，而R3，R6，R7，R8，R9，R10的取代基为H，F，Cl，Br，I，叔丁基，甲基，氰基，苯基，硝基或者其他含1～4个碳原子的直链或者支链烷基或者烷氧基，且如果R1，R2，R4，R5仅一个为R11、OR11、SR11时，则R2和R4不能同时为R11、OR11、SR11和H；
    R11为没有取代的或者卤素取代的碳原子数1～30的直链烷烃或者含支链的烷烃基团；
    OR11为没有取代的或者卤素取代的碳原子数1～30的直链烷烃或者含支链的烷氧基团
    SR11为没有取代的或者卤素取代的碳原子数1～30的直链烷烃或者含支链的烷硫基团。
  2. 根据权利要求1所述的在塑料中具有抗翘曲性能的颜料组合物，其特征在于，由如下重量百分比的组分组成：
    具有式(1)结构通式的DPP    0.01％～99.99％
    本体颜料                  0.01％～99.99％。
  3. 根据权利要求1所述的在塑料中具有抗翘曲性能的颜料组合物，其特征在于，由如下重量百分比的组分组成：
    具有式(1)结构通式的DPP颜料  0.03％～0.1％
    本体颜料                    余量。
  4. 根据权利要求1、2或3所述的在塑料中具有抗翘曲性能的颜料组合物，其特征在于，所述的本体颜料为喹吖啶酮类，苯并咪唑酮类，偶氮类，蒽醌类，喹酞酮累，DPP类，异吲哚啉酮或异吲哚啉类颜料。
  5. 根据权利要求4所述的在塑料中具有抗翘曲性能的颜料组合物， 其特征在于，具有式(1)结构通式的DPP颜料选自：
    Figure PCTCN2015086550-appb-100002
    新增结构、
    Figure PCTCN2015086550-appb-100003
PCT/CN2015/086550 2014-12-31 2015-08-10 在塑料中具有抗翘曲性能的颜料组合物 WO2016107184A1 (zh)

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