CN101111537A - 作为涂料施涂用防雾添加剂的星形支化硅酮聚合物 - Google Patents

作为涂料施涂用防雾添加剂的星形支化硅酮聚合物 Download PDF

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CN101111537A
CN101111537A CNA2005800477005A CN200580047700A CN101111537A CN 101111537 A CN101111537 A CN 101111537A CN A2005800477005 A CNA2005800477005 A CN A2005800477005A CN 200580047700 A CN200580047700 A CN 200580047700A CN 101111537 A CN101111537 A CN 101111537A
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约翰·阿尔弗雷德·基尔戈
埃德温·C·库阿
约翰·A·卡明斯
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Momentive Performance Materials Inc
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Abstract

在硅氢化条件下氢化-硅酮树脂与烯烃不完全反应以产生部分取代的氢化-硅酮,它进一步在氢化硅烷化条件下与含乙烯基的硅酮反应以消耗剩余的氢化物,从而产生在柔韧性载体的涂布中可用作防雾剂的组合物。

Description

作为涂料施涂用防雾添加剂的星形支化硅酮聚合物
技术领域
本发明涉及用硅酮组合物涂布柔韧性材料或载体如织造或非织造的纸或其它聚合材料的片。本发明也涉及用包含一种或多种可交联聚有机硅氧烷的液体组合物涂布柔韧性材料或载体,其中这样的聚有机硅氧烷可通过加成反应、缩合反应、阳离子反应或自由基反应而交联。本发明也涉及在将硅酮组合物(聚有机硅氧烷)施涂到柔韧性材料或载体上的过程中降低起雾的星形支化聚有机硅氧烷(硅酮聚合物)。柔韧性载体可以是纸、纸板、塑料膜、金属膜等。一些示例性应用是食品用纸、粘胶标签、胶带、封条等。
背景技术
用液体硅酮涂布柔韧性载体通常在以很高的速度连续运转的涂布装置上进行。这些装置通常包含由几个辊构成的涂布头,特别包括利用一系列相互邻接布置的辊连续供应可交联或不可交联的硅酮组合物的压力辊和涂布辊。将要涂布的预期材料的柔韧性载体条带高速地供应在压力辊和涂布辊之间,从而在其至少一个表面上涂布。当要使硅酮涂料交联时,将进行交联反应的设备设置在涂布头的下游。进行交联的设备可以为例如烘箱、或如紫外(UV)射线的射线的发射体、或电子束(EB)的发射体。
用硅酮高速涂布柔韧性载体涉及与将来自涂布辊的硅酮液体(或流体)转移到向前移动通过涂布设备的柔韧性载体上相关的问题。与将来自涂布辊的硅酮液体转移到柔韧性载体上相关的特别问题之一是,在涂布头最接近的附近、特别是涂布辊与待涂布的柔韧性载体之间的接触点附近出现雾、薄雾或烟雾。通常地,该雾、薄雾或烟雾的密度随设备涂布的柔韧性载体的前进速度增加而增加。
该转移问题的第一个效应是降低实际转移到柔韧性载体上的硅酮液体的量。第二个效应是包含雾、薄雾或烟雾的液滴冷凝到涂布辊下游的新涂布的柔韧性载体上,产生桔皮效应。该桔皮效应或涂布不均匀性产生覆盖度、如擦掉等涂料的机械性能和抗粘附性的问题。
涂布的不均匀性产生的另外问题涉及工业卫生和在涂布设备附近工作的涂布设备操作人员的安全。
发明内容
本发明提供一种组合物,其包含在贵金属氢化硅烷化催化剂存在下如下物质的反应产物:
MaMVi bDcDVi dTeTVi f和((M′gMjMH k-gD′hD1DH m-hT′iTnTH o-i)pQ)q
式中下标a、b、c、d、e、f、g、h、i、j、k、l、m、n、o、p为零或正值,q是非零且正值,对于化合物的混合物而言各下标的平均值最可能为非整数,对于特定化合物而言下标为整数,且
k+m+o-g-h-I<b+d+f,p在0.4~4.0范围中,
式中,
(b+d+f)/(((k+m+o-g-h-i)p)q)在4.59~0.25范围中,在MaMVi bDcDVi dTeTVi f中下标a+b之和在2~12范围中;c+d在0~1000范围中;e+f在0~10范围中,R1是选自卤素、氢和C1~C60一价烃基、聚酯、腈、卤代烷和聚醚的一价基;且
M=R2R3R4SiO1/2
MVi=RViR5R6SiO1/2
D=R7R8SiO2/2
DVi=RViR10SiO2/2
T=R11SiO3/2
TVi=RViSiO3/2
M′=(CH2CH2R1)R5R6SiO1/2
D′=(CH2CH2R1)R9SiO2/2;和
T′=(CH2CH2R1)SiO3/2
R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自独立地选自C1~C60一价烃基,RVi各自独立地选自C2~C60一价烯烃基
其中
((M′gMjMH k-gD′hD1DH m-hT′iTnTH o-i)pQ)q可以作为下列反应式的反应产物得到
((MjMH kDlDH mTnTH o)pQ)q+αCH2=CHR1
((M′gMjMH k-gD′hD1DH m-hT′iTnTH o-i)pQ)q
式中α+1≤k+m+o和g+h+i≤k+m+o,
且1.5≤k+m+o-g-h-i≤100;
R1是选自卤素、氢和C1~C60一价烃基、聚酯、腈、卤代烷和聚醚的一价基;且
M=R2R3R4SiO1/2
MH=HR5R6SiO1/2
D=R7R8SiO2/2
DH=HR9SiO2/2
T=R11SiO3/2
TH=HSiO3/2
Q=SiO4/2
M′=(CH2CH2R1)R5R6SiO1/2
D′=(CH2CH2R1)R9SiO2/2;和
T′=(CH2CH2R1)SiO3/2
R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自独立地选自C1~C60一价烃基。
本发明进一步提供一种在涂布柔韧性基质中减少起雾的方法,所述方法包括制备用于涂布所述基质的涂料组合物和向其中加入本发明的组合物。
具体实施方式
本发明的星形支化硅氧烷化合物作为在贵金属氢化硅烷化催化剂存在下如下物质的反应产物而制得:
MaMVi bDcDVi dTeTVi f和((M′gMjMH k-gD′hD1DH m-hT′iTnTH o-i)pQ)q
式中下标a、b、c、d、e、f、g、h、i、j、k、l、m、n、o、p为零或正值,q是非零且为正值,对于化合物的混合物而言各下标的平均值最可能为非整数,对于特定化合物则所述下标为整数,且
k+m+o-g-h-I<b+d+f,p在0.4~4.0,优选0.5~3.0,更优选0.5~2.5和最优选1.5~2.5和它们之间的所有子范围中,q在1~200,优选1~100,更优选1~75和最优选1~50和它们之间的所有子范围中,含氢化物的前体与含乙烯基的前体之间的比用前体的化学计量下标之间的如下数学关系式来定义,(b+d+f)/(((k+m+o-g-h-i)p)q)在4.59~0.25,优选4.5~0.25,更优选4.5~0.25和最优选4.0~0.25和它们之间所有子范围中,具体地包括3.5~0.25,3.0~0.25,2.5~0.25和2.0~0.25;化合物((M′gMjMH k-gD′hD1DH m-hT′iTnTH o-i)pQ)q可以由如下反应式得到
((MjMH kD1DH mTnTH o)pQ)q+αCH2=CHR1
((M′gMjMH k-gD′hD1DH m-hT′iTnTH o-i)pQ)q
式中α+1≤k+m+o和g+h+i≤k+m+o,
且1.5≤k+m+o-g-h-i≤100;
R1是选自卤素、氢和C1~C60一价烃基、聚酯、腈、卤代烷和聚醚的一价基;且
M=R2R3R4SiO1/2
MH=HR5R6SiO1/2
D=R7R8SiO2/2
DH=HR9SiO2/2
T=R11SiO3/2
TH=HSiO3/2
Q=SiO4/2
M′=(CH2CH2R1)R5R6SiO1/2
D′=(CH2CH2R1)R9SiO2/2;和
T′=(CH2CH2R1)SiO3/2
R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自独立地选自C1~C60一价烃基。制备MQ树脂如((MjMH kD1DH mTnTH o)pQ)q的方法描述在美国专利5,817,729、美国专利5,399,614和美国专利2,676,182中,这里以参考方式具体引入。
MaMVi bDcDVi dTeTVi f可以通过使用酸或碱催化,由组分氯硅烷经水解和缩合或缩合之后进行平衡而制得。下标a+b之和为2~12;c+d为0~1000;e+f为0~10,R1是选自卤素、氢和C1~C60一价烃基、聚酯、腈、卤代烷和聚醚的一价基;且
M=R2R3R4SiO1/2
MVi=RViR5R6SiO1/2
D=R7R8SiO2/2
DVi=RViR10SiO2/2
T=R11SiO3/2
TVi=RViSiO3/2
M′=(CH2CH2R1)R5R6SiO1/2
D′=(CH2CH2R1)R9SiO2/2;和
T′=(CH2CH2R1)SiO3/2
R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自独立地选自C1~C60一价烃基,RVi各自独立地选自C2~C60一价烯烃基。
因为对每种反应的组分分子具有许多可用于反应的氢化硅烷化位点,且难以将这样的随机化学反应降低至分析说明,所以以下列两个化合物的反应产物描述本发明的星形支化硅酮化合物:
MaMVi bDcDVi dTeTVi f和((M′gMjMH k-gD′hD1DH m-hT′iTnTH o-i)pQ)q
用于该氢化硅烷化反应的许多种贵金属催化剂是公知的,这样的催化剂可以用于本发明情形的反应中。当需要光学透明度时,优选的催化剂是可溶解在反应混合物中的催化剂。对贵金属而言,申请人将Ru、Rh、Pd、Os、Ir和Pt定义为贵金属,因为Ni的公知加氢活性,所以在该定义中也包括Ni。优选催化剂为铂化合物,铂化合物可以选自如美国专利3,159,601中描述的具有式(PtCl2Olefin)和H(PtCl3Olefin)的那些化合物,这里以参考方式引入。在前面两个式中所示的烯烃几乎可以为任意类型的烯烃,但优选为碳原子数为2~8的烯烃、原子数为5~7的环烯烃或苯乙烯。可用在上面式中的具体烯烃为乙烯、丙烯、丁烯的各种异构体、辛烯、环戊烯、环己烯、环庚烯等。
可用在本发明组合物中的另一种含铂材料是美国专利3,159,662中描述的氯化铂的环丙烷络合物,这里以参考方式引入。
另外,含铂材料可以是由氯铂酸与每克铂具有高至2摩尔的选自醇、醚、醛和其混合物的成分形成的络合物,如美国专利3,220,972中所述,这里以参考方式引入。
优选与液体注射成型组合物使用的催化剂描述在授权给Karstedt的美国专利3,715,334、3,775,452和3,814,730中。涉及本领域的另外的背景技术可以在the Academic Press出版由F.G.A.Stone和R.West编辑的Advances in Organometallic Chemistry,第17卷,第407~447页(New York,1979)中J.L.Spier的“Homogeneous Catalysis ofHydrosilation by Transition Metals”中找到。本领域的技术人员可以容易地确定铂催化剂的有效量。一般地,氢化硅烷化的有效量在全部有机聚硅氧烷组合物的约0.1~50ppm和它们之间的所有子范围中。
实验
实施例1
将200克(0.26摩尔)((MH)2Q)4硅酮和332克(1.4摩尔)C16-18末端烯烃与5ppm(重量%Pt)铂催化剂混合,在90℃下加热4小时。甲硅烷基氢化物的消失表示反应完成。加入6039克(0.69摩尔)约8710分子量的乙烯基封端的直链聚硅氧烷,在90℃下加热并搅拌该反应4小时。甲硅烷基氢化物的消失和粘度增加表示反应完成。
表1显示出基于上述途径的防雾添加剂的结构的合成实施例。SiH/SiVinyl是可用于反应的甲硅烷基氢化物的摩尔数与可用于反应的甲硅烷基乙烯基的摩尔数的比。在所示化合物中,SiH/SiVinyl比从0.2变化到2.75,但是更大的可用范围从0.22跨度到4.5。
表1:防雾添加剂合成
类型Five AMA’s:乙烯基封端的聚二甲基硅氧烷
实施例 烯烃 克数  ((MH)2Q)4克数   Ptppm SiH/Vinyl MviD115Mvi   Ptppm
  30   C16-18   33.3  20.0   5   0.5   604   5
  31   C16-18   5.0  5.0   5   0.25   544   5
  32   C16-18   7.0  7.0   5   0.35   544   5
  33   C16-18   33.3  20.0   5   0.6   503   5
  34   C16-18   7.0  7.0   5   0.5   380   5
  35   C16-18   33.3  20.0   5   0.75   403   5
  36   C16-18   33.3  20.0   5   0.75   403   5
  37   C16-18   41.6  25.0   5   0.9   419   5
  38   C16-18   9.0  9.0   5   0.45   544   5
  39   C16-18   58.2  35.0   5   1   528   5
  40   C16-18   2.2  3.5   5   0.2   594   5
  41   C16-18   4.4  7.0   5   0.4   594   5
  42   C16-18   3.1  5.0   5   0.3   566   5
表2显示本发明的防雾行为。以2000ft/min的线速度使用引导涂布机在2.5mil SC Rhi-Liner 12纸上运行时进行测定。用含有~2%防雾添加剂的标准硅酮松纸配方涂布该纸,目标是0.6~0.9磅每令(ream)。使用DustTrack Aerosol Monitor测定雾。入口定位在观察到的最高起雾区域,这样提供最高的预期值。该位置既不反映正常环境测试,也不能在所有操作条件下都确保特定值。测定单位为mg雾材料/立方米空气,该值越低越理想,这是由于它们表示较少起雾。
表2:防雾测定
类型Five AMA’s:有机甲硅烷基封端的聚二甲基硅氧烷
    AMA#     2000ft/min下mg/m3
    对照     102.00
    30     34.00
    31     75.00
    32     6.74
    33     80.00
    34     0.61
    35     71.30
    36     1.34
    37     34.20
    38     1.05
    39     7.49
    40     18.70
    41     0.51
    42     5.64
结果表明,与不含防雾添加剂的对照配方相比,本发明生成的防雾材料在2000ft/min下降低了产生的雾量。十分吃惊地发现,通常以大于10的因子降低了起雾,该因子通常约100,在两种情况中比几乎200的因子还更好。
前述实施例仅是解释本发明,起解释本发明的仅一些特征的作用。附带的权利要求将如已经设想的宽范围要求保护本发明,这里表示的实施例说明选自所有可能实施方案的诸多中的实施方案。因此,本申请人的发明的附带权利要求不受用来解释本发明的特点的实施例的选择所限制。如权利要求中使用的,术语“包含”及其语法变体也逻辑地对应和包括变化和不同程度的术语,例如但不局限于“基本由...组成”和“由...组成”。必要时提供了范围;那些范围包括它们之间的所有子范围。将预期到这些范围本身对本领域的技术人员具有启示,对于还没有贡献给公众的,则可能时应把那些变化解释为被附带的权利要求所覆盖。也预期科学技术的进步将作出因为语言不准确的原因现在还没预期的可能的等价物和代替物,可能时这些变化也应解释为被附带的权利要求所覆盖。本文参考的所有美国专利此处均以参考方式具体地引入。

Claims (30)

1.一种组合物,其包含在贵金属氢化硅烷化催化剂存在下如下物质的反应产物:
MaMVi bDcDVi dTeTVi f和((M′gMjMH k-gD′hDlDH m-hT′iTnTH o-i)pQ)q
式中下标a、b、c、d、e、f、g、h、i、j、k、l、m、n、o、p为零或正值,q是非零且为正值,对于化合物的混合物而言各下标的平均值极可能为非整数,对于特定化合物而言下标为整数,且
k+m+o-g-h-I<b+d+f,p在0.4~4.0范围中,
式中,
(b+d+f)/(((k+m+o-g-h-i)p)q)在4.59~0.25范围中,在MaMVi bDcDVi dTeTVi f中下标a+b之和在2~12范围中;c+d在0~1000范围中;e+f在0~10范围中,R1是选自卤素、氢和C1~C60一价烃基、聚酯、腈、卤代烷和聚醚的一价基;且
M=R2R3R4SiO1/2
MVi=RViR5R6SiO1/2
D=R7R8SiO2/2
DVi=RViR10SiO2/2
T=R11SiO3/2
TVi=RViSiO3/2
M′=(CH2CH2R1)R5R6SiO1/2
D′=(CH2CH2R1)R9SiO2/2;和
T′=(CH2CH2R1)SiO3/2
R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自独立地选自C1~C60一价烃基,RVi各自独立地选自C2~C60一价烯烃基
其中
((M′gMjMH k-gD′hDlDH m-hT′iTnTH o-i)pQ)q可以作为如下反应式的反应产物而得到
((MjMH kDlDH mTnTH o)pQ)q+αCH2=CHR1
((M′gMjMH k-gD′hDlDH m-hT′iTnTH o-i)pQ)q
式中α+1≤k+m+o和g+h+i≤k+m+o,
且1.5≤k+m+o-g-h-i≤100;
R1是选自卤素、氢和C1~C60一价烃基、聚酯、腈、卤代烷和聚醚的一价基;且
M=R2R3R4SiO1/2
MH=HR5R6SiO1/2
D=R7R8SiO2/2
DH=HR9SiO2/2
T=R11SiO3/2
TH=HSiO3/2
Q=SiO4/2
M′=(CH2CH2R1)R5R6SiO1/2
D′=(CH2CH2R1)R9SiO2/2;和
T′=(CH2CH2R1)SiO3/2
R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自独立地选自C1~C60一价烃基。
2.如权利要求1所述的组合物,其中R1选自C15~C60一价烃基、C15~C60一价聚酯基、C15~C60一价腈基、C15~C60一价卤代烷基、C15~C60一价聚醚基和它们的混合物。
3.如权利要求1所述的组合物,其中R1选自C30~C60一价烃基、C30~C60一价聚酯基、C30~C60一价腈基、C30~C60一价卤代烷基和C30~C60一价聚醚基和它们的混合物。
4.如权利要求1所述的组合物,其中R1选自C10~C40一价烃基、C10~C40一价聚酯基、C10~C40一价腈基、C10~C40一价卤代烷基和C10~C40一价聚醚基和它们的混合物。
5.如权利要求2所述的组合物,其中R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自为甲基。
6.如权利要求3所述的组合物,其中R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自为甲基。
7.如权利要求4所述的组合物,其中R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自为甲基。
8.如权利要求1所述的组合物,其中R1是苯乙烯基。
9.如权利要求7所述的组合物,其中R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自为甲基。
10.如权利要求7所述的组合物,其中R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自选自C30~C60一价烃基、C30~C60一价聚酯基、C30~C60一价腈基、C30~C60一价卤代烷基和C1~C60一价聚醚基和它们的混合物。
11.一种在柔韧性载体的涂布过程中用于减少起雾的组合物,其包含在贵金属氢化硅烷化催化剂存在下如下物质的反应产物:
MaMVi bDcDVi dTeTVi f和((M′gMjMH k-gD′hDlDH m-hT′iTnTH o-i)pQ)q
式中下标a、b、c、d、e、f、g、h、i、j、k、l、m、n、o、p为零或正值,q是非零且为正值,对于化合物的混合物而言各下标的平均值极可能为非整数,对于特定化合物而言下标为整数,且
k+m+o-g-h-I<b+d+f,p在0.4~4.0范围中,
式中,
(b+d+f)/(((k+m+o-g-h-i)p)q)在4.59~0.25范围中,MaMVi bDcDVi dTeTVi f中下标a+b之和在2~12范围中;c+d在0~1000范围中;e+f在0~10范围中,R1是选自卤素、氢和C1~C60一价烃基、聚酯、腈、卤代烷和聚醚的一价基;且
M=R2R3R4SiO1/2
MVi=RViR5R6SiO1/2
D=R7R8SiO2/2
DVi=RViR10SiO2/2
T=R11SiO3/2
TVi=RViSiO3/2
M′=(CH2CH2R1)R5R6SiO1/2
D′=(CH2CH2R1)R9SiO2/2;和
T′=(CH2CH2R1)SiO3/2
R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自独立地选自C1~C60一价烃基,RVi各自独立地选自C2~C60一价烯烃基
其中
((M′gMjMH k-gD′hDlDH m-hT′iTnTH o-i)pQ)q可以作为如下反应式的反应产物而得到
((MjMH kDlDH mTnTH o)pQ)q+αCH2=CHR1
((M′gMjMH k-gD′hDlDH m-hT′iTnTH o-i)pQ)q
式中α+1≤k+m+o和g+h+i≤k+m+o,
且1.5≤k+m+o-g-h-i≤100;
R1是选自卤素、氢和C1~C60一价烃基、聚酯、腈、卤代烷和聚醚的一价基;且
M=R2R3R4SiO1/2
MH=HR5R6SiO1/2
D=R7R8SiO2/2
DH=HR9SiO2/2
T=R11SiO3/2
TH=HSiO3/2
Q=SiO4/2
M′=(CH2CH2R1)R5R6SiO1/2
D′=(CH2CH2R1)R9SiO2/2;和
T′=(CH2CH2R1)SiO3/2
R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自独立地选自C1~C60一价烃基。
12.如权利要求11所述的组合物,其中R1选自C1~C60一价烃基、C1~C60一价聚酯基、C1~C60一价腈基、C1~C60一价卤代烷基和C1~C60一价聚醚基和它们的混合物。
13.如权利要求11所述的组合物,其中R1选自C15~C60一价烃基、C15~C60一价聚酯基、C15~C60一价腈基、C15~C60一价卤代烷基、C1~C60一价聚醚基和它们的混合物。
14.如权利要求11所述的组合物,其中R1选自C30~C60一价烃基、C30~C60一价聚酯基、C30~C60一价腈基、C30~C60一价卤代烷基、C1~C60一价聚醚基和它们的混合物。
15.如权利要求12所述的组合物,其中R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自为甲基。
16.如权利要求13所述的组合物,其中R2、R3、R3、R4、R6、R7、R8、R9、R10和R11各自为甲基。
17.如权利要求14所述的组合物,其中R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自为甲基。
18.如权利要求11所述的组合物,其中R1是苯乙烯基。
19.如权利要求17所述的组合物,其中R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自为甲基。
20.如权利要求17所述的组合物,其中R2、R3、R4、R5、R6、R7、R8、R9、R10和R11各自选自C30~C60一价烃基、C30~C60一价聚酯基、C30~C60一价腈基、C30~C60一价卤代烷基和C1~C60一价聚醚基和它们的混合物。
21.一种在柔韧性基质的涂布中降低起雾的方法,所述方法包括制备用于涂布所述基质的涂料组合物并向其中加入权利要求1所述的组合物。
22.一种在柔韧性基质的涂布中降低起雾的方法,所述方法包括制备用于涂布所述基质的涂料组合物并向其中加入权利要求2所述的组合物。
23.一种在柔韧性基质的涂布中降低起雾的方法,所述方法包括制备用于涂布所述基质的涂料组合物并向其中加入权利要求3所述的组合物。
24.一种在柔韧性基质的涂布中降低起雾的方法,所述方法包括制备用于涂布所述基质的涂料组合物并向其中加入权利要求4所述的组合物。
25.一种在柔韧性基质的涂布中降低起雾的方法,所述方法包括制备用于涂布所述基质的涂料组合物并向其中加入权利要求5所述的组合物。
26.一种在柔韧性基质的涂布中降低起雾的方法,所述方法包括制备用于涂布所述基质的涂料组合物并向其中加入权利要求6所述的组合物。
27.一种在柔韧性基质的涂布中降低起雾的方法,所述方法包括制备用于涂布所述基质的涂料组合物并向其中加入权利要求7所述的组合物。
28.一种在柔韧性基质的涂布中降低起雾的方法,所述方法包括制备用于涂布所述基质的涂料组合物并向其中加入权利要求8所述的组合物。
29.一种在柔韧性基质的涂布中降低起雾的方法,所述方法包括制备用于涂布所述基质的涂料组合物并向其中加入权利要求9所述的组合物。
30.一种在柔韧性基质的涂布中降低起雾的方法,所述方法包括制备用于涂布所述基质的涂料组合物并向其中加入权利要求10所述的组合物。
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