CN113631670B - 树脂片用改性剂、表面改性树脂片和成型品的制造方法 - Google Patents

树脂片用改性剂、表面改性树脂片和成型品的制造方法 Download PDF

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CN113631670B
CN113631670B CN202180001974.XA CN202180001974A CN113631670B CN 113631670 B CN113631670 B CN 113631670B CN 202180001974 A CN202180001974 A CN 202180001974A CN 113631670 B CN113631670 B CN 113631670B
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resin sheet
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CN113631670A (zh
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藤井淳介
小泽真贵子
八田明生
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Takemoto Oil and Fat Co Ltd
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Abstract

本发明的目的在于，提供：配置于一面侧的改性层具有优异的防雾性、光滑性和抗静电性的表面改性树脂片；适合作为形成该改性层的材料的树脂片用改性剂；以及，成型品的制造方法。本发明的树脂片用改性剂的特征在于，含有(A)包含碱金属元素(锂、钠或钾)的无机化合物。进而，可以含有(B)亲水性丙烯酸类树脂、(C)润滑剂等。

Description

树脂片用改性剂、表面改性树脂片和成型品的制造方法
技术领域
本发明涉及：配置于一面侧的改性层具有优异的防雾性、光滑性和抗静电性的表面改性树脂片；和，适合作为形成该改性层的材料的树脂片用改性剂。另外，本发明涉及：使用该表面改性树脂片制造成型品的方法。
背景技术
以往，为了包装各种部件、食品等制品而广泛使用有薄壁的树脂成型品(片、容器等)。而且，包装食品、电子部件等的情况下，在上述包装用成型品的、特别是内表面侧，有时需要防雾性、光滑性、抗静电性等。
为了赋予这些性能，已知有以下的技术。
例如，专利文献1中，为了赋予防雾性和抗静电性，公开了一种合成高分子薄膜用表面处理剂，其特征在于，以30/70～90/10(重量比)的比率含有具有特定结构且数均分子量为10000～100000的乙烯基共聚物、与选自有机羧酸、有机羧酸盐、有机羧酸酯、有机羧酸酰胺、聚乙烯蜡、硅油、二氧化硅颗粒、有机硅树脂颗粒和滑石粉末中的一者或二者以上的润滑剂。
专利文献2中，作为涂布于基材树脂片的防雾剂，公开了一种防雾剂，其含有蔗糖与碳数12～22的脂肪族单羧酸的偏酯化合物、以及碳数14～22的脂肪族单羧酸碱金属盐。
另外，专利文献3中公开了一种防雾层用涂覆液，其含有：由非离子性表面活性剂等构成的防雾剂(A)；和，防雾助剂(B)，其包含将二次成型的加热温度设为T℃时具有(T-90)℃～(T+20)℃的软化点的亲水性(甲基)丙烯酸类聚合物(B1)。而且记载了，该涂覆液可以含有金属化合物(D)，特别优选多价的金属离子的化合物(氯化镁等)。
现有技术文献
专利文献
专利文献1：日本特开2004-244605号公报
专利文献2：日本特开2007-031545号公报
专利文献3：日本特开2018-176740号公报
发明内容
发明要解决的问题
近年来，对于食品、电子部件等的包装容器、树脂片，除了要求防雾性和光滑性，还要求更高水平的抗静电性。
本发明要解决的课题在于，提供：配置于至少一面侧的改性层具有优异的防雾性、光滑性和抗静电性的表面改性树脂片；和，适合作为形成该改性层的材料的树脂片用改性剂。另外，另一课题在于，提供：使用该表面改性树脂片制造容器等成型品的方法。本说明书中，“防雾性”是指如下性能，利用表面改性树脂片(使改性层为物品侧)包装水分附着于含水性或表面的物品的状态下，例如载置于5℃以下的气氛下并放置后，基本不可见容易残留于改性层的表面的水滴，透过片可以良好地视觉识别物品。
用于解决问题的方案
本发明人等进行了深入研究，结果发现：在基材树脂片的表面形成包括含有包含碱金属元素的无机化合物的树脂片用改性剂的层(改性层)而得到的表面改性树脂片的防雾性、光滑性和抗静电性优异。
本发明如以下所示。
本发明的树脂片用改性剂的特征在于，其为用于树脂片(以下，称为“基材树脂片”)的表面改性的改性剂，其含有包含碱金属元素的无机化合物(A)。
本发明的树脂片用改性剂优选还含有亲水性丙烯酸类树脂(B)和有机羧酸盐(C)中的至少一者。
本发明的表面改性树脂片的特征在于，具备：包含树脂的基层；和，配置于该基层的至少一面侧的、包含上述树脂片用改性剂的改性层。
本发明的成型品的制造方法的特征在于，将上述表面改性树脂片供于成型加工。
发明的效果
本发明的树脂片用改性剂给基材树脂片的表面提供防雾性、光滑性和抗静电性优异的改性层，适合作为制造表面改性树脂片的原料。另外，本发明的表面改性树脂片具备包含上述本发明的树脂片用改性剂的改性层，因此，该改性层的表面具有优异的防雾性、光滑性和抗静电性。因此，使用这种表面改性树脂片，可以效率良好地制造防雾性、光滑性和抗静电性优异的容器等成型品。
具体实施方式
本发明的树脂片用改性剂含有包含碱金属元素的无机化合物即成分(A)。本发明中，树脂片用改性剂通过含有其他成分(后述)，从而可以给基材树脂片的至少一面侧提供防雾性、光滑性和抗静电性进一步优异的改性层。
上述成分(A)中所含的碱金属元素没有特别限定，可以设为选自锂、钠、钾、铷、铯等中的至少1者。这些之中，优选的元素为锂、钠和钾。需要说明的是，上述成分(A)中所含的碱金属元素可以为1者也可以为2者以上。
上述成分(A)为无机化合物，可以设为卤化物(氯化物、溴化物、碘化物)、硫酸盐、硝酸盐、磷酸盐、碳酸盐、氧化物、硫化物、氢氧化物等。这些之中，优选卤化物和硫酸盐，特别优选氯化物和硫酸盐。
本发明的树脂片用改性剂中所含的上述成分(A)的含有比率相对于树脂片用改性剂的整体，优选0.1～15质量％、更优选0.1～10质量％。
本发明的树脂片用改性剂用于在基材树脂片的至少一面侧形成改性层。形成改性层的情况下，作为其他成分之一，优选为含有粘接剂成分的组合物(以下，称为“改性层形成用组合物”)，但对于本发明的树脂片用改性剂，作为这种改性层形成用组合物的制备中使用的成分，可以同时包含粘接剂以外的其他成分、例如添加剂。
对于上述粘接剂成分，将改性层形成用组合物涂布于基材树脂片的情况下，从其涂布性的观点出发，通常与液体介质一起同时包含。因此，上述粘接剂成分通常根据该液体介质的液性而选择。本发明中，改性层形成用组合物优选包含水性的液体介质(水、或水与有机溶剂的混合液)，上述粘接剂成分优选为亲水性树脂。
上述亲水性树脂可以溶解于水性介质，也可以不溶解于水性介质而分散于其中。本发明中，上述亲水性树脂优选为溶解于水性介质的树脂，更优选为含有选自包含羧酸(包括其盐)结构的结构单元、包含羟基的结构单元、包含氨基的结构单元、包含酰胺基的结构单元和包含季铵结构的结构单元中的至少1种的树脂。
上述亲水性树脂特别优选为具有丙烯酰基或甲基丙烯酰基的化合物，且为包含源自具有选自羧酸(包括其盐)结构、羟基、氨基、酰胺基和季铵结构中的至少1种的化合物的1种或2种以上的结构单元的丙烯酸类树脂(以下，称为“亲水性丙烯酸类树脂(B)”或“成分(B)”)。上述成分(B)可以包含不具有亲水性基团的结构单元。
从对基材树脂片的粘接性、以及得到的表面改性树脂片的防雾性、光滑性和抗静电性的观点出发，上述成分(B)优选为包含源自下述式(1)所示的化合物的结构单元(以下，称为“结构单元(s-1)”)的聚合物。
Figure BDA0003181912220000041
(式中，R1为氢原子或甲基，R2为碳原子数1～4的2价的烃基，R3和R4为彼此相同或不同的碳原子数1～4的烃基。)
上述式(1)中，R1为氢原子或甲基，R2为亚甲基、亚乙基、三亚甲基或四亚甲基。R3和R4可以设为甲基、乙基、丙基、异丙基、丁基、异丁基等。R3和R4可以彼此相同也可以不同。
作为上述式(1)所示的化合物，优选以下的化合物。
(m1-1)R1为甲基、R2为亚乙基、R3和R4为甲基的化合物
(m1-2)R1为甲基、R2为亚乙基、R3和R4为乙基的化合物
(m1-3)R1为氢原子、R2为亚乙基、R3和R4为乙基的化合物
上述成分(B)包含上述结构单元(s-1)的情况下，其结构单元(s-1)的含有比率相对于构成聚合物的结构单元的总量，优选为10～60质量％。需要说明的是，上述成分(B)中所含的上述结构单元(s-1)可以仅为1种，也可以为2种以上。
上述成分(B)优选还包含选自源自下述式(2)所示的化合物的结构单元(以下，称为“结构单元(s-2)”)、源自下述式(3)所示的化合物的结构单元(以下，称为“结构单元(s-3)”)、和源自下述式(4)所示的化合物的结构单元(以下，称为“结构单元(s-4)”)中的至少一种。
Figure BDA0003181912220000051
(式中，R5为氢原子或甲基，R6为具有1个羟基的碳原子数1～4的烃基、或具有2个羟基的碳原子数2～4的烃基。)
Figure BDA0003181912220000052
(式中，R7为氢原子或甲基，R8为氢原子、或碳原子数1～18的烃基。)
Figure BDA0003181912220000061
(式中，R9为氢原子或甲基，R10和R11为彼此相同或不同的氢原子、或碳原子数1～3的烃基。其中，R10和R11这两者为氢原子的情况排除在外。)
上述式(2)中，R5为氢原子或甲基，R6可以设为羟基甲基、2-羟基乙基、3-羟基丙基、4-羟基丁基等单羟基烷基、或2,2-二羟基乙基、2,3-二羟基丙基、4,4-二羟基丁基等二羟基烷基。
作为上述式(2)所示的化合物，可以举出丙烯酸羟基甲酯、丙烯酸2-羟基乙酯、丙烯酸3-羟基丙酯、丙烯酸4-羟基丁酯、甲基丙烯酸羟基甲酯、甲基丙烯酸2-羟基乙酯、甲基丙烯酸3-羟基丙酯、甲基丙烯酸4-羟基丁酯、丙烯酸2,2-二羟基乙酯、丙烯酸2,3-二羟基丙酯、丙烯酸4,4-二羟基丁酯、甲基丙烯酸2,2-二羟基乙酯、甲基丙烯酸2,3-二羟基丙酯、甲基丙烯酸4,4-二羟基丁酯等。这些之中，优选丙烯酸2-羟基乙酯和甲基丙烯酸2-羟基乙酯，特别优选甲基丙烯酸2-羟基乙酯。
上述式(3)中，R7为氢原子或甲基，R8可以设为氢原子、或甲基、乙基、丙基、异丙基、丁基、己基、辛基、癸基、十二烷基、十六烷基、十八烷基、异十八烷基、环戊基、环己基等。
作为上述式(3)所示的化合物，可以举出丙烯酸、甲基丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸己酯、丙烯酸辛酯、丙烯酸癸酯、丙烯酸十二烷酯、丙烯酸十六烷酯、丙烯酸十八烷酯、丙烯酸异十八烷酯、丙烯酸环戊酯、丙烯酸环己酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、甲基丙烯酸己酯、甲基丙烯酸辛酯、甲基丙烯酸癸酯、甲基丙烯酸十二烷酯、甲基丙烯酸十六烷酯、甲基丙烯酸十八烷酯、甲基丙烯酸异十八烷酯、甲基丙烯酸硬脂酯、甲基丙烯酸环戊酯、甲基丙烯酸环己酯等。这些之中，优选丙烯酸乙酯、甲基丙烯酸甲酯和丙烯酸丁酯，特别优选甲基丙烯酸甲酯。
上述式(4)中，R9为氢原子或甲基，R10和R11可以设为氢原子、或甲基、乙基、丙基、异丙基等。需要说明的是，R10和R11不同时成为氢原子。
作为上述式(4)所示的化合物，可以举出N-甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-乙基丙烯酰胺、N,N-二乙基丙烯酰胺、N-异丙基丙烯酰胺、N,N-二异丙基丙烯酰胺等。这些之中，优选N,N-二甲基丙烯酰胺。
上述成分(B)为由结构单元(s-1)、和选自结构单元(s-2)、(s-3)和(s-4)中的至少1种构成的共聚物的情况下，将结构单元的总量设为100质量％的情况下，从防雾性、光滑性和抗静电性的观点出发，结构单元(s-1)的含有比率优选10～60质量％。另外，具有该构成的树脂的数均分子量优选为10000～100000。
上述数均分子量可以用水系GPC(凝胶渗透色谱法)、通过公知的方法而测定。
作为上述成分(B)，优选的共聚物如以下所示。
(B-1)由源自上述化合物(m1-1)的结构单元、源自甲基丙烯酸羟基乙酯的结构单元和源自甲基丙烯酸甲酯的结构单元构成的共聚物
(B-2)由源自上述化合物(m1-1)的结构单元、源自甲基丙烯酸羟基乙酯的结构单元和源自甲基丙烯酸甲酯的结构单元构成的共聚物
(B-3)由源自上述化合物(m1-1)的结构单元、源自甲基丙烯酸羟基乙酯的结构单元和源自甲基丙烯酸甲酯的结构单元构成的共聚物
(B-4)由源自上述化合物(m1-2)的结构单元、源自甲基丙烯酸羟基乙酯的结构单元和源自甲基丙烯酸甲酯的结构单元构成的共聚物
(B-5)由源自上述化合物(m1-3)的结构单元、源自丙烯酸羟基乙酯的结构单元和源自丙烯酸乙酯的结构单元构成的共聚物
(B-6)由源自上述化合物(m1-1)的结构单元、源自甲基丙烯酸羟基乙酯的结构单元和源自N,N-二甲基丙烯酰胺的结构单元构成的共聚物
(B-7)由源自上述化合物(m1-1)的结构单元、源自甲基丙烯酸羟基乙酯的结构单元和源自丙烯酸丁酯的结构单元构成的共聚物
(B-8)由源自甲基丙烯酸甲酯的结构单元、源自丙烯酸乙酯的结构单元、源自丙烯酸丁酯的结构单元和源自丙烯酸的结构单元构成的共聚物
作为上述成分(B)，可以使用如下合成而得到者：通过公知的方法、例如使上述式(1)所示的化合物、以及选自上述式(2)所示的化合物、上述式(3)所示的化合物和上述式(4)所示的化合物中的至少1种溶解于甲醇等溶剂，适宜添加聚合引发剂、链转移剂等后，在氮气气氛下，进行自由基聚合反应，从而合成。
本发明的树脂片用改性剂含有上述成分(B)的情况下，其含有比率相对于树脂片用改性剂的整体，优选35～85质量％、更优选38～65质量％。
制造本发明的树脂片用改性剂的情况下，作为上述亲水性树脂用的制造原料，优选使用上述成分(B)的水溶液。
如上所述，亲水性树脂可以为不溶解于水性介质而分散于其中者。该情况下，可以使用乳胶、乳剂等。
本发明的树脂片用改性剂含有添加剂的情况下，作为该添加剂，可以举出润滑剂、抗静电剂、抗氧化剂、紫外线吸收剂、阻燃剂、着色剂、脱模剂等。本发明的树脂片用改性剂优选含有润滑剂(以下，称为“成分(C)”)。
作为上述成分(C)，可以举出有机羧酸、有机羧酸盐、有机羧酸酯、有机羧酸酰胺、聚乙烯蜡、硅油、二氧化硅颗粒、有机硅树脂颗粒、滑石粉末等。本发明的树脂片用改性剂可以仅含有这些成分的1种，也可以含有2种以上。本发明中，特别优选有机羧酸盐(以下，称为“成分(C1)”)。
上述成分(C1)只要为有机羧酸的盐就没有特别限定。有机羧酸为R-COOH(R为任选包含羟基的烃基)所示的化合物，例如可以举出甲酸、乙酸、丙酸、丁酸、戊酸、己酸、山梨酸、庚酸、辛酸、壬酸、癸酸、十一烷酸、十一烯酸、月桂酸、十三烷酸、肉豆蔻酸、十五烷酸、棕榈酸、十七酸、硬脂酸、花生酸、二十酸、山萮酸、二十三酸、二十四酸、油酸、亚油酸、亚麻酸、芥酸、12-羟基硬脂酸、蓖麻油酸等。这些之中，从得到的表面改性树脂片中的光滑性的观点出发，优选碳原子数14～22的脂肪族羧酸(任选包含羟基)。另外，盐优选锂盐、钠盐、钾盐、铷盐、铯盐等1价的碱金属盐，特别优选钠盐和钾盐。
本发明的树脂片用改性剂优选含有成分(A)、成分(B)和成分(C)。该情况下，对于成分(A)与成分(B)和成分(C)的含有比率，从对使用树脂片用改性剂(改性层形成用组合物)的基材树脂片的粘接性、以及得到的表面改性树脂片的防雾性、光滑性和抗静电性的观点出发，在将它们的总和设为100质量％的情况下，分别优选0.1～15.0质量％、35.0～85.0质量％和15.0～60.0质量％，更优选0.1～10.0质量％、38.0～65.0质量％和30.0～60.0质量％。
本发明的树脂片用改性剂是制造在基材树脂片的表面具有防雾性、光滑性和抗静电性优异的改性层的表面改性树脂片的原料。优选同时包含成分(A)等、与液体介质(选自水、醇等中的至少1者，优选水、或水与碳原子数1～3的醇的混合液)，适合于对基材树脂片的涂布的液态的改性层形成用组合物。该液态组合物中，液体介质的含有比率没有特别限定。
在上述基材树脂片上涂布由液态的改性层形成用组合物形成的树脂片用改性剂的方法没有特别限定，可以利用公知的方法。例如可以举出喷涂法、凹版涂布法、气刀涂布法、棒涂法、唇涂法、流涂法、浸涂法等。涂布树脂片用改性剂后，通常进行涂膜的干燥。干燥温度优选60℃～120℃。
本发明中，作为涂布树脂片用改性剂而成的基材树脂片，可以使用包含公知的树脂者。上述基材树脂片优选热塑性树脂片，该热塑性树脂例如可以举出：1)聚苯乙烯、苯乙烯/丙烯腈共聚物等芳香族乙烯基树脂、2)聚对苯二甲酸乙二醇酯等聚酯树脂、3)聚乳酸等脂肪族酯树脂、4)聚氯乙烯、乙烯/氯乙烯共聚物等氯乙烯系树脂、5)聚甲基丙烯酸甲酯、甲基丙烯酸甲酯/苯乙烯共聚物等丙烯酸类树脂、6)6-尼龙、6,6-尼龙等聚酰胺树脂、7)聚碳酸酯树脂、8)聚乙烯、聚丙烯等聚烯烃树脂等。这些之中，优选聚苯乙烯等芳香族乙烯基树脂、聚对苯二甲酸乙二醇酯等聚酯树脂、和聚丙烯等聚烯烃树脂。这些包含热塑性树脂的片可以为无定形片、无拉伸片、同时双轴拉伸片、依次双轴拉伸片等，均可，可以使用以往以公知的片成型手段制造而成者。另外，上述基材树脂片根据需要可以实施电晕处理、等离子体处理、火焰处理、利用酸或碱的化学溶液处理等表面处理。涂布由液态的改性层形成用组合物形成的树脂片用改性剂的表面的、依据JIS K 6768而测得的润湿张力没有特别限制，从树脂片用改性剂的粘接性的观点出发，优选35mN/m～70mN/m。
上述基材树脂片的厚度没有特别限定。
本发明的表面改性树脂片具备：源自基材树脂片且包含树脂的基层；和，配置于该基层的至少一面侧的、包含上述本发明的树脂片用改性剂的改性层。优选由液态的改性层形成用组合物形成的树脂片用改性剂涂布于基材树脂片的至少一面侧而成者，特别是，为上述本发明的树脂片用改性剂在每一面侧按照以固体成分换算计优选10～200mg/m2、更优选30～200mg/m2的量浸渍于表面的树脂片。
本发明的表面改性树脂片中，改性层的厚度没有特别限定。本发明的表面改性树脂片在两面具备改性层的情况下，各改性层的厚度可以相同也可以不同。
本发明的表面改性树脂片在改性层的表面根据需要也可以具备脱模层。脱模层可以包含硅油、聚氧亚烷基聚合物等。作为制造依次具备改性层和脱模层的表面改性树脂片的方法，可以设为如下方法：在基材树脂片的表面形成改性层后、在该改性层的表面涂布脱模剂组合物的方法、将同时包含脱模剂的树脂片用改性剂涂布在基材树脂片的表面之后使脱模剂迁移至表面侧的方法等。本发明的表面改性树脂片仅在一面侧具备改性层的情况下，在无改性层的一侧可以具备脱模层。
本发明的表面改性树脂片的防雾性优异，因此，透过该片确认位于相反侧的物品的视觉识别性高，改性层的光滑性优异，因此，改性层与物品接触的情况下，无物品的损伤或改性层的断裂，改性层的抗静电性优异，因此，可以抑制灰尘、尘埃的附着。这种作用不仅在片中可以得到，在加工该片而得到的成型品中也可以得到。
上述成型品可以通过将上述本发明的表面改性树脂片成型而制造。作为成型方法，可以举出真空成型、压空成型等。另外，成型品可以用于饮料和食品用容器的盖、托盘、电子部件的包装容器等。
实施例
以下，为了使本发明的构成和效果更具体，列举实施例，但本发明不限定于这些实施例。需要说明的是，以下的实施例和比较例中，“％”和“份”为质量基准。
以下，示出例子：首先，制造含有液体介质的树脂片用改性剂(改性层形成用组合物)，之后，将该改性剂涂布于基材树脂片，制造表面改性树脂片，但本发明当然可以形成不含有液体介质的构成的树脂片用改性剂。
1.试验类别1(树脂片用改性剂的原料)
示出实施例和比较例中使用的原料。
1-1.原料(A)
对应于本发明的成分(A)的原料如以下所述。
(A-1)氯化钠粉末
(A-2)硫酸钠粉末
(A-3)氯化钾粉末
(A-4)氯化锂粉末
(a-1)氯化镁粉末
(a-2)硫酸镁粉末
(a-3)碳酸钙粉末
1-2.原料(B)
通过以下的合成例1～8得到对应于本发明的成分(B)的原料。
合成例1(乙烯基共聚物(B-1)的合成)
在具备搅拌装置和回流装置的反应容器中，投入异丙醇300g、甲基丙烯酸N,N-二甲基氨基乙酯65.9g(0.42摩尔)、甲基丙烯酸羟基乙酯45.1g(0.35摩尔)、甲基丙烯酸甲酯90.3g(0.90摩尔)和偶氮二异丁腈1.2g，将它们混合，在氮气气氛下、以80℃用3小时进行自由基聚合反应。接着，在得到的反应液中，用10分钟滴加由单氯乙酸钠48.7g(0.42摩尔)和水629g形成的水溶液，之后，升温至90℃，将异丙醇180g蒸馏去除。将得到的水溶液在电感耦合等离子体(ICP)发射光谱分析装置中用离子交换水和丙酮进行纯化直至氯化钠变得不残留。接着，分析水溶液中的反应产物，结果可知，以规定的比率包含下述的结构单元，基于GPC的数均分子量为55000。以下，将该亲水性丙烯酸类树脂称为“乙烯基共聚物(B-1)”。
Figure BDA0003181912220000121
之后，制造树脂片用改性剂时，使用以25％的浓度含有该乙烯基共聚物(B-1)的水溶液(以下，称为“水溶液(B-1x)”)。
合成例2～8(乙烯基共聚物(B-2)～(B-8)的合成)
与合成例1同样地合成乙烯基共聚物(B-2)～(B-8)。
乙烯基共聚物(B-2)是以规定的比率包含下述结构单元、且基于GPC的数均分子量为25000的共聚物。
Figure BDA0003181912220000131
乙烯基共聚物(B-3)是以规定的比率包含下述结构单元、且基于GPC的数均分子量为80000的共聚物。
Figure BDA0003181912220000132
乙烯基共聚物(B-4)是以规定的比率包含下述结构单元、且基于GPC的数均分子量为50000的共聚物。
Figure BDA0003181912220000141
乙烯基共聚物(B-5)是以规定的比率包含下述结构单元、且基于GPC的数均分子量为50000的共聚物。
Figure BDA0003181912220000142
乙烯基共聚物(B-6)是以规定的比率包含下述结构单元、且基于GPC的数均分子量为12000的共聚物。
Figure BDA0003181912220000151
乙烯基共聚物(B-7)是以规定的比率包含下述结构单元、且基于GPC的数均分子量为45000的共聚物。
Figure BDA0003181912220000152
乙烯基共聚物(B-8)是以规定的比率包含下述结构单元、且基于GPC的数均分子量为40000的共聚物。
Figure BDA0003181912220000161
之后，使用均以25％的浓度含有这些乙烯基共聚物(B-2)～(B-8)的水溶液(以下，称为“水溶液(B-2x)”～“水溶液(B-8x”)。
1-3.原料(C)
对应于本发明的成分(C)的原料如以下所述。
(C-1)十八烷酸钠粉末
(C-2)十八碳烯酸钠粉末
(C-3)十六碳烯酸钠粉末
(C-4)十八碳烯酸钾粉末
(C-5)十八烷酸钾粉末
(C-6)十四烷酸钠粉末
(C-7)二十二碳烯酸钾粉末
2.试验类别2(树脂片用改性剂的制备)
使用试验类别1所示的原料，制备用于涂布于基材树脂片的由液态的改性层形成用组合物形成的树脂片用改性剂(参照表1)。需要说明的是，在以下实验中，使用乙烯基共聚物(B-1)的水溶液(B-1x)作为制造液态的改性层形成用组合物的原料，但如上所述，其不是水溶液，也可以仅使用不含液体介质的经分离的乙烯基共聚物而制成树脂片用改性剂。
实施例1-1
将8.0份的水、4.4份的水溶液(B-1x)、0.8份的十八烷酸钠(C-1)和0.1份的氯化钠(A-1)混合，制备固体成分15％的树脂片用改性剂(E-1)。该树脂片用改性剂(E-1)中，含碱金属无机化合物/亲水性丙烯酸类树脂/有机羧酸盐的固体成分比(质量比)为5/55/40。
实施例1-2～1-13、比较例1-1～1-6
使用表1的原料，与实施例1同样地制备改性剂(E-2)～(E-13)和(e-1)～(e-6)。
[表1]
Figure BDA0003181912220000181
3.试验类别3(表面改性树脂片的制造和评价)
使用试验类别2中制造的树脂片用改性剂制备涂覆液，之后，使用该涂覆液和基材树脂片，制造表2所示的表面改性树脂片。以下示出所使用的基材树脂片。
(S-1)聚酯系树脂片(聚对苯二甲酸乙二醇酯树脂未结晶型)
(S-2)聚酯系树脂片(聚对苯二甲酸乙二醇酯树脂双轴拉伸型)
(S-3)脂肪族酯系树脂片(无拉伸型、通过电晕处理、依据JIS K 6768的润湿张力为44mN/m者)
(S-4)聚苯乙烯系树脂片(无拉伸型、通过电晕处理、依据JIS K 6768的润湿张力为44mN/m者)
(S-5)聚苯乙烯系树脂片(双轴拉伸型、通过电晕处理、依据JIS K 6768的润湿张力为44mN/m者)
(S-6)聚烯烃系树脂片(聚丙烯、无拉伸型、通过电晕处理、依据JIS K 6768的润湿张力为44mN/m者)
(S-7)聚甲基丙烯酸甲酯片(无拉伸型、通过电晕处理、依据JIS K 6768的润湿张力为44mN/m者)
实施例2-1
将实施例1-1中制作的固体成分15％的树脂片用改性剂(E-1)13.3g与水/异丙醇＝90/10(质量比)的溶剂86.7g混合，从而制备有效浓度2％的涂覆液。
之后，用棒涂机在聚酯系树脂片(S-1)上涂布制备好的涂覆液(涂布量：5g/m2)。之后，使涂膜以70℃干燥，制作具有绝干涂布量为100mg/m2的改性层的表面改性树脂片(P-1)。
接着，对于得到的表面改性树脂片(P-1)，进行改性层表面的防雾性、光滑性和抗静电性的评价。将其结果一并记载于表2。
(1)防雾性
将表面改性树脂片切成直径7cm的圆形，在放入了60℃的热水100ml的200ml体积的烧杯中，以改性层的表面成为烧杯的内侧的方式覆盖，在5℃的冰箱内放置24小时。之后，观察表面改性树脂片的改性层的表面的水滴的附着程度，以下述基准评价防雾性。
＜防雾性的评价基准＞
◎：无水滴的附着，透明(防雾性优异)
○：有大的水滴的附着，但透明(防雾性良好)
△：有水滴的附着，稍有不透明(防雾性差)
×：有小的水滴的附着，不透明(防雾性明显差，是不实用的)
(2)光滑性
依据JIS-K7125，测定改性层的表面的动摩擦系数，以下述的基准评价光滑性。
＜光滑性的评价基准＞
◎：动摩擦系数低于0.25
○：动摩擦系数为0.25以上且低于0.30
△：动摩擦系数为0.30以上且低于0.35
×：动摩擦系数为0.35以上
(3)抗静电性
将表面改性树脂片在温度20℃和相对湿度65％的条件下载置24小时进行湿度调节后，在同一条件下测定表面电阻率(Ω)。测定设备为SHISHIDO电气株式会社制表面电阻值测定装置(商品名：メガレスタHT-301)。根据表面电阻值以以下的基准评价抗静电性。
＜抗静电性的评价基准＞
◎：表面电阻率低于5.0×108Ω
○：表面电阻率为5.0×108Ω以上且低于1.0×109Ω
△：表面电阻率为1.0×109Ω以上且低于5.0×109Ω
×：表面电阻率为5.0×109Ω以上
实施例2-2～2-13和比较例2-1～2-6
使用树脂片用改性剂(E-2)～(E-13)和(e-1)～(e-6)代替树脂片用改性剂(E-1)，除此之外，与实施例2-1同样地，制备各涂覆液。接着，将涂覆液涂布于表2所示的基材树脂片的表面，得到具备改性层的表面改性树脂片(P-2)～(P-13)和(p-1)～(p-6)。
之后，与实施例2-1同样地，进行表面改性树脂片的评价。将其结果一并记载于表2。
[表2]
Figure BDA0003181912220000221
4.试验类别4(成型品的制造)
将试验类别3中制造的表面改性树脂片供于压空成型，制造以改性层为内表面的锥台状的成型品(开口部：70mm×70mm、底部：60mm×60mm、深度：30mm)。
实施例3-1
利用压空成型机加工实施例2-1中得到的表面改性树脂片(P-1)，制作锥台状的成型品。未见改性层的剥离等不良情况，外观性也良好。
实施例3-2～3-13
使用表2中记载的表面改性树脂片，与实施例3-1同样地，制作锥台状的成型品。任一成型品均未见改性层的剥离等不良情况，外观性也良好。
产业上的可利用性
通过将本发明的树脂片用改性剂涂布于基材树脂片的表面，从而可以制造具有防雾性、光滑性和抗静电性优异的改性层的表面改性树脂片。本发明的表面改性树脂片的该改性层的表面具有优异的防雾性、光滑性和抗静电性，因此，使用这种表面改性树脂片，可以效率良好地制造防雾性、光滑性和抗静电性优异的容器等成型品。而且，表面改性树脂片和成型品适合于食品包装材料、食品包装容器、电子材料的包装容器等广泛的用途。

Claims (7)

1.一种树脂片用改性剂，其特征在于，其为用于树脂片的表面改性的改性剂，其含有：
(A)包含碱金属元素的无机化合物、
(B)亲水性丙烯酸类树脂、
(C)润滑剂、和
(D)液体介质，
所述成分(A)为选自氯化物和硫酸盐中的至少一者，
所述成分(A)中所含的所述碱金属元素为选自锂、钠和钾中的至少1者，所述成分(B)为由源自下述式(1)所示的化合物的结构单元和选自源自下述式(2)所示的化合物的结构单元、源自下述式(3)所示的化合物的结构单元、和源自下述式(4)所示的化合物的结构单元中的至少一种构成的聚合物，
所述润滑剂(C)包含有机羧酸盐，
所述(D)液体介质为选自水及醇中的至少一种，
所述成分(A)、所述成分(B)和所述成分(C)的含有比率在将它们的总和设为100质量％的情况下，分别为0.1～10.0质量％、38.0～65.0质量％、和30.0～60.0质量％，
Figure FDA0004067889980000011
式(1)中，R1为氢原子或甲基，R2为碳原子数1～4的2价的烃基，R3和R4为彼此相同或不同的碳原子数1～4的烃基，
Figure FDA0004067889980000021
式(2)中，R5为氢原子或甲基，R6为具有1个羟基的碳原子数1～4的烃基、或具有2个羟基的碳原子数2～4的烃基，
Figure FDA0004067889980000022
式(3)中，R7为氢原子或甲基，R8为氢原子、或碳原子数1～18的烃基，
Figure FDA0004067889980000023
式(4)中，R9为氢原子或甲基，R10和R11为彼此相同或不同的氢原子、或碳原子数1～3的烃基，其中，R10和R11这两者为氢原子的情况排除在外。
2.根据权利要求1所述的树脂片用改性剂，其中，所述成分(B)的数均分子量为10000～100000。
3.根据权利要求1所述的树脂片用改性剂，其中，所述有机羧酸盐是烃基的碳原子数为14～22的脂肪族羧酸的碱金属盐。
4.一种表面改性树脂片，其特征在于，其具备：包含树脂的基层；和，配置于该基层的至少一面侧的、使用权利要求1～3中任一项所述的树脂片用改性剂形成的改性层。
5.根据权利要求4所述的表面改性树脂片，其中，所述基层中所含的所述树脂为选自聚酯树脂和烯烃树脂中的至少一种。
6.根据权利要求4所述的表面改性树脂片，其中，所述基层中所含的所述树脂为选自聚酯树脂和芳香族乙烯基树脂中的至少一种。
7.一种成型品的制造方法，其特征在于，将权利要求4～6中任一项所述的表面改性树脂片供于成型加工。
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