CN1310271C - 玻璃成形用模具及其生产方法,和阴极射线管用的玻璃产品的生产方法 - Google Patents
玻璃成形用模具及其生产方法,和阴极射线管用的玻璃产品的生产方法 Download PDFInfo
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- 230000015572 biosynthetic process Effects 0.000 title description 6
- FFNMBRCFFADNAO-UHFFFAOYSA-N pirenzepine hydrochloride Chemical compound [H+].[H+].[Cl-].[Cl-].C1CN(C)CCN1CC(=O)N1C2=NC=CC=C2NC(=O)C2=CC=CC=C21 FFNMBRCFFADNAO-UHFFFAOYSA-N 0.000 title 1
- 239000011651 chromium Substances 0.000 claims abstract description 53
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 50
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
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- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 28
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 28
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- 238000010438 heat treatment Methods 0.000 claims description 4
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- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 3
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
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- 239000001301 oxygen Substances 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
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- 238000004458 analytical method Methods 0.000 description 2
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- 230000001590 oxidative effect Effects 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
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- C03B23/217—Uniting glass rods, glass tubes, or hollow glassware for the production of cathode ray tubes or similarly shaped tubes
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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- C03B11/084—Construction of plunger or mould for making solid articles, e.g. lenses material composition or material properties of press dies therefor
- C03B11/086—Construction of plunger or mould for making solid articles, e.g. lenses material composition or material properties of press dies therefor of coated dies
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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Abstract
玻璃成形用模具,它包括具有成形表面的模具、在该成形表面上形成的铬涂膜和在该铬涂膜表面上形成的氧化硅膜。
Description
技术领域
本发明发明涉及玻璃成形用模具,具体是用于形成玻璃产品如电视机阴极射线管用的面板或玻锥的玻璃成形用模具。
背景技术
通过分别生产前(影像屏幕)面板和后玻锥,在面板的内表面涂上磷光体,连接上荫罩板、电极、电子枪等,接着使用釉料进行真空焊接,由此制得电视机的阴极射线管。由于面板作为影像屏幕,所以对它的内表面的表面精密度和状态(如表面不规则度)方面尤其要求进行非常严格的质量控制。通过在约1000℃的高温下在模具上压制熔融玻璃而制得面板和玻锥。因此,用于成形的模具需要具有如机械强度、热抗性、抗高温熔融玻璃的化学稳定性等方面的特性。
已知不锈钢是用作这种模具的一种基本的材料,因为它便宜并且能在高精密度下进行加工,且能被加工成复杂的形状。还已知可使用具有在不锈钢表面上形成的铬涂膜的模具,以便获得抗氧化性。
但是,如果含有大量氧化性物质(如二氧化硅、氧化钠、氧化钾、氧化锶、氧化钡和氧化铅)的高温熔融玻璃,如制备阴极射线管用的玻璃长时间成形,模具表面上的铬涂膜的表面逐渐被氧化成氧化铬膜。结果,该模具表面的表面粗糙度、表面精密度、与产品的脱模性能等将变差,该铬涂膜的表面将发生高温腐蚀。如果这种腐蚀进一步发展,玻璃产品的质量将变差,最终需要更换模具。换好模具后,需要一些时间才能使玻璃成形稳定,从而使得生产率显著下降。因此,控制铬涂膜的表面的高温腐蚀对提高生产率贡献极大。至于控制铬涂膜的高温腐蚀的方法,如对该铬涂膜进行阳极氧化以在其表面上形成抗腐蚀的氧化铬膜的方法是已知的。但是,通过这种阳极氧化得到的氧化物膜有个缺点,即该氧化物膜自身会变厚,并且当长时间用它来形成高温熔融玻璃时它会剥落。此外,还使用的一种方法,其中将热抗性碳涂在模具表面上的铬涂膜的表面上,以抑制该铬涂膜的腐蚀,但是,此方法仍然存在缺点,即抑制腐蚀的作用限制在相当短的时间内,并且该涂层部分易于脱落。
发明内容
本发明的一个目的是提供一种玻璃成形用模具,该模具几乎不发生高温腐蚀,也不发生脱落,且可长时间用于高温熔融玻璃的成形。
本发明提供的玻璃成形用模具包括具有成形表面的模具、在成形表面上形成的铬涂膜和在该铬涂膜表面上形成的氧化硅膜。
此外,本发明提供的玻璃成形用模具包括具有成形表面的模具、在该成形表面上形成的铬涂膜和经由氧化铬膜在该铬涂膜表面上形成的氧化硅膜。
本发明还提供一种玻璃成形用模具,该模具包括具有成形表面的模具、在该成形表面上形成的镀铬涂膜,其中,在该镀铬涂膜的表面上依次形成氧化铬膜和氧化硅膜。
还有,本发明提供了一种生产玻璃成形用模具的方法,该方法包括在模具的成形表面上形成铬涂膜,然后进一步在该铬涂膜的表面上涂上含有硅化合物的涂液。
铬涂膜的腐蚀机制如下。当在铬涂膜的表面上反复在1000℃的温度水平长时间成形高温熔融玻璃。该表面逐渐被氧化。尤其是在成形高温熔融玻璃时,以约1循环/10秒钟的非常短的循环时间连续和有规律地重复在模具上通过液压压制熔融玻璃然后释放压力的过程,从而使铬涂膜与高温熔融玻璃的接触反复进行,由此如上所述,铬涂膜表面的腐蚀将通过它与空气中的氧气和高温熔融玻璃的反应而发生,这样该铬涂膜表面的表面粗糙度、表面精密度、与产品的脱模性能等将变差。此外,铬涂膜表面的腐蚀机制除上述机制外,还存在另一种机制,即会形成含有铬和碱金属的粉末状双氧化物,并且现已发现这种双氧化物促进了该铬涂膜的表面精密度的不稳定性。
鉴于上述机制,已研究了抑制铬涂膜表面由于与空气中的氧气和高温熔融玻璃反应而被腐蚀的过程的方法。结果,已发现通过在铬涂膜的表面涂上含有用于形成氧化硅膜的Si化合物(下文称为硅化合物)的涂液(下文称为硅涂液),在该铬涂膜的表面上形成氧化铬膜,然后在此氧化铬膜的表面上进一步形成氧化硅膜。此外,已发现这种氧化铬膜和氧化硅膜具有优异的抑制铬涂膜表面的腐蚀过程的性能,它们具有高粘附强度,是致密的,并且稳定性优异。
已发现这种氧化铬膜与在长时间成形高温熔融玻璃的条件下形成的氧化铬膜比,其X射线衍射分析的结果显示具有不同的晶体取向。并不需要清楚地理解抑制腐蚀的机制,但可以认为,通过这种晶体取向的差异将获得抑制铬涂膜表面的腐蚀的优异性能。
此外,由于氧化硅膜中的Si原子会与存在在上述氧化铬膜的表面上的氧原子结合,所以可认为上述氧化硅膜具有高粘附强度,并且是致密的,且稳定性优异。还可进一步认为通过这种氧化硅膜的形成,防止了空气中的氧扩散到模具表面,从而可获得优异的抑制铬涂膜腐蚀的性能。
附图说明
图1是用于将阴极射线管的面板玻璃成形的模具的截面图。
具体实施方式
图1是用于形成阴极射线管用的面板的模具的截面图,该模具是玻璃成形用模具的例子。在模具10的成形表面上形成铬涂膜20。在铬涂层膜20的表面上涂上硅涂液,接着在室温下干燥、加热、水解等,在铬涂膜20的表面上形成氧化铬膜30,接着在氧化铬膜30上形成氧化硅膜40。
在本发明中,可采用已知的方法在模具的表面上形成铬涂膜。这些方法并无特殊限制,但常采用电镀方法。从防止模具的基材的氧化和确保与模具的基材的粘附强度的角度考虑,铬涂膜的厚度最佳为2-200μm。
本发明并不特殊限制硅化合物,只要该化合物能通过在室温中的干燥、加热。水解等形成氧化硅膜即可。举个例,选自二甲基硅氧烷型硅油、甲基化氢化二烯(methyl hydrodiene)型硅油和在Si-H基中具有经OH基或环氧基修饰的H的硅油的至少一种硅油可以作为上述硅化合物。此外,对于这种硅化合物,还可适当地使用选自烷氧基硅化合物(如四甲氧基硅基)和活性硅化合物(如硅氮烷)的至少一种化合物。
此外,该硅涂液可以仅由硅化合物组成,或者是硅化合物和无机溶剂和/或有机溶剂的混合物,以获得匀一的涂层。例如,最佳使用硅化合物和水以及醇的混合物。如下文所述,视需要,可根据氧化硅膜中Si沉积的量调整硅化合物的浓度。但是,在涂液中它的含量最佳为1-90质量%。对醇并没有特殊限制,最佳使用如甲醇或乙醇。为了防止溶剂有剩余,涂液中醇的浓度最佳为0.1-50质量%。
为了获得匀一的涂层,可在硅涂液中加入表面活性剂。对于表面活性剂,可以使用硅氧烷型、非离子型、阳离子型或阴离子型的表面活性剂。尤其优选硅氧烷型或非离子型的表面活性剂。
并不特殊限制涂覆硅涂液的方法。例如,可以采用喷洒法、旋转涂覆法或刷涂法。
涂覆硅涂液后,最佳将模具加热。为了防止溶剂残留,最佳在100-800℃在空气中加热模具1-12小时。
通过调整如加热处理条件或硅涂液的浓度,可调节通过涂覆硅涂液而形成的氧化铬膜的厚度,使用SEM观测该氧化铬膜的横截面结构,此厚度最佳是0.1-2μm。如果此厚度超过2μm,则它不是最佳的,因为氧化膜会剥落;如果它小于0.1μm,则也不是最佳的,因为它的抗腐蚀性变差。
可使用SEM以和在氧化铬膜的例子中相同的方式测量在该氧化铬膜上形成的氧化硅膜的厚度。但是,本发明没有使用SEM测量该膜的厚度,取而代之的是使用荧光X射线装置测量氧化硅膜上每单位面积沉积的Si量(下文简单地称为Si沉积量)。通过这种使用荧光X射线装置进行的测量,可增加测量的面积,从而具备使氧化硅膜的表面不规则的影响最小化的优点。上述Si沉积量最佳是0.1-300μg/cm2,以抑制铬涂膜表面的腐蚀并防止表面粗糙度变差。此外,该量特别优选为0.1-40μg/cm2,以防止氧化硅膜的剥落。
表面粗糙度变差意味着模具表面在外观上出现不均匀。如果表面粗糙度进一步变差,则成形的玻璃的表面粗糙度将不均匀,从而产品的质量变差。因此,通过目测观察判断该模具的表面粗糙度是否匀一来决定更换模具的时间。
长时间成形高温熔融玻璃导致铬涂膜表面的腐蚀,这种腐蚀形成了含有铬和碱金属的粉末状双氧化物。双氧化物的形成量随着铬涂膜表面的腐蚀的发展而增加。这种双氧化物的形成量依如玻璃的温度或成形时间而改变,但最佳至多为30ppm。如果该量超过30ppm,模具的表面精密度将变得不稳定,玻璃产品的质量变差。
此外,根据本发明,在玻璃成形用模具的铬涂膜的表面上形成了氧化铬膜,在该氧化铬膜上形成氧化硅膜,从而可提高该铬涂膜在高温下的抗腐蚀性。因此,这种玻璃成形用模具适用于使含有大量的氧化性物质的熔融玻璃成形,如形成含有如氧化硅、氧化钠、氧化钾、氧化锶、氧化钡和氧化铅的阴极射线管用的面板或玻锥玻璃。
现在,本发明将结合实施例进行更详细的描述。但是,不应认为本发明受到这些具体实施例的限制。
下面是实施例1-9(实施例1、2、6和9是比较例,实施例3-5、7和8是本发明的实施例)和测量方法。
1)Si沉积量:使用荧光X射线装置(RIX3000,理学电机株式会社制造),测量氧化硅膜上3cm直径范围内的Si沉积量。
2)铬浓度:将沉积在模具上的粉末状物质溶解在纯水中,用感应耦合等离子体发射光谱化学分析仪(SPS4000,SII制造),通过发射光谱化学分析测量该粉末状物质中所含的铬的浓度。
3)表面粗糙度:不论模具的表面粗糙度是否均匀,均以目测判断。符号“○”表示“均匀”,“×”表示“不均匀”。为了实用目的,“○”最佳。
4)晶体取向(峰值强度):使用X射线衍射装置(RINT2500,Rigaku Denki K.K.制造),测量氧化铬膜在(012)、(104)和(110)的峰值强度。在此,峰值强度代表基于在(104)的峰值强度的相对强度,(104)的峰值强度设为100。在本发明的实施例中,将在(104)的峰值强度设为100时,在(012)的峰值强度至少为50,在(110)的峰值强度至少为40。
此外,下面是实施例1-8中使用的阴极射线管用的面板玻璃的组成。氧化硅:62.0质量%;氧化钠:7.5质量%;氧化钾:8.1质量%;氧化锶:11.6质量%;氧化钡:2.2质量%和其它物质包括氧化锆:8.6质量%。
实施例1
采用电镀方法,在(用于形成29英寸的面板的)模具的成形表面上形成厚20μm的镀铬涂层膜,该模具用于成形阴极射线管用的玻璃面板,模具以SUS420J2(TIS-G4303)作为基材制成。使用这种模具,用96小时进行阴极射线管用的面板玻璃的成形,之后测量沉积在模具上的粉末状物质中铬的浓度和该模具的表面粗糙度。结果列在表1中。
实施例2-6
采用电镀的方法,在模具的成形表面上形成厚20μm的镀铬涂层膜,该模具用于形成阴极射线管用的玻璃面板,模具以SUS420J2作为基材制成。通过加入水进行调节制备硅涂液,以使在该涂液中硅氧烷乳液SH-490(Toray Dow CorningCo.,Ltd.制备)的各浓度如表1所示。采用喷洒法将这种硅涂液涂覆到上述镀铬涂层膜的表面上,然后在500℃在空气中加热4小时,以在该镀铬涂层膜的表面上形成氧化铬膜,接着在该氧化铬膜上形成氧化硅膜。测量该氧化硅膜中Si的沉积量,然后使用上述模具,用96小时进行阴极射线管用的面板玻璃的成形,之后测量沉积在模具上的粉末状物质中铬的浓度和该模具的表面粗糙度。结果列在表1中。
实施例7
采用电镀方法,在SUS420J2平板的表面上形成厚20μm的镀铬涂层膜。通过加入水加以调节制备硅涂液,以使该涂液中的硅氧烷乳液SH-490为90质量%。采用喷洒法将该硅涂液涂覆到上述镀铬涂层膜的表面上,然后在500℃在空气中加热上述SUS420J2平板4小时,从而在该镀铬涂层膜的表面上形成氧化铬膜,接着在该氧化铬膜上形成氧化硅膜。
采用荧光X射线法测量上述氧化硅膜中Si的沉积量,然后在800℃在空气中加热上述SUS420J2平板30分钟,之后测量该氧化铬膜的晶体取向。结果列在表2中。
实施例8
除了使用四甲氧基硅烷替换实施例7中使用的硅氧烷乳液SH-490外,采用与实施例7相同的方式进行处理,并进行测量。结果列在表2中。
实施例9
除了不用实施例7中使用的硅氧烷乳液SH-490进行涂覆外,采用与实施例7相同的方式进行处理,并进行测量。结果列在表2中。
表1
试样 | 涂液浓度(质量%) | Si沉积量(μg/cm2) | 铬浓度(ppm) | 表面粗糙度 |
实施例1 | 0 | 0 | 64 | × |
实施例2 | 1.0 | 0.08 | 47 | × |
实施例3 | 10 | 0.9 | 7.6 | ○ |
实施例4 | 15 | 1.6 | 4.6 | ○ |
实施例5 | 90 | 31 | 2.5 | ○ |
实施例6 | 100 | 350 | 1.6 | × |
表2
晶体取向(峰值强度) | ||||
试样 | Si沉积量(μg/cm2) | Cr2O3(012) | Cr2O3(104) | Cr2O3(110) |
实施例7 | 30 | 57 | 100 | 45 |
实施例8 | 12 | 59 | 100 | 43 |
实施例9 | 0 | 39 | 100 | 22 |
根据本发明,可以提供玻璃成形用模具,从而几乎不发生高温腐蚀,几乎不发生剥落,并且可长时间成形高温熔融玻璃;本发明还提供生产这种模具的方法以及使用这种模具的玻璃成形方法。本发明使用廉价的硅化合物,进行大量生产是可能的。因而,本发明的工业价值高。
在此引入2001年5月28日提交的日本专利申请第2001-158881号公开的全部内容(包括说明书、权利要求书、附图和摘要)作为参考。
Claims (10)
1.一种玻璃成形用模具,它包括具有成形表面的模具、在上述成形表面上形成的铬涂膜和在此涂层膜表面上借助氧化铬膜而形成的氧化硅膜。
2.如权利要求1所述的玻璃成形用模具,其特征在于,所述氧化铬膜是在其X射线衍射分析中在(012)、(104)和(110)具有峰值的氧化铬膜,其中,将在(104)的峰值强度设为100时,在(012)的峰值强度至少为50,在(110)的峰值强度至少为40。
3.如权利要求1-2中任一项所述的玻璃成形用模具,其特征在于,所述氧化铬膜的厚度为0.1-2μm。
4.如权利要求1-2中任一项所述的玻璃成形用模具,其特征在于,所述氧化硅膜的沉积量是0.1-300μg/cm2。
5.如权利要求1-2中任一项所述的玻璃成形用模具,其特征在于,所述氧化硅膜的沉积量是0.1-40μg/cm2。
6.一种生产玻璃成形用模具的方法,该方法包括在模具的成形表面上形成铬涂膜,接着将含有硅化合物的涂液涂覆到该铬涂膜表面上。
7.如权利要求6所述的生产玻璃成形用模具的方法,其特征在于,涂覆所述含有硅化合物的涂液并加热。
8.如权利要求6或7所述的生产玻璃成形用模具的方法,其特征在于,使用硅油作为所述硅化合物。
9.如权利要求6-7中任一项所述的生产玻璃成形用模具的方法,其特征在于,所述涂液中硅化合物的浓度为1-90质量%。
10.一种生产阴极射线管用的玻璃产品的方法,其特征在于,该方法包括使用权利要求1-5中任一项所述的玻璃成形用模具将阴极射线管用的玻璃成形。
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2002
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- 2002-05-28 CN CNB021220034A patent/CN1310271C/zh not_active Expired - Fee Related
- 2002-05-28 US US10/154,960 patent/US6868699B2/en not_active Expired - Fee Related
Patent Citations (5)
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JPS5453122A (en) * | 1977-10-04 | 1979-04-26 | Asahi Glass Co Ltd | Process for forming glass using release agent and releasing agent therefor |
JPH0483723A (ja) * | 1990-07-26 | 1992-03-17 | Olympus Optical Co Ltd | 光学素子成形用型 |
JPH0776250A (ja) * | 1993-09-07 | 1995-03-20 | Nissan Motor Co Ltd | 自動車用バッテリ冷却構造 |
CN1126703A (zh) * | 1994-08-15 | 1996-07-17 | 旭硝子株式会社 | 玻璃成型模及其制造方法以及在阴极射线管中的应用 |
US5964916A (en) * | 1997-05-27 | 1999-10-12 | Asahi Glass Company Ltd. | Mold for forming glass and method for forming glass |
Also Published As
Publication number | Publication date |
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US6868699B2 (en) | 2005-03-22 |
US20030005725A1 (en) | 2003-01-09 |
JP2002348131A (ja) | 2002-12-04 |
KR20020090865A (ko) | 2002-12-05 |
CN1388555A (zh) | 2003-01-01 |
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