CN1006707B - Mixture carrying out radiative polymerization and method for preparing copolymer - Google Patents

Mixture carrying out radiative polymerization and method for preparing copolymer

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Publication number
CN1006707B
CN1006707B CN 85106270 CN85106270A CN1006707B CN 1006707 B CN1006707 B CN 1006707B CN 85106270 CN85106270 CN 85106270 CN 85106270 A CN85106270 A CN 85106270A CN 1006707 B CN1006707 B CN 1006707B
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copolymer
capable
radiation
mixture
compound
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CN 85106270
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Chinese (zh)
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CN85106270A (en
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尤尔里克·格斯勒
克劳斯·艾尔伯里特
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赫彻斯特股份公司
勒姆有限公司化学工厂
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Priority to DE19843427519 priority Critical patent/DE3427519A1/en
Application filed by 赫彻斯特股份公司, 勒姆有限公司化学工厂 filed Critical 赫彻斯特股份公司
Priority to CN 85106270 priority patent/CN1006707B/en
Publication of CN85106270A publication Critical patent/CN85106270A/en
Publication of CN1006707B publication Critical patent/CN1006707B/en

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Abstract

本发明描述了一种能进行辐射聚合的混合物,其主要组成包含:a)一种能进行自由基聚合的化合物,它具有至少二个带烯键的不饱和端基,在大气压下沸点高于100℃,b)一种在光化性射线作用下能引发化合物a)聚合的化合物,c)一种在水中不溶而在碱性水溶液中可溶的共聚物,该共聚物的组成如说明书所述。 The present invention describes a mixture of radiation polymerizable capable consisting essentially comprising: a) one kind of compound capable of radical polymerization, having at least two ethylenically unsaturated bonds of the baseband, at atmospheric pressure boiling above 100 ℃, b) one kind of a compound capable of initiating the action of actinic rays) polymerizable compound, and a copolymer C is soluble in water and insoluble in alkaline aqueous solution), the composition of the copolymer specification as above. 这种混合物的特点是在未曝光及曝光的状态下具有高度的柔性与回弹性,它特别适合在遮掩技术中作为干法抗蚀剂材料使用。 This feature is a mixture having a high degree of flexibility and resilience in the exposed and non-exposed state, it is particularly suitable for the dry resist material used as a mask in the art.

Description

本发明是关于一种混合物,其主要组成包含:a)一种能进行自由基聚合的化合物,它具有至少二个带烯键的不饱和端基,在大气压下它的沸点高于100℃,b)一种在光化性射线的作用下能引发化合物a)聚合的化合物,c)一种在水中不溶,但是在碱性水溶液中能溶解的共聚物。 The present invention relates to a mixture consisting essentially comprising: a) one kind of compound capable of radical polymerization, having at least two ethylenically unsaturated end group with a bond, its boiling point at atmospheric pressure above 100 deg.] C, b) an actinic ray at initiator action of the compound can be a) a polymerizable compound, C an insoluble in water, but the copolymer can be dissolved in aqueous alkaline solution).

上面所述的这类能进行聚合的混合物是已知的,尤其是用于制备光聚合印刷板以及光致抗蚀剂材料。 The mixture described above can be polymerized such that the resist material, especially for the preparation of photopolymerizable printing plates and photo-known. 这类混合物的优先应用领域是制备干法光致抗蚀剂材料。 Priority fields of application of such a dry mixture is prepared in a photoresist material.

联邦德国专利申请展出说明书(DE-A)2064080描述了这类混合物,它们含有甲基丙烯酸和甲基丙烯酸烷基酯的共聚物作为粘合剂,在甲基丙烯酸烷基酯中的烷基至少有4个碳原子;用甲基丙烯酸,甲基丙烯酸甲酯或乙酯,以及一种烷基中有4至15个碳原子的甲基丙烯酸烷基酯制成的三元共聚物作粘合剂则更好。 Federal Republic of Germany Patent Application exhibited specification (DE-A) 2064080 describes such mixtures which contain a copolymer of methacrylic acid and methacrylic acid alkyl ester as the binder, the alkyl group in the alkyl methacrylate there are at least 4 carbon atoms; methacrylic acid, methyl methacrylate or ethyl acrylate, and an alkyl group in the alkyl methacrylate terpolymer has 4 to 15 carbon atoms, an ester formed as viscous mixture is better. 这些混合物形成柔性层,它们虽然粘附良好,但是当它们较厚时,例如厚度超过20微米时,就有冷流的倾向,以涂好的成卷的干性抗蚀剂膜的形式长期保存时会出现露边和发粘。 These mixtures form a flexible layer, although they are good adhesion, but when they are relatively thick, e.g. tendency thickness exceeds 20 m, there is a cold flow, in the form of a roll of the coated dry film resist long-term storage there will be exposed edges and tacky.

专利DE-A2363806描述了类似的混合物,它们含有甲基丙烯酸、一种烷基含有4个以上碳原子的甲基丙烯酸烷基酯和另一种单体的三元共聚物,与此第三种单体相对应的均聚物的玻璃化转变温度至少为80℃。 Patent DE-A2363806 describes similar mixtures which contain methacrylic acid, an alkyl-containing alkyl methacrylate terpolymers of 4 or more carbon atoms, and another monomer, with this third monomers corresponding homopolymer has a glass transition temperature of at least 80 ℃. 这类单体的具体例子有苯乙烯,取代苯乙烯和丙烯腈。 Specific examples of such monomers are styrene, substituted styrene and acrylonitrile. 这类混合物的冷流显著降低了,但是对于某些应用,例如遮盖基材中的孔洞,即所谓遮掩技术,它们完全不合用,或者用途非常有限。 Such mixtures cold significantly reduced, but for certain applications, for example covering the substrate holes, the so-called masking technology, they are completely out of use, or the use is very limited. 遮掩技术在印刷电路板的生产过程中越来越被采用。 Masking technology is increasingly being employed in the production of printed circuit boards. 在包铜法的加工过程中,打好孔并刷过的板,在打孔部分进行化学金属化,然后在电解镀铜浴中将整个表面增强到所要求的最终厚度。 In the copper-clad processing method, lay the plate aperture and the brush, a chemical metallization perforated portion, and to enhance the desired final thickness on the entire surface of the electrolytic copper plating bath. 再在板上覆盖一层光致抗蚀剂层,接着进行曝光。 Then the plate covered with a photoresist layer, followed by exposure. 在这一过程中抗蚀剂层在线路和焊眼部分发生固化。 Curing the resist layer in the process occurs in the eye portion and weld lines. 孔洞的两侧都被固化了的抗蚀剂层覆盖着,这些区域在显影时保留了下来。 Holes on both sides were cured resist layer covering these regions retained during development. 铜层裸露的部分被腐蚀去。 Part of the copper layer exposed to corrosion.

遮掩技术对于遮盖所谓操作孔和固定孔也是重要的,这些孔的直径大至6毫米或更大,板中备有这些孔以便在各个处理步骤进行操作。 Masking techniques is also important for the operation of a so-called cover hole and the fixing hole, the hole diameter of 6 mm or greater, the plate provided with apertures in order to operate various processing steps. 在半添加法(Semiadditive)中,金属被电解沉积在没有被抗蚀剂层覆盖的区域中。 In the semi-additive process (Semiadditive), the metal is electrolytically deposited in an area not covered by the resist layer. 在这一过程中固定孔也必须被覆盖住,否则它们会因金属的沉积而变小,因而可能在下面的步骤中不能使用。 In this process, the fixing holes must be covered, which would otherwise due to the deposition of the metal becomes smaller, and thus may not be used in the next step. 然后将抗蚀剂层除去,用腐蚀剂将下面的导电铜层腐蚀除去,在操作孔和固定孔中的铜也被除去。 The resist layer is then removed, and the underlying conductive copper layer was etched with an etchant to remove copper in the operation hole and the fixing hole is also removed.

因此光致抗蚀剂必须满足遮掩技术的高要求。 Therefore photoresist masking techniques must meet high requirements. 在曝光状态下它必须是柔软的,并能抵抗腐蚀浴和镀膜浴的作用,而且在遮盖6毫米或更大的孔洞时,它必须能支撑自己。 In the exposure state it must be flexible, and resistant to corrosion bath and plating bath effect, and in the cover aperture 6 mm or more, it must be able to support themselves.

DE-A2417656描述了其它类似的混合物,它们包含两种酸性聚合物结合在一起作为粘合剂,在某些条件下其中之一溶于稀的氢氧化钠水溶液中,而另一种不溶。 DE-A2417656 describes other similar mixtures thereof, an acidic polymer comprising two together as a binder, under certain conditions, one of which was dissolved in dilute aqueous sodium hydroxide, the insoluble and the other. 那里所描述的甲基丙烯酸共聚物在氢氧化钠水溶液中是不溶解的。 Methacrylic acid copolymer described therein in the aqueous sodium hydroxide it is insoluble.

本发明的目的是提出一种能进行辐射聚合的混合物,它适合于制备干法光致抗蚀剂材料,在碱性水溶液中容易完全显影,形成柔性很高而无冷流的膜,用于覆盖打过孔的镀铜绝缘板时适合于遮盖直径大于1毫米的钻孔,曝光之后成为自承膜、能耐进一步的处理如喷雾显影、蚀刻、电镀等而不受损伤。 Object of the present invention is to provide a radiation-polymerizable mixture can be performed, it is suitable for preparing a dry photoresist material easily fully developed in an aqueous alkaline solution to form a highly flexible film without cold flow, for when the cover is adapted to cover the insulating plate copper played hole drilling diameter greater than 1 mm, to become self-supporting film, after exposure, the ability to further processing, such as spray development, etching, plating and the like from damage.

本发明是关于一种能进行辐射聚合的混合物,其主要组成包含:a)一种能进行自由基聚合的化合物,它至少具有二个带烯键的不饱和端基,在大气压下沸点高于100℃。 The present invention relates to a mixture capable of polymerizing radiation, consisting essentially comprising: a) one kind of compound capable of radical polymerization, having at least two unsaturated end groups with olefinic bond, at atmospheric pressure boiling above 100 ℃.

b)一种在光化性辐照的作用下能引发化合物a)聚合的化合物,c)一种在水中不溶但是在碱性水溶液中能溶解的共聚物,它由下列成份组成:c1)一种α、β-不饱和脂肪酸,c2)一种甲基丙烯酸烷基酯,其烷基部分至少有4个碳原子,c3)如果适当的话再包含一种乙烯类单体不饱和化合物,这能与c1)和c2)共聚,它的均聚物的玻璃化转变温度至少为80℃。 b) an actinic radiation under the action of a compound capable of eliciting a) a polymerizable compound, c) one copolymer is insoluble in water but can be dissolved in aqueous alkaline solution, which is composed of the following ingredients: c1) a species α, β- unsaturated fatty acids, c2) methacrylic acid alkyl ester, the alkyl moiety having at least 4 carbon atoms, C3) if appropriate further monomer containing one ethylenic unsaturated compound, which can and c1) and c2) copolymer, which homopolymer has a glass transition temperature of at least 80 ℃.

按照本发明,混合物中的共聚物的平均分子量为50,000至200,000。 According to the present invention, the average molecular weight of the copolymer mixture is from 50,000 to 200,000.

按照本发明,进一步推荐一种共聚物,它由一种α、β-不饱和脂肪酸,一种烷基至少有4个碳原子的甲基丙烯酸烷基酯,如果合适的话,和至少一种能与不饱和脂肪酸及甲基丙烯酸酯共聚的乙烯类单体共聚而得,这种乙烯类单体的均聚物的玻璃化转变温度至少为80℃。 According to the present invention, a copolymer is further recommended that from one α, β- unsaturated fatty acid, an alkyl having at least 4 carbon atoms, methyl acrylate, if appropriate, and at least one energy and unsaturated fatty acids and methacrylate copolymer obtained by copolymerizing a vinyl monomer, a homopolymer glass vinyl monomer such transition temperature of at least 80 ℃.

按照本发明,共聚物的平均分子量大约在50,000至200,000范围内。 According to the present invention, the average molecular weight of the copolymer is approximately in the range of 50,000 to 200,000.

用共聚物的分子量为65,000至150,000的混合物得到柔性好而且坚韧的层状物,它在碱性水溶液中也能被适当地显影。 To obtain good flexibility and toughness of the layer was treated with a mixture of copolymer molecular weight is 65,000 to 150,000, it can also be suitably developable in alkaline aqueous solution.

共聚物所含的不饱和脂肪酸c1)最好是丙烯酸、甲基丙烯酸、丁烯酸、己二烯-2,4-酸、顺丁烯二酸、甲叉丁二酸或上述二元酸的单酯。 Unsaturated fatty acid contained in the copolymer c1) is preferably acrylic acid, methacrylic acid, crotonic acid, 2,4-hexadiene acid, maleic acid, itaconic acid or said dibasic acid monoester. 用甲基丙烯酸尤其有利。 Methacrylic acid is particularly advantageous.

甲基丙烯酸烷基酯c2)中的烷基应该有4至20个碳原子,最好是有6至12个碳原子,与它相应的均聚物的玻璃化温度应该不超过20℃。 Alkyl methacrylate c2), the alkyl group should have from 4 to 20 carbon atoms, preferably from 6 to 12 carbon atoms, and its corresponding homopolymer has a glass transition temperature should not exceed 20 ℃.

当不饱和酸c1)的均聚物的Tg在80℃以上,最好在100℃以上时,只含有组分c1)和c2)的共聚物适合作为粘合剂。 When the unsaturated acid copolymers c1) homopolymer Tg of at least 80 ℃, preferably at least 100 ℃, containing only components c1) and c2) are suitable as binders. 这样的共聚物的玻璃化转变温度随着酸的含量的增加而升高,即使不加入c3)组分。 Such a glass transition temperature of the copolymer with increasing acid content is raised, even without added c3) component. 共聚物有一个较高的玻璃化温度可以增加膜中单体含量而不导致冷流。 The copolymer has a high glass transition temperature can be increased without causing the film to cold flow monomer content. 通常对于许多应用来说,只含有两种组分的共聚物是可取的,因为制备方法简单,它们的组成比三个或更多组分的共聚物更容易重复。 For many applications, generally, the copolymer contains only two components is desirable, because the simple preparation method thereof and more easily repeatable than three or more copolymer components.

在许多情况下希望不改变酸值而提高玻璃化转变温度,或者希望有选择地改变某些性质,在这些情况下使用另一单体c3)是有利的,c3)所形成的均聚物的Tg至少为80℃,在100℃以上则更好。 Desired acid value is increased without changing the glass transition temperature, or to selectively alter certain properties, using other monomers c3) is advantageous in these cases, in many cases, c3) the formed homopolymer Tg of at least 80 ℃, even better at least 100 ℃. 这类适用的单体有:苯乙烯或取代苯乙烯,例如乙烯基甲苯,4-氯苯乙烯,2-甲基苯乙烯,1-氯苯,乙烯基乙基苯或2-甲氧基苯乙烯;乙烯基萘或取代乙烯基萘;乙烯基杂环化合物,例如N-乙烯基咔唑,乙烯基吡啶或乙烯基噁唑;乙烯基环烷烃,例如乙烯基环己烷和3,5-二甲基乙烯基环己烷;丙烯酰胺,甲基丙烯酰胺,N-取代丙烯酰胺和甲基丙烯酰胺,丙烯腈,甲基丙烯腈以及甲基丙烯酸芳烃基酯。 Such useful monomers are: styrene or substituted styrene such as vinyl toluene, 4-chlorostyrene, 2-methyl styrene, 1-chlorobenzene, ethylbenzene or vinyl 2-methoxyphenoxy ethylene; substituted vinyl naphthalene or vinyl naphthalene; vinyl heterocyclic compounds, such as N- vinyl carbazole, vinyl pyridine or vinyl oxazole; vinyl cycloalkanes, such as vinyl cyclohexane, and 3,5 dimethyl vinyl cyclohexane; acrylamide, methacrylamide, N- substituted acrylamides and methacrylamides, acrylonitrile, methacrylonitrile, acrylate and methacrylate aromatic hydrocarbon group.

苯乙烯及取代苯乙烯,丙烯酰胺,甲基丙烯酰胺,丙烯腈与甲基丙烯腈是可取的,苯乙烯尤其可取。 Styrene and substituted styrene, acrylamide, methacrylamide, acrylonitrile and methacrylonitrile are preferable, styrene particularly desirable.

当然组分c1,c2和c3每个组分同时有几种存在也是可能的。 Of course the components c1, c2 and c3 of each component are present at the same time there are several possible.

组分c1的量通常为20至60%(克分子),30至50%(克分子)则更好;组分c2的量通常为25至80%(克分子),35至65%(克分子)则更好,它取决于链长;组分c3的量为0至30%(克分子),3至20%(克分子)则更好。 The amount of component c1 is usually 20 to 60% (mole), 30 to 50% (mole) is better; c2 weight component is typically 25 to 80% (mole), 35 to 65% (g molecule) is better, it depends on the chain length; c3 weight component is 0 to 30% (mole), 3 to 20% (mole) is better. 聚合物的Tg至少为80℃的单体的总量,也即c1和c3的总量,最好至少占35%(克分子)。 Tg of the polymer is at least 80 deg.] C of the total amount of monomers, i.e. the total amount of c1 and c3, preferably comprises at least 35% (mol). 共聚物的酸值最好在170至250范围内。 The acid number of the copolymer is preferably in the range of 170-250.

为了使共聚物满足干法抗蚀剂的加工过程的要求,它们的玻璃化转变温度Tg处在一定范围内是必要的。 In order to meet the requirements of the copolymer dry processing resist, their glass transition temperature Tg is within a certain range is necessary. 共聚物的Tg值可以近似地从各组分的均聚物的Tg值按下式计算出来:100/(TgMP) = (mA)/(TgA) + (mB)/(TgB) + (mC)/(TgC) +……式中,Tgcp为共聚物的玻璃化转变温度(按开尔文温标),TgA(B,C..)为A(B、C等)的均聚物的玻璃化转变温度(按开尔文温标),mA(B,C..)为共聚物中A(B、C等)组分的量,按重量百分数计算。 Tg value of the copolymer can be approximately calculated as follows from the Tg values ​​for homopolymers of the components out: 100 / (TgMP) = (mA) / (TgA) + (mB) / (TgB) + (mC) / (TgC) + ...... where, Tgcp glass transition temperature of the copolymer (in Kelvin temperature scale), TgA (B, C ..) to a (B, C, etc.) a homopolymer glass transition temperature (in Kelvin scale), mA (B, C ..) of the copolymer a (B, C, etc.) amount of a component, by weight percent.

按照本发明,混合物中共聚物的Tg值通常在35至70℃之间,在40至60℃之间则更好。 According to the present invention, Tg of the mixture of the copolymer is typically between 35 and 70 ℃, between 40 and 60 deg.] C is even better.

共聚物最好在生成自由基的聚合引发剂存在下通过本体聚合法制备,也就是说不加入大量的溶剂或分散剂。 In the polymerization of the copolymer is preferably a radical polymerization initiator prepared by the presence of the body, that is to say without the addition of large amounts of solvents or dispersing agents.

制备按通常的方法在浅的容器中进行,以利于更好控制温度。 Prepared in the usual manner in a shallow container, facilitate a better temperature control. 过氧化物或偶氮化合物在加热时生成自由基,它们以已知的方式被用作引发剂。 Peroxides or azo compounds generate radicals upon heating, in a known manner are used as initiators. 为了得到均匀的分子量分布,加入少量的链调节剂例如硫醇化合物是有利的。 In order to obtain a uniform molecular weight distribution, a small amount of chain regulator, for example, the thiol compound is advantageous. 也可以加入少量,例如小于单体混合物重量的10%的溶剂,如水或低级醇。 It may also be added a small amount, for example less than 10% by weight of a monomer mixture of a solvent, such as water or a lower alcohol. 温度可在大约30至130℃之间。 Temperature may be between about 30 and 130 ℃.

显然,制备方法对于共聚物的柔性及回弹性有重大的影响,在混合物作为干法抗蚀剂用于遮掩技术时,这些性质是很重要的。 Clearly, there is prepared a significant impact on flexibility and resilience of the copolymer in the mixture as a dry resist masking technology used for these properties are important.

按照本发明,混合物含有可聚合的化合物,它们在分子末端具有至少2个乙烯类双键。 According to the present invention, the mixture containing a polymerizable compound, which has at least two terminal ethylenic double bonds in the molecule. 一般所用的这类能够聚合的化合物是多元醇,最好是一级醇的丙烯酸酯或甲基丙烯酸酯。 Such a polymerizable compound commonly used is a polyol, preferably an acrylate or methacrylate of an alcohol. 合适的多元醇的例子有乙二醇、丙二醇、1,4-丁二醇、1,3-丁二醇、一缩二乙二醇、二缩三乙二醇,分子量约为200至1000的聚乙二醇或聚丙二醇、季戊二醇、三羟甲基乙烷、三羟甲基丙烷、季戊四醇和双酚A的羟乙基衍生物。 Examples of suitable polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, diethylene glycol, triethylene glycol, of a molecular weight of from about 200 to 1000 polyethylene glycol or polypropylene glycol, neopentyl glycol hydroxyethyl derivative, trimethylol ethane, trimethylol propane, pentaerythritol and bisphenol-a. 含有氨基甲酸酯基的双丙烯酸酯或双甲基丙烯酸酯尤其合适,它们通过1克分子二醇与2克分子二异氰酸酯和2克分子丙烯酸或甲基丙烯酸羟基烷基反应而得到。 Diacrylate or dimethacrylate containing urethane groups particularly suitable are 2 moles diisocyanate and 2 moles of hydroxyalkyl acrylate or methacrylate reaction with 1 mole of a diol obtained by. 在DE-A2822190中描述了这类含有氨基甲酸酯基的单体。 In DE-A2822190 describes such monomers containing a urethane group. 在DE-A3048502中也描述了类似的单体。 In DE-A3048502 also described similar monomers.

很多化合物可以用作聚合引发剂,它们能被辐射尤其是光化性光照所活化、本发明的混合物中含有这类化合物。 Many compounds can be used as the polymerization initiator, radiation, especially they can be activated by actinic light, the present invention contains a mixture of such compounds. 例如安息香及其衍生物,三氯甲基-S-三嗪,含三卤甲基的羰基亚甲基杂环化合物,例如2-(对三氯甲基苯甲酰氨基亚甲基)-3-苯并噻唑啉,吖啶衍生物,例如9-苯基吖啶,9-对甲氧基吖啶,9-乙酰胺基吖啶或苯并吖啶;吩嗪衍生物,例如9,10-二甲基苯并吩嗪或10-甲氧基苯并吩嗪;喹噁啉衍生物,例如6,4′,4″-三甲氧基-2,3-二苯基喹噁啉或4′,4″-二甲氧基-2,3-二苯基-5-氮杂喹噁啉或者喹唑啉衍生物。 And derivatives thereof such as benzoin, -S- trichloromethyl-triazine, trihalomethyl-containing carbonyl methylene heterocyclic compounds such as 2- (p-trichloromethyl-benzoyl aminomethylene) -3 - benzothiazolinone, acridine derivatives such as 9-phenyl acridine, 9-p-methoxyphenyl acridine, 9-acetamido-benzo acridine or acridine; phenazine derivatives such as 9,10 - dimethylbenzo phenazine or phenazine 10- methoxybenzo; quinoxaline derivatives such as 6,4 ', 4 "- trimethoxy-2,3-diphenyl quinoxaline or 4 ', 4' - dimethoxy-2,3-diphenyl-5-aza-quinoxaline, or quinazoline derivative. 引发剂的用量通常为混合物中不挥发组分的重量的0.01%至10%,最好为0.05%至4%。 The amount of initiator is generally non-volatile weight of the components of the mixture 0.01 to 10%, preferably 0.05% to 4%.

按照本发明,混合物一般含有不挥发组分总重量的30%至70%粘合剂,40%至60%则更好,并含有不挥发组分总重量的30%至70%能够聚合的化合物,40%至60%则更好。 According to the present invention, the mixture will generally contain a nonvolatile component total weight of 30-70% binder, 40-60% even better, and 30-70% non-volatile polymerizable compound to the total weight of components comprising , 40-60% is better.

混合物中还可以含有通常的组分,如阻聚剂,氢给予体,敏感性调节剂,染料,颜料,增塑剂以及可以热活化的交联剂。 The mixture may further contain conventional components, such as a polymerization inhibitor, a hydrogen donor, sensitivity adjusting agents, dyes, pigments, plasticizers and crosslinking agents can be heat activated.

本发明的混合物敏感的、能够适用的光化性辐射是那些能量足以引发聚合的任何电磁辐射。 Sensitive mixtures of the present invention can be applied are those actinic radiation energy sufficient to initiate the polymerization of any electromagnetic radiation. 可见光,紫外线,X射线,电子辐射等尤其合适。 Visible light, ultraviolet, X-rays, electron radiation, etc. particularly suitable. 在可见区和紫外区中的激光也可以用。 Laser in the visible region and ultraviolet region may also be used. 最好用短波可见光或近紫外线。 Preferably visible or near ultraviolet light with a short wavelength.

采用本发明的混合物生产记录材料,合适的基材有铝,钢,铜以及由聚对苯二甲酸乙二醇酯等制成的塑料薄膜或网板。 Mixtures of the present invention is the production of the recording material, suitable substrates are aluminum, steel, copper, and a polyethylene terephthalate film or a plastic plate made of mesh. 基材表面可以用化学方法或机械方法进行预处理,以便把涂层的粘附力调节到适当的水平。 Surface of the substrate may be pretreated chemically or mechanically, so that the adhesion of the coating is adjusted to an appropriate level.

本发明的混合物用作干法光致抗蚀剂更好,已经证明在遮掩技术中尤其有用。 As a dry mixture of the present invention is better photoresists, it has proved particularly useful in masking techniques. 为此目的它可以制成预制的,可转移的干法抗蚀剂膜,用通常的方法覆盖到要进行处理的工件上,例如覆盖到印刷电路板的基材上去。 For this purpose it may be made of a prefabricated dry film resist can be transferred, overlaid onto a workpiece to be processed in the usual manner, for example to cover up the printed circuit board substrate. 通常干法抗蚀剂膜是通过把混合物在一种溶剂中的溶液涂到适当的基材,如聚酯薄膜上,并加以干燥而制成。 Typically the dry film resist method is a mixture of a solution in a solvent coated onto a suitable substrate, such as a polyester film, and dried and formed. 抗蚀剂膜的厚度可以是10至80微米左右,20至60微米则更好。 Thickness of the resist film may be about 10 to 80 microns, even better 20 to 60 microns. 涂层的自由表面最好用聚乙烯或聚丙烯薄膜覆盖。 The free surface of the coating is preferably covered with a polyethylene or polypropylene film. 制好的叠层物可以卷成大卷贮存,也可以根据要求切成各种宽度的抗蚀剂卷。 Good laminate can be made larger than the volume storage volume and to be cut in various resist roll width according to the requirements.

这些薄膜可以用干法抗蚀剂技术中常用的设备进行加工。 These films can be processed with a dry resist technology commonly used devices. 用工业用层压机将覆盖膜剥去,将光致抗蚀剂层与打好孔的镀铜基材复合在一起。 Industrial laminator with the cover film peeled off, the photoresist layer and the copper substrate composite lay-hole together. 这样制好的板在带图像的底片下进行曝光,在除去底膜后用通常的方法进行显影。 Such boards were exposed to film strip image is developed using a conventional method after removal of the base film.

适用的显影剂是水溶液,碱性水溶液更好,例如碱金属的磷酸盐,碳酸盐或硅酸盐的水溶液,如果需要的话可加少量,例如10重量%以下,与水溶液的溶剂或浸润剂。 Suitable developers are aqueous alkaline solution better, for example, an aqueous solution of alkali metal phosphates, silicates or carbonates, may be added if desired small amounts, e.g. 10 wt% or less, and an aqueous solvent or wetting agent, .

本发明的混合物的使用范围很广。 Use of mixtures of the present invention is very wide. 它们以干法抗蚀剂膜的形式使用特别有利,用于在金属基材如铜上构成防蚀剂或抗电镀的保护层。 They are used particularly advantageously in the form of a dry resist film, it is used on a metal substrate such as copper anticorrosive protective layer or an anti-plating.

在这种应用中由本发明的混合物制得的光致抗蚀剂的优异的回弹性和韧性无论在未曝光的状态下或者在曝光的状态下都充分显示出它们的优越性。 In this application a superior resiliency and toughness of the photoresist of the present invention have a mixture of both in the unexposed state or a state at the exposure fully exhibit their superiority. 与铜复合在一起能进行光聚合的层状物具有很高的内聚力,使覆盖于孔洞上的这层自承膜在除去基材时完整无损,不随基材撕走。 Together with the copper compound capable photopolymerizable layer substance having a high cohesive force, so that this layer is self-supporting film covers the hole when the substrate is removed intact with no Sizou substrate. 用本发明的混合物制成的层状物可以覆盖直径为6毫米或更大的孔,在除去基材、显影、电镀或蚀刻等步骤中保持完整无损。 Layer was formed with the mixture of the invention may cover a hole 6 mm in diameter or larger, while maintaining the substrate intact, developing, plating or etching step to remove the like. 虽然共聚物的分子量很高,由本发明的混合物制成的层状物能够用纯的微碱性显影剂水溶液完全显影。 Although the molecular weight of the copolymer is high, the layer was formed by the mixture of the invention can be fully developed with aqueous alkaline developer micro pure. 这样的粘合剂与比例更高的常用单体的混溶性比相应的分子量低的粘合剂要好;不必加入增塑剂。 Such miscibility with conventional adhesive monomer higher percentage better than the corresponding lower molecular weight binder; not necessary to add a plasticizer. 本发明的混合物对显影剂,蚀刻液及电镀浴的抵抗性良好。 Developer mixture of the invention, resistance to etching solution and the plating bath is good. 本发明的混合物特别适合于作干法抗蚀剂。 Mixtures of the invention are particularly suitable as dry resist. 它也适合于其它的应用,如果在这些应用中光敏层的柔性与韧性是重要的,例如制备光致抗蚀剂溶液,制备印刷板,制备浮雕图像,制备筛网印刷的筛网,制备彩色测试膜。 It is also suitable for other applications, if these applications the flexible and toughness of the photosensitive layer is important, for example, a photoresist solution was prepared, the preparation of printing plates, preparation of a relief image, the preparation of screen printing mesh, preparing a color test membrane.

下面的例子说明本发明的混合物可取的实施方法以及它的应用。 The following examples illustrate the present invention preferably mixtures embodiment of the method and its application. 如果没有特别说明,百分数及份数指的都是重量单位。 Unless otherwise indicated, percentages and parts are by weight refers to the unit. 重量份数与体积份数之关系就像克与立方厘米的关系一样。 The relationship between parts by weight and parts by volume of just the same as the relationship between grams and cubic centimeters.

实施例1配制下列组分的溶液:6.5份重量下述的三元共聚物,8.8份重量能进行聚合的二氨基甲酸酯,它由1克分子二缩三乙二醇,2克分子2,2,4-三甲基六亚甲基双异氰酸酯及2克分子甲基丙烯酸羟乙酯反应制得,0.25份重量9-苯基吖啶,0.025份重量兰色染料,它由2,4-二硝基-6-氯苯重氮盐与2-甲氧基-5-乙酰胺基-N,N-二乙基苯胺偶合制得,15份重量丁酮,15份重量乙醇。 Example 1 was prepared following components implemented: 6.5 parts by weight of terpolymer described below, 8.8 parts by weight of the polymerization can be performed dicarbamate which 1 mole of triethylene glycol two, 2 moles 2 , 2,4-bis-trimethyl hexamethylene diisocyanate and 2 moles of hydroxyethyl methacrylate prepared by the reaction, 0.25 parts by weight of 9-phenyl acridine, 0.025 parts by weight of blue dye, which consists of 2,4 - dinitro-6-chlorophenyl diazonium salt with 2-methoxy-5-acetamido -N, N- diethylaniline coupling in the system, 15 parts by weight of methyl ethyl ketone, 15 parts by weight of ethanol.

将上述溶液用回旋涂层法涂于厚度为25微米的经双轴拉伸、热定型了的聚对苯二甲酸乙二醇酯膜上,在100℃烘干后,得到单位面积上的重量为45g/m2。 The above solution was coated with a thickness of 25 microns swirl coating method of biaxially stretching, heat setting of a polyethylene terephthalate film, after drying at 100 deg.] C, a weight per unit area to 45g / m2.

三元共聚物的制法如下:将甲基丙烯酸正己酯,甲基丙烯酸及苯乙烯按重量比60∶30∶10混合,加入单体重量的0.05%的偶氮异丁腈,0.02%的过异壬酸叔丁酯以及0.5%的叔十二烷基硫醇混合,将混合物引入钢板做的中空的浅室中进行聚合,以水浴或空气浴加热至50℃,直到反应物变成固体。 Terpolymer was prepared as follows: n-hexyl acrylate, methyl methacrylate, styrene and mixed in a weight ratio of 60:30:10, was added 0.05% by weight of azoisobutyronitrile monomers, over 0.02% acid tert-butyl and t-dodecyl mercaptan 0.5% of the isononanoic, the mixture is introduced into the hollow chamber of shallow steel sheet made of polymerized in a water bath or air bath heated to 50 ℃, until the reaction becomes solid. 为了得到足够高的最终转化率,进一步将混合物加热到100℃,并在该温度下保持一些时间。 In order to obtain a sufficiently high final conversion, the mixture was further heated to 100 deg.] C, and held at this temperature for some time. 冷却后将室打开,用机械法将取出的聚合物块弄成粉末。 After the cooling chamber is opened, the polymer block mechanically removed inflicted powder. 聚合物的动力学粘度为0.32毫米2/秒(15%乙醇溶液),光散射法测得平均分子量Mw为128,000,酸值为195,转化率大于97%。 Dynamic viscosity of the polymer was 0.32 mm 2 / s (15% ethanol solution), measured by a light scattering average molecular weight Mw of 128,000, an acid value of 195, the conversion rate of greater than 97%.

用此法制得的干法抗蚀剂膜用市售层压机在115℃下与粘合有35微米厚的铜箔的酚醛层压板复合,在5千瓦金属囟化物灯下曝光8秒钟,灯与真空支架之间的距离为110厘米。 Dry resist film prepared by this method using a commercial laminator at 115 deg.] C with a 35 micron thick adhesive phenolic laminate composite copper foil in 5 kilowatts metal halide lamp 8 seconds exposure, the distance between the lamp holder and a vacuum of 110 cm. 使用划条的底片,条宽与间隔都是80微米。 Using negative draw bar, strip width and are spaced 80 microns.

曝光后除去聚酯膜,将层状物在喷雾显影器中用1%碳酸钠溶液显影120秒。 The polyester film was removed after the exposure, the layer was developed in a 1% sodium carbonate solution in a spray developer for 120 seconds. 然后用自来水将板冲洗30秒钟,在15%的过硫酸胺溶液中蚀刻30秒,用水冲洗,再在浓度为10%的硫酸中浸30秒,然后在下列电解浴中进行电镀:1.在从Schlotter公司(Geislingen/Steige,西德)得到的“Glanzkupfer-Bad”型镀铜浴中镀60分钟,电流密度:2.5安培/分米2金属层厚度:约30微米温度:室温。 The plates were then rinsed with tap water for 30 seconds, at 15% ammonium persulfate etching solution for 30 seconds, rinsed with water, and then immersed in a sulfuric acid concentration of 10% for 30 seconds, and then the electrolytic plating bath of the following: 1. plating 60 minutes "Glanzkupfer-Bad" type copper plating bath obtained from Schlotter company (Geislingen / Steige, West Germany), the current density: 2.5 a / dm 2 of the metal layer thickness: about 30 m temperature: room temperature.

2.在从Schiotter公司(Geislingen/Steige)得到的铅锡浴LA中镀15分钟:电流密度:2安培/分米2 2. The lead-tin plating bath for 15 minutes Schiotter LA obtained from the company (Geislingen / Steige) in: Current density: 2 A / dm 2

金属层厚度15微米温度:室温。 The thickness of the metal layer 15 m temperature: room temperature.

经过处理的板没有出现任何渗透或损伤。 After processing board without any penetration or damage. 接着就可以在5%KOH溶液中,在50℃下把抗蚀剂层从板上除掉,暴露出来的铜可以在常用的蚀刻介质中除去。 Then they may be 5% KOH solution at 50 deg.] C, the resist layer is removed from the board, the exposed copper may be removed in a conventional etching medium.

在另一实验中,光致抗蚀剂层与带有直径在1至6毫米之间的孔的粘铜试验板复合,通过相应于孔洞的照相负片(透明区的直径为1.4至6.4毫米)将抗蚀剂层曝光。 In another experiment, the photoresist layer and the adhesive composite copper test plate having pores with diameters between 1 and 6 millimeters, corresponding to the holes through the photographic negative (transparent zone diameter 1.4 to 6.4 mm) the exposed resist layer. 然后以1%碳酸钠溶液将未曝光部分洗去,并以氯化铜氨溶液将暴露出来的铜蚀刻掉。 Copper etching and then a 1% sodium carbonate solution to wash away the non-exposed portion, and copper chloride ammonia solution exposed out. 蚀刻后,发现所有的钻孔都覆盖有固化了的光致抗蚀剂。 After the etching, it was found that all the drill is covered with the cured photoresist.

为了比较,用DE-A2363806的分子量为33000的类似粘合剂(在33%的丁酮溶液中聚合制得,v=11毫米2/秒,15%乙醇溶液)代替本专利的粘合剂。 For comparison, the molecular weight is similar to DE-A2363806 adhesive 33000 (polymerization of methyl ethyl ketone at 33% solution, v = 11 mm2 / s, a 15% ethanol solution) was used instead of the adhesive of the present patent. 得到的是有粘性的加工困难的光致抗蚀剂层。 The resulting viscous is difficult to process the photoresist layer. 由于低分子量的粘合剂不利于生成固体层状物,抗蚀剂卷在贮存时,尤其在高温下,出现露边现象。 Because of the low molecular weight to form a solid adhesive layer was unfavorable, a resist roll during storage, particularly at elevated temperatures, exposed side of the phenomenon occurs. 和带孔的基材复合后,在每个钻孔的周围一圈厚度较低。 And a rear substrate composite apertured, lower circle around each borehole thickness. 这样的层状物不能用于遮掩技术。 Such technology mask layer was not used.

在DE-A2363806的实施例4及DE-A2822190的实施例1中所述的干法抗蚀剂层都含有上述的粘合剂,也不适用于遮盖直径大于1毫米的孔洞。 In Example 4 of DE-A2363806 and in the dry resist layer according to Example 1 of DE-A2822190 all containing the binder, is not suitable for covering the hole diameter greater than 1 mm.

实施例2在实施例1中用下面单体混合物代替氨基甲酸酯可以得到类似的结果。 1 Example 2 using the following monomer mixture in place of the urethane Example gives similar results.

a)5.8份重量实施例1中的氨基甲酸酯和1.5份重量的二缩三乙二醇双甲基丙烯酸酯,b)5.8份重量实施例1中的氨基甲酸酯和1.5份重量的聚乙二醇-400双甲基丙烯酸酯。 a) in Example 1 and urethane triethylene glycol bis methacrylate, 1.5 parts by weight 5.8 parts by weight of the embodiments, b) 5.8 parts by weight of urethane embodiment in Example 1 and 1.5 parts by weight polyethylene glycol-400 dimethacrylate.

这些光致抗蚀剂层的优点是显影时间短实施例的层状物1 2a 2b显影时间(秒) 95 75 75实施例3在实施例1中所述的涂膜溶液中的粘合剂用等量的下述三元共聚物代替:a)甲基丙烯酸正己酯、甲基丙烯酸与苯乙烯(60∶30∶10)的三元共聚物,平均分子量Mw约为185,000,动力粘度v(15%乙醇溶液)为74毫米2/秒,酸值195,b)甲基丙烯酸正己酯、甲基丙烯酸与苯乙烯(60∶35∶5)的三元共聚物,Mw约为74,000,动力粘度v(15%乙醇溶液)为23毫米2/秒,酸值228,c)甲基丙烯酸正己酯、甲基丙烯酸与苯乙烯(60∶35∶5)的三元共聚物,Mw约为94,000,动力粘度v(15%乙醇溶液)为32毫米2/秒,酸值228,d)甲基丙烯酸正己酯、甲基丙烯酸和甲基丙烯酸甲酯(60∶35∶5)的三元共聚物,动力粘度v(15%乙醇溶液)为36毫米2/秒,酸值228,e)甲基丙烯酸正己酯与甲基丙 These advantages of the photoresist layer is a layer of substance of Example 1 2a 2b developing time (second) embodiment of the developing time is shorter 957,575 in the coating solution of Example 3 described in Example 1 with the binder terpolymer for an equal amount of the following: a) methacrylate, n-hexyl methacrylate, and styrene (60:30:10) terpolymer, an average molecular weight Mw of about 185,000, kinematic viscosity v (15% ethanol solution) of 74 mm 2 / s, acid value 195, b) methacrylate, n-hexyl methacrylate, and styrene (60:35:5) terpolymer, Mw of about 74,000 , kinematic viscosity v (15% ethanol solution) of 23 mm2 / s, an acid value of 228, c) methacrylate, n-hexyl methacrylate, and styrene (60:35:5) terpolymer, Mw of about 94,000, kinematic viscosity v (15% ethanol solution) of 32 mm 2 / s, an acid value of 228, d) methacrylate, n-hexyl methacrylate, and methyl methacrylate (60:35:5) of terpolymers, kinematic viscosity v (15% ethanol solution) 36 mm 2 / s, an acid value of 228, e) n-hexyl acrylate and methacrylate, methyl propionate 酸(65∶35)的共聚物,动力粘度v(15%乙醇溶液)为34毫米2/秒,酸值228,在所有上述情况下都得到了对钻孔的满意的掩盖。 Acid copolymer (65:35), the kinematic viscosity v (15% ethanol solution) of 34 mm2 / s, an acid value of 228 in all the above cases have been satisfactory masking of the borehole.

实施例4以下列组分配制涂层溶液:4份重量实施例1所描述的三元共聚物,4份重量由1克分子2,2,4-三甲基六亚甲基二异氰酸酯与2克分子甲基丙烯酸羟乙酯反应得到的双氨基甲酸酯,0.17份重量9-苯基吖啶,0.02份重量兰色染料,它由2,4-二硝基-6-氯苯重氮盐与2-甲氧基-5-乙酰胺基-N-腈乙基-N-羟乙基苯胺偶合制得,0.01份重量5-硝基-2-[2-甲基-4-[N-乙基-N-腈乙基]-胺基苯偶氮]-苯并噻唑,17份重量丁酮,56份重量乙二醇单甲醚。 Example 4 The following components were formulated in the coating solution: terpolymer described in Example 4 parts by weight of an embodiment, 4 parts by weight of 1 mole of 2,2,4-trimethyl hexamethylene diisocyanate and 2 mole hydroxyethyl methacrylate obtained by reacting bis carbamate, 0.17 parts by weight of 9-phenyl acridine, 0.02 parts by weight of a blue dye and a 2,4-dinitro-6-chlorobenzene diazonium salt with 2-methoxy-5-acetamido-cyanoethyl -N- -N- prepared by coupling hydroxyethylaniline, 0.01 parts by weight of 5-nitro-2- [2-methyl -4- [N - cyanoethyl -N- ethyl] - amino phenylazo] - benzothiazole, 17 parts by weight of methyl ethyl ketone, 56 parts by weight of ethylene glycol monomethyl ether.

用回旋涂层法将上述溶液涂于电化学糙化过的并阳极化过的铝表面上,铝基氧化层厚度为2克/米2,它用聚乙烯基膦酸水溶液作过预处理,以得到干燥后膜重为3.5克/米。 And the treated anodized aluminum surface with a swirl coating solution is applied to the above-described method had electrochemical roughening, the aluminum oxide layer having a thickness of 2 g / m 2, which aqueous polyvinyl phosphonic acid as pretreated, after drying to obtain a film weight of 3.5 g / m. 在板上涂一层4克/米的聚乙烯醇覆盖层。 The plate coated with 4 g / m polyvinyl alcohol cover layer. 将印刷板切成两半,两块都在5千瓦金属囟化物灯下,在13挡连续光度调节光劈下,并在60条线/厘米及120条线/厘米的半光度分步光劈下曝光2秒钟。 The printing plate was cut in half, two in five kilowatts metal halide lamp, the stopper 13 pixia continuous light brightness adjustment, and the half-split light luminosity step 60 lines / cm and 120 lines / cm 2 seconds at the exposure. 在曝光之后,将其中一块再在通风干燥箱中在100℃下加热5秒钟。 After exposure, in which a heated 5 seconds at 100 deg.] C in a ventilated oven.

然后在由下列组分构成的显影液中进行显影: Then developed in a developing solution consisting of the following components:

3.0份重量硅酸钠NaSiO3·9H2O,0.03份重量非离子型润湿剂(椰油醇聚氧乙烯醚约含8个氧乙烯链节),0.03份重量消泡剂,96.967份重量去离子水。 3.0 parts by weight of sodium silicate NaSiO3 · 9H2O, 0.03 parts by weight of a nonionic wetting agent (polyoxyethylene coconut alcohol containing from about 8 oxyethylene units), 0.03 parts by weight of an antifoaming agent, 96.967 parts by weight of deionized water .

没有进一步加热的样品得到8(9)个完全固化了的光劈挡数,而经过加热的样品得到11(12)个完全固化了的光劈挡数。 No further heating the sample to give 8 (9) the number of fully cured wedge block, and after heating of the sample to give 11 (12) the number of fully cured blocking wedges.

Claims (5)

1.一种能进行辐射聚合的混合物,其特点是,主要组成包含:a)一种能进行自由基聚合的化合物,它具有至少二个带烯键的不饱和端基,在大气压下它的沸点高于100℃。 A radiation-polymerizable mixture can be performed, which is characterized by the main components comprising: a) one kind of compound capable of radical polymerization, having at least two unsaturated end groups with ethylenic bond, at atmospheric pressure it boiling above 100 ℃. b)一种在光化性射线作用下能引发化合物a)聚合的化合物。 b) one compound capable of initiating a role in the actinic rays) polymerizable compound. c)一种在水中不溶而在碱性水溶液中可溶的共聚物,它由下列成分构成:c1)一种α、β不饱和脂肪酸,c2)一种甲基丙烯酸烷基酯,其烷基部分至少有4个碳原子,c3)如果适当的话,再包含一种带烯健的不饱和化合物单体,它能与c1)和c2)共聚,它的均聚物的玻璃化转变温度至少为80℃,其中共聚物的平均分子量大约在50,000至200,000范围内,而且是通过本体聚合的方法制备的。 c) an alkaline aqueous solution and soluble in the water insoluble copolymer which is composed of the following ingredients: c1) one kind of α, β-unsaturated fatty acid, c2) an alkyl ester of methacrylic acid, the alkyl portion having at least 4 carbon atoms, C3) if appropriate, further comprising an unsaturated monomer a tape ethylenically compound, it can with c1) and c2) copolymer, which homopolymer has a glass transition temperature of at least 80 ℃, wherein the copolymer has an average molecular weight in the range of about 50,000 to 200,000 and is prepared by a process of bulk polymerization.
2.按照权利要求1所要求保护的能进行辐射聚合的混合物,其特点是其中的共聚物含有苯乙烯或取代苯乙烯的c3单元。 2. claimed in claim 1 capable of radiation-polymerizable mixture, which is characterized by containing a copolymer of styrene or substituted styrene unit c3.
3.按照权利要求1所要求保护的能进行辐射聚合的混合物,其特点是其中能辐射聚合的化合物是多元醇的丙烯酸酯或甲基丙烯酸酯。 3. The claimed in claim 1 capable of radiation-polymerizable mixture, which is characterized wherein the energy radiation polymerizable compound is an acrylate or methacrylate esters of polyols.
4.按照权利要求1所要求保护的能进行辐射聚合的混合物,其特点是其中的共聚物包含20至60%(克分子)的α、β-不饱和羧酸结构单元。 4. The claimed in claim 1 capable of radiation-polymerizable mixture, which is characterized by the copolymer comprises 20 to 60% (mole) of α, β- unsaturated carboxylic acid structural units.
5.按照权利要求1所要求保护的能进行辐射聚合的混合物,其特点是其中的α、β-不饱和羧酸是丙烯酸或甲基丙烯酸。 5. claimed in claim 1 capable of radiation-polymerizable mixture, which is characterized by the α, β- unsaturated carboxylic acid is acrylic acid or methacrylic acid.
CN 85106270 1984-07-26 1985-08-20 Mixture carrying out radiative polymerization and method for preparing copolymer CN1006707B (en)

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