CN1236906A - 用于工业射线照相术的新产品 - Google Patents
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- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Conversion Of X-Rays Into Visible Images (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
本发明涉及一种用于高能量电离辐射曝光的卤化银射线照相术产品。本发明还涉及一种形成射线照相术图像的新型射线照相术系统和方法。本发明的用于工业射线照相术的产品使潜像的保持能力得到提高,并提供了更高的感光速率。
Description
本发明涉及一种为高能电离辐射曝光而设计的卤化银射线照相术产品、一种新型工业射线照相术系统，和一种得到工业射线照相图像的方法。更具体地说，本发明涉及一种具有提高了潜像保持能力和更高感光速率的用于高能工业射线照相术的产品。
用于由例如玻璃、纸、木材或金属制成的物品的缺损的检查和分析的工业射线照相术是无破坏性的方法。该方法广泛用于航空工业、核工业和石油工业，用于飞机和核反应堆部件和管线中的物料结构和焊缝的缺损的探测。
该方法包括使含有卤化银乳液的射线照相术产品进行高能电离辐射曝光，一般是X射线或γ射线。射线照相乳液对X射线或γ射线的感光度取决于通过卤化银颗粒对这些射线部分的吸收，造成电子二次发射，从而形成内部潜像。该射线照相产品接着进行显影和定影。
与通过再放射可见光的发光屏曝光的医用放射照相胶片不同，用于工业射线照相术的胶片不需要对可见光感光，因此一般没有颜色感光。用于工业射线照相术的胶片既可以直接对电离辐射曝光，也可以通过强化电离辐射的屏曝光。这些强化屏一般由金属制造，增加了可以通过卤化银颗粒吸收的电离辐射的比率。
用于工业射线照相术的产品一般使用主要由粗颗粒(立方体的或其它固体形状)制得的卤化银乳液以吸收尽可能多的穿过乳液层的电离辐射。
还有公知的用于工业射线照相术的胶片包括由特殊的板状颗粒制得的乳液，例如它们公开于例如US专利4883748或专利申请EP757286。当包含板状颗粒乳液的工业射线照相术产品进行电离辐射曝光时，潜像的保持能力被减弱。
本发明的目的是提供一种用于工业射线照相术的新产品，其中通过电离辐射曝光得到的潜像的保持能力得以改善。本发明的另一个目的是提供一种改善射线照相感光度的工业射线照相术产品。
通过本发明这些目的和其它目的可以实现，其中涉及为能量至少是40KeV电离辐射曝光而设计的一种无色-感光射线照相术产品，含有至少50mg/dm2的银，包含涂敷在具有卤化银乳液层的其至少一个侧面上的支撑，该卤化银乳液层中至少50％的颗粒是板状颗粒，且其至少含有0.05mmol/molAg的下式化合物
其中R1和R2各自表示氢原子、包含1至5个碳原子的取代的或非取代的烷基，羟基或苄基，且R3和R4各自表示氢原子或包含1至5个碳原子的烷基，或共同表示构成4至6原子构成的取代的或非取代的杂环的必需的原子。
本发明还涉及一种以工业射线照相术产品形成图像的方法，包括用能量至少是40KeV的电离辐射对照相产品进行曝光以形成潜像，接着进行显影，以形成射线照相图像。
在本发明的一个实施方案中，射线照相术产品被曝光于能量范围在40KeV至20MeV内的射线中。
特别是这种新射线照相术产品出乎意料地显示出由电离辐射曝光得到的改善了的潜像保持能力。本发明的产品也显示出在能量大于或等于400KeV的电离辐射下曝光，感光速率变得更快。
一种或更多种化合物(Ⅰ)可以加入进本发明的射线照相术产品中。
优选地，加入化合物(Ⅰ)的量是0.1mmol/mol至0.5mmol/molAg的范围。
在本发明的范围内，R1和R2可以各自是直链或支链的烷基。R1和R2可以是甲基、乙基、丙基、丁基或戊基，优选甲基。在一个具体的实施方案中，R1是氢原子或羟基，而R2是烷基，优选甲基。
R3和R4可以各自是直链或支链的烷基。R3和R4可以各自是，例如，甲基、乙基、丙基、丁基或戊基。当R3和R4共同地包含有形成杂环必需的原子时，该杂环可以进一步含有氮和(或)氧原子。由此得到的杂环含有5至6个成员，形成，例如吗啉基、吡咯烷基、哌啶基或哌嗪基等。
本发明有用的化合物(Ⅰ)是例如：
在本发明中，所述的射线照相术产品包含有在50至200mg/dm2范围内的银。
本发明的射线照相术产品包括至少一个板状颗粒乳液。“板状颗粒”被规定为具有其表面积大于其它侧面的两个平行侧面的颗粒。这些颗粒其特征在于它们的纵横比(R)，就是平均等价圆直径(ECD)与平均颗粒厚度(e)之比。
在本发明的范围内，板状颗粒乳液是其中至少50％，且优选至少80％的颗粒是板状颗粒，且板状颗粒的纵横比大于或等于2，优选在5至20的范围内的乳液。
这样的乳液公开于例如Research Diselosure,1996年9月,591，节Ⅰ(以下被称为Research Disclosure)。
在本发明范围内有用的乳液，优选含卤化银颗粒，其基本上由溴化银制成，即在所述颗粒中主要的卤化银或溴化银。可以在本发明范围使用的卤化银颗粒还可以包括碘化银或氯化银。在一个实施方案中，本发明的射线照相术产品乳液中的颗粒含至少90％(mol)溴化银。这些颗粒还可以含数量小于或等于10％(mol)的氯化银或碘化银。
在一个优选的实施方案中，用于工业射线照相术乳液中的卤化银颗粒是含碘化物小于3％的溴-碘化银颗粒，该碘化物或集中于卤化银颗粒体内的一部分或均匀彻底散布于颗粒体。
在本发明射线照相术产品中的乳液包括卤化银颗粒分散其间的粘合剂，一般是可渗水的亲水胶体，例如明胶、明胶衍生物、白蛋白、聚乙烯醇、乙烯基聚合物等。
这些卤化银乳液可以含有一般是少量的掺杂剂，例如铑、铟、锇或铱离子等。(参见Research Disclosure的节Ⅰ-D3)。这些掺杂剂一般在制备乳液时添加。
该卤化银乳液可以采用Research Disclosure的节Ⅳ公开的方法被化学增感。一般使用的化学增感剂是硫和(或)硒和(或)金的化合物。
该卤化银乳液也一起含有荧光增白剂、防翳剂、表面活性剂、增塑剂、润滑剂、硬化剂、稳定剂、和吸收和(或)扩散剂，诸如在Research Disclosure的节Ⅱ-B、Ⅵ、Ⅶ、Ⅷ和Ⅸ中所描述的那些。
本发明的射线照相术产品除了卤化银乳液层以外，还可以包括用于射线照相术产品常采用的其它层，例如保护层(覆盖层)、中间层、过滤层或抗光晕层。所述的支撑可以是用于工业射线照相术产品的任何合适的支撑。常规的支撑是聚合物支撑，例如乙烯。
覆盖层可以包括抗静电剂、聚合物、消光剂等。
优选，本发明的工业射线照相术产品包括涂敷在具有卤化银乳液的两个侧面上的支撑；在支撑的两个侧面上的乳液可以是相同的，或在大小、组成、银含量等方面是不同的。
本发明的射线照相术产品可以使用硬化剂，例如公开在ResearchDisclosure节Ⅱ.B.中的那些硬化剂进行硬化。这些硬化剂可以是有机或无机硬化剂，例如，铬盐、醛、N-羟甲基化合物、二氧杂环乙烷衍生物、含活性乙烯基的化合物、含活性卤素的化合物等。
本发明的射线照相术产品可以用于由2个屏组成用以强化电离辐射的射线照相系统，所述的2个屏置于射线照相术产品的每一侧面上。
这些强化屏是通过卤化银颗粒增加了吸收电离辐射的比例的屏。所述的电离辐射与强化屏相互作用，得以在各个方向上释放电子。这些电子的一部分通过乳液层中的卤化银颗粒被吸收以形成潜像位点。通过增加颗粒方向上放射电子的数量，颗粒吸收电子的数量增加。这些屏一般是金属屏。
常用的屏包括铅板、氧化铅或致密金属例如铜和钢。这些屏的厚度范围是0.025mm至0.5mm，且取决于所采用的电离辐射类型。
通过对射线照相术产品进行直接电离辐射曝光或通过强化屏电离辐射曝光，就可以得到射线照相术图像。
用于工业射线照相术的制作方法包括含显影剂的黑白显影槽和含卤化银加溶剂例如硫代硫酸盐、硫氰酸盐或含硫有机化合物的定影槽。常用的显影剂一般是二羟苯、3-吡唑烷酮或氨基酚化合物。基于抗坏血酸或抗坏血酸衍生物的显影剂也可以使用。
通过下述实施例说明本发明，从中可以看出本发明的优点。
实施例实施例1
在本实施例中，使用的射线照相术产品由涂敷在其具有卤化银乳液层的两个侧面上的ESTAR支撑组成，所述的乳液包含具有75mg/dm2/侧面的银含量(总银含量150mg/dm2)的板状颗粒。
含板状颗粒的乳液AgBrI(I:0.6mole％),ECD=0.96μm,e=0.10μm。卤化银乳液的各层用含消光剂的明胶保护层涂敷。
该产品用等于产品中含的总干明胶重量3％的量的双(乙烯基磺酰基甲基)醚硬化。
板状颗粒具有的量超过乳液中总颗粒数量的90％。
通过双喷嘴沉淀作用制备所述乳液。接着用硫和金增感。在添加化学增感剂之后，乳液在65℃下，放置15分钟。当存在化合物(Ⅰ)时，在化学增感和恒温步骤之后，以如下所示的量在40℃加入。
各射线照相术产品置于两个具有8mm铜过滤的两个铅屏(25μm)之间，且接着在220KeV能量的辐射下曝光。
曝光之后，采用用于工业射线照相术的KodakMX800方法(8分钟，26℃，干燥后再干燥)将各产品显影，其中包括使用对苯二酚-苯基酮(phenidone)显影剂(2分钟)的硬化显影步骤，定影步骤(2.5分钟)，洗涤步骤(2分钟)和干燥步骤。
对于各样品，通过获得等于两倍以上的支撑的密度和胶片的雾翳的密度所必需的曝光，测定胶片的感光速率。
曝光胶片的样品在室温下存放1个月。在存放结束后，对胶片显影，且再一次测定胶片的感光速率。
下表给出新曝光射线照相术产品和贮藏后的曝光射线照相术产品在感光速率上的差值。
表1
| 化合物(Ⅰ) | 总量(Ⅰ)(mmol/molAg) | 初始感光速率 | 感光速率的差值 |
| - | - | 100 | -4 |
| A | 0.1 | 100 | -1 |
| C | 0.1 | 100 | -1 |
| E | 0.1 | 100 | -1 |
相对于不含化合物(Ⅰ)的标准值是100的对照胶片，计算感光速率。
这个实施例显示出当含有化合物(Ⅰ)的射线照相术产品进行电离辐射曝光时，潜像的保持能力实质上得到了提高。实施例2
在本实施例中实施例1的射线照相术产品通过钢楔进行Co60辐射(1.2MeV)曝光。该产品在实施例1所述的条件下显影。
通过用针对给定的钢楔区域的透射光密度计读显影曝光的胶片得到表2给出的密度。
表2
| 化合物(Ⅰ) | 总量(Ⅰ)(mmol/molAg) | 密度 |
| - | - | 4.67 |
| C | 0.1 | 5.10 |
| E | 0.1 | 5.02 |
| A | 0.1 | 5.04 |
上述结果显示出当含有化合物(Ⅰ)的射线照相术产品进行Co60辐射曝光时，该产品具有更高的射线照相感光度。
Claims (9)
1．用于进行能量至少是40KeV的电离辐射曝光的，具有至少50mg/dm2银含量的非光谱感光射线照相术产品，其中包括涂敷在具有卤化银乳液层的其至少一个侧面上的支撑，该乳液层中至少50％的颗粒是板状颗粒，且其至少含有0.05mmol/molAg的下式化合物
其中R1和R2各自表示氢原子、包含1至5个碳原子的取代的或非取代的烷基，羟基或苄基，且R3和R4各自表示氢原子或包含1至5个碳原子的烷基，或共同表示构成4至6原子构成的取代的或非取代的杂环的必需的原子。
2．根据权利要求1的射线照相术产品，其中R1选自氢原子或羟基，且R2是甲基。
3．根据权利要求1的射线照相术产品，其中卤化银乳液是主要由溴化银组成的板状颗粒乳液。
4．根据权利要求1的射线照相术产品，化合物(Ⅰ)的量是0.1mmol/mol至0.5mmol/molAg的范围。
5．根据权利要求1-4任一权利要求的射线照相术产品，包括涂敷在具有卤化银乳液层的两个侧面上的支撑。
6．式(Ⅰ)的化合物的用途是增加包含有板状颗粒的用于工业射线照相术的产品的感光速率。
7．式(Ⅰ)的化合物的用途是提高通过对包含有板状颗粒的工业X射线产品进行电离辐射曝光得到的潜像的保持能力。
8．工业射线照相术图像的形成方法，其中包括下述步骤：对根据权利要求1-5中任一权利要求所确定的工业射线照相术产品进行能量至少等于40KeV的电离辐射曝光以得到潜像；且将该产品显影形成射线照相术图像。
9．用于工业射线照相术的系统，包括用以强化电离辐射的两个屏和权利要求1-5中任一权利要求所确定的工业射线照相术产品，所述屏置于射线照相术产品的每一侧面。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR98/06867 | 1998-05-27 | ||
| FR9806867A FR2779242B1 (fr) | 1998-05-27 | 1998-05-27 | Nouveau produit pour radiographies industrielles |
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| US (1) | US6326135B1 (zh) |
| EP (1) | EP0961164B1 (zh) |
| JP (1) | JP4130516B2 (zh) |
| CN (1) | CN1236906A (zh) |
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| FR2879767B1 (fr) * | 2004-12-17 | 2007-03-09 | Eastman Kodak Co | Systeme pour radiographie industrielle |
| JP2010019923A (ja) * | 2008-07-08 | 2010-01-28 | Fujifilm Corp | 工業用ｘレイ感光材料 |
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| BE756535A (fr) * | 1969-09-23 | 1971-03-01 | Eastman Kodak Co | Emulsion photographique aux halogenures d'argent sursensibilisee |
| US3667958A (en) * | 1970-04-09 | 1972-06-06 | Eastman Kodak Co | Photosensitive and thermosensitive elements,compositions and processes |
| JPS599892B2 (ja) * | 1975-04-03 | 1984-03-06 | 富士写真フイルム株式会社 | 放射線写真を得る方法 |
| FR2737588B1 (fr) * | 1995-08-01 | 2001-11-02 | Kodak Pathe | Nouveau produit pour radiographie industrielle |
| US5773208A (en) * | 1996-11-27 | 1998-06-30 | Eastman Kodak Company | Latent image keeping improvement with a hexose reductone and green sensitized epitaxially-finished tabular grain emulsions |
| US5763145A (en) * | 1996-11-27 | 1998-06-09 | Eastman Kodak Company | Photographic element containing a reductone and, in the most blue light sensitive layer, a fine grain emulsion |
| US5876905A (en) * | 1997-03-20 | 1999-03-02 | Eastman Kodak Company | Dual-coated radiographic element capable of photothermographic imaging |
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1998
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- 1999-05-05 EP EP99420110A patent/EP0961164B1/en not_active Expired - Lifetime
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| US6326135B1 (en) | 2001-12-04 |
| DE69910118T2 (de) | 2004-06-24 |
| FR2779242B1 (fr) | 2000-06-30 |
| EP0961164A1 (en) | 1999-12-01 |
| FR2779242A1 (fr) | 1999-12-03 |
| JP2000002957A (ja) | 2000-01-07 |
| EP0961164B1 (en) | 2003-08-06 |
| JP4130516B2 (ja) | 2008-08-06 |
| DE69910118D1 (de) | 2003-09-11 |
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