CN115029077A - 粘合膜 - Google Patents
粘合膜 Download PDFInfo
- Publication number
- CN115029077A CN115029077A CN202210185895.5A CN202210185895A CN115029077A CN 115029077 A CN115029077 A CN 115029077A CN 202210185895 A CN202210185895 A CN 202210185895A CN 115029077 A CN115029077 A CN 115029077A
- Authority
- CN
- China
- Prior art keywords
- adhesive
- silane coupling
- substrate
- film
- coupling agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 61
- 239000010410 layer Substances 0.000 claims abstract description 56
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 47
- 239000012790 adhesive layer Substances 0.000 claims abstract description 40
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 34
- 239000010408 film Substances 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 32
- -1 acryl group Chemical group 0.000 claims description 30
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- 239000013039 cover film Substances 0.000 claims description 14
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- 229920000515 polycarbonate Polymers 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 11
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 3
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- 230000032683 aging Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
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- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
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- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
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- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
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- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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Abstract
本发明提供一种印刷层的密合性优异的粘合膜。粘合膜(10)的特征在于,具备基材(11)和层叠于基材(11)的单面的粘合层(12),基材(11)由含有硅烷偶联剂的聚氨酯树脂形成。可以在基材(11)的与粘合层(12)相反一侧的面形成印刷层(15)。可以在粘合层(12)的与基材(11)相反一侧的面贴合被粘物(20)。
Description
技术领域
本发明涉及粘合膜。
背景技术
出于保护物品的表面、或对表面施加装饰等目的,粘合膜被使用。
例如,专利文献1中记载了通过使用将聚氯乙烯膜作为基材并层叠有由丙烯酸类粘合剂形成的粘合层的装饰成形用膜,也能够柔软地跟随三维曲面部。
另外,专利文献2中记载了在用于粘贴于汽车的涂装钢板表面上的粘合片中,基材包含由聚碳酸酯类聚氨酯形成的硬质层和由聚酯类聚氨酯形成的软质层,粘合剂层由以含羧基的烯属不饱和单体等作为共聚成分的丙烯酸类粘合剂形成。
另外,专利文献3中记载了一种薄膜标记片(marking sheet),其在由聚酯类或聚碳酸酯类的聚氨酯树脂的无拉伸膜形成的基材的一面层叠有粘合剂层,并在基材的另一面设置有装饰显示层。
现有技术文献
专利文献
专利文献1:日本专利第6577380号公报
专利文献2:日本专利第4886969号公报
专利文献3:日本特开2003-295769号公报
发明内容
技术问题
关于物品的表面所使用的粘合膜而言,有时通过对基材进行印刷等来施加装饰。专利文献1中记载了通过在聚氯乙烯膜中添加增塑剂,使向三维曲面的贴附变得容易的伸长率和装饰成形用的印刷性优异。但是,由于使用有机氯类化合物,因此用途有可能受到限制。
在专利文献2中,记载有对于小石子等物体弹起而使车身损伤的现象即崩裂(chipping),为了保护车身而粘贴粘合片,但没有对粘合片施加印刷等的记载。
专利文献3中记载了通过金属蒸镀、印刷、烫铂等在基材的另一面形成装饰显示层,但优选在形成装饰显示层的基础上涂布透明树脂而形成保护层(表层透明层)。
如果在印刷层上形成保护层,则能够有效地抑制印刷层的剥离等。但是,形成保护层的工序繁杂。另外,根据物品的种类等,有时无法容易地实施涂布透明树脂的工序。为了提高印刷层与基材的密合性,也考虑在基材上的形成印刷层的面设置底漆等易粘接层。但是,形成易粘接层的工序繁杂。另外,根据物品的种类等,有时无法容易地实施形成易粘接层的工序。
本发明是鉴于上述情况而完成的,其目的在于提供一种印刷层的密合性优异的粘合膜。
技术方案
为了解决上述问题,本发明提供一种粘合膜,其特征在于,具备基材和层叠于上述基材的单面的粘合层,上述基材由含有硅烷偶联剂的聚氨酯树脂形成。
上述基材中的上述硅烷偶联剂的含量相对于上述聚氨酯树脂100重量份可以为0.1~2重量份。更优选可以为0.2~1.0重量份。
作为上述硅烷偶联剂,包含具有环氧基作为有机官能团的第一硅烷偶联剂和具有丙烯酰基作为有机官能团的第二硅烷偶联剂,上述第一硅烷偶联剂与上述第二硅烷偶联剂的重量比可以为0.5:1~1:0.5。重量比也可以为0.7:1~1:0.7。
上述聚氨酯树脂可以利用交联剂进行交联。
上述聚氨酯树脂可以为聚碳酸酯类聚氨酯。
在上述基材的与上述粘合层相反一侧的面可以具有覆盖膜。
在上述基材的与上述粘合层相反一侧的面可以形成印刷层。
在上述粘合层的与上述基材相反一侧的面可以具有剥离膜。
在上述粘合层的与上述基材相反一侧的面可以贴合有被粘物的玻璃。
发明效果
根据本发明,能够改善印刷层的密合性。
附图说明
图1是示出粘合膜的一例的截面图。
图2是示出贴合有粘合膜的被粘物的一例的截面图。
符号说明
10…粘合膜、11…基材、11a…装饰面、12…粘合层、12a…粘合面、13…覆盖膜、14…剥离膜、15…印刷层、20…被粘物。
具体实施方式
以下,基于优选的实施方式对本发明进行说明。
图1中示出粘合膜的一例。粘合膜10具备基材11和层叠于基材11的单面的粘合层12。基材11的与粘合层12相反一侧的面成为能够进行印刷等装饰的装饰面11a。粘合层12的与基材11相反一侧的面成为能够进行向物品等贴合的粘合面12a。
基材11由含有硅烷偶联剂的聚氨酯树脂形成。由此,在对装饰面11a施加印刷等装饰的情况下,也能够改善装饰对于基材11的密合性。
作为聚氨酯树脂,只要是以多元醇与多异氰酸酯的反应产物为主体的树脂就没有特别限定,可以从公知的聚氨酯树脂中适当选择使用。基材11可以含有1种聚氨酯树脂,也可以含有2种以上的聚氨酯树脂。
作为多元醇,可举出亚烷基二醇(alkylene glycol)、二亚烷基二醇(dialkyleneglycol)、聚亚烷基二醇(polyalkylene glycol)、聚醚类多元醇(polyether polyol)、聚氨酯类多元醇(polyurethane polyol)、聚酯类多元醇(polyester polyol)、聚碳酸酯类多元醇(polycarbonate polyols)、内酯类多元醇(lactone polyol)等。多元醇可以是1分子中具有2个羟基的二元醇,也可以是1分子中具有3个羟基的三元醇。多元醇可以具有4个以上的羟基。
作为多异氰酸酯(Polyisocyanate),可以是1分子中具有2个异氰酸酯基的二异氰酸酯,也可以是1分子中具有3个异氰酸酯基的三异氰酸酯。多异氰酸酯可以具有4个以上的异氰酸酯基。作为二异氰酸酯,可举出甲苯二异氰酸酯(Toluene diisocyanate,TDI)、苯二亚甲基二异氰酸酯(Xylylene diisocyanate,XDI)等芳香族二异氰酸酯、六亚甲基二异氰酸酯(Hexamethylene diisocyanate,HDI)、五亚甲基二异氰酸酯(Pentaethylenediisocyanate,PDI)、异佛尔酮二异氰酸酯(Isophorone diisocyanate,IPDI)等脂肪族二异氰酸酯。
通过使至少1种以上的二元醇与至少1种以上的二异氰酸酯反应,能够得到线状的聚氨酯树脂。通过使用1分子中具有3个以上羟基的化合物作为多元醇的至少一部分,或者使用1分子中具有3个以上异氰酸酯基的化合物作为多异氰酸酯的至少一部分,能够得到交联结构的聚氨酯树脂。若使用经交联的聚氨酯树脂,则即使在防飞散膜等要求机械强度和/或耐久性的粘合膜10的情况下,也能够提高基材11的机械强度和/或耐久性。
通过使多异氰酸酯作为交联剂与具有相对于异氰酸酯基未反应的羟基的聚氨酯树脂反应,能够使聚氨酯树脂交联。即使使多元醇作为交联剂与具有异氰酸酯基的聚氨酯树脂反应,也能够使聚氨酯树脂交联。对于聚氨酯树脂的交联剂并不限定于多异氰酸酯和/或多元醇,也可以使用能够与聚氨酯树脂所具有的羟基和/或异氰酸酯基等官能团反应的适当的交联剂。交联剂的比例可以适当设定,例如,相对于聚氨酯树脂100重量份,可举出交联剂5~20重量份。聚氨酯树脂可以使用上述任一种,也可以为聚碳酸酯类聚氨酯。在这种情况下,具有耐久性相对优异的优点。
基材11的厚度虽无特别限定,但可以列举出例如30~150μm左右。基材11的厚度更优选为100μm以下,进一步优选为80μm以下。作为形成基材11的方法,虽无特别限定,但可以列举出吹胀成型、挤出成型、溶液浇铸、热压、压延成型、切削等。
例如,在通过溶液浇铸形成基材11的情况下,通过将溶解于溶剂的聚氨酯树脂涂布于预定的涂布面后,使溶剂干燥,从而能够将聚氨酯树脂形成为膜状。作为溶剂,虽无特别限定,但可以列举出甲苯、环己烷等烃类溶剂;甲醇、乙醇、异丙醇等醇类溶剂;丙酮、甲乙酮、环己酮、甲基异丁基酮等酮类溶剂;乙酸乙酯等酯类溶剂等。
也可在将具有热塑性或溶剂可溶性的聚氨酯树脂形成为膜状后,使添加至聚氨酯树脂中的交联剂反应,从而使聚氨酯树脂交联。由此,容易兼顾适于基材11的形成的加工性和适于基材11的用途的耐久性。
从对水分等的耐久性的观点出发,优选使用水解性低的聚碳酸酯或聚醚类的聚氨酯树脂。从溶液浇铸等的涂布性(coating property)、生产率的观点考虑,交联前的聚氨酯树脂的重均分子量(Mw)优选为1万~10万左右,也可以为2.5万~6万左右。交联后的聚氨酯树脂的凝胶分数优选为50~90%左右,优选为70~80%左右。
实施方式的基材11含有硅烷偶联剂。作为(C)硅烷偶联剂,可举出在1分子中具有至少1个有机官能团和至少1个水解性基团的化合物。作为水解性基团,可举出与硅原子键合的甲氧基、乙氧基等烷氧基等。作为有机官能团,可举出环氧基、丙烯酰氧基、甲基丙烯酰氧基、乙烯基、氨基、异氰酸酯基、酸酐基等。在以下的说明中,有时将丙烯酰氧基或甲基丙烯酰氧基统称为(甲基)丙烯酰氧基。
作为具有环氧基的硅烷偶联剂,可列举出例如3-环氧丙氧基丙基三烷氧基硅烷(3-glycidoxy propyl trialkoxysilane)、3-环氧丙氧基丙基甲基二烷氧基硅烷(3-glycydoxy propyl methyl dialkoxysilane)、2-(3,4-环氧环己基)乙基三烷氧基硅烷(2-(3,4-epoxy cyclohexyl)ethyl trialkoxysilane)、2-(3,4-环氧环己基)乙基甲基二烷氧基硅烷(2-(3,4-epoxy cyclohexyl)ethyl methyl dialkoxysilane)、5,6-环氧己基三烷氧基硅烷(5,6-epoxy hexyl trialkoxysilane)、5,6-环氧己基甲基二烷氧基硅烷(5,6-epoxy hexyl methyl dialkoxysilane)等。
作为具有(甲基)丙烯酰氧基的硅烷偶联剂,可列举出例如3-(甲基)丙烯酰氧基丙基三烷氧基硅烷(3-(meta)acryloxy propyl trialkoxysilane)、3-(甲基)丙烯酰氧基丙基甲基二烷氧基硅烷(3-(meta)acryloxy propyl methyl dialkoxysilane)、3-(甲基)丙烯酰氧基丙基二甲基烷氧基硅烷(3-(meta)acryloxy propyl dimethyl alkoxysilane)等。
作为具有乙烯基的硅烷偶联剂,可列举出例如乙烯基三烷氧基硅烷(vinyltrialkoxysilane)、对苯乙烯基三烷氧基硅烷(p-styryl trialkoxysilane)等。
作为具有氨基的硅烷偶联剂,可列举出例如3-氨基丙基三烷氧基硅烷(3-aminopropyl trialkoxysilane)、3-(苯基氨基)丙基三烷氧基硅烷(3-(phenylamino)propyl trialkoxysilane)、3-(2-氨基乙基氨基)丙基三烷氧基硅烷(3-(2-aminoethylamino)propyl trialkoxysilane)、3-(2-氨基乙基氨基)丙基甲基二烷氧基硅烷(3-(2-aminoethyl amino)propyl methyl dialkoxysilane)等。
作为具有异氰酸酯基的硅烷偶联剂,可列举出例如3-异氰酸酯丙基三烷氧基硅烷(3-isocyanate propyl trialkoxysilane)、3-异氰酸酯丙基甲基二烷氧基硅烷(3-isocyanate propyl methyl dialkoxysilane)等。
作为具有酸酐基的硅烷偶联剂,可列举出例如3-(三烷氧基硅烷)丙基琥珀酸酐(3-(trialkoxysilyl)propyl succinic anhydride)、3-(甲基二烷氧基硅)丙基琥珀酸酐(3-(methyl dialkoxysilyl)propyl succinic anhydride)等。
硅烷偶联剂的比例可以适当设定,例如,可以列举出相对于聚氨酯树脂100重量份,硅烷偶联剂为0.1~2重量份。基材11可以含有2种以上的硅烷偶联剂。此时,2种以上的硅烷偶联剂的合计量相对于聚氨酯树脂100重量份可以为0.1~2重量份。硅烷偶联剂的有机官能团优选根据印刷油墨中所含的树脂的种类进行选择。
上述具有环氧基的硅烷偶联剂、以及具有氨基、脲基和/或异氰脲酸酯基的硅烷偶联剂的提高热固化油墨的密合性的效果相对高。此外,上述具有(甲基)丙烯酰氧基的硅烷偶联剂和具有乙烯基的硅烷偶联剂的提高UV固化油墨的密合性的效果相对高。
作为上述硅烷偶联剂,可以包含具有环氧基作为有机官能团的第一硅烷偶联剂和具有丙烯酰基作为有机官能团的第二硅烷偶联剂。在这种情况下,对于热固化油墨、以及对于UV固化油墨也能够提高密合性,并且能够提高通用性。上述第一硅烷偶联剂与上述第二硅烷偶联剂的重量比可以为0.5:1~1:0.5。在这种情况下,对于热固化油墨、以及对于UV固化油墨,均能够均衡地提高密合性。上述第一硅烷偶联剂与上述第二硅烷偶联剂的重量比可以为0.7:1~1:0.7。
基材11可以根据需要添加着色剂、稳定剂、抗氧化剂、阻燃剂等添加剂。基材11在不添加着色剂等的情况下,能够赋予高透明性。作为基材11的透明性,例如可列举出总光线透过率90%以上、雾度2%以下。
粘合层12由粘合剂形成。粘合剂没有特别限定,可以根据要贴合粘合膜10的物品等,从公知的粘合剂中适当选择使用。粘合层12可以以与基材11接触的方式层叠。也可以在基材11与粘合层12之间夹设其他层。从透明性、耐候性等观点出发,可列举出丙烯酸类粘合剂、聚酯类粘合剂等。
作为丙烯酸类粘合剂,可列举出使用了将丙烯酸正丁酯、丙烯酸-2-乙基己酯、丙烯酸异辛酯、丙烯酸异壬酯等主单体与丙烯腈、乙酸乙烯酯、甲基丙烯酸甲酯、丙烯酸乙酯等共聚单体、或者丙烯酸、甲基丙烯酸、丙烯酸羟基乙酯、丙烯酸羟基丁酯、甲基丙烯酸缩水甘油酯、N-羟甲基甲基丙烯酰胺等官能单体共聚而成的丙烯酸类聚合物的粘合剂。为了提高丙烯酸类聚合物的粘合力,可以使用多异氰酸酯化合物、多官能环氧化合物、多官能性环氧化合物、金属螯合化合物等交联剂进行交联。
作为聚酯类粘合剂,可列举出使用了使二元羧酸等多元羧酸与二元醇等多元醇缩聚而得到的聚酯类聚合物的粘合剂。作为二元羧酸,可举出己二酸、庚二酸、辛二酸、壬二酸、癸二酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、环己烷二羧酸等。作为二元醇,可举出亚烷基二醇、二亚烷基二醇、聚亚烷基二醇、聚醚二醇等。为了提高聚酯类聚合物的粘合力,可以使用多异氰酸酯化合物、多官能环氧化合物、多官能性环氧化合物、金属螯合化合物等交联剂进行交联。
形成粘合层12的方法没有特别限定,但可以将含有粘合剂(聚合物)和交联剂的粘合剂组合物涂布于基材11后,通过熟化(aging)将粘合剂用交联剂交联而形成粘合层12。交联剂的比例可以适当设定,例如,可列举出相对于粘合剂100重量份,交联剂为1~10重量份。也可以将粘合剂涂布成基材11以外的片状,使其干燥后,将粘合层12转印到基材11上。也可以在基材11与粘合层12之间夹设其他层,基材11与粘合层12也可以相互接触。
粘合层12的厚度虽无特别限定,但可以列举出例如10~50μm左右。粘合层12在常温(5~35℃的范围内)下可以具有粘性,在高于常温的温度下也可以具有粘性。
包含基材11及粘合层12的粘合膜10的厚度虽无特别限定,但可以列举出例如40~200μm左右。在此,粘合膜10的厚度不包括下述的覆盖膜13和剥离膜14的厚度。粘合膜10的厚度更优选为100μm以下。
为了保护装饰面11a,粘合膜10可以在基材11的与粘合层12相反一侧的面具有覆盖膜13。作为覆盖膜13,虽无特别限定,但可以使用聚酯树脂膜、聚酰胺类树脂膜、丙烯酸类树脂膜、聚烯烃类树脂膜、纤维素类树脂膜、玻璃纸膜、纸、树脂层压纸、金属箔、树脂层压金属箔、金属蒸镀树脂膜等。
覆盖膜13可以是不透明或半透明的,但在使用透明性高的覆盖膜13的情况下,即使不剥离覆盖膜13,也能够通过目视容易地确认装饰面11a的状态,因此优选。覆盖膜13可以是无拉伸的树脂膜或经拉伸的树脂膜。覆盖膜13可以在与装饰面11a接触的一侧的面具有有机硅类剥离剂、氟类剥离剂、长链烷基类剥离剂等剥离剂的层。覆盖膜13在与装饰面11a接触的一侧的面也可以不具有剥离剂。
为了保护粘合面12a,粘合膜10在粘合层12的与基材11相反一侧的面可以具有剥离膜14。作为剥离膜14,没有特别限定,但可以使用聚酯树脂膜、聚酰胺类树脂膜、丙烯酸类树脂膜、聚烯烃类树脂膜、纤维素类树脂膜、玻璃纸膜、纸、树脂层压纸、金属箔、树脂层压金属箔、金属蒸镀树脂膜等。
剥离膜14可以为不透明或半透明,但在使用透明性高的剥离膜14的情况下,即使不将剥离膜14剥离,也能够通过目视容易地确认粘合面12a的状态,因此优选。剥离膜14可以是无拉伸的树脂膜或经拉伸的树脂膜。剥离膜14可以在与粘合面12a接触的一侧的面具有有机硅类剥离剂、氟类剥离剂、长链烷基类剥离剂等剥离剂的层。剥离膜14也可以在与粘合面12a接触的一侧的面不具有剥离剂。
在图2示出贴合有粘合膜10的被粘物20的一例。在基材11形成有印刷层15,在粘合层12贴合有被粘物20。在基材11形成印刷层15的工序和在粘合层12贴合被粘物20的工序的顺序虽没有限定,但优选在基材11形成印刷层15后,在粘合层12贴合被粘物20。也可以具有将粘合膜10裁切成适合于被粘物20的尺寸的工序。针对基材11的印刷优选在粘合膜10的裁切前实施。
粘合膜10的装饰面11a由上述基材11形成,因此即使不设置底漆等易粘接层,也能够容易地使印刷层15密合。在为了保护装饰面11a而设置了覆盖膜13的情况下,在印刷前去除覆盖膜13。在形成基材11之后,可以在装饰面11a不设置覆盖膜13而形成印刷层15。
形成印刷层15的方法没有特别限定,但可以举出凹版印刷、凸版印刷、胶版印刷、丝网印刷、喷墨等印刷方式。印刷层15可以形成在装饰面11a的整个表面,也可以形成在装饰面11a的部分区域。也可以重叠两层以上的印刷层15。可以在装饰面11a的不同区域形成不同的印刷层15。也可以在装饰面11a施加除了印刷层15之外的装饰。作为其他装饰层,例如可以列举出基于溅射等的金属蒸镀层等。
用于形成印刷层15的油墨可以包含颜料、染料等着色材料和粘结剂。作为粘结剂,没有特别限定,但可举出聚酰胺树脂、聚氨酯树脂、聚酯树脂、聚氯乙烯树脂、聚乙酸乙烯酯树脂、丙烯酸树脂、环氧树脂、聚丁二烯树脂、环化橡胶等。油墨可以含有水、有机溶剂、植物油等溶剂。印刷后,可以通过溶剂的挥发、油墨的固化等使油墨干燥。为了促进油墨的干燥,可以实施加热、紫外线照射等。
在将粘合膜10贴合于被粘物20之前,从粘合层12除去剥离膜14。由此,经由粘合层12能够将粘合膜10贴合于被粘物20。被粘物20也可以是在显示面、壳体等使用了玻璃的电子设备。被粘物20中与粘合层12接触的面的材质虽然没有特别限定,但可以举出玻璃、金属、塑料等。被粘物20不限于供粘合膜10贴合的面为平面状的物品,也可以是具有曲面部的物品。
将粘合膜10贴合于被粘物20的方法没有特别限定,只要使用加压、抽吸等使粘合层12密合于被粘物20即可。作为加压方式,可以是辊部件、棒状部件、板状部件等机械方式,也可以是使用了液体或气体等流体的压力介质方式。优选使粘合膜10暂时附着于被粘物20后,从周围作用液体的压力而各向同性地进行加压。压力介质可以是温水。作为抽吸方式,可以列举出利用真空来抽吸粘合膜10与被粘物20之间的空气的方式。
以上,基于优选的实施方式对本发明进行了说明,但本发明并不限定于上述的实施方式,在不脱离本发明的主旨的范围内能够进行各种改变。
[实施例]
以下,通过实施例对本发明进行具体说明。
(实施例1)
使用含有聚碳酸酯类的聚氨酯树脂(大日精化工业株式会社制、商品名DAIFERAMINE(注册商标)MAU8288A、重均分子量5万)100重量份、作为交联剂的TDI类多异氰酸酯(东曹株式会社制、商品名Coronate(注册商标)L-45E)10重量份、作为硅烷偶联剂的3-环氧丙氧基丙基三甲氧基硅烷(信越化学工业株式会社制、商品名KBM-403)0.2重量份和3-丙烯酰氧基丙基三甲氧基硅烷(信越化学工业株式会社制、商品名KBM-5103)0.2重量份的聚氨酯溶液,通过溶液浇铸法形成厚度60μm的膜,来制作实施例1的基材。
(实施例2和3)
通过与实施例1同样的制造方法,仅将各硅烷偶联剂的添加量如表1中记载那样变更,来制作实施例2和3的基材。
(实施例4)
使用含有聚碳酸酯类的聚氨酯树脂(东曹株式会社制,商品名Nipporan(注册商标)5199、重均分子量3万)100重量份、作为交联剂的HDI类多异氰酸酯(东曹株式会社制、商品名Coronate(注册商标)LHX)4重量份、作为硅烷偶联剂的3-环氧丙氧基丙基三甲氧基硅烷(信越化学工业株式会社制、商品名KBM-403)0.5重量份和3-丙烯酰氧基丙基三甲氧基硅烷(信越化学工业株式会社制、商品名KBM-5103)0.5重量份的聚氨酯溶液,通过溶液浇铸法形成厚度60μm的膜,来制作实施例4的基材。
(实施例5和6)
通过与实施例1同样的制造方法,仅使用3-环氧丙氧基丙基三甲氧基硅烷(信越化学工业株式会社制、商品名KBM-403)作为硅烷偶联剂,并且变更为表1中记载的添加量,来制作实施例5和6的基材。
(实施例7和8)
通过与实施例1同样的制造方法,仅使用3-丙烯酰氧基丙基三甲氧基硅烷(信越化学工业株式会社制、商品名KBM-5103)作为硅烷偶联剂,且变更为表1中记载的添加量,来制作实施例7和8的基材。
(比较例1)
在聚氨酯溶液中不添加硅烷偶联剂,使用含有上述聚碳酸酯类的聚氨酯树脂100重量份和交联剂10重量份的聚氨酯溶液,通过溶液浇铸法形成厚度60μm的膜,来制作比较例1的基材。
(比较例2)
将市售的热塑性聚氨酯弹性体树脂(TPU)膜(大仓工业株式会社制,商品名:Silklon(注册商标)SNY97、厚度80μm)切割成预定的尺寸,来制作比较例2的基材。
(评价方法)
将UV固化油墨(丙烯酸类)和热固化油墨(环氧类)用于同一基材的不同区域,对基材实施印刷。作为UV固化油墨(丙烯酸类),使用藤仓化成株式会社制、商品名:VB2979U,将评价油墨原液以干燥厚度成为5μm的方式涂布在25μm厚度的剥离膜,在120℃下干燥1分钟。将干燥后的印刷层层压于基材的氨基甲酸酯面,从氨基甲酸酯面侧用金属卤化物灯(累积光量1000mJ/cm2)进行UV照射。固化后,将剥离膜剥离而形成印刷层。
作为热固化油墨(环氧类),使用精工油墨株式会社制、商品名:RUX-710black,在其原液100重量份中加入精工油墨株式会社制、商品名:RUX固化剂2重量份,搅拌至均匀,进行减压脱泡,来制成评价用油墨。将该评价油墨以干燥厚度成为5μm的方式涂布于氨基甲酸酯面,在80℃下干燥10分钟。
接着,将刚进行上述两种印刷后的基材作为对象,按照JIS K5400中规定的棋盘格试验法如下评价初期密合性。基于上述棋盘格试验法,在各印刷层的表面切入100格的切痕,在切割后的印刷层的表面以约50mm的长度附着的方式贴附玻璃纸粘合带,并用橡皮擦摩擦而使带附着于印刷层。从使带附着起算1~2分钟后,拿着带的端部保持与印刷层面成直角,且瞬间剥离,并对印刷被剥离的格数进行计数。通过刚印刷后的棋盘格试验法,在100格中的被剥离的格数为A的情况下,在表2中记载为“A/100”。
关于热水试验后的密合性,与初期密合性同样地制作对基材施加了印刷的印刷物,在80℃的热水中浸渍30分钟后,将从热水中取出的基材作为对象,通过上述棋盘格试验法对印刷层的剥离进行试验。
(评价结果)
在表2示出实施例1~8和比较例1~2的基材的评价结果。
【表1】
【表2】
如表2所示,关于初期密合性,在实施例1~8和比较例1~2的任一基材中,UV固化油墨和热固化油墨的各印刷层均没有被剥离。
在实施例1~4的基材中,即使在热水试验后,UV固化油墨和热固化油墨的任一印刷层均没有被剥离。
在实施例5和实施例6的基材中,UV固化油墨的印刷层在热水试验后全部格被剥离。在实施例5的基材中,即使在热水试验后热固化油墨的印刷层也没有被剥离,但在硅烷偶联剂少的实施例6的基材中,在热水试验后热固化油墨的印刷层被稍微剥离。
在实施例7和8的基材中,热固化油墨的印刷层在热水试验后全部格被剥离。在实施例7的基材中,即使在热水试验后UV固化油墨的印刷层也没有被剥离,但在硅烷偶联剂少的实施例8的基材中,在热水试验后UV固化油墨的印刷层被稍微剥离。
在比较例1~2的基材中,在热水试验后,在UV固化油墨和热固化油墨的任一印刷层中均确认到全部格的剥离。
(粘合膜的制造方法)
可以使用聚酯类粘合剂或丙烯酸类粘合剂在实施例1的基材(厚度60μm)的单面形成粘合层。例如,可以以干燥后的厚度成为20μm的方式将含有交联剂和溶剂的粘合剂涂布于基材后,使溶剂干燥,进而通过熟化(aging)使粘合剂交联。实施例2~8也可以与实施例1同样地形成粘合层。
Claims (9)
1.一种粘合膜,其特征在于,具备基材和层叠于所述基材的单面的粘合层,
所述基材由含有硅烷偶联剂的聚氨酯树脂形成。
2.根据权利要求1所述的粘合膜,其特征在于,所述基材的所述硅烷偶联剂的含量相对于所述聚氨酯树脂100重量份为0.1~2重量份。
3.根据权利要求1或2所述的粘合膜,其特征在于,作为所述硅烷偶联剂,包含具有环氧基作为有机官能团的第一硅烷偶联剂和具有丙烯酰基作为有机官能团的第二硅烷偶联剂,所述第一硅烷偶联剂与所述第二硅烷偶联剂的重量比为0.5:1~1:0.5。
4.根据权利要求1或2所述的粘合膜,其特征在于,所述聚氨酯树脂被交联剂交联。
5.根据权利要求1或2所述的粘合膜,其特征在于,所述聚氨酯树脂为聚碳酸酯类聚氨酯。
6.根据权利要求1或2所述的粘合膜,其特征在于,在所述基材的与所述粘合层相反一侧的面具有覆盖膜。
7.根据权利要求1或2所述的粘合膜,其特征在于,在所述基材的与所述粘合层相反一侧的面形成有印刷层。
8.根据权利要求1或2所述的粘合膜,其特征在于,在所述粘合层的与所述基材相反一侧的面具有剥离膜。
9.根据权利要求1或2所述的粘合膜,其特征在于,在所述粘合层的与所述基材相反一侧的面贴合有被粘物的玻璃。
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JP4886969B2 (ja) | 2004-03-24 | 2012-02-29 | リンテック株式会社 | 粘着シート |
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