CN106917063A

CN106917063A - Metal mask material and metal mask

Info

Publication number: CN106917063A
Application number: CN201610963957.5A
Authority: CN
Inventors: 近藤祐幸
Original assignee: JX Nippon Mining and Metals Corp
Current assignee: JX Nippon Mining and Metals Corp
Priority date: 2015-11-04
Filing date: 2016-11-04
Publication date: 2017-07-04
Anticipated expiration: 2036-11-04
Also published as: JP2017088915A; TWI621719B; TW201718904A; KR20170052472A; JP6177299B2; KR101879052B1; CN106917063B

Abstract

[problem] is provided can improve etching and processing precision and can be with the metal mask material of good accuracy detection self-defect and metal mask.[solution] metal mask material, it is formed by the milled sheet of Fe Ni systems alloy, the milled sheet of the Fe Ni systems alloy includes the Ni and Co for amounting to 30 ~ 45 mass %, the wherein Co containing 0 ~ 6 mass %, and remainder is made up of Fe and unavoidable impurity, thickness t is more than 0.08mm, it it is 0.01 ~ 0.20 μm according to the arithmetic average roughness Ra that JIS B0601 are determined along rolling parallel direction and rolling vertical direction, also, it is 200 ~ 600 according to 60 degree of glossiness G60 that JIS Z8741 are determined along rolling parallel direction and rolling vertical direction.

Description

Metal mask material and metal mask

Technical field

The middle metal mask material and metal mask for using such as the manufacture the present invention relates to organic el display.

Background technology

In flat-panel monitor, compared with the liquid crystal display of present main flow, organic el display has following characteristics：Due to Simple structure, therefore can cause that product is thinner；The display of fast-changing image is smooth；Also visual field angular width etc..This is organic The EL display mass production in the mini-plants such as portable terminal device, as the main force of display of future generation, in large-scale displays Practical advanced.

As the method for EL (luminous) layer for making organic el display, vapour deposition method and print process are roughly divided into.Vapour deposition method It is the method for making the EL materials for heating in a vacuum, evaporating that the surface of substrate is attached in the form of thin layer.Additionally, print process is By printing EL layers on a surface of a substrate so as to the method for being made.It is further (red green in the presence of RGB is sent in vapour deposition method It is blue) type of three coloured light and make the EL layers of type for sending white light.

In vapour deposition method, in order to make EL layers at the assigned position of substrate with the pattern for specifying, exist in vapor deposition source and base The multicolour pattern that metal mask is set between plate forms (color patterning) operation.Metal mask by with EL layers The metal plate or paper tinsel of the corresponding opening portion of pattern are formed.Evaporated from vapor deposition source and the EL materials in being disengaged to vacuum are reached Metal mask, the EL materials through the opening portion of metal mask are attached to substrate, so as to form EL layers with predetermined pattern.

However, in multicolour pattern formation process, due to the radiant heat and then temperature that are sent from vapor deposition source organic material high Material is attached on metal mask surface, so as to the situation for causing the temperature that there is metal mask to rise to 100 DEG C or so, in order to protect The precision of the shaping position on substrate is held, is needed to use for metal mask with below the equal extent compared with substrate The material of thermal expansion.Especially, for EL layers in the type for sending RGB three coloured lights pattern, it is necessary to form the three of RGB respectively Color, it is therefore important that suppressing because of the deviation of shaping position caused by the expansion of metal mask.

For the thickness of metal mask, the main paper tinsel using 0.02 ~ 0.08mm in the type for sending RGB three coloured lights, Make the main plate using 0.08 ~ 0.25mm in the EL layers of type for sending white light.

However, if the pattern of metal mask is formed becomes fine, the masking part clamped by the opening portion of mask becomes Carefully, so that intensity decreases, have bending and cause the risk of opening portion shape distortion.

Accordingly, as the intensity and the method for the form accuracy of aperture portion of taking into account metal mask, disclose part setting and add Gu metal wire is so as to prevent the technology (patent document 1) of the bending of the metal mask of thickness of thin, make perforate forming layer thinning and incite somebody to action It is engaged with other support layer so as to make the technology (patent document 2,3) of piece of metal mask.Furthermore disclosed control Surface roughness is so as to improve the technology (patent document 4) of etching and processing precision.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 10-50478 publications

Patent document 2：No. 4126648 publications of Japanese Patent No.

Patent document 3：Japanese Unexamined Patent Publication 2004-039628 publications

Patent document 4：Japanese Unexamined Patent Publication 2010-214447 publications.

The content of the invention

The invention problem to be solved

However, in the case of technology disclosed in patent document 1, because organic material will not be attached to as reinforcing metal wire Shade part, therefore there is the phenomenon similar with shadow effect, the form accuracy change of the organic material being formed on substrate Difference.Additionally, in the case of technology disclosed in patent document 2,3, two panels metal is needed in order to manufacture piece of metal mask Paper tinsel, needs further exist for engaging these metal foils with good precision, therefore the molding procedure of metal mask becomes complicated, manufacture Cost increase.

On the other hand, in by operation of the method by metal mask material manufacture metal mask such as etchings, by visual observation Or there is zero defect on the surface of the monitoring metal mask material such as CCD camera, and defective metal mask material is picked from operation Remove.

Additionally, for the position beyond the opening portion of metal mask, although do not reach the shielded evaporation thing on substrate Matter can be deposited, but be reused such that it is able to be used as metal mask by washing.For such reusable metal mask Surface have zero defect, be monitored also by visual or CCD camera etc., defective metal mask is picked from operation Remove.

Used as the defect of metal mask, it is bad to enumerate foreign matter, local discoloration and the gloss for adhering on the surface, right The tiny flaw that cannot be confirmed by visual observation in these defects, shooting is amplified to surface by using CCD camera etc. Obtained from image checked.The tone foreign matter drawn game different from metal mask material among defect can easily be detected Portion changes colour.Additionally, for tone and metal mask material identical foreign matter, such as sheet metal, foreign matter, the part different from tone Discoloration is compared to be become to be difficult to detect.Further, it is bad for local gloss, because profile is unintelligible and tone is covered with metal Mold materials is identical, therefore becomes more difficult to be identified on CCD camera image.

Therefore, when the concavo-convex and texture on the surface of metal mask material is obvious, checks be difficult to detect above-mentioned office by visual observation The slight and faint defect of the bad grade of gloss in portion, further, even CCD camera image, there is also also undetectable Risk, for this point, the technology that patent document 4 is recorded is although by making surface roughness moderately roughening so as to improve etching Machining accuracy, but caused above-mentioned local with good accuracy detection by CCD camera image due to the concavo-convex of surface The bad aspect of gloss is insufficient.

Therefore, problem of the invention is, there is provided can improve etching and processing precision and can be with good accuracy detection The metal mask material and metal mask of self-defect.

Means for solving the problems

The present inventor etc. has been repeated further investigation, as a result finds, is controlled in the model for specifying by by 60 degree of glossiness G60 Enclose, can have can improve etching and processing precision and can be recessed with the appropriate surface of good accuracy detection self-defect It is convex.

That is, metal mask material of the invention formed by the milled sheet of Fe-Ni systems alloy, and Fe-Ni systems alloy rolls Making sheet includes the Ni and Co for amounting to 30 ~ 45 mass %, wherein the Co containing 0 ~ 6 mass %, and remainder is by Fe and cannot avoid Impurity constitute, thickness t is more than 0.08mm, along rolling parallel direction and the rolling calculation that is determined according to JIS-B0601 of vertical direction Art average roughness Ra is 0.01 ~ 0.20 μm, also, is surveyed according to JIS-Z8741 along rolling parallel direction and rolling vertical direction 60 degree of fixed glossiness G60 are 200 ~ 600.

Additionally, metal mask of the invention is to be formed using aforementioned metal mask material.

The effect of invention

According to the present invention it is possible to providing, etching and processing precision and can be with good accuracy detection self-defect can be improved Metal mask material and metal mask.

Brief description of the drawings

Fig. 1 is the figure of the optical microscope image for showing the texture formed because crystal grain is blocked after finish rolling.

Specific embodiment

Hereinafter, the metal mask material involved by embodiments of the present invention is illustrated.Should illustrate, without spy Do not mentionlet alone it is bright in the case of, " % " expression " quality % ".

(alloying component)

For the substrate of organic EL, using glass, it is necessary to adjust alloying component so that the metal mask being arranged on substrate Thermal coefficient of expansion reaches the thermal coefficient of expansion 10 × 10 of glass^-6/ DEG C below.Thermal coefficient of expansion can be by adding regulation in Fe The Ni and/or Co of concentration are adjusted, and form Ni and Co and add up to the Fe-Ni systems alloy that 30 ~ 45% and Co is 0 ~ 6%.If The total concentration of Ni and Co and the deviation of concentration of the Co scope, then the thermal coefficient of expansion of metal mask go above the hot swollen of glass Swollen coefficient, therefore be inappropriate.It is preferred that it is 0 ~ 6% that Ni and Co add up to 34 ~ 38% and Co.

(thickness)

The thickness of metal mask material of the invention more than 0.08mm, preferably 0.08 ~ 0.25mm, more preferably 0.10 ~ 0.20mm.If the thickness of metal mask material is below 0.08mm, cause in metal mask because of the deposition of organic material In easily produce strain or deform, therefore there is the situation of the positional precision difference for being formed at organic material on substrate.If golden The thickness for belonging to mask material is more than 0.25mm, then exist and the situation of following so-called shadow effects significantly occurs：Away from evaporation The position in source, aperture portion wall turns into shade when the incidence angle of organic material shoals, so that the pattern form shaping of organic material It is the shapes different from aperture portion, it becomes difficult to keep form accuracy.

(arithmetic average roughness Ra)

Surface to metal mask material of the invention determines along rolling parallel direction and rolling vertical direction according to JIS-B0601 Arithmetic average roughness Ra be 0.01 ~ 0.20 μm, preferably 0.01 ~ 0.08 μm.If Ra is less than 0.01 μm so as to exceedingly Reduce surface roughness, then because surface is smooth, therefore easily by etching by metal mask material manufacture metal mask Production line material guide roll (send paper tinsel roller, send plate roller) place occur slide so as to produce damage.If additionally, Ra is more than 0.20 μm so as to excessively increasing surface roughness, then become to be difficult to the unintelligible contour identification on CCD camera image and tone and gold The local gloss of category mask material identical is bad.

Additionally, rolling parallel direction and rolling vertical direction according to JIS- to the surface edge of metal mask material of the invention The maximum height Ry that B0601 is determined is preferably 0.1 ~ 2.0 μm.

(60 degree of glossiness G60)

The edge rolling parallel direction and rolling vertical direction on the surface of metal mask material of the invention are determined according to JIS-Z8741 60 degree of glossiness G60 be 200 ~ 600, preferably 400 ~ 600.If the G60 of metal mask material is less than 200, surface Concavo-convex and texture is obvious, it becomes difficult to by the way that CCD camera image detection profile is unintelligible and tone and metal mask material phase The gloss of together local is bad.If the G60 of metal mask material is more than 600, because surface becomes excessively to smooth, therefore The granule surface contral factor (shape of such as Rolling roller, surface roughness, the viscosity of ROLLING OIL, in rolling roller surface and metal mask Between material surface formed oil film thickness and rolling before metal mask material surface roughness) deviation shadow Ring lower G60 significantly to change, it becomes difficult to the uniformity on surface is ensured, so as to easily produce bad (such as bar of apparent quality Line, inequality).

(manufacture method of metal mask material)

Metal mask material of the invention can be manufactured for example in the following manner, but be not intended to be defined in following shown sides Method.

First, raw materials melt is obtained into the fused solution of above-mentioned Fe-Ni systems alloy composition in melting furnace.Now, if molten The oxygen concentration for melting liquid is high, then the growing amount that there is the crystals such as oxide increases so as to turn into the situation of the reason for etching bad, Therefore addition carbon and carry out vacuum induction melting etc. and improve the purity of fused solution by conventional method of deoxidation, for example, then Casting ingot.Then, after hot rolling, grinding are except oxide layer, cold rolling and annealing is repeated so as to be finish-machined to the thickness of regulation Degree.For cold rolling and annealing, for example, intermediate recrystallization annealing, middle cold rolling, final recrystallization annealing, essence can be carried out successively Cold rolling, stress relief annealing operation.

(intermediate recrystallization annealing)

It is preferred that carrying out grain size number numbering GSNO. (specified in JIS G 0551 " the micrographic test method of steel-grain size number " Numbering) reach 9.0 ~ 11.0 recrystallization annealing.By increasing grain size number numbering GSNO., so as to be moved back by final recrystallization Fire is oriented to the metal structure of (200).For the metal structure that (200) are oriented to by final recrystallization annealing, Crystal grain is not likely to produce in pinch pass blocks texture, can effectively make 60 degree of glossiness G60 be more than 200.If crystal grain Degree numbering GSNO. is small, i.e. crystal grain is big, then existing cannot be fully oriented to the gold of (200) by final recrystallization annealing Belong to the situation of tissue, therefore the lower limit of grain size number numbering GSNO. is 9.0.On the other hand, if grain size number numbering GSNO. Excessive, i.e. crystal grain is too small, then will disperse generation non-recrystallization portion in recrystallized structure, as in final recrystallization annealing The reason for producing uneven recrystallized structure, therefore the upper limit of grain size number numbering GSNO. is 11.0.

If here, improving temperature or the extension time of intermediate recrystallization annealing, GSNO. diminishes, if reducing temperature Or shortening the time, then GSNO. becomes big.

(middle cold rolling)

It is preferred that degree of finish defined in carrying out following formula be more than 85% it is cold rolling.

Degree of finish={ (thickness of slab after thickness of slab-rolling before rolling)/(thickness of slab before rolling) } × 100 (%).

By improving degree of finish, so as to be oriented to the metal structure of (200) by final recrystallization annealing, as above institute State, 60 degree of glossiness G60 are uprised.If degree of finish is small, existing cannot be fully orientated by final recrystallization annealing It is the situation of the metal structure of (200), therefore the lower limit of degree of finish is 85%.On the other hand, even if degree of finish is too high, also will not Further increase the degree of orientation of (200) in final recrystallization annealing, hardness is uprised so as to productivity ratio reduction in addition, therefore processing The upper limit of degree is 90%.

(final recrystallization annealing)

In final recrystallization annealing, if carrying out the recrystallization annealing that grain size number numbering GSNO. reaches 9.0 ~ 11.0, root According to it is identical with the situation that intermediate recrystallization is annealed the reasons why, can effectively make 60 degree of glossiness G60 be more than 200.

(pinch pass)

The surface texture (arithmetic average roughness Ra and 60 degree of glossiness G60) of metal mask material is according to generation in pinch pass Concave-convex surface difference and change.In pinch pass, rolling slivering is transferred to material, so as to cause to produce concave-convex surface. Additionally, ROLLING OIL is flowed between Rolling roller and material in pinch pass, oil pit (oil pit) is produced, thus also produce surface It is concavo-convex.In other words, there is oil film between Rolling roller and material, in the partly thick part of oil film, Rolling roller and material Contact becomes insufficient, so that non-transfer roll slivering and the concavo-convex of hole shape is presented, this turns into oil pit.As ROLLING OIL partly Thickening the reason for, the deviation of the processability of the concavo-convex and material of rolling roller surface can be enumerated.Especially, if surface becomes flat Sliding, then the sensitiveness of the influence of deviation is improved, and easily produces the deviation of the thickness of oil film.

Further, crystal grain is blocked so as to produce texture in pinch pass, and 60 degree of glossiness G60 are produced a very large impact.

The optical microscope image of the texture formed because crystal grain is blocked after Fig. 1 display pinch passes.Because crystal grain is blocked The texture of formation is discontinuously scattered in a row along rolling direction RD, as indicated in the arrow of Fig. 1, each texture be with rolling direction The striated that the side that RD intersects upwardly extends.Should illustrate, in Fig. 1,2 (2 row) clearly line be generated along rolling direction RD Reason.

Here, the mark G of Fig. 1 represents elliptoid 1 crystal grain extended on rolling direction RD in cold rolling.Understand, Block the inside that texture results from crystal grain G.

Should illustrate, in Fig. 1, be focused due to the focus for making optical microscope image and block texture, therefore focus in crystal grain Position is blocked the concave-convex surfaces such as oil pit, the transfer of rolling slivering that texture is very different and is not mirrored in Fig. 1 with crystal grain.

From from the viewpoint of productivity ratio, the cold rolling of andante is entered with degree of finish high, therefore crystal grain is extended by more long, so as to become Obtain and easily block.The crystal grain for blocking is rendered as texture on the surface as illustrated in fig. 1, causes 60 degree of reductions of glossiness G60.

Here, the difficulty blocked that crystal grain occurs is influenceed by the orientation of crystal grain, the difference of the orientation according to crystal grain is blocked Difficulty is different.Its reason is the deformability for crystallizing according to the different and different of crystalline orientation.Also, metal of the invention Main diffraction peak in the alloy system of mask material is (200) face, (220) face, (311) face and (111) face, but in (200) Crystal grain is most difficult to block on face.Therefore, it is oriented to it as described above by intermediate recrystallization annealing and final recrystallization annealing (200) face, thus becomes to be difficult blocking for crystal grain because of pinch pass, and 60 degree of glossiness G60 can be made to be more than 200.

It is preferred that making the degree of finish of pinch pass turns into more than 70%.Degree of finish is higher, then cause because of the effect of compression process The texture that blocks of the crystal grain generated in pinch pass becomes smaller, and 60 degree of glossiness G60 become higher.On the other hand, even if processing Spend height, because crystal grain caused by compression process the effect for blocking texture faintization also can saturation, in addition hardness uprise so as to Productivity ratio reduction, therefore, the upper limit of degree of finish is 90%.

Here, carried out using diameter Rolling roller as small as possible it is cold rolling so that being involved in for ROLLING OIL tails off, rolling stock Surface it is smoothened.When i.e., using the small Rolling roller of diameter, the generation of oil pit can be suppressed, and then cutting for crystal grain can be made Disconnected texture diminishes.Additionally, it is same with rolling roll neck, by making mill speed for low speed, so that being involved in for ROLLING OIL tails off, rolling The surface of material is smoothened.That is, when making mill speed for low speed, the generation of oil pit can be suppressed, and then can cut crystal grain Disconnected texture diminishes.

Should illustrate, thickness, the width of the diameter and mill speed of cold rolling Rolling roller according to the metal mask material of manufacture Spend and change, the diameter and mill speed of appropriate setting Rolling roller in the range of Ra and G60 can controlled, preferably make to roll Speed processed is 60m/ minutes following.

Should illustrate, it is each to be produced because of the different factors that oil pit and crystal grain block texture, therefore preferably confirm Setting can suppress both manufacturing conditions while oil pit and crystal grain block the production of texture.

(stress relief annealing)

Further, stress relief annealing is preferably finally carried out at 200 ~ 400 DEG C.The time of stress relief annealing for example can be 1 ~ 24 Hour.

Embodiment

Hereinafter, embodiments of the invention are shown, but these embodiments are to provide for a better understanding of the present invention, and It is not intended to the limitation present invention.

(1) manufacture of metal mask material

By vacuum induction melting, melting making adds raw material obtained from the Ni of 36 mass % in Fe, and cast thickness is 50mm Ingot.8mm is hot rolled to, after grinding removes the oxide-film on surface, cold rolling and annealing is repeated, be made cold rolling material, so Afterwards, intermediate recrystallization annealing, middle cold rolling, final recrystallization annealing, the work of pinch pass are carried out successively under the conditions shown in Table 1 Sequence, is finish-machined to embodiment 1 ~ 8, the metal mask material of the product thickness of comparative example 1 ~ 4 of table 1.Further, at 300 DEG C Carry out the stress relief annealing of 12 hours.Additionally, used as embodiment 9, the Co of the Ni and 5 mass % of 31 mass % is added in manufacture in Fe Obtained from constitute material.The manufacturing process of embodiment 9 is identical with other embodiment.

Should illustrate, the grain size number numbering GSNO. in intermediate recrystallization annealing is 10.0.Additionally, for each implementation Example, the arithmetic average roughness Ra that the surface roughness of Rolling roller is adjusted respectively to cause product surface reaches 0.07 ~ 0.08 (0.065~0.084)。

The metal mask material of each embodiment and comparative example after for stress relief annealing, carries out following evaluation.

(1) arithmetic average roughness Ra

It is measured as described above.Determine using contact surface roughness meter (small slope studies made SE-3400), obtain with n >=3 be measured obtained from average value.

(2) 60 degree of glossiness G60

It is measured as described above.Determine using the handheld Grossmeters PG-1 of electricity Se Industrial Co., Ltd of Japan system, obtain Average value obtained from being measured with n >=3.

(3) error measurement of surface defect whether there is

5 surface defects of grade of crime of willfully making or propagating computer viruses and other destructive programs on the metal mask material of each embodiment and comparative example, are taken a picture with CCD respectively Machine determines surface defect.

Specifically, the acidproof adhesive tape of 50mm × 50mm is pasted on the surface of each metal mask material, is set at its center The opening portion of 10mm × 10mm is put so that surface portion is exposed.On the exposed division, be coated with the etching solution of following 5 kinds of concentration from And concave-convex surface is formed it into, it is made surface defect.The exposed division can confirm fuzzyyer compared with surrounding by visual observation State, therefore it is regarded as turning into the surface defect of benchmark.

Etching solution be by the ferric chloride in aqueous solution of 47 Baume degrees directly using, with water it is diluted to respectively 2 times, 4 times, 8 Again, 16 times of solution for obtaining amount to 5 kinds, and the absorbent cotton for being impregnated with etching solution is clamped with tweezers, and exposed division 15 is wiped with absorbent cotton Second is so as to be etched.After etching, etching solution is wiped away with the cloth for being impregnated with water, peel off acidproof adhesive tape, fulfiled assignment.Should say Bright, by ferric chloride in aqueous solution, when being used to etch in the case of undiluted, the metallic luster of exposed division completely loses, presentation is white Color, as dilution rate is uprised, the fog-level of exposed division dies down.Additionally, when dilution rate is 32 times, it is impossible to confirm by visual observation To the fuzzy of exposed division, it is accordingly regarded as not forming surface defect, so as to reach the etching solution untill 16 times using dilution rate.Cause This, by the etching that above-mentioned 5 kinds of etching solutions are carried out, forming the surface defect that can be confirmed by visual observation, as long as by gold Belong to the influence of the concave-convex surface of mask material, then should also be as being detected as surface defect by CCD originally.

Then, for above-mentioned 5 kinds of surface defects, 256 grades of pixel datas of (± 128) are shot by CCD camera. This, will block the state of reflected light as most dark reflection, be -128 by its brightness settings, by the table from metal mask material The reflection of constant portion (position around exposed division) is set as ± 0 in face.Also, reflection brightness fallen in the range of ± 20 The regular reflection in constant portion is defined as, the exception that the reflection of the scope of brightness disengaging ± 20 is defined as in surface defect is anti- Penetrate, can confirmation detect the abnormal reflection at exposed division.

For each embodiment and the metal mask material of comparative example, all above-mentioned 5 kinds of surface defects will can be detected Situation is judged as " error measurement free of surface defects ", and the situation that will fail to detect more than a kind of surface defect in 5 kinds is judged as " having the error measurement of surface defect ".

【Table 1】

Show in the case of each embodiment that Ra is 0.01 ~ 0.20 μm, G60 is 200 ~ 600, surface does not occur and lacks by table 1 Sunken error measurement.

On the other hand, it is more than 60m/ in the comparative example 1 of the degree of finish less than 70% of pinch pass and the mill speed of pinch pass In the case of the comparative example 2 of minute, G60 is less than 200, the error measurement that surface defect occurs.

Final recrystallization annealing is carried out under conditions of the crystallization particle diameter (GSNo.) of final recrystallization annealing is less than 9.0 In the case of comparative example 3 and in the case of middle comparative example 4 of the cold rolling degree of finish less than 85%, G60 is less than 200, and table occurs The error measurement of planar defect.

Claims

1. metal mask material, it is formed by the milled sheet of Fe-Ni systems alloy, and the milled sheet of Fe-Ni systems alloy is comprising total The Ni and Co of 30 ~ 45 mass % are counted, wherein the Co containing 0 ~ 6 mass %, and remainder is made up of Fe and unavoidable impurity,

Thickness t is more than 0.08mm,

The arithmetic average roughness Ra determined according to JIS-B0601 along rolling parallel direction and rolling vertical direction is 0.01 ~ 0.20 μm,

Also, along 60 degree of glossiness G60 that rolling parallel direction and rolling vertical direction are determined according to JIS-Z8741 be 200 ~ 600。

2. metal mask, the metal mask material described in its usage right requirement 1 is obtained.